TW201036230A - Electrochemical element - Google Patents

Electrochemical element Download PDF

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Publication number
TW201036230A
TW201036230A TW098137609A TW98137609A TW201036230A TW 201036230 A TW201036230 A TW 201036230A TW 098137609 A TW098137609 A TW 098137609A TW 98137609 A TW98137609 A TW 98137609A TW 201036230 A TW201036230 A TW 201036230A
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porous layer
negative electrode
separator
electrochemical element
temperature
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TW098137609A
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Chinese (zh)
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TWI390788B (en
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Keisuke Yoneda
Akira Yamashita
Fusaji Kita
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Hitachi Maxell
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/52—Separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/02—Diaphragms; Separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Secondary Cells (AREA)
  • Cell Separators (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

Disclosed is an electrochemical element comprising a positive electrode, a negative electrode, a nonaqueous electrolysis solution, and a separator. The separator comprises a porous layer (I) formed of a microporous film composed mainly of a thermoplastic resin and a porous layer (II) composed mainly of a filler having a heat resistant temperature of 150 DEG C or above. The porous layer (II) faces at least the positive electrode. The negative electrode contains a graphite as a negative electrode active material that has an R value, defined as a peak intensity ratio of a peak intensity at 1360 cm-1 to a peak intensity at 1580 cm-1 in an argon ion laser Raman spectrum, i.e., I1360/I1580, of 0.1 to 0.5 and has a spacing of (002) plane (d002) of not more than 0.338 nm. The content of the graphite in the negative electrode active material is not less than 30% by mass.

Description

201036230 六、發明說明： 【發明所屬之技術領域】 本發明關於過充電時的安全性及在低溫的充電特性優 異之電化學元件。 【先前技術】 鋰蓄電池等的電化學元件，由於能量密度高的特徵， Ο 故廣用作爲攜帶式電話或筆記型個人電腦等的攜帶機器之 電源。例如’於鋰蓄電池中’隨著攜帶機器的高性能，有 更往高容量化前進的傾向，安全性的確保係成爲重要。 於現行的鋰蓄電池中’作爲在正極與負極之間所存在 的隔板中’例如使用厚度爲20〜30μιη左右的聚烯烴系微 多孔膜。又’作爲隔板的原材料，爲了確保在電池的熱失 控溫度以下使隔板的構成樹脂熔融而堵塞空孔，藉此使電 池的內部電阻上升，而在短路之際等使電池的安全性提高 〇 之所謂停機效果，有採用熔點低的聚乙烯。 不過，作爲如此的隔板，例如爲了多孔化及強度提高 ，使用經一軸拉伸或二軸拉伸的薄膜。如此的隔板，爲了 供應作爲單獨存在的膜，在作業性等之點要求一定的強度 ，藉由上述拉伸來確保此。但是，於如此的拉伸薄膜中， 由於結晶化度增大，停機溫度亦升高到接近電池的熱失控 溫度之溫度爲止，用於確保電池的安全性之容限（margin )係難以說是充分。 又，由於上述拉伸而在薄膜發生應變，若此暴露於高 -5- 201036230 溫中’有因殘留應力而發生收縮的問題。收縮溫度係非常 接近熔點，即停機溫度。因此，使用聚烯烴系的微多孔膜 隔板時，在充電異常時等若電池溫度達到停機溫度，則必 須立刻減少電流而防止電池的溫度上升。此係因爲當不充 分堵塞空孔而無法立刻減少電流時，由於電池的溫度容易 上升到隔板的收縮溫度爲止，有內部短路的危險性。 作爲防止如此隔板的熱收縮所致的短路，而提高電池 的可靠性之技術，例如有提案使用一種多孔質的隔板來構 成電化學元件，該多孔質的隔板具有含以用於確保停機機 能的樹脂當作主體之第1隔板層、與含以耐熱溫度爲 1 5 0 °C以上的塡料當作主體之第2隔板層（專利文獻1 )。 若依照專利文獻1的技術，可提供即使在異常過熱之 際，也難以發生熱失控而安全性優異的鋰蓄電池等之電化 學元件。 又’於鋰蓄電池等的電化學元件中，如上述之安全性 以外的特性提高亦有各種檢討。例如，專利文獻2、3中 揭示’藉由使用表面經結晶性低的碳材料所被覆的負極活 性物質，可增大容量，而且減小初期充放電循環時的不可 逆容量，提高充放電循環的容量維持率，更可大幅改良急 速充放電特性。 先前技術文獻 [專利文獻1]國際公開第20〇7/66768號公報 [專利文獻2]特開2000-223120號公報 [專利文獻3]特開2000-340232號公報 201036230 【發明內容】 發明所欲解決的問題 可是’在最近的鋰蓄電池等之電化學元件中，隨著 採用的機器之高性能化’例如有謀求高容量化的傾向， 是與此之同時’對於過充電的安全性亦要求可確保更高 水平。專利文獻1中所揭示的電化學元件，雖然對於過 電的安全性亦良好’但是亦預料將來會要求更超越此的 Ο 術。 又’若考慮在各式各樣的溫度環境下使用電化學元 ’則要求即使在電化學元件之反應性低的低溫環境下， 具備實用上沒有障礙的充電特性。 本發明係鑑於上述情事而完成者，提供過充電時的 全性與在低溫的充電特性優異之電化學元件。 解決問題的手段 〇 本發明的電化學元件係含有正極、負極、非水電解 及隔板的電化學元件，其特徵爲：上述隔板具有以熱塑 樹脂當作主體的微多孔膜所成的多孔質層（I)、與含 以耐熱溫度爲1 50°C以上的塡料當作主體的多孔質層（ )，上述多孔質層（II)係至少面向正極，上述負極含 在氬離子雷射拉曼光譜中相對於ISSOcnr1的尖峰強度 言’ 1 360cm·1的尖峰強度比之R値爲0.1〜0.5、且002 的面間隔心。2爲0.33 8nm以下的石墨當作負極活性物質 上述負極活性物質中的上述石墨之比例爲30質量％以上 所 但 的 充 技 件 也 安 液 性 有 II 有 而 面 201036230 發明的效果 若依照本發明，可提供過充電時的安全性與在低溫（ 尤其〇 °c以下的低溫）的充電特性優異之電化學元件。 【實施方式】 實施發明的形態 本發明的電化學元件使用一種負極，其含有在氬離子 雷射拉曼光譜中相對於1580 cm·1的尖峰強度而言， 1360cnT1的尖峰強度比之R値爲〇.1〜0.5、且002面的面 間隔dQ()2爲0.3 3 8nm以下的石墨當作負極活性物質，上述 負極活性物質中的上述石墨之比例爲3 0質量％以上。藉由 使用含有上述負極活性物質的負極，可在電化學元件之反 應性降低的低溫（例如0°c以下的低溫）中維持優異的充 電特性。 又，本發明者們重複專心致力的檢討，結果發現藉由 對含有上述負極活性物質的負極，組合厚度薄、孔徑寬的 隔板，可更發揮用含有上述負極活性物質的負極所致的效 果。但是，若僅減薄隔板的厚度，由於無法確保隔板的強 度’故在本發明中，決定使用具有以熱塑性樹脂當作當作 主體的微多孔膜所成的多孔質層（I)、與含有耐熱溫度 爲150°c以上的塡料當作主體的多孔質之多孔質層（II) 之隔板。藉此，可一邊確保隔板的形狀安定性與過充電時 的安定性，一邊提高使用上述負極所致的效果。 再者，於本發明中，以多孔質層（II)至少面向正極 -8- 201036230 的方式，配置隔板。藉此，可抑制在過充電時隔板之氧化 降解。 於本發明的電化學元件中，藉由上述各作用’可一邊 確保過充電時的安全性，一邊謀求在低溫（尤其0°c以下 的低溫）之特性提高。 再者，除了後述的多孔質基體以外，本說明書中所言 的「耐熱溫度爲150°C以上」係意味在至少15〇°C中’沒有 〇 看到軟化等的變形。 又，本說明書中所言的多孔質層（I)之「以熱塑性 樹脂當作主體」，係意味以多孔質層（I)內的固體成分 比率計，熱塑性樹脂的樹脂（A )係50體積％以上。再者 ，本說明書中所言的多孔質層（II)之「含有以耐熱溫度 爲150°C以上的塡料當作主體」，係意味以層內的固體成 分比率（惟，在具有後述的多孔質基體之情況中，係多孔 質基體以外的固體成分比率）計，耐熱溫度爲1 5 0°C以上 Ο 的塡料係5 0體積％以上。 本發明的電化學元件係沒有特別的限定，除了非水電 解液的鋰蓄電池，亦包含有鋰蓄電池或超級電容器等，特 佳可使用於在過充電時或高溫要求安全性的用途。 以下說明本發明的電化學元件之各構成要素。首先， 在此詳細說明本發明的電化學元件所用的隔板。 隔板的多孔質層（I)主要係用於確保停機機能。當 本發明的電化學元件之溫度達到多孔質層（I )之主體成 分的熱塑性樹脂[以下稱爲樹脂（a )]之熔點以上時，多 -9 - 201036230 孔質層（I )的樹脂（A )係熔融而堵塞隔板的空孔，發生 抑制電化學反應的進行之停機。 又，隔板的多孔質層（II )，係具備即使在電化學元 件的內部溫度上升之際，也可防止正極與負極的直接接觸 所致的短路之機能者，藉由耐熱溫度爲150 °C以上的塡料 ，可確保其機能。即，當電化學元件成爲高溫時，即使多 孔質層（I)進行收縮，藉由不易收縮的多孔質層（II)， 也可防止在隔板熱收縮時所能發生的正負極之直接接觸所 致的短路。又，如後述地，當多孔質層（I)與多孔質層 (11 )係一體化構成時，此耐熱性的多孔質層（11 )係具 有當作隔板的骨架之作用，可抑制多孔質層（I)的熱收 縮，即隔板全體的熱收縮。 多孔質層（I)的樹脂（A)，只要是具有電絕緣性， 電化學上安定，而且在以下詳述的電化學元件所具有的非 水電解液、或隔板製造之際所使用的溶劑（詳如後述）中 安定的熱塑性樹脂即可，而沒有特別的限制，較佳爲聚乙 烯（PE)、聚丙烯（PP)、乙烯-丙烯共聚物等的聚烯烴 ，聚對苯二甲酸乙二酯或共聚合聚酯等的聚酯等。 再者，本發明的隔板較佳爲在8 0 °c以上1 5 〇 °C以下（ 更佳爲1 〇〇 °C以上）中’具有將其孔堵塞的性質（即停機 機能）。因此，多孔質膜（I )更佳係以熔點，即依照曰 本工業規格（JIS) K 7121的規定，使用差示掃描熱量計 (D S C )所測定的熔解溫度爲8 0 °C以上1 5 0 °C以下（更佳 爲1 00°C以上）的熱塑性樹脂當作其構成成分者，較佳係 -10- 201036230 以PE當作主成分的單層之微多孔膜，或層合有2〜5層的 PE與PP之積層微多孔膜等。 當倂用如P E之熔點爲8 0 °C以上1 5 0 °C以下的熱塑性 樹脂、與如P P等之熔點超過1 5 0 °C的熱塑性樹脂來構成多 孔質層（I )時，例如以混合PE與PP等之比PE還高熔點 的樹脂所構成的微多孔膜當作多孔質層（I )，或以層合 PE層與PP層等之比PE還高熔點的樹脂所構成的層而構 Ο 成的積層微多孔膜當作多孔質層（I)時，在構成多孔質 層（I )的樹脂（A )中，熔點爲8 0 °c以上1 5 (TC以下的樹 月旨（例如PE )較佳係30質量％以上，更佳係50質量％以 上。 作爲如上述的微多孔膜，例如可用以習知的鋰蓄電池 等所使用的上述例示之熱塑性樹脂所構成的微多孔膜，即 藉由溶劑萃取法、乾式或濕式拉伸法等所製作的離子透過 性之微多孔膜。 0 又，於多孔質層（I)中，在不損害對隔板賦予停機 機能的作用之範圍內，爲了提高其強度等，亦可含有塡料 等。作爲多孔質層（I )中所可使用的塡料，例如可舉出 與後述的多孔質層（II)中所可用的塡料（耐熱溫度爲 1 5 (TC以上的塡料）相同者。 塡料的粒徑，以平均粒徑而言，例如較佳爲0.01 μπι 以上，更佳爲〇·1 μιη以上，較佳爲ΙΟμιη以下，更佳爲 1 μιη以下。再者，本說明書中所言的平均粒徑係可規定作 爲，例如使用雷射散射粒度分布計（例如Η Ο RIΒ Α公司製 -11 - 201036230 「LA-920」）’將在不溶解塡料溶解的介質中，使此等微 粒子分散而測定的數平均粒子徑。關於後述的多孔質層（ 11 )之塡料，亦相同。 藉由具備如上述的構成之多孔質層（I)，可容易對 隔板賦予停機機能，在電化學元件的內部溫度上升時，可 容易達成安全性的確保。 多孔質層（I)中的樹脂（A)含量，爲了更容易得到 停機效果，例如較佳爲如下述。在多孔質層（I )的全部 構成成分中，主體的樹脂（A )之體積係50體積％以上， 更佳係70體積％以上，也可爲1 〇〇體積％。再者，由後述 方法所求得的多孔質層（II )之空孔率係20〜60%，而且 樹脂（A )的體積較佳係多孔質層（II )的空孔體積之 5 0%以上。 多孔質層（II)中的塡料，只要是耐熱溫度爲15 0°C 以上’在電化學元件所具有的電解液中安定，而且在電化 學元件的作動電壓範圍中不易氧化還原而電化學上安定者 ’則可爲有機粒子或無機粒子，從分散等之點來看，較佳 係微粒子，從安定性（尤其耐氧化性）等之點來看，更佳 爲使用無機微粒子。 作爲無機粒子的構成材料之具體例，例如可舉出氧化 鐵、Al2〇3 (氧化鋁）、Si〇2 (矽石）、Ti〇2、BaTi〇3、 Zr02等的無機氧化物，氮化鋁、氮化矽等的無機氮化物， 氟化鈣、氟化鋇、硫酸鋇等的難溶性離子鍵結性化合物， 砂、金鋼石等的共價性化合物，蒙脫石等的黏土等。此處 •12- 201036230 ，上述無機氧化物亦可爲勃姆石、沸石、磷灰石、高嶺土 、模來石、尖晶石、橄欖石、雲母等的礦物資源而來的物 質或此等的人造物等。又’亦可爲對以金屬、Sn02、錫-銦氧化物（ITO )等的導電性氧化物、碳黑、石墨等的碳 質材料等所例示的導電性材料之表面，用具有電絕緣性的 材料（例如上述無機氧化物等）來被覆而使具有電絕緣性 的粒子。作爲無機粒子，從更提高多孔質層（II)的耐氧 〇 化性之觀點來看，較佳爲上述無機氧化物的粒子（微粒子 )，其中較佳爲氧化鋁、矽石及勃姆石等的板狀粒子。 又，作爲有機粒子（有機粉末），可例示交聯聚甲基 丙烯酸甲酯、交聯聚苯乙烯、交聯聚二乙烯基苯、苯乙 烯-二乙烯基苯共聚物交聯物、聚醯亞胺、蜜胺樹脂、酚 樹脂、苯并胍胺-甲醛縮合物等的各種交聯高分子粒子、 或聚颯、聚丙烯腈、芳香族聚醯胺、聚縮醛、熱塑性聚醯 亞胺等的耐熱性高分子粒子等。又，構成此等有機粒子的 ® 有機樹脂（高分子）亦可爲上述例示的材料之混合物、改 性體、衍生物、共聚物（無規共聚物、交替共聚物、嵌段 共聚物、接枝共聚物）、交聯體（上述耐熱性高分子的情 況）。 作爲耐熱溫度1 5〇°C以上的塡料之形態，例如可爲具 有接近球狀的形狀，也可具有板狀的形狀，較佳爲多孔質 層（II)中所含有的上述塡料之至少一部分係板狀粒子。 上述塡料的全部也可爲板狀粒子。由於多孔質層（η )含 有板狀粒子，即使在多孔質層（π)與多孔質層（I) 一體 -13- 201036230 化時，也可藉由板狀粒子彼此的衝突’而抑制多孔質膜（ I)的收縮力。又，藉由使用板狀粒子’隔板中的正極負 極間之路徑，即所謂曲路率會變大。因此，即使生成樹枝 狀結晶時，該樹枝狀結晶難以由負極到達正極’可提高對 於樹枝狀結晶短路而言的可靠性。 作爲板狀的上述塡料，可舉出各種市售品，例如旭硝 子SI科技公司製「Sunlovery(商品名）」（Si〇2)、石 原產業公司製「NST-B1 (商品名）」的粉碎品（Ti02 )、 堺化學工業公司製的板狀硫酸鋇「Η系列（商品名）」、 「HL系列（商品名）」、林化成公司製「Micronwhite ( 商品名）」（滑石）、林化成公司製「Bengel (商品名） 」（膨土）、河合石灰公司製「BMM (商品名）」或「 BMT (商品名）」（勃姆石）、河合石灰公司製「201036230 VI. Description of the Invention: [Technical Field] The present invention relates to an electrochemical element which is excellent in safety at the time of overcharge and excellent in charging characteristics at a low temperature. [Prior Art] Electrochemical elements such as lithium batteries have a high energy density and are widely used as power sources for portable devices such as portable telephones and notebook personal computers. For example, in the lithium battery, the higher the capacity of the portable device, the higher the capacity is, and the safety is ensured. In the conventional lithium secondary battery, 'as a separator existing between the positive electrode and the negative electrode', for example, a polyolefin-based microporous film having a thickness of about 20 to 30 μm is used. In addition, in order to ensure that the resin of the separator is melted to block the pores below the thermal runaway temperature of the battery, the internal resistance of the battery is increased, and the safety of the battery is improved during a short circuit. The so-called shutdown effect of 〇 has a low melting point of polyethylene. However, as such a separator, for example, for the purpose of porosification and strength improvement, a film which is subjected to monoaxial stretching or biaxial stretching is used. Such a separator is required to have a certain strength at the point of workability or the like in order to supply a film which is present alone, and this is ensured by the above stretching. However, in such a stretched film, since the degree of crystallization increases and the shutdown temperature rises to a temperature close to the thermal runaway temperature of the battery, the margin for ensuring the safety of the battery is difficult to say. full. Further, strain is generated in the film due to the above stretching, and if it is exposed to a high temperature of -5 - 201036230, there is a problem that shrinkage occurs due to residual stress. The shrinkage temperature is very close to the melting point, which is the shutdown temperature. Therefore, when a polyolefin-based microporous membrane separator is used, if the battery temperature reaches the shutdown temperature during charging abnormality, the current must be immediately reduced to prevent the temperature of the battery from rising. This is because when the current cannot be reduced immediately without clogging the pores, there is a risk of internal short-circuiting because the temperature of the battery easily rises to the contraction temperature of the separator. As a technique for preventing the short circuit caused by the heat shrinkage of the separator and improving the reliability of the battery, for example, it is proposed to use a porous separator to constitute an electrochemical element, and the porous separator has a content for ensuring The resin of the shutdown function is used as the first separator layer of the main body and the second separator layer containing the crucible having a heat resistance temperature of 150 ° C or higher as a main component (Patent Document 1). According to the technique of Patent Document 1, it is possible to provide an electrochemical cell such as a lithium secondary battery which is less likely to cause thermal runaway and is excellent in safety even in the case of abnormal overheating. Further, in an electrochemical device such as a lithium secondary battery, there have been various reviews for improving the characteristics other than the above-described safety. For example, Patent Literatures 2 and 3 disclose that by using a negative electrode active material coated with a carbon material having a low crystallinity, the capacity can be increased, and the irreversible capacity at the initial charge and discharge cycle can be reduced, and the charge and discharge cycle can be improved. The capacity retention rate can greatly improve the rapid charge and discharge characteristics. [Patent Document 1] [Publication No. 2000-223120] [Patent Document 3] JP-A-2000-340232A Publication No. 200036230 The problem to be solved is that, in the electrochemical devices such as the lithium-ion battery, the performance of the device to be used has increased in productivity, for example, at the same time as the safety of overcharging. Can ensure a higher level. The electrochemical element disclosed in Patent Document 1 is good in safety for over-electricity, but it is expected that a more advanced technique will be required in the future. Further, when it is considered to use an electrochemical element in various temperature environments, it is required to have a charging characteristic which is practically unobstructed even in a low-temperature environment in which the reactivity of the electrochemical element is low. The present invention has been made in view of the above circumstances, and provides an electrochemical element excellent in overcharge and excellent in charging characteristics at low temperatures. Means for Solving the Problem The electrochemical device of the present invention comprises an electrochemical element comprising a positive electrode, a negative electrode, a non-aqueous electrolysis and a separator, wherein the separator has a microporous membrane mainly composed of a thermoplastic resin. a porous layer (I) and a porous layer ( ) having a heat-resistant temperature of 150 ° C or higher as a main component, wherein the porous layer (II) is at least facing the positive electrode, and the negative electrode is contained in an argon ion In the Raman spectrum, the intensity of the peak relative to the ISSOcnr1 is '1 360 cm·1, and the R 値 is 0.1 to 0.5, and the surface separation of 002. 2 is 0.33 8 nm or less of graphite as a negative electrode active material, and the ratio of the above-mentioned graphite in the negative electrode active material is 30% by mass or more, but the charging material is also liquid-repellent, and the surface of the invention is 201036230. According to the present invention, It can provide safety in over-charging and electrochemical components excellent in charging characteristics at low temperatures (especially low temperatures below 〇°c). [Embodiment] Embodiment of the Invention The electrochemical device of the present invention uses a negative electrode containing a peak intensity ratio of 1360cnT1 in the argon ion laser Raman spectrum with respect to a peak intensity of 1580 cm·1. The graphite having a surface spacing dQ()2 of 002 is 0.33 8 nm or less is used as the negative electrode active material, and the ratio of the graphite in the negative electrode active material is 30% by mass or more. By using the negative electrode containing the above negative electrode active material, excellent charging characteristics can be maintained at a low temperature (e.g., a low temperature of 0 ° C or lower) at which the reactivity of the electrochemical device is lowered. In addition, the inventors of the present invention have repeatedly conducted an intensive review, and found that by combining a negative electrode having a small thickness and a wide pore diameter with a negative electrode containing the negative electrode active material, the effect of using the negative electrode containing the negative electrode active material can be further exhibited. . However, in the present invention, it is decided to use a porous layer (I) having a microporous film having a thermoplastic resin as a main body, and the thickness of the separator is not reduced, so that the strength of the separator cannot be ensured. A separator which is a porous porous layer (II) having a heat-resistant temperature of 150 ° C or more as a main component. Thereby, the effect of using the above negative electrode can be improved while ensuring the shape stability of the separator and the stability at the time of overcharge. Further, in the present invention, the separator is disposed such that the porous layer (II) faces at least the positive electrode -8 to 201036230. Thereby, oxidative degradation of the separator during overcharge can be suppressed. In the electrochemical device of the present invention, it is possible to improve the characteristics at a low temperature (especially a low temperature of 0 ° C or less) while ensuring safety at the time of overcharge by the above-mentioned respective actions. In addition, the "heat-resistant temperature of 150 ° C or more" as used in the present specification means that, in at least 15 ° C, no deformation such as softening is observed in addition to the porous substrate described later. In the porous layer (I) described in the present specification, "the thermoplastic resin is mainly used" means that the resin (A) of the thermoplastic resin is 50 by volume based on the solid content ratio in the porous layer (I). %the above. In addition, the "layer containing a heat-resistant temperature of 150 ° C or more as a main component" in the porous layer (II) as used in the present specification means a solid content ratio in a layer (however, it has a later description) In the case of the porous substrate, the ratio of the solid content other than the porous matrix is 50% by volume or more of the heat-resistant temperature of 150 ° C or more. The electrochemical element of the present invention is not particularly limited, and a lithium secondary battery other than the non-aqueous electrolyte solution also includes a lithium secondary battery or a supercapacitor, and the like, and is preferably used for applications requiring safety at the time of overcharging or high temperature. Hereinafter, each constituent element of the electrochemical device of the present invention will be described. First, the separator used in the electrochemical