TW501299B - Electrode compositions having improved cycling behavior - Google Patents

Abstract

An electrode composition that includes a plurality of composite particles and a plurality of electrically conductive diluent particles admixed with the composite particles. Each of the composite particles includes an electrochemically active metal particle and an electrically conductive layer partially covering the particle. In one aspect, the layer is present in an amount no greater than about 75 wt.% of the composite, while in another aspect the layer is present in an amount no greater than about 75 vol.% of the composite. Also featured are lithium ion batteries featuring electrodes made from these compositions.

Description

501299 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（1 ) 優先權陳述 本申請案自2000年1月13日提出申請之臨時申請案序號 6〇/175,893引得優先權。 技術範疇 本發明係關於有用於二次鋰電池之電極材料。 發明背景 有兩類材料被提出作爲二次鋰電池之陽極。其中一類包 括可夾入鋰之材料，諸如石墨及其他形式的碳。雖然爽入 陽極一般展現良好的循環壽命及庫侖效率，但其之容量相 當低。 第二類包括與鋰金屬合金化的金屬。雖然此等合金型陽 極一般相對於夾入型陽極展現較高的容量，但其有循環壽 命及庫侖效率相當差的缺點。一項原因爲合金型陽極在充 電及放電過程中會經歷大的體積變化。此將導致在活性顆 粒與典型上與活性顆粒結合以形成陽極之導電性稀釋劑（例 反）顆粒之間之接觸的劣化。此接觸的劣化依序將導致 減小的循環作用速率行爲。 發明總結 本發明提供適用於二次鋰電池之電極組合物，其中此電 合物具有即使係於重複的循環作用後仍可保持之高起 士口备里。亦可容易地製造此電極組合物，及加入此等組人 物之電池。 · 0 口 =達此等目的，本發明之特徵爲—種電極組合物，其包 括多數複合物顆粒與多數導電性稀釋劑顆粒（例如，導電性 -4- (請先閱讀背面之注咅？事項再填寫本頁) 裝--------訂-丨------·線*·1501299 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (1) Priority statement This application has received priority from the provisional application number 60 / 175,893 filed on January 13, 2000. TECHNICAL FIELD The present invention relates to an electrode material useful for a secondary lithium battery. BACKGROUND OF THE INVENTION Two types of materials have been proposed as anodes for secondary lithium batteries. One category includes materials that can trap lithium, such as graphite and other forms of carbon. Although the refresh anode generally exhibits good cycle life and coulomb efficiency, its capacity is relatively low. The second category includes metals alloyed with lithium metal. Although these alloy anodes generally exhibit higher capacity than sandwich anodes, they have the disadvantages of relatively poor cycle life and relatively low Coulomb efficiency. One reason is that alloy-type anodes experience large volume changes during charging and discharging. This will lead to deterioration of the contact between the active particles and the conductive diluent (example) particles that are typically combined with the active particles to form an anode. The degradation of this contact in turn will result in a reduced cyclic action rate behavior. Summary of the Invention The present invention provides an electrode composition suitable for use in a secondary lithium battery, wherein the electrode has a high viscosity that can be maintained even after being subjected to repeated cycling. It is also possible to easily manufacture the electrode composition and batteries incorporating such groups of people. 0 port = to achieve these purposes, the present invention is characterized by an electrode composition, which includes most composite particles and most conductive diluent particles (for example, conductivity -4- (Please read the note on the back? Please fill in this page for matters) Packing -------- Order- 丨 ------ · Line * · 1

x 297公釐） A7五、發明說明（2 B7 經濟部智慧財產局員工消費合作社印製 果、粒）。此组合物可更包括使複合物顆粒及稀釋劑顆 粒分散於其中的聚合黏合劑（例如，聚偏二氟乙烯黏合劑）。'、 複合物顆粒包括電化學活性金屬顆粒及部分覆蓋金屬顆 -〈導電性層。在一態樣中，此層係以不大於複合物顆粒 〈約75重量百分比的量存在。此層係以不大於複合物顆粒 广〇重量百分比的量存在較佳，且可以不大於複合物顆 約25重量百分比之量存在。在第二態樣中，此層係以 不大於複合物顆粒之約75體積百分比之量存在，且可以不 大於複合物顆粒之約㈣積百分比或25體積百分比的量存 在。此層㈣降低在循環作用過程中在電化學活性金屬顆粒與導電性稀釋劑顆粒之間之電接觸的劣化，而改良電極 之效率。「電化學活性金屬」係在鋰電池之充電及放電過程中典 型上會遭遇到之條件τ可與鐘反應的金屬。相對地，「電 化學不活性元素金屬」係在該等條件下不與叙反應之金屬。在兩種情況中’術語「金屬」冑包括有時亦被稱爲「類 金屬」之材料諸如矽。 / 「導I性層」係具有至少在半導體範圍之整體導電性， 例如，在約1〇力歐姆·公分左右以上之層。 術w「冲为覆盍」係指當使複合物顆粒與包括鋰電解質 鹽之電解質接觸時，此層可使電解質到達下方的電化學活 性金屬顆粒。在-些情況中，此包括此層爲在顆粒上之不 連續塗層之形態，以致下方的金屬顆粒材料可使用χ_射線 光電子光譜術（XPS)偵測的配置。在其他情況中，此層可爲 本紙張尺度適用中國國家標準（CNS〉A4規格（21〇 χ 297公釐） (請先閱讀背面之注音？事項再填寫本頁) I I I I I I I . •線画蠢—！ — 經濟部智慧財產局員工消費合作社印製 A7 〜--— _ —_ 五、發明說明（3 ) 多孔性，·以使電解質可穿透層及到達下方的金屬顆粒。層 的孔隙度百分比係根據記述於以下實施例中之程序測定。 此層具有在約90%左右的孔隙度較佳。 當加入至鋰電池中時，電極組合物以展現（^對3〇個完整 的充電-放電循環至少約1〇〇毫安培小時（mAh)/每克活性金 屬I比容量，及（b)當循環作用至達到約100亳安培小時/每 克組合物之活性金屬時，對30個完整的充電_放電循環至少 99% (以至少99.5%較佳，至少99 9%更佳）之庫侖效率較佳 。對500個循環達到此性能値較佳，對1〇〇〇個循環更佳。 在另一較佳具體實例中，當-將電極組合物加入至鋰電池 中時，其展現（a)對30個完整的充電-放電循環至少約5〇〇亳 安培小時每克活性金屬之比容量，及（1})當循環至達到約5〇〇 笔安培小時每克組合物之活性金屬時，對3〇個完整的充電_ 放電循環至少99% (以至少99 5%較佳，至少99 9%更佳）之 庫命效率。對200個循環達到此性能値較佳，對5〇〇個循環 更佳。 電化學活性金屬顆粒之適當金屬的例子包括鋁、矽（例如 ’無定形矽）、錫、銻、鉛、鍺、鎂、鋅、鎘、鉍、及銦。 顆粒亦可包括一或多種電化學不活性元素金屬。適當的電 化學不活性元素金屬之例子包括第IB族至第VIIB族之元素 金屬’以及第VIII族及稀土元素金屬。明確的例子包括Ti、 v、Cr、Μη、Fe、Co、Ni、Cu、Y、Zr、Nb、Mo、La、Hf 、Ta、W、Ce、Pr、Nd、Eu、Gd、Tb、Dy、Ho、Er、Yb 、Lu、Be、及Sm。