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TWI377725B - Non-aqueous lithium storage device - Google Patents

Non-aqueous lithium storage device Download PDF

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Publication number
TWI377725B
TWI377725B TW097144272A TW97144272A TWI377725B TW I377725 B TWI377725 B TW I377725B TW 097144272 A TW097144272 A TW 097144272A TW 97144272 A TW97144272 A TW 97144272A TW I377725 B TWI377725 B TW I377725B
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TW200929660A (en
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Toshio Tsubata
Michiko Shimoyamada
Akihiro Mabuchi
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Asahi Chemical Ind
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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
    • 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
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    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B01J20/28071—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B01J20/28073—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being in the range 0.5-1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/2808—Pore diameter being less than 2 nm, i.e. micropores or nanopores
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28088—Pore-size distribution
    • B01J20/28092—Bimodal, polymodal, different types of pores or different pore size distributions in different parts of the sorbent
    • 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
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • 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
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • 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
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/485—Plants or land vegetals, e.g. cereals, wheat, corn, rice, sphagnum, peat moss
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • 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
    • Y02E60/13—Energy storage using capacitors
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

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  • Microelectronics & Electronic Packaging (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Battery Electrode And Active Subsutance (AREA)
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Description

1377725 九、發明說明： 【發明所屬之技術領域】 本發明係有關於一種兼具高能量密度與高輸出之非水系 链型蓄電元件。 【先前技術】 近年來，因考慮到旨在實現地球環似節能之能量有效 利用，故而深夜電力儲存系統、依據太陽能發電技術之家 庭用分散型蓄電系統、電動汽車用之蓄電系統等越來越多 地受到關注。 該等蓄電系統中之第一要求事項係所用電池之能量密度 必須較高。作為能夠應對如此要求之高能量密度電池之有 力候選，鋰離子電池之開發正不斷積極發展。 :二要求事項係輸出特性必須較高。例如於高效引擎 與系統之組合(例如’油電混合車)，或者燃料電池與 ^、統之組合（例如，燃料電池電動汽車）中，加速時要 求畜電系統中具備高輸出放電特性。 二作為高輪出蓄電元件，已開發有電極中使用活性 石厌之電雙層雷宜$ , 性（循環特，Η：、古.下’亦簡稱為「電容器」）’其耐久 、尚溫保存特性）較高，具備〇 5〜1 kW/L左右 之輸出特性。可切盔兮铉命 ，、侑^ ! kW/L左右 之領域中之最：雙層電容器係要求上述高輸出 實際使用中鉍⑦件’但其能量密度僅為卜5 Wh/L左右， 中輪出持續時間將成為阻礙。 了與電雙：電混f車中所採用之錄氫電池，實現 S 之阿輸出’且具備160 Wh/L左右之 I36184.doc 1377725 能量密度。然而，用以更進一 並且進而改善高溫下之穩定性 斷積極發展。 步提昇其能量密度、輸出， ，提昇耐久性之研究仍在不 又’即i離子電池’適於高輪出化之研究亦不斷發 展，例如，開發有如下鐘離子電池，於放電深度（表示元 件之放電容量之百分之幾已被放電之狀態之值）篇中，獲 付超出3讀[之高輸出，但其能量密度為刚Wh/L以下，