device of the present invention will be described in detail herein. The porous layer (I) of the separator is mainly used to ensure shutdown performance. When the temperature of the electrochemical element of the present invention reaches the melting point of the thermoplastic resin (hereinafter referred to as the resin (a)) which is the main component of the porous layer (I), the resin of the porous layer (I) is more than 9 - 201036230 ( A) The pores which are melted to block the separator, and the shutdown of the electrochemical reaction is inhibited. In addition, the porous layer (II) of the separator has a function of preventing short-circuiting caused by direct contact between the positive electrode and the negative electrode even when the internal temperature of the electrochemical device rises, and the heat resistance temperature is 150 °. The above materials of C can ensure its function. That is, when the electrochemical element becomes high temperature, even if the porous layer (I) shrinks, the direct contact between the positive and negative electrodes which can occur when the separator is thermally contracted can be prevented by the porous layer (II) which is not easily contracted. Short circuit caused. Further, as described later, when the porous layer (I) and the porous layer (11) are integrally formed, the heat-resistant porous layer (11) functions as a skeleton of the separator, and the porous structure can be suppressed. The heat shrinkage of the layer (I), that is, the heat shrinkage of the entire separator. The resin (A) of the porous layer (I) is electrochemically stable as long as it is electrically insulating, and is used in the production of a non-aqueous electrolyte or an separator which is described below. The thermoplastic resin which is stable in the solvent (described later) is not particularly limited, and is preferably a polyolefin such as polyethylene (PE), polypropylene (PP) or ethylene-propylene copolymer, or polyterephthalic acid. A polyester such as ethylene glycol or a copolymerized polyester. Further, the separator of the present invention preferably has a property of blocking its pores (i.e., shutdown function) in the range of 80 ° C or more and 15 ° C or less (more preferably 1 〇〇 ° C or more). Therefore, the porous film (I) is preferably a melting point, that is, a melting temperature of 80 ° C or more as measured by a differential scanning calorimeter (DSC) according to the specification of the Industrial Standard (JIS) K 7121. A thermoplastic resin having a temperature of 0 ° C or less (more preferably 100 ° C or more) is preferably used as a constituent component thereof, preferably 10-10636230 a single-layer microporous film having PE as a main component, or a laminate of 2 ~5 layers of PE and PP laminated microporous membranes. When the porous layer (I) is formed by using a thermoplastic resin having a melting point of PE of 80 ° C or more and 150 ° C or less and a thermoplastic resin having a melting point of more than 150 ° C such as PP, for example, A microporous membrane composed of a resin having a high melting point ratio of PE and PP, such as PE, is used as the porous layer (I), or a layer composed of a resin having a higher melting point than a PE layer such as a PE layer and a PP layer. When the laminated microporous membrane is formed as the porous layer (I), the melting point is 80 ° C or more and 15 ° in the resin (A ) constituting the porous layer (I ). (e.g., PE) is preferably 30% by mass or more, and more preferably 50% by mass or more. As the microporous film as described above, for example, a microporous material composed of the above-exemplified thermoplastic resin used in a conventional lithium secondary battery or the like can be used. The membrane is an ion-permeable microporous membrane produced by a solvent extraction method, a dry method or a wet stretching method. 0 Further, in the porous layer (I), the shutdown function is not impaired in the separator. In the range of the action, in order to increase the strength and the like, it may contain a dip material or the like as the porous layer (I). The dip material which can be used is, for example, the same as the crucible which can be used in the porous layer (II) to be described later (the heat-resistant temperature is 15 (TC or more)). The particle size of the dip is the average particle size. The diameter is, for example, preferably 0.01 μm or more, more preferably 〇1 μmη or more, more preferably ΙΟμηη or less, still more preferably 1 μηη or less. Furthermore, the average particle diameter as described in the present specification can be specified as For example, a laser scattering particle size distribution meter (for example, "LA-920" manufactured by Β Β Β Α Α -11 -11 -11 Β -11 -11 -11 -11 -11 -11 ) Β Β Β Β Β Β Β Β Β Β Β Β 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 数The same applies to the material of the porous layer (11) to be described later. By providing the porous layer (I) having the above configuration, the shutdown function can be easily imparted to the separator, and the internal temperature of the electrochemical element rises. In the case of the resin (A) content in the porous layer (I), in order to more easily obtain a shutdown effect, for example, it is preferably as follows. Among all the constituents of the porous layer (I) , the main resin (A) 50% by volume or more, more preferably 70% by volume or more, and may be 1% by volume. Further, the porosity of the porous layer (II) obtained by the method described later is 20 to 60%. Further, the volume of the resin (A) is preferably 50% or more of the pore volume of the porous layer (II). The material in the porous layer (II) is heated at a temperature of 150 ° C or higher. The electrolyte in the element is stable, and it is not easy to be oxidized and reduced in the range of the operating voltage of the electrochemical element, and the electrochemically stable one can be an organic particle or an inorganic particle. From the viewpoint of dispersion, etc., it is preferred. The fine particles are more preferably inorganic fine particles from the viewpoint of stability (especially oxidation resistance) and the like. Specific examples of the constituent material of the inorganic particles include inorganic oxides such as iron oxide, Al 2 〇 3 (alumina), Si 〇 2 ( vermiculite), Ti 〇 2, BaTi 〇 3, and ZrO 2 , and nitriding. Inorganic nitrides such as aluminum and tantalum nitride, poorly soluble ionic bonding compounds such as calcium fluoride, barium fluoride, and barium sulfate, covalent compounds such as sand and diamond, clays such as montmorillonite, etc. . Here, 12-201036230, the above inorganic oxide may be a mineral resource derived from boehmite, zeolite, apatite, kaolin, mullite, spinel, olivine, mica or the like or the like. Artificial objects, etc. In addition, the surface of the conductive material exemplified by a conductive oxide such as a metal, Sn02 or tin-indium oxide (ITO), or a carbonaceous material such as carbon black or graphite may be electrically insulating. The material (for example, the above inorganic oxide or the like) is coated to have electrically insulating particles. The inorganic particles are preferably particles (fine particles) of the above inorganic oxide from the viewpoint of further improving the oxidation resistance of the porous layer (II), and among them, alumina, vermiculite and boehmite are preferred. Plate-like particles. Further, examples of the organic particles (organic powder) include crosslinked polymethyl methacrylate, crosslinked polystyrene, crosslinked polydivinylbenzene, styrene-divinylbenzene copolymer crosslinked product, and polyfluorene. Various crosslinked polymer particles such as imine, melamine resin, phenol resin, benzoguanamine-formaldehyde condensate, or polyfluorene, polyacrylonitrile, aromatic polyamine, polyacetal, thermoplastic polyimine Heat resistant polymer particles and the like. Further, the organic resin (polymer) constituting the organic particles may be a mixture, a modified product, a derivative, or a copolymer of the above-exemplified materials (random copolymer, alternating copolymer, block copolymer, and graft). Branch copolymer), crosslinked body (in the case of the above heat resistant polymer). The form of the heat-resistant temperature of 15 ° C or more may be, for example, a shape having a nearly spherical shape, or may have a plate shape, and is preferably a material of the above-mentioned material contained in the porous layer (II). At least a portion of the plate-like particles. All of the above materials may also be plate-like particles. Since the porous layer (η) contains plate-like particles, even when the porous layer (π) is integrated with the porous layer (I)-13-201036230, the porous particles can be suppressed by the collision of the plate-like particles. The contraction force of the membrane (I). Further, by using the path between the positive electrode negative electrodes in the plate-like particle 'separator, the so-called curve path rate becomes large. Therefore, even when dendrites are formed, it is difficult for the dendrites to reach the positive electrode from the negative electrode, and the reliability against the dendrite short circuit can be improved. As a plate-shaped material, various commercially available products, such as "Sunlovery (product name)" (Si〇2) manufactured by Asahi Glass Technology Co., Ltd., and "NST-B1 (trade name)" manufactured by Ishihara Sangyo Co., Ltd., are smashed. Product (Ti02), slab-shaped barium sulfate manufactured by Suga Chemical Industry Co., Ltd. "Η series (product name)", "HL series (product name)", "Micronwhite (product name)" (talc) manufactured by Linhua Chemical Co., Ltd., Lin Huacheng "Bengel (trade name)" (expanded soil) made by the company, "BMM (product name)" or "BMT (product name)" (Bom stone) manufactured by Kawasaki Co., Ltd.

Seraseul BMT-B(商品名）」[氧化銘（A!2〇3)]、 KINSEIMATEC公司製「Seraph (商品名）」（氧化錯） 、斐川礦業公司製「斐川雲母Z-20 (商品名）」（絹雲母 )等係能取得。另外，關於Si02、Al2〇3、ZrO ' Ce02， 可藉由特開2003·206475號公報中所揭示的方法來製作。 於上述塡料爲板狀粒子時之形態中，縱橫比（板狀粒 子中的最大長度與板狀粒子的厚度之比）較佳爲5以上， 更佳爲10以上’較佳爲1 〇〇以下，更佳爲5 〇以下。板狀 粒子的縱橫比’例如可藉由對以掃描型電子顯微鏡（S ΕΜ )所拍攝的影像進行影像解析而求得。 又’板狀的上述塡料，由於若厚度小則有由於衝撃而 -14- 201036230 容易破裂的問題，故其平均厚度較佳爲0.02μηι以上，更 佳爲0.05μπι以上。但是，板狀的上述塡料之厚度若過大 ，則隔板的厚度變厚，放電容量降低，在電化學元件的製 作時，多孔質層（II)變容易破裂，故其平均厚度較佳爲 0·7μηι以下，更佳爲〇·5μιη以下。 再者，多孔質層（Π )中所含有上述塡料之至少一部 分，較佳爲具有一次粒子所凝聚的二次粒子構造之微粒子 〇 。上述塡料的全部亦可爲具有上述二次粒子構造的微粒子 。由於多孔質層（II)含有上述二次粒子構造的塡料，可 得到與用前述板狀粒子時同樣的熱收縮抑制效果、或樹枝 狀結晶短路的抑制效果。作爲上述二次粒子構造的塡料之 例’可舉出大明化學公司製「勃姆石C06 (商品名）」、 「勃姆石C20 (商品名）」（勃姆石）、米庄石灰工業公 司製「ED-1 (商品名）」（CaC03) 、J. Μ· Huber公司製 「Zeolex 94HP (商品名）」（黏土）等。 ® 多孔質層（II )中的上述塡料之平均粒徑（關於二次 粒子構造的塡料，亦爲以上述測定法所求得的平均粒徑） ’例如較佳爲Ο.ΟΙμιη以上，更佳爲Ο.ίμιη以上，較佳爲 15μιη以下，更佳爲5μιη以下 多孔質層（Π)中的耐熱溫度爲15 0°C以上之塡料的 量’係多孔質層（II )的構成成分之全體積中[惟，使用後 述的多孔質基體時，係多孔質基體以外的構成成分之全體 積中’關於多孔質層（II)的各構成成分之含量，以下相 同]之50體積％以上，較佳爲70體積％以上，尤佳爲80 -15- 201036230 體積％以上，更佳爲90體積％以上。藉由使多孔質層（H )中的塡料成爲如上述的高含量，可更良好地抑制在電化 學元件成爲高溫之際，正極與負極的直接接觸所致的短路 之發生，而且尤其在將多孔質層（I)與多孔質層（II) 一 體化的構成之隔板時，可良好地抑制隔板全體的熱收縮。 又’於多孔質層（II)中，爲了黏結耐熱溫度爲 1 5 0°C以上的塡料彼此，或按照需要黏結多孔質層（I)與 多孔質層（II )，較佳爲含有有機黏結劑，從如此的觀點 來看，多孔質層（II)中的耐熱溫度爲15 0°C以上之塡料 量的合適上限値，例如係多孔質層（II )的構成成分之全 體積中的99.5體積％。再者，多孔質層（II)中的耐熱溫 度爲1 5(TC以上的塡料量若未達70體積％，則例如發生必 須增多多孔質層（II)中的有機黏結劑量，於該情況下， 多孔質層（II )的空孔容易被有機黏結劑所掩埋，而作爲 隔板的機能有降低之虞，而且當使用開孔劑等來多孔質化 時，上述塡料彼此的間隔變過大，抑制熱收縮的效果有降 低之虞。 使用板狀粒子當作耐熱溫度爲150°C以上的塡料時， 多孔質層（II )中的板狀粒子之存在形態，較佳爲平板面 係對隔板的面呈略平行，更具體地，關於在隔板的表面附 近之板狀粒子，較佳爲其平板面與隔板面的平均角度係30° 以下。最佳爲該平均角度係〇°，在隔板的表面附近之板狀 的平板面係對隔板的面呈平行。此處所言的「表面附近」 係指自隔板的表面起相對於全體厚度而言約1 〇%的範圍。 -16 - 201036230 藉由使板狀粒子的存在形態成爲如上述的狀態而提 粒子的配向性，可更強地發揮上述多孔質層（II) 縮抑制作用，而且可更有效地防止由於電極表面上 的鋰樹枝狀結晶或電極表面的活性物質之突起所容 的內部短路。再者，多孔質層（II)中的板狀粒子 形態，係可藉由SEM來觀察的隔板的截而容易掌握 又，使用板狀粒子當作耐熱溫度爲1 50°C以上 〇 時，在多孔質層（II)中，較佳爲彼等板狀面係層 形成平板的寬面在厚度方向中層合，或上下的塡料 位置互相錯開），而且塡料的層合數係5以上，更· 以上。於隔板的多孔質層（II )中，由於板狀的上 係如此地存在，故可提高隔板的強度（例如藉由後 定方法所測定的貫穿強度）。但是，板狀的上述塡 孔質層（II )中的層合數若過多，則引起多孔質層 的厚度增大，進而隔板的厚度增大，有引起電化學 〇 能量密度降低之虞。因此，多孔質層（Π)中的板 塡料之層合數較佳爲50以下，更佳爲20以下。再 孔質層（Π)中的板狀上述塡料之層合數’係可藉 實施例所採用的方法來測定。 於多孔質層（II )中，爲了隔板的形狀安定性 、或多孔質層（II)與多孔質層（I)的一體化等’ 含有有機黏結劑。作爲有機黏結劑，可舉出乙烯_ 烯酯共聚物（ΕγΑ，來自醋酸乙烯酯由的構造單位;ί 35莫耳％者）' 乙烯-丙烯酸乙酯共聚物等的乙烯_ 高板狀 的熱收 所析出 易發生 之存在 〇 的塡料 合（以 之水平 圭係1 0 述塡料 述的測 料在多 (II ) 元件的 狀上述 者，多 由後述 之確保 較佳爲 醋酸乙 爵20〜 丙烯酸 -17- 201036230 共聚物、氟系橡膠、苯乙烯丁二烯橡膠（SBR)、羧甲基 纖維素（CMC )、羥乙基纖維素（HEC )、聚乙烯醇（ PVA )、聚乙烯縮丁醛（PVB )、聚乙烯吡咯烷酮（PVP )、交聯丙烯酸樹脂、聚胺甲酸酯、環氧樹脂等’特佳爲 使用具有1 50°C以上的耐熱溫度之耐熱性的黏結劑。有機 黏結劑可單獨使用1種上述例示者，也可倂用2種以上。 於上述例示的有機黏結劑之中，較佳爲EVA、乙烯-丙烯酸共聚物、氟系橡膠、S B R等的柔軟性高之黏結劑。 如此柔軟性高的有機黏結劑之具體例，有三井杜邦聚化學 公司的「Evaflex系列（EVA)」、日本UNICAR公司的 EVA、三井杜邦聚化學公司的「Evaflex-EEA系歹!](乙烯-丙烯酸共聚物）」、日本UNICAR公司的 EEA、DAIKIN 工業公司的「Dai-Ellatex系列（氟橡膠）」、JSR公司的 「TRD-2001 (SBR)」、日本 ΖΕΟΝ 公司的「ΕΜ-400Β( SBR )」等。 再者，使用上述有機黏結劑於多孔質層（II)時，可 以使溶解在後述的多孔質層（II )形成用的組成物的溶劑 中或使分散的乳液之形態來使用。 又，爲了確保隔板的形狀安定性或柔軟性，於多孔質 層（II)中，亦可使纖維狀物等與上述塡料混合存在。作 爲纖維狀物，若是耐熱溫度爲15 0°C以上，具有電絕緣性 ，電化學上安定，而且在下述詳述的電解液或隔板製造之 際所使用的溶劑中安定，則在材質上沒有特別限制。再者 ，本說明書中所言的「纖維狀物」係意味縱橫比[長度方 -18- 201036230 向的長度/與長尺方向正交的方向之寬度（直徑）]爲4以 上者，縱橫比較佳爲10以上。 作爲纖維狀物的具體構成材料，例如可舉出纖維素或 其改性物[羧甲基纖維素（CMC)、羥丙基纖維素（HP c) 等]、聚烯烴[聚丙烯（PP)、丙烯的共聚物等]、聚酯[聚 對苯二甲酸乙二酯（PET)、聚萘二甲酸乙二酯（PEN ) 、聚對苯二甲酸丁二酯（PBT)等]、聚丙烯腈（PAN )、 〇 芳香族聚酿胺、聚醯胺酸亞胺、聚酿亞胺等的樹脂；玻璃 、氧化鋁、氧化锆、矽石等的無機氧化物等，可倂用2種 以上的此等構成材料來構成纖維狀物。又，纖維狀物視需 要亦可含有眾所周知的各種添加劑（例如於樹脂時係抗氧 化劑等）。 又，本發明的電化學元件中所用的隔板，尤其不將多 孔質層（I)和多孔質層（H ) 一體化而使用多孔質層（II )當作獨立膜時，爲了提高操作性等，可於多孔質層（II 〇 )中使用多孔質基體。多孔質基體係由上述纖維狀物形成 織布、不織布（含紙）等的薄片狀物所成的耐熱溫度爲 1 5 (TC以上者，可使用市售的不織布等當作基體。於此態 樣的隔板中’較佳爲在多孔質基體的空隙內含有耐熱溫度 爲150 °C以上的上述塡料，但是爲了黏結多孔質基體與上 述塡料，亦可使用上述有機黏結劑。 再者，多孔質基體的「耐熱性」係意味不發生由於軟 化等所致的實質尺寸變化，以對象物的長度變化，即在多 孔質基體中’對於在室溫的長度而言’收縮的比例（收縮 -19- 201036230 率）可維持5%以下的上限溫度（耐熱溫度），是否比隔 板的停機溫度還充分高來評價耐熱性。爲了提高停機後的 電化學元件之安全性，多孔質基體宜具有比停機溫度還高 2 0°C以上的耐熱溫度，更具體地，多孔質基體的耐熱溫度 較佳爲150°c以上，更佳爲180°C以上。 使用多孔質基體來構成多孔質層（II)時，耐熱濕度 爲1 50°C以上的塡料之全部或一部分較佳係成爲存在於多 孔質基體的空隙內之形態。藉由成爲如此的形態，可更有 效發揮上述塡料的作用。 纖維狀物（構成多孔質基體的纖維狀物，包含其它纖 維狀物）的直徑只要是多孔質層（Π )的厚度以即可，例 如較佳爲0.01〜5μιη。纖維狀物的直徑若過大，則由於纖 維狀物彼此的絡合不足’例如在形成薄片狀物而構成多孔 質基體時，其強度變小而操作會變困難。又，纖維狀物的 直徑若過小，則由於隔板的空孔變過小，離子透過性有降 低的傾向，會降低電化學元件的負荷特性。 於多孔質層（Π )中使用纖維狀物時（包含使用纖維 狀物當作多孔質基體時），其含量例如在多孔質層（II ) 的全部構成成分中較佳爲1〇體積％以上，更佳爲20體積 %以上，較佳爲90體積％以下，更佳爲80體積％以下。多 孔質層（II )中的纖維狀物之存在狀態，例如長軸（長度 方向的軸）相對於隔板面的角度較佳係平均3 0 °以下，更 佳係20°以下。 本發明的電化學元件中的隔板，從使電特性成爲良好 -20- 201036230 的觀點來看’其細孔徑較佳爲〇·〇25μχη以上，更佳爲 0.0 3 μιη以上。又’隔板的細孔徑若過大，則隔板的強度 有降低之虞’故其細孔徑爲0.07pm以下，較佳爲〇.〇4μιη 以下。再者’本說明書中所言的隔板之細孔徑，係依照 JIS Κ 3832所規定的方法’例如用使用ρΜΙ公司製^^-1 5 00AEX Perm-Porometer」所測定的起泡點値p ( Pa)， 藉由下述式所算出的細孔徑（最大孔徑）。Seraseul BMT-B (product name)" [Ozone (A! 2〇3)], "Seraph (trade name)" (oxidation error) manufactured by KINSEIMATEC Co., Ltd., "Fichuan Mica Z-20 (trade name)" (Silicon) can be obtained. Further, SiO 2 , Al 2 〇 3 , and ZrO ' CeO 2 can be produced by the method disclosed in JP-A-2003-206475. In the form in which the above-mentioned coating material is a plate-like particle, the aspect ratio (ratio of the maximum length of the plate-like particles to the thickness of the plate-like particles) is preferably 5 or more, more preferably 10 or more, and more preferably 1 〇〇. Below, it is more preferably 5 inches or less. The aspect ratio of the plate-like particles can be obtained, for example, by image analysis of an image taken by a scanning electron microscope (S ΕΜ ). Further, when the thickness of the sheet is small, the thickness of the film is easily broken due to the smashing, and the average thickness is preferably 0.02 μm or more, and more preferably 0.05 μm or more. However, if the thickness of the plate-shaped material is too large, the thickness of the separator becomes thick, and the discharge capacity is lowered. When the electrochemical element is produced, the porous layer (II) is easily broken, so the average thickness is preferably 0·7μηι or less, more preferably 〇·5μιη or less. Further, at least a part of the above-mentioned dip material contained in the porous layer (Π) is preferably a fine particle structure having a secondary particle structure in which primary particles are aggregated. All of the above-mentioned dips may also be microparticles having the above-described secondary particle structure. When the porous layer (II) contains the above-described secondary particle structure, it is possible to obtain the same heat shrinkage suppressing effect or the dendritic crystal short-circuit suppressing effect as in the case of using the above-mentioned plate-like particles. As an example of the material of the secondary particle structure, "Bomstone C06 (trade name)" manufactured by Daming Chemical Co., Ltd., "Bohmite C20 (trade name)" (Bohm stone), and Mizhuang lime industry can be cited. "ED-1 (product name)" (CaC03) manufactured by the company, "Zeolex 94HP (trade name)" (clay) manufactured by J. Hub Huber. The average particle diameter of the above-mentioned dip in the porous layer (II) (the average particle diameter obtained by the above measurement method for the secondary particle structure) is, for example, preferably Ο.