其中鉬、鈮、鎢、妲、鐵、鎳、錳、及 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁)x 297 mm) A7 V. Description of the invention (2 B7 Fruits and tablets printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs). The composition may further include a polymer binder (for example, a polyvinylidene fluoride binder) in which the composite particles and the diluent particles are dispersed. ', Composite particles include electrochemically active metal particles and partially covered metal particles-a conductive layer. In one aspect, this layer is present in an amount not greater than about 75 weight percent of the composite particles. This layer is preferably present in an amount not greater than 0% by weight of the composite particles, and may be present in an amount not greater than about 25% by weight of the composite particles. In the second aspect, this layer is present in an amount not greater than about 75 volume percent of the composite particles, and may be present in an amount not greater than the approximate volume percentage or 25 volume percent of the composite particles. This layer reduces the degradation of the electrical contact between the electrochemically active metal particles and the conductive diluent particles during cycling, and improves the efficiency of the electrode. "Electrochemically active metals" are metals that typically meet conditions τ that can react with the clock during the charging and discharging of lithium batteries. In contrast, "electrochemically inactive element metals" are metals that do not react with Syria under these conditions. In both cases, the term "metal" includes materials such as silicon, which is sometimes also referred to as "metal-like". / "I-conducting layer" refers to a layer having an overall conductivity at least in the semiconductor region, for example, about 10 force ohm · cm or more. The term "impact for covering" means that when the composite particles are brought into contact with an electrolyte including a lithium electrolyte salt, this layer allows the electrolyte to reach the electrochemically active metal particles below. In some cases, this includes configurations where this layer is a discontinuous coating on the particles such that the underlying metal particulate material can be detected using x-ray photoelectron spectroscopy (XPS). In other cases, this layer can apply the Chinese national standard (CNS> A4 size (21 × χ297 mm)) for the paper size (please read the note on the back? Matters before filling out this page) IIIIIII. • Line drawing stupid—! — Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 ~ --—— _ —_ V. Description of the invention (3) Porosity so that the electrolyte can penetrate the layer and the metal particles below. The percentage of porosity of the layer is Measured according to the procedures described in the following examples. This layer preferably has a porosity of about 90%. When added to a lithium battery, the electrode composition exhibits (^ to 30 complete charge-discharge cycles). At least about 100 milliampere-hours (mAh) per gram of active metal I specific capacity, and (b) 30 cycles of full charge when the cycle is reached to reach about 100 ampere-hours per gram of active metal _ Coulomb efficiency is better with at least 99% discharge cycle (preferably at least 99.5%, more preferably at least 99 9%). This performance is better for 500 cycles, and better for 1000 cycles. In a preferred embodiment, when-the electricity When the composition is added to a lithium battery, it exhibits (a) a specific capacity of at least about 500 ampere-hours per gram of active metal for 30 complete charge-discharge cycles, and (1)) when cycled to reach about 5 〇00 ampere-hours per gram of the active metal of the composition, for 30 complete charge-discharge cycles of at least 99% (preferably at least 99 5%, better at least 99 9%) of the library life. For 200 It is better to achieve this performance in one cycle, and better for 500 cycles. Examples of suitable metals for electrochemically active metal particles include aluminum, silicon (eg, 'amorphous silicon'), tin, antimony, lead, germanium, magnesium, Zinc, cadmium, bismuth, and indium. Particles may also include one or more electrochemically inactive element metals. Examples of suitable electrochemically inactive element metals include Group IB to Group VIIB element metals' and Group VIII and Rare earth element metals. Specific examples include Ti, v, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, La, Hf, Ta, W, Ce, Pr, Nd, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu, Be, and Sm. Among them, molybdenum, niobium, tungsten, thorium, iron, nickel, manganese, This paper scale applicable Chinese National Standard (CNS) A4 size (210 X 297 mm) (Please read the back of the precautions to fill out this page)

經濟部智慧財產局員工消費合作社印制衣 501299 A7 ----__B7 — 五、發明說明（4 ) 一 ----- 銅爲較佳。 ‘在-具體實例中，金屬顆粒基本上係由在環境溫度下呈 ^形混合物形態之至少—種電化學不活性元素金屬及至 ^ 一種電化學活性元素金屬所組成。舉例來説，混合物可 ^本上由矽、錫、及銅所組成。當將電極組合物加入至鋰 電池中，並在環境溫度下循環作用通過至少_個完整的充 電道電循環時，此混合物仍保持爲無定形。「無定形」材 料係缺 <如由X-射線繞射、透射電子顯微術或示差掃描量 熱法所觀察得之結晶材料之遠距原子次序特徵的材料。 八導電性層可具有許多形態二在一具體實例中，此層包括 分散於聚合黏合劑（例如，聚偏二氟乙烯黏合劑）中之導電性 碳顆粒。在其他具體實例中，此層爲金屬層諸如銅祕層 。在一特佳具體實例中，複合物顆粒之特徵爲一層導電性 碳顆粒分散於部分覆蓋活性金屬顆粒之聚偏二氟乙晞黏合 劑中，及電極組合物係經由將複合物顆粒與導電性碳稀釋 浏顆粒結合於第二聚偏二氟乙烯黏合劑中而製備得。 可將包含前述電極組合物之鋰電池使用作爲在各種應用 中之電源。其例子包括汽車、電腦、動力工具、及通訊裝 置之電源。 本發明之其他特徵及優點將可由以下之其較佳具體實例 之説明，及由申請專利範園而明瞭。 圖示説明 圖1A説明如實施例1所説明之有及沒有導電性層之電極之 以可逆比容量表示的循環作用性能。 本紙張尺度適用中國國家標準（CNS〉A4規格（2i〇 X 2抑公^ 1 ^ IL—ΦΜ-----—tr---------線 *·—^------1--------------- (請先閱讀背面之注音？事項再填寫本頁) 501299 A7 五、發明說明（5 ) 圖1B説明如實施例冰説明之有及沒有導電性層之電極之 以庫侖效率表示的循環作用性能。 η圖2係説明於實施例2之具有導電性層切务銅樣品在循 環作用之前得到的X-射線繞射分佈。 圖3説明於實施例2中所説明之矽_錫_銅樣品及具有導電性 石夕-錫_鋼樣品〈以充電休止電壓㈣咖v〇ha㈣及 >同流容量（trickle capacity)表示的循環作用性能。 圖:説明於實施例3之具有導電性層之石夕樣品在循環作 用之前得到的X-射線繞射分佈。 圖5説明於實施例3中所説明之矽樣品及具有導電性層 石夕樣品之以充電休止電壓及渭流容量表示的循環作用性能 圖6係説明於實施例4之具有導電性層之石夕樣品在循環 用之前得到的X-射線繞射分佈。 