TW201101560A

TW201101560A - Porous membrane for nonaqueous secondary battery, separator for nonaqueous secondary battery, adsorbent for nonaqueous secondary battery, and nonaqueous secondary battery

Info

Publication number: TW201101560A
Application number: TW099105326A
Authority: TW
Inventors: Satoshi Nishikawa; Atsuhiro Otsuka
Original assignee: Teijin Ltd
Priority date: 2009-02-24
Filing date: 2010-02-24
Publication date: 2011-01-01
Also published as: JP4625142B2; JP5226763B2; JPWO2010098497A1; JP4685974B2; JP2011077052A; JP2010278018A; WO2010098497A1

Abstract

The first purpose of the present invention is to provide a technique for improving both the safety and durability of a nonaqueous secondary battery. The second purpose of the present invention is to provide a technique for improving the cycle characteristics in view of the reaction with HF or the adsorption. Specifically disclosed is a porous membrane for a nonaqueous secondary battery, which is configured so as to contain a heat-resistant resin and an inorganic filler. The porous membrane for a nonaqueous secondary battery is characterized in that the inorganic filler is composed of a porous filler having an average particle diameter of 0.1-5.0 μm and a specific surface area of 40-3,000 m2/g, or amorphous alumina particles. Also specifically disclosed is a separator which is obtained by arranging the porous membrane, which serves as a heat-resistant porous layer, on a porous base. Also disclosed is an adsorbent for hydrogen fluoride that has entered into a nonaqueous secondary battery, which is characterized by being composed of active alumina particles having a specific surface area of 300-1,000 m2/g, or amorphous alumina.

Description

201101560 六、發明說明：【發明所屬之技術領域】本發明係有關一種非水系蓄電池用多孔膜、非水系蓄電池用隔板、非水系蓄電池用吸附劑及非水系蓄電池。【先前技術】鋰離子蓄電池之典型的非水系蓄電池，廣泛地普遍作 0 爲手機或手提電腦之攜帶型電子機器的主電源。該非水系蓄電池被要求高能量密度化、高容量化及高出力化，預測今後對該要求將更爲提高。對應於該要求而言，確保電池之安全性爲更重要的技術要素。一般而言，非水系蓄電池係具備正極、負極及配置於此等電極間的隔板之構成。隔板係在不會妨礙離子透過下，具有防止正極與負極間之內部短路的功能。一般而言，隔板係使用聚烯烴微多孔膜。其次，由聚烯烴微多孔膜所 Q 形成的隔板’因過充電等原因而使電池的溫度上昇時，由於聚烯烴熔融而導致空孔阻塞，遮斷電池內部電流的關機功能。藉由該功能，尙可防止電池之發熱情形，提高在高溫下之電池的安全性。而且，即使於空孔被阻塞後，電池之內部溫度上昇時，會使隔板破裂，引起內部短路而導致火災等之危險性。因此，以往提高非水系蓄電池之安全性時，著重於具有耐熱性之多孔膜。藉由該耐熱性多孔膜，於電池異常地被暴露於高溫時，可防止正負極間之內部短路情形。例如 -5- 201101560 ，於隔板中使用由耐熱性樹脂所形成的多孔膜之技術（專利文獻1 )、或於隔板中使用由耐熱性樹脂與陶瓷粉末所形成的多孔膜之技術（專利文獻2、3 )、在電極表面上形成由無機塡料與黏合劑樹脂所形成的多孔膜之技術（專利文獻4)等。另外，於由聚烯烴微多孔膜所形成的隔板中分散無機塡料的技術，亦爲已知（專利文獻5)。於此等之技術中，陶瓷粉末之典型的無機塡料，由於耐熱性與壓縮強度高，就可更爲確實地防止正負極間之內部短路情形而言有效。然而，使用該無機塡料之電池，恐會有降低循環特性或保存特性之電池耐久性的問題。該耐久性降低的要因之一，係使於電池內微量存在的氟化氫（HF )與無機塡料進行反應，無機塡料之表面被氟化，此時會有水分生成，該水分使電解液或在電極表面上所形成的SEI ( Solid Electrolyte Interface)皮膜分解的情形。該電解液或SEI 皮膜分解時，由於電池之內部電阻上昇、且於充放電時會使必要的鋰失活，恐有電池之耐久性降低的情形。而且，由於引起該分解反應而產生氣體時，藉此恐有電池之耐久性降低的情形。因此，該分解反應當然亦會成爲電池之安全性降低的原因。特別是使用無機塡料與如芳香族聚醯胺樹脂之耐熱性樹脂時，一般而言由於耐熱性樹脂爲容易吸附水分的物質，故較爲容易產生前述分解反應的問題。另外，於專利文獻6中提案藉由無機塡料改善電池內氣體產生的技術。該技術係在由聚烯烴所形成的隔板中混 -6- 201101560 入由無機粉末所形成的氣體吸收劑，以氣體吸收劑捕捉電池內所產生的氣體。然而，該隔板恐會有耐熱性不充分的問題。而且，在擔當關機功能之聚烯烴微多孔膜中混入有氣體吸收劑之無機塡料，恐會有關機功能顯著降低的情形。因此，雖可顯著抑制氣體產生，惟與使用習知的聚烯烴微多孔膜相比時，恐有電池之安全性降低的問題。如上所述，非水系蓄電池雖要求高性能化，惟目前爲 0 確保達成該目的時之安全性與耐久性倂立的技術上會有困難。此外，爲提高安全性時，推測使用由無機塡料與耐熱性樹脂所形成的多孔膜係爲有效，惟尙未發現可使安全性與耐久性倂立的構成。此處，前述說明有關於隔板或多孔膜之技術領域中，使電池之安全性與耐久性倂立的課題。然而，畢竟就防止起因於存在電池內之HF或水的電池之耐久性降低而言，雖考慮擴大至非水系蓄電池之全部技術領域爲止，以往沒有 Q 提案充分的改善技術。於下述中，說明有關此點。一般而言，鋰離子蓄電池係由鋰過渡金屬複合氧化物等之正極、碳材料等之負極、溶解有Li鹽之有機電解液、及聚乙烯微多孔膜等之隔板所構成。因此，該鋰離子蓄電池，就循環特性及安全性而言，在電池系內沒有混入水分或雜質之嚴格管理下予以製造。然而，無法實質上自電池系內完全除去電池構成構件中所吸附的微量水分、或於電池組裝時所混入的水分。此處，電池系內存在的水分，與六氟化磷酸鋰等之Li 201101560 鹽反應而使HF游離，經游離的HF如下述（1 )〜（3 )進行反應，導致電池之循環特性惡化，係爲已知。 (1 )使正極中所使用的過渡金屬溶解。 (2 )使用鋁作爲正極集電體時，會導致鋁腐蝕。 (3)使用黑鉛作爲負極時，會使負極之界面電阻變高（參照非專利文獻1 )。因此，以往提高循環特性的方法之一，報告有在電池系內添加沸石或二氧化矽凝膠、活性氧化鋁、活性碳等之多孔質無機塡料的技術（例如參照專利文獻7〜9 )。換言之，於專利文獻7中揭示，在隔板中含有比表面積爲15〜300 m2/g之無機物的技術，藉由該無機物以使循環特性變佳。於專利文獻8中揭示，在負極或正極中含有比表面積爲30〜300 m2/g之氧化鋁的技術，可得良好的循環特性。於專利文獻9中揭示，在電池系內含有比表面積爲1 000 m2/g以上之活性碳及無機物的構成，藉由活性碳等可得良好的循環特性。如上所述，報告具有一特定的比表面積之多孔質無機塡料，具有提高電池之循環特性的效果。然而，考慮前述（1)〜（3)之與HF反應或吸附時，推測於各吸附劑中存在可得良好循環特性之比表面積的範圍，惟目前有關該點仍爲未知。而且，藉由無機塡料之比表面積外的要素，以抑制與HF之反應且提高循環特性之技術，亦仍爲未知。 201101560 [習知技術文獻] [專利文獻] [專利文獻1]日本特開2008-266588號公報 [專利文獻2]日本專利第3 1 7573 〇號公報 [專利文獻3]國際公開第2〇〇8/62727號手冊 [專利文獻4]日本特開2〇〇8_2〇4788號公報 [專利文獻5]日本專利第4074 1 1 6號公報 [專利文獻6]日本特開2008_146963號公報 [專利文獻7]日本專利第4 1 45762號公報 [專利文獻8]日本專利第3 70478 0號公報 [專利文獻9]日本特開2000-77103號公報 [非專利文獻] [非專利文獻1 ]鋰離子蓄電池第二版（日刊工業新聞社、芳尾真幸偏）材料與應用第76〜77頁【發明內容】因此’本發明有鑑於前述問題，第一目的係提供可提供一種可提高非水系蓄電池之安全性與耐久性雙方的技術 ’而且’第二目的係就考慮與HF之反應或吸附而言，提供一種可提高循環特性的技術。本發明人等爲解決前述課題時，再三深入硏究檢討的結果’發現可藉由下述之構成以解決課題，遂而完成本發明。 201101560 1. 一種非水系蓄電池用多孔膜，其係含有耐熱性樹及無機塡料所構成的非水系蓄電池用多孔膜，其特徵爲述無機塡料係平均粒徑爲01〜5 0μηι，且比表面積爲4〇 3000 m2/g之多孔質塡料。 2 ‘如前述1記載之非水系蓄電池用多孔膜，其中前多孔質塡料係比表面積爲3〇〇〜i〇〇〇m2/g之活性氧化鋁。 3 . —種非水系蓄電池用多孔膜，其係含有耐熱性樹及無機塡料所構成的非水系蓄電池用多孔膜，其特徵爲述無機塡料爲非晶狀氧化銘粒子。 4.一種非水系蓄電池，其係至少具備正極及負極之水系蓄電池’其特徵爲在前述正極及前述負極之至少一的表面上形成如前述1〜3中任一項記載之非水系蓄電池多孔膜、或使用該非水系蓄電池用多孔膜作爲隔板使用 5 . —種非水系蓄電池用隔板，其係具備多孔質基材被層合於此多孔質基材之一面或兩面上含有耐熱性樹脂無機塡料之耐熱性多孔質層的非水系蓄電池用隔板，其徵爲前述無機塡料係平均粒徑爲〇_1〜5.0μιη，且比表面爲40〜3 000m2/g之多孔質塡料。 6. 如前述5記載之非水系蓄電池用隔板，其中前述孔質塡料係比表面積爲3〇〇〜l〇〇〇m2/g之活性氧化鋁。 7. —種非水系蓄電池用隔板’其係具備多孔質基材被層合於此多孔質基材之一面或兩面上含有耐熱性樹脂無機塡料之耐熱性多孔質層的非水系蓄電池用隔板，其徵爲前述無機塡料爲非晶狀氧化銘粒子。述脂、身- 刖非方用及特積，多及特 -10- 201101560 8. —種非水系蓄電池，其係具備正極、負極及隔板之非水系蓄電池，其特徵爲使用如前述5〜7中任一項記載之非水系蓄電池用隔板作爲前述隔板。 9. 一種非水系蓄電池用吸附劑，其係混入於非水系蓄電池內之氟化氫的吸附劑，其特徵爲該吸附劑爲比表面積爲3 00〜1 000 m2/g之活性氧化鋁粒子。 1 〇· —種非水系蓄電池用吸附劑，其係混入於非水系 0 蓄電池內之氟化氫的吸附劑，其特徵爲該吸附劑爲非晶狀氧化鋁粒子。 11. 一種非水系蓄電池用多孔膜，其係含有無機塡料及黏合劑樹脂所構成的非水系蓄電池用多孔膜，其特徵爲含有如前述9或1 〇記載之非水系蓄電池用吸附劑作爲前述無機塡料。 1 2 · —種非水系蓄電池用隔板，其係具備多孔質基材、與被層合於此多孔質基材之一面或兩面上含有無機塡料 Q 及黏合劑樹脂之多孔質層的非水系蓄電池用隔板，其特徵爲含有如前述9或1 0項之非水系蓄電池用吸附劑作爲前述無機塡料。 1 3 . —種非水系蓄電池，其係具備正極、負極、非水電解質及隔板之非水系蓄電池，其特徵爲在該電池內含有如前述9或1 0記載之非水系蓄電池用吸附劑。 [發明效果] 藉由本發明之第一側面，提供一種可提高非水系蓄電 -11 - 201101560 池之安全性與耐久性雙方的技術。而且，藉由本發明之第二側面’就考慮與HF之反應或吸附'而言，提供一種可提高循環特性之技術。 [爲實施發明之形態] (1 )第一之本發明 (1 -1 )第一之形態 [非水系蓄電池用多孔膜] 本發明第一形態之非水系蓄電池用多孔膜，其係含有耐熱性樹脂及無機塡料所構成的非水系蓄電池用多孔膜，其特徵爲前述無機塡料係平均粒徑爲0.1〜5·0μιη，且比表面積爲40〜3000 m2/g之多孔質塡料。本發明藉由含有耐熱性樹脂及無機塡料，即使電池暴露於高溫下，仍可確保爲防止內部短路時之充分耐熱性，且可確保電池之安全性。而且，由於無機塡料爲平均粒徑爲0.1〜5_0μιη、且比表面積爲40〜3000 m2/g之多孔質塡料 ’藉由抑制電池內降低耐久性之副反應、且除去因副反應所生成的氣體，可提高電池之循環特性或保存特性等之耐久性。特別是由於耐熱性樹脂一般爲容易吸附水分之物質，故本發明中形成容易產生前述HF與無機塡料之副反應的構成，惟本發明中藉由使用前述之多孔質塡料，可顯著降低電池內微量存在的水分或HF之活性，抑制因電解質分解等所導致的氣體產生情形。而且，假設即使產生氣體，仍可 -12- 201101560 捕捉在多孔質塡料中之該氣體。因此，可大幅地改善電池之耐久性。此處，本發明之電池用多孔膜，爲含有耐熱性樹脂與無機塡料所構成’係指在內部具有多數的空孔或空隙’且形成此等空孔等互相連結的多孔質構造。於本發明之耐熱性樹脂中，含有熔點爲200°C以上之樹脂，除熔點爲200°C以上之樹脂外，亦包含實質上熔點 0 不存在下、熱分解溫度爲200°C以上樹脂者。該耐熱性樹脂例如全芳香族聚醯胺、聚醯亞胺、聚醯胺醯亞胺、聚楓、聚酮、聚醚酮、聚醚颯、聚醚醯亞胺、纖維素、此等2 種以上的組合等。其中，就多孔質構造之形成容易性、與無機塡料之黏合性、伴隨於此之多孔膜的強度、耐氧化性等耐久性而言，以全芳香族聚醯胺較佳。此外，於全芳香族聚醯胺中，使對型與間型相比時，間型全芳香族聚醯胺就容易成形而言較佳，特別是以聚間亞苯基異酞醯胺爲宜使用間型全芳香族聚醯胺時，該間型全芳香族聚醯胺溶解於N -甲基-2-吡咯烷酮時，以下述（1)之對數黏度爲 0.8〜2.5 dl/g之範圍者較佳、以1.0〜2.2 dl/g之範圍者更佳。脫離該範圍時，會有成形性惡化的情形，故不爲企求〇對數黏度（單位：dl/g)= ln(T/T0)/C ---(1) T :在l〇〇ml之N-甲基-2-吡咯烷酮中溶解有0.5 g之間型全芳香族聚醯胺樹脂的溶液在3 0°C之毛細管黏度計的流動 -13- 201101560 時間 TO : N-甲基-2-吡略烷酮在30°C之毛細管黏度計的流動時間 C :溶液中之間型全芳香族聚醯胺樹脂的濃度（g/dl ) 本發明中可使用的多孔質塡料，例如沸石、活性碳、活性氧化鋁、多孔質二氧化矽、氫氧化鎂或氫氧化鋁等之金屬氫氧化物進行熱處理所得的多孔質塡料、由有機化合物所合成的多孔質塡料等。其中，特別是以活性氧化鋁爲宜。本發明之活性氧化鋁，係以示性式爲Α1203·χΗ20 ( X 係爲0以上、3以下之値）所表示的多孔質塡料。活性氧化鋁之表面爲非晶狀之Α12〇3、γ-Α1203、χ-Α1203、三水鋁石 (Gibbsite)狀之 Α1(ΟΗ)3、勃姆石（Boehmite)狀之 Λ1203 · Η20等之構造較佳’多孔構造爲以此等之表面構造所形成時，就會降低水分或HF之活性而言更佳。而且，無機塡料除前述之多孔質塡料外，亦可適當地加入α-氧化鋁等金屬氧化物或氫氧化鋁等金屬氫氧化物等之其他的非多孔質無機塡料。該多孔質塡料以50nm以下之介孔或2ntn之微孔所構成較佳，特別是形成發展爲2nm以下之微孔的構造’就具有本發明之效果而言較佳。而且，該多孔質塡料之平均粒徑，以〇.1〜5·〇μιη之範圍爲宜。多孔質塡料之平均粒徑小於〇. 1 μηι時，變得無法使多孔膜成形，且使多孔性之平滑性惡化，導致變得不易 -14 - 201101560 處理’故不爲企求。多孔質塡料之平均粒徑大於5 ·0μιη時 ’於使多孔膜予以薄薄成形時，就表面粗糙度而言不易成形，故不爲企求。於本發明中，該多孔質塡料之比表面積以40〜3 000 m2/g較佳。比表面積未達40 m2/g時，無法充分地降低水分或HF之活性，故不爲企求。而且，大於3000 m2/g時，會有不易使多孔膜成形，多孔質膜之強度顯著降低的情形。 0 此時，由於處理上會產生障礙，故不爲企求。有關多孔質塡料之比表面積，就本發明之效果而言更爲詳細地檢證時，多孔質塡料之比表面積以40〜1 000 m2/g 更佳。比表面積爲1 000 m2/g以下時，就機械強度及抑制氣體產生而言變得更爲優異。較佳者多孔質塡料之比表面積爲40〜500 m2/g。比表面積爲500 m2/g以下時，就機械強度及抑制氣體產生而言更爲優異。更佳者多孔質塡料之比表面積爲150〜500 m2/g。比表面積爲150 m2/g以上時，就 Q 抑制氣體產生而言更爲優異。此處，比表面積係藉由使氮氣氣體吸附法所測定的吸附等溫線以BET式進行解析予以求得。特別是於本發明中，多孔質塡料以比表面積爲300〜 1 0 00 m2/g之活性氧化鋁較佳。該活性氧化鋁可藉由吸附電池內微量產生的HF或與HF反應，可降低HF之活性，更爲提高非水系蓄電池之循環特性。存在於前述活性氧化鋁粒子表面上之Ο/Al的元素比，使用X光電子分光裝置測定時，Ο/Al之元素比以1.〇〜2.5 -15- 201101560 較佳。更佳的O/Al之元素比爲1.2〜1.8。以該元素比形成表面時’就降低HF等之活性而言較佳。前述活性氧化鋁之真密度，以2.7〜3.8 g/cm3較佳，以2.8〜3.3§/(：1113之範圍更佳。真密度未達2.7§/(；„13時，變得接近氫氧化鋁等，恐會不易得到HF之活性降低效果，故不爲企求。此外’真密度大於3.8 g/cm3時，恐會有填料之構造變得緻密，塡入電解液之隙間變小，電池之循環特性降低，故不爲企求。前述活性氧化鋁之比表面積，以3 00 tn2/g以上較佳。比表面積未達300 m2/g時，無法使HF等之活性充分降低。另外’活性氧化鋁之比表面積以1 000 m2/g以下較佳，更佳者爲5 00 m2/g以下。比表面積超過1 000 ^化時，以目前的技術無製法得活性氧化鋁。本發明之非水系蓄電池用多孔膜，配置於正極與負極之兩電極間時，可在任何部位使用。換言之’例如本發明之非水系蓄電池用多孔膜，可使用作爲配置於電極間之隔板。此時，以具有穿刺強度爲 200g以上之充分的機械強度較佳。而且，以具有哥雷値（ Gurley No.)爲10〜300秒/l〇〇cc之透過性者較佳。爲得該物性時，對耐熱性樹脂與多孔質塡料之合計重量而言，本發明之電池用多孔膜的構成以多孔質塡料之重量爲1〇〜5〇重量％較佳。多孔質塡料之重量大於50重量％時，不易得到充分的機械強度。另外，多孔質塡料之重量小於1 〇重量 %時’由於會降低抑制電池內之副反應的效果，且會降低 -16- 201101560 透過性，故不爲企求。另外，在電極間配置本發明之電池用多孔膜作爲隔板時，亦可單獨使用該電池用多孔膜。而且，爲附加關機功能時，與具有該功能之聚烯烴微多孔膜層合，在該電池用多孔膜上塗佈由聚烯烴微粒子所形成的分散液。此外，本發明之電池用多孔膜直接在電極上形成。此時，由於電極形成具有充分強度之支持體，與單獨使用該 0 電池用多孔膜作爲隔板時相比，不需機械強度。就該觀點而言，對耐熱性樹脂與多孔質塡料之合計重量而言，多孔質塡料之重量以〜90重量％較佳，以50〜90重量％更佳。多孔質塡料之重量小於1 〇重量％時，由於會降低抑制電池內之副反應的效果，故不爲企求。而且，大於90重量％時，由於實質上不易成形，故不爲企求。如此直接在電極上形成本發明之電池用多孔膜時，由於亦可兼具該電池用多孔膜與隔板，可在正負極間配置爲 Q 防止短路時之隔板。而且，除本發明之電池用多孔膜外，亦可僅使用如聚烯烴微多孔膜之一般的隔板，製作電池。此外，直接在電極上形成本發明之電池用多孔膜時，亦可使用正極及負極中任何一種。惟就在正極上形成者可提高電池之耐久性而言較佳，以在正極與負極雙方上形成更佳 [電池用多孔膜之製造方法] 本發明之非水系蓄電池用多孔膜的製造方法，沒有特 -17- 201101560 別的限制，例如可藉由含有下述（i )〜（iv )步驟之製造方法予以製造。換言之’係由實施（i)製作含有耐熱性樹脂、無機塡料及水溶性有機溶劑之塗佈用漿料的步驟、 (ii )將所得的塗佈用漿料塗佈於支持體的步驟、（iii ) 使所塗佈的漿料中之耐熱性樹脂予以凝固的步驟、與（iv )使該凝固步驟後之薄片進行水洗及乾燥的步驟所形成的製造方法。於前述步驟（i)中，水溶性有機溶劑只要是對耐熱性樹脂而言爲良溶劑之溶劑即可，沒有特別的限制。該水溶性有機溶劑之具體例’如N-甲基吡咯烷酮、二甲基乙醯胺、二甲基甲醯胺、二甲基亞碾等之極性溶劑。而且，在漿料中亦可另外使用部分混合對耐熱性樹脂而言爲貧溶劑所形成的溶劑。藉由使用該貧溶劑，誘發微相分離構造，就形成耐熱性多孔質層而言容易形成多孔化。貧溶劑以醇類爲宜，特別是以如醇之多元醇較佳。於前述步驟（Π )中’漿料對支持體之塗佈量以約1 〇〜60 g/m2較佳。塗佈方法例如刀塗佈法、照相凹版塗佈法、舖網印刷法、邁耶棒法 '塑模塗佈法、可逆輕塗佈法、噴墨法、噴霧法、輥塗佈法等。其中，就均勻地塗佈塗膜而言，以可逆輥塗佈法爲宜。於前述步驟（iii)中，使漿料中之耐熱性樹脂凝固的方法’例如對塗佈後之支持體而言以噴霧吹附凝固液之方法、或在加入有凝固液之浴（凝固液）中浸漬該基材的方法等。凝固液只要是可使耐熱性樹脂凝固者即可，沒有特 -18- 201101560 別的限制，以水、或在漿料中使用的良溶劑中含有適量的水之混合液較佳。此處，水之混合量對凝固液而言以40〜 80重量％爲宜。於前述步驟（iv )中，乾燥方法沒有特別的限制，以乾燥溫度爲50〜100。(：爲宜。使用高的乾燥溫度時，爲不會因熱收縮而引起尺寸變化時，以使用接觸輥之方法較佳〇 0 另外’爲製得本發明之非水系蓄電池用多孔膜時之第二製造方法’例如於前述（i)及（ii)之步驟後，亦可實施（V )使所塗佈的薄片乾燥的步驟。此時，前述步驟（V )之乾燥溫度，只要是可除去該水溶性溶劑之溫度即可，任何溫度皆沒有問題，以約50〜200°c爲宜。使用高的乾燥溫度時，爲不會因熱收縮而引起尺寸變化時，以使用接觸輥的方法較佳。亦可於前述任何的製造方法中使用支持體，該支持體 Q 可使用玻璃板或聚對苯二甲酸乙二酯（PET)製薄膜等、對乾燥溫度而言具有充分的耐熱性者即可，皆適合使用。而且，使用此等之支持體時，包含於前述（iv) (v)之乾燥後，自支持體剝離本發明之電池用多孔膜的步驟。於本發明中亦可在支持體使用聚烯烴微多孔膜或不織布等之多孔質材料。此時，由於亦可作爲含支持體之電池用多孔膜使用，故不需進行剝離步驟。而且，亦可在支持體上使用電極，且在電極上直接形成本發明之電池用多孔膜。此時當然亦不需進行剝離步驟。 -19- 201101560 [非水系蓄電池] 本發明之非水系蓄電池，係至少具備正極及負極之非水系蓄電池’其特徵爲在前述正極及前述負極之至少一方的表面上形成前述的非水系蓄電池用多孔膜、或使用該非水系蓄電池用多孔膜作爲隔板使用。本發明之非水系蓄電池，藉由使用耐熱性優異的電池用多孔膜’可提高電池之安全性，且可藉由電池用多孔膜中之多孔質塡料以抑制氣體產生，且循環特性或保存特性等之耐久性亦爲優異。如上所述’本發明之電池用多孔膜可適合使用作爲隔板’亦可在電極表面上形成。使用作爲隔板時，可僅單獨使用該電池用多孔膜，亦可層合該電池用多孔膜與聚烯烴微多孔膜使用。在電極表面上形成該電池用多孔膜時，可在正極及負極中任何一方形成，亦可在兩方上形成。在電極表面上形成該電池用多孔膜時，可使用聚烯烴微多孔膜等作爲隔板，由於可預先在電極表面上形成本發明之電池用多孔膜，故亦可在沒有經由隔板下接合正極與負極。惟使用聚烯烴微多孔膜作爲隔板時’以至少在聚烯烴微多孔膜與正極之間具有本發明之電池用多孔膜的構成較佳。聚烯烴微多孔膜之耐氧化性，使用於非水系蓄電池時不一定充分，且聚烯烴微多孔膜與正極接觸之面會有被氧化的電池惡化的情形’藉由如前述配置本發明之電池用多孔膜，可大幅地抑制該惡化情形。 -20- 201101560 #胃明之非水系蓄電池的種類或構成，除前述構成以 '沒_任何的限制，只要是在順序層合有正極與隔板與負極的電池要素中含浸電解液，只要形成使其封入外裝之構造的構成即可，皆可使用。惟如上所述亦可省略隔板。負極係在集電體上形成有由負極活物質、導電助劑及黏合劑所形成的負極合劑之構造所形成。集電體係使用例如銅箱或不銹鋼箔、鎳箔等。負極活物質係使用可進行電 0 化學性捕捉鋰之材料，例如碳材料、矽、鋁、錫等。正極係在集電體上形成由正極活物質、導電助劑及黏合劑所形成的正極合劑之構造所形成。集電體係使用例如銅箔或不銹鋼箔、鎳箔等。正極活物質係使用含鋰之過渡金屬氧化物，例如 LiCo02、LiNi02、LiMn〇.5Ni〇.502、 LiC〇i/3Ni1/3Mni/3〇2、LiMn2〇4、LiFeP〇4。電解液係使鋰鹽溶解於非水系溶劑之構成。鋰鹽例如 LiPF6 、 LiBF4 、 LiC104等。非水系溶齊!J例如碳酸丙二醋、 Q 碳酸乙二酯、碳酸二甲酯、碳酸二乙酯、甲基碳酸乙酯、 γ-丁內酯、碳酸亞乙烯酯等。外裝材料例如金屬罐或鋁層合袋等。電池的形狀有方型、圓筒型、銅板型等，本發明之隔板可使用任何的形狀。惟在電極上形成有本發明之電池用多孔膜時，以使用於圓筒型電池較佳。 (1-2)第二形態本發明第二形態之非水系蓄電池用多孔膜，係含有耐 -21 - 201101560 熱性樹脂及無機塡料所構成的非水系蓄電池用多孔膜，其特徵爲則述無機塡料非晶狀氧化鋁粒子（以下適當稱爲非晶狀氧化銘）^ 藉由本發明’可達成與前述第一形態時相同的效果。特別是由於使非晶狀氧化鋁吸附存在於電池內之微量雜質或HF等之副生成物’可更爲提高電池之循環特性。而且’此第二形態係與上述第一形態除將無機塡料改爲非晶狀氧化鋁外，其餘皆相同，故於下述中適當省略說明有關與第一形態相同的構成。而且，該第二形態之「非晶狀氧化鋁」係達成與前述第一形態之「比表面積爲300 〜1 000 m2/g之活性氧化鋁」類似的作用效果者，就比表面積而言本發明所捉著者相當於第一形態，就結晶構造而言本發明所捉住者相當於第二形態。於本發明中，非晶狀氧化鋁粒子係以示性式爲ai2o3 • xH20 ( X爲0以上、3以下之値）所示之塡料，且藉由X 光繞射予以分析，無法確認明確的結晶波峰。而且’非晶狀氧化鋁除藉由X光繞射予以分析確認沒有明確的結晶波峰外，包含確認在寬波峰中僅明確的結晶波峰者（非晶狀與其他組成的混合組成）° 前述「其他組成」係包含三水銘石狀或三經銘石（[Technical Field] The present invention relates to a porous film for a nonaqueous battery, a separator for a nonaqueous battery, an adsorbent for a nonaqueous battery, and a nonaqueous battery. [Prior Art] A typical non-aqueous battery of a lithium ion battery is widely used as a main power source for a portable electronic device of a mobile phone or a portable computer. This non-aqueous battery is required to have high energy density, high capacity, and high output, and it is predicted that this demand will be further improved in the future. Corresponding to this requirement, ensuring the safety of the battery is a more important technical element. In general, a non-aqueous battery system includes a positive electrode, a negative electrode, and a separator disposed between the electrodes. The separator has a function of preventing internal short-circuit between the positive electrode and the negative electrode without impeding ion permeation. In general, the separator is a polyolefin microporous membrane. When the temperature of the battery rises due to overcharge or the like due to overcharge or the like, the separator of the polyolefin microporous film Q is blocked by the pores of the polyolefin, and the shutdown function of the internal current of the battery is blocked. With this function, 尙 prevents the heat of the battery and improves the safety of the battery at high temperatures. Further, even if the internal temperature of the battery rises after the hole is blocked, the separator is broken, causing an internal short circuit and causing a fire or the like. Therefore, in the past, when improving the safety of a nonaqueous battery, attention has been focused on a porous film having heat resistance. According to the heat resistant porous film, when the battery is abnormally exposed to a high temperature, the internal short circuit between the positive and negative electrodes can be prevented. For example, -5-201101560, a technique of using a porous film formed of a heat-resistant resin in a separator (Patent Document 1), or a technique of using a porous film formed of a heat-resistant resin and a ceramic powder in a separator (patent Documents 2 and 3), a technique of forming a porous film formed of an inorganic pigment and a binder resin on the surface of an electrode (Patent Document 4). Further, a technique of dispersing an inorganic cerium in a separator formed of a polyolefin microporous membrane is also known (Patent Document 5). Among these techniques, a typical inorganic pigment of a ceramic powder is effective in preventing an internal short circuit between the positive and negative electrodes because of high heat resistance and compression strength. However, the battery using the inorganic coating may have a problem of lowering the battery durability of the cycle characteristics or the storage characteristics. One of the reasons for the decrease in durability is that hydrogen fluoride (HF) present in a small amount in the battery reacts with the inorganic material, and the surface of the inorganic material is fluorinated, and moisture is generated at this time, and the moisture causes the electrolyte or The SEI (Solid Electrolyte Interface) film formed on the surface of the electrode is decomposed. When the electrolytic solution or the SEI film is decomposed, the internal resistance of the battery rises and the necessary lithium is deactivated during charge and discharge, and the durability of the battery may be lowered. Further, when a gas is generated by the decomposition reaction, there is a fear that the durability of the battery is lowered. Therefore, the decomposition reaction naturally becomes a cause of a decrease in the safety of the battery. In particular, when an inorganic pigment and a heat-resistant resin such as an aromatic polyamide resin are used, generally, since the heat-resistant resin is a substance which easily absorbs moisture, the above decomposition reaction is likely to occur. Further, Patent Document 6 proposes a technique for improving the generation of gas in a battery by an inorganic mash. This technique incorporates a gas absorbent formed of an inorganic powder in a separator formed of a polyolefin, and captures a gas generated in the battery with a gas absorbent. However, this separator may have a problem of insufficient heat resistance. Further, in the case where the inorganic fine material in which the gas absorbent is mixed in the polyolefin microporous membrane which functions as a shutdown function, there is a fear that the shutdown function is remarkably lowered. Therefore, although gas generation can be remarkably suppressed, there is a fear that the safety of the battery is lowered when compared with the conventional polyolefin microporous membrane. As described above, although non-aqueous batteries are required to have high performance, it is currently technically difficult to ensure the safety and durability of this purpose. Further, in order to improve the safety, it is presumed that a porous film formed of an inorganic pigment and a heat-resistant resin is effective, but a structure which can stand for safety and durability has not been found. Here, the above description relates to the problem of the safety and durability of the battery in the technical field of the separator or the porous film. However, in order to prevent the deterioration of the durability of the battery due to the presence of HF or water in the battery, it is considered that there is no adequate improvement technique proposed by Q in consideration of the expansion of all technical fields of the nonaqueous battery. In this regard, the relevant point is explained. In general, a lithium ion secondary battery is composed of a positive electrode such as a lithium transition metal composite oxide, a negative electrode such as a carbon material, an organic electrolytic solution in which a Li salt is dissolved, and a separator such as a polyethylene microporous film. Therefore, the lithium ion battery is manufactured under strict management in which the battery system is not mixed with moisture or impurities in terms of cycle characteristics and safety. However, it is not possible to completely remove a trace amount of moisture adsorbed from the battery constituent member or water mixed in the battery assembly during the battery system. Here, the moisture present in the battery system reacts with Li 201101560 salt such as lithium hexafluorophosphate to release HF, and the free HF reacts as follows (1) to (3), resulting in deterioration of cycle characteristics of the battery. The system is known. (1) Dissolving the transition metal used in the positive electrode. (2) When aluminum is used as the positive electrode current collector, aluminum corrosion is caused. (3) When black lead is used as the negative electrode, the interface resistance of the negative electrode is increased (see Non-Patent Document 1). Therefore, in one of the methods for improving the cycle characteristics, a technique of adding a porous inorganic material such as zeolite or cerium oxide gel, activated alumina or activated carbon to a battery system has been reported (for example, refer to Patent Documents 7 to 9). . In other words, Patent Document 7 discloses a technique in which a separator contains an inorganic material having a surface area of 15 to 300 m 2 /g, and the inorganic material is used to improve the cycle characteristics. According to Patent Document 8, a technique of containing alumina having a specific surface area of 30 to 300 m2/g in a negative electrode or a positive electrode provides good cycle characteristics. According to Patent Document 9, a battery having a specific surface area of activated carbon and an inorganic material having a specific surface area of 1 000 m 2 /g or more is disclosed, and good cycle characteristics can be obtained by using activated carbon or the like. As described above, the porous inorganic tantalum having a specific specific surface area is reported to have an effect of improving the cycle characteristics of the battery. However, in consideration of the reaction or adsorption of HF with the above (1) to (3), it is presumed that there is a range of specific surface area in which each of the adsorbents can obtain good cycle characteristics, but this point is still unknown at present. Further, the technique of suppressing the reaction with HF and improving the cycle characteristics by means of elements other than the specific surface area of the inorganic tantalum is still unknown. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2008-266588 [Patent Document 2] Japanese Patent No. 3 1 7573 No. [Patent Document 3] International Publication No. 2-8 Japanese Patent Laid-Open Publication No. 2008-146963 [Patent Document 7] [Patent Document 5] Japanese Patent No. 4 1 45 762 [Patent Document 8] Japanese Patent No. 3,070, 478 [Patent Document 9] Japanese Laid-Open Patent Publication No. 2000-77103 [Non-Patent Document] [Non-Patent Document 1] Lithium ion battery second Edition (Nikko Industry News Agency, Fukuo Shinji) Materials and Applications, pp. 76-77 [Invention] Therefore, the present invention has been made in view of the foregoing problems, and the first object is to provide a safety improvement of a non-aqueous battery. Both the technology and the second purpose of the durability are to provide a technique for improving the cycle characteristics in consideration of the reaction or adsorption with HF. In order to solve the above problems, the inventors of the present invention have further studied the results of the review and found that the present invention can be solved by the following configuration. 201101560 1. A porous film for a non-aqueous battery, comprising a porous film for a non-aqueous battery comprising a heat-resistant tree and an inorganic material, wherein the inorganic material has an average particle diameter of 01 to 50 μm and a ratio A porous crucible having a surface area of 4 〇 3000 m 2 /g. (2) The porous film for a nonaqueous battery according to the above 1, wherein the front porous material is activated alumina having a specific surface area of 3 〇〇 to i〇〇〇m 2 /g. A non-aqueous battery porous film comprising a heat-resistant tree and an inorganic material, wherein the inorganic material is an amorphous oxide particle. 4. A non-aqueous battery according to any one of the above 1 to 3, wherein the non-aqueous battery porous film according to any one of the above-mentioned 1 to 3 is formed on the surface of at least one of the positive electrode and the negative electrode. Or a non-aqueous battery separator is used as the separator, and the porous substrate is laminated on one or both sides of the porous substrate to contain a heat-resistant resin inorganic The non-aqueous battery separator for the heat-resistant porous layer of the material is characterized in that the inorganic material has an average particle diameter of 〇_1 to 5.0 μm and a specific surface of 40 to 3 000 m 2 /g. . 6. The separator for a non-aqueous battery according to the above 5, wherein the porous material is an activated alumina having a specific surface area of 3 〇〇 to 1 〇〇〇 m 2 /g. 7. A non-aqueous battery separator comprising a porous substrate which is laminated on one surface of the porous substrate or a heat-resistant porous layer containing a heat-resistant resin inorganic material on both surfaces The separator is characterized in that the inorganic inorganic material is amorphous oxide-shaped particles. Illustrated as a non-aqueous battery, which is a non-aqueous battery having a positive electrode, a negative electrode and a separator, and is characterized in that it is used as described above 5~ The separator for a non-aqueous battery according to any one of the seventh aspects is the separator. An adsorbent for a nonaqueous battery, which is an adsorbent for hydrogen fluoride mixed in a nonaqueous battery, characterized in that the adsorbent is activated alumina particles having a specific surface area of from 300 to 1 000 m2/g. An adsorbent for a non-aqueous battery, which is an adsorbent for hydrogen fluoride mixed in a non-aqueous battery, characterized in that the adsorbent is amorphous alumina particles. 11. A non-aqueous battery porous film comprising a non-aqueous battery for a non-aqueous battery according to the above-mentioned item 9 or 1 as a porous film for a non-aqueous battery, comprising the inorganic film and the binder resin; Unexpected. 1 2 - A non-aqueous battery separator comprising a porous substrate and a porous layer comprising an inorganic coating Q and a binder resin laminated on one surface or both surfaces of the porous substrate The separator for a water-based battery is characterized in that the adsorbent for a non-aqueous battery according to the above 9 or 10 is used as the inorganic material. A non-aqueous secondary battery comprising a positive electrode, a negative electrode, a non-aqueous electrolyte, and a separator, wherein the battery contains the adsorbent for a non-aqueous battery according to the above 9 or 10. [Effect of the Invention] According to the first aspect of the present invention, there is provided a technique for improving both safety and durability of a non-aqueous storage battery -11 - 201101560. Further, by the second aspect of the present invention, in consideration of the reaction or adsorption with HF, a technique for improving the cycle characteristics is provided. [Form of the invention] (1) The first aspect of the invention (1 -1) [The porous film for a non-aqueous battery] The porous film for a non-aqueous battery according to the first aspect of the invention contains heat resistance. A porous film for a nonaqueous battery according to a resin and an inorganic material, characterized in that the inorganic material has a porous particle size of 0.1 to 5·0 μm and a specific surface area of 40 to 3000 m 2 /g. According to the present invention, by containing a heat-resistant resin and an inorganic coating material, even when the battery is exposed to a high temperature, sufficient heat resistance during internal short-circuit prevention can be ensured, and the safety of the battery can be ensured. Further, since the inorganic tantalum is a porous tantalum having an average particle diameter of 0.1 to 5_0 μη and a specific surface area of 40 to 3000 m 2 /g, by suppressing side reactions which reduce durability in the battery and removing by side reactions The gas can improve the durability of the cycle characteristics or storage characteristics of the battery. In particular, since the heat-resistant resin is generally a substance which easily adsorbs moisture, the present invention has a configuration in which a side reaction of the HF and the inorganic material is likely to occur, but in the present invention, the porous material can be remarkably reduced by using the above-described porous material. The amount of moisture or HF present in the battery is small, and the generation of gas due to decomposition of the electrolyte or the like is suppressed. Moreover, it is assumed that even if a gas is generated, the gas in the porous crucible can be captured by -12-201101560. Therefore, the durability of the battery can be greatly improved. Here, the porous film for a battery of the present invention is a porous structure in which a heat resistant resin and an inorganic binder are used to mean that a plurality of pores or voids are formed therein, and such pores are formed to be connected to each other. The heat-resistant resin of the present invention contains a resin having a melting point of 200 ° C or higher, and a resin having a melting point of 200 ° C or higher, and a resin having a melting point of not more than 0 ° C and a thermal decomposition temperature of 200 ° C or more. . The heat resistant resin such as wholly aromatic polyamine, polyimine, polyamidimide, poly maple, polyketone, polyether ketone, polyether oxime, polyether oximine, cellulose, etc. 2 Combinations of the above and the like. Among them, a wholly aromatic polyamine is preferable in terms of ease of formation of a porous structure, adhesion to an inorganic coating, strength of a porous film, and oxidation resistance. Further, in the case of the wholly aromatic polyamine, when the para-type is compared with the inter-type, the meta-type wholly aromatic polyamine is preferably formed, particularly poly(m-phenylene isodecylamine). When a meta-type wholly aromatic polyamine is preferably used, when the inter-type wholly aromatic polyamine is dissolved in N-methyl-2-pyrrolidone, the logarithmic viscosity of the following (1) is in the range of 0.8 to 2.5 dl/g. Preferably, it is preferably in the range of 1.0 to 2.2 dl/g. When it is out of this range, the formability is deteriorated, so the logarithmic viscosity is not required (unit: dl/g) = ln(T/T0)/C ---(1) T : in l〇〇ml Flow of a capillary viscosity meter at a temperature of 30 ° C in a solution of a solution of 0.5 g of a wholly aromatic polyamine resin dissolved in N-methyl-2-pyrrolidone - 13: 201101560 Time TO : N-methyl-2- Flow time of a pyrrolidone at a capillary viscometer at 30 ° C: concentration of a wholly aromatic polyamine resin in solution (g/dl) Porous tantalum which can be used in the present invention, such as zeolite, A porous tantalum obtained by heat-treating a metal hydroxide such as activated carbon, activated alumina, porous ceria, magnesium hydroxide or aluminum hydroxide, or a porous tantalum synthesized from an organic compound. Among them, activated alumina is particularly preferred. The activated alumina of the present invention is a porous tantalum represented by the formula Α1203·χΗ20 (X-based is 0 or more and 3 or less). The surface of the activated alumina is amorphous Α12〇3, γ-Α1203, χ-Α1203, Gibbsite-like Α1(ΟΗ)3, Boehmite-like Λ1203·Η20, etc. The preferred structure of the porous structure is preferably formed by reducing the surface activity of the water or HF. Further, in addition to the above-described porous material, the inorganic material may be appropriately added with a metal oxide such as α-alumina or another non-porous inorganic material such as a metal hydroxide such as aluminum hydroxide. The porous material is preferably composed of mesopores of 50 nm or less or 2 ntn of micropores, and in particular, a structure in which micropores having a diameter of 2 nm or less are formed, which is preferable in view of the effects of the present invention. Further, the average particle diameter of the porous tantalum is preferably in the range of 〇1 to 5·〇μηη. When the average particle diameter of the porous material is less than 〇. 1 μηι, the porous film cannot be formed, and the smoothness of the porous property is deteriorated, which makes it difficult to handle it. When the average particle diameter of the porous tantalum is more than 5 · 0 μm, when the porous film is formed into a thin shape, it is difficult to form in terms of surface roughness, and thus it is not desirable. In the present invention, the porous tantalum has a specific surface area of preferably 40 to 3 000 m 2 /g. When the specific surface area is less than 40 m2/g, the activity of moisture or HF cannot be sufficiently lowered, so that it is not desirable. Further, when it is more than 3,000 m2/g, the porous film may not be easily formed, and the strength of the porous film may be remarkably lowered. 0 At this time, there is an obstacle in processing, so it is not an attempt. Regarding the specific surface area of the porous tantalum, the specific surface area of the porous tantalum is preferably 40 to 1 000 m 2 /g when it is examined in more detail for the effects of the present invention. When the specific surface area is 1 000 m 2 /g or less, it is more excellent in terms of mechanical strength and suppression of gas generation. Preferably, the porous tantalum has a specific surface area of 40 to 500 m2/g. When the specific surface area is 500 m2/g or less, it is more excellent in terms of mechanical strength and gas generation. More preferably, the porous crucible has a specific surface area of from 150 to 500 m2/g. When the specific surface area is 150 m2/g or more, it is more excellent in suppressing gas generation by Q. Here, the specific surface area is obtained by analyzing the adsorption isotherm measured by the nitrogen gas adsorption method in the BET equation. Particularly in the present invention, the porous tantalum is preferably activated alumina having a specific surface area of from 300 to 100 m 2 /g. The activated alumina can reduce the activity of HF and increase the cycle characteristics of the non-aqueous battery by adsorbing HF generated in the battery or reacting with HF. The element ratio of ruthenium/Al present on the surface of the above-mentioned activated alumina particles is preferably 0.1 to 2.5 -15 to 201101560 when measured by X-ray photoelectron spectroscopy. A more desirable O/Al element ratio is 1.2 to 1.8. When the surface ratio is formed by the element ratio, it is preferable to reduce the activity of HF or the like. The true density of the activated alumina is preferably 2.7 to 3.8 g/cm3, more preferably 2.8 to 3.3 §/(:1113. The true density is less than 2.7 §/(; 13°, it becomes close to the hydroxide Aluminum or the like may not easily obtain the effect of reducing the activity of HF, so it is not desirable. In addition, when the true density is more than 3.8 g/cm3, the structure of the filler may become dense, and the gap between the electrolytes becomes small, and the battery is small. The specific surface area of the activated alumina is preferably 300 sec/g or more. When the specific surface area is less than 300 m2/g, the activity of HF or the like cannot be sufficiently lowered. The specific surface area of aluminum is preferably 1 000 m 2 /g or less, more preferably 500 00 m 2 /g or less. When the specific surface area exceeds 1 000 ^, the activated alumina is obtained by the prior art without a process. When the porous film for a battery is disposed between the electrodes of the positive electrode and the negative electrode, it can be used in any position. In other words, for example, the porous film for a non-aqueous battery of the present invention can be used as a separator disposed between the electrodes. Fully with a puncture strength of 200g or more It is preferable to have a mechanical strength, and it is preferable to have a permeability of Gurley No. of 10 to 300 sec/l cc. In order to obtain the physical properties, the heat resistant resin and the porous mash are used. The weight of the porous film for a battery of the present invention is preferably from 1 to 5 % by weight based on the weight of the porous material. When the weight of the porous material is more than 50% by weight, sufficient mechanical strength is not easily obtained. In addition, when the weight of the porous tantalum is less than 1% by weight, the effect of suppressing the side reaction in the battery is lowered, and the permeability of -16-201101560 is lowered, so that it is not required. When the porous film for a battery of the invention is used as a separator, the porous film for a battery can be used alone. When a shutdown function is added, the polyolefin microporous film having the function is laminated and coated on the porous film for the battery. Further, the porous film for a battery of the present invention is formed directly on the electrode. At this time, since the electrode forms a support having sufficient strength, the porous battery for use alone is used. The mechanical strength is not required as the separator. From this point of view, the weight of the porous tantalum is preferably -90% by weight, preferably 50%, based on the total weight of the heat resistant resin and the porous tantalum. More preferably, 90% by weight, when the weight of the porous tantalum is less than 1% by weight, the effect of suppressing side reactions in the battery is lowered, so that it is not desirable, and when it is more than 90% by weight, it is substantially difficult to form. When the porous film for a battery of the present invention is formed directly on the electrode, the porous film for the battery and the separator can be used in combination, and the separator can be disposed between the positive and negative electrodes to prevent short-circuiting. In addition to the porous film for a battery of the present invention, a battery can be produced by using only a separator which is generally a polyolefin microporous film. Further, when the porous film for a battery of the present invention is formed directly on the electrode, any of a positive electrode and a negative electrode can also be used. However, it is preferable that the positive electrode is formed to improve the durability of the battery, and it is preferably formed on both the positive electrode and the negative electrode. [Method for Producing Porous Film for Battery] The method for producing a porous film for a nonaqueous battery according to the present invention, There is no other limitation, for example, it can be produced by a production method including the following steps (i) to (iv). In other words, it is a step of producing (i) a coating slurry containing a heat resistant resin, an inorganic pigment, and a water-soluble organic solvent, and (ii) a step of applying the obtained coating slurry to a support, ( Iii) a step of solidifying the heat-resistant resin in the applied slurry and (iv) a step of washing and drying the sheet after the solidification step. In the above step (i), the water-soluble organic solvent is not particularly limited as long as it is a solvent which is a good solvent for the heat resistant resin. Specific examples of the water-soluble organic solvent include a polar solvent such as N-methylpyrrolidone, dimethylacetamide, dimethylformamide or dimethyl amide. Further, a solvent which is partially mixed with a poor solvent for the heat resistant resin may be additionally used in the slurry. By using the poor solvent, the microphase separation structure is induced, and the porous layer is easily formed by forming the heat resistant porous layer. The poor solvent is preferably an alcohol, particularly preferably a polyol such as an alcohol. In the foregoing step (Π), the coating amount of the slurry to the support is preferably from about 1 〜 to 60 g/m 2 . The coating method is, for example, a knife coating method, a gravure coating method, a screen printing method, a Meyer bar method, a mold coating method, a reversible light coating method, an inkjet method, a spray method, a roll coating method, or the like. Among them, in terms of uniformly coating the coating film, a reversible roll coating method is preferred. In the above step (iii), a method of solidifying a heat resistant resin in a slurry, for example, a method of spray-coating a coagulating liquid to a coated support, or a bath containing a coagulating liquid (coagulating liquid) a method of immersing the substrate or the like. The coagulation liquid is not particularly limited as long as it can coagulate the heat-resistant resin, and it is preferred to contain a suitable amount of water in water or a good solvent used in the slurry. Here, the mixing amount of water is preferably 40 to 80% by weight based on the coagulating liquid. In the aforementioned step (iv), the drying method is not particularly limited, and the drying temperature is 50 to 100. (When it is preferable to use a contact roll in a high drying temperature, it is preferable to use a contact roll in order to obtain a porous film for a nonaqueous battery of the present invention. The second manufacturing method 'for example, after the steps (i) and (ii) above, may also be carried out by (V) drying the coated sheet. At this time, the drying temperature of the step (V) may be The temperature of the water-soluble solvent may be removed, and any temperature is not problematic, and is preferably about 50 to 200 ° C. When a high drying temperature is used, when the dimensional change is not caused by heat shrinkage, the contact roll is used. Preferably, the support may be used in any of the foregoing manufacturing methods, and the support Q may be made of a glass plate or a polyethylene terephthalate (PET) film, etc., and has sufficient heat resistance for drying temperature. In the case where the support is used, the step of removing the porous film for a battery of the present invention from the support after drying of the above (iv) (v) is included. Can also use polyene in the support A porous material such as a hydrocarbon microporous membrane or a nonwoven fabric. In this case, since it can also be used as a porous membrane for a battery containing a support, it is not necessary to carry out a peeling step. Further, an electrode can be used for the support, and the electrode can be used. The porous film for a battery of the present invention is formed directly. In this case, the peeling step is not required. -19- 201101560 [Non-aqueous battery] The non-aqueous battery of the present invention is characterized by a non-aqueous battery having at least a positive electrode and a negative electrode. The non-aqueous battery porous film or the porous film for a non-aqueous battery is used as a separator on the surface of at least one of the positive electrode and the negative electrode. The non-aqueous battery of the present invention is excellent in heat resistance. The porous film for a battery can improve the safety of the battery, and can suppress gas generation by the porous material in the porous film for a battery, and is excellent in durability such as cycle characteristics or storage characteristics. The porous film for a battery of the invention can be suitably used as a separator, and can also be formed on the surface of the electrode. The porous film for a battery may be used alone or in combination with the polyolefin microporous film. When the porous film for a battery is formed on the surface of the electrode, either the positive electrode or the negative electrode may be formed. When the porous film for a battery is formed on the surface of the electrode, a polyolefin microporous film or the like can be used as the separator, and since the porous film for a battery of the present invention can be formed on the surface of the electrode in advance, it is possible to The positive electrode and the negative electrode are bonded to each other via a separator. When a polyolefin microporous film is used as the separator, it is preferable to have a porous film for a battery of the present invention at least between the polyolefin microporous film and the positive electrode. The oxidation resistance of the film is not necessarily sufficient when used in a non-aqueous battery, and the surface of the polyolefin microporous film that is in contact with the positive electrode may be deteriorated by the oxidized battery. By arranging the porous film for a battery of the present invention as described above, This deterioration can be greatly suppressed. -20- 201101560 The type and configuration of the non-aqueous battery of the stomach are not limited by the above-mentioned configuration, as long as the electrolyte is impregnated in the battery elements in which the positive electrode, the separator, and the negative electrode are laminated in this order, Any structure that encloses the exterior structure can be used. However, the separator may be omitted as described above. The negative electrode is formed by a structure in which a negative electrode mixture composed of a negative electrode active material, a conductive auxiliary agent, and a binder is formed on a current collector. The use of the current collection system is, for example, a copper box or a stainless steel foil or a nickel foil. As the negative electrode active material, a material capable of chemically capturing lithium, such as carbon material, ruthenium, aluminum, tin, or the like, is used. The positive electrode is formed by forming a structure of a positive electrode mixture formed of a positive electrode active material, a conductive auxiliary agent, and a binder on a current collector. The current collecting system uses, for example, copper foil or stainless steel foil, nickel foil or the like. The positive electrode active material is a lithium-containing transition metal oxide such as LiCoO 2 , LiNi 2 , LiMn 〇 5 Ni 〇 502, Li C 〇 i / 3 Ni 1/3 Mni / 3 〇 2 , Li Mn 2 〇 4 , LiFeP 〇 4 . The electrolytic solution is a structure in which a lithium salt is dissolved in a nonaqueous solvent. Lithium salts such as LiPF6, LiBF4, LiC104 and the like. The non-aqueous system is dissolved! J is, for example, propylene carbonate, Q ethylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, γ-butyrolactone, vinylene carbonate or the like. The exterior material is, for example, a metal can or an aluminum laminate bag. The shape of the battery is square, cylindrical, copper plate or the like, and the separator of the present invention can be used in any shape. When the porous film for a battery of the present invention is formed on an electrode, it is preferably used for a cylindrical battery. (1-2) Second Aspect The porous film for a non-aqueous battery according to a second aspect of the present invention includes a porous film for a non-aqueous battery comprising a thermo-resin resistant to -21 to 201101560 and an inorganic coating material, wherein the inorganic ruthenium is characterized by The amorphous alumina particles (hereinafter referred to as amorphous oxides as appropriate) can achieve the same effects as in the first embodiment described above. In particular, since the amorphous alumina adsorbs a trace amount of impurities present in the battery or a by-product such as HF, the cycle characteristics of the battery can be further improved. Further, the second embodiment and the first embodiment are the same except that the inorganic material is changed to the amorphous alumina. Therefore, the configuration similar to that of the first embodiment will be appropriately omitted in the following description. Further, the "amorphous alumina" of the second embodiment is similar to the "effective alumina having a specific surface area of 300 to 1,000 m2/g" in the first embodiment, and the specific surface area is The present inventors correspond to the first form, and the person caught by the present invention corresponds to the second form in terms of the crystal structure. In the present invention, the amorphous alumina particles are represented by an anisotropic formula of ai2o3 • xH20 (X is 0 or more and 3 or less), and are analyzed by X-ray diffraction. Crystallized peaks. Further, 'the amorphous alumina is analyzed by X-ray diffraction to confirm that there is no clear crystal peak, and it is confirmed that only the crystal peak of the broad peak is clearly defined (a mixture of amorphous and other components). "Other composition" includes Sanshui Mingshi or Sanjing Mingshi (