ΟΙμηη or more. More preferably, the composition of the porous layer (II) is 量. ίμιη or more, preferably 15 μm or less, more preferably 5 μπη or less in the porous layer (Π), which has a heat-resistant temperature of 150 ° C or more. In the whole volume of the component, when the porous matrix described later is used, the content of each component of the porous layer (II) in the entire volume of the constituent component other than the porous matrix is the same as 50% by volume. The above is preferably 70% by volume or more, and particularly preferably 80 -15 to 201036230% by volume or more, more preferably 90% by volume or more. By making the pigment in the porous layer (H) a high content as described above, it is possible to more satisfactorily suppress the occurrence of a short circuit caused by direct contact between the positive electrode and the negative electrode when the electrochemical device is at a high temperature, and particularly When the separator having the porous layer (I) and the porous layer (II) is integrated, the heat shrinkage of the entire separator can be satisfactorily suppressed. Further, in the porous layer (II), in order to bond the heat-resistant temperature to 150 ° C or more, or to bond the porous layer (I) and the porous layer (II) as needed, it is preferable to contain organic From such a viewpoint, the heat-resistant temperature in the porous layer (II) is a suitable upper limit of the amount of the slurry of 150 ° C or more, for example, in the entire volume of the constituent component of the porous layer (II). 99.5 vol%. Further, in the porous layer (II), the heat resistance temperature is 15 (if the amount of the TC or more is less than 70% by volume, for example, it is necessary to increase the organic bonding amount in the porous layer (II), in which case Then, the pores of the porous layer (II) are easily buried by the organic binder, and the function as a separator is lowered, and when the pores are made porous using a pore former or the like, the gaps of the above-mentioned materials are changed. When the plate-like particles are used as a heat-resistant temperature of 150 ° C or more, the presence of the plate-like particles in the porous layer (II ) is preferably a flat surface. The surface of the separator is slightly parallel, and more specifically, the plate-like particles in the vicinity of the surface of the separator preferably have an average angle of 30° or less between the flat surface and the separator surface. Preferably, the average angle is The plate-like flat surface near the surface of the separator is parallel to the surface of the separator. The term "near the surface" as used herein means about 1 相对 from the surface of the separator to the entire thickness. Range of %. -16 - 201036230 by making the presence of plate-like particles When the state is as described above, the alignment of the particles is extracted, and the porous layer (II) can be more strongly suppressed, and the lithium dendrites on the electrode surface or the active material on the electrode surface can be more effectively prevented. The internal short circuit of the protrusions is formed. Further, the shape of the plate-like particles in the porous layer (II) can be easily grasped by the interception of the separator observed by SEM, and the plate-like particles are used as the heat-resistant temperature. When the temperature is above 50 ° C, in the porous layer (II), it is preferred that the flat faces of the plate-like surface layer forming the flat plate are laminated in the thickness direction, or the upper and lower material positions are shifted from each other), and The number of layers of the material is 5 or more, more or more. In the porous layer (II) of the separator, since the plate-like upper layer is present as described above, the strength of the separator (e.g., the penetration strength measured by the subsequent method) can be increased. However, if the number of laminations in the plate-like porous layer (II) is too large, the thickness of the porous layer is increased, and the thickness of the separator is increased to cause a decrease in the electrochemical energy density. Therefore, the number of laminations of the sheet material in the porous layer is preferably 50 or less, more preferably 20 or less. The number of laminations of the plate-like material in the porous layer (Π) can be determined by the method employed in the examples. In the porous layer (II), the organic binder is contained in order to ensure the shape stability of the separator or the integration of the porous layer (II) and the porous layer (I). Examples of the organic binder include ethylene-ene ester copolymer (ΕγΑ, a structural unit derived from vinyl acetate; ί 35 mol%), ethylene such as ethylene-ethyl acrylate copolymer, and high plate-like heat. In the case of the occurrence of the 易 易 ( ( ( ( ( ( ( ( ( ( ( ( ( ( 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 ~ Acrylic-17- 201036230 Copolymer, fluorine rubber, styrene butadiene rubber (SBR), carboxymethyl cellulose (CMC), hydroxyethyl cellulose (HEC), polyvinyl alcohol (PVA), polyethylene A butadiene aldehyde (PVB), a polyvinylpyrrolidone (PVP), a crosslinked acrylic resin, a polyurethane, an epoxy resin, or the like is particularly preferably a binder having heat resistance at a heat resistance temperature of 150 ° C or higher. The organic binder may be used alone or in combination of two or more kinds. Among the organic binders exemplified above, flexibility such as EVA, ethylene-acrylic acid copolymer, fluorine rubber, and SBR is preferable. High binder. So soft organic sticky Specific examples of the agent include "Evaflex series (EVA)" by Mitsui DuPont Poly Chemical Co., EVA of Japan UNICAR, "Evaflex-EEA system of Mitsui DuPont Poly Chemical Co., Ltd." (ethylene-acrylic acid copolymer), Japan EICAR's EEA, DAIKIN Industries' "Dai-Ellatex series (fluororubber)", JSR's "TRD-2001 (SBR)", and Japanese company's "ΕΜ-400Β (SBR)", etc. When the organic binder is in the porous layer (II), it can be used in a solvent dissolved in a composition for forming a porous layer (II) to be described later or in the form of a dispersed emulsion. In the porous layer (II), a fibrous material or the like may be mixed with the above-mentioned kneading material, and the fibrous material may have electrical insulation properties if the heat resistance temperature is 150 ° C or higher. Electrochemically stable, and it is stable in the solvent used in the production of the electrolyte or the separator described in detail below, and the material is not particularly limited. Further, the term "fibrous" as used in the present specification means aspect ratio[ In the case of the length of the length of the fiber -18-201036230, the width (diameter) of the direction orthogonal to the direction of the long dimension is 4 or more, and the aspect ratio is preferably 10 or more. The specific constituent material of the fibrous material is, for example, a fiber. Or its modified substance [carboxymethyl cellulose (CMC), hydroxypropyl cellulose (HP c), etc.], polyolefin [polypropylene (PP), copolymer of propylene, etc.], polyester [polyparaphenylene] Ethylene dicarboxylate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), etc., polyacrylonitrile (PAN), anthracene aromatic polyamine, polyfluorene A resin such as an amine imide or a polyacrylonitrile; an inorganic oxide such as glass, alumina, zirconia or vermiculite may be used as the fibrous material by using two or more of these constituent materials. Further, the fibrous material may contain various well-known additives as needed (e.g., an antioxidant in the case of a resin). Further, in the separator used in the electrochemical device of the present invention, in particular, when the porous layer (I) and the porous layer (H) are integrated and the porous layer (II) is used as a separate film, in order to improve workability Alternatively, a porous substrate can be used in the porous layer (II 〇). In the porous substrate system, the heat-resistant temperature of the fibrous material such as a woven fabric or a non-woven fabric (paper-containing) is 15 (TC or more), and a commercially available nonwoven fabric or the like can be used as the substrate. In the separator, it is preferable to contain the above-mentioned coating material having a heat-resistant temperature of 150 ° C or more in the void of the porous substrate, but the organic binder may be used in order to bond the porous substrate and the above-mentioned coating material. The "heat resistance" of the porous substrate means that the substantial dimensional change due to softening or the like does not occur, and the length of the object changes, that is, the ratio of 'shrinkage to the length at room temperature in the porous matrix ( Shrinkage-19- 201036230 rate) The upper limit temperature (heat-resistant temperature) of 5% or less can be maintained, and the heat resistance is evaluated to be higher than the shutdown temperature of the separator. In order to improve the safety of the electrochemical component after shutdown, the porous substrate It is preferable to have a heat-resistant temperature higher than the shutdown temperature by 20 ° C or higher, and more specifically, the heat-resistant temperature of the porous substrate is preferably 150 ° C or more, more preferably 180 ° C or more. When the porous layer (II) is formed, it is preferable that all or a part of the material having a heat-resistant humidity of 150 ° C or more is present in the voids of the porous substrate. By adopting such a form, it is possible to exhibit more effectively The diameter of the fibrous material (the fibrous material constituting the porous substrate, including other fibrous materials) may be as long as the thickness of the porous layer (Π), for example, preferably 0.01 to 5 μm. If the diameter of the material is too large, the complexation of the fibrous materials is insufficient. For example, when a porous substrate is formed by forming a sheet, the strength thereof becomes small and the operation becomes difficult. Further, the diameter of the fibrous material is too small. In addition, since the pores of the separator become too small, the ion permeability tends to decrease, and the load characteristics of the electrochemical element are lowered. When the fibrous layer is used in the porous layer (Π) (including the use of the fibrous material as a porous In the case of the porous substrate, the content thereof is preferably 1% by volume or more, more preferably 20% by volume or more, more preferably 90% by volume or less, and even more preferably 80% of all the constituent components of the porous layer (II). The product is less than or equal to the following. The existence state of the fibrous material in the porous layer (II), for example, the angle of the long axis (the axis in the longitudinal direction) with respect to the separator surface is preferably 30 ° or less, more preferably 20 ° or less. The separator in the electrochemical device of the present invention has a pore diameter of preferably 〇·〇25 μχη or more, more preferably 0.0 3 μmη or more, from the viewpoint of improving electrical properties to be good -20-201036230. If the pore diameter of the sheet is too large, the strength of the separator is lowered. Therefore, the pore diameter is 0.07 pm or less, preferably 〇.〇4 μιη or less. Further, the pore diameter of the separator as described in the present specification, According to the method specified in JIS Κ 3832, for example, the bubble point (p (Pa) measured by using the ^ 5 5 5 5 5 5 , , , , , ( ( ( ( ( ( 最大 最大 最大 最大 最大 最大 最大 最大Aperture).

〇 d= ( K4ycos0) /P 此處，上述式中’ d:起泡點細孔徑（pm) ，γ:表面 張力（mN/m) ，0:接觸角（。），K:毛細管常數。 再者’於本發明的隔板中，爲了如上述地調整其細孔 徑，可採用對隔板在接近其原材料的熔點之溫度，一邊進 行溫度與隔板的保持力之調整，一邊進行熱處理的方法， 藉此可將隔板的細孔徑調整至恰當的値。 本發明中的隔板之厚度，從更確實隔離正極與負極的 ® 觀點來看，較佳爲6μπι以上，更佳爲1〇μΐη以上。另一方 面，隔板的厚度若過大，則電化學元件的能量密度會降低 ，故其厚度較佳爲50μηι以下，更佳爲30μιη以下。 又，當構成隔板的多孔質層（I )之厚度爲Μ ( μπι ) ，多孔質層（Π)的厚度爲Ν(μη〇時，Μ與Ν的比率 Μ/Ν較佳爲1〇以下’更佳爲5以下，而且較佳爲1以上 ，更佳爲2以上。於本發明的隔板中，即使增大多孔質層 (I)的厚度比率而減薄多孔質層（II)，也可一邊確保良 好的停機機能，一邊高度抑制隔板的熱收縮所致的短路發 -21 - 201036230 生。再者’於隔板中’當多孔質層（I)以複數存在時， 厚度Μ係其總厚度，當多孔質層（Η)以複數存在時，厚 度Ν係其總厚度。 再者，若以具體的植來表現，則當多孔質層（】）的 厚度Μ[隔板具有複數的多孔質層時，係其總厚度]較 佳爲5μιη以上，且較佳爲30μιη以下。而且，當多孔質層 (II)的厚度Ν[隔板具有複數的多孔質層（11)時，係其 總厚度]較佳爲1 μιη以上，尤佳爲2 μιη以上，更佳爲4 μιη 以上，而且較佳爲20μιη以下，尤佳爲ΐ〇μιη以下，更佳 爲6 μιη以下。多孔質層（I )若過薄，則停機機能有變弱 之虞，而若過厚，則有引起電化學元件的能量密度降低之 虞，而且熱收縮的力變大，例如於多孔質層（I)與多孔 質層（II) 一體化的構成中，抑制隔板全體的熱收縮之作 用有變小之虞。又，多孔質層（II )若過薄，則抑制起因 於隔板的熱收縮所致的短路發生之效果有變小之虞，而若 過厚，則會引起隔板全體的厚度增大。 作爲隔板全體的空孔率，爲了確保電解液的保液量而 使離子透過性成爲良好，在乾燥的狀態下，較佳爲30%以 上。另一方面，從隔板強度的確保與內部短路的防止之觀 點來看，隔板的空孔率在乾燥的狀態較佳爲70%以下。再 者，隔板的空孔率：Ρ ( % )係可由隔板的厚度、每面積的 質量、構成成分的密度，使用下述（1)式求出各成分i 的總和而計算。 P = 1 00- ( Σ aj/pj ) X ( m/t ) ( 1 ) 22- 201036230 此處，上述式中，ai:以質量％所表示的成分 率，Pi :成分i的密度（g/cm3 ) ，m :隔板每單位 質量（g/cm ) ’ t·隔板的厚度（cm)。 又，於上述（1)式中’亦可將m設定爲多孔: )每單位面積的質量（g/cm2 ) ’將t設定爲多孔】 )的厚度（cm) ’使用上述（1)式來求得多孔質J 的空孔率：P ( % )。由此方法所求得的多孔質層 〇 空孔率較佳爲3 0〜70%。 再者，於上述（1)式中，亦可將m設定爲多 (II)每單位面積的質量（g/cm2 )，將t設定爲多 (II)的厚度（cm)，使用上述（1)式來求得多 (II )的空孔率：P ( % )。由此方法所求得的多孔 11 )之空孔率較佳爲2 0〜60 %。 又，本發明中的隔板係藉由根據JIS P 8117的 測定，在0.879g/mm2的壓力下以l〇〇ml的空氣透 〇 秒數所示的格雷（Gurley )値（透氣度）宜爲10〜 。透氣度若過大，則離子透過性變小，另一方面， ，則隔板的強度會變小。再者，作爲隔板的強度， 徑1mm的針之突刺強度計，宜爲50g以上。該突 若過小，則在鋰的樹枝狀結晶結晶發生時，會發生 突破所致的短路。藉由採用上述的構成，可成爲具 透氣度或突剌強度的隔板。 具備有上述構成的隔板之本發明的電化學元件 特性，例如可藉由電化學元件的內部電阻之溫度變 i之比 面積的 質層（I f層（I i ( η (I)之 孔質層 孔質層 孔質層 質層（ 方法來 過膜的 3 0 0 s e c 若過小 以用直 刺強度 隔板的 有上述 之停機 化來求 -23- 201036230 得。具體地，將電化學元件設置在恆溫槽中，使溫度從室 溫起以每分鐘11的比例上升，求得電化學元件的內部電 阻之上升溫度而測定。於此情況下，在1 5 0 °C的電化學元 件之內部電阻較佳爲室溫的5倍以上，更佳爲1 0倍以上 ，藉由使用上述構成的隔板，可確保如此的特性。 又，本發明的電化學元件中之隔板，較佳爲1 5 0 °c的 熱收縮率係5%以下。若爲如此特性的隔板，則即使電化 學元件內部成爲1 50°C左右，也幾乎不會發生隔板的收縮 ，故可更確實地防止由於正負極的接觸所致的短路，可更 提高在高溫的電化學元件之安全性。藉由採用上述的構成 ，可成爲具有如上述的熱收縮率之隔板。 此處所言的熱收縮率，在多孔質層（I)與多孔質層 (II) 一體化時，指該一體化的隔板全體之收縮率，在多 孔質層（I)與多孔質層（II)獨立時，指各自的收縮率之 小者的値。又，如後述地，多孔質層（I )及/或多孔質層 (II)亦可成爲與電極一體化的構成，於該情況下，指與 電極一體化的狀態下所測定的熱收縮率。 再者’上述「15〇°c的熱收縮率」，係將隔板或多孔 質層（I)及多孔質層（II)(與電極一體化時係在與電極 一體化的狀態下）置入恆溫槽中，使溫度上升到1 5 0。(：爲 止，靜置3小時後取出，藉由比較置入恆溫槽前的隔板或 多孔質層（I )及多孔質層（II )的尺寸，將所求得的尺寸 減少比例以百分率表示者。 作爲本發明的電化學元件中的隔板之製造方法，例如 -24- 201036230 可採用下述（a)或（b)的方法。製造方名 孔質基體上’塗佈含有耐熱溫度爲1 5 0 °C以 孔質層（Π)形成用組成物（漿體等的液狀 ，在指定的溫度進行乾燥而形成多孔質層（ 與以上述方法所製作的構成多孔質層（I ) 而成爲1個隔板之方法。於此情況下，多] 多孔質層（II)可一體化，也可爲各自獨立 〇 化學元件的組裝，於在元件內爲疊合的狀態 隔板之機能者。 於了將多孔質層（I)與多孔質層（II) 可採用使多孔質層（I)與多孔質層（II)疊 機等將兩者貼合的方法等。 作爲上述情況下的多孔質基體，具體地 成成分中含有上述例示的各材料之纖維狀物 構成之織布、或具有此等纖維狀物彼此絡合 ® 布等的多孔質薄片等。更具體地，可例示敍 、聚酯不織布（PET不織布、PEN不織布、 )、P AN不織布等的不織布。 多孔質層（II )形成用組成物，除了含 1 5 0°C以上的塡料，視需要亦可含有有機黏 等分散在溶劑（包含分散介質，以下相同） 關於有機黏結劑，亦可使溶解在溶劑中。多 形成用組成物所用的溶劑，只要是可均勻分 而且可均勻溶解或分散者即可，例如甲苯等 艮（a )係在多 上的塡料之多 組成物等）後 II )，疊合此 之微多孔膜， :L質層（I)與 的膜，藉由電 下成爲一體的 —體化，例如 合，藉由輥壓 可舉出以在構 的至少1種所 的構造之不織 £、PP不織布 PBT不織布等 有耐熱溫度爲 結劑等，使此 中者。再者， ‘孔質層（II ) 散上述塡料等 的芳香族烴、 -25- 201036230 四氫呋喃等的呋喃類、甲基乙基酮、甲基異丁基酮等的酮 類等、一般的有機溶劑係適用。再者，於此等溶劑中，以 控制界面張力爲目的’亦可適宜添加醇（乙二醇、丙二醇 等）、或醋酸單甲酯等的各種環氧丙烷系二醇醚等。又， 當有機黏結劑爲水溶性時，在作爲乳液使用的情況等中， 可以水當作溶劑’在此情況下也可適宜添加醇類（甲醇、 乙醇、異丙醇、乙二醇等）來控制界面張力。 多孔質層（II )形成用組成物之含有耐熱溫度爲 1 5 0°c以上的塡料及有機黏結劑的固體成分含量，例如較 佳爲10〜80質量％。 上述多孔質基體的空孔之開口徑若比較大時，例如在 5 μπι以上時’則此容易成爲電化學元件的短路之主要原因 。因此’在此情況下，如上述地，耐熱溫度爲1 5 0 °C以上 的塡料等之全部或一部分較佳係成爲存在於多孔質基體的 空隙內之構造。爲了使上述塡料等存在於多孔質基體的空 隙內’例如可用在將含有此等的多孔質層（II )形成用組 成物塗佈多孔質基體上後，通過一定的間隙，去除多餘的 組成物後，使用乾燥等的步驟。 又，於多孔質層（II)中，如上述地，爲了提高板狀 的上述塡料之配向性，可使用在將含有板狀的上述塡料之 多孔質層（II)形成用組成物塗佈於多孔質基體上及使含 浸後，對上述組成物施予剪切或磁場等的方法。例如，如 上述地，可在將含有板狀的上述塡料之多孔質層（II)形 成用組成物塗佈於多孔質基體上後，通過一定的間隙，而 -26- 201036230 對上述組成物施予剪切。 再者’爲了更有效地發揮上述塡料或構成多孔質層（ II)的其它成分所具有的作用，亦可使此等成分局部存在 ’與隔板的面呈平行或略平行地’使上述成分成爲層狀集 中的形態。 隔板的製造方法（b ) ’係在多孔質層（】〗）形成用組 成物中，使更按照需要含有纖維狀物，將此塗佈在薄膜或 〇 金屬箔等的基板上，在指定的溫度進行乾燥後，按照需要 由上述基板剝離的方法。藉此，可形成當作多孔質層（π )的多孔質膜。 於製造方法（b)中’亦與製造方法（a)同樣地，由 以樹脂（A )當作主體的微多孔膜所成的多孔質層（I )、 與含有塡料當作主體的多孔質層（II)，係可爲各自獨立 的構成，也可爲一體化的構成。爲了將多孔質層（I)與 多孔質層（II) 一體化，除了藉由輥壓機等將個別所形成 ^ 的多孔質層（II)與多孔質層（I)貼合的方法，亦可採用 不用上述基板，而在多孔質層（I)的表面上塗佈多孔質 層（Π)形成用組成物，進行乾燥，在多孔質層（I)的表 面上直接形成多孔質層（Π)之方法。 又，亦可藉由製造方法（b)，在構成電化學元件的 電極之表面上形成多孔質層（II)，而成爲隔板與電極一 體化的構造。 於採用（a ) 、（ b )任一製造方法的情況中，多孔質 層（I)亦可與正極及負極的至少一個電極進行一體化。 -27- 201036230 爲了將多孔質層（I)與電極一體化，例如可採用將多孔 質層（I)的微多孔膜與電極重疊後，進行輥壓的方法等 。再者’可藉由製造方法（b)，在正極的表面上形成多 孔質層（Π) ’在負極的表面上黏貼多孔質層（I)的微多 孔膜而一體化，也可藉由將以製造方法（a)或（b)所製 造的多孔質層（I)與多孔質層（II )所一體化的隔板，黏 貼在正極及負極的任一者之表面上，進行一體化。爲了將 多孔質層（I)與多孔質層（Π)所一體化的隔板黏貼在電 0 極的表面上而進行一體化，例如可採用將隔板與電極重疊 後，進行輥壓的方法等。 再者，多孔質層（I)與多孔質層（II)係未必是各自 1層，而可複數的層在隔板中。例如，可爲在多孔質層（ II)的兩面上配置有多孔質層（I)的構成，或在多孔質層 (I)的兩面上配置有多孔質層（Π)的構成。但是，由於 增加層數，而增加隔板的厚度，有導致電化學元件的內部 電阻之增加或能量密度的降低之虞，層數過多者係不宜， 隔板中的多孔質層（I )與多孔質層（II)之合計層數較佳 爲5層以下。 又，如上述地，所謂的多孔質層（I)與多孔質層（II )，除了一體化作爲獨立膜而構成隔板以外，亦可爲各自 獨立的構成要素，在電化學元件組裝後的階段中，成爲在 電化學元件內疊合的狀態，作爲正極與負極之間存在的隔 板之機能。再者，多孔質層（I)與多孔質層（II)不一定 要相接，彼等之間可有其它層的存在，例如構成多孔質基 -28- 201036230 體的纖維狀物之層等係可存在其間。 接著，使用本發明的電化學元件來詳細說明非水電解 液。 作爲本發明的電化學元件中之非水電解液，可使用在 有機溶劑中溶解有鋰鹽之溶液，較佳爲含有在苯環中鍵結 有烷基的化合物。當非水電解液含有在苯環中鍵結有烷基 的化合物時，於電化學元件的過充電時，非水電解液中之 Ο 在苯環中鍵結有烷基的化合物係進行聚合，而在隔板的孔 內形成導電路，藉此而發生軟短路，故可抑制過充電所致 的電化學元件之急劇的溫度上升。 於通常的電化學元件中，在過充電時，由於正極而隔 板容易被氧化，若因此而隔板劣化，則無法安定地發生上 述短路，有無法良好地確保過充電時的安全性之虞。但是 ，於本發明的電化學元件中，如上述地，藉由於以含有耐 熱溫度爲1 5 0 °C以上的塡料當作主體之耐氧化性更良好的 © 多孔質層（Π)至少面向正極的方式來配置隔板，在過充 電時可抑制隔板的氧化降解，故可更安定地發生上述軟短 路。 在苯環中鍵結有烷基的化合物，例如可舉出環己基苯 、第三丁基苯、第三戊基苯、辛基苯等。 於用於電化學元件的非水電解液中，在苯環中鍵結有 烷基的化合物之含量（配合量），從更有效地確保上述化 合物之使用所致的效果之觀點來看，較佳爲0.5質量％以 上，更佳爲1 ·〇質量％以上。但是，在苯環中鍵結有烷基 -29- 201036230 的化合物之量若過多，則電特性有降低的傾向，故在用於 電化學元件的非水電解液中上述化合物的含量（配合量） 較佳爲1 〇重量％以下，更佳爲5質量％以下，特佳爲4質 量％以下。 用於非水電解液的鋰鹽’只要是在溶劑中解離而形成 Li +離子，在作爲電池使用的電壓範圍內不易發生分解等 的副反應者，則沒有特別的限制。例如，可使用L i C10 4、 LiPF6、LiBF4、LiAsF6、LiSbF6 等的無機鋰鹽、LiCF3S03 、LiCF3C02、Li2C2F4(S03)2、LiN(CF3S〇2)2、LiC(CF3S02)3 、LiCnF2+1S03 ( 2 S n S 5 ) 、LiN(Rf0S02)2 [此處，Rf 係氟 烷基]等的有機鋰鹽等。 用於非水電解液的有機溶劑，只要是將上述鋰鹽溶解 ，在作爲電化學元件使用的電壓範圍內不易發生分解等的 副反應者，則沒有特別的限定。例如可舉出碳酸伸乙酯、 碳酸伸丙酯、碳酸伸丁酯、碳酸伸乙烯酯等的環狀碳酸酯 、碳酸二甲酯、碳酸二乙酯、碳酸甲基乙酯等的鏈狀碳酸 酯，丙酸甲酯等的鏈狀酯，γ-己內酯等的環狀酯，二甲氧 基乙烷、二乙基醚、1,3 -二噁茂烷、二甘醇二甲醚、三甘 醇二甲醚、四甘醇二甲醚等的鏈狀醚；二噁烷、四氫呋喃 、2 -甲基四氫呋喃等的環狀醚，乙腈、丙腈、甲氧基丙腈 等的腈類，乙二醇亞硫酸酯等的亞硫酸酯類等’此等亦可 混2種以上來使用。再者，爲了成爲更良好特性的電池’ 宜以碳酸伸乙酯與鏈狀碳酸酯的混合溶劑等之可得到高導 電率的組合來使用。 -30- 201036230 又，於此等非水電解液中’以提供安全性或充放電循 環性、高溫儲存性等的特性爲目的’亦可適宜添加碳酸伸 乙烯酯類、1，3-丙磺酸內酯、二苯基二硫化物、聯苯、氟 苯等的添加劑。 非水電解液中的鋰鹽之濃度，較佳爲0.5〜1 .5mol/l， 更佳爲 0.9 〜1.25mol/l。 接著，詳細說明本發明中的負極。 Ο 於本發明的電化學元件中，如上述地，作爲負極活性 物質，使用負極活性物質全量中含有30質量％以上之比例 的在氬離子雷射拉曼光譜中相對於1 5 80CHT1的尖峰強度 而言，1 3 60cm·1的尖峰強度比之R値（1, 3 60/1 ,58。）