圖7説明於實施例4中所説明之矽樣品及具有導電性層 矽樣品之以充電休止電壓及涓流容量表示的猶環作用性 之 作 之 (請先閱讀背面之注音3事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 能 圖8係説明於實施例5之具有導電性層之石夕樣品在循環作 用之前得到的X-射線繞射分佈。 圖9説明於實施例5中所説明之矽樣品及具有導電性層之 石夕樣品之以充電休止電壓及、;胃流容量表示的循環作用性能。 ㈣圖10係比較經製備成具有及不具有導電性層之樣品之循 5哀作用前後之行爲的一系列光學顯微照片。 詳述 本電極組合物包括與導電性稀釋劑諸如碳黑混合之複合 ϋ I n n n I 一-eJ· ϋ n n 1 n 線丨· -8 - M31299 A7 ---~--— B7 __ 五、發明說明（6 ) 、· 物顆粒。此組合物可更包括使複合物顆粒及稀釋劑顆粒分 散於其中的聚合黏合劑，諸如聚偏二氟乙烯。複合物鳄= 具有説明於以上之發明總結中的化學組合物及微結構。^ 可使用諸如化學及蒸氣沈積、眞空沈積（即濺鍍）、眞空蒸發 、熔融抽絲、邊帶冷卻（splat cooling)、噴霧霧化、電化與 沈積等等之技術製備爲薄膜之形態，然後再粉碎。其亦可 使用諸如球磨或活性金屬之化學還原的技術而製備得。 此電極組合物尤其有用於鋰離子電池。爲製備電池，將 複合物顆粒及導電性稀釋劑與黏合劑（例如，聚偏二氣乙缔 黏合劑）及溶劑結合形成料漿，然後再使用習知之塗布技術 將其塗布於襯料上，並乾燥形成電極。然後將電極與電解 質及相對電極結合。 電解質可爲固態或液態電解質。固態電解質之例子包括 聚合電解質，諸如聚環氧乙烷、聚四氟乙晞、含氟共聚物 、及其組合。液態電解質之例子包括碳酸乙二酯、碳酸二 乙酯、碳酸丙二酯、及其組合。電解質具有鋰電解質鹽。 適當鹽的例子包括LiPF6、LiBF4、及LiC104。 供含液態電解質之電池用之適當相對電極組合物的例子 包括LiCo02、LiCo0 2Ni0.8O2、及LiMn204。供含固態電解質 之電池用之適當相對電極組合物的例子包括LiV308及 LiV2〇5 〇 本發明現將經由以下的實施例而作進一步的説明。 實施例 A·電極製備 • 9 - 本紙張尺度適用中國國家標準（CNS)A4規格（21〇 χ 297公釐） c請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 * * -· n n B— I 1 n 一：OJt n n n n n t— n I 線 ----------------------- 501299 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（7 ) 根據以下的程序利用濺鍍將電極製備成薄膜形態。 濺鍍程序# 1 使用改良的珀金埃爾曼蘭德斯（perkin_Eliner Randex) 2400-8SA型濺鍍系統，經由連續或單革巴濺鍍製備得薄膜。 將原來之8英吋直徑的濺鍍源更換爲購自加州聖地牙哥材料 科學（Materials Science)之6英吋直徑的直流磁控管濺鍍源。 濺鍍源係使用以恆流模式操作的先進能源（Advanced Energy) MDX-10直流型濺鍍電源供電。將蘭德斯系統之轉 盤驅動單元更換爲分檔器馬達，以改良旋轉速度範圍及控 制。此系統係利用由習知之旋^轉輪葉泵支持的未設陷油擴 散栗（untrapped oil diffusion pump)泵送。 在3-30毫托爾（mT〇rr)範圍内的氬壓力下進行濺鍍。經由 控制氬流量並結合置於擴散系上方之活動百葉窗型電導限 制器，而維持壓力。 使用雙面膠帶（3M Brand Y9415，購自明尼蘇達州聖保羅 市3M公司）將銅箔（厚度=0·001英吋）黏合至蘭德斯系統的水 冷基材轉盤。將系統關閉及抽眞空，典型上係至低於1 χ 1〇-5 托爾的基壓（沈積前的基壓並不重要）。在沈積之前使用蘭德 斯系統之「濺鍍蝕刻（Sputter Etch)」模式，將13.56 MHz之 功率施加至基材轉盤及使用8毫托爾之在濺鍍室中之氬壓力 將樣品進行蚀刻。此程序使銅箔表面被適度能量的氬離子 (100-15〇電子伏特（eV))轟擊，而將銅進一步清潔，及確保 錢鍍薄膜的良好黏著至銅表面。典型的清潔循環爲15〇瓦3〇 分鐘’在循環作用過程中使基材台面旋轉。 -10- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ^--------------------訂 (請先閱讀背面之注意事項再填寫本頁)Printing of clothing by employees' cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 501299 A7 ----__ B7 — V. Description of the invention (4) 1 ----- Copper is better. ‘In a specific example, the metal particles are basically composed of at least one electrochemically inactive element metal and ^ one electrochemically active element metal in the shape of a mixture at ambient temperature. For example, the mixture may consist essentially of silicon, tin, and copper. When the electrode composition is added to a lithium battery and is circulated through at least one full charging circuit at ambient temperature, the mixture remains amorphous. "Amorphous" materials are missing < such as those with distant atomic order characteristics of crystalline materials as observed by X-ray diffraction, transmission electron microscopy, or differential scanning calorimetry. The eight conductive layer may have many forms. In a specific example, this layer includes conductive carbon particles dispersed in a polymer binder (for example, a polyvinylidene fluoride binder). In other specific examples, this layer is a metal layer such as a copper layer. In a particularly preferred embodiment, the composite particles are characterized by a layer of conductive carbon particles dispersed in a polyvinylidene fluoride binder that partially covers the active metal particles, and the electrode composition is obtained by combining the composite particles with electrical conductivity. Carbon diluent particles are prepared by combining with a second polyvinylidene fluoride adhesive. A lithium battery containing the foregoing electrode composition can be used as a power source in various applications. Examples include power supplies for automobiles, computers, power tools, and communication devices. Other features and advantages of the present invention will be explained by the following preferred specific examples, and will be apparent from the patent application park. Illustrative Figure 1A illustrates the cyclic performance in terms of reversible specific capacity of an electrode with and without a conductive layer as described in Example 1. This paper size applies to Chinese National Standards (CNS> A4 specifications (2i〇X 2 suppression) ^ 1 ^ IL—ΦΜ -----— tr --------- line * · — ^ ---- --1 --------------- (Please read the note on the back? Matters before filling out this page) 501299 A7 V. Description of the invention (5) Figure 1B Cyclic action performance in terms of Coulomb efficiency for electrodes with and without a conductive layer. Η Figure 2 illustrates the X-ray diffraction distribution obtained before the cyclic effect of a copper sample with a conductive layer in Example 2 before cycling. 