Bayerite)狀之Al(〇H)3、勃姆石狀或硬水鋁石（DiasP〇re )狀之Α12〇3·Η20、γ-Αΐ2〇3或χ-Αΐ2〇3等之中間氧化銘、及剛玉（Corundum )之a-Ah〇3，於此等之中’就可得本發明效果而言以勃姆石或三水銘石較佳。 -22- 201101560 前述「僅明確的結晶波峰」，例如以在非晶狀氧化鋁中含有勃姆石構造爲例時，以下述實施例記載的條件測定時’係指在2Θ = 14°附近所觀察的主波峰之積分強度爲1〇 cps· deg以上的波峰’該積分強度對施加20=1〇〜6〇deg 存在的寬波峰的積分強度而言爲0.30以下時，係指無機塡料全體爲非晶狀。而且，例如爲三水鋁石構造時，在2 Θ = 18°附近；爲三羥鋁石構造時，在2Θ = 19。附近；爲硬水鋁 0 石構造時，在2Θ = 20°附近；爲γ-Α1203構造時，在2Θ = 46。附近；爲χ- Α12〇3時，在2Θ=67。附近；爲α- Α12〇3構造時 ’在2Θ=43°附近；各觀察的主波峰之積分強度對在2Θ = 10〜60deg存在的寬波峰之積分強度而言爲0.30以下時，無機塡料全體爲非晶狀。在前述非晶狀氧化鋁之表面上存在的O/Al之元素比例，使用X光電子分光裝置測定時，O/Al之元素比例以1 .〇〜 2 · 5較佳。更佳的〇/Α1之元素比例爲1 . 2〜1 . 8。以該元素比〇例形成表面時，就降低電池中氟化氫（HF )等之活性而言較佳。前述之非晶狀氧化鋁，就吸附混入電池系內之各種雜質、副生成物而言，以具有吸附面積大的多孔質構造較佳。此處所指的多孔質構造，係指在粒子內部或表面上形成有多數的微小孔或微小空隙之構造。前述非晶狀氧化鋁，係以含有50nm以下之介孔或2nm 以下之微孔所構成較佳，特別是就具有本發明之效果而言，以發展成2nm以下之微孔的構造更佳。 -23- 201101560 此外，前述非晶狀氧化鋁之比表面積，以50 m2/g以上較佳。比表面積未達50 m2/g時，無法充分抑制因水分或雜質等所導致的循環特性惡化情形。另外，非晶狀氧化鋁之比表面積以1 000 m2/g以下較佳，以5〇〇 m2/g以下更佳。爲製得比表面積超過1 000 m2/g之活性氧化鋁時，目前在技術上有所困難。此外，前述非晶狀氧化鋁之平均粒徑，以0.1〜5.0 μπι 之範圍爲宜。非晶狀氧化鋁之平均粒徑小於0.1 μηι時，不易使多孔膜成形，且會使多孔膜之平滑性惡化，不易處理，故不爲企求。而且，非晶狀氧化鋁之平均粒徑大於 5. Ομιη時，於多孔膜薄薄成形時，就表面粗糙度而言變得不易成形，故不爲企求。而且，於非晶狀氧化鋁中，亦可混合α-氧化鋁等之金屬氧化物、或氫氧化鋁等之金屬氫氧化物等其他的無機塡料使用。 (1-3 )第三形態 [非水系蓄電池用隔板] 本發明第三形態之非水系蓄電池用隔板，其係具備多孔質基材、被層合於此多孔質基材之一面或兩面上所含有耐熱性樹脂及無機塡料之耐熱性多孔質層的非水系蓄電用隔板，其特徵爲前述無機塡料係平均粒徑爲0.1〜5. Ομιη，且比表面積爲40〜3000 m2/g之多孔質塡料。本發明可藉由含有耐熱性樹脂及無機塡料，即使電池 -24- 201101560 暴露於高溫下，爲防止內部短路時仍可確保充分的耐熱性，且可確保電池之安全性。另外，由於爲在多孔質基材上形成耐熱性多孔質層之構成，容易確保作爲隔板之充分的機械強度。其次，無機塡料由於平均粒徑爲0.1〜5.Ομιη、且比表面積爲40〜3 000 m2/g之多孔質塡料，藉由抑制電池內之耐久性降低的副反應，且除去因副反應所生成的氣體 ’可提高電池之循環特性或保存特性等之耐久性。 0 而且’該第三形態由於以前述第一形態之電池用多孔膜作爲耐熱性多孔質，在多孔質基材上形成該層之構成，於下述中適當省略說明有關與第一形態相同的構成。於本發明中’多孔質基材只要是在內部具有多數的空孔或空隙’且具有此等空孔等互相連結的多孔質構造者即可’沒有特別的限制，例如微多孔膜、不織布、紙狀薄片、其他具有三次元網路構造之薄片等。其中，就處理性或強度而言’以微多孔膜較佳。構成多孔質基材之材料，可〇使用有機材料及無機材料中任何一種，就可得關機特性而 w以聚烧烴等之熱可塑性樹脂較佳。因此，使用該聚烯烴多孔質基材時’可使耐熱性或關機功能倂立。前述聚烯烴樹脂，例如聚乙·烧、聚丙烯、聚甲基戊烯等。其中’就可得良好的關機特性而言，以含有90重量％聚乙稀者爲宜。聚乙烯以使用例如低密度聚乙烯、高密度聚乙燃、超高分子量聚乙烯等，特別是以高密度聚乙烯、超筒分子量聚乙烯爲宜。此外，由高密度聚乙烯與超高分子量聚乙嫌之混合物所形成的聚乙烯，就強度與成形性而 -25- 201101560 言較佳。聚乙烯之分子量，以重量平均分子量爲10萬〜 1 000萬爲宜，特別是以至少含有1重量。/。以上之重里平均分子量1〇〇萬以上之超高分子量聚乙烯的聚乙烯組成物較佳。另外，本發明之多孔質基材’除聚乙嫌外亦可混合聚丙烯、聚甲基戊烯等之其他聚烯烴予以構成’此外’亦可爲聚乙烯微多孔膜與聚丙烯微多孔膜之2層以上的層合體構成。於本發明中，多孔質基材之膜厚沒有特別的限制’以約5〜20μηι之範圍爲宜。膜厚較5μιη更薄時’由於在無法得到充分的強度下變得不易進行處理’且電池之處理性顯著降低的情形’故不爲企求。膜厚大於2〇Km時’由於離子之移動變得困難，且在電池內隔板所佔的容積增加，電池之能量密度降低，故不爲企求。多孔質基材之空孔率以10〜60%爲宜，較佳者爲20〜 5 0%。空孔率低於10%時，由於不易保持電池運作時充分量之電解液，電池之充放電特性顯著降低的情形，故不爲企求。空孔率超過60%時，關機特性變得不充分，且強度降低，故不爲企求。多孔質基材之穿刺強度，以200g以上較佳，更佳者爲 250g以上，最佳者爲300g以上。穿刺強度低於2〇〇g時，由於爲防止電池之正負極間短路時的強度不充分，產生無法提高製造處理性之缺點，故不爲企求。多孔質基材之哥雷値（Gurley No·) (JIS P8117)，以100〜500秒/100CC之範圍爲宜，較佳者爲1〇〇〜3〇〇秒 -26- 201101560 /100CC之範圍。哥雷値低於100秒/l〇〇cc時，雖爲離子透過性優異者，惟由於關機特性或機械強度降低，故不爲企求。此外，哥雷値大於500秒/100CC時，由於會有離子透過性變得不充分，電池之負荷特性惡化的情形，故不爲企求。多孔質基材之平均孔徑，以1〇〜l〇〇nm較佳。平均孔徑小於1 〇nm之孔時，由於不易含浸電解液，故不爲企求。平均孔徑大於lOOnm時，由於形成該耐熱性多孔質層時會 0 在界面上產生阻塞情形，且形成多孔質層時會產生關機特性顯著降低的情形，故不爲企求。本發明之耐熱性多孔質層，係含有耐熱性樹脂與無機塡料所構成’在內部具有多數的空孔或空隙，且變成此等空孔等互相連結的多孔質構造。該耐熱性多孔質層，係以無機塡料在耐熱性樹脂中分散•黏結的狀態，直接固定於多孔質基材上的形態，惟就處理性等而言較佳。而且，亦可在多孔質基材上形成僅由耐熱性樹脂所形成的多孔質層〇 ’然後’藉由塗佈•浸漬等含有無機塡料之溶液的方法，在耐熱性樹脂層之孔內或表面上附著有無機塡料的形態。此外’亦可使耐熱性多孔質層作爲微多孔膜或不織布、紙布薄片等獨立的多孔性薄片予以構成，且使該多孔性薄片黏合於前述多孔質基材上之構成。 #發明之非水系蓄電池用隔板，其特徵爲在耐熱性多孔質層中含有前述的無機塡料，在多孔質基材中不含該無機塡料亦爲其特徵之一。該無機塡料之功能，即使不存在於該多孔質層中’仍可期待具有該功能，例如即使在多孔 -27- 201101560 質基材中含有無機塡料，仍可得抑制氣體產生的效果。然而，該構成於使用於聚烯烴多孔質基材時，由於會有顯著損害關機功能的缺點，故不爲企求。因此，在期待具有關機功能之層中不含無機塡料，而在期待耐熱性之多孔質層中含有，就構成而言較佳。該多孔質層之構成，以重量比爲耐熱性樹脂：無機塡料=10: 90〜80: 20之範圍爲宜，以10: 90〜50: 50之範圍較佳。無機塡料之含有量小於20重量％時，由於無法充分得到無機塡料之特徵，故不爲企求。無機塡料之含有量大於90重量％時，由於無法成形，故不爲企求。另外，無機塡料爲50%以上時，由於可提高抑制熱收縮之效果等耐熱特性，故較佳。耐熱性多孔質層之空孔率，以3 0〜8 0%之範圍爲宜。另外，耐熱性多孔質層之空孔率以較多孔質基材之空孔率更高者較佳。該構成者之離子透過性優異，亦可得良好的關機功能等，可產生特性上之優點。耐熱性多孔質層之厚度，於耐熱性多孔質層在多孔質層基材之兩面上形成時，該耐熱性多孔質層之厚度的合計量，以2μιη以上、12μιη以下較佳，耐熱性多孔質層僅在一面形成時，以2μιη以上、12μιη以下較佳。本發明之非水系蓄電池用隔板，膜厚以7〜25 μπι之範圍爲宜，以10〜20μιη較佳。膜厚薄於7μιη時，就機械強度而言不爲企求。而且，超過25μιη時，就離子透過性而言不爲企求，另外，就於電池內隔板所佔的體積變大而導致能 -28- 201101560 量密度降低而言，亦不爲企求。本發明之非水系蓄電池用隔板的空孔率，以20〜7〇% 爲宜’較佳者爲30〜60%。空孔率低於20%時，由於電池運作時無法保持充分量之電解液，故不爲企求。空孔率超過70%時，關機特性變得不充分，且強度或耐熱性降低，故不爲企求。本發明之非水系蓄電池用隔板的穿刺強度，以2〇0§以 0 上較佳’以25〇g以上更佳，以3 00g以上最佳。穿刺強度低於200g時’爲防止電池之正負極間的短路情形時之強度不充分，會產生無法提高製造處理性的缺點，故不爲企求。本發明之非水系蓄電池用隔板的哥雷値（J I s P 8 1 1 7 ) ，以150〜600秒/l〇〇cc之範圍爲宜，較佳者爲15〇〜4〇〇秒 /100cc之範圍。哥雷値低於15〇秒/ l〇〇cc時，離子透過性雖優異，惟會降低關機特性或機械強度，故不爲企求。另外 ’形成該多孔質層時，於多孔質基材與耐熱性多孔質層之 Q 界面會產生阻塞情形，故不爲企求。哥雷値大於600秒 /100cc時’恐會使離子透過性變得不充分，且電池之負荷特性惡化的情形。此外’由本發明之非水系蓄電池用隔板的哥蟄値減去使用於此之多孔質基材的哥雷値之値，以25 0秒/lOOcc以下爲宜，以200秒/lOOcc以下較佳。該値小者，就關機特性變佳、且提高離子透過性的特性而言較佳。於本發明中’耐熱性多孔質層可在多孔質基材之至少一面上形成’以在多孔質基材之表裏兩面上形成更佳。藉 -29- 201101560 由在多孔質基材之表裏兩面上形成耐熱性多孔質層’不會有翹曲情形，處理性佳，可得提高高溫時之尺寸安定性的耐熱性，且顯著提高電池之循環特性等的效果。 [非水系蓄電池用隔板之製造方法] 本發明之非水系蓄電池用隔板的製造方法’沒有特別的限制，例如可藉由含有下述（i )〜（iv )之步驟的製造方法予以製造。換言之，係由（i)製作含有耐熱性樹脂、無機塡料及水溶性有機溶劑之塗佈用漿料的步驟、（ii )在多孔質基材之一面或兩面上塗佈所得的塗佈用漿料之步驟、（iii )使所塗佈的漿料中之耐熱性樹脂凝固的步驟、與（iv)使該凝固步驟後之薄片進行水洗及乾燥的步驟所形成的製造方法。而且，此等步驟（i )〜（iv )係與前述之第一形態時相同。於本發明中，有關多孔質基材之製造方法，沒有特別的限制，例如可製造下述作爲多孔質基材之聚烯烴微孔膜。換言之，自塑模押出聚烯烴與流動石蠟之凝膠狀混合物 ’然後’藉由冷卻製作基體膠帶，使該基體膠帶延伸，予以熱固定處理。其次’藉由使流動石蠟浸漬於二氯甲烷等之萃取溶劑中進行萃取，再使萃取溶劑進行乾燥，可製得聚烯烴微多孔膜。 [非水系蓄電池] 本發明第三形態之非水系蓄電池，其係具備正極、負 -30- 201101560 極及隔板之非水系蓄電池，其特徵爲前述隔板係使用前述非水系蓄電池用隔板。該分水系蓄電池在高溫時之安全性或耐久性優異，且循環特性等亦優異。而且，其他之電池構成，與前述第一形態相同。 (1-4)第四形態本發明第四形態之非水系蓄電池用隔板，其係具備多 0 孔質基材、被層合於此多孔質基材之一面或兩面上含有耐熱性樹脂及無機塡料之耐熱性多孔質層的非水系蓄電用隔板，其特徵爲前述無機塡料爲非晶狀氧化鋁粒子。藉由本發明，可達成與前述第三形態時相同的效果。特別是由於非晶狀氧化鋁吸附存在於電池內之微量雜質或 HF等之副生成物，故可更爲提高電池之循環特性。而且，該第四形態由於除將前述第三形態之無機塡料改爲非晶狀氧化鋁外皆相同，故可省略說明有關與第三形 Q 態相同的構成。 (2 )第二之本發明前述之第一本發明，係爲解決於隔板等之技術領域中電池之安全性與耐久性倂立之課題的構成，惟於其中，特別是使用「比表面積爲300〜1 000 m2/g之活性氧化鋁」或「非晶狀氧化鋁」之構成，由於HF之活性顯著降低，提高電池之循環特性的效果優異。因此，第二本發明之該作用效果顯著，說明有關「活性氧化鋁」及「非晶狀氧化鋁」 -31 - 201101560 作爲氟化氫之吸附劑’使該吸附劑使用於非各部位之例。 (2-1 )第五形態本發明第五形態之非水系蓄電池用吸附系蓄電池內混入氟化氫之吸附劑，該吸附劑面積爲300〜1000 m2/g之活性氧化鋁粒子。本發明由於使用比表面積爲300〜1〇〇〇化鋁粒子作爲非水系蓄電池用吸附劑，藉由鋁吸附電池內之微量產生的HF或與HF反應活性，提高非水系蓄電池之循環特性。以往特定多孔質塡料之種類下，僅特定比表面積發明中具有特定的比表面積之活性氧化鋁，低外，具有與其他多孔質之無機塡料不同的。活性氧化鋁優異的詳細理由不知。然而，由於氧化鋁爲作爲路易斯酸•路易斯鹼之已物，推測可使HF分極，有效地捕捉HF。而表面積爲3 00 m2/g以上，可順利地進行表面環特性。目前在技術上對製得比表面積超過性氧化鋁而言有所困難。而且’有關該第五形態之「比表面ϋ m2/g之活性氧化鋁粒子」之構成，由於與前相同，故省略說明。水系蓄電池的劑，係在非水之特徵係比表 m2/g之活性氧使該活性氧化，可降低HF之，雖有在沒有之技術，惟本除HF之活性降優異循環特性其理由之一，知的兩性氧化且，藉由使比反應，提高循 1 000 m2/g之活 ί 爲 3 00 〜1 〇〇〇述第一形態者 -32 - 201101560 [活性氧化鋁之含有場所]Bayerite-like Al(〇H)3, boehmite or diasporerite (DiasP〇re) in the form of 〇12〇3·Η20, γ-Αΐ2〇3 or χ-Αΐ2〇3, etc. Corundum a-Ah〇3, among them, is preferable to boehmite or Sanshui Mingshi in terms of the effect of the present invention. -22-201101560 The above-mentioned "clear crystal peaks only", for example, when the boehmite structure is included in the amorphous alumina, when measured under the conditions described in the following examples, the term "belongs to 2 Θ = 14 °" The integrated intensity of the observed main peak is a peak of 1 〇 cps·deg or more. The integrated intensity is 0.30 or less when the integrated intensity of the broad peak existing by applying 20 = 1 〇 6 〇 deg is 0.3% or less. It is amorphous. Further, for example, in the case of a gibbsite structure, it is in the vicinity of 2 Θ = 18°; in the case of a bayerite structure, it is 2 Θ = 19. Near; for hard water aluminum 0 stone structure, near 2Θ = 20°; for γ-Α1203 structure, at 2Θ = 46. Nearby; for χ-Α12〇3, at 2Θ=67. In the vicinity of α-Α12〇3, the structure is in the vicinity of 2Θ=43°; the integrated intensity of the main peak observed for each observation is 0.30 or less when the integrated intensity of the broad peak existing at 2Θ = 10~60deg is 0.30 or less. The whole is amorphous. When the ratio of the element of O/Al present on the surface of the amorphous alumina is measured by X-ray photoelectron spectroscopy, the element ratio of O/Al is preferably 1. 〇 to 2.5. The ratio of the elements of the better 〇/Α1 is 1. 2~1. 8. When the surface is formed by this element, the activity of hydrogen fluoride (HF) or the like in the battery is preferably lowered. The amorphous alumina described above is preferably a porous structure having a large adsorption area for adsorbing various impurities and by-products mixed in the battery system. The porous structure referred to herein means a structure in which a large number of minute pores or minute voids are formed in or on the surface of the particles. The amorphous alumina is preferably composed of mesopores having a thickness of 50 nm or less or micropores of 2 nm or less. Particularly, in view of the effects of the present invention, a structure in which micropores of 2 nm or less are developed is more preferable. Further, the specific surface area of the amorphous alumina described above is preferably 50 m 2 /g or more. When the specific surface area is less than 50 m2/g, deterioration of cycle characteristics due to moisture or impurities cannot be sufficiently suppressed. Further, the specific surface area of the amorphous alumina is preferably 1 000 m 2 /g or less, more preferably 5 〇〇 m 2 /g or less. In order to obtain activated alumina having a specific surface area of more than 1 000 m2/g, it is currently technically difficult. Further, the average particle diameter of the amorphous alumina is preferably in the range of 0.1 to 5.0 μm. When the average particle diameter of the amorphous alumina is less than 0.1 μm, the porous film is not easily formed, and the smoothness of the porous film is deteriorated, which is difficult to handle, and therefore it is not desirable. Further, when the average particle diameter of the amorphous alumina is more than 5. Ομιη, when the porous film is formed thin, it is difficult to form the surface roughness, which is not desirable. Further, in the amorphous alumina, other inorganic materials such as a metal oxide such as α-alumina or a metal hydroxide such as aluminum hydroxide may be used. (1-3) A non-aqueous battery separator according to a third aspect of the present invention, which is characterized in that the separator for a non-aqueous battery is provided with a porous substrate and is laminated on one or both sides of the porous substrate. The non-aqueous storage battery separator having a heat-resistant porous layer containing a heat-resistant resin and an inorganic material, wherein the inorganic material has an average particle diameter of 0.1 to 5. Ομιη, and a specific surface area of 40 to 3000 m 2 /g of porous tanning material. The present invention can contain a heat-resistant resin and an inorganic coating, and even if the battery is exposed to a high temperature, it can ensure sufficient heat resistance to prevent internal short-circuit and ensure the safety of the battery. In addition, it is easy to ensure sufficient mechanical strength as a separator because the heat-resistant porous layer is formed on the porous substrate. Next, the inorganic material is a porous material having an average particle diameter of 0.1 to 5. Ομιη and a specific surface area of 40 to 3 000 m 2 /g, by suppressing side reactions with reduced durability in the battery, and removing the side effect The gas generated by the reaction can improve the durability of the cycle characteristics or storage characteristics of the battery. In the third aspect, the porous film for a battery of the first embodiment is formed of a heat-resistant porous material, and the layer is formed on the porous substrate. The description of the first embodiment is omitted as follows. Composition. In the present invention, the porous substrate is not particularly limited as long as it has a plurality of pores or voids therein, and has a porous structure such as such pores. For example, a microporous membrane, a non-woven fabric, or the like Paper-like sheets, other sheets having a three-dimensional network structure, and the like. Among them, a microporous film is preferred in terms of handleability or strength. The material constituting the porous substrate may be any one of an organic material and an inorganic material, and a shutdown resin may be used to obtain a thermoplastic resin such as a polyalkylene. Therefore, when the polyolefin porous substrate is used, heat resistance or shutdown function can be maintained. The aforementioned polyolefin resin is, for example, polyethylene, polypropylene, polymethylpentene or the like. Among them, in terms of good shutdown characteristics, it is preferable to contain 90% by weight of polyethylene. The polyethylene is preferably used, for example, as a low density polyethylene, a high density polyacetal, an ultrahigh molecular weight polyethylene, or the like, particularly a high density polyethylene or a ultrahigh molecular weight polyethylene. In addition, polyethylene formed from a mixture of high-density polyethylene and ultra-high molecular weight polyethylene is preferred in terms of strength and formability -25-201101560. The molecular weight of the polyethylene is preferably from 100,000 to 10,000,000 by weight average molecular weight, particularly at least 1 part by weight. /. The polyethylene composition of the ultrahigh molecular weight polyethylene having an average molecular weight of more than 1,000,000 in the above weight is preferred. Further, the porous base material of the present invention may be mixed with other polyolefins such as polypropylene and polymethylpentene in addition to polyethylene, and may be a polyethylene microporous membrane and a polypropylene microporous membrane. It is composed of two or more laminates. In the present invention, the film thickness of the porous substrate is not particularly limited, and is preferably in the range of about 5 to 20 μm. When the film thickness is thinner than 5 μm, it is not desirable because the film becomes difficult to handle when sufficient strength is not obtained, and the battery is reasonably lowered. When the film thickness is more than 2 〇Km, the movement of ions becomes difficult, and the volume occupied by the separator in the battery increases, and the energy density of the battery is lowered, so that it is not desirable. The porosity of the porous substrate is preferably from 10 to 60%, preferably from 20 to 50%. When the porosity is less than 10%, it is not easy to maintain a sufficient amount of electrolyte during battery operation, and the charge and discharge characteristics of the battery are remarkably lowered. When the porosity is more than 60%, the shutdown characteristics are insufficient and the strength is lowered, so that it is not desirable. The puncture strength of the porous substrate is preferably 200 g or more, more preferably 250 g or more, and most preferably 300 g or more. When the puncture strength is less than 2 〇〇g, since the strength at the time of preventing a short circuit between the positive and negative electrodes of the battery is insufficient, there is a disadvantage that the manufacturing processability cannot be improved, and therefore it is not desirable. Gurley No. (JIS P8117) of a porous substrate is preferably in the range of 100 to 500 sec / 100 cc, preferably 1 〇〇 to 3 sec -26 - 201101560 / 100 cc. . When the Gresian is less than 100 sec/l 〇〇cc, it is excellent in ion permeability, but it is not desirable because of shutdown characteristics or mechanical strength. In addition, when the Gurley is larger than 500 sec/100 cc, the ion permeability is insufficient, and the load characteristics of the battery are deteriorated, so it is not desirable. The average pore diameter of the porous substrate is preferably from 1 Torr to 1 〇〇 nm. When the average pore diameter is less than 1 〇 nm, it is not desirable because it is difficult to impregnate the electrolyte. When the average pore diameter is larger than 100 nm, the formation of the heat-resistant porous layer causes a blockage at the interface, and when the porous layer is formed, a shutdown characteristic is remarkably lowered, which is not desirable. The heat-resistant porous layer of the present invention contains a porous structure in which a plurality of pores or voids are formed inside the heat-resistant resin and the inorganic material, and these pores are connected to each other. The heat-resistant porous layer is a form in which the inorganic material is dispersed and bonded to the heat-resistant resin and is directly fixed to the porous substrate, but is preferably treated. Further, a porous layer formed of only a heat resistant resin may be formed on the porous substrate, and then a solution containing an inorganic tantalum such as coating or dipping may be formed in the pores of the heat resistant resin layer. Or a form of inorganic tantalum attached to the surface. Further, the heat-resistant porous layer may be configured as a microporous film, an independent porous sheet such as a nonwoven fabric or a paper sheet, and the porous sheet may be bonded to the porous substrate. The non-aqueous battery separator according to the invention is characterized in that the inorganic binder is contained in the heat-resistant porous layer, and the inorganic substrate is not included in the porous substrate. The function of the inorganic tantalum is expected to have such a function even if it is not present in the porous layer. For example, even if the porous material is contained in the porous substrate -27-201101560, the effect of suppressing gas generation can be obtained. However, when the structure is used for a polyolefin porous substrate, it is not desirable because it has a disadvantage of significantly impairing the shutdown function. Therefore, it is preferable to have a structure in which a layer having a shutdown function is not contained, and it is contained in a porous layer which is expected to have heat resistance. The composition of the porous layer is preferably in the range of a heat resistant resin: inorganic binder = 10: 90 to 80: 20, preferably in the range of 10: 90 to 50: 50. When the content of the inorganic tantalum is less than 20% by weight, since the characteristics of the inorganic tantalum are not sufficiently obtained, it is not desired. When the content of the inorganic tantalum is more than 90% by weight, it is not required because it cannot be formed. Further, when the inorganic coating is 50% or more, heat resistance such as an effect of suppressing heat shrinkage can be improved, which is preferable. The porosity of the heat-resistant porous layer is preferably in the range of from 30 to 80%. Further, the porosity of the heat-resistant porous layer is preferably higher than the porosity of the porous substrate. This component is excellent in ion permeability, and can also provide a good shutdown function and the like, and can produce characteristics. When the thickness of the heat-resistant porous layer is formed on both surfaces of the porous layer substrate, the total thickness of the heat-resistant porous layer is preferably 2 μm or more and 12 μm or less, and heat-resistant porous. When the layer is formed on only one side, it is preferably 2 μm or more and 12 μm or less. The separator for a non-aqueous battery of the present invention preferably has a film thickness of from 7 to 25 μm, preferably from 10 to 20 μm. When the film thickness is thinner than 7 μm, it is not desirable in terms of mechanical strength. Further, when it exceeds 25 μm, it is not desirable in terms of ion permeability, and the volume occupied by the battery inner separator is increased, and the amount of energy reduction is not required. The porosity of the separator for a non-aqueous battery of the present invention is preferably 20 to 7 % by weight, and preferably 30 to 60%. When the porosity is less than 20%, it is not desirable because the electrolyte cannot maintain a sufficient amount of electrolyte during operation. When the porosity is more than 70%, the shutdown characteristics are insufficient, and the strength or heat resistance is lowered, so that it is not desirable. The puncture strength of the separator for a non-aqueous battery of the present invention is preferably 2 〇 0 § 0 or more preferably 25 〇 g or more, and more preferably 300 MPa or more. When the puncture strength is less than 200 g, in order to prevent the short circuit between the positive and negative electrodes of the battery, the strength is insufficient, and there is a disadvantage that the manufacturing processability cannot be improved, so that it is not desired. The JI s P 8 1 1 7 of the separator for a non-aqueous battery of the present invention preferably has a range of 150 to 600 sec/l 〇〇cc, preferably 15 〇 to 4 〇〇 sec / The range of 100cc. When Gore is less than 15 sec/l 〇〇cc, the ion permeability is excellent, but it will reduce the shutdown characteristics or mechanical strength, so it is not desirable. Further, when the porous layer is formed, a blocking phenomenon occurs at the Q interface between the porous substrate and the heat-resistant porous layer, which is not desirable. When the content of the battery is greater than 600 sec / 100 cc, the ion permeability may be insufficient and the load characteristics of the battery may be deteriorated. In addition, the sputum of the porous substrate for use in the non-aqueous battery separator of the present invention is preferably 0.25 sec/100 cc or less, preferably 200 sec/100 cc or less. . The smaller one is preferable in that the shutdown characteristics are improved and the ion permeability is improved. In the present invention, the 'heat-resistant porous layer can be formed on at least one side of the porous substrate' to form more preferably on both sides of the surface of the porous substrate. -29-201101560 The heat-resistant porous layer is formed on both sides of the surface of the porous substrate, and there is no warpage. The handleability is good, and heat resistance for improving the dimensional stability at high temperatures can be obtained, and the battery can be remarkably improved. The effect of the cycle characteristics and the like. [Manufacturing Method of Non-aqueous Battery Separator] The method for producing a non-aqueous battery separator according to the present invention is not particularly limited, and can be produced, for example, by a production method including the following steps (i) to (iv). . In other words, (i) a step of preparing a coating slurry containing a heat resistant resin, an inorganic coating, and a water-soluble organic solvent, and (ii) coating the coating slurry obtained on one surface or both surfaces of the porous substrate. The step of preparing the material, (iii) the step of solidifying the heat-resistant resin in the applied slurry, and the step of (iv) washing and drying the sheet after the solidification step. Further, the steps (i) to (iv) are the same as in the first embodiment described above. In the present invention, the method for producing the porous substrate is not particularly limited, and for example, a polyolefin microporous film which is a porous substrate described below can be produced. In other words, the gel-like mixture of polyolefin and flowing paraffin is extruded from the mold and then the base tape is formed by cooling to extend the base tape to be heat-fixed. Next, a polyolefin microporous film can be obtained by immersing the flowing paraffin in an extraction solvent such as dichloromethane to carry out extraction and drying the extraction solvent. [Non-aqueous battery] The non-aqueous battery according to the third aspect of the present invention is a non-aqueous battery including a positive electrode, a negative -30-201101560, and a separator, and the separator is a non-aqueous battery separator. The water-separated battery is excellent in safety or durability at high temperatures, and is excellent in cycle characteristics and the like. Further, other battery configurations are the same as those of the first embodiment described above. (1-4) A non-aqueous battery separator according to a fourth aspect of the present invention, comprising a multi-hole porous substrate, laminated on one or both sides of the porous substrate, and containing a heat-resistant resin and A separator for a non-aqueous storage battery of a heat-resistant porous layer of an inorganic material, characterized in that the inorganic tantalum is amorphous alumina particles. According to the present invention, the same effects as in the third embodiment described above can be achieved. In particular, since the amorphous alumina adsorbs a trace amount of impurities present in the battery or a by-product such as HF, the cycle characteristics of the battery can be further improved. Further, in the fourth embodiment, since the inorganic material of the third embodiment is changed to the amorphous alumina, the same configuration as that of the third Q state can be omitted. (2) The second invention of the present invention is a configuration that solves the problem of safety and durability of batteries in the technical field of separators, and the like, in particular, "specific surface area" is used. The composition of activated alumina or amorphous alumina of 300 to 1 000 m 2 /g is excellent in the effect of improving the cycle characteristics of the battery because the activity of HF is remarkably lowered. Therefore, the effect of the second aspect of the present invention is remarkable, and an example will be described in which "activated alumina" and "amorphous alumina" -31 - 201101560 are used as adsorbents for hydrogen fluoride, and the adsorbent is used in various parts. (2-1) Fifth aspect The adsorbent for a nonaqueous battery according to a fifth aspect of the present invention contains an adsorbent having hydrogen fluoride in an area of 300 to 1000 m 2 /g of adsorbent. In the present invention, since the aluminum hydroxide particles having a specific surface area of 300 to 1 are used as the adsorbent for the nonaqueous battery, the HF generated by the aluminum adsorption battery or the reactivity with HF is used to improve the cycle characteristics of the nonaqueous battery. In the conventional type of specific porous material, only the specific specific surface area of the activated alumina having a specific specific surface area in the invention is different from that of other porous inorganic materials. The detailed reasons for the excellent activity of activated alumina are unknown. However, since alumina is a precursor of Lewis acid and Lewis base, it is presumed that HF can be polarized to efficiently capture HF. The surface area is more than 300 m2/g, and the surface ring characteristics can be smoothly performed. It is currently technically difficult to produce a specific surface area exceeding alumina. Further, the configuration of the "active alumina particles having a specific surface ϋ m2/g" in the fifth embodiment is the same as that in the foregoing, and thus the description thereof will be omitted. The agent of the water-based battery is oxidized by the active oxygen of the non-aqueous characteristic ratio m2/g, and the HF can be reduced. Although there is no technique, the activity of the HF is excellent, and the cycle characteristic is excellent. I. Knowing the amphoteric oxidation and, by making the specific reaction, increase the activity of 1 000 m2/g to 3 00 〜1. Describing the first form -32 - 201101560 [Contents of activated alumina]