爲0.1 以上0.5以下、且002面的面間隔dGG2爲0.3 3 8 nm以下的 石墨之負極。藉由使用含有如此負極活性物質的負極，如 在苯環中鍵結有烷基的化合物地，即便在使用含有在低溫 容易使電化學元件的反應性降低的添加劑之非水電解液時 D ，也可維持低溫的優異充電特性。 R値及dou滿足上述之値的石墨，例如可舉出表面經 低結晶性的碳材料所被覆的石墨。如此的石墨係可將d002 爲〇.338nm以下的天然石墨或人造石墨形成球狀者當作母 材，以有機化合物被覆其表面，在800〜1 50CTC煅燒後， 進行粉碎’通過篩進行整粒而得。再者，作爲被覆上述母 材的有機化合物’可舉出芳香族烴，將芳香族烴在加熱加 壓下聚縮合而得之焦油或瀝青類，以芳香族烴的混合物當 作主成分的焦油、瀝青或柏油類等。爲了用上述有機化合 -31 - 201036230 物來被覆上述母材，可採用在上述有機化合物中含浸•混 合上述母材的方法。又，藉由將丙烷或乙块等的烴氣熱分 解而碳化’將此沈積在dotn爲0.3 3 8nm以下的石墨之表面 上的氣相法’亦可製作R値及d〇()2滿足上述之値的石墨。 R値及dC()2滿足上述之値的石墨係平均粒子徑d50 ( 可藉由與隔板有關的上述塡料之數平均粒徑的測定時相同 的裝置來測定）較佳爲1 0 μιη以上，而且較佳爲3 0 μηι以 下。再者，上述石墨的比表面積較佳爲1.0m2/g以上，而 且較佳爲5.0m2/g以下。 又’於負極活性物質中，可僅使用R値及dG()2滿足上 述之値的石墨，也可與上述石墨一起，倂用其它負極活性 物質。作爲如此的負極活性物質，例如可舉出R値未達 〇. 1的石墨（表面結晶性高的石墨）、熱分解碳類、焦炭 類、玻璃狀炭素類、有機高分子化合物的燒成體、中間相 碳微珠（MCMB )、碳纖維等之可吸藏、放出以離子的碳 系材料。再者，於倂用此等碳系材料時，如上述地，在與 負極有關的負極活性物質全量中，R値及dQQ2滿足上述之 値的石墨之比例較佳爲30質量％以上，更佳爲70質量％ 以上’特佳爲8 0質量％以上。 於負極中’例如可使用由含有上述負極活性物質、黏 結劑及視需要的導電助劑之負極合劑所成的負極合劑層形 成在集電體的一面或雨面上之構造者。如此的負極，例如 可經由將在溶劑中分散有上述負極合劑的漿體狀或糊狀含 負極合劑的組成物塗佈在集電體的一面或兩面上，進行乾 -32- 201036230 燥後，按照需要施予加壓處理，以調整負極合劑層的厚度 之步驟來製作。再者，本發明中的負極亦可藉由上述以外 的方法來製作。負極合劑層的厚度例如爲每集電體的一面 爲 10〜ΙΟΟμηι。 於負極的黏結劑中，可使用聚偏二氟乙烯（PVDF ) 等的氟樹脂、或SBR、CMC等。又，於負極的導電助劑中 ’可使用碳黑等的碳材料等。 〇 作爲負極的集電體，可使用銅製或鎳製的箔、冲孔金 屬、網、多孔金屬等’但通常使用銅箔。此負極集電體， 當爲了得到高能量密度的電池而減薄負極全體的厚度時， 厚度的上限較佳爲30μιη，下限宜爲5μιη。 負極側的引線部，於通常負極的製作時，藉由在集電 體的一部分上不形成負極合劑層，而殘留集電體的露出部 ，以其當作引線部而設置。但是，不要求引線部一定要自 最初起與集電體一體化，而可藉由後來在集電體上連接銅 © 製的箔等而設置。 於本發明的負極中，藉由上述負極活性物質的使用， 負極合劑層表面的算術平均粗縫度（Ra)變成0.7〜1.2μιη 之比較粗，但是於本發明的電化學元件中，如上述地，由 於使用強度大的本發明之隔板，可防止負極表面的凸部貫 通隔板所致的微小短路之發生，提高其生產性。 再者’本說明書中所言的負極之負極合劑層表面的算 術平均粗糙度（Ra)係JIS Β 0601中規定的算術平均粗糙 度，具體地使用共焦點雷射顯微鏡（LASERTEC株式會社 -33- 201036230 製「即時掃描型雷射顯微鏡1LM-2 ID」），以512x512畫 素測定1 mmx 1 mm的視野，藉由對來自各點的平均線之絕 對値作算術平均而求得的數値。 如以上地’本發明的電化學元件只要具備上述的隔板 、負極及非水電解液，則其它構成•構造係沒有特別的限 制，可採用習知的具有非水電解液之各種電化學元件（鋰 蓄電池、鋰原電池、超級電容器等）所採用的各種構成· 構造。 以下，作爲一例，以對鋰蓄電池的適用爲中心進行說 明。作爲鋰蓄電池的形態，可舉出以不銹鋼罐或鋁罐等當 作外包裝罐所使用的筒形（四方筒形或圓筒形等）等。又 ，亦可爲以蒸鍍有金屬的積層薄膜當作外包裝體的軟包裝 電池。 鋰蓄電池等的電化學元件，較佳爲具有在溫度上升之 際將電池內部的氣體排出到外部的機構。作爲該機構，可 使用習知的機構。即，於以不銹鋼罐或鋁罐等的金屬罐當 作外包裝罐的電池中，可使用在一定壓力下發生龜裂的金 屬製之裂開式通氣口、在一定壓力下破裂的樹脂製之通氣 口、在一定壓力下開蓋的橡膠製之通氣口等，其中較佳爲 使用金屬製的裂開式通氣口。 另一方面，於軟包裝電池中，由於藉由樹脂的熱熔黏 來密封封閉部分，在各自溫度與內壓上升時，成爲耐得住 此高溫、高壓的構造係困難，即使沒有設置特別的機構’ 當溫度上升時，亦可成爲將電池內部的氣體排出到外部的 -34- 201036230 構成。即，於軟包裝電池中，外包裝體的封閉部（熱熔黏 部）係具有當作將上述電池內部的氣體排出到外部的機構 之作用。又，於軟包裝電池的情況，藉由使封閉部分的寬 度僅在特定位置變狹窄等的方法，在溫度上升時，亦可成 爲將電池內部的氣體排出到外部的構成。即，上述特定位 置係具有將上述電池內部的氣體排出到外部的機構之作用 〇 Ο 作爲正極，只要是習知的鋰蓄電池中所用的正極，即 含有可吸藏放出Li離子的活性物質之正極，則沒有特別 的限制。例如，作爲活性物質，可使用Li1 + xM02 ( -0.1<x<0.1 ，Μ : Co、Ni、Μη、A1、Mg等。再者，元素Μ亦可經Li 以外的其它金屬元素取代到1 0原子％爲止）所示層狀構造 之含鋰的過渡金屬氧化物、LiMn204或其元素的一部分被 其它元素所取代的尖晶石構造之鋰錳氧化物、LiMP04 ( Μ :Co、Ni、Μη、Fe等）所示的橄欖石型化合物等。作爲 〇 上述層狀構造之含鋰的過渡金屬氧化物之具體例，可例示 LiCo〇2 或 LiNii-xCox.yAly02 ( 0.1^x^0.3 ' 0.01^y^0.2) 等，以及至少含有Co、Ni及Μη的氧化物（LiMni/3Nii/3C〇i/3〇2 、Li Mils/12Ni5/12 Co 1/6〇2、LiNi 3/5M111/5C01/5 〇2 等）等。特別 地，當含有4〇%以上的Ni之活性物質時，由於電池成爲 高容量而較宜’再者〇(氧原子）亦可經氟、硫原子取代 到1原子％爲止。 作爲導電助劑，使用碳黑等的碳材料，作爲黏齊||， 使用PVDF等氟樹脂’由混合有此等材料與活性物質的正 -35- 201036230 極合劑，將正極合劑層例如形成在集電體的一面或兩面上 〇 又，作爲正極的集電體，可使用鋁等的金屬之箔、冲 孔金屬、網、多孔金屬等，通常厚度爲10〜30μιη的鋁箔 係適用。 正極側的引線部，通常藉由在正極製作時，於集電體 的一部分上不形成正極合劑層而殘留集電體的露出部，以 其當作引線部而設置。但是，不要求引線部一定要自最初 起與集電體一體化，而可藉由後來在集電體上連接鋁製的 箔等而設置。 電極係可以隔著上述隔板層合有上述正極與上述負極 的積層電極體、或更將此捲繞的捲繞式電極體之形態來使 用。再者，於本發明的電化學元件中，如上述地，爲了特 別在過充電時抑制隔板的氧化降解，隔板的多孔質層（II )必須至少面向正極，如上述的電極體要求隔板的多孔質 層（II)面向負極而形成。 又，於本發明的電化學元件中，更佳爲以隔板的多孔 質層（I)面向負極的方式作配置。雖詳細的理由不明， 但是當以多孔質層（I)至少面向負極的方式配置隔板時 ’與配置在正極側的情況相比，當發生停機時，於由多孔 質層（I )所熔融的樹脂（A )之中，電極合劑層中所吸收 的比例變少，由於更有效地利用所熔融的樹脂（A )於堵 塞隔板的孔，故停機所致的效果變更良好。 再者，例如電化學元件具有在因爲溫度上升而電化學 -36- 201036230 元件的內壓上升之際，將電化學元件內部的氣體排出到外 部而降低電化學元件的內壓之機構時，當此機構作動之際 ，內部的非水電解液會揮發，電極有成爲直接暴露在空氣 中的狀態之虞。當電化學元件爲充電狀態時，若成爲上述 的狀態而負極與空氣（氧或水分）接觸，則負極所吸藏的 Li離子或在負極表面上析出的鋰與空氣係進行反應而發熱 ，有時亦會起火。又，由於此發熱而電化學元件的溫度上 〇 升，引起正極活性物質的熱失控反應，結果電化學元件亦 會起火。 然而，於以樹脂（A)當作主體的多孔質層（I)面向 負極的方式所構成的電化學元件之情況中，由於高溫時多 孔質層（I)的主體之樹脂（A)進行熔融而覆蓋負極表面 ，故可抑制將上述電化學元件內部的氣體排出到外部的機 構之作動所伴隨的負極與空氣之反應。因此，可消除將上 述電化學元件內部的氣體排出到外部的機構之作動所致的 Ο 發熱之虞，可更安全地保持電化學元件。 因此，例如在具有複數的以樹脂（A )當作主體的多 孔質層（I )或多孔質層（II )之隔板的情況中，較佳爲以 正極側成爲多孔質層（II )，且負極側成爲多孔質層（I ) 的方式來構成隔板。 再者，如上述之具有正極合劑層的正極或具有負極合 劑層的負極，例如係藉由將使正極合劑分散在N-甲基-2-吡略烷酮（NMP )等的溶劑中所成的正極合劑層形成用組 成物（漿體等）、或使負極合劑分散在NMP等的溶劑中 -37- 201036230 所成的負極合劑層形成用組成物（漿體 上，進行乾燥而製作。於此情況下，例 表面上塗佈正極合劑層形成用組成物， 前，塗佈多孔質層（11 )形成用組成物 孔質層（II)之一體化物，或於在集電 合劑層形成用組成物，將該組成物乾燥 層（Π)形成用組成物而製作的負極與 —體化物，亦可構成鋰蓄電池（電化學 本發明的電化學元件係可較佳地使 池等的電化學元件所適用的各種用途（ 筆記型個人電腦等的攜帶電子機器之電 用途。 〔實施例〕 以下以實施例爲基礎來詳細說明本 施例係不限制本發明。 (實施例1 ) <負極的製作> 將平均粒徑D5G爲18μηι、dC()2爲〇 譜中的R値爲0.18、比表面積爲3.2m2 粒徑 D5〇 爲 16μηι、d〇〇2 爲 〇.336nm、R-質量比85:15所混合成的混合物：95質 PVDF : 5質量份，以NMP當作溶劑均 等）塗佈在集電體 如使用於在集電體 將該組成物乾燥之 而製作的正極與多 體表面上塗佈負極 之前，塗佈多孔質 多孔質層（II )之 记件）。 用於與習知鋰蓄電 例如攜帶式電話或 源用途等）相同的 發明。惟，下述實 • 3 3 8nm、在拉曼光 /g之石墨、與平均 暄爲0.05之石墨以 量份、與黏結劑的 勻地混合，而調製 -38- 201036230 溶劑系的含負極合劑之糊。將此含負極合劑之糊間歇地塗 佈在由銅箔所成的厚度1 〇μιη之集電體的兩面上’乾燥後 ，進行輥軋處理，以全厚成爲142 μιη的方式，調整負極合 劑層的厚度。用共焦點雷射顯微鏡所求得的上述負極之負 極合劑層表面的算術平均粗糙度（Ra)係0·75μπι。 然後，裁切成爲寬度45mm，而得到負極。再者，將 翼片（tab )焊接於此負極的銅箔之露出部而形成引線部 〇 <正極的製作> 將正極活性物質的LiCo02 : 70質量份' LiNiQ.8C〇().202 :15質量份、導電助劑的乙炔黑：1〇質量份、及黏結劑 的PVDF : 5質量份，以NMP當作溶劑均勻地混合，而調 製含正極合劑之糊。將此糊間歇地塗佈在集電體的厚度 1 5 μπι之鋁箔的兩面上，乾燥後，進行輥軋處理，以全厚 成爲150μηι的方式，調整正極合劑層的厚度，裁切成爲寬 Ο 度43mm，以製作正極。再者，將翼片（tab )焊接於此正 極的鋁箔之露出部而形成引線部。 <隔板的製作> 將有機黏結劑的SBR之乳液（固體成分比率4〇質量 %) : 100克與水：6000克置入容器內，在室溫攪拌到均 勻分散爲止。於此分散液中分4次添加2000克耐熱溫度 爲150 °C以上的塡料之勃姆石粉末（板狀、平均粒徑Ιμηι 、縱橫比10)，藉由分散機在2 8 00rpm攪拌5小時以調 製均勻的漿體[多孔質層（II)形成用漿體、固體成分比率 -39- 201036230 25.3質量％]。於PE製微多孔膜[多孔質層（【）：厚度 I 2 μ m、空孔率4 0 %、細孔徑0 · 0 3 3 μ m、溶點1 3 5。〇]上，藉 由微凹槽輥塗佈機塗佈上述漿體及使乾燥，而形成厚度爲 2.6μπι的多孔質層（II)，得到隔板。 所得到的隔板中之多孔質層（II )係每單位面積的質 量爲3.4g/m2。又’此隔板的多孔質層（II)之突刺強度爲 3 ·9Ν，板狀勃姆石的體積含有率爲88體積％，多孔質層（ II )的空孔率爲5 5 %。再者，以上述方法所測定的隔板之 細孔徑（起泡點細孔徑）爲〇.〇3 3 μηι。 又，藉由橫斷面拋光法，在減壓環境下以氬離子雷射 光束來切斷隔板，以SEM來觀察截面所求得的多孔質層 (Π)中板狀勃姆石的層合片數係6〜8片（於後述的各實 施例中，亦藉由同樣的方法來測定板狀塡料的層合片數） <電池的組裝> 一邊以多孔質層（I )面向負極側存在於之間的方式 重疊如上述所得之正極與負極及隔板，一邊捲繞成渦捲狀 而製造捲繞式電極體。壓垮所得之捲繞式電極體而成爲扁 平狀，置入厚度6mm、高度50mm、寬度34mm的鋁製外 包裝罐內，將電解液（於碳酸伸乙酯、碳酸乙基甲酯以體 積比1:2所混合成的溶劑中，溶解濃度1.2mol/l的LiPF6 ，添加3質量％的碳酸伸乙烯酯，添加4質量％的環己基 苯者）注入後，進行封閉，以製作圖1 A、B所示構造、圖 2所示外觀的鋰蓄電池。再者，此電池係在罐的上部具備 -40 - 201036230 有在內壓上升時用於降低壓力的裂開式通氣口。 此處，說明圖ΙΑ、B及圖2所示的電池，圖1A係槪 略平面圖、圖1B係部分截面圖，如圖1B所示地’在正極 1與負極2如上述地隔著隔板3而捲繞渦捲狀後’以成爲 扁平狀的方式進行加壓，而成爲扁平狀的捲繞式電極體6 ，與電解液一起收納在四方筒形的外包裝罐4內。但是’ 於圖1B中，爲了避免繁雜化，未圖示在正極1或負極2 〇 的製作時作爲所使用的集電體之金屬箔或電解液等。又， 亦沒有區別地顯示隔板的各層。 外包裝罐4係以鋁合金製構成電池的外包裝體者，此 外包裝罐4兼具正極端子。而且，在外包裝罐4的底部配 置由聚乙烯薄片所成的絕緣體5，從由正極1、負極2及 隔板3所成的扁平狀捲繞式電極體6，拉出在正極1及負 極2的各自一端所連接的正極引線體7與負極引線體8。 又，於將外包裝罐4的開口部封口的鋁合金製之封口用蓋 © 板9上’隔著聚丙烯製的絕緣襯墊1〇，安裝不銹鋼製的端 子11，於此端子11上，隔著絕緣體12，安裝不銹鋼製的 引線板13。 而且’此蓋板9係***外包裝罐4的開口部，藉由將 兩者的接合部焊接，而將外包裝罐4的開口部封口，電池 內部被密閉。又，於圖ΙΑ、B的電池中，蓋板9中設有非 水電解液注入口 14，於此非水電解液注入口 14中，在插 入封閉構件的狀態下，例如藉由雷射焊接等來焊接封閉， 而確保電池的密閉性（因此，於圖1 A、B及圖2的電池中 -41 - 201036230 ，實際上非水電解液注入口 1 4係非水電解液注入口與封 閉構件，但是爲了容易說明，顯示作爲非水電解液注入口 14)。再者，於蓋板9中設有裂開式通氣口 15，以當作在 電池的溫度上升之際將內部的氣體排出到外部的機構。 於此實施例1的電池中，藉由將正極引線體7直接焊 接在蓋板9，外包裝罐5與蓋板9係具有作爲正極端子的 機能’將負極引線體8焊接於引線板1 3，經由該引線1 3 而使負極引線體8與端子1 1導通，因此端子1 1成爲具有 作爲負極端子的機能，但是取決於外包裝罐4的材質等， 其正負亦有變成相反的情況。 圖2係示意地顯示上述圖ία、B所示的電池之外觀的 斜視圖’此圖2係以顯示上述電池爲四方形電池者當作目 的而圖示者，此圖2中槪略地顯示電池，只有圖示電池的 構成構件中之特定者。又，於圖1中，電極群的內周側之 部分亦沒有成爲剖面。 (實施例2 ) 除了調整微凹槽輥塗佈機的間隙，乾燥後的多孔質層 (II)的厚度成爲4·3μπι以外，與實施例1同樣地在聚乙 烯（ΡΕ)製微多孔膜[多孔質層（D ]上形成多孔質層（Π )，以製作隔板。 所得到的隔板中之多孔質層（II )係每單位面積的質 量爲6. Og/m2。又，此隔板的多孔質層（π )之突刺強度爲 3.9N，板狀勃姆石的體積含有率爲86體積％，多孔質層（ -42 - 201036230 II )的空孔率爲5 5 %。再者，以上述方法所測 細孔徑（起泡點細孔徑）爲0.033 μιη。又，多 )中的板狀勃姆石之層合片數係12〜16片。 除了使用上述隔板以外，與實施例1同樣 電池。 (實施例3 ) 〇 除了調整微凹槽輥塗佈機的間隙與泵吐出 後的多孔質層（Π)之厚度成爲7.5μηι以外， 同樣地在聚乙烯（ΡΕ)製微多孔膜[多孔質層 成多孔質層（II)，以製作隔板。 所得到的隔板中之多孔質層（II )係每單 量爲9.8g/m2。又，此隔板的多孔質層（Η)之 4.0N，板狀勃姆石的體積含有率爲88體積％， 11 )的空孔率爲5 3 %。再者，以上述方法所測 Ο 細孔徑（起泡點細孔徑）爲〇.〇33μιη。又，多 )中的板狀勃姆石之層合片數係22〜28片》 除了使用上述隔板以外，與實施例1同樣 電池。 (實施例4 ) 除了負極活性物質的R値爲0.18的上述 爲0.05的上述石墨之質量比係90:10以外，劈 樣地製作負極。所得到的負極在輥軋處理 定的隔板之 孔質層（11 地製作鋰蓄 量，使乾燥 與實施例1 (Π)]上形 位面積的質 突剌強度爲 多孔質層（ 定的隔板之 孔質層（II 地製作鋰蓄 石墨與R値 •實施例1同 後的全厚係 -43- 201036230 1 44 μηι ’用共焦點雷射顯微鏡所求得的負極合劑層表面之 算術平均粗糙度（Ra)係〇·9μιη。 除了使用上述負極以外，與實施例1同樣地製作鋰蓄 電池。 (實施例5 ) 除了用與實施例4所製作者相同的負極、及與實施例 2所製作者相同的隔板以外，與實施例i同樣地製作鋰蓄 電池。 (實施例6 ) 除了用與實施例4所製作者相同的負極、及與實施例 3所製作者相同的隔板以外’與實施例1同樣地製作鋰蓄 電池。 (實施例7 ) 除了於負極活性物質，僅用與實施例1所用者相同的 R値爲0 · 1 8的上述石墨以外’與實施例1同樣地製作負極 。所得到的負極在輥軋處理後的全厚係i 4 5 μπ1，用共焦點 雷射顯微鏡所求得的上述負極之負極合劑層表面的算衡平 均粗糙度（Ra)係Ι.ΐμχη。 除了使用上述負極以外’與實施例1同樣地製作鋰蓄 電池。 -44- 201036230 (實施例ο 除了用與實施例7所製作者相同的負極、及與實施例 2所製作者相同的隔板以外，與實施例1同樣地製作鋰蓄 電池。 (實施例9) 除了用與實施例7所製作者相同的負極、及與實施例 Ο 3所製作者相同的隔板以外，與實施例1同樣地製作鋰蓄 電池。 (實施例1 〇 ) 除了用第三丁基苯來代替環己基苯以外，與實施例1 同樣地調製非水電解液。除了用此非水電解液以外，與實 施例1同樣地製作鋰蓄電池。 ® (實施例1 1 ) 除了在正極活性物質僅用L i C 0 0 2以外，與實施例1 同樣地製作鋰蓄電池。 (實施例1 2 )〇 d= ( K4ycos0) /P Here, in the above formula, 'd: bubble point fine pore diameter (pm), γ: surface tension (mN/m), 0: contact angle (.), K: capillary constant. Further, in the separator of the present invention, in order to adjust the pore diameter as described above, it is possible to carry out heat treatment while adjusting the temperature and the holding force of the separator at a temperature close to the melting point of the raw material of the separator. In this way, the pore size of the separator can be adjusted to the proper crucible. The thickness of the separator in the present invention is preferably 6 μm or more, and more preferably 1 μm or more from the viewpoint of more surely isolating the positive electrode from the negative electrode. On the other hand, if the thickness of the separator is too large, the energy density of the electrochemical device is lowered, so the thickness thereof is preferably 50 μm or less, more preferably 30 μm or less. Further, when the thickness of the porous layer (I) constituting the separator is Μ (μπι) and the thickness of the porous layer (Π) is Ν (μη〇, the ratio Μ/Ν of Μ to Ν is preferably 1 〇 or less. It is more preferably 5 or less, and is preferably 1 or more, more preferably 2 or more. In the separator of the present invention, even if the thickness ratio of the porous layer (I) is increased, the porous layer (II) is thinned, It is also possible to ensure a good shutdown function while highly suppressing the short-circuiting caused by the heat shrinkage of the separator. In addition, in the separator, when the porous layer (I) is present in plural, the thickness is Μ The total thickness of the porous layer (Η) is the total thickness when the porous layer (Η) is present in a plurality. Further, if it is expressed by a specific plant, when the thickness of the porous layer (】) is Μ [the separator has In the case of a plurality of porous layers, the total thickness thereof is preferably 5 μm or more, and preferably 30 μm or less. Further, when the thickness of the porous layer (II) is Ν [the separator has a plurality of porous layers (11) , the total thickness thereof is preferably 1 μιη or more, particularly preferably 2 μιη or more, more preferably 4 μιη or more, and preferably 20 μιη. In the following, it is preferably ΐ〇μιη or less, more preferably 6 μηη or less. If the porous layer (I) is too thin, the shutdown function is weak, and if it is too thick, the energy density of the electrochemical element is caused. In the configuration in which the porous layer (I) and the porous layer (II) are integrated, the effect of suppressing the heat shrinkage of the entire separator is small, and the pressure is reduced. When the porous layer (II) is too thin, the effect of suppressing the occurrence of a short circuit due to thermal contraction of the separator is reduced, and if it is too thick, the thickness of the entire separator is increased. The porosity of the entire plate is excellent in ion permeability in order to secure the liquid retention amount of the electrolytic solution, and is preferably 30% or more in a dry state. On the other hand, the strength of the separator is ensured and the internal short circuit is ensured. From the viewpoint of prevention, the porosity of the separator is preferably 70% or less in a dry state. Further, the porosity of the separator: Ρ (%) can be composed of the thickness of the separator, the mass per area, and the composition. The density of the component is calculated by calculating the sum of the components i using the following formula (1). P = 1 00- ( Σ aj / pj ) X ( m / t ) ( 1 ) 22 - 201036230 Here, in the above formula, ai: component ratio expressed by mass%, Pi: density of component i (g /cm3),m: thickness per unit mass (g/cm) of the separator (cm). Further, in the above formula (1), 'm can also be set to be porous:) per unit area Mass (g/cm2) 'Setting the thickness of t to be porous】) Thickness (cm) The porosity of the porous J was determined by the above formula (1): P (%). The porosity of the porous layer obtained by this method is preferably from 30 to 70%. Further, in the above formula (1), m may be set to a mass (g/cm 2 ) per unit area of (II), and a thickness (cm) of t (II) may be used, and the above (1) may be used. The formula to find much (II) porosity: P (%). The porosity of the porous 11) obtained by this method is preferably from 20 to 60%. Further, the separator in the present invention is preferably a Gurley® (gas permeability) represented by an air permeation number of 10 μm under a pressure of 0.879 g/mm 2 as measured according to JIS P 8117. For 10~. If the air permeability is too large, the ion permeability is small, and on the other hand, the strength of the separator is small. Further, as the strength of the separator, the burr strength of the needle having a diameter of 1 mm is preferably 50 g or more. If the protrusion is too small, a short circuit due to a breakthrough occurs when dendritic crystals of lithium occur. By adopting the above configuration, it is possible to form a separator having air permeability or sudden strength. The characteristics of the electrochemical device of the present invention having the separator having the above-described constitution, for example, a layer of the I f layer (I i (η (I)) by the temperature of the internal resistance of the electrochemical element The porous layer of the porous layer (the method to pass through the film of 300 sec if too small to use the straight spur strength of the separator to achieve the above-mentioned shutdown to obtain -23-201036230. Specifically, the electrochemical components It is set in a constant temperature bath, and the temperature is raised from room temperature at a ratio of 11 per minute, and the temperature at which the internal resistance of the electrochemical device rises is measured. In this case, the electrochemical element at 150 ° C is used. The internal resistance is preferably 5 times or more, more preferably 10 times or more of the room temperature, and such a property can be ensured by using the separator having the above constitution. Further, the separator in the electrochemical device of the present invention is preferably. The heat shrinkage ratio of 150 ° C is 5% or less. If the separator has such a characteristic, even if the inside of the electrochemical device is about 150 ° C, the shrinkage of the separator hardly occurs, so that it is more reliable. To prevent short circuit caused by contact between positive and negative electrodes, which can be improved The safety of the high-temperature electrochemical element can be a separator having the above-described heat shrinkage ratio by the above configuration. The heat shrinkage ratio as described herein is in the porous layer (I) and the porous layer (II). In the case of integration, the shrinkage ratio of the entire separator is independent of the porous layer (I) and the porous layer (II), and is referred to as the smaller one of the shrinkage ratios. The porous layer (I) and/or the porous layer (II) may be integrated with the electrode, and in this case, the heat shrinkage ratio measured in a state of being integrated with the electrode. "The heat shrinkage rate of 15 ° ° C" is such that the separator or the porous layer (I) and the porous layer (II) (in the state of being integrated with the electrode when integrated with the electrode) are placed in the thermostatic chamber. The temperature is raised to 150. (:: After standing for 3 hours, it is taken out, and by comparing the size of the separator or the porous layer (I) and the porous layer (II) placed before the constant temperature bath, The ratio of reduction in size is expressed as a percentage. As a method of manufacturing the separator in the electrochemical device of the present invention, For example, the method of (a) or (b) below can be used. The manufacturer's name on the porous substrate is coated with a composition containing a heat-resistant temperature of 150 ° C to form a pore layer (Π). The liquid state such as a slurry is dried at a predetermined temperature to form a porous layer (a method of forming a porous layer (I) produced by the above method to form one separator. In this case, more] porous The layer (II) can be integrated, or it can be assembled independently of the chemical elements, and it is a function of a superimposed state separator in the element. The porous layer (I) and the porous layer (II) A method in which the porous layer (I) and the porous layer (II) are laminated, etc., may be used. Specifically, the porous substrate in the above-mentioned case contains a woven fabric composed of a fibrous material of each of the above-exemplified materials, or a porous sheet having such a fibrous material that is entangled with each other, such as a cloth. More specifically, a non-woven fabric such as a polyester non-woven fabric (PET nonwoven fabric, PEN non-woven fabric), P AN nonwoven fabric, or the like can be exemplified. The composition for forming the porous layer (II) may be dispersed in a solvent (including a dispersion medium, the same applies hereinafter) in addition to a material containing 150° C. or more, or may be added to the