3 Explain the cycle of silicon_tin_copper sample and conductive stone xi_tin_steel sample described in Example 2 (represented by the charging stop voltage ㈣ カ v〇ha㈣ and > trickle capacity) Performance: Figure: illustrates the X-ray diffraction distribution of the Shi Xi sample with a conductive layer obtained in Example 3 before cyclic action. Figure 5 illustrates the silicon sample and a conductive layer described in Example 3. Cyclic performance of the Shi Xi sample in terms of the charging rest voltage and the current capacity. Figure 6 illustrates the Shi Xi sample with a conductive layer in Example 4. The X-ray diffraction distribution obtained before was used. Fig. 7 illustrates the behavior of the Si sample and the Si sample with a conductive layer described in Example 4 in terms of charge stopping voltage and trickle capacity. (Please read the note 3 on the back before filling out this page) Printed energy of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Figure 8 illustrates the X- Ray Diffraction Distribution. Figure 9 illustrates the cyclic action performance in terms of the charging rest voltage and the gastric flow capacity of the silicon sample and the stone sample with a conductive layer described in Example 5. ㈣Figure 10 is a comparison of A series of optical micrographs of the behavior before and after the preparation of samples with and without a conductive layer. Detailed description The electrode composition includes a composite with a conductive diluent such as carbon black ϋ I nnn I- -eJ · ϋ nn 1 n line 丨 · -8-M31299 A7 --- ~ --- B7 __ V. Description of the invention (6), ... particles. This composition may further include composite particles and diluent particles Disperse polymerization Adhesives, such as polyvinylidene fluoride. Composite crocodiles = have the chemical composition and microstructure described in the summary of the invention above. ^ Such as chemical and vapor deposition, vacuum deposition (ie sputtering), vacuum evaporation, Melt wire drawing, splat cooling, spray atomization, electrification, deposition, etc. are prepared into the form of a thin film and then pulverized. It can also be prepared using techniques such as ball milling or chemical reduction of active metals. This electrode composition is particularly useful in lithium ion batteries. To prepare batteries, the composite particles and conductive diluent are combined with a binder (for example, polyvinylidene diene binder) and a solvent to form a slurry, and then used Conventional coating techniques are applied to the substrate and dried to form an electrode. The electrode is then combined with the electrolyte and the counter electrode. The electrolyte may be a solid or liquid electrolyte. Examples of the solid electrolyte include a polyelectrolyte such as polyethylene oxide, polytetrafluoroacetamidine, a fluorinated copolymer, and combinations thereof. Examples of the liquid electrolyte include ethylene carbonate, diethyl carbonate, propylene carbonate, and combinations thereof. The electrolyte has a lithium electrolyte salt. Examples of suitable salts include LiPF6, LiBF4, and LiC104. Examples of suitable counter electrode compositions for batteries containing a liquid electrolyte include LiCo02, LiCo0 2Ni0.8O2, and LiMn204. Examples of suitable counter electrode compositions for batteries containing solid electrolytes include LiV308 and LiV205. The present invention will now be further illustrated by the following examples. Example A · Electrode Preparation • 9-This paper size is in accordance with the Chinese National Standard (CNS) A4 specification (21〇 × 297 mm) c Please read the notes on the back before filling this page) Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs Printed * *-· nn B— I 1 n One: OJt nnnnnt— n I line ----------------------- 501299 Employees of Intellectual Property Bureau, Ministry of Economic Affairs Printed by the Consumer Cooperative A7 B7 V. Description of the invention (7) The electrode was prepared into a thin film form by sputtering according to the following procedure. Sputtering Procedure # 1 A thin film was prepared by continuous or single-bar sputtering using a modified Perkin_Eliner Randex 2400-8SA sputtering system. The original 8-inch diameter sputtering source was replaced with a 6-inch diameter DC magnetron sputtering source purchased from Materials Science, California. The sputtering source is powered by an Advanced Energy MDX-10 DC-type sputtering power source operating in constant current mode. The rotary drive unit of the Landes system was replaced with a stepper motor to improve the range of rotation speed and control. This system is pumped using an untrapted oil diffusion pump supported by a conventional rotary vane pump. Sputtering is performed at an argon pressure in the range of 3-30 millitorr (mTorr). The pressure is maintained by controlling the flow of argon in combination with a movable shutter-type conductivity limiter placed above the diffusion system. A double-sided tape (3M Brand Y9415, purchased from 3M, St. Paul, Minnesota) was used to bond copper foil (thickness = 0.001 inch) to the Landers system's water-cooled substrate turntable. The system is shut down and evacuated, typically to a base pressure below 1 x 10-5 Torr (the base pressure before deposition is not important). Prior to sedimentation, the power of 13.56 MHz was applied to the substrate turntable using the "Sputter Etch" mode of the Landes system and the samples were etched using an argon pressure in a sputtering chamber of 8 mTorr. This procedure allows the copper foil surface to be bombarded with moderate energy argon ions (100 to 150 electron volts (eV)), further cleans the copper, and ensures the good adhesion of the copper plating film to the copper surface. A typical cleaning cycle is 15 watts and 30 minutes' during which the substrate table is rotated. -10- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ^ -------------------- Order (please read the first (Please fill in this page again)