前述含有活性氧化鋁之形態，例如下述之（A )〜（C )° (A ) —種非水系蓄電池用多孔膜，係含有無機塡料及黏合樹脂所構成的非水系蓄電池用多孔膜，其特徵爲含有前述活性氧化鋁作爲前述無機塡料。 (B ) —種非水系蓄電池用隔板，其係具備多孔質基 0 材、被層合於此多孔質基材之一面或兩面上含有耐熱性樹脂及無機塡料之耐熱性多孔質層的非水系蓄電用隔板，其特徵含有非晶狀氧化鋁作爲前述無機塡料。 (C) 一種非水系蓄電池’其係具備正極、負極、非水電解質及隔板之非水系蓄電池，其特徵爲在該電池內含有前述活性氧化鋁。如前述（A)〜（C )所示’前述活性氧化鋁可含於隔板中，亦可含於層合於隔板或電極上之多孔膜中，亦可含 Q 於正極及負極中，另外，亦可含於電解液中。然而，混入於電極合劑時，由於活物質之體積的份量減少而損害電池容量，以在隔板中含有活性氧化鋁的形態較佳。另外，爲使關機功能與耐熱性等兩功能併立時，在由聚乙燒等之熱可塑性樹脂所形成的多孔質基材之表面上，被覆由聚醯胺等之耐熱性樹脂所形成的耐熱性多孔質層，以在該耐熱性多孔質層中含有活性氧化鋁之形態較佳。在正極中含有前述活性氧化鋁時，均勻地混合前述第一形態之正極活物質、黏合劑及導電劑與活性氧化鋁，製 -33- 201101560 作正極合劑，且在溶劑中分散該正極合劑，形成正極合劑漿料。然後，使該正極合劑例如藉由刮刀塗佈法等塗佈於正極集電體上。然後，藉由在高溫下予以乾燥，使溶劑揮發且加壓，製得含有活性氧化鋁之正極。而且，藉由在正極合劑中不含活性氧化鋁，使活性氧化鋁分散於NMP等溶劑之塗佈液塗佈於正極之活物質側且進行乾燥，使活性氧化鋁固定於正極上亦爲有效。在負極中含有前述氧化錦時，均勻地混合前述第一形態之負極活物質、黏合劑及導電劑與活性氧化鋁，製作負極合劑，且在溶劑中分散該負極合劑，形成負極合劑漿料。然後，使該負極合劑例如藉由與正極相同的方法等塗佈於負極集電體上。然後，藉由使該負極合劑在高溫下予以乾燥，使溶劑揮發且加壓，製得含有活性氧化鋁之負極。而且，藉由在負極合劑中不含活性氧化銘，使活性氧化銘分散於NMP等溶劑之塗佈液塗佈於負極之活物質側且進行乾燥，使活性氧化鋁固定於負極上亦爲有效。在隔板中含有前述活性氧化鋁時，例如可經由在由聚乙烯等之熱塑性樹脂中添加活性氧化鋁後，進行熔融退火處理，調製含有活性氧化鋁之熱塑性樹脂溶液的步驟，使該溶液自塑模押出予以冷卻，形成凝膠狀成型物的步驟，自一次延伸步驟及二次延伸步驟之凝膠狀成型物除去液體溶劑之步驟，以及藉由使所得的膜乾燥的步驟，製得隔板作爲含有活性氧化鋁之熱塑性樹脂微多孔膜。而且，例如亦可使均勻地分散有芳香族聚醯胺等之黏合樹脂與活性氧 -34- 201101560 化鋁的塗佈液塗佈於聚丙烯薄膜等之基體薄膜上，進行凝固•水洗•乾燥後，剝離塗佈膜予以製得。此外，爲層合型隔板時，亦可在各層之任何一層中含有活性氧化鋁’亦可含於全部之層中。例如將均勻地分散有芳香族聚醯胺等之耐熱性樹脂與活性氧化鋁的塗佈液，塗佈於聚乙烯微多孔膜或不織布等之多孔質基材的一面或兩面時’製得含有活性氧化鋁之層合型隔板。另外，例如 0 使不織布等之多孔質基材浸漬於均勻地分散有PVdF等之黏合劑樹脂與活性氧化鋁的塗佈液中，取出該物後，進行水洗•乾燥，製得作爲複合型隔板。而且’於前述之隔板或多孔膜中，黏合活性氧化鋁之黏合樹脂，除芳香族聚醯胺等之耐熱性樹脂外，例如聚氟化次乙烯基（PVdF)或PVdF共聚物、聚乙烯等之熱塑性樹脂等。有關前述耐熱性樹脂或多孔質基材 '非水系蓄電池中之電極、電解液、外裝材料等之構成’由於在前述第〇 ~形態中有詳述，故省略說明。 (2-2)第六形態本發明第六形態之非水系蓄電池用吸附劑，係混入於非水系蓄電池內之氟化氫的吸附劑，其特徵爲該吸附劑爲非晶狀氧化鋁粒子。本發明由於使用非晶狀氧化鋁作爲非水系蓄電池用吸附劑，非晶狀氧化鋁會吸附電池內產生的微量雜質或HF等之副生成物’故可提高非水系蓄電池之循環特性。 -35- 201101560 而且’該第六形態由於除使前述第五形態之吸附劑改爲非晶狀氧化鋁外，其餘皆相同，故省略說明有關與前述第五形態相同的構成。此外，如前述之「比表面積爲3 0 0 〜1 000 m2/g之活性氧化鋁」與「非晶狀氧化鋁」可達成互相類似的作用效果’就比表面積而言本發明之主要爲活性氧化鋁，就結晶構造而言本發明之主要爲非晶狀氧化鋁。含有前述非晶狀氧化鋁之形態，係與前述第五形態之（A )〜（C)之形態相同。另外，前述之非晶狀氧化鋁，就抑制內部短路而言以在正極與負極間之任何部位中含有較佳。【實施方式】 [實施例] (1 )第一、第二實施形態之實施例於下述中，說明有關本發明之第一、第二形態的實施例。本實施例中使用的測定方法如下所述。 [無機塡料之平均粒徑] 藉由雷射繞射式粒度分布測定裝置（島津製作所公司製：SALD-2000J)進行測定。使用水作爲分散媒，使用微量的非離子性界面活性劑「Triton X -1 00」作爲分散劑。所得的體積粒度分布之中心粒徑（D 5 0 )作爲平均粒徑。 [無機塡料之比表面積] -36- 201101560In the form of the non-aqueous battery for a non-aqueous battery, the porous film for a non-aqueous battery, comprising a porous film for a non-aqueous battery, comprising the inorganic film and the adhesive resin, is a porous film for a non-aqueous battery. It is characterized in that it contains the aforementioned activated alumina as the above-mentioned inorganic tantalum. (B) A separator for a non-aqueous battery, which comprises a porous base material, a heat-resistant porous layer which is laminated on one surface of the porous base material or both surfaces and which contains a heat-resistant resin and an inorganic coating material. The separator for non-aqueous storage batteries is characterized in that amorphous alumina is used as the inorganic binder. (C) A non-aqueous battery which is a non-aqueous battery including a positive electrode, a negative electrode, a non-aqueous electrolyte and a separator, and characterized in that the battery contains the activated alumina. As described in the above (A) to (C), the activated alumina may be contained in the separator, or may be contained in a porous film laminated on the separator or the electrode, or may contain Q in the positive electrode and the negative electrode. In addition, it may be contained in the electrolyte. However, when it is mixed in the electrode mixture, the battery capacity is impaired due to a decrease in the volume of the active material, and the form in which the activated alumina is contained in the separator is preferable. In addition, in order to prevent the two functions of the shutdown function and the heat resistance, the heat-resistant resin formed of a heat-resistant resin such as polyamine is coated on the surface of the porous base material formed of a thermoplastic resin such as polyethyl bromide. The porous layer is preferably in the form of containing activated alumina in the heat resistant porous layer. When the positive electrode contains the activated alumina, the positive electrode active material, the binder, and the conductive agent of the first embodiment are uniformly mixed with activated alumina to prepare a positive electrode mixture of -33-201101560, and the positive electrode mixture is dispersed in a solvent. A positive electrode mixture slurry was formed. Then, the positive electrode mixture is applied onto the positive electrode current collector by, for example, a doctor blade method. Then, by drying at a high temperature, the solvent is volatilized and pressurized to obtain a positive electrode containing activated alumina. Further, by not including the activated alumina in the positive electrode mixture, the coating liquid in which the activated alumina is dispersed in a solvent such as NMP is applied to the living material side of the positive electrode and dried to fix the activated alumina on the positive electrode. . When the oxidized bromine is contained in the negative electrode, the negative electrode active material, the binder, and the conductive agent in the first form are uniformly mixed with the activated alumina to prepare a negative electrode mixture, and the negative electrode mixture is dispersed in a solvent to form a negative electrode mixture slurry. Then, the negative electrode mixture is applied to the negative electrode current collector by, for example, the same method as the positive electrode. Then, the negative electrode mixture is dried at a high temperature to volatilize and pressurize the solvent to obtain a negative electrode containing activated alumina. Further, by not including the active oxidation in the negative electrode mixture, the coating liquid in which the active oxidation is dispersed in a solvent such as NMP is applied to the living material side of the negative electrode and dried, and the activated alumina is also fixed on the negative electrode. . When the active alumina is contained in the separator, for example, a step of preparing a thermoplastic resin solution containing activated alumina by adding activated alumina to a thermoplastic resin such as polyethylene may be carried out to prepare the solution. a step of cooling the mold to form a gel-like molded product, a step of removing the liquid solvent from the gel-like molded product in the first stretching step and the second stretching step, and a step of drying the obtained film to obtain a partition The plate was used as a thermoplastic resin microporous film containing activated alumina. Further, for example, a coating liquid in which an aromatic polyamine or the like is uniformly dispersed and a coating liquid of active oxygen-34-201101560 aluminum may be applied to a base film such as a polypropylene film to perform solidification, washing, and drying. Thereafter, the coated film was peeled off. Further, in the case of a laminated separator, activated alumina may be contained in any of the layers or may be contained in all of the layers. For example, when a coating liquid of a heat-resistant resin such as an aromatic polyamine or a reactive alumina is uniformly dispersed and applied to one or both sides of a porous substrate such as a polyethylene microporous film or a nonwoven fabric, it is prepared to contain A laminated separator of activated alumina. In addition, for example, a porous substrate such as a nonwoven fabric is immersed in a coating liquid in which a binder resin such as PVdF or the like is uniformly dispersed, and the material is taken out, and then washed and dried to obtain a composite separator. board. Further, 'in the above separator or porous film, a binder resin of activating activated alumina, in addition to a heat resistant resin such as aromatic polyamide or the like, such as polyfluorinated vinylidene (PVdF) or PVdF copolymer, polyethylene Such as thermoplastic resins and the like. The heat-resistant resin or the porous substrate "the composition of the electrode, the electrolytic solution, the exterior material, and the like in the non-aqueous battery" will be described in detail in the above-described first embodiment, and thus the description thereof will be omitted. (2-2) Sixth Aspect The adsorbent for a nonaqueous battery according to a sixth aspect of the present invention is an adsorbent for hydrogen fluoride mixed in a nonaqueous battery, characterized in that the adsorbent is amorphous alumina particles. In the present invention, amorphous alumina is used as a non-aqueous battery adsorbent, and amorphous alumina adsorbs a trace amount of impurities or a by-product such as HF generated in the battery, so that the cycle characteristics of the nonaqueous battery can be improved. Further, the sixth embodiment is the same as the fifth embodiment except that the adsorbent of the fifth embodiment is changed to amorphous alumina. Therefore, the configuration similar to the fifth embodiment will be omitted. Further, as described above, "activated alumina having a specific surface area of 300 to 1 000 m2/g" and "amorphous alumina" can achieve mutually similar effects. In terms of specific surface area, the present invention is mainly active. Alumina, the present invention is mainly amorphous alumina in terms of crystal structure. The form containing the amorphous alumina is the same as the form of (A) to (C) of the fifth embodiment. Further, the amorphous alumina described above is preferably contained in any portion between the positive electrode and the negative electrode in order to suppress internal short-circuiting. [Embodiment] [Embodiment] (1) First and Second Embodiments Hereinafter, embodiments of the first and second aspects of the present invention will be described. The measurement method used in the present embodiment is as follows. [Average particle size of the inorganic material] The measurement was carried out by a laser diffraction type particle size distribution measuring apparatus (manufactured by Shimadzu Corporation: SALD-2000J). Water was used as a dispersing medium, and a small amount of a nonionic surfactant "Triton X -1 00" was used as a dispersing agent. The center particle diameter (D 5 0 ) of the obtained volume particle size distribution was taken as the average particle diameter. [Specific surface area of inorganic tantalum] -36- 201101560