organic binder. Dissolved in a solvent. The solvent used for the multi-form composition may be uniformly divided and uniformly dissolved or dispersed, for example, ruthenium (a) such as toluene or the like, which is a plurality of materials, etc.) (II), superimposed In the microporous film, the film of the L layer (I) and the film are integrated by electricity, for example, by rolling, the structure of at least one of the structures is not Weaving £, PP non-woven PBT non-woven fabric, etc. have heat-resistant temperature as a knot, etc., which makes this. In addition, the 'porous layer (II) disperses aromatic hydrocarbons such as the above-mentioned materials, urethanes such as -25-201036230 tetrahydrofuran, ketones such as methyl ethyl ketone and methyl isobutyl ketone, etc. Organic solvents are suitable. Further, in the above-mentioned solvents, various propylene oxide-based glycol ethers such as alcohol (ethylene glycol, propylene glycol, etc.) or monomethyl acetate may be suitably added for the purpose of controlling the interfacial tension. Further, when the organic binder is water-soluble, in the case of use as an emulsion, water may be used as a solvent. In this case, an alcohol (methanol, ethanol, isopropanol, ethylene glycol, etc.) may be suitably added. To control the interface tension. The content of the solid content of the binder containing the heat-resistant temperature of 150 ° C or more and the organic binder of the composition for forming a porous layer (II) is, for example, preferably 10 to 80% by mass. When the opening diameter of the pores of the porous substrate is relatively large, for example, when it is 5 μm or more, it is likely to cause a short circuit of the electrochemical device. Therefore, in this case, as described above, all or a part of the material having a heat-resistant temperature of 150 ° C or more is preferably a structure existing in the void of the porous substrate. In order to allow the above-mentioned dip material or the like to be present in the voids of the porous substrate, for example, after the porous layer (II)-forming composition containing the above-described porous substrate is coated on the porous substrate, the excess composition is removed by a certain gap. After the object, a step such as drying is used. In the porous layer (II), as described above, in order to improve the orientation of the plate-like material, a composition for forming a porous layer (II) containing a plate-like material may be used. A method of applying shear, a magnetic field, or the like to the above composition after being coated on a porous substrate and impregnated. For example, as described above, the porous layer (II) forming composition containing the plate-like material may be applied to the porous substrate, and then passed through a predetermined gap, and -26-201036230 may be used for the above composition. Apply shear. Furthermore, in order to more effectively exert the above-described effects of the above-mentioned materials or other components constituting the porous layer (II), it is also possible to locally present these components in a 'parallel or slightly parallel with the surface of the separator'. The components are in a layered form. The method for producing a separator (b) is based on a composition for forming a porous layer (], and further contains a fibrous material as needed, and is applied to a substrate such as a film or a ruthenium metal foil. After the temperature is dried, the substrate is peeled off as needed. Thereby, a porous film which is a porous layer (π) can be formed. In the production method (b), in the same manner as in the production method (a), the porous layer (I) composed of the microporous film mainly composed of the resin (A) and the porous material containing the tantalum as a main body The layer (II) may be of a separate structure or an integrated structure. In order to integrate the porous layer (I) and the porous layer (II), in addition to the method of bonding the porous layer (II) formed by the porous layer (I) to the porous layer (I) by a roll press or the like, A porous layer (Π) forming composition is applied onto the surface of the porous layer (I) without using the above substrate, and dried to form a porous layer directly on the surface of the porous layer (I). ) method. Further, the porous layer (II) may be formed on the surface of the electrode constituting the electrochemical element by the production method (b), and the separator and the electrode may be integrated. In the case of using any of the production methods (a) and (b), the porous layer (I) may be integrated with at least one of the positive electrode and the negative electrode. -27- 201036230 In order to integrate the porous layer (I) and the electrode, for example, a method in which the microporous membrane of the porous layer (I) is superposed on the electrode and then rolled, and the like may be employed. Further, 'the porous layer (Π) can be formed on the surface of the positive electrode by the production method (b), and the microporous film of the porous layer (I) is adhered to the surface of the negative electrode to be integrated, or The separator in which the porous layer (I) produced by the production method (a) or (b) and the porous layer (II) are integrated is adhered to the surface of either of the positive electrode and the negative electrode, and is integrated. In order to integrate the separator in which the porous layer (I) and the porous layer are integrated on the surface of the electrode, for example, a method in which the separator and the electrode are overlapped and then rolled is used. Wait. Further, the porous layer (I) and the porous layer (II) are not necessarily one layer each, and a plurality of layers may be in the separator. For example, a configuration in which the porous layer (I) is disposed on both surfaces of the porous layer (II) or a porous layer (Π) may be disposed on both surfaces of the porous layer (I). However, increasing the number of layers increases the thickness of the separator, which leads to an increase in the internal resistance of the electrochemical element or a decrease in the energy density. If the number of layers is too large, the porous layer (I) in the separator is not suitable. The total number of layers of the porous layer (II) is preferably 5 or less. Further, as described above, the porous layer (I) and the porous layer (II) may be formed as separate films to form a separator, or may be independent constituent elements, after assembly of the electrochemical element. In the stage, it is in a state of being superposed in the electrochemical element, and functions as a separator existing between the positive electrode and the negative electrode. Further, the porous layer (I) and the porous layer (II) do not have to be in contact with each other, and there may be other layers between them, for example, a layer of fibrous material constituting the porous matrix -28-201036230. The system can exist between them. Next, the nonaqueous electrolytic solution will be described in detail using the electrochemical element of the present invention. As the nonaqueous electrolytic solution in the electrochemical device of the present invention, a solution in which a lithium salt is dissolved in an organic solvent can be used, and a compound having an alkyl group bonded to a benzene ring is preferable. When the nonaqueous electrolytic solution contains a compound in which an alkyl group is bonded to a benzene ring, a compound in which a hydrazine in the nonaqueous electrolytic solution is bonded to an alkyl group in the benzene ring is polymerized during overcharge of the electrochemical device. Further, a conductive circuit is formed in the hole of the spacer, whereby a soft short circuit occurs, so that an abrupt temperature rise of the electrochemical element due to overcharging can be suppressed. In the case of the above-mentioned electrochemical device, the separator is easily oxidized by the positive electrode during the overcharge, and if the separator is deteriorated, the short circuit cannot be stably formed, and the safety at the time of overcharge cannot be satisfactorily ensured. . However, in the electrochemical device of the present invention, as described above, the porous layer (Π) having a more excellent oxidation resistance as a main component containing a heat-resistant temperature of 150 ° C or higher is at least oriented. The separator is disposed in a positive electrode manner, and oxidative degradation of the separator can be suppressed during overcharge, so that the above soft short circuit can be more stably performed. The compound having an alkyl group bonded to the benzene ring may, for example, be cyclohexylbenzene, tert-butylbenzene, third amylbenzene or octylbenzene. In the nonaqueous electrolytic solution used for the electrochemical device, the content (combination amount) of the compound in which the alkyl group is bonded to the benzene ring is more effective in ensuring the effect of the use of the above compound. Preferably, it is 0.5% by mass or more, more preferably 1% by mass or more. However, if the amount of the compound having an alkyl group of -29 to 201036230 bonded to the benzene ring is too large, the electrical properties tend to be lowered, so the content of the above compound (the amount of the compound in the nonaqueous electrolytic solution used for the electrochemical device) It is preferably 1% by weight or less, more preferably 5% by mass or less, and particularly preferably 4% by mass or less. The lithium salt used in the non-aqueous electrolyte solution is not particularly limited as long as it is dissociated in a solvent to form Li + ions and is not easily decomposed in a voltage range used as a battery. For example, an inorganic lithium salt such as Lic104, LiPF6, LiBF4, LiAsF6, LiSbF6, LiCF3S03, LiCF3C02, Li2C2F4(S03)2, LiN(CF3S〇2)2, LiC(CF3S02)3, LiCnF2+1S03 ( An organic lithium salt such as 2 S n S 5 ) or LiN(Rf0S02) 2 [here, Rf is a fluoroalkyl group]. The organic solvent to be used in the non-aqueous electrolyte solution is not particularly limited as long as it dissolves the lithium salt and is less likely to cause decomposition or the like in a voltage range used as an electrochemical element. For example, a chain carbonate of a carbonate such as ethyl carbonate, propyl carbonate, butyl carbonate or vinyl carbonate, a carbonate such as dimethyl carbonate, diethyl carbonate or methyl ethyl carbonate may be mentioned. Chain ester of ester, methyl propionate, cyclic ester of γ-caprolactone, etc., dimethoxyethane, diethyl ether, 1,3-dioxane, diglyme a chain ether such as triglyme or tetraglyme; a cyclic ether such as dioxane, tetrahydrofuran or 2-methyltetrahydrofuran; a nitrile such as acetonitrile, propionitrile or methoxypropionitrile. For example, a sulfite such as ethylene glycol sulfite may be used in combination of two or more kinds. Further, in order to obtain a battery having better characteristics, it is preferable to use a combination of a high-conductivity of a mixed solvent of ethyl carbonate and a chain carbonate. -30- 201036230 In addition, in the non-aqueous electrolytes, 'the purpose of providing safety, charge and discharge cycle properties, high-temperature storage properties, etc.' may also be suitable for the addition of ethylene carbonate and 1,3-propane sulfonate. Additives such as acid lactone, diphenyl disulfide, biphenyl, fluorobenzene, and the like. The concentration of the lithium salt in the nonaqueous electrolytic solution is preferably from 0.5 to 1.5 mol/l, more preferably from 0.9 to 1.25 mol/l. Next, the negative electrode in the present invention will be described in detail. In the electrochemical device of the present invention, as the negative electrode active material, the peak intensity of the negative electrode active material in a total amount of 30% by mass or more in the argon ion laser Raman spectrum with respect to 1 5 80 CHT1 is used. In other words, the peak intensity ratio of 1 3 60 cm·1 is R 値 (1, 3 60/1 , 58 . ) is 0.1 or less and 0.5 or less, and the surface spacing dGG2 of the 002 plane is 0.3 3 8 nm or less. By using a negative electrode containing such a negative electrode active material, such as a compound having an alkyl group bonded to a benzene ring, even when a non-aqueous electrolyte containing an additive which is liable to lower the reactivity of the electrochemical element at a low temperature is used, It also maintains excellent charging characteristics at low temperatures. R and dou satisfy the above-mentioned graphite, and examples thereof include graphite coated with a carbon material having a low crystallinity. Such a graphite system can use a natural graphite or artificial graphite having a d002 of 338 nm or less to form a spherical shape as a base material, and coating the surface with an organic compound, and calcining at 800 to 150 CTC, and then pulverizing And got it. In addition, as the organic compound which coats the base material, an aromatic hydrocarbon, a tar or a pitch obtained by polycondensing an aromatic hydrocarbon under heat and pressure, and a tar containing a mixture of aromatic hydrocarbons as a main component may be mentioned. , asphalt or asphalt. In order to coat the above-mentioned base material with the above-mentioned organic compound -31 - 201036230, a method of impregnating and mixing the above-mentioned base material with the above organic compound may be employed. Further, carbonization by thermally decomposing a hydrocarbon gas such as propane or an ethylene block, which is deposited on the surface of graphite having a dotn of 0.33 8 nm or less, can also be made to satisfy R値 and d〇()2. The above-mentioned graphite. R値 and dC()2 satisfy the above-described graphite-based average particle diameter d50 (which can be measured by the same apparatus as the measurement of the number average particle diameter of the above-mentioned separator related to the separator), preferably 10 μm The above is preferably 30 μηη or less. Further, the specific surface area of the graphite is preferably 1.0 m 2 /g or more, and preferably 5.0 m 2 /g or less. Further, in the negative electrode active material, the above-mentioned graphite may be used only by using R値 and dG()2, and other negative electrode active materials may be used together with the above graphite. Examples of such a negative electrode active material include graphite having a R 値 〇 〇 1 1 (a graphite having a high surface crystallinity), a pyrolytic carbon, a coke, a glassy carbon, and a fired body of an organic polymer compound. Mesophase carbon microbeads (MCMB), carbon fibers, etc., which are capable of occluding and releasing ionic carbon-based materials. In the case of using the carbon-based material, as described above, in the total amount of the negative electrode active material related to the negative electrode, the ratio of R値 and dQQ2 satisfying the above-described graphite is preferably 30% by mass or more, more preferably 70% by mass or more is particularly preferably 80% by mass or more. In the negative electrode, for example, a negative electrode mixture layer made of a negative electrode mixture containing the above negative electrode active material, a binder, and an optional conductive auxiliary agent can be used to form a structure on one surface or a rain surface of the current collector. Such a negative electrode can be applied to one surface or both surfaces of a current collector by, for example, a slurry-like or paste-form negative electrode mixture-dispersing composition in which the negative electrode mixture is dispersed in a solvent, and dried at -32 to 201036230. It is produced by the step of applying a pressure treatment as needed to adjust the thickness of the negative electrode mixture layer. Further, the negative electrode in the present invention can also be produced by a method other than the above. The thickness of the negative electrode mixture layer is, for example, 10 to ΙΟΟμηι on one side of each current collector. As the binder of the negative electrode, a fluororesin such as polyvinylidene fluoride (PVDF) or SBR, CMC or the like can be used. Further, a carbon material such as carbon black can be used as the conductive auxiliary agent for the negative electrode. 〇 As the current collector of the negative electrode, a foil made of copper or nickel, a punched metal, a mesh, a porous metal or the like can be used, but a copper foil is usually used. In the negative electrode current collector, when the thickness of the entire negative electrode is reduced in order to obtain a battery having a high energy density, the upper limit of the thickness is preferably 30 μm, and the lower limit is preferably 5 μm. In the lead portion on the negative electrode side, when the negative electrode is not formed in a part of the current collector, the exposed portion of the current collector remains, and is provided as a lead portion. However, the lead portion is not required to be integrated with the current collector from the beginning, and may be provided by connecting a copper foil or the like to the current collector. In the negative electrode of the present invention, the arithmetic mean rough degree (Ra) of the surface of the negative electrode mixture layer becomes relatively coarse by 0.7 to 1.2 μm by the use of the above negative electrode active material, but in the electrochemical device of the present invention, as described above In the ground, since the separator of the present invention having high strength is used, occurrence of a micro short circuit due to the convex portion of the surface of the negative electrode penetrating the separator can be prevented, and productivity can be improved. In addition, the arithmetic mean roughness (Ra) of the surface of the negative electrode mixture layer of the negative electrode described in the present specification is the arithmetic mean roughness specified in JIS Β 0601, specifically, a confocal laser microscope (LASERTEC Co., Ltd.