經濟部智慧財產局員工消費合作社印製 501299 A7 *1,1111111 - .............. — — 五、發明綱（8 ) "s 於蚀刻後，使用在濺鍍源與銅基材之間的機械樓門將賤 艘源啓動。此可將污染物自濺鍍源表面移除，而不會使其 沈積於基材表面上。接下來使兩濺鍍源在預定的電流値; 啓動，並開始沈積。於適當的沈積時間後，將—二兩Ί賤 鍍源關掉。 / 濺鍍程序#2 使用由在相對於三個6英吋長水冷濺鍍靶之水冷驟冷輥上 驅動6英忖寬基料之習知之基料操控系統所组成的㈣塗布 機製備薄膜。大量的水冷屏蔽限制住濺鍍電漿，並界定移 動基料的暴露面積。使用— 由習知之粗泵支持的cti_ CRYOGENICS ON-BORD⑧高眞空深冷泵及Uyb〇ld高眞空 輪機泵220型將塗布機抽眞空。利用以定功率模式操作的 ADVANCED ENERGY MDX Π直流電源對靶供電。在川毫 托爾下在氬氣環境中進行濺鍍。調整濺鍍功率及基料速度 以控制沈積材料量（塗布重量）。 濺艘程序# 3 於P4 Mill Lane濺鍍系統中使用個別的濺鍍靶製備得薄膜 。濺鍍源係使用以定功率模式操作的先進能源MDX_ 1〇直流 型濺鍍電源供電。此系統係使用六個CTI-Cry〇genics ON-BORD®南眞空深冷泵（1個1〇英吋的泵及5個8英吋的泵） 泵送。將銅箔（厚度=0.001英吋）縛至濺鍍系統之24英吋的驟 冷輥。將系統關閉及抽眞空，典型上係至低於3 χ 1〇·6托爾 的基壓。接下來利用2分鐘使功率升至最終功率値，而將兩 濺鍍源啓動’並開始沈積。於適當的沈積時間後，將矽關 -11 - 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公髮） (請先閱讀背面之注音？事項再填寫本頁)Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 501299 A7 * 1,1111111-.............. — V. Outline of Invention (8) " s After etching, use in splash The mechanical building door between the plating source and the copper substrate will start the low ship source. This removes contaminants from the surface of the sputtering source without causing them to deposit on the surface of the substrate. Next, the two sputtering sources were started at a predetermined current, and deposition was started. After a proper deposition time, turn off the two or two low-grade plating sources. / Sputtering Procedure # 2 A film was prepared using a conventional coater consisting of a conventional substrate control system that drives a 6-inch wide substrate against three 6-inch long water-cooled sputtering targets. A large number of water-cooled shields limit the sputtering plasma and define the exposed area of the mobile substrate. Use — cti_ CRYOGENICS ON-BORD (high-air cryogenic pump) and Uybold high-turbine pump 220, which are supported by the conventional rough pump, evacuate the coater. The target is powered by an ADVANCED ENERGY MDX Π DC power source operating in a constant power mode. Sputtering was performed in an argon atmosphere under Chuan Torr. Adjust the sputtering power and base material speed to control the amount of deposited material (coating weight). Splash Vessel Procedure # 3 A thin film was prepared in a P4 Mill Lane sputtering system using individual sputtering targets. The sputtering source is powered by an advanced energy source MDX_10 DC type sputtering power source operating in a constant power mode. This system was pumped using six CTI-Cryogenics ON-BORD® Nanyu Air Cryogenic Pumps (1 10-inch pump and 5 8-inch pumps). Tie the copper foil (thickness = 0.001 inches) to the 24 inch quench roll of the sputtering system. The system is shut down and evacuated, typically tied to a base pressure below 3 x 10.6 Torr. Next, the power was raised to the final power in 2 minutes, and the two sputtering sources were started 'and the deposition was started. After a proper deposition time, the silicon gate will be -11-This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297) (please read the note on the back? Matters before filling out this page)

501299 A7 B7__ 五、發明說明（9 ) 閉，及將銅或鉻靶打開，以產生面塗層。 B. X-射線繞射 使用設有鉬靶X-射線管及繞射射束單色器的西門子 (Siemens)Kristalloflex 805 D500型繞射儀收集繞射圖案。將 樣品安裝於樣品爽具上。 C. 孔隙度 孔隙度係由以下方程式定義·· m觀察 m理想 V孔隙 v觀察理想 P觀察 P理想 p =-=-=- V觀察 V觀察 -111觀察 P觀察 其中P係爲計算孔隙度，V係指體積，V之下標係指示體積 係指孔隙之體積、觀察體積、及理想體積。體積可經由將 指定成份i之質量m除以其密度r而計算得。所考慮的觀察質 量及理想質量係相等；因此孔隙度可單獨自觀察及理想密 度計算得。理想及觀察密度係以兩種不同方式得到。理想 密度係計算如下： ，501299 A7 B7__ 5. Description of the invention (9) Close and open the copper or chromium target to produce a top coat. B. X-Ray Diffraction The Siemens Kristalloflex 805 D500 diffractometer equipped with a molybdenum target X-ray tube and a diffraction beam monochromator was used to collect diffraction patterns. The sample is mounted on the sample holder. C. Porosity Porosity is defined by the following equation: m observation m ideal V pore v observation ideal P observation P ideal p =-=-=-V observation V observation -111 observation P observation where P is the calculated porosity, V refers to the volume, and the subscript V refers to the volume of the pores, the observed volume, and the ideal volume. The volume can be calculated by dividing the mass m of the specified component i by its density r. The observed quality and the ideal quality are considered equal; therefore, the porosity can be calculated from the observation and the ideal density separately. The ideal and observed density are obtained in two different ways. The ideal density is calculated as follows:

r -I rtij Wj P 理想=mT/VT = mT/ Σ--= Σ-- i Pi i Ρ i y 其中T係指包含i部分之理想、全體的非孔隙性層，及％係 指歸因於指定部分i之全體層的重量百分比。當製造層時， 層之各部分的重量百分比係爲已知。各部分的密度係由製 -12- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ----^---K----·裝--------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局員工消費合作社印製 501299 A7 B7___ 五、發明說明（10 ) 造者所提供，或經實驗測定，及將理想部分假設爲零孔隙 度。觀察密度係計算如下： P觀察一mT觀察/VT觀察=觀察/[Ατ觀察tT觀察] 其中1觀察係指全體多孔性層的觀察値，A係指面積，及_指 厚度。將一組大面積層的質量平均。厚度係以微米測得之 一組的平均。 現説明特定電極樣品的製備及定性。 實施例1 將銘-秒之單靶（64重量百分比鋁及36重量百分比矽）賤鍍 於乾淨、冷卻、1密爾（mil)、竽完全退火的冷軋i丨〇銅襯料 (Allfoils，Brooklyn Hts·，Ohio)上。濺鍍係依照濺鍍程序#1 在12¾托爾之氬下使用38 rpm之基材旋轉速率及24埃/仟瓦 分鐘之速率完成。功率爲8仟瓦，及總濺鍍時間爲4小時。 濺鍍沈積薄膜具有4.5微米之厚度，且對銅基材展現不良的 黏著。 接下來將一層厚度1 · 2微米之銅錢錄沈積索—半的濺鍍沈 積鋁-矽薄膜上。濺鍍係在12毫托爾之氬下使用38 rpm之基 材旋轉速率及200埃/仟瓦分鐘之速率完成。功率爲2仟瓦， 及總濺鍍時間爲〇·5小時。然後分別將具有及不具有銅上層 的鋁-矽薄膜自厚的銅襯料剝除，並經由使用研缽及杵將各 薄膜粉碎，而將其轉變爲薄片。 經由將2·4克之各粉碎薄膜與026克之聚偏二氟乙晞黏合 劑及〇· 14克之Super S導電性碳結合於小甲基吡咯啶酮中 ，而製備得10%固體分散液。然後將各分散液於滾子輾粉機 ___~13' 本紙張尺度適用中國國家標準（CNS)A4規格（21G X 297公爱)------- (請先閱讀背面之注意事項再填寫本頁) 一 .eJ· ϋ I n X n n n I n ft— n ·ϋ n n n n n n n n n n ϋ n i·— n n n n ϋ n _ 501299 A7 --------— B7 ____ 五、發明說明（11 ) 中利用陶资介負在l〇G rpm下研磨隔夜，隨後塗布於銅箱上 ，及於中乾燥數小時，以移除殘留溶劑。然後使用經 箔（約300微米厚，購自威斯康辛州密爾瓦基市⑽職㈣ 艾矩化學品公司（Aldrich Chemical c〇 ))作爲相對電極，使 用所產生之塗布樣於構造1225幣形電池。電池係使用別 微米厚的聚乙烯分離器構成。電解質爲溶於碳酸乙二醋及 碳酸一乙酯: 1 v/v混合物中之i體積莫耳濃度的以吓〆 將銅隔離片使用作爲集電器，並填補電池中之空隙區域。 使用MACCOR循環作用器測量電池的電化學性能。利用 在1.0伏特與〇·〇伏特之間的恆流充電及放電進行循環作用。 私池的可逆比容量及庫侖效率分別示於圖以及丨B。結果顯 π具有邵分覆盍活性鋁-矽顆粒之導電性銅層的電極相對於 特徵爲缺乏此一層之鋁_矽顆粒之電極，展現優良的庫侖效 率及循環作用性能。 實施例2 經由根據前述的濺鍍程序#2對三個個別的靶使用丨丨什瓦 的總功率濺鍍沈積，而製備得包含30重量百分比矽、66重 量百分比錫、及4重量百分比銅之薄膜。濺鍍係在3〇毫托爾 之氬下使用0.24英尺/分鐘之基料速度進行。在约3克/仟瓦 小時之速率下濺鍍沈積相同矽/錫/銅組合物之三個靶。將1〇 微米厚的銅箔（日本）使用作爲襯料。濺鍍沈積薄膜具有約5 微米之厚度及約4克/立方公分之密度。使用刮鬍刀片將薄 膜自銅箔刮除，將其粉碎，並使用270網目之篩網（美國標 準篩尺寸；ASTME-11-61)過篩。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 訂— 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局員工消費合作社印製 501299 五、發明說明（12 ) 使用所產生之粉末於構造供循環作用實驗用之2325幣形 電池。製備具有50重量百分比之粉末、32重量百分比 P碳（比利時碳（MMM Carbon))、及丨8_重量百分比聚偏 二氟乙烯黏合劑於N_甲基_2.轉淀酮中之分散液。然後將 分散夜塗布於第二銅箱上，並在眞空中乾燥數小時，以將 殘留溶劑移除。使用趣箱（約300微米厚，購自威斯康辛州 密爾瓦基市艾麵化學品公司）作爲相對電極，使用所得的經 '圼布落於構造2325带形電池。電池係使用5〇微米厚的聚乙 烯分離器構成。電解質爲溶於碳酸乙二酯及碳酸二乙酯之 1: 1 v/v混合物中之丨重量莫耳_LiPF6。將銅隔離片使用^爲 集電器’並填補電池中之空隙區域。 使用MACCOR循環作用器測量以涓滴充電容量及充電休 止電壓表示之電池的電化學性能。先使電池在35〇毫安培/ 克之高速率下放電至700毫安培小時/克之固定容量，以將 電極鋰化。然後使電池在35〇毫安培/克之速率下充電至 伏特4電壓，以自電極引出鋰。接下來使電池休止（零電流） 15分鐘，之後電池電壓可降至低於1〇伏特。將在此休止期 終點的位能記錄爲「充電休止電壓J 。其提供殘留於電極 中之鋰之夏的量度。一般而言，充電休止電壓愈高，且其 對循環數愈穩定，則鋰被愈有效地移除。 在休止期終止時，使電池在35毫安培/克之低速率（「涓滴 充電」）下充電至1·2伏特，以將未於較高速率（35〇亳安培/ 克）下移除之任何麵移除。涓滴充電容量係鋰移除程度的量 度，因此其類似於庫侖效率。一般而言，在進行涓滴充電 -15 ‘紙張尺度適用中國國家標準（CNS)A4規格（21〇 X 297公爱 -l·-------1----------- (請先閱讀背面之注意事項再填寫本頁) -線丨·----------------------- 501299 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（13) 時移除愈多鍾，則電極在高速率充電時的釋出鋰愈無效。 因此，希望使一定循環的涓滴充電容量減至最小，及於重 複的循環作用後維持低的涓滴充電容量。矽_錫_銅樣品的結 果示於圖3。 接下來重複前述的程序，除了在濺鍍之前，將銅箔溶液 塗布由40重量百分比Super_P碳及60重量百分比聚偏二氟乙 烯於N-甲基-2-吡咯啶酮中而製備得之黏合劑。使用8密爾的 缺口試棒將黏合劑塗布於箔上，然後在6(rc下在眞空中乾 燥4小時，以移除溶劑。乾燥黏合劑之厚度爲約8微米，及 濺鍍薄膜之厚度爲5微米。因土匕，複合物中之黏合劑層之體 積百分比爲60%。根據前述程序所測得，黏合劑層具有9〇% 之孔隙度。結合的黏合劑/濺鍍薄膜複合物包含87重量百分 比之矽-錫-銅薄膜及13重量百分比之黏合劑。 樣品之x_射線繞射分佈記述於圖2。其之特徵爲不存在結 晶錫及碎。大的波峰係由於銅箔集電器所產生。 使用丙酮將複合物自銅襯料移除，隨後將其自銅羯到除 。將刮除的材料粉碎，過篩，與含碳黏合劑層結合，及塗 布於第二銅箔上，而形成如前所述的電極。最終的乾燥塗 層包含50重量百分比之活性矽_錫_銅顆粒、32重量百分比之 S—r-P碳、及18重量百分比之聚偏二氣乙缔，其中㈣心 碳及聚偏二氟乙稀之量呈現在石夕_錫_銅顆粒上之層與用於形 成最終電極之分散液兩者中之此等材料的總和。 使用電極於構造2325幣形電池，並如前；f述進行測試。 圖3顯示以m電容量及充電休止電壓表示的循環作用結 本紙張尺度適用中國國家標準(CNS)A4規格（210 X 297公羞) (請先閱讀背面之注意事項再填寫本頁) --------訂-丨 -線_#-------------------1! 501299r -I rtij Wj P ideal = mT / VT = mT / Σ-= Σ-- i Pi i Ρ iy where T refers to the ideal, non-porous layer as a whole including part i, and% refers to attributable to Specify the weight percentage of the entire layer of part i. When manufacturing a layer, the weight percentages of the parts of the layer are known. The density of each part is made by -12- This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) ---- ^ --- K ---- · installation ------ --Order --------- line (Please read the notes on the back before filling out this page) Printed by the Employees 'Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 501299 A7 B7___ Five 2. Description of the invention (10) Provided by the manufacturer, or experimentally determined, and the ideal part is assumed to be zero porosity. The observation density is calculated as follows: P observation—mT observation / VT observation = observation / [Aτ observation tT observation] where 1 observation refers to the observation of the entire porous layer, A refers to the area, and _ refers to the thickness. Average the mass of a set of large area layers. Thickness is the average of a group measured in microns. The preparation and characterization of specific electrode samples will now be described. Example 1 A single target (64 weight percent aluminum and 36 weight percent silicon) of min-second was plated on a clean, cooled, 1 mil, and fully annealed cold-rolled copper lining (Allfoils, Brooklyn Hts., Ohio). Sputtering was performed in accordance with sputtering procedure # 1 under a 12¾ Torr argon using a substrate rotation rate of 38 rpm and a rate of 24 Angstroms per kilowatt minute. The power is 8 watts, and the total sputtering time is 4 hours. The sputter-deposited film has a thickness of 4.5 m and exhibits poor adhesion to a copper substrate. Next, a layer of copper with a thickness of 1.2 microns was deposited on a semi-sputtered aluminum-silicon film. Sputtering was performed at 12 mTorr of argon using a substrate rotation rate of 38 rpm and a rate of 200 Angstroms per kilowatt minute. The power was 2 watts, and the total sputtering time was 0.5 hours. Then, the aluminum-silicon film with and without the copper upper layer was stripped from the thick copper lining, and each film was pulverized by using a mortar and pestle to convert it into a sheet. A 10% solid dispersion was prepared by combining 2.4 grams of each