以JIS Κ 8 8 3 0爲基準進行測定。使用NOVA-1 200 ( YUAS A IONICS公司製），藉由氮氣氣體吸附法、以BET 式進行解析求取。測定時之試料重量爲0.1〜0.2g。解析係以3點法予以實施，由BET標繪圖求取比表面積。 [無機塡料之結晶構造的解析] 無機塡料之結晶構造，係藉由粉末X光繞射裝置以測 0 定無機塡料之XRD繞射光譜，由該光譜解析整體結構中之結晶構造。X光繞射裝置係使用Rigaku公司製、X光產生裝置ultrax 18，使用Cu-ka線。測定條件係45KV-60mA、試料間隔0.020° 、測定範圍（2Θ ) 5°〜90° 、掃描速度 5 ° /min。測定試料係使用瑪瑕乳缽、以人力粉碎無機塡料、且在玻璃試料板上所完成者。在玻璃試料板上具有縱 18mm、寬20mm、深〇.2mm之溝，試料之厚度係玻璃試料板之深度。 ❹ [無機塡料之元素比例的測定] 存在於無機塡料表面上之Ο/Al的元素比例，係使用χ 光電子分光裝置（VG公司製、ESCALAB200 )進行測定，由所得的Ols與Al2p強度比求得。X光源係使用MgKa線。 [膜厚] 以接觸式膜厚計（Mitutoyo公司製）測定20點，藉由平均求得。此處，接觸端子係使用底面爲直徑0.5 cm之_ -37- 201101560 柱狀者。 [實施例1-1] 使氫氧化鋁（昭和電工製：H-43M )在2 8 0t下進行熱處理，製得平均粒徑〇.8μιη、比表面積400m2/g之活性氧化鋁。有關該活性氧化鋁進行XRD解析時，在寬圖中僅觀察有來自勃姆石之波峰，2Θ = 14.39°之波峰的積分強度爲98 cps· deg，對該主波峰之積分強度爲2Θ = 10〜60 deg存在的寬波峰之積分強度而言爲〇.〇7。藉此可知，該活性氧化鋁主要以非晶狀整體結構僅稍微混有勃姆石相，故亦可說爲非晶狀氧化鋁。而且，該活性氧化鋁表面之Ο/Al的元素比例爲1 . 5 4。使用聚間亞苯基酞酸胺的Conex (註冊商標：Teijin technoproducts公司製）作爲間型全芳香族聚醯胺。以二甲基乙醯胺（DMAc):三丙二醇（TPG) = 60: 40之重量比，使Conex爲7重量％下溶解，製作Conex溶液。在活性氧化銘：Conex=30: 70 (重量比）下’於該 Conex溶液中分散該活性氧化鋁，調整漿料。將該漿料塗佈於玻璃板上，使該物以重量比爲水： DMAc: TPG=70: 18: 12(重量比）、浸漬於30 °C之凝固液中’然後，進行水洗、乾燥。其次’剝離在玻璃板上所形成的多孔膜，製得處理性充分的膜厚1 Mm之多孔膜》 [實施例1 - 2 ] -38- 201101560 除將活性氧化銘改爲平均粒徑4 μ m、比表面積7 0 0 m2/g之沸石（HSZ-341NHA; Tosoh公司製）外，以與實施例1 -1相同的方法，製得處理性充分的膜厚1 Ομηι之多孔膜 [實施例1-3] 對活性碳（關西熱化學公司製：MSP-20 )而言，藉由 0 進行以二甲基乙醯胺（DMAc )作爲分散溶劑之濕式粉碎處理（2mm直徑之氧化銷珠磨機），製得平均粒徑0.6μιη 、比表面積1 600 m2/g之活性碳。除將活性氧化鋁改爲前述活性碳外，以與實施例1 -1 相同的方法，製得膜厚10 μπι之多孔膜。而且，該多孔膜與實施例1 -1者相比時，稍微較脆、處理性不佳者。 [實施例I-4] 〇除使活性氧化鋁與c ο n e X之重量比以活性氧化鋁：The measurement was performed based on JIS Κ 8 8 3 0. Using NOVA-1 200 (manufactured by YUAS A IONICS Co., Ltd.), it was analyzed by a nitrogen gas adsorption method in a BET equation. The weight of the sample at the time of measurement was 0.1 to 0.2 g. The analytical system was implemented by the 3-point method, and the specific surface area was obtained from the BET plot. [Analysis of crystal structure of inorganic cerium] The crystal structure of the inorganic cerium was determined by measuring the XRD diffraction spectrum of the inorganic cerium by a powder X-ray diffraction apparatus, and the crystal structure in the overall structure was analyzed from the spectrum. As the X-ray diffraction device, an ultralight 18 manufactured by Rigaku Co., Ltd. and an X-ray generating device were used, and a Cu-ka wire was used. The measurement conditions were 45 KV-60 mA, the sample interval was 0.020°, the measurement range was (2 Θ) 5° to 90°, and the scanning speed was 5 ° /min. The measurement sample was obtained by using a Malang nipple, pulverizing the inorganic mash by a human, and completing it on a glass sample plate. The glass sample plate has a groove of 18 mm in length, 20 mm in width, and 2 mm in depth, and the thickness of the sample is the depth of the glass sample plate. ❹ [Determination of the element ratio of the inorganic material] The element ratio of cerium/Al present on the surface of the inorganic cerium is measured by using a krypton photoelectron spectrometer (manufactured by VG, ESCALAB200), and the obtained Ols and Al2p intensity ratio Seek. The X-ray source uses a MgKa line. [Film thickness] 20 points were measured by a contact type film thickness meter (manufactured by Mitutoyo Co., Ltd.), and the average was obtained. Here, the contact terminal is a column having a bottom surface of 0.5 cm in diameter of -37-201101560. [Example 1-1] Aluminum hydroxide (manufactured by Showa Denko: H-43M) was heat-treated at 280 Torr to obtain an active aluminum oxide having an average particle diameter of 88 μm and a specific surface area of 400 m 2 /g. When XRD analysis was performed on the activated alumina, only the peak from the boehmite was observed in the broad view, and the integrated intensity of the peak of 2Θ = 14.39° was 98 cps·deg, and the integrated intensity of the main peak was 2Θ = 10 The integral intensity of the broad peaks present at ~60 deg is 〇.〇7. From this, it is understood that the active aluminum oxide is mainly amorphous in a single crystal structure, and is only slightly mixed with a boehmite phase. Further, the element ratio of Ο/Al of the surface of the activated alumina is 1.54. Conex (registered trademark: manufactured by Teijin technoproducts Co., Ltd.) using poly(m-phenylene decanoate) was used as a meta-type wholly aromatic polyamine. A Conex solution was prepared by dissolving Conex at 7% by weight in a weight ratio of dimethylacetamide (DMAc): tripropylene glycol (TPG) = 60:40. The activated alumina was dispersed in the Conex solution under active oxidation: Conex = 30:70 (by weight) to adjust the slurry. The slurry was applied to a glass plate so that the weight ratio of water was: DMAc: TPG = 70: 18: 12 (weight ratio), immersed in a coagulating liquid at 30 ° C. Then, it was washed with water and dried. . Next, 'the porous film formed on the glass plate was peeled off to obtain a porous film having a film thickness of 1 Mm. [Example 1 - 2 ] -38 - 201101560 In addition to changing the active oxidation to an average particle diameter of 4 μ A porous film having a film thickness of 1 Ομηι having a sufficient handleability was obtained in the same manner as in Example 1-1 except for a zeolite having a specific surface area of 700 m 2 /g (HSZ-341NHA; manufactured by Tosoh Corporation). 1-3] For activated carbon (MSP-20 manufactured by Kansai Thermochemical Co., Ltd.), wet pulverization treatment (2 mm diameter oxidized beads) with dimethylacetamide (DMAc) as a dispersion solvent was carried out by 0. Grinding machine) An activated carbon having an average particle diameter of 0.6 μm and a specific surface area of 1,600 m 2 /g was obtained. A porous film having a film thickness of 10 μm was obtained in the same manner as in Example 1-1 except that the activated alumina was changed to the above activated carbon. Further, the porous film was slightly brittle and had poor handleability when compared with the case of Example 1-1. [Example I-4] 〇 In addition to the weight ratio of activated alumina to c ο n e X as activated alumina:

Conex = 70 : 3 0 (重量比）外，與實施例1-1相同的方法，製得膜厚1 Ομηι之多孔膜。該多孔膜與實施例1 -1相比時，稍微較脆且處理性不佳。 [實施例1-5] 在以實施例1 -1所製作的電池用多孔膜上塗佈聚乙烯水分散液（Chemipearl W900 :三井化學股份有限公司製 )，藉由乾燥，製得膜厚13μιη之多孔膜。 -39- 201101560 [比較例1 -1 ] 除將活性氧化鋁改爲平均粒徑〇·8μηι、比表面積8m2/g 之氧化鋁（昭和電工製：H-43M)外，以與實施例1-1相同的方法，製得膜厚1 Ομηι之處理性充分的處理性充分的多孔膜。 [比較例1-2] 除將活性氧化鋁改爲平均粒徑〇.6μιη、比表面積6m2/g 之氧化鋁（昭和電工製：AL160SG-3)外，以與實施例1-1 相同的方法，製得膜厚1 Ομηι之處理性充分的處理性充分的多孔膜。 [比較例1-3] 使用聚間亞苯基異酞醯胺的Coiiex (註冊商標：Teijin technoproducts公司製）作爲間型全芳香族聚醯胺。以二甲基乙醯胺（DMAc ):三丙二醇（TPG ) = 60 : 40之重量比，使C ο n e X爲7重量％下溶解，製作C ο n e X溶液。將該Conex溶液塗佈於玻璃板上，使該物以重量比爲水：DMAc : TPG = 70 : 1 8 : 12 (重量比）、浸漬於 3 0 °C 之凝固液中，然後，進行水洗、乾燥。其次，剝離在玻璃板上所形成的多孔膜，製得處理性充分的膜厚1 Ομιη之處理性充分的多孔膜。 -40- 201101560 [比較例1-4] 使用Ticona公司製之GUR2126 (重量平均分子量415萬、熔點141 °C )與GURX143 (重量平均分子量56萬、熔點 135°C )作爲聚乙烯粉末。在GUR2126與GURX143爲1 : 9 (重量比）、聚乙烯濃度爲15重量％下，溶解於流動石蠟 (松村石油硏究所公司製；Smoil P-350P;沸點480°C)與萘烷之混合溶劑中，製作聚乙烯溶液。該聚乙烯溶液之組 0 成係聚乙烯：流動石蠟：萘烷=30 : 45 : 25 (重量比）。製作在聚乙烯溶液中分散有沸石（HSZ-500KOA ; Tosoh公司製）之漿料。此處，聚乙烯與沸石之混合比，以重量比爲50 : 50。沸石係平均粒徑3μιη、比表面積290 m2/g。在148 °C下、自塑模押出該漿料，在水浴中冷卻，製作凝膠狀膠帶（基體膠帶）。使該基體膠帶在6〇°C下進行乾燥8分鐘，在95 °C下進行乾燥15分鐘，且使基體膠帶逐〇次進行縱延伸、橫延伸之二軸延伸處理。此處’縱延伸係延伸倍率5.5倍、延伸溫度90 °c，橫延伸係延伸倍率11.0倍、延伸溫度1 0 5 t。於橫延伸後，在1 2 5 °C下進行熱固定處理。其次，將其浸漬於二氯甲烷浴中，萃取流動石蠟與萘烷。然後，在5(TC下進行乾燥，且在12〇°C下進行退火處理，製得ΙΟμπι之處理性充分的多孔膜。 [比較例1-5] 使氫氧化鋁（昭和電工製：Η-43Μ)在205°C下進行熱 -41 - 201101560 處理，製得平均粒徑0.8μιη、比表面積30 m2/g之活性氧化鋁。有關該活性氧化鋁以XRD進行構造解析時，由於確認沒有來自非晶狀構造之寬波峰，確認有來自三水鋁石之波峰，可知整體結構主要爲三水鋁石，不爲非晶狀氧化銘。除將該活性氧化鋁改爲實施例1 -1之活性氧化鋁外’ 以與實施例1-1相同的方法，製得膜厚ΙΟμιη之處理性充分的多孔膜。 [破膜試驗]A porous film having a film thickness of 1 Ομηι was obtained in the same manner as in Example 1-1 except that Conex = 70 : 30 (weight ratio). When the porous film was compared with Example 1-1, it was slightly brittle and the handleability was poor. [Example 1-5] A polyethylene aqueous dispersion (Chemipearl W900: manufactured by Mitsui Chemicals, Inc.) was applied to the porous film for a battery produced in Example 1-1, and dried to obtain a film thickness of 13 μm. Porous membrane. -39-201101560 [Comparative Example 1 -1] Except that the activated alumina was changed to alumina having an average particle diameter of 〇·8 μηι and a specific surface area of 8 m 2 /g (manufactured by Showa Denko: H-43M) 1 In the same manner, a porous film having a sufficient film thickness of 1 Ομηι was obtained. [Comparative Example 1-2] The same procedure as in Example 1-1 except that the activated alumina was changed to alumina having an average particle diameter of 66 μm and a specific surface area of 6 m 2 /g (manufactured by Showa Denko: AL160SG-3) A porous film having a sufficient handleability and a sufficient film thickness of 1 Ομηι was obtained. [Comparative Example 1-3] Coiiex (registered trademark: manufactured by Teijin technoproducts Co., Ltd.) using polym-phenyleneisodecylamine was used as the meta-type wholly aromatic polyamine. The C ο n e X solution was prepared by dissolving C ο n e X at 7% by weight in a weight ratio of dimethylacetamide (DMAc): tripropylene glycol (TPG) = 60:40. The Conex solution was applied to a glass plate to make a weight ratio of water: DMAc : TPG = 70 : 1 8 : 12 (weight ratio), immersed in a coagulating liquid at 30 ° C, and then washed with water. ,dry. Next, the porous film formed on the glass plate was peeled off to obtain a sufficiently porous film having a film thickness of 1 μm. -40-201101560 [Comparative Example 1-4] GUR 2126 (weight average molecular weight: 4.15 million, melting point: 141 ° C) manufactured by Ticona Co., Ltd. and GURX 143 (weight average molecular weight: 560,000, melting point: 135 ° C) were used as polyethylene powder. In the case of GUR2126 and GURX143 with a ratio of 1:9 (weight ratio) and a polyethylene concentration of 15% by weight, it is dissolved in a mixture of mobile paraffin (made by Matsumura Petroleum Research Institute; Smoil P-350P; boiling point 480 ° C) and decalin. A polyethylene solution was prepared in the solvent. The polyethylene solution group 0 is a polyethylene: mobile paraffin: decalin = 30: 45: 25 (weight ratio). A slurry in which zeolite (HSZ-500 KOA; manufactured by Tosoh Corporation) was dispersed in a polyethylene solution was prepared. Here, the mixing ratio of polyethylene to zeolite is 50:50 by weight. The zeolite has an average particle diameter of 3 μm and a specific surface area of 290 m 2 /g. The slurry was self-molded at 148 ° C and cooled in a water bath to prepare a gel-like tape (base tape). The base tape was dried at 6 ° C for 8 minutes, dried at 95 ° C for 15 minutes, and the base tape was subjected to a two-axis stretching treatment of longitudinal stretching and lateral stretching. Here, the longitudinal extension has a stretching ratio of 5.5 times, an elongation temperature of 90 ° C, a lateral stretching ratio of 11.0 times, and an extension temperature of 1 0 5 t. After the transverse stretching, heat setting treatment was carried out at 1 2 5 °C. Next, it was immersed in a dichloromethane bath to extract flowing paraffin and decalin. Then, it was dried at 5 (TC) and annealed at 12 ° C to obtain a sufficiently porous film of ΙΟμπι. [Comparative Example 1-5] Aluminum hydroxide (manufactured by Showa Denko: Η- 43Μ) The hot-41 - 201101560 treatment was carried out at 205 ° C to obtain an activated alumina having an average particle diameter of 0.8 μm and a specific surface area of 30 m 2 /g. When the structure of the activated alumina was analyzed by XRD, it was confirmed that there was no The broad peak of the amorphous structure was confirmed to have a peak from gibbsite, and it was found that the overall structure was mainly gibbsite, which was not amorphous oxide. The activated alumina was changed to the example 1-1. In the same manner as in Example 1-1, a sufficiently porous film having a film thickness of ΙΟμηη was obtained. [Broken film test]

有關前述製作的實施例1-1〜1-5及比較例1-1〜1-5之各多孔膜，如下述實施破膜試驗。首先，將試料之多孔膜固定於縱6.5cm、橫4.5cm之金框上。使烤箱溫度爲175°C ，將固定於金框的試料置於烤箱中，保持1小時。此時沒有膜破裂的情形，可維持形狀者評估爲〇，反之評估爲X 。結果如表1所示。 [氣體產生量試驗] 有關前述製作的實施例1-1〜1-5及比較例1-1〜1-5之各多孔膜，如下述實施破膜試驗。首先，將試料所形成的各多孔膜切出240cm2之大小，使其在85°C下進行真空乾燥 16小時。在露點-60 °C以下之環境下，將該物置於鋁袋中，再注入電解液，以真空密封劑密封鋁袋，製作測定晶胞。此處，電解液係1M LiPF0碳酸乙二酯（EC) /甲基碳酸乙酯（EMC) = 3/7 (重量比）（Kishida Chemical 公司製） -42- 201101560 。使測定晶胞在85°C下保存3曰，測定保存前後之測定晶胞的體積。以自保存後之測定晶胞的體積減去保存前之測定晶胞的體積之値作爲氣體產生量。此處，測定晶胞之體積測定係在23 °C下進行’以阿基米德原理爲基準，使用電子比重計（Alfa Mirage股份有限公司製：EW-3 00SG )進行。結果如表1所示。 [表1] 破膜試驗氣體產生量試驗(CC) 實施例1-1 〇 0.4 實施例1-2 〇 2.0 實施例1-3 〇 2.1 實施例1-4 〇 0.2 實施例1-5 〇 0.4 比較例1-1 〇 18.9 比較例1-2 〇 4.2 比較例1-3 〇 0 比較例1-4 X 1.7 比較例1-5 〇 12.5 〇 [非水系蓄電池之製作] 使用前述所製作的實施例1-1〜1-5及比較例1-1〜1-5 之各多孔膜，製作如下述之非水系蓄電池。在鈷酸鋰（LiCo02:日本化學工業公司製）粉末89.5 重量份、乙炔黑（電氣化學工業公司製；商品名DenkaThe porous films of Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-5 produced as described above were subjected to a film breaking test as follows. First, the porous film of the sample was fixed to a gold frame of 6.5 cm in length and 4.5 cm in width. The oven temperature was 175 ° C, and the sample fixed to the gold frame was placed in the oven for 1 hour. In the case where there is no film rupture at this time, the person who can maintain the shape is evaluated as 〇, and the evaluation is evaluated as X. The results are shown in Table 1. [Gas generation amount test] Each of the porous films of Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-5 prepared as described above was subjected to a film rupture test as follows. First, each porous film formed of the sample was cut into a size of 240 cm 2 and vacuum dried at 85 ° C for 16 hours. The material was placed in an aluminum bag under a dew point of -60 ° C or lower, and then an electrolyte solution was injected to seal the aluminum bag with a vacuum sealant to prepare a cell. Here, the electrolytic solution was 1 M LiPF0 ethylene carbonate (EC) / ethyl methyl carbonate (EMC) = 3/7 (weight ratio) (manufactured by Kishida Chemical Co., Ltd.) -42 - 201101560. The measurement unit cell was stored at 85 ° C for 3 Torr, and the volume of the measurement cell before and after storage was measured. The amount of enthalpy of the measured unit cell before storage is subtracted from the volume of the unit cell after storage as the gas generation amount. Here, the measurement of the volume of the unit cell was carried out at 23 ° C. Using an electron pycnometer (manufactured by Alfa Mirage Co., Ltd.: EW-3 00SG), based on the Archimedes principle. The results are shown in Table 1. [Table 1] Film Breaking Test Gas Production Amount Test (CC) Example 1-1 〇 0.4 Example 1-2 〇 2.0 Example 1-3 〇 2.1 Example 1-4 〇 0.2 Example 1-5 〇 0.4 Comparison Example 1-1 〇18.9 Comparative Example 1-2 〇4.2 Comparative Example 1-3 〇0 Comparative Example 1-4 X 1.7 Comparative Example 1-5 〇12.5 〇 [Production of Nonaqueous Battery] The above-described Example 1 was used. Each of the porous films of -1 to 1-5 and Comparative Examples 1-1 to 1-5 was prepared as follows. 89.5 parts by weight of a powder of lithium cobaltate (LiCo02: manufactured by Nippon Chemical Industry Co., Ltd.), acetylene black (manufactured by Electric Chemical Industry Co., Ltd.; trade name Denka)

Black ) 4.5重量份、聚氟化次乙烯基（Kureha化學公司製 )6重量份下，使用N-甲基-2 -吡咯烷酮溶劑，使此等進行退火處理，製作漿料。將所得的漿料塗佈於厚度爲之 -43- 201101560 鋁箱上予以乾燥後’進行壓製處理’製得正極。在中間相碳微珠（MCMB :大阪瓦斯化學公司製）粉末8 7重量份、乙炔黑（電氣化學工業公司製；商品名 Denka Black) 3重量份、聚氟化次乙烯基（Kureha化學公司製）10重量份下，使用N-甲基-2-吡咯烷酮溶劑，使此等進行退火處理，製作漿料。將所得的漿料塗佈於厚度爲 18μηι之銅箔上予以乾燥後，進行壓製處理，製得90μιη之負極。使前述正極及負極經由隔板予以對向，於其中含浸電解液，封入由鋁層合薄膜所形成的外裝中，製作非水系蓄電池。此處，電解液係使用1Μ LiPF6碳酸乙二酯/甲基碳酸乙酯（3/7重量比）（Kishida化學公司製）。此處，隔板係使用實施例1-1〜1 - 5及比較例1 - 1〜1 - 5 之各多孔膜’各製作表2所示之實施例1-6〜1-10及比較例 I·6〜1-10之各非水系蓄電池。而且，實施例丨_3、丨-4之多孔膜’係與聚乙烯微多孔膜（PE微多孔膜）層合使用。此處所使用的PE微多孔膜如下述方法製作。首先’使用Tic〇na公司製之GUR2126 (重量平均分子量415萬、熔點141。(：）與〇1；11又143(重量平均分子量56萬、溶點135°C )作爲聚乙烯粉末。在GUR2126與GURX143 爲1:9(重量比）、聚乙烯濃度爲30重量％下，溶解於流動石蠟（松村石油硏究所公司製；Sm〇il P-3 50P ;沸點 480°C )與萘烷之混合溶劑中，製作聚乙烯溶液。該聚乙嫌溶液之組成係聚乙烯：流動石蠟：萘烷= 30: 45: 25 ( -44 - 201101560 重量比）。在148 °C下自塑模押出該聚乙烯溶液，在水浴中冷卻，製作凝膠狀膠帶（基體膠帶）。使該基體膠帶在6〇°C下進行乾燥8分鐘，在95 °C下進行乾燥15分鐘，且使基體膠帶逐次進行縱延伸、橫延伸之二軸延伸處理。此處’縱延伸係延伸倍率5.5倍、延伸溫度90 °C，橫延伸係延伸倍率 1 1.0倍 '延伸溫度1 〇 5 °C。於橫延伸後，在1 2 5 °C下進行熱 0 固定處理。其次，將其浸漬於二氯甲烷浴中，萃取流動石蠟與萘烷。然後，在50°C下進行乾燥，且在120°C下進行退火處理，製得膜厚9μπι之聚乙烯微多孔膜。 [烤箱試驗] 使前述所製作的各電池以0.2C、4.2V之定電壓•定電流充電進行充電處理8小時。於其上施加1.8 kg/cm2之荷重狀態下置於烤箱中，以昇溫速度5°C/min、自30°C昇溫至 Q 150°C後，在150t下保持1小時。此時，有發煙者評估爲X ，完全沒有者評估爲〇。結果如表2所示。 [循環特性] 評估前述所製作的各電池之循環特性。循環特性之評估係以1C、4.2V之定電壓•定電流充電進行充電處理2小時，以1C、2.75V切斷的定電流放電進行充電處理，以第1次循環之容量爲基準時之第3 00次循環之容量維持率作爲循環特性之指標。而且，測定時之溫度爲3 。結果如表2 -45- 201101560 所示。 [保存試驗] 使前述所製作的電池以〇.2C、4·2ν之定電壓·定電流充電進行充電處理8小時。於其上施加I·8 kg/cm2之荷重的狀態下置於烤箱中，在85°C下保存3日。於保存後’進行 0.2C、2.75 V切斷的定電流放電處理，求取殘存容量。使殘存容量除以初期容量之値乘以1 00，計算容量維持率。以該容量維持率作爲保存試驗之評估指標。結果如表2所不 ° [電池之膨脹] 以目視確認前述保存試驗後之各電池，可知電池有膨脹情形者判斷爲X，在外觀上沒有電池之膨脹情形者爲〇。而且，此時電池之膨脹情形，係在電池內產生氣體者。結果如表2所示。 -46- 201101560 [表2]Black) Under a weight of 4.5 parts by weight of polyfluorinated vinylidene (manufactured by Kureha Chemical Co., Ltd.), an N-methyl-2-pyrrolidone solvent was used, and these were annealed to prepare a slurry. The obtained slurry was applied to an aluminum box having a thickness of -43 to 201101560, dried, and then subjected to press treatment to obtain a positive electrode. 8 parts by weight of powder of mesocarbon microbeads (MCMB: manufactured by Osaka Gas Chemical Co., Ltd.), acetylene black (manufactured by Denki Kagaku Co., Ltd.; trade name Denka Black), 3 parts by weight, polyfluorinated vinylidene (Kureha Chemical Co., Ltd.) In 10 parts by weight, an N-methyl-2-pyrrolidone solvent was used, and these were annealed to prepare a slurry. The obtained slurry was applied onto a copper foil having a thickness of 18 μm and dried, followed by pressing to obtain a negative electrode of 90 μm. The positive electrode and the negative electrode were opposed to each other via a separator, and the electrolytic solution was impregnated therein, and sealed in an exterior formed of an aluminum laminate film to prepare a nonaqueous battery. Here, as the electrolytic solution, 1 Μ LiPF6 ethylene carbonate/ethyl methyl carbonate (3/7 by weight) (manufactured by Kishida Chemical Co., Ltd.) was used. Here, in the separator, Examples 1-6 to 1-10 and Comparative Examples shown in Table 2 were produced using each of the porous films of Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-5. Each of the non-aqueous batteries of I·6 to 1-10. Further, the porous film of the examples 丨3 and 丨-4 was laminated with a polyethylene microporous film (PE microporous film). The PE microporous membrane used in this place was produced by the following method. First, 'GUR2126 manufactured by Tic〇na Co., Ltd. (weight average molecular weight 4.15 million, melting point 141. (:) and 〇1; 11 and 143 (weight average molecular weight 560,000, melting point 135 ° C) was used as the polyethylene powder. It is dissolved in mobile paraffin (Sm〇il P-3 50P; boiling point 480 ° C) and decalin with a GURX143 ratio of 1:9 (weight ratio) and a polyethylene concentration of 30% by weight. In a mixed solvent, a polyethylene solution is prepared. The composition of the polyethylene solution is polyethylene: mobile paraffin: decalin = 30: 45: 25 (-44 - 201101560 by weight). The mold is extruded at 148 ° C. The polyethylene solution was cooled in a water bath to prepare a gel-like tape (base tape). The base tape was dried at 6 ° C for 8 minutes, dried at 95 ° C for 15 minutes, and the base tape was successively applied. Longitudinal extension and transverse extension of the two-axis extension process. Here, the longitudinal extension has a stretch ratio of 5.5 times, an extension temperature of 90 ° C, and a transverse extension stretch ratio of 1 1.0 times and an extension temperature of 1 〇 5 ° C. After the lateral extension, Heat 0 fixed treatment at 1 2 5 ° C. Secondly, it is impregnated The paraffin wax and decalin were extracted in a dichloromethane bath, and then dried at 50 ° C and annealed at 120 ° C to obtain a polyethylene microporous film having a film thickness of 9 μm. Each of the batteries prepared above was charged and charged at a constant voltage of 0.2 C and 4.2 V for 8 hours, and placed in an oven under a load of 1.8 kg/cm 2 thereon at a temperature increase rate of 5 ° C/min. After heating from 30 ° C to Q 150 ° C, it was kept at 150 t for 1 hour. At this time, smokers were evaluated as X, and none at all evaluated as 〇. The results are shown in Table 2. [Cycle characteristics] Evaluation The cycle characteristics of each of the batteries produced as described above. The evaluation of the cycle characteristics was carried out by charging at a constant voltage of 1 C and 4.2 V and charging at a constant current for 2 hours, and charging was performed at a constant current discharge cut at 1 C and 2.75 V. The capacity retention rate of the 30th cycle at the time of the first cycle is used as an index of the cycle characteristics. Moreover, the temperature at the time of measurement is 3. The results are shown in Table 2-45-201101560. [Save Test] The fabricated battery has a constant voltage of 2.2C, 4·2ν· The current was charged and charged for 8 hours, placed in an oven with a load of 1·8 kg/cm 2 applied thereto, and stored at 85 ° C for 3 days. After storage, 'cut 0.2C, 2.75 V was cut. The current is discharged and the residual capacity is obtained. The remaining capacity is divided by the initial capacity and multiplied by 100 to calculate the capacity retention rate. The capacity retention rate is used as an evaluation index for the storage test. The results are not shown in Table 2. [Battery Expansion] The respective batteries after the storage test were visually confirmed, and it was found that the battery was inflated and judged to be X, and the appearance of the battery was not expanded. Moreover, at this time, the expansion of the battery is caused by gas generated in the battery. The results are shown in Table 2. -46- 201101560 [Table 2]

隔板烤箱試驗循環特性 (%) 保存試驗 (%) 電池之膨脹實施例1-6 實施例1-1之多孔膜〇 76 73 〇實施例1-7 實施例1-2之多孔膜〇 65 66 〇實施例1-8 實施例1-3之多孔膜/ΡΕ微多孔膜〇 60 63 〇實施例1-9 實施例1-4之多孔膜/ΡΕ微多孔膜〇 77 75 〇實施例1-10 實施例1-5之多孔膜〇 71 71 〇比較例1-6 比較例1-1之多孔膜〇 59 62 X 比較例1-7 比較例1-2之多孔膜〇 59 63 X 比較例1—8 比較例1-3之多孔膜〇 35 31 〇比較例1-9 比較例1-4之多孔膜 X 52 58 〇比較例1-10 比較例1-5之多孔膜〇 61 65 XSeparator oven test cycle characteristics (%) Storage test (%) Expansion of the battery Example 1-6 Porous film 〇76 of Example 1-1 76 〇 Example 1-7 Porous film of Example 1-2 〇 65 66 〇Example 1-8 Porous film / ΡΕ microporous film of Example 1-3 〇 60 63 〇 Examples 1-9 Porous film / ΡΕ microporous film of Example 1-4 〇 77 75 〇 Examples 1-10 Porous film of Example 1-5 71 71 〇 Comparative Example 1-6 Porous film of Comparative Example 1-1 59 62 X Comparative Example 1-7 Porous film of Comparative Example 1-2 59 63 X Comparative Example 1 - 8 Comparative Example 1-3 Porous Membrane 35 31 〇 Comparative Example 1-9 Porous Membrane of Comparative Example 1-4 X 52 58 〇 Comparative Example 1-10 Porous Membrane 比较 61 65 X of Comparative Example 1-5