-33- 201036230 "Instant Scanning Laser Microscope 1LM-2 ID"), which measures 1 mm x 1 mm field of view with 512 x 512 pixels, and obtains the number obtained by arithmetically averaging the absolute lines from the average points of the points. As described above, the electrochemical element of the present invention is not particularly limited as long as it has the separator, the negative electrode, and the non-aqueous electrolyte solution described above, and various conventional electrochemical elements having a non-aqueous electrolyte can be used. Various configurations and structures used in (lithium batteries, lithium primary batteries, supercapacitors, etc.). Hereinafter, the application of the lithium secondary battery will be mainly described as an example. Examples of the form of the lithium secondary battery include a cylindrical shape (such as a rectangular tube shape or a cylindrical shape) used as an outer can of a stainless steel can or an aluminum can. Further, it may be a flexible packaging battery in which a laminated film of a metal is vapor-deposited as an outer package. The electrochemical device such as a lithium secondary battery preferably has a mechanism for discharging the gas inside the battery to the outside when the temperature rises. As the mechanism, a conventional mechanism can be used. In other words, in a battery in which a metal can such as a stainless steel can or an aluminum can is used as an outer can, a metal split vent which is cracked under a certain pressure and a resin which is broken under a certain pressure can be used. A vent, a rubber vent which is opened under a certain pressure, and the like, and preferably a metal split vent is used. On the other hand, in the flexible packaging battery, since the closed portion is sealed by heat fusion of the resin, it is difficult to withstand the high temperature and high pressure when the respective temperatures and internal pressures rise, even if no special mechanism is provided. When the temperature rises, it can also be used to discharge the gas inside the battery to the outside -34- 201036230. That is, in the flexible packaging battery, the closed portion (hot-melt adhesive portion) of the outer package functions as a mechanism for discharging the gas inside the battery to the outside. Further, in the case of a flexible package battery, the method of narrowing the width of the closed portion to a specific position can be used to discharge the gas inside the battery to the outside when the temperature rises. In other words, the specific position is a function of a mechanism for discharging the gas inside the battery to the outside. As the positive electrode, a positive electrode used in a conventional lithium secondary battery, that is, a positive electrode containing an active material capable of occluding and releasing Li ions is provided. , there are no special restrictions. For example, as an active substance, Li1 + xM02 ( -0.1 can be used) <x <0.1, Μ: Co, Ni, Μη, A1, Mg, and the like. Further, the elemental lanthanum may be substituted with a lithium-containing transition metal oxide of a layered structure represented by a metal element other than Li to 10 atomic %, LiMn204 or a part thereof whose element is substituted by other elements. Lithium manganese oxide as a stone structure, olivine-type compound represented by LiMP04 (Μ: Co, Ni, Μη, Fe, etc.). Specific examples of the lithium-containing transition metal oxide having the above layered structure include LiCo〇2 or LiNii-xCox.yAly02 (0.1^x^0.3'0.01^y^0.2), and at least Co and Ni. And Μη oxide (LiMni/3Nii/3C〇i/3〇2, Li Mils/12Ni5/12 Co 1/6〇2, LiNi 3/5M111/5C01/5 〇2, etc.) and the like. In particular, when the active material of Ni is contained in an amount of 4% by mass or more, it is preferable that the battery has a high capacity. Further, the argon (oxygen atom) may be substituted with 1 atom% of fluorine or a sulfur atom. As a conductive auxiliary agent, a carbon material such as carbon black is used, and as a bonding||, a fluororesin such as PVDF is used, and a positive electrode mixture layer is formed, for example, by using a positive-35-201036230 polar agent in which such a material and an active material are mixed. On one or both sides of the current collector, as the current collector of the positive electrode, a metal foil such as aluminum, a punched metal, a mesh, a porous metal or the like can be used, and an aluminum foil having a thickness of usually 10 to 30 μm is preferably used. In the lead portion on the positive electrode side, the exposed portion of the current collector is left on a part of the current collector without forming a positive electrode mixture layer in a part of the current collector, and is provided as a lead portion. However, the lead portion is not required to be integrated with the current collector from the beginning, and may be provided by subsequently connecting an aluminum foil or the like to the current collector. The electrode system can be used by laminating a laminated electrode body of the above positive electrode and the negative electrode or a wound electrode body wound therethrough via the separator. Further, in the electrochemical device of the present invention, as described above, in order to suppress oxidative degradation of the separator particularly during overcharge, the porous layer (II) of the separator must face at least the positive electrode, and the electrode body as described above is required to be separated. The porous layer (II) of the plate is formed facing the negative electrode. Further, in the electrochemical device of the present invention, it is more preferable to arrange the porous layer (I) of the separator to face the negative electrode. Although the reason for the details is not clear, when the separator is disposed such that the porous layer (I) faces at least the negative electrode, it is melted by the porous layer (I) when the shutdown occurs as compared with the case where it is disposed on the positive electrode side. Among the resins (A), the ratio of absorption in the electrode mixture layer is small, and the effect of shutdown is changed by using the molten resin (A) more effectively to block the pores of the separator. Further, for example, when the electrochemical element has a mechanism for discharging the gas inside the electrochemical element to the outside and lowering the internal pressure of the electrochemical element when the internal pressure of the electrochemical element is increased due to an increase in temperature, When the mechanism is activated, the internal non-aqueous electrolyte will volatilize and the electrode will become directly exposed to the air. When the electrochemical device is in a charged state, if the negative electrode is in contact with air (oxygen or moisture) in the above state, the Li ions absorbed by the negative electrode or the lithium deposited on the surface of the negative electrode react with the air to generate heat. It will also catch fire. Further, the temperature of the electrochemical element rises due to the heat generation, causing a thermal runaway reaction of the positive electrode active material, and as a result, the electrochemical element is also ignited. However, in the case of an electrochemical device in which the porous layer (I) mainly composed of the resin (A) faces the negative electrode, the resin (A) of the main body of the porous layer (I) is melted at a high temperature. Since the surface of the negative electrode is covered, it is possible to suppress the reaction between the negative electrode and the air accompanying the operation of the mechanism for discharging the gas inside the electrochemical element to the outside. Therefore, heat generation due to the action of the mechanism for discharging the gas inside the electrochemical element to the outside can be eliminated, and the electrochemical element can be more safely held. Therefore, for example, in the case of a separator having a plurality of porous layers (I) or porous layers (II) mainly composed of a resin (A), it is preferred that the positive electrode side be a porous layer (II). The separator is formed in such a manner that the negative electrode side becomes the porous layer (I). In addition, the positive electrode having the positive electrode mixture layer or the negative electrode having the negative electrode mixture layer described above is formed, for example, by dispersing the positive electrode mixture in a solvent such as N-methyl-2-pyrrolidone (NMP). The composition for forming a positive electrode mixture layer (such as a slurry) or a composition for forming a negative electrode mixture layer formed by dissolving a negative electrode mixture in a solvent such as NMP (37-201036230) (dried on a slurry). In this case, the composition for forming a positive electrode mixture layer is applied to the surface of the sample, and the integrated layer of the porous layer (11) forming composition porous layer (II) is applied or formed for the current collector layer. The composition, the negative electrode and the compound obtained by forming the composition to form a dry layer, can also constitute a lithium secondary battery (electrochemical device of the present invention can preferably electrochemically be used for a cell or the like Various uses for the components (electrical applications of portable electronic devices such as notebook computers) [Embodiment] Hereinafter, the present invention will be described in detail based on the embodiments. (Example 1) <Preparation of Negative Electrode> The average particle diameter D5G was 18 μm, and dC() 2 was R値 in the 〇 spectrum of 0.18, the specific surface area was 3.2 m2, the particle diameter D5〇 was 16 μm, and d〇〇2 was 〇.336 nm. a mixture of R-mass ratio of 85:15: 95 mass PVDF: 5 parts by mass, NMP is used as a solvent, and is uniformly applied to a current collector, for example, for drying the composition in a current collector. The porous porous layer (II) is coated before the negative electrode and the multi-body surface are coated with the negative electrode. It is used for the same invention as conventional lithium storage such as portable telephones or source applications. However, the following is true: 3 3 8 nm, graphite in Raman light / g, graphite with an average enthalpy of 0.05 in parts, and uniformly mixed with a binder, and prepared -38- 201036230 solvent-based negative electrode mixture Paste. The paste containing the negative electrode mixture was intermittently applied to both surfaces of a current collector having a thickness of 1 〇μηη formed of a copper foil, and then subjected to a rolling treatment to adjust the negative electrode mixture so as to have a full thickness of 142 μm. The thickness of the layer. The arithmetic mean roughness (Ra) of the surface of the negative electrode layer of the above negative electrode obtained by a confocal laser microscope was 0·75 μm. Then, the cut was made to have a width of 45 mm to obtain a negative electrode. Further, a tab is welded to the exposed portion of the copper foil of the negative electrode to form a lead portion. <Preparation of positive electrode> LiCo02 of a positive electrode active material: 70 parts by mass 'LiNiQ.8C〇().202: 15 parts by mass, acetylene black of a conductive auxiliary agent: 1 part by mass, and PVDF of a binder: 5 The mass fraction was uniformly mixed with NMP as a solvent to prepare a paste containing a positive electrode mixture. This paste was applied to both sides of an aluminum foil having a thickness of 15 μm on the current collector, dried, and then subjected to a rolling treatment to adjust the thickness of the positive electrode mixture layer so that the thickness became 150 μm. The degree is 43 mm to make a positive electrode. Further, a tab is welded to the exposed portion of the aluminum foil of the positive electrode to form a lead portion. <Preparation of separator> An emulsion of SBR of organic binder (solid content ratio: 4% by mass): 100 g and water: 6000 g were placed in a container, and stirred at room temperature until uniformly dispersed. To this dispersion, 2000 g of boehmite powder (plate shape, average particle diameter Ιμηι, aspect ratio 10) having a heat resistance temperature of 150 ° C or higher was added in four portions, and the mixture was stirred at 2 800 rpm by a disperser. The slurry was prepared in a uniform manner [the slurry for forming a porous layer (II), and the solid content ratio was -39 - 201036230 25.3 mass%]. Microporous film made of PE [Porous layer ([): thickness I 2 μ m, porosity of 40%, pore diameter 0 · 0 3 3 μ m, melting point 135). On the other hand, the slurry was applied by a micro-groove roll coater and dried to form a porous layer (II) having a thickness of 2.6 μm to obtain a separator. The porous layer (II) in the obtained separator had a mass per unit area of 3.4 g/m2. Further, the porous layer (II) of the separator had a spur strength of 3 · 9 Å, the volume content of the plate-like boehmite was 88 vol%, and the porosity of the porous layer (II ) was 55 %. Further, the pore diameter (foaming point pore diameter) of the separator measured by the above method was 〇. 3 3 μηι. Further, the separator was cut by an argon ion laser beam in a reduced pressure environment by a cross-sectional polishing method, and the layer of the plate-like boehmite in the porous layer (Π) obtained by the cross section was observed by SEM. The number of pieces is 6 to 8 pieces (in the respective examples described later, the number of laminated sheets of the plate-like material was also measured by the same method) <Assembling of the battery> The positive electrode, the negative electrode, and the separator obtained as described above are superposed on each other so that the porous layer (I) faces the negative electrode side, and the wound electrode body is wound in a spiral shape. . The wound electrode body obtained by compression was flattened, and placed in an aluminum outer can having a thickness of 6 mm, a height of 50 mm, and a width of 34 mm, and an electrolytic solution (ethyl carbonate and ethyl methyl carbonate in a volume ratio) In the solvent to be mixed in 1:2, LiPF6 having a concentration of 1.2 mol/l was dissolved, and 3% by mass of ethylene carbonate was added thereto, and 4% by mass of cyclohexylbenzene was added thereto, and the mixture was sealed to prepare FIG. 1A. A lithium battery having the appearance shown in B and the appearance shown in Fig. 2. Further, this battery is provided with a split vent for lowering the pressure when the internal pressure rises in the upper portion of the tank -40 - 201036230. Here, the batteries shown in FIGS. 2B and 2 are explained. FIG. 1A is a schematic plan view and FIG. 1B is a partial cross-sectional view. As shown in FIG. 1B, 'the positive electrode 1 and the negative electrode 2 are separated by a separator as described above. (3) After winding in a spiral shape, the wound electrode body 6 is pressed in a flat shape, and is housed in a rectangular tubular outer casing 4 together with an electrolytic solution. However, in Fig. 1B, in order to avoid complication, a metal foil or an electrolytic solution which is a current collector used in the production of the positive electrode 1 or the negative electrode 2 is not shown. Moreover, the layers of the separator are also displayed without distinction. The outer can 4 is an outer casing of a battery made of an aluminum alloy, and the outer can 4 has a positive electrode terminal. Further, an insulator 5 made of a polyethylene sheet is placed on the bottom of the outer can 4, and the flat wound electrode body 6 made of the positive electrode 1, the negative electrode 2, and the separator 3 is pulled out at the positive electrode 1 and the negative electrode 2 The positive electrode lead body 7 and the negative electrode lead body 8 to which the respective ends are connected. In addition, a cover 11 made of aluminum is attached to the cover plate 9 for sealing of the aluminum alloy, which is sealed by the opening of the outer can 4, and a terminal 11 made of stainless steel is attached to the terminal 11. A lead plate 13 made of stainless steel is attached via the insulator 12. Further, the cover plate 9 is inserted into the opening of the outer can 4, and the opening of the outer can 4 is sealed by welding the joint portions of the both, and the inside of the battery is sealed. Further, in the batteries of Figs. 2 and B, the cover plate 9 is provided with a non-aqueous electrolyte injection port 14 in which the non-aqueous electrolyte injection port 14 is inserted, for example, by laser welding. Wait for the welding to close, and ensure the tightness of the battery (hence, in the battery of Figure 1 A, B and Figure -41 - 201036230, in fact, the non-aqueous electrolyte injection port 14 non-aqueous electrolyte injection port and closed The member is shown as a non-aqueous electrolyte injection port 14) for ease of explanation. Further, a split vent 15 is provided in the cover plate 9 as a mechanism for discharging the internal gas to the outside when the temperature of the battery rises. In the battery of the first embodiment, the positive electrode lead body 7 is directly welded to the cover plate 9, and the outer package can 5 and the cover plate 9 have a function as a positive electrode terminal. The negative electrode lead body 8 is welded to the lead plate 13. Since the negative electrode lead body 8 and the terminal 1 1 are electrically connected via the lead wire 1, the terminal 11 has a function as a negative electrode terminal, but depending on the material of the outer can 4 or the like, the positive and negative may be reversed. 