導致設計反而抑制了作隸離子電池最大特徵之高能量密 度》又，其耐久性（循環特性、高溫保存特性）方面劣於電 雙層電容器1此，為使之具備較為實用㈣久性，而僅 能於放電深度小於〇〜麵之範圍内進行使用。因此能夠 實際使用之容量進而更小用以更進一步提昇耐久性之 研究正不斷積極發展。 :上所述’強烈需求兼具高輸出、高能量密度及耐久性 之蓄電元件之實用化，自目前階段，作為充分滿；I該技術 性要求m件’被稱作裡離子電容器之蓄電元件之 發較為盛行。 一電容器之能量密度與電容及耐受電壓成比例。電雙層電 容器之耐受電壓為2〜3 V左纟，曾經嘗試使用電解液中含 ,、非水系電解液來提昇财受電壓。例如，建議有如下 電容器’其於正極、負極中使用活性碳，並使用電解液中 含經鹽之非Μ電解液（參照專利文獻1、2収3)，但因負 極活性妷對鋰離子之充放電效率差之故，循環特性中存有 問題又，亦研究於正極中使用活性碳，而於負極中使用 136184.doc 1377725 石墨等碳質材料（參照專利文獻4、5及6)，但因負極中之石 墨之輸入輸出特性欠佳之故，於實施循環測試後，鋰易於 生成樹枝狀結晶等循環特性中存有問題。 進而’建議有於正極中使用如下烴材料之蓄電元件，該 煙材料具有碳質材料之氫/碳之原子比為0.05〜0.5，BET比 ‘ 表面積為 300〜2_ m2/g，BJH(Barrett-J0yner-Halenda)法 ' 計算之中扎容積為 0.02〜0.3 ml/g，MPOnathematicai
Pr〇gra_ing ’數學規劃）法計算之總細孔容積為0.3〜1.0 籲 ml/g之細孔構造（參·照專利文獻7)，但本發明者等進行追加 測試後’獲知尚存靜電電容雖大但輸出特性並不充分之課 ， 題。 - 另一方面，建議有如下蓄電元件用負極材料作為吸存釋 放鋰離子之負極材料，其係沈積於活性碳之表面上之碳質 材料，令取自直棱為2〇 A以上5〇〇 A以下之細孔之中孔量 為Vml(cc/g)，取自直徑未達2〇 a之細孔之微孔量為 參 Vm2(cc/g)時，則 〇.(n $ Vml $ 〇 2〇 且 〇 〇1 ^ Vm2^ 〇 帽參 照專利文獻8)。該負極材料係對鋰離子之充放電效率高， 輸出特性優異之材料。 [專利文獻1 ]日本專利特開平1丨·丨2丨285號公報 [專利文獻2]日本專利特開平1 ^297578號公報 [專利文獻3]日本專利特開2〇〇〇_丨24〇81號公報 [專利文獻4]日本專利特開昭6〇_18267〇號公報 [專利文獻5]曰本專利特開平〇8_1〇7〇48號公報 [專利文獻6]日本專利特開平1〇_〇27733號公報 136184.doc m2/g以上 2500 m2/g以下。 作為用作上述活性碳原料之碳質材料，只要為普通用作 活性碳原料之碳源則並無特別限定，例如可列舉木材木 粉、椰子殼、紙漿製造時之副產品、甘蔗渣、廢糖蜜等植 物系原料；泥戾、黑褐煤、褐炭、瀝青炭、無煙煤、石油 蒸餾殘渣成分 '石油瀝青、焦碳、煤焦油等化石系原料； 酚系樹脂、氣乙烯樹脂、乙酸乙烯酯樹脂、三聚氰胺樹 曰尿素樹知、間笨二齡樹脂、赛路路、環氧樹脂、聚胺 酯樹脂、聚酯樹脂、聚醯胺樹脂等各種合成樹脂；聚丁 烯、聚丁二烯、聚氣丁烯等合成橡膠；其它合成木材、合 成紙漿等、或者其等之碳化物。該等原料之中，較好的是 椰子殼、木粉等植物系原料或者其等之碳化物，尤其好的 是椰子殼碳。 作為用以將該等原料製成上述活性碳之碳化、活化方 式’可採關如固定床方式、移動床方式、流體化床方 式、漿體方式、旋轉黑方式等公知之方式。 ’作：該等原料之碳化方法，可舉例如下方法，將氮、二 氧尸反氦氬、氣、氖、一氧化碳、燃燒排放氣體等惰 性氣體，《以該等惰性氣體為主成分與其它氣體混合之混 合氣體，並於大致400〜7峨(尤其係450〜峨)下煅燒3〇 分鐘〜10小時左右。 作為由上述碳化方法所得之碳化物之活化方法，可使用 氣體活化法，即，釗田uγ ^ 水？…軋、二氧化碳、氧等活化氣體 進行般燒。其中，作Α 為活化軋體’較好的是水蒸氣或者二 I36l84.doc 1377725
Joyner, Halenda建議者（Ε· P Η3)ρηΗ τ Α U> L· α J〇yner and Ρ. 她nda，；.A黯 上述正極活性物質、負極活性物質，藉由公知方法而成 型於電極上之後，便可用作組 D有含鋰鹽之非水系電解液 與包含活性碳之正極之非水系鋰型蓄電元件之構成材料。
作為成型於電極之方法’可藉由公知之链離子電池、電 容器等電㈣造技術進行製造，例如，使用作為黏結劑之 樹脂之有機溶劑溶液，將活性物質層塗佈於作為集電體之 金屬上進行乾燥，並視情況進行衝壓而由此獲得。又活 性物謝’視情況除了活性物質以外，還可含有微粒子 石墨、乙炔黑、導電碳黑、氣相成長碳纖維等。 經成型之正極、負極，介隔隔離膜進行積層或者捲繞積 層，並插入至由罐或者層合薄膜形成之外圍部件中。隔離 膜可使用链離子二次電池中所用之聚乙烯製微多孔膜聚 丙烯製微多扎膜'或者電雙層電容器中所用之纖維素製合 成紙專。隔離膜之厚度，考慮到減小内部微短路引起之自 我放電’故校好的是10 μπι以上，又，考慮到使蓄電元件 之月b里也度達到最大’且抑制輸出特性下降，故較好的是 50 μπι以下。 作為本發明之蓄電元件中所用之非水系電解液之溶媒， 可使用以碳酸乙烯酯（EC)、碳酸丙烯酯（ρ〇為代表之環狀 碳酸酷、以碳酸二乙醋（DEC，Diethyl carbonate)、碳酸二 甲醋（DMC ’ Dimethyl carbonate)、曱基碳酸乙酿（MEC，
Ethyl methyl carbonate)為代表之鍵狀碳酸酯、γ_ 丁内醋 136l84.doc -16- t S3 (yBL)等内酯類以及其等之混合溶媒。 溶解於該等溶媒中之電解質必須係鋰鹽，若例示較佳之
鐘鹽，則可列舉 LiBF4、LiPF6、LiN(S02C2F5)2、LiN (S02CF3)(S02C2F5)、LiN(S02CF3)(S02C2F4H)以及其等之 混合鹽。非水系電解液中之電解質濃度，為抑制陰離子不 足引起之蓄電元件電容下降，故較好的是〇.5 m〇i/L以上， 又’考慮到為了防止因未溶解之鹽析出至該電解液中，或 者因該電解液黏度變得過高，反過來導致傳導性降低使得 輸出特性下降’故較好的是該非水系電解液中之電解質濃 度為2.0 mol/L以下。 用於本發明之非水系鋰型蓄電元件之負極中可預先摻 雜鐘可藉由預先掺雜經，來控制元件之電容以及作動電 壓。 [實施例] 頁示實施例、比較例，並就本發明之特徵更明確 加以說明。 <實施例1> 。碎裂之椰子殼碳化品，置於小型碳化爐中於氛中以 之^ C進仃碳化。其後，取代氮，將經預熱爐加溫之狀態 =1 kg/h之水蒸氣投人爐内’㈣小時升溫至_。〇為止之 2該椰子殼碳化品取出，於氮氣環境下進行冷卻，獲得 乾' =對所得活性碳進行流水清洗叫時後將水份沒 後，於保持為U5°C之電動乾燥機内乾燥1〇小時之 ’用球磨機研磨1小時，獲得作為正極材料之活性 I36184.doc 1377725 21 負極集電體 22 負極活性物質層 31 隔離膜 41 外殼 ❿ I36184.doc -25-