pulverized film with 026 grams of polyvinylidene fluoride adhesive and 0.14 grams of Super S conductive carbon in small methylpyrrolidone. Then disperse each dispersion in a roller mill ___ ~ 13 'This paper size is applicable to China National Standard (CNS) A4 (21G X 297 public love) ------- (Please read the precautions on the back first (Fill in this page again) I. eJ · n I n X nnn I n ft— n · ϋ nnnnnnnnnn ϋ ni · — nnnn ϋ n _ 501299 A7 ---------- B7 ____ 5. Description of the invention (11) China uses ceramics to grind overnight at 10G rpm, then coated on a copper box, and dried in China for several hours to remove residual solvents. Then a warp foil (about 300 microns thick, purchased from Aldrich Chemical Co., Milwaukee, Wisconsin) was used as the counter electrode, and the resulting coated sample was used to construct a 1225 coin cell . The battery system uses a polyethylene separator with a thickness of another micrometer. Electrolyte is dissolved in ethylene carbonate and monoethyl carbonate: 1 v / v mixture with a volumetric molar concentration of i to scare the use of copper separator as a current collector and fill the void area in the battery. The MACCOR cycle effector was used to measure the electrochemical performance of the battery. Cycling is performed by constant current charging and discharging between 1.0 volt and 0.00 volt. The reversible specific capacity and coulomb efficiency of the private pool are shown in the graph and 丨 B, respectively. The results show that the π electrode with a conductive copper layer coated with active aluminum-silicon particles exhibits excellent Coulomb efficiency and cycling performance compared to an electrode characterized by the absence of this layer of aluminum-silicon particles. Example 2 A total of 30 weight percent silicon, 66 weight percent tin, and 4 weight percent copper were prepared by sputter deposition using three watts of total power in accordance with the aforementioned sputtering procedure # 2 on three individual targets. film. Sputtering was performed under a 30 millitorr argon using a base material speed of 0.24 feet / minute. Three targets of the same silicon / tin / copper composition were sputter deposited at a rate of about 3 g / Watt hour. A 10 micron-thick copper foil (Japan) was used as the backing. The sputter-deposited film has a thickness of about 5 microns and a density of about 4 grams per cubic centimeter. The film was scraped from the copper foil using a razor blade, pulverized, and sieved using a 270 mesh screen (U.S. standard sieve size; ASTME-11-61). This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling out this page) Order — Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives, Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Consumer Cooperative 501299 5. Description of the invention (12) Use the resulting powder to construct a 2325 coin-shaped battery for cyclic experiments. Preparation of a dispersion with 50 weight percent powder, 32 weight percent P carbon (MMM Carbon), and 8 weight percent polyvinylidene fluoride adhesive in N_methyl_2. . The dispersion was then coated on a second copper box and dried in the air for several hours to remove residual solvents. A fun box (approximately 300 micrometers thick, purchased from Ai Huan Chemical Co., Milwaukee, Wisconsin) was used as a counter electrode, and the resulting warp cloth was used to construct a 2325 strip battery. The battery system was constructed using a 50-micron-thick polyethylene separator. The electrolyte is mol_LiPF6 in a 1: 1 v / v mixture of ethylene carbonate and diethyl carbonate. The copper separator is used as a current collector 'and fills the void area in the battery. The MACCOR cycle effector was used to measure the electrochemical performance of the battery in terms of trickle charge capacity and charge stop voltage. First, the battery was discharged at a high rate of 35 mAh / g to a fixed capacity of 700 mAh / g to lithify the electrodes. The battery was then charged to a voltage of 4 volts at a rate of 35 mA / g to draw lithium from the electrode. The battery is then halted (zero current) for 15 minutes, after which the battery voltage can drop below 10 volts. The bit energy at the end of this resting period is recorded as "charging resting voltage J. It provides a measure of the summer of lithium remaining in the electrode. Generally speaking, the higher the charging resting voltage and the more stable its cycle number, the lithium Is removed more effectively. At the end of the resting period, the battery is charged to 1.2 volts at a low rate of 35 milliamps / gram ("trickle charge") in order to reduce G) Remove any faces that were removed. Trickle charge capacity is a measure of the extent of lithium removal, so it is similar to Coulomb efficiency. Generally speaking, when carrying out trickle charging -15 'paper size applies Chinese National Standard (CNS) A4 specification (21〇X 297 public love-l · ------- 1 ---------- -(Please read the precautions on the back before filling this page) -Online 丨 · ----------------------- 501299 Employee Consumer Cooperatives, Bureau of Intellectual Property, Ministry of Economic Affairs Print A7 B7 V. Description of the invention (13) The more minutes it is