2 is a perspective view schematically showing the appearance of the battery shown in the above drawings ία, B. FIG. 2 is a diagram showing that the battery is a square battery, and the figure is schematically shown in FIG. The battery is only a specific one of the constituent members of the illustrated battery. Further, in Fig. 1, the portion on the inner peripheral side of the electrode group is not a cross section. (Example 2) A microporous film made of polyethylene (ΡΕ) was used in the same manner as in Example 1 except that the gap of the microgroove roll coater was adjusted so that the thickness of the porous layer (II) after drying was 4·3 μm. Og/m2。 The mass of the porous layer (II) in the obtained separator is 6. Og / m2. The spur strength of the porous layer (π) of the separator was 3.9 N, the volume fraction of the plate-like boehmite was 86% by volume, and the porosity of the porous layer (-42 - 201036230 II) was 55 %. The pore diameter (foaming point pore diameter) measured by the above method was 0.033 μm. Further, the number of lamellar boehmite laminate sheets was 12 to 16 sheets. A battery was used in the same manner as in Example 1 except that the above separator was used. (Example 3) A microporous film made of polyethylene (ΡΕ) was prepared in the same manner except that the gap between the microgroove roll coater and the thickness of the porous layer after the pump discharge was 7.5 μm. The porous layer (II) was laminated to form a separator. The porous layer (II) in the obtained separator was 9.8 g/m2 per unit amount. Further, 4.0N of the porous layer of the separator, the volume fraction of the plate-like boehmite was 88% by volume, and the porosity of 11) was 53%. Further, the pore diameter (bubble point pore diameter) measured by the above method was 〇. 33 μιη. In addition, the number of laminated sheets of plate-like boehmite is 22 to 28 pieces. The battery is the same as that of the first embodiment except that the above-mentioned separator is used. (Example 4) A negative electrode was produced in the same manner as in the case where the mass ratio of the above-mentioned graphite of 0.05 in which R? of the negative electrode active material was 0.18 was 90:10. The obtained negative electrode was made into a porous layer in the pore layer of the separator which was subjected to the rolling treatment (the lithium storage amount was 11 and the dry matter and the surface area of Example 1 (Π)] were made into a porous layer. The porous layer of the separator (II made of lithium-storage graphite and R値• the full thickness of the same example 1 -43- 201036230 1 44 μηι' The arithmetic of the surface of the negative electrode mixture layer obtained by confocal laser microscopy The average roughness (Ra) was 〇·9 μm. A lithium secondary battery was produced in the same manner as in Example 1 except that the above negative electrode was used. (Example 5) The same negative electrode as in Example 4 and Example 2 were used. A lithium secondary battery was produced in the same manner as in Example i except for the same separator as that of the producer. (Example 6) The same negative electrode as that produced in Example 4 and the same separator as that produced in Example 3 were used. A lithium secondary battery was produced in the same manner as in Example 1. (Example 7) In the same manner as in Example 1, except that the above-mentioned graphite having the same R値 of 0·1 8 as that used in Example 1 was used. Making a negative electrode. The obtained negative electrode is at the rolling point. The calculated full-thickness i 4 5 μπ1, the average roughness (Ra) of the surface of the negative electrode mixture layer of the above-mentioned negative electrode obtained by a confocal laser microscope is Ι.ΐμχη. In the same manner as in Example 1, except that the same negative electrode as that produced in Example 7 and the same separator as that produced in Example 2 were produced in the same manner as in Example 1. (Liquid Example 9) A lithium secondary battery was produced in the same manner as in Example 1 except that the same negative electrode as that produced in Example 7 and the same separator as that produced in Example 。 3 were used.非) A non-aqueous electrolyte solution was prepared in the same manner as in Example 1 except that the third butylbenzene was used instead of the cyclohexylbenzene. A lithium secondary battery was produced in the same manner as in Example 1 except that the non-aqueous electrolyte solution was used. Example 1 1) A lithium secondary battery was produced in the same manner as in Example 1 except that only the positive electrode active material was only L i C 0 0 2 (Example 1 2 )

除了將隔板中所用的PE製微多孔膜之厚度變更爲 1 6 μιη，於非水電解液中不添加環己基苯以外，與實施例i 同樣地製作鋰蓄電池。再者，上述隔板的突剌強度係49N -45 - 201036230 (實施例1 3 ) 將平均松徑D5Q爲18μιη、d〇()2爲〇 0.18、比表面積爲3.2m2/g之石墨粒子、 爲 16μιη、d。。：爲 〇.336nm、R 値爲 0.05 30:70所混合成的混合物：98質量份、與 質量％之濃度的羧甲基纖維素水溶液、及 乙烯-丁二烯橡膠，以離子交換水當作溶 調製水系的含負極合劑之糊。將此含負極 塗佈在由銅箔所成的厚度10 μιη之集電體 後，進行輥軋處理，以全厚成爲142 μιη的 合劑層的厚度。用共焦點雷射顯微鏡所求 負極合劑層表面的算術平均粗糙度（Ra ) ，裁切成爲寬度45mm，而得到負極。再 於此負極的銅箔之露出部而形成引線部。 除了用上述負極以外，與實施例1同 池。 (實施例1 4 ) 除了負極活性物質的R値爲〇.18的 R値爲0.05的上述石墨之質量比係5〇:5〇 1 3同樣地製作負極。所得到的負極在輕軋 1 44 μηι，用共焦點雷射顯微鏡所求得的負 算術平均粗糖度（Ra)係0.4μΐη。 除了使用上述負極以外，與實施例1 .3 3 8 nm ' R 値爲 與平均粒徑D50 之石墨以質量比 1 . 0質量份的1 1 . 0質量份的苯 劑進行混合，而 合劑之糊間歇地 的兩面上，乾燥 方式，調整負極 得的上述負極之 係0.3 μιη。然後 者，將翼片焊接 樣地製作鋰蓄電 上述石墨粒子與 以外，與實施例 處理後的全厚係 極合劑層表面之 同樣地製作鋰蓄 -46 - 201036230 電池。 (實施例1 5 ) 除了負極活性物質的R値爲0.18的上 R値爲0.05的上述石墨之質量比係70:30以 1 3同樣地製作負極。所得到的負極在輥軋處 144μιη，用共焦點雷射顯微鏡所求得的負極' Ο 算術平均粗糙度（Ra )係〇·6μΐη。 除了使用上述負極以外，與實施例1同 電池。 (實施例1 6 ) 除了負極活性物質的R値爲〇.18的上 R値爲0.05的上述石墨之質量比係85:15以 1 3同樣地製作負極。所得到的負極在輕軋處 〇 w 144μηι，用共焦點雷射顯微鏡所求得的負極-算術平均粗糙度（Ra)係0·7μιη。 除了使用上述負極，且於非水電解液中 苯以外，與實施例1同樣地製作鋰蓄電池。 (實施例1 7 ) 除了用平均粒徑D5〇爲18μπι、d〇〇2爲0 爲0.48、比表面積爲3.2m2/g的石墨粒子 D50 爲 16μιη、d〇〇2 爲 〇.336nm、R 値爲 0_05 述石墨粒子與 外，與實施例 理後的全厚係 合劑層表面之 樣地製作鋰蓄 述石墨粒子與 外，與實施例 理後的全厚係 合劑層表面之 不添加環己基 • 3 3 8 n m、R 値 、與平均粒徑 之石墨以質量 -47- 201036230 比8 5 ·· 1 5所混合成的混合物以外，與實施例1 3同樣地製 作負極。所得到的負極在輥軋處理後的全厚係1 44 μιη，用 共焦點雷射顯微鏡所求得的負極合劑層表面之算術平均粗 糙度（Ra)係 0·73μιη。 除了使用上述負極以外，與實施例1同樣地製作鋰蓄 電池。 (實施例1 8 ) 除了用平均粒徑D5Q爲18pm、dQ()2爲0.337nm'R値 爲0.11、比表面積爲3.2m2/g的石墨粒子、與平均粒徑 D5〇爲16μηι、d〇G2爲0.336nm、R値爲0.05之石墨以質量 比85 ·_ 1 5所混合成的混合物以外，與實施例1 3同樣地製 作負極。所得到的負極在輥軋處理後的全厚係144μιη，用 共焦點雷射顯微鏡所求得的負極合劑層表面之算術平均粗 縫度（Ra)係 0.69μιη。 除了使用上述負極以外，與實施例1同樣地製作鋰蓄 電池。 (比較例1 ) 除了於負極活性物質僅用與實施例1所用者相的R値 爲〇.〇5之上述石墨以外，與實施例1同樣地製作負極。 所得到的負極在輥軋處理後的全厚係1 42 μπι，用共焦點雷 射顯微鏡所求得的負極合劑層表面之算術平均粗糙度（Ra )係〇·1 5μπι。然後，除了用上述負極以外，與實施例1 -48- 201036230 同樣地製作鋰蓄電池。 (比較例2) 除了用與實施例1所製作者相同的負極，且不形成多 孔質層（II)，而用與實施例1的隔板之製作時所用者相 同的P E製微多孔膜當作隔板，再者’不添加環己基苯以 外’用與實施例1同樣調製的非水電解液以外，與實施例 Ο 1同樣地製作鋰蓄電池。再者，上述隔板係突剌強度爲 3.7N，以上述方法所測定的細孔徑（起泡點細孔徑）係 0.0 3 3 μιη。 (比較例3 ) 除了負極活性物質的R値爲0.18的上述石墨與R値 爲0.05的上述石墨之質量比係50:5〇以外，與實施例1同 樣地製作負極。所得到的負極在輥軋處理後的全厚係 1 44 μιη，用共焦點雷射顯微鏡所求得的負極合劑層表面之 算術平均粗糙度（Ra)係〇·45μιη。 除了使用上述負極以外，與比較例2同樣地製作鋰蓄 電池。 (比較例4 ) 除了於捲繞式電極體的製作時，以多孔質層（II)面 向負極側的方式配置隔板以外，與實施例1同樣地製作鋰 蓄電池。 -49- 201036230 (比較例5 ) 除了不形成多孔質層（Π ) ’而用與實施例1的隔板 之製作時所用者相同的PE製微多孔膜當作隔板以外，與 實施例7同樣地製作鋰蓄電池。 (比較例6 ) 除了負極活性物質的R値爲0.18的上述石墨與r値 爲0.05的上述石墨之質量比係20:80以外，與實施例13 同樣地製作負極。所得到的負極在輥軋處理後的全厚係 1 44 μιη，用共焦點雷射顯微鏡所求得的負極合劑層表面之 算術平均粗糙度（Ra)係0·2μιη。 除了使用上述負極以外，與實施例1同樣地製作鋰蓄 電池。 (比較例7 ) 除了用平均粒徑D5〇爲1 8μιη、dQ〇2爲0.3 3 9nm、R値 爲0.53、比表面積爲3.2m2/g的石墨、與平均粒徑D5Q爲 16μπι、dGG2爲〇.336nm、R値爲 0.05之石墨以質量比 8 5 : 1 5所混合成的混合物以外’與實施例1 3同樣地製作負 極。所得到的負極在輥軋處理後的全厚係1 44 μιη，用共焦 點雷射顯微鏡所求得的負極合劑層表面之算術平均粗糙度 (R a )係 0.4 μ m。 除了使用上述負極’以多孔質層（Π )面向負極側的 方式配置隔板以外，與實施例1同樣地製作鋰蓄電池。 -50- 201036230 對於實施例1〜18及比較例1〜7的鋰蓄電池，進行 下述的常溫放電容量測定、-5°C · 10%充電深度的充電電 流測定、耐電壓實驗及電池的高溫儲存試驗。表1及2中 顯示此等的結果。 <常溫放電容量測定> 對於實施例1〜1 8及比較例1〜7的鋰蓄電池，在常 〇 溫（25°c )，以240mA ( 0.2C )的恆定電流，進行恆定電 流放電直到電池電壓成爲3.0V爲止，繼續以240mA ( 0.2C )的恆定電流充電直到4.2V爲止後，在4.2V進行恆 定電壓充電直到總發電時間成爲8小時爲止，接著以 240mA ( 0.2C )的恆定電流進行恆定電流放電直到電池電 壓成爲3·〇ν爲止，測定放電容量。再者，表1及表2中 顯示當比較例1的電池之値爲1〇〇時，各電池的常溫放電 容量之相對値。 〇 <在-5°c . 1 0%充電的充電電流測定〉 將實施例1〜18及比較例1〜7的鋰蓄電池靜置在-5 °C 的恆溫槽內5小時，然後對於各電池以1 200mA ( 1.0C ) 的恆定電流進行充電直到4.2V爲止，達到4.2V後，以 4.2 V進行恆定電壓充電，測定當充電深度（相對於規格容 量而言實際充電的容量之比例）達到1 0 %時的電流値。再 者，表1及表2中顯示當比較例1的電池之値爲100時， 各電池的上述充電電流。 -51 - 201036230 <耐電壓實驗> 對於非水電解液注入前的實施例〗〜1 8及比較例〗〜7 的鋰蓄電池各20個，施加650V(AC60Hz)的電壓，在以 7mA以上的電流所流動的電池中，將有短路跡象者當作不 良，調查其發生個數。 耐電壓實驗係爲了知道即使不短路但電極間的距離也 變小，在極端的狀況下，隨著充放電循環而容量容易變低 的充放電循環可靠性，係可確保怎樣的程度之試驗手段。 對於一定的耐電壓，如果沒有發生絕緣破壞，則意味電極 間距離係保持在基準以上。此處，爲了使差異成爲明確， 以較高的値來進行試驗。 耐電壓實驗所測定的可靠性提高效果，在隔板的多孔 質層（I )之厚度爲20μιη以下係變明顯，在14μπι以下效 果更高，在12 μιη以下的導入時效果變更高而較宜。 <過充電試驗> 對於實施例1〜1 8及比較例1〜7的鋰蓄電池，於1C (1 200mA)使電池放電直到3.0V爲止後，在23°C的環境 下，將上限電壓設定爲15V，進行〇.5C( 6 00mA )的充電 ’測定此時各電池的表面溫度，求得其最高溫度。 <高溫儲存試驗> 對於實施例1〜1 8及比較例1〜7的鋰蓄電池，以 1 .0 C的電流値進行恆定電流充電，直到電池電壓成爲 -52- 201036230A lithium secondary battery was produced in the same manner as in Example i except that the thickness of the PE microporous membrane used in the separator was changed to 16 μm, and cyclohexylbenzene was not added to the nonaqueous electrolytic solution. Further, the protrusion strength of the separator is 49N - 45 - 201036230 (Example 13). Graphite particles having an average loin diameter D5Q of 18 μm, d〇() 2 of 〇 0.18, and a specific surface area of 3.2 m 2 /g, It is 16μηη, d. . : a mixture of 336336mm and R 値 0.05: 30:70: 98 parts by mass, a concentration by mass of carboxymethylcellulose aqueous solution, and ethylene-butadiene rubber, treated with ion-exchanged water A paste containing a negative electrode mixture in a water-soluble system. This negative electrode was applied to a current collector having a thickness of 10 μm made of a copper foil, and then subjected to a rolling treatment to have a thickness of 142 μm of the mixture layer. The arithmetic mean roughness (Ra) of the surface of the negative electrode mixture layer was measured by a confocal laser microscope, and cut to a width of 45 mm to obtain a negative electrode. Further, a lead portion is formed by the exposed portion of the copper foil of the negative electrode. The same as in Example 1 except that the above negative electrode was used. (Example 1 4) A negative electrode was produced in the same manner as in the case where the R値 of the negative electrode active material was 〇.18 and the mass ratio of the graphite of 0.05 was 0.05 〇:5〇1 3 . The obtained negative electrode was lightly rolled at 1,44 μm, and the negative arithmetic mean coarse sugar (Ra) obtained by confocal laser microscopy was 0.4 μΐη. In addition to the use of the above-mentioned negative electrode, the mixture of Example 1.3.38 nm 'R 値 is a benzene agent having a mass ratio of D50 and a mass ratio of 1.0 part by mass to 1 part by mass of the benzene agent, and the mixture is mixed. The two sides of the paste were intermittently dried, and the negative electrode obtained by the negative electrode was adjusted to 0.3 μm. Then, a battery of lithium storage - 46 - 201036230 was produced in the same manner as in the surface of the full-thickness electrode layer after the treatment of the graphite particles, in which the fins were soldered. (Example 1 5) A negative electrode was produced in the same manner as in the above-described graphite mass ratio of 70:30 in which the R値 of the negative electrode active material was 0.18 and the above R R was 0.05. The obtained negative electrode was 144 μm at the rolling point, and the negative electrode ' 算术 arithmetic mean roughness (Ra ) obtained by a confocal laser microscope was 〇·6 μΐη. A battery was used in the same manner as in Example 1 except that the above negative electrode was used. (Example 1 6) A negative electrode was produced in the same manner as in the above, except that the R値 of the negative electrode active material was 〇18 in which the above R値 was 0.05 and the mass ratio of the above-mentioned graphite was 85:15. The obtained negative electrode was lightly rolled at 〇 w 144 μηι, and the negative electrode-arithmetic mean roughness (Ra) obtained by a confocal laser microscope was 0·7 μmη. A lithium secondary battery was produced in the same manner as in Example 1 except that the above negative electrode was used and benzene was used in the nonaqueous electrolytic solution. (Example 1 7) Graphite particles D50 having an average particle diameter D5 18 of 18 μm, d〇〇2 of 0 of 0.48, and a specific surface area of 3.2 m 2 /g were 16 μm, and d〇〇2 was 336.336 nm, R 値For the graphite particles of 0_05 and the surface of the full-thickness mixture layer after the example, the lithium-deposited graphite particles were prepared, and the surface of the full-thickness mixture layer after the example was not added with cyclohexyl group. A negative electrode was produced in the same manner as in Example 13 except that a mixture of 3 3 8 nm, R 値 and graphite having an average particle diameter was mixed at a mass of -47 to 201036230 to 8 5 ··15. The obtained negative electrode had a full thickness of 1 44 μm after the rolling treatment, and the arithmetic mean roughness (Ra) of the surface of the negative electrode mixture layer obtained by the confocal laser microscope was 0·73 μm. A lithium battery was produced in the same manner as in Example 1 except that the above negative electrode was used. (Example 1 8) Graphite particles having an average particle diameter D5Q of 18 pm, dQ()2 of 0.337 nm'R値 of 0.11, a specific surface area of 3.2 m2/g, and an average particle diameter D5〇 of 16 μm, d〇 were used. A negative electrode was produced in the same manner as in Example 13 except that a mixture of G36 of 0.336 nm and R値 of 0.05 was mixed at a mass ratio of 85·_15. The obtained negative electrode had a full thickness of 144 μm after the rolling treatment, and the arithmetic mean roughness (Ra) of the surface of the negative electrode mixture layer obtained by the confocal laser microscope was 0.69 μm. A lithium battery was produced in the same manner as in Example 1 except that the above negative electrode was used. (Comparative Example 1) A negative electrode was produced in the same manner as in Example 1 except that the above-mentioned graphite having R値 of 〇.〇5 was used only for the negative electrode active material. The obtained negative electrode was subjected to a full thickness of 1 42 μm after the rolling treatment, and the arithmetic mean roughness (Ra) of the surface of the negative electrode mixture layer obtained by a confocal laser microscope was 〇·1 5 μm. Then, a lithium secondary battery was fabricated in the same manner as in Example 1-48-201036230 except that the above negative electrode was used. (Comparative Example 2) A microporous film made of PE was used in the same manner as in the production of the separator of Example 1, except that the same negative electrode as that produced in Example 1 was used and the porous layer (II) was not formed. A lithium secondary battery was produced in the same manner as in Example 1 except that a non-aqueous electrolyte solution prepared in the same manner as in Example 1 was used. Further, the separator had a projecting strength of 3.7 N, and the pore diameter (foaming point pore diameter) measured by the above method was 0.0 3 3 μm. (Comparative Example 3) A negative electrode was produced in the same manner as in Example 1 except that the graphite of the negative electrode active material having a R値 of 0.18 and the graphite having an R値 of 0.05 were 50:5〇. The obtained negative electrode was subjected to a full thickness of 1 44 μm after the rolling treatment, and the arithmetic mean roughness (Ra) of the surface of the negative electrode mixture layer obtained by a confocal laser microscope was 〇·45 μm. A lithium battery was produced in the same manner as in Comparative Example 2 except that the above negative electrode was used. (Comparative Example 4) A lithium secondary battery was produced in the same manner as in Example 1 except that the separator was placed such that the porous layer (II) faced the negative electrode side in the production of the wound electrode assembly. -49-201036230 (Comparative Example 5) The same manner as in the case of using the separator of Example 1 as the separator, except that the porous layer (Π) was not formed, was used as the separator. A lithium secondary battery was fabricated in the same manner. (Comparative Example 6) A negative electrode was produced in the same manner as in Example 13 except that the graphite of the negative electrode active material having a R値 of 0.18 and the graphite having a r値 of 0.05 were 20:80. The obtained negative electrode had a full thickness of 1 44 μm after the rolling treatment, and the arithmetic mean roughness (Ra) of the surface of the negative electrode mixture layer obtained by a confocal laser microscope was 0·2 μm. A lithium battery was produced in the same manner as in Example 1 except that the above negative electrode was used. (Comparative Example 7) Graphite having an average particle diameter D5〇 of 18 μm, dQ〇2 of 0.33 9 nm, R値 of 0.53, specific surface area of 3.2 m 2 /g, and an average particle diameter D5Q of 16 μm and dGG2 were used. A negative electrode was produced in the same manner as in Example 13 except that a mixture of .336 nm and R 値 0.05 was mixed at a mass ratio of 8 5 : 15 . The obtained negative electrode had a full thickness of 1 44 μm after the rolling treatment, and the arithmetic mean roughness (R a ) of the surface of the negative electrode mixture layer obtained by a confocal laser microscope was 0.4 μm. A lithium secondary battery was fabricated in the same manner as in Example 1 except that the separator was disposed such that the porous layer (Π) faced the negative electrode side. -50-201036230 For the lithium secondary batteries of Examples 1 to 18 and Comparative Examples 1 to 7, the following normal temperature discharge capacity measurement, charging current measurement at -5 ° C · 10% charge depth, withstand voltage test, and high temperature of the battery were performed. Store the test. The results of these are shown in Tables 1 and 2. <Measurement of normal temperature discharge capacity> The lithium batteries of Examples 1 to 18 and Comparative Examples 1 to 7 were subjected to constant current discharge at a constant current of 240 mA (0.2 C) at a normal temperature (25 ° C). When the battery voltage is 3.0V, continue to charge at a constant current of 240mA (0.2C) until 4.2V, and then perform constant voltage charging at 4.2V until the total power generation time becomes 8 hours, followed by a constant current of 240 mA (0.2C). The constant current discharge was performed until the battery voltage became 3·〇ν, and the discharge capacity was measured. Further, Tables 1 and 2 show the relative enthalpy of the normal temperature discharge capacity of each battery when the battery of Comparative Example 1 is 1 Torr. 