[實施例1-11] 在鈷酸鋰（1^(：〇02:日本化學工業公司製）粉末89.5 重量份、乙炔黑（電氣化學工業公司製；商品名Denka Black ) 4.5重量份、聚氟化次乙烯基（Kureha化學公司製 )6重量份下，使用N-甲基-2-吡咯烷酮溶劑，使此等進行 Ο 退火處理，製作漿料。將所得的漿料塗佈於厚度爲20μηι之鋁箔上，予以乾燥後，進行壓製處理，製得ΙΟΟμπι之正極〇在前述之正極表面上塗佈以實施例1 -4所製作的漿料，使該物浸漬於以重量比爲水：DM Ac : TPG = 70 : 1 8 : 1 2 (重量比）、3 (TC之凝固液中，然後，進行水洗、乾燥處理，在正極表面上形成厚度3μιη之本發明的電池用多孔膜。在中間相碳微珠（MCMB :大阪瓦斯化學公司製）粉 -47- 201101560 末87重量份、乙炔黑（電氣化學工業公司製；商品名 Denka Black) 3重量份、聚氟化次乙嫌基（Kureha化學公司製）1〇重量份下，使用N-甲基-2-吡咯烷酮溶劑，使此等進行退火處理，製作漿料。將所得的漿料塗佈於厚度爲 18μηι之銅箔上，予以乾燥後，進行壓製處理，製得90μιη 之負極。使前述正極及負極經由隔板予以對向，於其中含浸電解液，封入由鋁層合薄膜所形成的外裝中，製作非水系蓄電池。此處，電解液係使用1Μ LiPF6碳酸乙二酯/甲基碳酸乙酯（3/7重量比）（Kishida化學公司製）。而且，隔板係使用前述實施例1-8、1-9之PE微多孔膜。有關該實施例1 -11之電池，進行評估有關前述之烤箱試驗、循環特性、保存試驗、及電池之膨脹情形。結果如表3所示。 [實施例1-12] 在鈷酸鋰（1^<：〇02:日本化學工業公司製）粉末89.5 重量份、乙炔黑（電氣化學工業公司製；商品名Denka Black ) 4.5重量份、聚氟化次乙烯基（Kureha化學公司製 )6重量份下，使用N-甲基-2-吡咯烷酮溶劑，使此等進行退火處理，製作漿料。將所得的漿料塗佈於厚度爲20μηι之鋁箔上，予以乾燥後，進行壓製處理，製得ΙΟΟμιη之正極〇在中間相碳微珠（MCMB :大阪瓦斯化學公司製）粉 -48- 201101560 末87重量份、乙炔黑（電氣化學工業公司製；商品名 Denka Black) 3重量份、聚氟化次乙烯基（Kureha化學公司製）10重量份下，使用N-甲基-2-吡咯烷酮溶劑，使此等進行退火處理，製作漿料。將所得的漿料塗佈於厚度爲 18μιη之銅箔上，予以乾燥後，進行壓製處理，製得90μιη 之負極。在前述之負極表面上塗佈以實施例1-4所製作的漿料 0 ，使該物浸漬於以重量比爲水：DMAc : TPG= 70 : 18 : 12 (重量比）、30°C之凝固液中，然後，進行水洗、乾燥處理，在負極表面上形成厚度3μιη之本發明的電池用多孔膜。使前述正極及負極經由隔板予以對向，於其中含浸電解液，封入由鋁層合薄膜所形成的外裝中，製作非水系蓄電池。此處，電解液係使用1Μ LiPF6碳酸乙二酯/甲基碳酸乙酯（3/7重量比）（Kishida化學公司製）。而且，隔〇板係使用前述實施例卜8、1-9之PE微多孔膜。有關該實施例1 -1 2之電池’進行評估有關前述之烤箱試驗、循環特性、保存試驗、及電池之膨脹情形。結果如表3所示。 [實施例1-13] 在鈷酸鋰（1^(：〇〇2:日本化學工業公司製）粉末89.5 重量份、乙炔黑（電氣化學工業公司製：商品名Denka Black) 4.5重量份_、聚氟化次乙稀基（Kureha化學公司製 -49- 201101560 )6重量份下’使用N-甲基-2-吡咯烷酮溶劑，使此等進行退火處理，製作漿料。將所得的漿料塗佈於厚度爲20μιη之鋁箔上，予以乾燥後’進行壓製處理，製得1〇〇 μιη之正極〇在中間相碳微珠（MCMB :大阪瓦斯化學公司製）粉末8 7重量份、乙炔黑（電氣化學工業公司製；商品名 Denka Black ) 3重量份、聚氟化次乙烯基（Kureha化學公司製）10重量份下’使用N-甲基-2-吡咯烷酮溶劑，使此等進行退火處理’製作漿料。將所得的漿料塗佈於厚度爲 18μιη之銅箔上，予以乾燥後，進行壓製處理，製得90μιη 之負極。在前述之正極及負極表面上塗佈以實施例1-4所製作的漿料，使該物浸漬於以重量比爲水：DM Ac : TPG = 70 :1 8 : 1 2 (重量比）、3 0°C之凝固液中，然後，進行水洗、乾燥處理，在正極及負極表面上形成厚度3μιη之本發明的電池用多孔膜。使前述正極及負極經由隔板予以對向，於其中含浸電解液，封入鋁層合薄膜所形成的外裝中，製作非水系蓄電池。此處，電解液係使用1Μ LiPF6碳酸乙二酯/甲基碳酸乙酯（3/7重量比）（Kishida化學公司製）。而且，隔板係使用前述實施例1-8、1-9之PE微多孔膜。有關該實施例卜1 3之電池，進行評估有關前述之烤箱試驗、循環特性、保存試驗、及電池之膨脹情形。結果如表3所示。 -50- 201101560 [表3] 隔板電池用多孔膜之場所烤箱試驗循環特性保存試驗 (0/Λ 電池之膨脹實施例1-11 PE微多孔膜正極〇 79 Q〇〇實施例1-12 PE微多孔膜負極〇 --- 76 77 〇實施例1-13 PE微多孔膜正極與負極〇 ---— 82 85 〇 (3 )第三 '四形態之實施例於下述中，說明有關本發明之第^、四形態之實施例〇。本發明使用的測定方法如下所述。而且，有關無機塡料之平均Ιϋ徑、比表面積、，結晶構造及元素比例、以及膜厚之測定法，係與前述第—、第二形態之實施例時相同。另外，有關隔板之破裂試驗及氣體產生量試驗，亦與前述第一、第二形態之實施例時相同。 [空孔率] 有關試料所形成的膜，使各構成材料之重量（wi: 〇 g/m2 )除以真密度（di : g/cm3 ) ’求得此等之和（Σ ([Example 1-11] In a lithium cobaltate (1^(:〇02: manufactured by Nippon Chemical Industry Co., Ltd.) powder, 89.5 parts by weight, acetylene black (manufactured by Denki Kagaku Co., Ltd.; trade name Denka Black) 4.5 parts by weight, polyfluorinated 6 parts by weight of a vinylidene group (manufactured by Kureha Chemical Co., Ltd.) was subjected to ruthenium annealing treatment using N-methyl-2-pyrrolidone solvent to prepare a slurry. The obtained slurry was applied to a thickness of 20 μm. The aluminum foil was dried, and then subjected to a pressing treatment to obtain a positive electrode of ΙΟΟμπι. The slurry prepared in Example 1-4 was coated on the surface of the above positive electrode, and the material was immersed in water by weight: DM Ac : TPG = 70 : 1 8 : 1 2 (weight ratio), 3 (the coagulation liquid of TC, and then washed with water and dried to form a porous film for a battery of the present invention having a thickness of 3 μm on the surface of the positive electrode. Carbon microbeads (MCMB: manufactured by Osaka Gas Chemical Co., Ltd.) powder -47- 201101560 End 87 parts by weight, acetylene black (manufactured by Denki Kagaku Co., Ltd.; trade name Denka Black) 3 parts by weight, polyfluorinated secondary sulphur (Kureha Chemical) Company-made) 1 part by weight, using N- The methyl-2-pyrrolidone solvent was subjected to annealing treatment to prepare a slurry, and the obtained slurry was applied onto a copper foil having a thickness of 18 μm, dried, and then subjected to a pressing treatment to obtain a negative electrode of 90 μm. The positive electrode and the negative electrode are opposed to each other via a separator, and an electrolyte solution is impregnated therein, and the outer casing formed of the aluminum laminate film is sealed to prepare a non-aqueous battery. Here, the electrolyte is made of 1 Μ LiPF6 ethylene carbonate/A Ethyl carbonate (3/7 by weight) (manufactured by Kishida Chemical Co., Ltd.) Further, the separator was a PE microporous film of the above Examples 1-8 and 1-9. The evaluation was carried out regarding the aforementioned oven test, cycle characteristics, storage test, and expansion of the battery. The results are shown in Table 3. [Example 1-12] Lithium cobaltate (1^<:〇02: Japanese chemical industry 89.5 parts by weight of a product, acetylene black (manufactured by Denki Kagaku Co., Ltd.; trade name Denka Black) 4.5 parts by weight, polyfluorinated vinylidene (manufactured by Kureha Chemical Co., Ltd.) 6 parts by weight, using N-methyl-2 -pyrrolidone solvent to make this The slurry was applied to an aluminum foil having a thickness of 20 μm, dried, and then subjected to a pressing treatment to obtain a positive electrode of ΙΟΟμηη in a mesophase carbon microbead (MCMB: manufactured by Osaka Gas Chemical Co., Ltd. ) powder-48- 201101560 At the end of 87 parts by weight, acetylene black (manufactured by Denki Kagaku Co., Ltd.; trade name Denka Black), 3 parts by weight, polyfluorinated vinylidene (manufactured by Kureha Chemical Co., Ltd.), 10 parts by weight, using N-A The quinol-2-pyrrolidone solvent was subjected to annealing treatment to prepare a slurry. The obtained slurry was applied onto a copper foil having a thickness of 18 μm, dried, and then subjected to a pressing treatment to obtain a negative electrode of 90 μm. The slurry 0 prepared in Example 1-4 was coated on the surface of the above negative electrode, and the material was immersed in water by weight: DMAc : TPG = 70 : 18 : 12 (weight ratio), 30 ° C In the coagulating liquid, water washing and drying treatment were carried out to form a porous film for a battery of the present invention having a thickness of 3 μm on the surface of the negative electrode. The positive electrode and the negative electrode were opposed to each other via a separator, and the electrolytic solution was impregnated therein, and sealed in an exterior formed of an aluminum laminate film to prepare a nonaqueous battery. Here, as the electrolytic solution, 1 Μ LiPF6 ethylene carbonate/ethyl methyl carbonate (3/7 by weight) (manufactured by Kishida Chemical Co., Ltd.) was used. Further, as the barrier sheet, the PE microporous film of the above Examples 8 and 1-9 was used. The battery of this Example 1-1 was evaluated for the aforementioned oven test, cycle characteristics, storage test, and expansion of the battery. The results are shown in Table 3. [Example 1-13] In a lithium cobaltate (1^(:2: manufactured by Nippon Chemical Industry Co., Ltd.) powder, 89.5 parts by weight, acetylene black (manufactured by Denki Kagaku Co., Ltd.: trade name Denka Black) 4.5 parts by weight _, Polyfluorinated vinylidene group (Kureha Chemical Co., Ltd. - 49-201101560) 6 parts by weight of 'N-methyl-2-pyrrolidone solvent was used, and these were annealed to prepare a slurry. The obtained slurry was coated. After being dried on an aluminum foil having a thickness of 20 μm, it was dried and then subjected to a pressing treatment to obtain a positive electrode of 1 〇〇μιη in a mesophase carbon microbead (MCMB: manufactured by Osaka Gas Chemical Co., Ltd.) powder of 87 parts by weight, acetylene black ( 3K parts by weight, polyfluorinated vinylidene (manufactured by Kureha Chemical Co., Ltd.) under 10 parts by weight of 'N-methyl-2-pyrrolidone solvent, and these are annealed' A slurry was prepared, and the obtained slurry was applied onto a copper foil having a thickness of 18 μm, dried, and then subjected to a pressing treatment to obtain a negative electrode of 90 μm. The above-mentioned positive and negative electrode surfaces were coated with Examples 1-4. Produced slurry to make the material The water is applied in a weight ratio of water: DM Ac : TPG = 70 : 1 8 : 1 2 (weight ratio), 30 ° C in the coagulating liquid, and then washed with water, dried to form a thickness on the surface of the positive electrode and the negative electrode. a porous film for a battery of the present invention, wherein the positive electrode and the negative electrode are opposed to each other via a separator, and an electrolyte solution is impregnated therein, and an outer layer of the aluminum laminate film is sealed to prepare a non-aqueous battery. One liter of LiPF6 ethylene carbonate/methyl ethyl carbonate (3/7 by weight) (manufactured by Kishida Chemical Co., Ltd.) was used. Further, as the separator, the PE microporous membranes of the above Examples 1-8 and 1-9 were used. Regarding the battery of this embodiment, evaluation was made regarding the aforementioned oven test, cycle characteristics, storage test, and expansion of the battery. The results are shown in Table 3. -50- 201101560 [Table 3] Porous separator battery Membrane place oven test cycle characteristics storage test (0 / 电池 battery expansion Example 1-11 PE microporous membrane positive electrode 〇〇 79 Q 〇〇 Example 1-12 PE microporous membrane negative electrode 〇 - 76 77 〇 Example 1-13 PE microporous membrane positive and negative --- 82 85 〇 (3) Example of the third 'fourth embodiment>> In the following, the embodiment of the fourth and fourth aspects of the present invention will be described. The measurement method used in the present invention is as follows. The method for measuring the average diameter, specific surface area, crystal structure, element ratio, and film thickness of the inorganic tantalum is the same as in the first and second embodiments. The gas generation amount test is also the same as in the first and second embodiments. [Void ratio] For the film formed by the sample, the weight of each constituent material (wi: 〇 g/m2 ) is divided by the true density (di : g/cm 3 ) ′ to obtain the sum of these (Σ (