Claims (1)

  1. 第097144272號專利申請案 中文申請專利範圍替換本(101年6月） · · ♦ ... 其係於負極浪4主使 其特徵在於，令該元件之正
    ^377725 ^ 十、申請專利範圍： 1. 一種非水系鐘型蓄電元件 吸存釋放鋰離子之材料者 極活性物質中所用活性碳藉由BJH法計算之取自直徑為 2〇 A以上500 A以下之細孔之中孔容積量svl(cc/g)，藉 由MP法叶算之取自直徑未達2〇 A之細孔之微孔容積量為 V2(cc/g)時’則 〇·3<νι^〇 8且〇 V2$ i 〇。 2.如請求項1之非水系鋰型蓄電元件，其中，令正極活性 物質中所用活性碳藉由BJH法計算之取自直徑為2〇人以 上500 A以下之細孔之中孔容積量為V1(cc/g)，藉由Mp 法什算之取自直徑未達2〇 A之細孔之微孔容積量為 V2(cc/g)時，則 0.3SV1/V2S0.9。 3. 如請求項1或2之非水系鋰型蓄電元件，其中，用於正極 活性物質之活性碳之平均細孔徑為17 A以上25 A以下。 4. 如請求項1或2之非水系鋰型蓄電元件，其中，用於正極 活性物質之活性碳之BET比表面積為1 5 00 m2/g以上3 000 φ m2/g以下。 5 ·如請求項1或2之非水系鋰型蓄電元件，其中，用作負極 活性物質且吸存釋放鋰離子之材料為碳質材料，令該碳 質材料藉由BJH法計算之取自直徑為20 A以上500 A以下 之細孔之中孔容積量為Vml(cc/g)，藉由MP法計算之取 自直徑未達20 A之細孔之微孔容積量為Vm2(cc/g)時，則 0.01 $ Vml $ 0.20且 0.01 $ Vm2 S 0.40。 6·如請求項3之非水系鋰型蓄電元件，其中，用於正極活 136184-1010618.doc 眭物質之活性碳之BET比表面積為1500 m2/g以上3〇〇〇 m2/g以下。 .如請求項3之非水系鋰型蓄電元件，其中，用作負極活 眭物質且吸存釋放鋰離子之材料為碳質材料，令該碳質 材料藉由BJH法計算之取自直徑為2〇 A以上5〇〇 a以下之 細孔之中孔容積量為Vml(cc/g)，藉由MP法計算之取自 直杈未達20 A之細孔之微孔容積量為vm2(cc/g)時，則 〇.〇1 ^ Vml $ 0.20且 〇.〇1 g Vm2$ 0.40。 8 ’如清求項4之非水系鋰型蓄電元件，其中，用作負極活 性物質且吸存釋放鋰離子之材料為碳質材料，令該碳質 材料藉由BJH法計算之取自直徑為20 A以上500 A以下之 細孔之中孔容積量為Vml(cc/g)，藉由MP法計算之取自 直徑未達20 A之細孔之微孔容積量為Vm2(cc/g)時，則 0.0lSVmlS0.20 且 0.01$ Vm2S 0.40。 9,如請求項6之非水系鋰型蓄電元件，其中，用作負極活 性物質且吸存釋放鋰離子之材料為碳質材料，令該碳質 材料藉由BJH法計算之取自直徑為20 A以上500 A以下之 細孔之中孔容積量為Vml(cc/g)，藉由MP法計算之取自 直控未達20 A之細孔之微孔容積量為Vm2(cc/g)時，則 0.01 $ Vml $ 0.20且0.01 $ Vm2S 0.40。 136184-1010618.doc
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