〇<Measurement of charging current at -5 ° C. 10% charging> The lithium batteries of Examples 1 to 18 and Comparative Examples 1 to 7 were allowed to stand in a thermostatic bath at -5 ° C for 5 hours, and then The battery is charged at a constant current of 1 200 mA (1.0 C) until 4.2 V. After reaching 4.2 V, constant voltage charging is performed at 4.2 V, and the charging depth (the ratio of the actual charged capacity with respect to the specification capacity) is measured. The current 1 at 10%. Further, in Tables 1 and 2, the above charging current of each battery was shown when the battery of Comparative Example 1 was 100. -51 - 201036230 <Withstand voltage test> For each of the lithium batteries of Examples ～1 8 and Comparative Examples 7-14 to 7 before the injection of the non-aqueous electrolyte, a voltage of 650 V (AC 60 Hz) was applied, and 7 mA or more was applied. In the battery in which the current flows, the person with the short circuit sign is regarded as defective, and the number of occurrences is investigated. In order to know the reliability of the charge/discharge cycle in which the capacity is likely to be low with the charge and discharge cycle, the voltage withstand test can be used to determine the degree of the test. . For a certain withstand voltage, if no insulation breakdown occurs, it means that the distance between the electrodes is kept above the reference. Here, in order to make the difference clear, the test was carried out with a high degree of enthalpy. The reliability improvement effect measured by the withstand voltage test is obvious when the thickness of the porous layer (I) of the separator is 20 μm or less, and the effect is higher at 14 μm or less, and the effect is preferably changed when the introduction is less than 12 μmη. . <Overcharge Test> For the lithium secondary batteries of Examples 1 to 18 and Comparative Examples 1 to 7, the battery was discharged at 1 C (1 200 mA) until 3.0 V, and the upper limit voltage was applied in an environment of 23 ° C. Set to 15 V and perform charging of 〇5C (600 mA). Measure the surface temperature of each battery at this time and find the maximum temperature. <High-temperature storage test> The lithium batteries of Examples 1 to 18 and Comparative Examples 1 to 7 were subjected to constant current charging at a current of 1.0 C until the battery voltage became -52 - 201036230

4.2 5 V爲止’接著進行以4.2 5 V進行的恆定電壓充電之恒 定電流-恆定電壓充電。到充電結束爲止的總發電時間係 2.5小時。將經上述條件所充電的各電池置入恆溫槽內， 從30°C到150t爲止’以每分鐘5°C的比例進行升溫，然後 繼續在15 0°C放置3小時’測定電池的表面溫度。於表1 及表2中，將上述的電池表面溫度上升到160 °C以上爲止 者表示成「F」’將沒有看到如此的溫度上升者表示成「S4.2 5 V until then a constant current-constant voltage charging with constant voltage charging at 4.2 5 V is performed. The total power generation time until the end of charging is 2.5 hours. Each battery charged under the above conditions was placed in a thermostatic chamber, and the temperature was raised at a rate of 5 ° C per minute from 30 ° C to 150 t, and then left at 150 ° C for 3 hours to determine the surface temperature of the battery. . In Tables 1 and 2, when the above-mentioned battery surface temperature is raised to 160 °C or higher, it is expressed as "F"', and those who do not see such a temperature rise are indicated as "S".

[表1][Table 1]

常溫放電容量 在-5。〇10% 充電的電流値 耐電壓試驗 不良發生個數 (20個中） 過充電最高 表面溫度rc) 高溫儲存 試驗評價 實施例1 100 124 0 110 S 實施例21 101 124 0 110 S 實施例3 100 123 0 110 S 實施例4 100 126 0 110 S 實施例5 100 125 0 110 S 實施例6 99 125 0 110 S 實施例7 100 128 0 110 S 實施例8 99 127 0 110 S 實施例9 99 127 0 110 S 實施例1〇 100 125 0 120 S 實施例11 96 120 0 108 S 實施例12 100 125 0 130°c以上 S 實施例13 100 118 0 110 S 實施例14 100 116 0 113 S 實施例15 100 119 0 110 S 實施例16 101 126 0 130°c以上 S 實施例17 99 117 0 109 S 實施例18 101 122 0 110 S -53- 201036230 [表2]The normal temperature discharge capacity is -5. 〇10% Charging current 値 Withstand voltage test failure number (20 out) Overcharge maximum surface temperature rc) High temperature storage test evaluation Example 1 100 124 0 110 S Example 21 101 124 0 110 S Example 3 100 123 0 110 S embodiment 4 100 126 0 110 S embodiment 5 100 125 0 110 S embodiment 6 99 125 0 110 S embodiment 7 100 128 0 110 S embodiment 8 99 127 0 110 S embodiment 9 99 127 0 110 S Example 1 〇 100 125 0 120 S Example 11 96 120 0 108 S Example 12 100 125 0 130 ° C or more S Example 13 100 118 0 110 S Example 14 100 116 0 113 S Example 15 100 119 0 110 S Example 16 101 126 0 130 °c or more S Example 17 99 117 0 109 S Example 18 101 122 0 110 S -53- 201036230 [Table 2]

常溫放電容量 在-5。〇1〇% 充電的電流値 耐電壓試驗 不良發生個數 (20個中） 過充電最阔 表面溫度(。〇 高溫儲存 試驗評價 比較例1 100 100 0 118°C S 比較例2 101 125 2 130°C以上 F 比較例3 102 115 1 130°C以上 F 比較例4 100 124 0 130°C以上 F 比較例5 100 125 2 115°C F 比較例ό 100 106 0 116。。 S 比較例7 98 113 0 130°C以上 F 如表1及表2所示地，可知於用R値爲0.1〜0.5、 d 002爲0.3 3 8nm以下的石墨之含量未達30%的負極活性物 質之比較例1、6中，在低溫的充電特性差。 於不形成多孔質層（II )，在非水電解液中不含有添 加劑的比較例2、3中，由於放充電循環的可靠性低，而 且過充電時的電池表面之最高溫度係上升到1 30°C以上爲 止，亦得不到高溫儲存安定性，故可知無法確保過充電時 的安定性。 於未形成多孔質層（11 )，但在非水電解液中含有添 加劑的比較例5中，藉由添加劑雖然可壓低過充電時的電 池表面之最高溫度，但是與比較例2、3同樣地，可知無 法確保過充電時的安定性。 若如比較例4地將隔板的多孔質層（Π )配置在負極 側’可知反而過充電時的電池之最高溫度有上升的傾向， 無法確保過充電時的安定性。 -54- 201036230 於負極活性物質中含有3 0質量％以上的石墨，但不滿 足R値爲0.1〜0.5、dG〇2爲〇.338nm以下的條件，而在負 極側配置有隔板的多孔質層（II )之比較例7中，可知無 .法壓低過充電時的電池表面之最高溫度，高溫儲存安定性 亦差，故無法確保過充電時的安定性。 另一方面’於使用以多孔質層（II)面向正極的方式 所配置的隔板、與在負極活性物質全量中以3 0質量。/。以上 Ο 的比例含有R値爲〇.1〜0.5、d〇()2爲〇.338nm以下的石墨 之負極的實施例12、16中，可知能提高低溫的充電特性 ’而且高溫儲存安定性優異，故即使因爲過充電而電化學 元件的溫度上升，也可確保過充電的安全性。 又，於非水電解液中添加有在苯環中鍵結有烷基的化 合物之實施例1〜1 1、1 3〜1 5、1 7、1 8中，可知能抑制過 充電所致的電化學元件之溫度上升。即，可知能改善過充 電的安全性。 0 再者，與在負極側配有多孔質層（II )比較例4、或 在非水電解液中不含有環己基苯的實施例1 2、1 6相比， 在正極側配置有多孔質層（II )、在非水電解液中含有環 己基苯的實施例1係過充電時的電池表面之最高溫度降低 ，故可判斷藉由在正極側配置隔板的多孔質層（II )之作 用、與藉由與非水電解液有關的在苯環中鍵結有烷基的添 加劑之作用，係在正極側具有相乘的機能。 另外，一般地若欲使用1 4μιη以下的薄聚烯烴之隔板 來構成電池，則生產步驟的良率有變差的傾向，但是在本 -55- 201036230 發明的電化學元件（鋰蓄電池）中，由於用形成有多孔質 層（II )的隔板，故其生產性亦爲良好。 本發明在不脫其宗旨的範圍內，上述以外的形態係亦 可能實施。本申請案中所揭示實施形態係一例，不受此等 所限定。與上述說明書相比，本發明的範圍係優先以所附 的申請專利範圍之記載作解釋，在與申請專利範圍均等的 範圍內之所有變更係包含在申請專利範圍內。 產業上的利用可能性 若依照本發明，可提供在低溫的充電特性優異’即使 由於過充電等而使電池溫度異常上升時’安全性也優異的 電化學元件。 【圖式簡單說明】 圖1中的圖1A係本發明的電化學元件之槪略平面圖 ，圖1 B係本發明的電化學元件之部分縱剖面圖。 圖2係顯示本發明的電化學元件之外觀的斜視圖。 【主要元件符號說明】 1 :正極 2 :負極 3 :隔板 4 :外包裝罐 5 :絕緣體 -56- 201036230 6 :捲繞式電極體 7 :正極引線體 8 =負極引線體 9 :封口用蓋板 1 〇 :絕緣襯墊 1 1 :端子 1 2 :絕緣體 Ο 13 :引線板 1 4 :非水電解液注入口 1 5 :裂開式通氣口The normal temperature discharge capacity is -5. 〇1〇% Charging current 値 Withstand voltage test failure number (20 out) Overcharged maximum surface temperature (. 〇 High temperature storage test evaluation Comparative example 1 100 100 0 118°CS Comparative example 2 101 125 2 130° C or more F Comparative Example 3 102 115 1 130 ° C or more F Comparative Example 4 100 124 0 130 ° C or more F Comparative Example 5 100 125 2 115 ° CF Comparative Example ό 100 106 0 116. S Comparative Example 7 98 113 0 130° C. or more and F. As shown in Table 1 and Table 2, Comparative Examples 1 and 6 in which the content of graphite having R値 of 0.1 to 0.5 and d002 of 0.33 8 nm or less is less than 30% is known. Among them, in the case of not forming the porous layer (II), in Comparative Examples 2 and 3 in which the additive is not contained in the non-aqueous electrolyte, the reliability of the charge-and-charge cycle is low, and during overcharge When the maximum temperature of the surface of the battery rises above 130 °C, high-temperature storage stability is not obtained, so that it is impossible to ensure the stability during overcharging. The porous layer (11) is not formed, but in the non-aqueous electrolysis In Comparative Example 5 containing an additive in the liquid, although the additive can be depressed In the same manner as in Comparative Examples 2 and 3, it was found that the stability at the time of overcharge could not be ensured. The porous layer (Π) of the separator was placed on the negative electrode side as in Comparative Example 4 It is understood that the maximum temperature of the battery during overcharging tends to increase, and the stability at the time of overcharging cannot be ensured. -54- 201036230 Graphite containing 30% by mass or more of the negative electrode active material, but not satisfying R値 is 0.1~ 0.5, dG〇2 is a condition of 338338 nm or less, and in Comparative Example 7 in which the porous layer (II) having a separator is disposed on the negative electrode side, it is understood that the maximum temperature of the surface of the battery at the time of overcharge is low, and the high temperature is high. The storage stability is also poor, so the stability at the time of overcharging cannot be ensured. On the other hand, the separator disposed so as to face the positive electrode with the porous layer (II) and the mass of 30% in the total amount of the negative electrode active material are used. In the examples 12 and 16 in which the ratio of the above Ο contains R 値 1 1 1 1 1 1 1 1 338 338 338 338 338 338 338 338 338 338 338 338 338 338 338 338 338 338 338 338 338 338 338 338 338 338 338 338 338 338 338 338 338 338 338 Excellent stability, so even In the case of overcharging, the temperature of the electrochemical device is increased, and the safety of overcharging can be ensured. Further, in the nonaqueous electrolytic solution, a compound in which an alkyl group is bonded to a benzene ring is added, and Examples 1 to 1 and 1 are added. In 3 to 1 5, 1 7 and 1 8 , it can be seen that the temperature rise of the electrochemical device due to overcharging can be suppressed. That is, it can be seen that the safety of overcharge can be improved. 0 Further, porous material is provided on the negative electrode side. In the layer (II), the porous layer (II) was disposed on the positive electrode side, and the non-aqueous electrolyte solution was contained in Comparative Example 4 or in Examples 1 and 2, which did not contain cyclohexylbenzene in the nonaqueous electrolytic solution. In the first embodiment of the cyclohexylbenzene, the maximum temperature of the surface of the battery during the overcharge is lowered, so that the action of the porous layer (II) on which the separator is disposed on the positive electrode side and the non-aqueous electrolyte solution can be determined. The function of an additive having an alkyl group bonded to the benzene ring has a function of multiplication on the positive electrode side. In addition, in general, if a battery is used to form a battery using a thin polyolefin separator of 14 μm or less, the yield of the production step tends to be deteriorated, but in the electrochemical element (lithium battery) of the invention of the present invention-55-201036230 Since the separator having the porous layer (II) is formed, the productivity is also good. The present invention may be carried out in a form other than the above without departing from the spirit and scope of the invention. The embodiment disclosed in the present application is an example and is not limited thereto. The scope of the present invention is to be construed as being limited by the scope of the appended claims, and all modifications within the scope of the claims are included in the scope of the claims. Industrial Applicability According to the present invention, it is possible to provide an electrochemical device which is excellent in charge characteristics at low temperatures, and which is excellent in safety even when the battery temperature is abnormally increased by overcharge or the like. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1A is a schematic plan view of an electrochemical device of the present invention, and Fig. 1B is a partial longitudinal sectional view of an electrochemical device of the present invention. Fig. 2 is a perspective view showing the appearance of the electrochemical element of the present invention. [Main component symbol description] 1 : Positive electrode 2 : Negative electrode 3 : Separator 4 : Outer package can 5 : Insulator - 56 - 201036230 6 : Winding electrode body 7 : Positive electrode lead body 8 = Negative electrode lead body 9 : Sealing cap Plate 1 〇: Insulation pad 1 1 : Terminal 1 2 : Insulator Ο 13 : Lead plate 1 4 : Non-aqueous electrolyte injection port 1 5 : Split vent

Claims (1)

201036230 七、申請專利範圍： 1. 一種電化學元件，其係含有正極、負極、非水電解 液及隔板的電化學元件，其特徵爲： 前述隔板具有以熱塑性樹脂當作主體的微多孔膜所成 的多孔質層（I)、與含有以耐熱溫度爲150°C以上的塡料 當作主體的多孔質層（II )，前述多孔質層（II )係至少 面向正極， 前述負極含有在氬離子雷射拉曼光譜中相對於 0 1 5 8 0CHT1的尖峰強度而言，1 3 60(^^的尖峰強度比之R値 爲0.1〜0.5、且002面的面間隔dQG2爲0.3 3 8nm以下的石 墨當作負極活性物質， 前述負極活性物質中的前述石墨之比例爲3 〇質量％以 上。 2 ·如申請專利範圍第1項之電化學元件，其中前述非 水電解液含有在苯環中鍵結有烷基的化合物。 3 ·如申請專利範圍第1項之電化學元件，其中前述負 〇 極更含有作爲負極活性物質的R値未達〇」之石墨。 4.如申請專利範圍第1項之電化學元件，其中前述隔 板的細孔徑爲〇·〇25〜0·07μιη。 5 .如申請專利範圍第1項之電化學元件，其中前述多 孔質層（11 )中所含有的塡料之至少一部分係板狀粒子。 6 .如申請專利範圍第1項之電化學元件，其中前述多 孔質層（II )中所含有的塡料之至少一部分係具有一次粒 子所凝聚的二次粒子構造。 -58- 201036230 7·如申請專利範圍第1項之電化學元件，其中前述多 孔質層（II)中所含有的塡料係由氧化鋁、矽石及勃姆石 所組成族群所選出的至少1種之粒子。 8 ·如申請專利範圍第1項之電化學元件，其中前述多 孔質層（I)含有溶點爲80〜i5〇〇c的聚嫌烴。 9. 如申請專利範圍第2項之電化學元件，其中前述在 苯環中鍵結有烷基的化合物之含量爲0.5〜5質量％。 10. 如申請專利範圍第2項之電化學元件，其中前述 在本環中鍵結有烷基的化合物係環己基苯。 • 59 -201036230 VII. Patent application scope: 1. An electrochemical component, which is an electrochemical component comprising a positive electrode, a negative electrode, a non-aqueous electrolyte and a separator, characterized in that: the separator has microporous body with a thermoplastic resin as a main body. a porous layer (I) formed of a film and a porous layer (II) containing a crucible having a heat-resistant temperature of 150 ° C or higher as a main component, wherein the porous layer (II) is at least facing the positive electrode, and the negative electrode contains In the argon ion Raman spectroscopy, the peak intensity of 135 is higher than that of 0 1 5 8 0 CHT1, and the peak intensity ratio of R 値 is 0.1 to 0.5, and the interplanar spacing dQG2 of 002 is 0.3 3 . The graphite of 8 nm or less is used as the negative electrode active material, and the ratio of the graphite in the negative electrode active material is 3 〇 mass % or more. The electrochemical element of the first aspect of the invention, wherein the nonaqueous electrolyte is contained in benzene. A compound having an alkyl group bonded to the ring. 3. The electrochemical device according to claim 1, wherein the negative electrode further contains graphite as a negative electrode active material. range The electrochemical element of the first aspect, wherein the pore size of the separator is 〇·〇25 〜0·07μιη. 5. The electrochemical element according to claim 1, wherein the porous layer (11) At least a part of the coating material is a plate-like particle. The electrochemical element according to the first aspect of the invention, wherein at least a part of the material contained in the porous layer (II) has a secondary aggregation of primary particles. The electrochemical element of the first aspect of the invention, wherein the tantalum contained in the porous layer (II) is composed of a group consisting of alumina, vermiculite and boehmite. The at least one type of the selected particles. The electrochemical element according to the first aspect of the invention, wherein the porous layer (I) contains a polyene hydrocarbon having a melting point of 80 to 5 〇〇c. The electrochemical element of the second aspect, wherein the content of the compound in which the alkyl group is bonded to the benzene ring is 0.5 to 5% by mass. 10. The electrochemical element according to claim 2, wherein the aforementioned a compound ring with an alkyl group bonded to the middle . Benzene • 59 -
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