Wi/di ))。使該値除以膜厚，藉由自1減去之値乘以1〇0 ，求得空孔率（％ )。 [哥雷値（Gurley No.)] 以JIS P8117爲基準予以測定。 [穿刺強度] 使用KES公司製KES-G5手動壓縮試驗器，以針前端 -51 - 201101560 之曲率半徑〇.5mm、穿刺速度2mm/秒之條件進行穿刺試驗，以最大穿刺荷重作爲穿刺強度。此處’試料夾於具有 Φ11.3mm之孔的金框（試料固定器）予以固定。 [關機特性（SD特性）] 首先，使試料所形成的隔板以直徑1 9mm進行穿孔，浸漬於非離子性界面活性劑（花王公司製：Emulgeti 210P )之3重量％甲醇溶液中，予以風乾。然後，在隔板中夾住含浸有電解液之SUS板（Φ15.5ιηιη)。此處，電解液係使用1Μ LiBF4碳酸丙二酯/碳酸乙酯（1/1重量比）。將該物封入2 0 3 2型線圈晶胞。自線圈晶胞拉出導線，附設熱電對，置於烤箱中。藉由以昇溫速度1.6°C/分鐘進行昇溫，同時施加振幅1 OmV、1 kHz之周波數的交流，測定晶胞之電阻。於前述測定時，在1 35〜1 50°C之範圍內，電阻値爲 103ohm*cm2以上時SD特性爲〇，不是時爲X。 [電池保存特性] 使用下述實施例及比較例所製作的隔板，製作如下述之非水系蓄電池。在鈷酸鋰（Li Co 02 :日本化學工業公司製）粉末89.5 重量份、乙炔黑（電氣化學工業公司製；商品名Denka 81&^〇4.5重量份、聚氟化次乙烯基（1<：11^113化學公司製 )6重量份下，使用N-甲基-2-吡咯烷酮溶劑，使此等進行 -52- 201101560 退火處理，製作漿料。將所得的漿料塗佈於厚度爲20 鋁箔上，予以乾燥後，進行壓製處理，製得之正極〇在中間相碳微珠（MCMB :大阪瓦斯化學公司製）粉末8 7重量份、乙炔黑（電氣化學工業公司製；商品名 Denka Black) 3重量份、聚氟化次乙稀基（Kureha化學公司製）1〇重量份下，使用N-甲基-2-吡咯烷酮溶劑，使此 0 等進行退火處理，製作漿料。將所得的漿料塗佈於厚度爲 18μίη之銅箔上，予以乾燥後，進行壓製處理，製得90μιη 之負極。使前述正極及負極經由下述實施例及比較例所製作的隔板予以對向，於其中含浸電解液，封入由鋁層合薄膜所形成的外裝中，製作非水系蓄電池。此處，電解液係使用 1Μ LiPF6碳酸乙二酯/甲基碳酸乙酯（3/7重量比）（ Kishida化學公司製）。 0 有關該非水系蓄電池，進行〇.2C' 4.2V之定電壓•定電流進行充電8小時、0.2C、2.75 V切斷的定電流進行放電處理。使第5刺循環所得的放電容量作爲該晶胞之初期容量。然後，在0.2C、4.2V之定電壓·定電流進行充電處理8 小時，在85°C下保存3日。然後，在〇.2C、2.75V切斷之定電流進行放電，在85°C下保存3日，求取其殘存容量。以使殘存容量除以初期容量、乘以1〇〇之値作爲容量維持率，以該容量維持率作爲電池之保存特性的指標。 -53- 201101560 [電池之膨脹] 以目視確認前述電池之保存試驗後之各電池，可知電池有膨脹情形者判斷爲X ’在外觀上沒有電池之膨脹情形者爲〇。而且，此時電池之膨脹情形，係在電池內產生氣體者。 [實施例2 -1 ] 使用Ticona公司製之GUR2126 (重量平均分子量415萬、熔點141 t：)與GURX 143 (重量平均分子量56萬、熔點 135°C)作爲聚乙烯粉末。在GUR2126與GURX143爲1: 9 (重量比）、聚乙烯濃度爲30重量％下，溶解於流動石蠟 (松村石油硏究所公司製；Smoil P-3 50P ;沸點480°C )與萘烷之混合溶劑中，製作聚乙烯溶液。該聚乙烯溶液之組成係聚乙烯：流動石蠟：萘烷= 30: 45: 25(重量比）。在148 °C下自塑模押出該聚乙烯溶液，在水浴中冷卻 ’製作凝膠狀膠帶（基體膠帶）。使該基體膠帶在60°C下進行乾燥8分鐘，在95t下進行乾燥15分鐘，且使該基體膠帶逐次進行縱延伸、橫延伸之二軸延伸處理。此處，縱延伸係延伸倍率5·5倍、延伸溫度901：，橫延伸係延伸倍率 11.0倍、延伸溫度105它。於橫延伸後，在125°C下進行熱固定處理。其次，將其浸漬於二氯甲烷浴中，萃取流動石蠟與萘烷。然後，在50°C下進行乾燥，且在12〇°C下進行退火處理’製得聚乙烯微多孔膜。所得的聚乙烯微多孔膜，係篩目4·7 g/m2、膜厚9μη! -54- 201101560 、空孔率45%、哥雷値150秒/l〇〇cc、穿刺強度3 00g。使用聚間亞苯基異酞醯胺之Conex (註冊商標；Teijin technoproducts公司製）作爲間型全芳香族聚醯胺。在二甲基乙醯胺（DM Ac):三丙二醇（TPG) = 60: 40 (重量比）中溶解6重量％conex下’製作Conex溶液。使用平均粒徑3μιη、比表面積290 m2/g之沸石（HSZ_ 500KOA; Tosoh公司製）作爲多孔質塡料。在沸石： 0 Conex= 50: 50 (重量比）下，在該Conex溶液中分散該沸石，調整分散液。使用2條邁耶棒（Meyer bar )，於其間適量載負該分散液。使聚乙烯微多孔膜通過載負有分散液之邁耶棒間，在聚乙烯微多孔膜之兩面上塗佈分散液。此處，邁耶棒間之間隙爲30μηι，同時使用2條編號爲#6之邁耶棒。使其浸漬於以重量比爲水：DMAc : TPG=70: 18: 12(重量比 )、3 0°C之凝固液中，然後進行水洗、乾燥，在聚乙烯微〇多孔膜之表裏形成由沸石與Conex所形成的耐熱性多孔質層，製得本發明之非水系蓄電池。所得的非水系蓄電池用隔板之特性’如表4、5所示。而且，有關下述實施例及比較例之隔板的特性，同樣地如表4、5所示。 [實施例2-2] 除使用平均粒徑2μιη、比表面積400 m2/g之沸石（ HSZ-9 8 0HOA; Tosoh公司製）作爲多孔質塡料外，與實施例2 -1相同地’製得本發明之非水系蓄電池用隔板。 -55- 201101560 [實施例2-3] 除使用平均粒徑4μηι、比表面積700 HSZ-341NHA ; Tosoh公司製）作爲多孔質与例2 - 1相同地’製得本發明之非水系蓄電池/ [實施例2-4] 除藉由使活性碳（關西熱化學公司製；以二甲基乙醯胺（DM Ac )作爲分散劑之溶直徑之錐珠磨）’製得平均粒徑0.6μιη、 m2/g之活性碳。除使用該活性碳作爲多孔| 施例2 -1相同地，製得本發明之非水系蓄電、) [實施例2-5] 除使用平均粒徑1·4μιη、比表面積190 (住友化學公司製；KC-501)作爲多孔質墙例2 -1相同地，製得本發明之非水系蓄電池月 [實施例2-6] 除使氫氧化鋁（昭和電工製；Η - 4 3 Μ ) 熱處理，製得平均粒徑〇·8μιη、比表面積60 化鋁。而且，有關該活性氧化鋁之結晶構廷解析時，確認沒有來自非晶狀構造之寬波_ 三水鋁石之波峰’故整體結構主要爲三水發 m2/g之沸石（料外，與實施丨隔板。 MSP-20 )進行式粉碎（2mm 比表面積1600 塡料外，與實【用隔板。 m2/g之活性碳 ;料外，與實施丨隔板。在220°C下進行 m2/g之活性氧 i，以XRD進行 :，確認有來自丨石，不爲非晶 -56- 201101560 狀氧化鋁。除使用該活性氧化鋁作爲多孔質塡料外，與實施例2 -1相同地’製得本發明之非水系蓄電池用隔板。 [實施例2_7] 除使氫氧化鋁（昭和電工製；H-43M)在280°C下進行熱處理，製得平均粒徑〇.8μιη、比表面積400 m2/g之活性 0 氧化鋁。有關該活性氧化鋁，以XRD進行解析時，在寬標繪圖中僅觀察到來自勃姆石之波峰，2Θ = 14.39°之波峰的積分強度爲98cpS*deg，該主要波峰之積分強度對2Θ=10〜 6 Odeg所存在的寬波峰之積分強度而言爲0.07。因此，該活性氧化鋁主要爲非晶狀整體結構，由於僅稍微混有勃姆石，亦稱爲非晶狀氧化鋁。此外，該活性氧化鋁表面之 Ο/Al的元素比例爲1.54。除使用該活性氧化鋁作爲多孔質塡料外，與實施例2-Q 1相同地，製得本發明之非水系蓄電池用隔板。 [實施例2-8] 除僅在聚乙烯微多孔膜之一面上塗佈分散液’形成多孔質層外，與實施例2 - 7相同地’製得本發明之非水系蓄電池用隔板。 [比較例2 -1 ] 除使用平均粒徑〇.6μιη、比表面積6 m2/g之α-氧化鋁（ -57- 201101560 昭和電工製；AL160SG-3)作爲無機塡料以取代實施例2-1 所使用的.多孔質塡料外，與實施例2 -1相同地，製得本發明之非水系蓄電池用隔板。 [比較例2-2] 除使用平均粒徑〇.6μηι、比表面積15 m2/g之勃姆石（大明化學工業公司製；C06 )作爲無機塡料以取代實施例1 所使用的多孔質塡料外，與實施例2-1相同地，製得本發明之非水系蓄電池用隔板。 [比較例2 - 3 ] 除使氫氧化鋁（昭和電工製；Η - 4 3 Μ )在2 0 5 °C下進行熱處理，製得平均粒徑〇·8μιη、比表面積30 m2/g之活性氧化鋁。而且，有關該活性氧化鋁之結晶構造，以XRD進行解析時，確認沒有來自非晶狀構造之寬波峰，確認有來自三水鋁石之波峰，故整體結構主要爲三水鋁石，不爲非晶狀氧化鋁。除使多孔質塡料改爲該活性氧化鋁外，與實施例2- 1相同地，製得本發明之非水系蓄電池用隔板。 [比較例2 - 4 ] 使用Ticona公司製之GUR2126 (重量平均分子量415萬 '熔點141 °C)與GURX 143 (重量平均分子量56萬、熔點 135°C)作爲聚乙烯粉末。在GUR2126與GURX143爲1 : 9 (重量比）、聚乙烯濃度爲15重量％下，溶解於流動石蠟 -58- 201101560 (松村石油硏究所公司製；Smoil P-350P;沸點480 °C)與萘烷之混合溶劑中，製作聚乙烯溶液。該聚乙烯溶液之組成係聚乙烯：流動石蠟：萘烷=3 0 : 45 : 25 (重量比）。製作在該聚乙烯溶液中以重量比爲聚乙烯：沸石（ HSZ-500KOA; Tosoh公司製）= 50: 50下分散的漿料。此處，該沸石係平均粒徑3μηι、比表面積290 m2/g。在1 4 8 °C下自塑模押出該漀料，在水浴中冷卻，製作 0 凝膠狀膠帶（基體膠帶）。使該基體膠帶在60°C下進行乾燥8分鐘，在95°C下進行乾燥15分鐘，且使基體膠帶逐次進行縱延伸、橫延伸之二軸延伸處理。此處，縱延伸係延伸倍率5.5倍、延伸溫度90°C，橫延伸係延伸倍率Π ·〇倍、延伸溫度1 〇 5 °C。於延伸後，在1 2 5 °C下進行熱固定處理。其次，將其浸漬於二氯甲烷浴中，萃取流動石蠟與萘烷。然後，在50°C下進行乾燥，且在120 °C下進行退火處理，製得含有多孔質塡料之聚乙烯微多孔膜（非水系蓄電池用隔〇板）。 [比較例2-5] 使用聚間亞苯基酞醯胺的Conex (註冊商標：Teijin technoproducts公司製）作爲間型全芳香族聚酿胺。以二甲基乙醯胺（DM Ac ):三丙二醇（TPG) = 60: 40之重量比，使Conex爲6重量％下溶解’製作Conex溶液。使用2條邁耶棒，於其間適量載負該C ο n e X溶液。使比較例2-4所製作的含有多孔質塡料之聚乙烯微多孔膜通過 -59- 201101560 載負有Conex分散液之邁耶棒間，；面上塗佈Conex溶液。此處，邁耶| 時使用2條編號爲#6之邁耶棒。使； :DMAc: TPG=70: 18: 12(重量，然後進行水洗、乾燥，在含有多孔膜之表裏形成由C ο n e X所形成的之非水系蓄電池用隔板。聚乙烯微多孔膜之兩間之間隙爲3〇μιη ’同浸漬於以重量比爲水：)、30°C之凝固液中質塡料之聚乙烯微多孔質層，製得本發明 -60- 201101560 [表4] 隔板構成耐熱層配置面塡料種類塡料粒徑 (μηι) 塡料比表面積 (m2/g) 膜厚 (μηι) 空孔率 (%) 實施例2-1 耐熱層(含塡料)/PE膜兩面沸石 3.0 290 16 55 實施例2-2 耐熱層(含塡料)/PE膜兩面沸石 2.0 400 16 54 實施例2-3 耐熱層(含塡料)/PE膜兩面沸石 4.0 700 16 56 實施例2-4 耐熱層(含塡料)/PE膜兩囱活性碳 0.6 1600 16 56 實施例2-5 耐熱層(含塡料)/PE膜兩面活性氧化鋁 1.4 190 16 55 實施例2-6 耐熱層(含塡料)/PE膜兩面活性氧化鋁 0.8 60 16 54 實施例2-7 耐熱層(含塡料)/PE膜兩面活性氧化鋁 0.8 400 16 55 實施例2-8 耐熱層(含塡料)/PE膜一面活性氧化鋁 0.8 400 16 65 比較例2-1 耐熱層(含塡料)/PE膜兩面 α-氧化鋁 0.6 6 16 53 比較例2-2 耐熱層(含塡料)/PE膜兩面勃姆石 0.6 15 16 53 比較例2-3 耐熱層(含塡料)/PE膜兩面活性氧化鋁 0.8 30 16 53 比較例2-4 ΓΕ膜(含塡料）一沸石 3.0 290 9 58 比較例2-5 耐熱層/PE膜(含塡料）兩面沸石 3.0 290 16 65 [表5] 哥雷値 (sec/100cc) 穿刺強度 ω SD 特性破膜試驗氣體產生量 (CC) 電池保存特性 (%) 電池之膨脹實施例2-1 283 310 〇〇 1.5 58 〇實施例2-2 276 315 〇〇 1.1 60 〇實施例2-3 286 308 〇〇 0.8 63 〇實施例2-4 268 309 〇〇 0.8 62 〇實施例2-5 270 311 〇〇 1.8 74 〇實施例2-6 271 310 〇〇 2.5 73 〇實施例2-7 275 310 〇〇 0.4 75 〇實施例2-8 288 310 〇〇 0.5 65 〇比較例2-1 279 315 〇〇 3.5 67 X 比較例2-2 283 314 〇〇 8.8 65 X 比較例2-3 279 311 〇〇 10.3 62 X 比較例2-4 85 163 X X 1.7 45 〇比較例2-5 300 175 X 〇 1.5 58 〇 -61 - 201101560 [循環特性評估] 其次，有關在多孔質基材之一面或兩面上形成有耐熱性多孔質層之隔板，如下所述製作非水系蓄電池，進行檢討循環特性是否有不同處。在鈷酸鋰（1^(：〇02:日本化學工業公司製）粉末89.5 重量份、乙炔黑（電氣化學工業公司製；商品名Denka Black ) 4.5重量份、聚氟化次乙烯基（Kureha化學公司製 )6重量份下，使用N-甲基-2-吡咯烷酮溶劑，使此等進行退火處理，製作漿料。將所得的漿料塗佈於厚度爲20μιη之鋁箔上，予以乾燥後，進行壓製處理，製得100 μηι之正極〇在中間相碳微珠（MCMB :大阪瓦斯化學公司製）粉末8 7重量份、乙炔黑（電氣化學工業公司製；商品名 Denka Black) 3重量份、聚氟化次乙嫌基（Kureha化學公司製）10重量份下，使用N-甲基-2-吡略烷酮溶劑，使此等進行退火處理，製作漿料。將所得的漿料塗佈於厚度爲 18μιη之銅箔上，予以乾燥後，進行壓製處理，製得90μιη 之負極。使前述正極及負極經由隔板予以對向，於其中含浸電解液，封入由鋁層合薄膜所形成的外裝中，製作非水系蓄電池。此處，電解液係使用1Μ LiPF6碳酸乙二酯/甲基碳酸乙酯（3/7重量比）（Kishida化學公司製）。此處，隔板係使用實施例2-7及實施例2-8者’製作表6 所示之實施例2-9〜2_11之電池。 -62- 201101560 循環特性之評估係進行1c、4.2V之2小時定電壓•定電流充電，1C、2.75V切斷之定量流放電處理’以第1次循環之容量爲基準時之第3〇〇次循環的容量維持率作爲循環特性的指標。而且，測定時之溫度爲3 0 。結果如表ό所示 [表6] 隔板容量維持率％實施例2-9 實施例2-7 85 實施例2-10 實施例2-8(在正極側配置聚乙烯微多孔膜） 50 實施例2-11 實施例2-8(在負極側配置聚乙烯微多孔膜） 60 由表6之結果可知，在多孔質基材之兩面上形成有耐熱性多孔質層之構成者，容量維持率較一面構成者更爲優異。另外，即使爲一面構成，在負極側配置有聚乙烯微多孔膜者，容量維持率變高。〇 (3 )有關第三形態之特殊活性氧化鋁的效果於下述中，檢討有關本發明之第三形態中使用比表面積3 00〜100 0 m2/g之活性氧化鋁的構成。下述實施例使用的測定方法，如下所述。而且，有關無機塡料之平均粒徑、比表面積、結晶構造及元素比例的測定法，與前述第一、第二形態之實施例相同。 [氧化鋁之真密度的測定] -63- 201101560 有關下述實施例及比較例使用的氧化鋁，係藉由超微真幣度分析儀（Micro Ultra Pycnometer) (Yuasa Ionics 公司製MUPY-2 IT )求取真密度。而且，測定係利用氦氣 [實施例3-1] (i) PE微多孔膜之製造使用Ticona公司製之GUR2126 (重量平均分子量415萬、熔點141°C)與GURX143(重量平均分子量56萬、熔點作爲聚乙烯粉末。在GUR2 126與GURX143爲1 : 9 (重量比）、聚乙烯濃度爲30重量％下，溶解於流動石蠟 (松村石油硏究所公司製；Smoil P-3 50P ;沸點480°C )與萘烷之混合溶劑中，製作聚乙烯溶液。該聚乙烯溶液之組成係聚乙烯：流動石蠟：萘烷=3 0 : 45 : 25 (重量比）。在148 °C下自塑模押出該聚乙烯溶液，在水浴中冷卻 ’製作凝膠狀膠帶（基體膠帶）。使該基體膠帶在6〇°C下進行乾燥8分鐘，在95 °C下進行乾燥15分鐘’且使基體膠帶逐次進行縱延伸、橫延伸之二軸延伸處理。此處’縱延伸係延伸倍率5 · 5倍、延伸溫度9 0 °C ’橫延伸係延伸倍率 1 1.0倍、延伸溫度1 0 5 °C。於橫延伸後，在1 2 5 °C下進行熱固定處理。其次，將其浸漬於二氯甲烷浴中，萃取流動石蠟與萘烷。然後，在50。(：下進行乾燥’且在120 °C下進行退火處理，製得PE微多孔膜。 -64 - 201101560 (ii)聚間亞苯基異酞醯胺之製造在具備溫度計、攪拌裝置及原料投入口之反應容器中，加入75 3 g之水分率爲l〇〇PPm以下之NMP，在該NMP中溶解間亞苯基二胺 85.2g與苯胺〇.5g ’且在0°C下冷卻。在該經冷卻的二胺溶液中、攪拌下慢慢地添加160.5 g之氯化異苯二甲酸，進行反應。該反應之溶液溫度上昇爲7〇°C。黏度變化停止後，添加58_4g之氫氧化鈣粉末，再進行攪 ^ 拌40分鐘以完成反應，取出聚合溶液，製得184.0g再沉澱於水中之聚間亞苯基異酞醯胺。 (i i i )活性氧化銘之製造除使氫氧化鋁（昭和電工製；H-43M)在28 0°C下進行熱處理，製得平均粒徑0.hm、比表面積400 m2/g之活性氧化鋁。該活性氧化鋁之真密度爲3. 1 g/cm2。而且，以 XRD進行解析時，確認寬標繪圖中僅有來自勃姆石的波峰 Q ，2Θ=14·39°之波峰的積分強度爲98cps*deg,該主波峰之積分強度對在2Θ = 10〜60deg存在的寬波峰之積分強度而言爲0.07。因此，該活性氧化鋁主要爲非晶狀整體結構，由於僅稍微混有勃姆石相，故亦稱爲非晶狀氧化鋁。 (iv)層合隔板之製造如前述所得的聚間亞苯基異酞醯胺與活性氧化鋁，以重量比爲4 0 : 6 0予以調製’使此等在聚間亞苯基異酞醯胺濃度爲5.5重量％下混合於二甲基乙醯胺（DMAc)與三丙 -65- 201101560 二醇（TPG )之重量比爲5 0 : 50的混合溶劑中，製得塗佈用漿料。在邁耶棒上載負適量的前述塗佈用獎料，藉由在一對邁耶棒間通過前述所得的PE薄膜，在PE薄膜之兩面上塗佈塗佈用漿料。使其浸漬於以重量比爲水：DM Ac : TPG = 50 : 2 5 : 25、40°C之凝固液中。然後，使所得的薄膜進行水洗•乾燥。藉此，可得塗佈有耐熱性多孔質層之積層隔板。 (v) 正極之製造在鈷酸鋰（1^(：0〇2:日本化學工業公司製）粉末89.5 重量份、乙炔黑（電氣化學工業公司製；商品名Denka Black ) 4.5重量份、聚氟化次乙烯基（Kureha化學公司製 )6重量份下，使用6重量％之聚氟化次乙烯基之NMP溶液，製作正極劑漿料。將所得的漿料塗佈於厚度爲20 μπι之鋁箔上，予以乾燥後，製得97μιη之正極。 (vi) 負極之製造在作爲負極活物質之中間相碳微珠（MCMB :大阪瓦斯化學公司製）粉末87重量份、乙炔黑（電氣化學工業公司製；商品名Denka Black) 3重量份及聚氟化次乙烯基（ Kureha化學公司製）10重量份下，使用6重量％之聚氟化次乙烯基之NMP溶液，製作負極劑漿料。將所得的漿料塗佈於厚度爲18μιη之銅箔上，予以乾燥後，進行壓製處理’製 -66- 201101560 得90μιη之負極。 (vii) 非水電解質之調製使用在碳酸乙二酯與甲基碳酸乙酯以3: 7之重量比混合的溶液中，以LiPF6爲lmol/L下予以溶解者。 (viii) 非水系蓄電池之製造 0 使前述所得的正極及負極經由層合隔板予以對向，於其中含浸電解液，封入由鋁層合薄膜所形成的外裝中，製作非水系蓄電池。 [比較例3 -1 ] 使用Ticona公司製之GUR2126 (重量平均分子量415萬、熔點141°C )與GURX143 (重量平均分子量56萬、熔點 135°C)作爲聚乙烯粉末。在GUR2126與GURX143爲1: 9 〇 ( 重量比）、聚乙烯濃度爲30重量％下，溶解於流動石蠟 (松村石油硏究所公司製；Smoil P-350P;沸點480。〇與萘烷之混合溶劑中，再使作爲塡料之平均粒徑0.5 μιη、比表面積7 m2/g之α-氧化鋁（AL-160SG-3;昭和電工製）分 @ ’製作聚乙烯溶液。該聚乙烯溶液之組成係聚乙烯：氧化銘：流動石蠟：萘院= 30: 10: 55: 30(重量比）。在148 °C下自塑模押出該聚乙烯溶液，在水浴中冷卻 ’製作凝膠狀膠帶（基體膠帶）。使該基體膠帶在6(TC下進行乾燥8分鐘，在95°C下進行乾燥15分鐘’且使基體膠 -67- 201101560 帶逐次進行縱延伸、橫延伸之二軸延伸處理。此處’縱延伸係延伸倍率5.5倍、延伸溫度9〇°C ’橫延伸係延伸倍率 1 1.0倍、延伸溫度1 0 5 °C。於橫延伸後’在1 2 5 °C下進行熱固定處理。其次，將其浸漬於二氯甲烷浴中’萃取流動石蠟與萘烷。然後，在5(TC下進行乾燥，且在〗20°0下進行退火處理，製得由PE微多孔膜所形成的隔板。除使用該隔板外，與實施例3 -1相同地’製作非水系蓄電池。 [比較例3 - 2 ] 除使氫氧化鋁（昭和電工製；H-43M)在22〇°C下進行熱處理，製得平均粒徑0.8μιη、比表面積60 m2/g之活性氧化鋁。該活性氧化鋁之真密度爲2.5 g/cm3。而且，以XRD 進行解析時，確認沒有來自非晶狀構造之寬波峰’而確認有來自三水鋁石的波峰，故該活性氧化鋁之整體結構主要爲三水銘石。除使用該活性氧化鋁作爲無機塡料外，與比較例3 - 1 相同地’製得非水系蓄電池。 [比較例3 - 3 ] 除使氫氧化鋁（昭和電工製；H-43M)在240°C下進行熱處理，製得平均粒徑〇·8μηι、比表面積200 m2/g之活性氧化鋁。該活性氧化鋁之真密度爲2.6 g/cm3。而且，有關該活性氧化鋁，以XRD進行解析時，確認有來自三水鋁石 -68- 201101560 的波峰，2Θ= 18.27°之波峰的積分強度爲371 cps · deg，該主波峰之積分強度對在2Θ= 10〜60deg存在的寬波峰之積分強度而言爲0.35。因此，該活性氧化鋁之整體結構，主要爲三水鋁石。除使用該活性氧化鋁作爲無機塡料外，與比較例3 - 1 相同地，製得非水系蓄電池。 Q [比較例3 - 4 ] 除使用平均粒徑2μιη、比表面積4〇〇 m2/g之沸石（ HSZ_980HOA ; Tosoh公司製）作爲無機塡料外，與比較例 3 -1相同地，製得非水系蓄電池。 [比較例3 - 5 ] 除使用平均粒徑2μιη、比表面積3 00 m2/g之二氧化矽 (東海化學工業所製；ML-3 84 )作爲無機塡料外，與比較 Q 例3 -1相同地，製得非水系蓄電池。 [比較例3-6] 藉由使活性碳（關西熱化學公司製；MSP-20)進行以二甲基乙醯胺（DMAc )作爲分散劑之濕式粉碎（2mm直徑之锆珠磨）’製得平均粒徑〇.6μιη、比表面積1600 m2/g 之活性碳。除使用該活性氧化鋁作爲無機塡料外，與比較例3 -1 相同地，製得非水系蓄電池。 -69- 201101560 [容量維持率之測定] 有關前述所製作的實施例及比較例之非水系蓄電池，於60 °C之恆溫槽中，使用充放電測定裝置（北斗電工公司製HJ-101SM6)，測定充放電特性。有關充放電條件，充電係以0.2C、至4.2V進行充電處理8小時，有關放電係以 0.2C、至2.75 V進行放電處理，容量維持率係對初期放電容量而言5 00次循環時之放電容量的比例。測定結果如表7 所示。 [^7] 塡料之翻塡料之比表面積 rg/m2l 氧化鋁之真密度 Γ g/cm3l 隔板之種類容量維持率 [%1 實施例3-1 活性氧化鋁 400 3.1 聚醯胺/PE隔板 83 比較例3-1 α-氧化鋁 7 3.9 PE隔板 52 比較例3-2 活性氧化鋁 60 2.5 ΓΕ隔板 55 比較例3-3 活性氧化鋁 200 2.6 PE隔板 59 比較例3-4 沸石 400 _ PE隔板 62 比較例3-5 二氧化矽 300 罐 PE隔板 59 比較例3-6 活性碳 1600 • PE隔板 62 由表7可知’使用比表面積300〜1〇〇〇 m2/g之活性氧化鋁的實施例3 -1，與比表面積在前述範圍外之活性氧化鋁 (比較例3 - 2、3 - 3 )、或α -氧化鋁（比較例3 -1 )、其他的多孔質塡料（比較例3-3〜3-6 )相比時，第5 00次循環特性試驗後之容量維持率更爲優異。此係推測因比表面積3 0 0 〜1 0 0 0 m2/g之活性氧化鋁會降低電池內之H F的活性之故 -70- 201101560 。而且，實施例係在複合隔板之耐熱性多孔質層中使用塡料，比較例係在PE隔板中使用塡料等之不同點，惟兩者就在隔板中使用塡料而言爲一致，前述不同點對容量維持率沒有很大的影響。 (4 )有關第四形態之非晶狀氧化鋁的效果於下述中，檢討有關本發明第四形態中使用非晶狀氧 0 化鋁之構成。有關各種測定方法，如上所述。 [實施例4 - 1 ] 與實施例3 -1相同地，製作實施例4 -1之非水系蓄電池 [比較例4 -1 ] 使用Ticona公司製之GUR2126(重量平均分子量415萬 Q 、熔點141°C )與GURX143 (重量平均分子量56萬、熔點 135°C )作爲聚乙烯粉末。在GUR2126與GURX143爲1 : 9 (重量比）、聚乙稀濃度爲30重夏％下，溶解於流動石螺 (松村石油硏究所公司製；Smoil P-350P;沸點480°C)與萘烷之混合溶劑中，再使作爲塡料之平均粒徑0.5μηι、比表面積7 m2/g之α-氧化鋁（AL-160SG-3;昭和電工製）分散’製作聚乙烯溶液。該聚乙烯溶液之組成係聚乙烯：氧化鋁：流動石蠟：萘烷= 30: 10: 55: 30(重量比）。在148°C下自塑模押出該聚乙烯溶液，在水浴中冷卻 -71 - 201101560 ，製作凝膠狀膠帶（基體膠帶）。使該基體膠帶在60°c下進行乾燥8分鐘’在95T：下進行乾燥15分鐘’且使基體膠帶逐次進行縱延伸、橫延伸之二軸延伸處理。此處’縱延伸係延伸倍率5 · 5倍、延伸溫度9 0 °C ’橫延伸係延伸倍率 11 · 0倍、延伸溫度1 0 5 °C。於橫延伸後’在1 2 5 °C下進行熱固定處理。其次，將其浸漬於二氯甲垸浴中’萃取流動石蠟與萘烷。然後，在50 °C下進行乾燥’且在120 °C下進行退火處理，製得由PE微多孔膜所形成的隔板。除使用該隔板外’與前述實施例3 -1相同地’製作非水系蓄電池。 [比較例4 - 2 ] 除使用平均粒徑〇·6μιη、比表面積15 m2/g之非多孔質之氧化鋁（大明化學工業製：C〇6 )作爲無機塡料外，與比較例4-1相同地，製得非水系蓄電池。而且，有關該氧化鋁進行XRD解析時，確認有來自勃姆石之明確波峰。 [比較例4-3] 除使用平均粒徑0.8μηι、比表面積7 m2/g之非多孔皙之氫氧化銘（昭和電工製；H-43M)作爲無機塡料外，與比較例4 -1相同地’製得非水系蓄電池。而且，有關該氧化銘進行XRD解析時，確認有來自三水鋁石之明確波峰。 [容量維持率之測定] -72- 201101560 有關前述所製作的實施例及比較例非水系蓄電池，於 6 〇°C之恆溫槽中，使用充放電測定裝置（北斗電工公司製 HJ-101SM6 )，測定充放電特性。有關充放電條件，充電係以0.2C、至4.2V進行充電處理8小時，有關放電係以 0.2C、至2.75V進行放電處理，容量維持率係對初期放電容量而言4 0 0次循環時之放電容量的比例。測定結果如表8 所示。 ❹ [表8] 塡料之種類結晶構造隔板之種類容量維持率[%] 72 實施例4-1 活性氧化鋁非晶狀聚醯胺/ΡΕ隔板比較例4-1 氧化鋁 α-氧化鋁 ΡΕ隔板 57 比較例4-2 氧化鋁勃姆石 Ι*Ε隔板 58 比較例4-3 氫氧化鋁三水鋁石 ΡΕ隔板 54 由表8可知，使用非晶狀氧化鋸的實施例4 -1，與α -氧化錯（比較例4 -1 )或勃姆石（比較例4 - 2 )、三水銘石（ ^ 比較例4-3等）等其他的氧化鋁系塡料相比時，第4〇〇次循環特性試驗後之容量維持率更爲優異。此係因非晶狀氧化鋁會降低電池內之HF的活性之故。 (5 )第五形態之實施例於下述中，說明有關本發明第五形態之實施例。而且 ’無機塡料之平均粒徑、比表面積、真密度、結晶構造及兀素比例、以及膜厚之測定法，如下所述。 -73- 201101560 [實施例5 -1 ] (i )活性氧化鋁之製造與前述實施例3 -1相同地，製造活性氧化鋁A。 (Π )正極、負極、非水電解質之製造有關正極、負極、非水電解質，與前述實施例3-1相同地製造。 (iii)隔板之製造使用Ticona公司製之GURU26 (重量平均分子量415萬、溶點141°C )與GURXI43 (重量平均分子量56萬、熔點 135°C)作爲聚乙烯粉末。在GUR2 126與GURX143爲1 : 9 (重量比）、聚乙烯濃度爲3 0重量％下，溶解於流動石蠟 (松村石油硏究所公司製；Smoil P-3 5 0P ;沸點48 0°C )與萘烷之混合溶劑中，再使作爲無機塡料之前述的活性氧化鋁A分散，製作聚乙烯溶液。該聚乙烯溶液之組成係聚乙烯：無機塡料：流動石蠟：萘烷= 30: 10: 55: 30(重量比）。在148 °C下自塑模押出該聚乙烯溶液，在水浴中冷卻，製作凝膠狀膠帶（基體膠帶）。使該基體膠帶在60°C下進行乾燥8分鐘’在95 °C下進行乾燥15分鐘’且使基體膠帶逐次進行縱延伸、橫延伸之二軸延伸處理。此處’縱延伸係延伸倍率5.5倍、延伸溫度9 0 °C，橫延伸係延伸倍率 11. 〇倍、延伸溫度10 5 °c °於橫延伸後’在12 5 °c下進行熱 -74- 201101560 固定處理。其次，將其浸漬於二氯甲烷浴中，萃取流動石蠟與萘烷。然後，在50°C下進行乾燥，且在120 °C下進行退火處理，製得由聚乙烯微多孔膜所形成的PE隔板。 (iv)非水系蓄電池使前述所得正極及負極經由隔板予以對向，於其中含浸有電解液，封入由鋁層合薄膜所形成的外裝中，製作本 0 發明之實施例的非水系蓄電池。 [實施例5-2] 除使氫氧化鋁（昭和電工製；H_43M )在260°C下進行熱處理’製得平均粒徑0·8μιη、比表面積350 m2/g、真密度爲3 · 0 g/ cm3之活性氧化鋁B。有關該活性氧化鋁b，以 XRD進行構造解析時，確認寬標繪圖中僅有來自勃姆石的波峰’ 2Θ=14·40°之波峰的積分強度爲83cps. deg，該主 Q 波峰之積分強度對在2Θ== 10〜60deg存在的寬波峰之積分強度而_爲〇. 0 5。因此’該活性氧化銘係主要爲非晶狀之整體結構，僅稍微混有勃姆石相。除使用該活性氧化銘B作爲無機塡料外，與實施例相同地，製得非水系蓄電池。 [實施例5-3] 以氟化次乙稀基：六氟化丙烧：氯化三氟乙嫌=97: Ϊ: 2之莫耳比共聚合的聚合物（重量平均分子量4〇〇〇〇〇 ) -75- 201101560 、及前述活性氧化鋁A、與二甲基乙醯胺（DMAc)與三丙二醇（TPG )之重量比爲聚合物：活性氧化鋁·· DMAc : TPG= 1 2 : 4 : 49 : 3 5下充分地進行攪拌，製得漿料。然後 ’在由PET短纖維與聚烯烴之短纖維所形成的不織布中充分含浸前述漿料，使其在凝固浴中凝固後，進行水洗•乾燥。藉此製得聚氟化次乙烯基與不織布之複合隔板（ PVdF/不織布隔板）。而且，凝固浴之組成以重量比爲水 :二甲基乙醯胺：三丙二醇= 57: 30: 13。其次，除使用 PVdF/不織布隔板取代PE隔板外，與實施例5-1相同地，製得本發明之非水系蓄電池。 [實施例5 - 4 ] 以聚氟化次乙烯基5重量份、活性氧化鋁A 1重量份、 DMAc 94重量份之組成比例混合，充分攪拌以形成均勻的溶液，製作塗佈液。其次，在聚丙稀隔板（Celgard#2400 )之一面上藉由棒塗佈器塗佈前述之塗佈液後，使其在 6〇°C下乾燥。藉此製得具有厚度4μιη之塗佈層的聚丙烯隔板（PVdF/PP隔板）。其次，除在塗佈層與正極連接下使用PVdF/PP隔板取代PE隔板外，與實施例5-1相同地，製得本發明之非水系蓄電池。 [實施例5-5] 除在塗佈層與負極連接下，使用實施例5-4所製得的 PVdF/PP隔板外，與實施例5-4同樣地，製得本發明之非水 -76- 201101560 系蓄電池。 [實施例5-6] 在鐘酸鋰（LiMn2〇4:日揮化學公司製）粉末89.5重量份、乙炔黑（電氣化學工業公司製；商品名Denka Black ) 4.5重量份、聚氟化次乙烯基（Kureha化學公司製 )之乾燥重量爲6重量份下，使用6重量％之聚氟化次乙烯 q 基之NMP溶液，製作正極劑漿料。將所得的漿料塗佈於厚度爲20μηι之鋁箔上，予以乾燥後，製得厚度爲70μιη之正極。除使用該正極外，與實施例5 -1相同地，製得本發明之非水系蓄電池。 [實施例5-7] 在鈷酸鋰（1^0〇02:日本化學工業公司製）粉末89.5 Q 重量份、乙炔黑（Denka Black、電氣化學工業公司製） 4.5重量份、活性氧化鋁A 3重量份及聚氟化次乙烯基（ Kureha化學公司製）之乾燥重量爲6重量份下，使用6重量 %之聚氟化次乙烯基之NMP溶液，製作正極劑漿料。將所得的漿料塗佈於厚度爲20μιη之鋁箔上，予以乾燥後，進行壓製處理，製得厚度爲97 μπι之正極。使用Ticona公司製之GUR2.126 (重量平均分子量415萬、熔點141°C )與GURX143 (重量平均分子量56萬、熔點 135°C)作爲聚乙烯粉末。在GUR2126與GURX143爲1 : 9 -77- 201101560 (重量比）、聚乙烯濃度爲30重量％下’溶解於流動石蠟 (松村石油硏究所公司製；Smoil P-350P;沸點480°C)與萘烷之混合溶劑中，製作聚乙烯溶液。該聚乙烯溶液之組成係聚乙烯：流動石蠟：萘烷=30 : 45 : 25 (重量比）。在148。(：下、自塑模押出聚乙烯溶液，在水浴中冷卻，製作凝膠狀膠帶（基體膠帶）。使該基體膠帶在60°c下進行乾燥8分鐘，在95 °C下進行乾燥15分鐘’且使基體膠帶逐次進行縱延伸、橫延伸之二軸延伸處理。此處’縱延伸係延伸倍率5.5倍、延伸溫度9 0 °C，橫延伸係延伸倍率 1 1.0倍、延伸溫度1 0 5 t。於橫延伸後，在1 2 5 °C下進行熱固定處理。其次，將其浸漬於二氯甲烷浴中，萃取流動石蠟與萘烷。然後，在5CTC下進行乾燥，且在120°C下進行退火處理，製得聚乙烯微多孔膜所形成的PE隔板。除使用前述所製作的正極及P E隔板外’與實施例5 -1 相同地，製得本發明之非水系蓄電池。 [實施例5-7] 在作爲負極活物質之中間相碳微珠（MCMB :大阪瓦斯化學公司製）粉末87重量份、乙炔黑爲3重量份與活性氧化鋁A爲3重量份與聚氟化次乙烯基之乾燥重量爲1〇重量份下，使用6重量％之聚氟化次乙烯基之NMP溶液，製作負極劑槳料。將所得的漿料塗佈於厚度爲18μιη之銅箔上’予以乾燥後，進行壓製處理，製得91 μπι之負極。除使用該負極’且使用實施例5-7之ΡΕ隔板外’與實 -78- 201101560 施例5 -1相同地，製得本發明之非水系蓄電池。 [實施例5-9] 使實施例5 -4所調製的塗佈液，使用棒塗佈器塗佈於實施例5-1所製造的正極之活物質側後’使其在60°C下進行乾燥。藉此製得具有厚度4μιη之塗佈層（正極表面層）之正極。 0 除使用該正極且使用實施例5 - 7之Ρ Ε隔板外，與實施例5-1相同地，製得本發明之非水系蓄電池。 [實施例5-10] 使實施例5-4所調製的塗佈液，使用棒塗佈器塗佈於實施例5-1所製造的負極之活物質側後，使其在60°C下進行乾燥。藉此製得具有厚度4μιη之塗佈層（負極表面層）之負極。 Q 除使用該負極且使用實施例5-7之ΡΕ隔板外，與實施例5-1相同地，製得本發明之非水系蓄電池。 [比較例5 - 1 ] 除使用實施例5-7之ΡΕ隔板外，與實施例5-1相同地，製得非水系蓄電池。 [比較例5 - 2 ] 以氟化次乙烯基：六氟化丙烯：氯化三氟乙烯= 97: -79- 201101560 1: 2之莫耳比共聚合的聚合物（重量平均分子量4〇〇 000 ) 、及二甲基乙醯胺（DM Ac )與三丙二醇（TPG )之重量比爲聚合物：DM Ac : TPG = 12 : 48 : 40下充分地進行攪拌’製得漿料。然後，在由PET短纖維與聚烯烴之短纖維所形成的不織布中充分含浸前述漿料，使其在凝固浴中凝固後’進行水洗•乾燥。藉此製得聚氟化次乙烯基與不織布經複合化的隔板（PVdF/不織布隔板）。而且，凝固浴之組成以重量比爲水：二甲基乙醯胺··三丙二醇=5 7 : 3 0 ：13 ° 其次，除使用該PVdF/不織布隔板外，與實施例、{相同地’製得本發明之非水系蓄電池。 [比較例5-3] 除使用聚丙燃隔板（Seluga #24〇0)取代pe隔板外與比較例1相同地，製得非水系蓄電池。 [比較例5-4] 除使用平均粒徑〇·5μιη、比表面積7 m2/gia_氧化銘（ AL-l6〇SG-3;昭和電工製）作爲無機塡料外，與實施例5 1相同地，製得非水系蓄電池。 [比較例5-5] 除使氫氧化鋁（昭和電工製；H-43M)在220°C下進行熱處理’製得平均粒徑〇·8μιη、比表面積6〇 m2/g、真密度 -80- 201101560 爲2.5 g/cm3之活性氧化鋁C。有關該活性氧化鋁C以XRD進行構造解析時，確認沒有來自非晶狀構造之寬波峰，而確認有來自三水鋁石之波峰，可知活性氧化鋁C之整體結構主要爲三水鋁石。除使用該活性氧化鋁C作爲無機塡料外，與實施例5_i 相同地，製得非水系蓄電池。 0 [比較例5-6] 除使氫氧化鋁（昭和電工製；H-43M )在240°C下進行熱處理，製得平均粒徑0.8μιη、比表面積200 m2/g、真密度爲2.6 g/cm3之活性氧化銘D。有關該活性氧化銘d以XRD 進行構造解析時，確認有來自三水鋁石的波峰，2Θ = 18_27°之波峰的積分強度爲371cps*deg，該主波峰之積分強度對在2Θ = 10〜60deg存在的寬波峰之積分強度而言爲 0.3 5。因此’可知該活性氧化鋁D之整體結構中含有三水〇銘石。除使用該活性氧化鋁D作爲無機塡料外，與實施例5 _ i 相同地，製得非水系蓄電池。 [比較例5 - 7 ] 除使用平均粒徑2μηι、比表面積4〇〇 m2/g之沸石（ HSZ-98 0HOA ; Tosoh公司製）外，與實施例5_丨相同地，製得非水系蓄電池。 -81 - 201101560 [比較例5-8] 除沒有使用活性氧化鋁作爲無機塡料，使用平均粒徑 2μιη、比表面積3 00 m2/g之二氧化矽（東海化學工業所製 ;ML-3 84 )外’與實施例1相同地，製得非水系蓄電池。 [比較例5-9] 對活性碳（關西熱化學公司製：MSP-20)而言，藉由進行以二甲基乙醯胺（DM Ac )作爲分散溶劑之濕式粉碎處理（2mm直徑之氧化锆珠磨機），製得平均粒徑0.6 μιη 、比表面積1 600 m2/g之活性碳。除使用該活性碳作爲無機塡料外，與實施例5-1相同地，製得非水系蓄電池。 [比較例5 -1 〇 ] 除使用以實施例5 - 6所製造的正極外，與比較例5 - 1相同地，製得非水系蓄電池。 [容量維持率之測定] 有關前述所製作的實施例及比較例之非水系蓄電池，於6(TC之恆溫槽中，使用充放電測定裝置（北斗電工公司製HI-101SM6 )，測定充放電特性。有關充放電條件，充電係以0.2C、至4.2V進行充電處理8小時，有關放電係以 0.2C、至2.75V進行放電處理’容量維持率係對初期放電容量而言500次循環時之放電容量的比例。測定結果如表9 -82- 201101560 所示。 [表9] 塡料之種類塡料之比表面積 rg/m2l 活性氧化鋁之真密度 [g/cm3l 塡料之場所隔板之種類容量維持率 [%1 實施例5-1 活性氧化鋁A 400 3.1 隔板 PE隔板 79 實施例5-2 活性氧化鋁B 350 3.0 隔板 PE隔板 75 實施例5-3 活性氧化鋁A 400 3.1 隔板 PVdF/不織布隔板 73 實施例5-4 活性氧化鋁A 400 3.1 隔板 PVdF/PP 隔板 (PVdF層爲正極侧 76 實施例5-5 活性氧化鋁A 400 3.1 隔板 PVdF/PP 隔板 (PVdF層爲負極側） 74 實施例5-6 活性氧化鋁A 400 3.1 隔板 PE隔板 72 實施例5-7 活性氧化鋁A 400 3.1 正極 PE隔板 71 實施例5-8 活性氧化鋁A 400 3.1 負極 PE隔板 72 實施例5-9 活性氧化鋁A 400 3.1 正極表面層 PE隔板 76 實施例5-10 活性氧化鋁A 400 3.1 負極表面層 PE隔板 75 比較例5-1 te - - - PE隔板 51 比較例5-2 Μ j \ \\ - - PVdF/不織布隔板 48 比較例5-3 Μ / \ \\ - - - PP隔板 52 比較例5-4 α-氧化銘 7 3.9 隔板 PE隔板 52 比較例5-5 活性氧化鋁C 60 2.5 隔板 PE隔板 55 比較例5-6 活性氧化鋁D 200 2.6 隔板 PE隔板 59 比較例5-7 沸石 400 - 隔板 PE隔板 62 比較例5-8 二氧化砂 300 - 隔板 PE隔板 59 比較例5-9 活性碳 1600 - 隔板 PE隔板 62 比較例5-10 Μ j \ \\ - - - PE隔板 42 [性能評估] 由實施例5-1〜5-3及比較例5-1〜5-3之結果可知，在隔板中含有活性氧化鋁之實施例，全部具有70%以上之優異的容量維持率。然而，不含活性氧化鋁之比較例5-1〜5-3，容量維持率約爲50%之低値。另外，實施例5-3〜5-5係 -83- 201101560 在隔板上層合含有氧化鋁之層的構成，全部的容量維持率皆爲70%之優異値。而且，與實施例5-4與5-5相比時，在正極及負極中至少一方存在含有活性氧化鋁之層時，確認爲有效。由實施例5-1〜5-2及比較例5-4〜5-6之結果可知，伴隨活性氧化鋁之比表面積增加，會有容量維持量優異的傾向。其次，比較例5-6之比表面積爲200 m2/g時，效果不充分，實施例5-2之比表面積爲3 5 0 m2/g之活性氧化鋁時，可確認爲效果充分，活性氧化鋁之比表面積以300 m2/g以上較佳。而且，比較例5-7及5-8中，使用比表面積爲300 m2/g以上之沸石與二氧化矽取代活性氧化鋁，惟容量維持率爲62%以下時，不具活性氧化鋁之優異效果。此外，使用比表面積爲1 600 m2/g之活性碳的比較例5-9，與實施例 5-1〜5-2相比時，容量維持率爲62%之低値。藉此，比表面積以1 000 m2/g以下較佳，更佳者爲5 00 m2/g以下。另外，真密度爲2.7 g/cm3以下及3.9 g/cm3時，容量維持率低，爲2.8〜3.3 g/cm3之範圍時，可得較佳的結果。由前述可推測，由於活性氧化鋁特有的表面狀態會降低HF之活性，可提高容量維持率。以錳酸鋰爲正極活物質之實施例5-6與比較例5-10，藉由使用含有活性氧化鋁之隔板，可得容量維持率爲70%以上之優異結果。而且，由於比較例5 -1 0中使用錳酸鋰，較鈷酸鋰更容易因HF自正極導致金屬溶解的情形，容量維持率爲4 2 %之低値。 -84- 201101560 在電極中含有活性氧化鋁之系、與在電極表面上層合有活性氧化鋁之層的系之實施例5 - 7〜5 -1 0相比時’全部的實施例之容量維持率爲70%以上之優異效果。藉此可確認活性氧化鋁之存在場所，係在電極中含有或層合於電極表面，皆具效果。確認前述之性能評估結果時，爲得容量維持率優異的非水系蓄電池時，發現在非水系蓄電池中含有比表面積爲 0 3 00〜1 000 m2/g之活性氧化鋁，且活性氧化鋁之存在場所沒有特別的限制。 [HF之除去性能] 有關前述實施例5-1、5-2及比較例5-1之非水系蓄電池，進行測定前述之容量維持率後，使電池分解，且萃取非水電解質。然後，測定該電解質中HF之含有量。具體而言，使HF含有量之測定係藉由此測定容量維持〇率後之非水系蓄電池分解後，使碳酸乙二酯與甲基碳酸乙酯以3: 7之重量比混合的所定量之溶液中放置1周，以溶液萃取電池內所存在的HF。其次，以溴百里酚藍（ Biromothymol Blue)作爲指示劑，以氫氧化鈉水溶液進行滴定’求取所萃取的溶液中之酸濃度。最後，使所求得的酸濃度換算成非水系蓄電池中所使用的電解液重量之値，作爲HF含有量（ppm )。有關該試料之測定結果，如下述表10所示。而且，構成電池前之電解質中的HF含有量爲 3 Oppm ° -85- 201101560 L ^ A ^ J HF含有量(ppm) 實施例5-1 140 實施例5-2 150 比較例5-1 330 -------- 由表1 〇之結果可知’實施例5 -1、5 _ 2中使用活性氧化鋁之電池，與比較例5 -1相比時，HF之殘存量少。此係推測藉由本發明之活性氧化鋁，可適當地捕捉HF之故。 (6 )第六形態之實施例於下述中說明有關本發明之第六形態。而且’有關無機塡料之平均粒徑、比表面積、真密度、結晶構造及元素比例、以及膜厚之測定法，如上所述。 [實施例6-1] 與前述實施例5-1相同地’製作非水系蓄電池。 [實施例6 - 2 ] 與前述實施例5-2相同地，製作非水系蓄電池。 [實施例6-3] 與前述實施例5-3相同地’製作非水系蓄電池。 [實施例6-4] 86 - 201101560 與前述實施例5-4相同地，製作非水系蓄電池。 [實施例6-5] 與前述實施例5-5相同地，製作非水系蓄電池。 [實施例6-6] 與前述實施例5-9相同地，製作非水系蓄電池。〇 [實施例6-7] 與前述實施例5-1〇相同地，製作非水系蓄電池。 [比較例6-1] 與前述比較例5 -1相同地，製作非水系蓄電池。 [比較例6 - 2 ] 〇與前述比較例5-2相同地，製作非水系蓄電池。 [比較例6 - 3 ] 與前述比較例5 - 3相同地，製作非水系蓄電池。 [比較例6 - 4 ] 除沒有使用氧化鋁A作爲無機塡料下，使用平均粒徑〇.5μηι、比表面積7 m2/g之非多孔質之氧化鋁£ (昭和電工製；AL-l6〇SG-3)外，與實施例6-1相同地，製得非水系 -87- 201101560 蓄電池。而且’有關該氧化鋁E’以Xrd進行解析時，確認有來自α-氧化鋁之明確波峰。 [比較例6-5] 除沒有使用氧化鋁Α作爲無機塡料下，使用平均粒徑 0·6μιη、比表面積15 m2/g之非多孔質之氧化鋁ρ (大明化學工業製；C06 )外’與實施例6_：1相同地，製得非水系蓄電池。而且’有關該氧化銘F，以X R D進行解析時，確萨有來自勃姆石之明確波峰。 [比較例6-6] 除沒有使用氧化鋁A作爲無機塡料下，使用平均粒徑 0.8μιη、比表面積7 m2/g之非多孔質之氫氧化鋁（昭和電工製；H-43M)外，與實施例6]相同地，製得非水系蓄電池。而且，有關該氫氧化鋁以XRD進行解析時，確認有來自三水鋁石之明確波峰。 [比較例6-7] 與前述比較例5-7相同地，製作非水系蓄電池。 [比較例6 - 8 ] 除沒有使用氧化鋁A作爲無機塡料下，使用平均粒徑 2 μιη、比表面積600 m2/g之二氧化矽（東海化學工業所製 ;M L - 6 4 4 )外’與實施例6 -1相同地，製得非水系蓄電池 -88 - 201101560 [比較例6 - 9 ] 與前述比較例5 - 9相同地，製作非水系蓄電 '池〇 [容量維持率之測定] 有關前述所製作的實施例及比較例之非水系w 於60°c之恆溫槽中，使用充放電測定裝置（北斗電製HJ-101SM6 )，測定充放電特性。有關充放電條電係以0.2C、至4.2V進行充電處理8小時，有關放 0.2C、至2.75V進行放電處理，容量維持率係對初容量而言400次循環時之放電容量的比例。測定結 1 1所示。電池，工公司件，充電係以期放電果如表 [140°C之烤箱試驗] 有關前述所製作的實施例及比較例之非水系蓄以0.2C、至4.2V進行8小時充電處理後’於140°C之燥機中保管24小時。結果，確認有發火情形時評f 沒有發火情形時評估爲〇。結果如表11所示° 電池，防暴乾 ί爲X， -89- 201101560 [表η]Wi/di )). The enthalpy was divided by the film thickness, and the porosity (%) was determined by multiplying 1 by 1 minus 0 。. [Gurley No.] Measured on the basis of JIS P8117. [Puncture strength] Using a KES-G5 manual compression tester manufactured by KES Co., the puncture test was carried out under the conditions of a curvature radius of 针5 mm and a puncture speed of 2 mm/sec at the needle tip end -51 - 201101560, and the maximum puncture load was used as the puncture strength. Here, the sample was clamped to a gold frame (sample holder) having a hole of Φ 11.3 mm. [Shutdown characteristics (SD characteristics)] First, the separator formed of the sample was perforated with a diameter of 19 mm, and immersed in a 3 wt% methanol solution of a nonionic surfactant (manufactured by Kao Co., Ltd.: Emulgeti 210P), and air-dried. . Then, a SUS plate (Φ15.5ιηιη) impregnated with the electrolyte was sandwiched in the separator. Here, as the electrolytic solution, 1 Μ LiBF4 propylene carbonate/ethyl carbonate (1/1 by weight) was used. This material was sealed in a 2 0 3 2 type coil unit cell. Pull the wire from the coil cell, attach a thermoelectric pair, and place it in the oven. The temperature of the cell was measured at a temperature increase rate of 1.6 ° C / min, and an alternating current having an amplitude of 1 OmV and 1 kHz was applied thereto to measure the resistance of the cell. In the above measurement, in the range of 1 35 to 150 ° C, when the resistance 値 is 103 ohm*cm 2 or more, the SD characteristic is 〇, and when it is not X. [Battery Storage Characteristics] Using the separators produced in the following Examples and Comparative Examples, a nonaqueous battery as described below was produced. 89.5 parts by weight of powder of lithium cobaltate (Li Co 02: manufactured by Nippon Chemical Industry Co., Ltd.), acetylene black (manufactured by Electric Chemical Industry Co., Ltd.; trade name Denka 81 & 4.5 parts by weight, polyfluorinated vinylidene group (1) <:11^113 Chemical Co., Ltd.) 6 parts by weight of N-methyl-2-pyrrolidone solvent was used, and these were subjected to annealing treatment at -52 to 201101560 to prepare a slurry. The obtained slurry was applied to a thickness of 20 aluminum foil, dried, and then subjected to a pressing treatment to obtain a positive electrode 〇 in a mesophase carbon microbead (MCMB: manufactured by Osaka Gas Chemical Co., Ltd.) powder of 87 parts by weight, acetylene black. (manufactured by Electric Chemical Industry Co., Ltd.; trade name Denka Black) 3 parts by weight, polyfluorinated vinylidene group (Kureha Chemical Co., Ltd.), 1 part by weight, using N-methyl-2-pyrrolidone solvent, such a 0 An annealing treatment is performed to prepare a slurry. The obtained slurry was applied onto a copper foil having a thickness of 18 μηη, dried, and then subjected to a pressing treatment to obtain a negative electrode of 90 μm. The positive electrode and the negative electrode were opposed to each other via a separator produced in the following examples and comparative examples, and an electrolyte solution was impregnated therein, and an outer casing formed of an aluminum laminate film was sealed to prepare a nonaqueous battery. Here, as the electrolytic solution, 1 Μ LiPF6 ethylene carbonate/methyl ethyl carbonate (3/7 by weight) (manufactured by Kishida Chemical Co., Ltd.) was used. 0 For this non-aqueous battery, carry out 〇. 2C' 4. 2V constant voltage • Constant current for charging for 8 hours, 0. 2C, 2. The 75 V cut constant current is discharged. The discharge capacity obtained by the fifth puncturing cycle was taken as the initial capacity of the unit cell. Then, at 0. 2C, 4. The constant voltage of 2V and the constant current were charged for 8 hours and stored at 85 °C for 3 days. Then, in 〇. 2C, 2. The current was discharged at 75 V, and stored at 85 ° C for 3 days to obtain the remaining capacity. The remaining capacity is divided by the initial capacity and multiplied by 1 値 as the capacity retention rate, and the capacity retention ratio is used as an index of the storage characteristics of the battery. -53- 201101560 [Expansion of battery] It was confirmed that each battery after the storage test of the battery was visually observed, and it was found that the battery was swollen, and it was judged that X ′ had no expansion of the battery in appearance. Moreover, the expansion of the battery at this time is caused by the generation of gas in the battery. [Example 2 - 1] GUR 2126 (weight average molecular weight: 4.15 million, melting point: 141 t:) manufactured by Ticona Co., Ltd. and GURX 143 (weight average molecular weight: 560,000, melting point: 135 ° C) were used as the polyethylene powder. Dissolved in mobile paraffin (Smoil P-3 50P; boiling point 480 ° C) and decalin in a ratio of 1:9 (by weight) and 30% by weight of GUR2126 and GURX143. A polyethylene solution was prepared in a mixed solvent. The composition of the polyethylene solution is polyethylene: mobile paraffin: decalin = 30: 45: 25 (weight ratio). The polyethylene solution was self-molded at 148 ° C and cooled in a water bath to make a gel-like tape (base tape). The base tape was dried at 60 ° C for 8 minutes, dried at 95 t for 15 minutes, and the base tape was subjected to a two-axis stretching treatment of longitudinal stretching and lateral stretching. Here, the longitudinal extension has a stretching ratio of 5. 5 times, an extension temperature of 901:, and a transverse extension stretching ratio. 0 times, extension temperature 105 it. After the lateral stretching, heat setting treatment was carried out at 125 °C. Next, it was immersed in a dichloromethane bath to extract flowing paraffin and decalin. Then, drying was carried out at 50 ° C, and annealing treatment was carried out at 12 ° C to prepare a polyethylene microporous film. The obtained polyethylene microporous membrane was meshed with 4·7 g/m 2 , membrane thickness of 9 μηη -54-201101560, porosity of 45%, Gurley of 150 seconds/l〇〇cc, and puncture strength of 300 g. Conex (registered trademark; manufactured by Teijin technoproducts Co., Ltd.) of polym-phenylene isodecylamine was used as the meta-type wholly aromatic polyamine. A Conex solution was prepared by dissolving 6% by weight of conex in dimethylacetamide (DM Ac): tripropylene glycol (TPG) = 60:40 (by weight). A zeolite having a mean particle diameter of 3 μm and a specific surface area of 290 m 2 /g (HSZ_500 KOA; manufactured by Tosoh Corporation) was used as the porous material. The zeolite was dispersed in the Conex solution at a zeolite: 0 Conex = 50:50 (weight ratio) to adjust the dispersion. Use 2 Meyer bars to load the dispersion in moderation. The polyethylene microporous membrane was passed between the Meyer rods carrying the dispersion, and the dispersion was applied to both sides of the polyethylene microporous membrane. Here, the gap between the Meyer bars is 30μηι, and two Meyer bars numbered #6 are used at the same time. It is immersed in a coagulating liquid having a weight ratio of water: DMAc : TPG = 70: 18: 12 (weight ratio), 30 ° C, then washed with water, dried, and formed in the surface of the polyethylene microporous porous film. The non-aqueous secondary battery of the present invention is obtained from a heat-resistant porous layer formed of zeolite and Conex. The characteristics of the obtained separator for a non-aqueous battery are shown in Tables 4 and 5. Further, the characteristics of the separators of the following examples and comparative examples are similarly shown in Tables 4 and 5. [Example 2-2] The same procedure as in Example 2-1 was carried out except that a zeolite having an average particle diameter of 2 μm and a specific surface area of 400 m 2 /g (HSZ-9 8 HOA; manufactured by Tosoh Corporation) was used as the porous material. A separator for a non-aqueous battery of the present invention is obtained. -55-201101560 [Example 2-3] A nonaqueous battery of the present invention was produced in the same manner as in Example 2-1 except that an average particle diameter of 4 μm and a specific surface area of 700 HSZ-341NHA was used. Example 2-4] An average particle diameter of 0 was obtained by using activated carbon (manufactured by Kansai ThermoChem Co., Ltd.; a bead bead mill having a dissolved diameter of dimethylacetamide (DM Ac) as a dispersing agent). 6μιη, m2/g of activated carbon. The non-aqueous electricity storage of the present invention was obtained in the same manner as in the case of using the activated carbon as the porous material. Example 2 -1 [Example 2-5] Except for using an average particle diameter of 1·4 μm and a specific surface area of 190 (manufactured by Sumitomo Chemical Co., Ltd.) ; KC-501) The non-aqueous battery of the present invention was obtained in the same manner as in the porous wall example 2-1 [Example 2-6] In addition to heat treatment of aluminum hydroxide (manufactured by Showa Denko; Η - 4 3 Μ), An average particle diameter of 〇·8 μmη and a specific surface area of 60 aluminum were obtained. Further, when the crystal structure of the activated alumina was analyzed, it was confirmed that there was no peak of the broad-wave gibbsite from the amorphous structure, so the overall structure was mainly a zeolite of m2/g of Mishui (outside,丨丨。 MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS MS The active oxygen i of m2/g was carried out by XRD: it was confirmed that it was derived from vermiculite and was not amorphous-56-201101560 alumina. Except that the activated alumina was used as the porous tantalum, and Example 2-1 The separator for a non-aqueous battery of the present invention was produced in the same manner. [Example 2-7] An aluminum hydroxide (manufactured by Showa Denko Co., Ltd.; H-43M) was heat-treated at 280 ° C to obtain an average particle diameter 〇. 8 μιηη, specific surface area 400 m2/g activity 0 alumina. Regarding the activated alumina, when it was analyzed by XRD, only the peak from the boehmite was observed in the wide-scale plot, 2Θ = 14. The integrated intensity of the peak of 39° is 98cpS*deg, and the integrated intensity of the main peak is 0 for the integrated intensity of the broad peak existing at 2Θ=10~6 Odeg. 07. Therefore, the activated alumina is mainly an amorphous monolithic structure, and is also called amorphous alumina because it is only slightly mixed with boehmite. Further, the element ratio of Ο/Al of the surface of the activated alumina is 1. 54. A separator for a non-aqueous battery of the present invention was obtained in the same manner as in Example 2-Q except that the activated alumina was used as the porous material. [Example 2-8] A separator for a nonaqueous battery according to the present invention was produced in the same manner as in Example 2-7 except that the dispersion liquid was applied only to one side of the polyethylene microporous membrane to form a porous layer. [Comparative Example 2 -1] In addition to the use of the average particle size 〇. 6μιη, a specific surface area of 6 m2 / g of α-alumina (-57- 201101560 made by Showa Denko; AL160SG-3) as an inorganic tantalum instead of the use of Example 2-1. A separator for a non-aqueous battery of the present invention was obtained in the same manner as in Example 2-1 except for the porous material. [Comparative Example 2-2] Except for the use of the average particle diameter 〇. A boehmite (manufactured by Daming Chemical Co., Ltd.; C06) having a specific surface area of 15 m 2 /g (manufactured by Daming Chemical Industry Co., Ltd.; C06) was used as an inorganic tantalum material in the same manner as in Example 2-1 except that the porous tantalum material used in Example 1 was used. The separator for a non-aqueous battery of the present invention. [Comparative Example 2 - 3] In addition to heat treatment of aluminum hydroxide (manufactured by Showa Denko Co., Ltd.; Η - 4 3 Μ ) at 250 ° C, an activity of an average particle diameter of 〇·8 μmη and a specific surface area of 30 m 2 /g was obtained. Alumina. Further, when the crystal structure of the activated alumina was analyzed by XRD, it was confirmed that there was no broad peak derived from the amorphous structure, and the peak from the gibbsite was confirmed, so the overall structure was mainly gibbsite, not Amorphous alumina. The separator for a non-aqueous battery of the present invention was obtained in the same manner as in Example 2-1 except that the porous material was changed to the activated alumina. [Comparative Example 2 - 4] GUR 2126 (weight average molecular weight: 4.15 million 'melting point 141 ° C) manufactured by Ticona Co., Ltd. and GURX 143 (weight average molecular weight: 560,000, melting point: 135 ° C) were used as polyethylene powder. Dissolved in mobile paraffin-58- 201101560 (Smoil P-350P; boiling point 480 °C) with GUR2126 and GURX143 of 1: 9 (weight ratio) and polyethylene concentration of 15% by weight. A polyethylene solution was prepared in a mixed solvent of decalin. The composition of the polyethylene solution is polyethylene: mobile paraffin: decalin = 3 0: 45: 25 (weight ratio). A slurry which was dispersed in the polyethylene solution in a weight ratio of polyethylene: zeolite (HSZ-500 KOA; manufactured by Tosoh Corporation) = 50:50 was prepared. Here, the zeolite has an average particle diameter of 3 μm and a specific surface area of 290 m 2 /g. The crucible was self-molded at 1 4 8 ° C and cooled in a water bath to prepare a gel-like tape (base tape). The base tape was dried at 60 ° C for 8 minutes, dried at 95 ° C for 15 minutes, and the base tape was subjected to a two-axis stretching treatment of longitudinal stretching and lateral stretching. Here, the longitudinal extension is extended by 5. 5 times, extension temperature 90 ° C, transverse extension stretching ratio Π · 〇 times, extension temperature 1 〇 5 °C. After the extension, heat setting treatment was carried out at 1 2 5 °C. Next, it was immersed in a dichloromethane bath to extract flowing paraffin and decalin. Then, the film was dried at 50 ° C and annealed at 120 ° C to obtain a polyethylene microporous film (non-aqueous battery separator) containing a porous tantalum. [Comparative Example 2-5] Conex (registered trademark: manufactured by Teijin technoproducts Co., Ltd.) using poly(m-phenylene decylamine) was used as the meta-type wholly aromatic polyamine. A Conex solution was prepared by dissolving Conex at 6% by weight in a weight ratio of dimethyl acetamide (DM Ac ): tripropylene glycol (TPG) = 60:40. Use 2 Meyer rods to load the C ο n e X solution in moderation. The polyethylene microporous membrane containing the porous tantalum produced in Comparative Example 2-4 was passed through a Meyer bar loaded with a Conex dispersion at -59-201101560; the Conex solution was coated on the surface. Here, Meyer | uses 2 Meyer sticks numbered #6. : DMAc: TPG = 70: 18: 12 (weight, then washed with water, dried, and formed into a non-aqueous battery separator formed of C ne ne X in a surface containing a porous film. Polyethylene microporous film The gap between the two is 3 〇 μιη 'with the polyethylene microporous layer immersed in the coagulating liquid at a weight ratio of water:) at 30 ° C to obtain the present invention -60-201101560 [Table 4] The separator constitutes the heat-resistant layer. The surface area of the heat-resistant layer is the particle size (μηι). The specific surface area (m2/g). The film thickness (μηι). The porosity (%). Example 2-1 Heat-resistant layer (containing mash) / PE film double sided zeolite 3. 0 290 16 55 Example 2-2 Heat-resistant layer (containing mash) / PE film Both sides Zeolite 2. 0 400 16 54 Example 2-3 Heat-resistant layer (containing tantalum) / PE film Both sides Zeolite 4. 0 700 16 56 Example 2-4 Heat-resistant layer (containing mash) / PE film Two-shell activated carbon 0. 6 1600 16 56 Example 2-5 Heat-resistant layer (containing mash) / PE film Both sides Activated alumina 1. 4 190 16 55 Example 2-6 Heat-resistant layer (containing tantalum) / PE film Both sides Activated alumina 0. 8 60 16 54 Example 2-7 Heat-resistant layer (containing mash) / PE film Both sides Activated alumina 0. 8 400 16 55 Example 2-8 Heat-resistant layer (containing mash) / PE film One side Activated alumina 0. 8 400 16 65 Comparative Example 2-1 Heat-resistant layer (containing tantalum) / PE film Both sides α-alumina 0. 6 6 16 53 Comparative Example 2-2 Heat-resistant layer (including tantalum) / PE film Both sides Boehmite 0. 6 15 16 53 Comparative Example 2-3 Heat-resistant layer (containing tantalum) / PE film Both sides Activated alumina 0. 8 30 16 53 Comparative Example 2-4 ΓΕ film (containing mash) - zeolite 3. 0 290 9 58 Comparative Example 2-5 Heat-resistant layer/PE film (containing tincture) Both sides Zeolite 3. 0 290 16 65 [Table 5] Gore (sec/100cc) Puncture strength ω SD Characteristics Breaking film test Gas generation amount (CC) Battery storage characteristics (%) Expansion of the battery Example 2-1 283 310 〇〇 1. 5 58 实施 Example 2-2 276 315 〇〇 1. 1 60 实施 Example 2-3 286 308 〇〇 0. 8 63 实施 Example 2-4 268 309 〇〇 0. 8 62 实施 Example 2-5 270 311 〇〇 1. 8 74 实施 Example 2-6 271 310 〇〇 2. 5 73 实施 Example 2-7 275 310 〇〇 0. 4 75 实施 Example 2-8 288 310 〇〇 0. 5 65 〇 Comparative Example 2-1 279 315 〇〇 3. 5 67 X Comparative Example 2-2 283 314 〇〇 8. 8 65 X Comparative Example 2-3 279 311 〇〇 10. 3 62 X Comparative Example 2-4 85 163 X X 1. 7 45 〇 Comparative Example 2-5 300 175 X 〇 1. 5 58 〇-61 - 201101560 [Evaluation of the cycle characteristics] Next, a separator made of a heat-resistant porous layer on one surface or both surfaces of a porous substrate is prepared as follows, and a non-aqueous battery is prepared as described below. Different places. Lithium cobaltate (1^(:〇02: manufactured by Nippon Chemical Industry Co., Ltd.) powder 89. 5 parts by weight, acetylene black (manufactured by Electric Chemical Industry Co., Ltd.; trade name Denka Black) 4. 5 parts by weight of a polyfluorinated vinylidene group (manufactured by Kureha Chemical Co., Ltd.) was used, and N-methyl-2-pyrrolidone solvent was used for annealing treatment to prepare a slurry. The obtained slurry was applied onto an aluminum foil having a thickness of 20 μm, dried, and then subjected to a pressing treatment to obtain a positive electrode of 100 μm of yttrium in a mesophase carbon microbead (MCMB: manufactured by Osaka Gas Chemical Co., Ltd.) powder of 7 7 parts by weight. , acetylene black (manufactured by Denki Kagaku Co., Ltd.; trade name Denka Black), using N-methyl-2-pyrrolidone solvent under 10 parts by weight of polyfluorinated secondary ethylene (manufactured by Kureha Chemical Co., Ltd.) under 10 parts by weight These were subjected to annealing treatment to prepare a slurry. The obtained slurry was applied onto a copper foil having a thickness of 18 μm, dried, and then subjected to a pressing treatment to obtain a negative electrode of 90 μm. The positive electrode and the negative electrode were opposed to each other via a separator, and the electrolytic solution was impregnated therein, and sealed in an exterior formed of an aluminum laminate film to prepare a nonaqueous battery. Here, as the electrolytic solution, 1 Μ LiPF6 ethylene carbonate/ethyl methyl carbonate (3/7 by weight) (manufactured by Kishida Chemical Co., Ltd.) was used. Here, in the separator, the batteries of Examples 2-9 to 2_11 shown in Table 6 were produced using Examples 2-7 and 2-8. -62- 201101560 The evaluation of the cycle characteristics is carried out 1c, 4. 2V 2 hour constant voltage • Constant current charging, 1C, 2. The quantitative flow discharge treatment of the 75V cut-off is the capacity retention rate of the third cycle when the capacity of the first cycle is used as an index of the cycle characteristics. Moreover, the temperature at the time of measurement was 30. The results are shown in Table [ [Table 6] Separator capacity retention rate % Example 2-9 Example 2-7 85 Example 2-10 Example 2-8 (Polyethylene microporous film was disposed on the positive electrode side) 50 Implementation Example 2-11 Example 2-8 (Polyethylene microporous film was disposed on the negative electrode side) 60 As a result of Table 6, it was found that a heat-resistant porous layer was formed on both surfaces of the porous substrate, and the capacity retention ratio was maintained. It is more excellent than one side. Further, even in the one-side configuration, when the polyethylene microporous film is disposed on the negative electrode side, the capacity retention ratio is high. (3) Effect of the special activated alumina of the third aspect In the following, the constitution of the activated alumina having a specific surface area of 30,000 to 100 m 2 /g in the third aspect of the present invention is reviewed. The measurement methods used in the following examples are as follows. Further, the method for measuring the average particle diameter, specific surface area, crystal structure, and element ratio of the inorganic tantalum is the same as in the first and second embodiments. [Measurement of true density of alumina] -63- 201101560 The alumina used in the following examples and comparative examples was obtained by Micro Ultra Pycnometer (MUPY-2 IT manufactured by Yuasa Ionics Co., Ltd.). ) Find the true density. Further, the measurement system utilizes helium gas [Example 3-1] (i) The PE microporous membrane was produced by using GUR2126 (weight average molecular weight: 4.15 million, melting point: 141 ° C) manufactured by Ticona Co., Ltd. and GURX 143 (weight average molecular weight: 560,000, The melting point is used as a polyethylene powder. It is dissolved in mobile paraffin (Smoil P-3 50P; boiling point 480) when GUR2 126 and GURX143 are 1:9 (weight ratio) and polyethylene concentration is 30% by weight. In a mixed solvent of decalin and decalin, a polyethylene solution is prepared. The composition of the polyethylene solution is polyethylene: mobile paraffin: decalin = 3 0: 45: 25 (weight ratio). Self-plasticizing at 148 °C The polyethylene solution was molded and cooled in a water bath to make a gel-like tape (base tape). The base tape was dried at 6 ° C for 8 minutes, dried at 95 ° C for 15 minutes, and the substrate was allowed to stand. The tape is successively subjected to two-axis extension processing of longitudinal extension and lateral extension. Here, the longitudinal extension has a stretching ratio of 5 · 5 times and an extension temperature of 90 ° C. The transverse extension stretching ratio 1 1. 0 times, extension temperature 1 0 5 °C. After the transverse stretching, heat setting treatment was carried out at 1 2 5 °C. Next, it was immersed in a dichloromethane bath to extract flowing paraffin and decalin. Then, at 50. (: Drying underneath) and annealing at 120 ° C to obtain a PE microporous membrane. -64 - 201101560 (ii) Production of poly(m-phenylene isodecylamine) with thermometer, stirring device and raw material input In the reaction vessel of the mouth, 75 3 g of NMP having a water content of 1 〇〇 ppm or less is added, and m-phenylenediamine 85 is dissolved in the NMP. 2g with aniline 〇. 5g' and cooled at 0 °C. In the cooled diamine solution, stirring is slowly added 160. 5 g of chlorinated isophthalic acid is reacted. The temperature of the solution in the reaction rose to 7 ° C. After the viscosity change was stopped, 58_4 g of calcium hydroxide powder was added, and the mixture was stirred for 40 minutes to complete the reaction, and the polymerization solution was taken out to obtain 184. 0 g of poly(methylenephenylisodecylamine) reprecipitated in water. (i i i ) Production of Active Oxidation In addition to heat treatment of aluminum hydroxide (manufactured by Showa Denko; H-43M) at 28 ° C, an average particle diameter of 0 was obtained. Hm, active alumina with a specific surface area of 400 m2/g. The true density of the activated alumina is 3. 1 g/cm2. Moreover, when analyzing by XRD, it is confirmed that only the peak Q from the boehmite in the wide-scale plot, the integrated intensity of the peak of 2Θ=14·39° is 98 cps*deg, and the integrated intensity of the main peak is 2Θ = 10 The integral intensity of the broad peak existing at ~60deg is 0. 07. Therefore, the activated alumina is mainly an amorphous monolithic structure, and is also called amorphous alumina because it is only slightly mixed with the boehmite phase. (iv) Manufacture of laminated separators The poly(methylenephenylisodecylamine) obtained as described above and activated alumina are prepared in a weight ratio of 40:60 to make these poly(m-phenylene isoindoles) The concentration of guanamine is 5. 5 wt% was mixed in a mixed solvent of dimethylacetamide (DMAc) and tripropylene-65-201101560 diol (TPG) in a weight ratio of 50:50 to prepare a coating slurry. A suitable amount of the coating material was applied to the Meyer bar, and the coating slurry was applied to both surfaces of the PE film by passing the PE film obtained as described above between a pair of Meyer rods. It was immersed in a coagulating liquid having a weight ratio of water: DM Ac : TPG = 50 : 2 5 : 25, 40 °C. Then, the obtained film was washed with water and dried. Thereby, a laminated separator coated with a heat-resistant porous layer can be obtained. (v) Production of positive electrode In lithium cobaltate (1^(:0〇2: manufactured by Nippon Chemical Industry Co., Ltd.) powder 89. 5 parts by weight, acetylene black (manufactured by Electric Chemical Industry Co., Ltd.; trade name Denka Black) 4. A 6 wt%, polyfluorinated vinylidene group (manufactured by Kureha Chemical Co., Ltd.) was used in an amount of 6 wt% of a polyfluorinated vinylidene NMP solution to prepare a positive electrode slurry. The obtained slurry was applied onto an aluminum foil having a thickness of 20 μm and dried to obtain a positive electrode of 97 μm. (vi) Production of a negative electrode: 87 parts by weight of a mesocarbon microbead (MCMB: manufactured by Osaka Gas Chemical Co., Ltd.) as a negative electrode active material, acetylene black (manufactured by Denki Kagaku Co., Ltd.; trade name Denka Black), 3 parts by weight, and poly Under a 10 parts by weight of a fluorinated vinylidene group (manufactured by Kureha Chemical Co., Ltd.), a 6 wt% polyfluorinated vinylidene NMP solution was used to prepare a negative electrode slurry. The obtained slurry was applied onto a copper foil having a thickness of 18 μm, dried, and then subjected to a press treatment to prepare a negative electrode of 90 μm. (vii) Preparation of nonaqueous electrolyte The solution was prepared by dissolving LiPF6 at 1 mol/L in a solution in which ethylene carbonate and methyl ethyl carbonate were mixed at a weight ratio of 3:7. (viii) Production of a non-aqueous battery The positive electrode and the negative electrode obtained as described above are opposed to each other via a laminated separator, and an electrolytic solution is impregnated therein, and sealed in an exterior formed of an aluminum laminated film to produce a non-aqueous secondary battery. [Comparative Example 3 -1] GUR 2126 (weight average molecular weight: 4.15 million, melting point: 141 ° C) manufactured by Ticona Co., Ltd. and GURX 143 (weight average molecular weight: 560,000, melting point: 135 ° C) were used as the polyethylene powder. Dissolved in mobile paraffin (Smoil P-350P; Smoil P-350P; boiling point 480. Mixture of hydrazine and decalin) with GUR2126 and GURX143 at a ratio of 1:9 〇 (by weight) and a concentration of polyethylene of 30% by weight. In the solvent, the average particle size of the material is 0. A 5 μιη, α-alumina (AL-160SG-3; manufactured by Showa Denko) having a specific surface area of 7 m 2 /g was prepared as a polyethylene solution. The composition of the polyethylene solution is polyethylene: Oxidation: mobile paraffin: naphthalene = 30: 10: 55: 30 (weight ratio). The polyethylene solution was self-molded at 148 ° C and cooled in a water bath to make a gel-like tape (base tape). The base tape was dried at 6 (TC for 8 minutes, dried at 95 ° C for 15 minutes), and the base rubber-67-201101560 was subjected to a two-axis extension process of longitudinal extension and lateral extension. Extension extension ratio 5. 5 times, extension temperature 9 〇 ° C ‘ transverse extension extension ratio 1 1. 0 times, extension temperature 1 0 5 °C. After the transverse stretching, the heat setting treatment was carried out at 1 2 5 °C. Next, it was immersed in a dichloromethane bath to extract the flowing paraffin and decalin. Then, it was dried at 5 (TC) and annealed at 20 ° 0 to obtain a separator formed of a PE microporous film. The same as Example 3-1 except that the separator was used. [Comparative Example 3 - 2] The aluminum hydroxide (manufactured by Showa Denko; H-43M) was heat-treated at 22 ° C to obtain an average particle diameter of 0. 8 μιη, active alumina having a specific surface area of 60 m2/g. The true density of the activated alumina is 2. 5 g/cm3. Further, when the analysis was carried out by XRD, it was confirmed that there was no broad peak from the amorphous structure and the peak from the gibbsite was confirmed. Therefore, the overall structure of the activated alumina was mainly Sanshui Mingshi. A non-aqueous secondary battery was produced in the same manner as in Comparative Example 3-1 except that the activated alumina was used as the inorganic cerium. [Comparative Example 3 - 3] Alumina hydroxide (manufactured by Showa Denko Co., Ltd.; H-43M) was heat-treated at 240 ° C to obtain an activated alumina having an average particle diameter of 〇·8 μm and a specific surface area of 200 m 2 /g. The true density of the activated alumina is 2. 6 g/cm3. Further, when the active alumina was analyzed by XRD, it was confirmed that there was a peak from gibbsite-68-201101560, and 2Θ = 18. The integrated intensity of the 27° peak is 371 cps · deg, and the integrated intensity of the main peak is 0 for the integrated intensity of the broad peak existing at 2 Θ = 10 to 60 deg. 35. Therefore, the overall structure of the activated alumina is mainly gibbsite. A non-aqueous secondary battery was produced in the same manner as in Comparative Example 3-1 except that the activated alumina was used as the inorganic cerium. [Comparative Example 3 - 4] In the same manner as in Comparative Example 3-1 except that a zeolite having an average particle diameter of 2 μm and a specific surface area of 4 μm 2 /g (HSZ_980HOA; manufactured by Tosoh Corporation) was used as the inorganic tantalum Water battery. [Comparative Example 3 - 5 ] In addition to the use of cerium oxide (manufactured by Tokai Chemical Industry Co., Ltd.; ML-3 84) having an average particle diameter of 2 μm and a specific surface area of 300 μm/g as an inorganic tantalum, comparison with Q Example 3-1 Similarly, a non-aqueous battery was produced. [Comparative Example 3-6] Wet pulverization (2 mm diameter zirconium bead mill) using dimethyl acetamide (DMAc) as a dispersing agent was carried out by using activated carbon (manufactured by Kansai Thermo Chemical Co., Ltd.; MSP-20) The average particle size is obtained. 6 μιη, activated carbon having a specific surface area of 1600 m 2 /g. A non-aqueous secondary battery was produced in the same manner as in Comparative Example 3-1 except that the activated alumina was used as the inorganic cerium. -69-201101560 [Measurement of capacity retention rate] For the non-aqueous battery of the examples and the comparative examples produced above, a charge and discharge measuring device (HJ-101SM6 manufactured by Hokuto Denko Corporation) was used in a thermostat at 60 °C. The charge and discharge characteristics were measured. For charging and discharging conditions, the charging system is 0. 2C, to 4. 2V is charged for 8 hours, and the relevant discharge system is 0. 2C, to 2. The discharge treatment was performed at 75 V, and the capacity retention ratio is the ratio of the discharge capacity at 500 cycles to the initial discharge capacity. The measurement results are shown in Table 7. [^7] The ratio of the material to the material surface area rg/m2l The true density of alumina Γ g/cm3l Type of separator Capacity retention [%1 Example 3-1 Activated alumina 400 3. 1 Polyamide / PE separator 83 Comparative Example 3-1 α-alumina 7 3. 9 PE separator 52 Comparative Example 3-2 Activated alumina 60 2. 5 ΓΕ baffle 55 Comparative Example 3-3 Activated Alumina 200 2. 6 PE separator 59 Comparative Example 3-4 Zeolite 400 _ PE separator 62 Comparative Example 3-5 Ceria 300 cans PE separator 59 Comparative Example 3-6 Activated carbon 1600 • PE separator 62 As shown in Table 7, 'Use Example 3-1 of activated alumina having a specific surface area of 300 to 1 〇〇〇m 2 /g, and activated alumina having a specific surface area outside the foregoing range (Comparative Examples 3 - 2, 3 - 3 ), or α-alumina (Comparative Example 3-1) and the other porous materials (Comparative Examples 3-3 to 3-6) were more excellent in the capacity retention ratio after the 00th cycle characteristic test. This is presumed that the activated alumina with a specific surface area of 300 to 1 0 0 m2/g reduces the activity of H F in the battery -70-201101560. Further, in the examples, the crucible was used in the heat-resistant porous layer of the composite separator, and the comparative example used the difference in the use of the crucible in the PE separator, but the two were used in the separator. Consistently, the aforementioned differences have no significant effect on the capacity retention rate. (4) Effect of amorphous aluminum oxide according to the fourth aspect In the following, a configuration in which amorphous aluminum oxide is used in the fourth embodiment of the present invention is reviewed. The various assay methods are as described above. [Example 4 - 1] A non-aqueous storage battery of Example 4-1 was produced in the same manner as in Example 3-1. [Comparative Example 4-1] GUR2126 (weight average molecular weight: 4.15 million Q, melting point 141 °) manufactured by Ticona Co., Ltd. was used. C) and GURX143 (weight average molecular weight 560,000, melting point 135 ° C) were used as polyethylene powder. Dissolved in mobile stone snail (Smoil P-350P; boiling point 480 ° C) and naphthalene in GUR2126 and GURX143 with a ratio of 1:9 (weight ratio) and polyethylene concentration of 30% by weight. In the mixed solvent of the alkane, the average particle diameter of the material is 0. A polyethylene solution was prepared by dispersing αμ-alumina (AL-160SG-3; manufactured by Showa Denko) having a specific surface area of 7 m2/g at 5 μm. The composition of the polyethylene solution is polyethylene: alumina: mobile paraffin: decalin = 30: 10: 55: 30 (weight ratio). The polyethylene solution was molded by self-molding at 148 ° C, and cooled in a water bath -71 - 201101560 to prepare a gel-like tape (base tape). The base tape was dried at 60 ° C for 8 minutes and dried at 95 ° C for 15 minutes, and the base tape was subjected to a two-axis stretching treatment of longitudinal stretching and lateral stretching. Here, the elongation of the extension is 5 · 5 times, the elongation temperature is 90 ° C, the transverse extension is 11 × 0 times, and the elongation temperature is 1 0 5 ° C. After the transverse stretching, the heat setting treatment was carried out at 1 2 5 °C. Next, it was immersed in a bath of methylene chloride to extract the flowing paraffin and decalin. Then, drying was carried out at 50 ° C and the annealing treatment was carried out at 120 ° C to obtain a separator formed of a PE microporous film. A non-aqueous secondary battery was produced in the same manner as in the above Example 3-1 except that the separator was used. [Comparative Example 4 - 2] In addition to the non-porous alumina (manufactured by Damien Chemical Industry Co., Ltd.: C〇6) having an average particle diameter of 〇·6 μmη and a specific surface area of 15 m 2 /g, and Comparative Example 4 In the same manner, a non-aqueous battery was produced. Further, when the aluminum oxide was subjected to XRD analysis, it was confirmed that there was a clear peak derived from boehmite. [Comparative Example 4-3] Except for using an average particle diameter of 0. A non-aqueous battery was produced in the same manner as in Comparative Example 4-1 except that the non-porous 皙氢氧化 ( ( ( ( ( ( 。 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( Further, when XRD analysis was performed on the oxidation, it was confirmed that there was a clear peak from gibbsite. [Measurement of capacity retention rate] -72-201101560 For the non-aqueous battery of the above-described examples and comparative examples, a charge/discharge measuring device (HJ-101SM6 manufactured by Hokuto Denko Corporation) was used in a thermostatic chamber at 6 °C. The charge and discharge characteristics were measured. For charging and discharging conditions, the charging is 0. 2C, to 4. 2V is charged for 8 hours, and the relevant discharge system is 0. 2C, to 2. The discharge treatment was performed at 75 V, and the capacity retention ratio is the ratio of the discharge capacity at the time of the 40-cycle of the initial discharge capacity. The measurement results are shown in Table 8. ❹ [Table 8] Type of Dilution Type of Crystal Structure Partition Capacity Retention Rate [%] 72 Example 4-1 Activated Alumina Amorphous Polyamide/ΡΕ Separator Comparative Example 4-1 Alumina α-Oxidation Aluminum crucible separator 57 Comparative Example 4-2 Alumina boehmite*Ε separator 58 Comparative Example 4-3 Aluminum hydroxide gibbsite separator 54 It is understood from Table 8 that the use of an amorphous oxide saw is carried out. Example 4-1, and other alumina-based materials such as α-oxidation (Comparative Example 4-1) or Boehmite (Comparative Example 4-2), Sanshui Mingshi (^ Comparative Example 4-3, etc.) In comparison, the capacity retention rate after the fourth cycle characteristic test was more excellent. This is because amorphous aluminum oxide reduces the activity of HF in the battery. (5) Embodiment of the fifth aspect In the following, an embodiment relating to the fifth aspect of the present invention will be described. Further, the measurement method of the average particle diameter, specific surface area, true density, crystal structure, halogen ratio, and film thickness of the inorganic fine material is as follows. -73-201101560 [Example 5 - 1] (i) Production of activated alumina The activated alumina A was produced in the same manner as in the above Example 3-1. (Π) Production of positive electrode, negative electrode, and nonaqueous electrolyte The positive electrode, the negative electrode, and the nonaqueous electrolyte were produced in the same manner as in the above Example 3-1. (iii) Production of separator A GURU26 (weight average molecular weight: 4.15 million, melting point: 141 ° C) manufactured by Ticona Co., Ltd. and GURXI 43 (weight average molecular weight: 560,000, melting point: 135 ° C) were used as polyethylene powder. Dissolved in mobile paraffin (Smoil P-3 5 0P; boiling point 48 0 ° C) when GUR2 126 and GURX143 are 1: 9 (weight ratio) and polyethylene concentration is 30% by weight. In the mixed solvent with decalin, the above-mentioned activated alumina A as an inorganic crucible was further dispersed to prepare a polyethylene solution. The composition of the polyethylene solution is polyethylene: inorganic mash: mobile paraffin: decalin = 30: 10: 55: 30 (weight ratio). The polyethylene solution was molded by self-molding at 148 ° C, and cooled in a water bath to prepare a gel-like tape (base tape). The base tape was dried at 60 ° C for 8 minutes and dried at 95 ° C for 15 minutes, and the base tape was subjected to a two-axis stretching treatment of longitudinal stretching and lateral stretching. Here, the extension stretch ratio is 5. 5 times, extension temperature 90 °C, transverse extension extension ratio 11. 〇 times, extension temperature 10 5 °c ° after horizontal extension ‘ heat treatment at 12 5 °c -74- 201101560 fixed treatment. Next, it was immersed in a dichloromethane bath to extract flowing paraffin and decalin. Then, drying was carried out at 50 ° C, and annealing treatment was carried out at 120 ° C to obtain a PE separator formed of a polyethylene microporous film. (iv) A non-aqueous battery in which the positive electrode and the negative electrode obtained as described above are opposed to each other via a separator, and an electrolyte solution is impregnated therein, and sealed in an exterior formed of an aluminum laminate film to produce a non-aqueous battery according to an embodiment of the present invention. . [Example 5-2] In addition to heat treatment of aluminum hydroxide (manufactured by Showa Denko; H_43M) at 260 ° C, an average particle diameter of 0.8 μm, a specific surface area of 350 m 2 /g, and a true density of 3 · 0 g were obtained. / cm3 of activated alumina B. Regarding the structural analysis of the activated alumina b by XRD, it was confirmed that only the peak intensity of the peak from the boehmite of the boehmite '2Θ=14·40° in the broad-label plot was 83 cps. Deg, the integral intensity of the main Q peak is the integral intensity of the broad peak present at 2Θ== 10~60deg and _ is 〇. 0 5. Therefore, the active oxidation is mainly an amorphous overall structure with only a slight mixed boehmite phase. A non-aqueous secondary battery was produced in the same manner as in the Example except that the active oxidized B was used as the inorganic cerium. [Example 5-3] Fluorinated vinylidene group: propylene fluoride: trifluoroethylene chloride = 97: Ϊ: 2 molar ratio copolymerized polymer (weight average molecular weight 4 〇〇〇) 〇〇) -75- 201101560, and the above-mentioned activated alumina A, and the weight ratio of dimethylacetamide (DMAc) to tripropylene glycol (TPG) are polymers: activated alumina · DMAc : TPG = 1 2 : 4: 49 : 3 5 Fully stirred to obtain a slurry. Then, the slurry is sufficiently impregnated into a nonwoven fabric formed of short staple fibers of PET and short fibers of polyolefin, and solidified in a coagulation bath, followed by washing with water and drying. Thereby, a composite separator (PVdF/non-woven separator) of polyfluorinated vinylidene and non-woven fabric was obtained. Further, the composition of the coagulation bath is water in a weight ratio: dimethylacetamide: tripropylene glycol = 57:30:13. Next, the nonaqueous battery of the present invention was obtained in the same manner as in Example 5-1 except that the PVdF/nonwoven spacer was used instead of the PE separator. [Example 5 - 4] The mixture was mixed at a composition ratio of 5 parts by weight of polyfluorinated vinylidene, 1 part by weight of activated alumina A, and 94 parts by weight of DMAc, and sufficiently stirred to form a uniform solution to prepare a coating liquid. Next, the above coating liquid was applied onto one surface of a polypropylene separator (Celgard #2400) by a bar coater, and then dried at 6 °C. Thus, a polypropylene separator (PVdF/PP separator) having a coating layer having a thickness of 4 μm was obtained. Next, a non-aqueous secondary battery of the present invention was obtained in the same manner as in Example 5-1 except that a PVdF/PP separator was used instead of the PE separator under the connection of the coating layer and the positive electrode. [Example 5-5] The non-aqueous of the present invention was obtained in the same manner as in Example 5-4 except that the coating layer and the negative electrode were connected, and the PVdF/PP separator obtained in Example 5-4 was used. -76- 201101560 is a battery. [Example 5-6] In lithium niobate (LiMn2〇4: manufactured by Nikko Chemical Co., Ltd.) powder 89. 5 parts by weight, acetylene black (manufactured by Electric Chemical Industry Co., Ltd.; trade name Denka Black) 4. A negative electrode slurry was prepared by using a 6 wt% NPO solution of a polyfluorinated vinylidene group at 6 parts by weight of a dry weight of a polyfluorinated vinylidene group (manufactured by Kureha Chemical Co., Ltd.). The obtained slurry was applied onto an aluminum foil having a thickness of 20 μm, and dried to obtain a positive electrode having a thickness of 70 μm. A non-aqueous secondary battery of the present invention was obtained in the same manner as in Example 5-1 except that the positive electrode was used. [Example 5-7] Lithium cobaltate (1^0〇02: manufactured by Nippon Chemical Industry Co., Ltd.) powder 89. 5 Q parts by weight, acetylene black (Denka Black, made by Electric Chemical Industry Co., Ltd.) 4. 5 parts by weight, 3 parts by weight of activated alumina A, and 6 parts by weight of dry weight of polyfluorinated vinylidene (Kureha Chemical Co., Ltd.) were used, and 6 wt% of a polyfluorinated vinylidene NMP solution was used to prepare a positive electrode. Agent slurry. The obtained slurry was applied onto an aluminum foil having a thickness of 20 μm, dried, and subjected to a pressing treatment to obtain a positive electrode having a thickness of 97 μm. Use GUR2 made by Ticona. 126 (weight average molecular weight: 4.15 million, melting point: 141 ° C) and GURX 143 (weight average molecular weight: 560,000, melting point: 135 ° C) were used as polyethylene powder. When GUR2126 and GURX143 are 1: 9 -77- 201101560 (weight ratio) and polyethylene concentration is 30% by weight, 'dissolved in mobile paraffin (Smoil P-350P; Smoil P-350P; boiling point 480 ° C) A polyethylene solution was prepared in a mixed solvent of decalin. The composition of the polyethylene solution is polyethylene: mobile paraffin: decalin = 30: 45: 25 (weight ratio). At 148. (: Next, self-molding the polyethylene solution, and cooling in a water bath to prepare a gel-like tape (base tape). The base tape was dried at 60 ° C for 8 minutes and dried at 95 ° C for 15 minutes. 'And the base tape is successively subjected to the two-axis extension treatment of the longitudinal extension and the lateral extension. Here, the longitudinal extension has a stretching ratio of 5. 5 times, extension temperature 90 °C, transverse extension stretching ratio 1 1. 0 times, extension temperature 1 0 5 t. After the transverse stretching, heat setting treatment was carried out at 1 2 5 °C. Next, it was immersed in a dichloromethane bath to extract flowing paraffin and decalin. Then, drying was carried out at 5 CTC, and annealing treatment was carried out at 120 ° C to obtain a PE separator formed of a polyethylene microporous film. The nonaqueous battery of the present invention was obtained in the same manner as in Example 5-1 except that the positive electrode and the P E separator produced above were used. [Example 5-7] 87 parts by weight of mesocarbon microbeads (MCMB: manufactured by Osaka Gas Chemical Co., Ltd.) as a negative electrode active material, 3 parts by weight of acetylene black, and 3 parts by weight of activated alumina A and polyfluorinated The dry weight of the vinyl group was 1 part by weight, and a 6 wt% polyfluorinated vinyl group NMP solution was used to prepare a negative electrode slurry. The obtained slurry was applied onto a copper foil having a thickness of 18 μm. After drying, it was subjected to a pressing treatment to obtain a negative electrode of 91 μm. The non-aqueous secondary battery of the present invention was obtained in the same manner as in Example 5-1, except that the negative electrode was used and the separator of Example 5-7 was used. [Example 5-9] The coating liquid prepared in Example 2-4 was applied to the living material side of the positive electrode produced in Example 5-1 using a bar coater, and then allowed to make it at 60 ° C. Dry. Thus, a positive electrode having a coating layer (positive electrode surface layer) having a thickness of 4 μm was obtained. A non-aqueous secondary battery of the present invention was obtained in the same manner as in Example 5-1 except that the positive electrode was used and the crucible separator of Example 5-7 was used. [Example 5-10] The coating liquid prepared in Example 5-4 was applied to the living material side of the negative electrode produced in Example 5-1 using a bar coater, and then allowed to stand at 60 ° C. Dry. Thus, a negative electrode having a coating layer (negative electrode surface layer) having a thickness of 4 μm was obtained. Q The nonaqueous battery of the present invention was obtained in the same manner as in Example 5-1 except that the negative electrode was used and the crucible of Example 5-7 was used. [Comparative Example 5 - 1] A non-aqueous secondary battery was produced in the same manner as in Example 5-1 except that the separator of Example 5-7 was used. [Comparative Example 5 - 2 ] A fluorinated vinylidene group: hexafluoropropylene: chlorotrifluoroethylene = 97: -79 - 201101560 1: 2 molar ratio copolymerized polymer (weight average molecular weight 4 〇〇) The weight ratio of dimethyl acetamide (DM Ac ) to tripropylene glycol (TPG ) is polymer: DM Ac : TPG = 12 : 48 : 40 is fully stirred to prepare a slurry. Then, the slurry is sufficiently impregnated into the nonwoven fabric formed of the short fibers of PET and the short fibers of polyolefin to be solidified in the coagulation bath, and then washed and dried. Thereby, a separator (PVdF/non-woven separator) in which a polyfluorinated vinylidene group and a nonwoven fabric were composited was obtained. Further, the composition of the coagulation bath is water in a weight ratio: dimethylacetamide·tripropylene glycol = 5 7 : 3 0 : 13 °, and the same as the embodiment, {except for the use of the PVdF/non-woven separator 'The non-aqueous battery of the present invention is produced. [Comparative Example 5-3] A non-aqueous secondary battery was produced in the same manner as in Comparative Example 1, except that a polypropylene fire separator (Seluga #24〇0) was used instead of the pe separator. [Comparative Example 5-4] The same as Example 51 except that the average particle diameter 〇·5 μmη and the specific surface area of 7 m2/gia_Oxide (AL-l6〇SG-3; manufactured by Showa Denko) were used as the inorganic mash. Ground, a non-aqueous battery is produced. [Comparative Example 5-5] An aluminum hydroxide (manufactured by Showa Denko; H-43M) was heat-treated at 220 ° C to obtain an average particle diameter of 〇·8 μm, a specific surface area of 6 〇m 2 /g, and a true density of -80. - 201101560 is 2. 5 g/cm3 of activated alumina C. When the structure of the activated alumina C was analyzed by XRD, it was confirmed that there was no broad peak derived from the amorphous structure, and it was confirmed that there was a peak derived from gibbsite. It was found that the overall structure of the activated alumina C was mainly gibbsite. A non-aqueous secondary battery was produced in the same manner as in Example 5_i except that the activated alumina C was used as the inorganic coating. [Comparative Example 5-6] An aluminum hydroxide (manufactured by Showa Denko; H-43M) was heat-treated at 240 ° C to obtain an average particle diameter of 0. 8μιη, specific surface area 200 m2/g, true density 2. Active oxidation of 6 g/cm3. When the structure of the active oxidation was analyzed by XRD, it was confirmed that there was a peak from gibbsite, and the integrated intensity of the peak of 2Θ = 18_27° was 371 cps*deg, and the integrated intensity of the main peak was 2 Θ = 10 to 60 deg. The integrated intensity of the broad peaks present is 0. 3 5. Therefore, it can be seen that the entire structure of the activated alumina D contains the trihydrate enamel. A non-aqueous secondary battery was produced in the same manner as in Example 5_i except that the activated alumina D was used as the inorganic cerium. [Comparative Example 5-7] A non-aqueous battery was produced in the same manner as in Example 5_丨 except that a zeolite having an average particle diameter of 2 μm and a specific surface area of 4 〇〇m 2 /g (HSZ-98 0HOA; manufactured by Tosoh Corporation) was used. . -81 - 201101560 [Comparative Example 5-8] In addition to the use of activated alumina as the inorganic tantalum, cerium oxide having an average particle diameter of 2 μm and a specific surface area of 300 m 2 /g (manufactured by Tokai Chemical Industry Co., Ltd.; ML-3 84) was used. In the same manner as in Example 1, a nonaqueous battery was produced. [Comparative Example 5-9] For activated carbon (manufactured by Kansai Thermochemical Co., Ltd.: MSP-20), a wet pulverization treatment (2 mm diameter) was carried out by using dimethylacetamide (DM Ac ) as a dispersion solvent. Zirconia bead mill), the average particle size of 0. 6 μιη, activated carbon with a specific surface area of 1 600 m2/g. A non-aqueous storage battery was produced in the same manner as in Example 5-1, except that the activated carbon was used as the inorganic mash. [Comparative Example 5 -1 〇] A nonaqueous secondary battery was produced in the same manner as in Comparative Example 5-1 except that the positive electrode produced in Example 5-6 was used. [Measurement of the capacity retention rate] The non-aqueous storage battery of the examples and the comparative examples produced above was measured for charge and discharge characteristics using a charge/discharge measuring device (HI-101SM6 manufactured by Hokuto Denko Co., Ltd.) in a thermostat of 6 (TC). For charging and discharging conditions, the charging system is 0. 2C, to 4. 2V is charged for 8 hours, and the relevant discharge system is 0. 2C, to 2. Discharge treatment at 75 V The capacity retention ratio is the ratio of the discharge capacity at 500 cycles to the initial discharge capacity. The measurement results are shown in Table 9-82-201101560. [Table 9] Type of Dipping Material Specific Surface Area rg/m2l True Density of Activated Alumina [g/cm3l Type of Substrate Separation Capacity Capacity [%1 Example 5-1 Activated Alumina A 400 3. 1 Separator PE partition 79 Example 5-2 Activated alumina B 350 3. 0 separator PE separator 75 Example 5-3 Activated alumina A 400 3. 1 Separator PVdF/non-woven separator 73 Example 5-4 Activated alumina A 400 3. 1 Separator PVdF/PP separator (PVdF layer is positive side 76 Example 5-5 Activated alumina A 400 3. 1 Separator PVdF/PP separator (PVdF layer is the negative side) 74 Example 5-6 Activated alumina A 400 3. 1 Separator PE separator 72 Example 5-7 Activated alumina A 400 3. 1 Positive PE separator 71 Example 5-8 Activated alumina A 400 3. 1 Negative electrode PE separator 72 Example 5-9 Activated alumina A 400 3. 1 Positive surface layer PE separator 76 Example 5-10 Activated alumina A 400 3. 1 Negative electrode surface layer PE separator 75 Comparative Example 5-1 te - - - PE separator 51 Comparative Example 5-2 Μ j \ \\ - - PVdF/non-woven spacer 48 Comparative Example 5-3 Μ / \ \\ - - - PP partition 52 Comparative Example 5-4 α-oxidation Ming 7 3. 9 Separator PE separator 52 Comparative Example 5-5 Activated alumina C 60 2. 5 Separator PE separator 55 Comparative Example 5-6 Activated alumina D 200 2. 6 Separator PE separator 59 Comparative Example 5-7 Zeolite 400 - Separator PE separator 62 Comparative Example 5-8 Silica sand 300 - Separator PE separator 59 Comparative Example 5-9 Activated carbon 1600 - Separator PE partition Plate 62 Comparative Example 5-10 Μ j \ \\ - - - PE separator 42 [Performance evaluation] From the results of Examples 5-1 to 5-3 and Comparative Examples 5-1 to 5-3, it is known that the separator The examples containing activated alumina therein all have an excellent capacity retention ratio of 70% or more. However, in Comparative Examples 5-1 to 5-3 which did not contain activated alumina, the capacity retention ratio was about 50%. Further, Examples 5-3 to 5-5 were -83-201101560, and a layer containing an alumina layer was laminated on the separator, and all of the capacity retention ratios were excellent at 70%. Further, when compared with Examples 5-4 and 5-5, it was confirmed to be effective when at least one of the positive electrode and the negative electrode had a layer containing activated alumina. From the results of Examples 5-1 to 5-2 and Comparative Examples 5-4 to 5-6, it is understood that the specific surface area of the activated alumina increases, and the capacity retention amount is excellent. When the specific surface area of Comparative Example 5-6 was 200 m2/g, the effect was insufficient, and when the specific surface area of Example 5-2 was 3500 m2/g of activated alumina, it was confirmed that the effect was sufficient and active oxidation was observed. The specific surface area of aluminum is preferably 300 m 2 /g or more. Further, in Comparative Examples 5-7 and 5-8, the zeolite having a specific surface area of 300 m 2 /g or more and the cerium oxide were substituted for the activated alumina, but the capacity retention rate was 62% or less, and the excellent effect of the activated alumina was not obtained. . Further, in Comparative Examples 5 to 9 using activated carbon having a specific surface area of 1,600 m 2 /g, the capacity retention ratio was as low as 62% as compared with Examples 5-1 to 5-2. Therefore, the specific surface area is preferably 1 000 m 2 /g or less, and more preferably 500 00 m 2 /g or less. In addition, the true density is 2. 7 g/cm3 or less and 3. At 9 g/cm3, the capacity retention rate is low, being 2. 8~3. Better results are obtained in the range of 3 g/cm3. From the foregoing, it is presumed that since the surface state peculiar to the activated alumina lowers the activity of HF, the capacity retention ratio can be improved. In Examples 5-6 and Comparative Examples 5-10, in which lithium manganate was used as the positive electrode active material, an excellent result of a capacity retention ratio of 70% or more was obtained by using a separator containing activated alumina. Further, since lithium manganate was used in Comparative Example 5-1, it was easier to dissolve the metal from the positive electrode due to HF than the lithium cobaltate, and the capacity retention rate was as low as 42%. -84- 201101560 Capacity maintenance of all the examples when the electrode containing the activated alumina and the layer of the activated alumina layer laminated on the electrode surface are compared with the embodiment 5-7~5 -10 The rate is superior to 70%. This confirms that the place where the activated alumina is present is contained in the electrode or laminated on the surface of the electrode, and has an effect. When confirming the performance evaluation results described above, in order to obtain a nonaqueous battery having excellent capacity retention, it was found that the non-aqueous secondary battery contains activated alumina having a specific surface area of 0 3 00 to 1 000 m 2 /g, and the presence of activated alumina There are no special restrictions on the place. [Removal performance of HF] With respect to the nonaqueous batteries of the above-described Examples 5-1 and 5-2 and Comparative Example 5-1, after the capacity retention ratio described above was measured, the battery was decomposed and the nonaqueous electrolyte was extracted. Then, the content of HF in the electrolyte was measured. Specifically, the measurement of the HF content is carried out by measuring the capacity of the non-aqueous battery after the decomposition of the capacity, and then the ethylene carbonate and the methyl carbonate are mixed in a weight ratio of 3:7. The solution was allowed to stand for 1 week, and the HF present in the battery was extracted with a solution. Next, quaternary thymol blue (Biromothymol Blue) was used as an indicator, and titration was carried out with an aqueous sodium hydroxide solution to determine the acid concentration in the extracted solution. Finally, the obtained acid concentration is converted into the HF content (ppm) in terms of the weight of the electrolyte used in the nonaqueous battery. The measurement results of the sample are shown in Table 10 below. Further, the HF content in the electrolyte before constituting the battery was 3 Oppm ° -85 - 201101560 L ^ A ^ J HF content (ppm) Example 5-1 140 Example 5-2 150 Comparative Example 5-1 330 - From the results of Table 1, it is understood that the batteries using activated alumina in Examples 5-1 and 5-2 have a small residual amount of HF when compared with Comparative Example 5-1. It is estimated that HF can be appropriately captured by the activated alumina of the present invention. (6) Example of the sixth embodiment The sixth aspect of the present invention will be described below. Further, the measurement method of the average particle diameter, the specific surface area, the true density, the crystal structure and the element ratio, and the film thickness of the inorganic coating is as described above. [Example 6-1] A nonaqueous battery was produced in the same manner as in the above Example 5-1. [Example 6 - 2] A non-aqueous battery was produced in the same manner as in the above Example 5-2. [Example 6-3] A nonaqueous battery was produced in the same manner as in the above Example 5-3. [Example 6-4] 86 - 201101560 A non-aqueous battery was produced in the same manner as in the above Example 5-4. [Example 6-5] A non-aqueous storage battery was produced in the same manner as in the above Example 5-5. [Example 6-6] A nonaqueous battery was produced in the same manner as in the above Example 5-9.实施 [Example 6-7] A non-aqueous battery was produced in the same manner as in the above Example 5-1. [Comparative Example 6-1] A non-aqueous storage battery was produced in the same manner as in Comparative Example 5-1 described above. [Comparative Example 6 - 2 ] 非 A non-aqueous secondary battery was produced in the same manner as in the above Comparative Example 5-2. [Comparative Example 6 - 3] A non-aqueous storage battery was produced in the same manner as in the above Comparative Example 5-3. [Comparative Example 6 - 4] The average particle diameter 〇 was used except that alumina A was not used as the inorganic mash. A non-aqueous -87-201101560 battery was produced in the same manner as in Example 6-1 except that a non-porous alumina having a specific surface area of 7 m2/g (manufactured by Showa Denko Co., Ltd.; AL-l6〇SG-3) was used. Further, when the aluminum oxide E' was analyzed by Xrd, a clear peak derived from α-alumina was confirmed. [Comparative Example 6-5] A non-porous alumina ρ (manufactured by Daming Chemical Industry Co., Ltd.; C06) having an average particle diameter of 0·6 μm and a specific surface area of 15 m 2 /g was used, except that alumina crucible was not used as the inorganic crucible. In the same manner as in Example 6_: 1, a nonaqueous battery was produced. Moreover, regarding the oxidation of F, when analyzed by X R D , it is clear that there is a clear peak from the boehmite. [Comparative Example 6-6] An average particle diameter of 0 was used except that alumina A was not used as the inorganic tantalum. A non-aqueous battery was produced in the same manner as in Example 6 except that a non-porous aluminum hydroxide (manufactured by Showa Electric Co., Ltd.; H-43M) having a specific surface area of 7 m2/g was used. Further, when the aluminum hydroxide was analyzed by XRD, a clear peak derived from gibbsite was confirmed. [Comparative Example 6-7] A non-aqueous storage battery was produced in the same manner as in Comparative Example 5-7 described above. [Comparative Example 6 - 8] Except that alumina A was not used as the inorganic tantalum, a cerium oxide having an average particle diameter of 2 μηη and a specific surface area of 600 m 2 /g (manufactured by Tokai Chemical Industry Co., Ltd.; ML-6 4 4 ) was used. In the same manner as in Example 6-1, a non-aqueous battery was produced - 88 - 201101560 [Comparative Example 6 - 9] A non-aqueous storage battery was prepared in the same manner as in Comparative Example 5 - 9 [Measurement of capacity retention rate] The charge/discharge characteristics were measured using a charge and discharge measuring device (HJ-101SM6 manufactured by Hokuto Electric Co., Ltd.) in a non-aqueous system of the above-described examples and comparative examples in a thermostat of 60 ° C. The charging and discharging strips are based on 0. 2C, to 4. 2V is charged for 8 hours, related to 0. 2C, to 2. The discharge treatment was carried out at 75 V, and the capacity retention ratio was a ratio of the discharge capacity at the time of 400 cycles for the initial capacity. The measurement is shown in Figure 1 1. The battery, the company, and the charging system are expected to discharge. Table [140 °C oven test] The non-aqueous system of the above-described examples and comparative examples was stored. 2C, to 4. After 2 hours of charging treatment at 2 V, it was stored in a dryer at 140 ° C for 24 hours. As a result, when it is confirmed that there is a fire situation, it is evaluated as 〇 when there is no fire. The results are shown in Table 11. ° Battery, riot-proof ί is X, -89- 201101560 [Table η]

塡料之種類結晶構造塡料之場所隔板之麵容量維持率[%] 140°C 烤箱試驗實施例6-1 活性氧化鋁A 非晶狀隔板 ΡΕ隔板 75 〇實施例6-2 活性氧化鋁B 非晶狀隔板 ΡΕ隔板 73 〇實施例6-3 活性氧化鋁A 非晶狀隔板 PVdF/不織布隔板 75 〇實施例6-4 活性氧化鋁A 非晶狀隔板 PVdF/PP 隔板 (PVdF層爲正極側） 76 〇實施例6-5 活性氧化鋁A 非晶狀隔板 PVdF/PP 隔板 (PVdF層爲負極側） 73 〇實施例6-6 活性氧化鋁A 非晶狀正極表面層 PE隔板 74 〇實施例6-7 活性氧化鋁A 非晶狀負極表面層 PE隔板 73 〇比較例6-1 無 - - PE隔板 54 X 比較例6-2 Μ j\\\ - - PVdF/不織布隔板 54 〇比較例6-3 Μ j\w - - PP隔板 52 〇比較例6-4 氧化銘E α-氧化鋁隔板 PE隔板 57 X 比較例6-5 氧化鋁F 勃姆石隔板 PE隔板 58 X 比較例6-6 氫氧化銘三水鋁石隔板 PE隔板 54 X 比較例6-7 沸石 - 隔板 PE隔板 63 X 比較例6-8 二氧化矽 - 隔板 PE隔板 63 X 比較例6-9 活性碳 - 隔板 PE隔板 62 XType of Dip Material Crystal Structure Tendency Site Area Capacity Maintenance Rate [%] 140°C Oven Test Example 6-1 Activated Alumina A Amorphous Separator ΡΕ Separator 75 〇 Example 6-2 Activity Alumina B Amorphous separator ΡΕ separator 73 〇 Example 6-3 Activated alumina A Amorphous separator PVdF/non-woven separator 75 〇 Example 6-4 Activated alumina A Amorphous separator PVdF/ PP separator (PVdF layer is positive side) 76 〇Example 6-5 Activated alumina A Amorphous separator PVdF/PP separator (PVdF layer is negative side) 73 〇Example 6-6 Activated alumina A Crystalline positive electrode surface layer PE separator 74 〇 Example 6-7 Activated alumina A Amorphous negative electrode surface layer PE separator 73 〇 Comparative Example 6-1 None - - PE separator 54 X Comparative Example 6-2 Μ j \\\ - - PVdF/non-woven partition 54 〇Comparative example 6-3 Μ j\w - - PP partition 52 〇Comparative example 6-4 Oxidation Ming E α-alumina separator PE partition 57 X Comparative example 6 -5 Alumina F Boehmite separator PE separator 58 X Comparative Example 6-6 Hydroxide gibbsite separator PE separator 54 X Comparative Example 6-7 Zeolite - Separator PE separator 63 X ratio Examples 6-8 silicon dioxide - PE separator separator 63 X Comparative Examples 6-9 Activated carbon - PE separator separator 62 X

[性能評估] 於表1 1中，由實施例6 - 1〜6 - 2及比較例6 - 1〜6 - 6之結果可知，在隔板中含有非晶狀氧化鋁之構成時，具有70% 以上之優異的容量維持率。不含塡料之比較例6-1〜6-3，容量維持率爲60%以下之低値。另外，藉由14(TC之烤箱試驗，確認實施例6- 1〜6-2沒有發火的情形，而確認比較例 6-1有發火情形，可知實施例6-1〜6-2在內部短路之安全性亦優異。而且，比較氧化鋁之構造時，具有非晶狀以外之構造的比較例6-4〜6-6，容量維持率爲60%以下之低値，且於 1 4(TC之烤箱試驗中確認有發火情形。藉此可知，非晶狀 -90- 201101560 氧化鋁之循環特性與內部短路之安全性等兩者皆優異。此外’評估比較例6-7〜6-9中作爲其他無機塡料之沸石、二氧化矽、活性碳，與實施例6 - ；!〜6 - 2相比時，容量維持率爲稍大於60%之低値，於！40t之烤箱試驗中確認有發火情形。由此可知，添加的無機塡料爲非晶狀氧化鋁時優異。氧化鋁之存在場所，使實施例6 -1〜6 - 8相比時，全部皆容量維持率爲70%以上係優異，於烤箱試驗中亦沒有發火情形’可知非晶狀氧化鋁之存在場所存在於正極與負極間之任何部位時’循環特性與內部短路之安全性優異。 [熱收縮率之測定] 爲調查140 °C烤箱試驗中是否有發火情形的原因時，有關實施例6 - 1〜6 - 2、及比較例6 -1、6 - 4〜6 - 9之隔板，測定熱收縮率。具體而言，先將由試料所形成的隔板朝l8cm ( MD方向）x6cm ( TD )方向切出。在TD方向分爲2等份的線上，由上至下距離2cm、17cm之處（點A、點B )上附加記號。而且，在MD方向分爲2等份的線上，由左至右之lcm、5cm 之處附加記號。於其上使用夾子，置於調整爲1〇5 °C之烤箱中’在無張力下進行熱處理30分鐘。在熱處理前後測定 2點AB間、CD間長度，且以下述2式求取熱收縮率。有關各試料之測定結果’如表1 2所示。 MD方向熱收縮率=(熱處理前之ab間長度-熱處理 -91 - 201101560 後之AB間長度）/ (熱處理前之AB間長度）χΐ 〇〇 TD方向熱收縮率=(熱處理前之CD間長度-熱處理後之CD間長度）/(熱處理前之CD間長度）xl 〇〇 [表 12] 熱收縮率 MD方向[%] TD方向[%] 實施例6-1 13 2 實施例6-2 12 2 比較例6-1 30 5 比較例6-4 21 3 比較例6-5 24 4 比較例6·6 22 4 比較例6-7 27 3 比較例6-8 24 4 赚例6-9 25 4 由表1 2可知，在1 4 0 °C烤箱試驗中沒有發火情形之實施例6-1〜6-2，熱收縮率於MD方向爲15 %以下，有關TD方向爲2%之低値。對此而言，不含塡料之比較例6-1、除非晶狀外之氧化鋁或氫氧化鋁的比較例6-4〜6-6，以及除氧化鋁外之塡料的比較例6-7〜6-9，MD方向之熱收縮率爲 20%以上，TD方向之熱收縮率爲3%以上，與實施例6-1〜 6-2相比時爲較高値。因此，推測熱收縮率在MD方向爲 20%以上、TD方向爲3%以上時，於140 °C烤箱試驗中非水系蓄電池內隔板有破裂情形，因內部短路而引起發火情形〇由前述之性能評估結果可知，爲製得容量維持率優異 -92- 201101560 、且在1 4(TC烤箱試驗中沒有發火情形之安全性優異的非水系蓄電池時，在負極與正極之間含有非晶狀氧化鋁較佳[Performance Evaluation] In Table 1, it is understood from the results of Examples 6-1 to 6-2 and Comparative Examples 6-1 to 6-6 that when the separator contains amorphous alumina, it has 70 Excellent capacity retention rate above %. Comparative Examples 6-1 to 6-3 containing no dip, the capacity retention rate was as low as 60% or less. Further, it was confirmed by the oven test of 14 (TC) that the examples 6-1 to 6-2 did not ignite, and it was confirmed that the comparative example 6-1 had a case of ignition, and it was found that the examples 6-1 to 6-2 were short-circuited internally. In addition, when comparing the structure of alumina, Comparative Examples 6-4 to 6-6 having a structure other than an amorphous shape have a capacity retention ratio of 60% or less, and are at 14 (TC). In the oven test, it was confirmed that there was a fire. It was found that both the amorphous-90-201101560 alumina cycle characteristics and the safety of the internal short circuit were excellent. Further, 'Evaluation Comparative Examples 6-7 to 6-9 As another inorganic cerium zeolite, cerium oxide, activated carbon, when compared with Example 6 -;!~6-2, the capacity retention rate is slightly more than 60%, which is confirmed in the oven test of 40 ton. In the case of a fire, it is understood that the inorganic binder added is excellent in amorphous alumina. When the alumina is present, the capacity retention rate is 70% when compared with Examples 6-1 to 6-8. The above is excellent, and there is no ignition in the oven test. 'The existence of amorphous alumina exists. When it is in any part between the positive electrode and the negative electrode, the safety of the cycle characteristics and the internal short circuit is excellent. [Measurement of heat shrinkage rate] In order to investigate whether there is a cause of ignition in the 140 °C oven test, the relevant embodiment 6-1~ 6 - 2, and Comparative Example 6 -1, 6 - 4 to 6 - 9 of the separator, the heat shrinkage rate was measured. Specifically, the separator formed by the sample was first oriented in the direction of l8 cm (MD direction) x 6 cm (TD) Cut out. In the TD direction, the line is divided into 2 equal parts, and the mark is added from the top to the bottom of the distance of 2cm and 17cm (point A, point B). Moreover, the line divided into 2 equal parts in the MD direction is left. Add a mark to the right lcm, 5cm. Use a clip on it and place it in an oven adjusted to 1〇5 °C. Heat treatment under tension for 30 minutes. Determine between 2 points of AB and CD before and after heat treatment. The length is determined by the following formula: The measurement result of each sample is shown in Table 12. The MD direction heat shrinkage rate = (the length of the ab before the heat treatment - the heat treatment -91 - 201101560) Length) / (length between AB before heat treatment) χΐ 〇〇 TD direction heat shrinkage rate = (CD before heat treatment) Length - length between CDs after heat treatment) / (length between CDs before heat treatment) xl 〇〇 [Table 12] Heat shrinkage rate MD direction [%] TD direction [%] Example 6-1 13 2 Example 6-2 12 2 Comparative Example 6-1 30 5 Comparative Example 6-4 21 3 Comparative Example 6-5 24 4 Comparative Example 6·6 22 4 Comparative Example 6-7 27 3 Comparative Example 6-8 24 4 Earnings 6-9 25 4 As can be seen from Table 12, in Examples 6-1 to 6-2 where there was no ignition in the oven test at 140 °C, the heat shrinkage rate was 15% or less in the MD direction, and the TD direction was 2%. . In this regard, Comparative Example 6-1 without the dip, Comparative Examples 6-4 to 6-6 of the alumina or aluminum hydroxide except the crystal, and Comparative Example 6 of the dice except the alumina -7 to 6-9, the heat shrinkage ratio in the MD direction was 20% or more, and the heat shrinkage ratio in the TD direction was 3% or more, which was higher than that in Examples 6-1 to 6-2. Therefore, when the heat shrinkage rate is 20% or more in the MD direction and 3% or more in the TD direction, the separator in the non-aqueous battery in the oven test at 140 °C is broken, and the ignition is caused by the internal short circuit. As a result of the performance evaluation, it is known that in order to obtain a non-aqueous battery excellent in capacity retention rate - 92 - 201101560 and excellent in safety in the case of no fire in the TC oven test, amorphous oxidation is contained between the negative electrode and the positive electrode. Aluminum is better

-93--93-

Claims

201101560 VII. Patent application range: 1 . A porous film for a non-aqueous battery, comprising a porous film for a non-aqueous battery comprising a heat-resistant resin and an inorganic material, wherein the inorganic material has an average particle diameter of 〇〜5. 〇μπι, and a porous material having a specific surface area of 4 〇 to 3 〇 00 m 2 /g. 2. The porous film for a non-aqueous battery according to the first aspect of the invention, wherein the porous material is an active alumina having a specific surface area of 3 〇〇 1 〇〇〇 m2 / g. A non-aqueous battery porous film comprising a heat-resistant resin and an inorganic material, wherein the inorganic material is an amorphous oxide particle. 4. A non-aqueous storage battery comprising a non-aqueous battery including at least a positive electrode and a negative electrode, wherein a surface of at least one of the positive electrode and the negative electrode is formed on the surface of any one of claims 1 to 3 of the patent application. A porous film for a water-based battery or a porous film for a non-aqueous battery is used as a separator. (5) A non-aqueous battery separator comprising a porous substrate and a non-aqueous system laminated on one surface of the porous substrate or a heat-resistant porous layer containing a heat-resistant resin and an inorganic material on both surfaces The separator for a battery is characterized in that the inorganic tantalum is a porous tantalum having an average particle diameter of 0.1 to 5·0 μm and a specific surface area of 40 to 3 000 m 2 /g. 6. The separator for a non-aqueous battery according to claim 5, wherein the porous tantalum is an active alumina having a specific surface area of 300 to 1000 m2/g. -94-201101560 7. A non-aqueous battery separator comprising a porous substrate, a heat-resistant porous material comprising a heat-resistant resin and an inorganic coating laminated on one surface or both surfaces of the porous substrate The separator for a non-aqueous battery according to the layer is characterized in that the inorganic tantalum is amorphous alumina particles. 8. A non-aqueous battery comprising a non-aqueous battery according to any one of claims 5 to 7 as a non-aqueous battery, wherein the non-aqueous battery is used as the separator. . An adsorbent for a non-aqueous battery, which is an adsorbent for hydrogen fluoride mixed in a non-aqueous battery, characterized in that the adsorbent is an activated alumina particle having a specific surface area of 300 to 100 m 2 /g. . 1 . An adsorbent for a non-aqueous battery, which is an adsorbent for hydrogen fluoride mixed in a non-aqueous battery, characterized in that the adsorbent is amorphous alumina particles. A porous film for a non-aqueous battery comprising a porous film for a non-aqueous battery comprising an inorganic coating material and a binder resin, which is characterized by containing a non-aqueous battery for adsorption according to claim 9 or 10 of the patent application. The agent 〇v/ is used as the aforementioned inorganic mash. I2. A non-aqueous battery separator comprising a porous substrate and a non-aqueous battery that is laminated on one surface of the porous substrate or a porous layer containing inorganic binder and binder resin on both surfaces The separator is characterized in that it contains the adsorbent for a nonaqueous battery according to the ninth or tenth aspect of the patent application as the inorganic tantalum. A non-aqueous storage battery comprising a positive electrode, a negative electrode, a non-aqueous electrolyte, and a separator, wherein the battery comprises a non-aqueous battery according to claim 9 or i. Adsorbent. -95- 201101560 IV. Designated representative map: (1) The representative representative of the case is: None (2) The symbol of the representative figure is simple: No

〇 201101560 V If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: none