removed, the more ineffective the lithium released by the electrode during high-rate charging. Therefore, it is hoped to minimize the trickle charge capacity in a certain cycle and to repeat the Maintains a low trickle charge capacity after cycling. The results for the silicon_tin_copper sample are shown in Figure 3. The previous procedure was then repeated, except that the copper foil solution was coated with 40 weight percent Super_P carbon and 60 weight before sputtering. Adhesive prepared by the percentage of polyvinylidene fluoride in N-methyl-2-pyrrolidone. The adhesive was coated on the foil using a notched test bar of 8 mils and then in the air at 6 (rc Dry for 4 hours to remove the solvent. The thickness of the dry adhesive is about 8 microns, and the thickness of the sputtered film is 5 microns. Due to the adhesion of the soil, the compound The volume percentage of the layer is 60%. The adhesive layer has a porosity of 90% measured according to the foregoing procedure. The combined adhesive / sputter film composite contains 87 weight percent of a silicon-tin-copper film and 13 weight Percentage of the binder. The x-ray diffraction distribution of the sample is described in Figure 2. It is characterized by the absence of crystalline tin and debris. The large peaks are generated by the copper foil current collector. The compound is removed from the copper lining using acetone. It is removed and then removed from the copper scoop. The scraped material is crushed, sieved, combined with a carbon-containing adhesive layer, and coated on a second copper foil to form an electrode as previously described. The final The dry coating contains 50% by weight of active silicon_tin_copper particles, 32% by weight of S-rP carbon, and 18% by weight of polyvinylidene chloride, of which the amount of core carbon and polyvinylidene fluoride is The sum of these materials in the layer on the stone xi_tin_copper particles and the dispersion used to form the final electrode. The electrode was used to construct a 2325 coin cell and tested as previously described in f. Figure 3 Displayed in m capacity and charging rest voltage The ring size paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 male shame) (Please read the precautions on the back before filling this page) -------- Order- 丨-线 _ # ------------------- 1! 501299

五、發明說明（14 ) 經濟部智慧財產局員工消費合作社印製 果，圖中並顯示經製備成不具有導電性層之相同材料的結 果。經製嬙成具有導電性層之樣品在多數循環中展現較高 的充電休止電壓及較低的涓滴充電容量，其顯示以分散於 聚偏二氟乙烯中之碳之導電性層部分覆蓋矽_錫_鋼顆粒可改 良電極的充電效率。 實施例3 將銅箔塗布如實施例2所説明之黏合劑。接下來，依照濺 鍍程序#3，將含有1〇〇重量百分比無定形矽之薄膜濺鍍沈積 於乾燥黏合劑上。濺鍍係在13毫托爾之氬下使用3 8卬瓜之 基材旋轉速率及40· 10埃/仟瓦f鐘之速率完成。功率爲5 2 什瓦，及總濺鍍時間爲3小時又48分鐘。濺鍍沈積薄膜具有 4.8微米之厚度。黏合劑之厚度爲8微米。因此，黏合劑相 對於全體複合物（即濺鍍薄膜加上黏合劑）之量爲約25重量百 分比及約60體積百分比。濺鍍薄膜之組合物係使用珀金埃 爾曼Optima 3 3 00 DV利用感應偶合電漿測定。 於濺鍍後，使用丙酮將複合物（濺蟑沈積矽薄膜加上黏合 劑）自銅箔移除，隨後再將其自箔刮除。將經刮除的材料粉 碎並過篩，而形成粉末。 粉末之x_射線繞射圖案示於圖4。其之特徵爲不存在結晶 石夕。 依照實施例2之程序將粉末與黏合劑結合，並塗布於第二 銅箔上，而形成電極。最終的乾燥塗層包含5〇重量百分比 之典疋形矽、35重量百分比之Super-P碳、及15重量百分比 之聚偏二氟乙晞，其中Super-p碳及聚偏二氟乙烯之量呈現 -17- 本紙張尺度適用中關家標準(CNS)A4規格（210 X 297公爱） ----—— (請先閱讀背面之注意事項再填寫本頁) ~ j ^ -------^---------—---------------------- 501299 經濟部智慧財產局員工消費合作社印製 發明說明（15 , 在矽-錫-鋼顆粒上之層與用於形成最終電極之分散液兩者中 I此等材料的總和。如實施例2所説明，使用電極於構造 2325幣形電池並進行測試，除了使電池放電至1400毫安培 小時/克之固定容量，而非7〇〇毫安培小時/克，以將電極鋰 化。圖5顯示以涓滴充電容量及充電休止電壓表示的循環作 用結果。 爲作比較之用，經由將〇·5克之無定形矽（I〇wa TMn FUms， Ames，ΙΑ)與含有30重量百分比聚偏二氟乙晞及7〇重量百分 比Super Ρ碳之黏合劑結合於斗曱基_2_吡咯啶酮中形成分散 液，而製備得電極。使用20密_爾刮刀塗布機將分散液塗布 於銅箔襯料（0.5密爾）上，並於眞空中乾燥4小時。最終的乾 燥塗層包含50重量百分比之無定形矽、35重量百分比之 Super P碳、及15重量百分比之聚偏二氟乙烯。然後依照前 述程序組裝及測試2325幣形電池。圖5顯示以谓滴充電容量 及充電休止電壓表示的結果。經製備成具有分散於聚偏二 氟乙烯中之碳之導電性層之樣品在多數循環中展現較高的 充電休止電壓及較低的涓滴充電容量，其顯示以導電性層 部分覆蓋無定形矽核心可改良電極的充電效率。 實施例4 經由使用矽靶及鉻靶依照濺鍍程序#3濺鍍沈積，而製備 得包含82.0重量百分比無定形矽及18〇重量百分比絡之層狀 薄膜。矽係在13耄托爾之氬下使用3·8 rpmi基材旋轉速率 及40.10埃/仟瓦分鐘之速率濺鍍於銅箔上。功率爲5 5什瓦 ，及總錢艘時間爲2小時。賤錢沈積梦薄膜具有2 6 5微米之 一 18- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐〉 I--------裝 *-------^----------^ IAWI (請先閱讀背面之注意事項再填寫本頁) 501299V. Description of the invention (14) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the figure also shows the results of the same material prepared without the conductive layer. The sample prepared with a conductive layer exhibited a higher charge rest voltage and a lower trickle charge capacity in most cycles, and it was shown that the conductive layer of carbon dispersed in polyvinylidene fluoride partially covered the silicon_ Tin_steel particles can improve the charging efficiency of the electrode. Example 3 A copper foil was coated with the adhesive as described in Example 2. Next, according to the sputtering procedure # 3, a thin film containing 100% by weight of amorphous silicon was sputter deposited on the dry adhesive. Sputtering was performed under a argon of 13 mTorr using a substrate rotation rate of 3 8 卬 and a rate of 40 · 10 Angstroms / 仟 W f clock. The power was 5 2 shW, and the total sputtering time was 3 hours and 48 minutes. The sputter deposited film has a thickness of 4.8 microns. The thickness of the adhesive is 8 microns. Therefore, the amount of the adhesive relative to the entire composite (i.e., the sputtered film plus the adhesive) is about 25% by weight and about 60% by volume. The composition of the sputtered film was determined using a PerkinElman Optima 3 3 00 DV using an inductive coupling plasma. After sputtering, the compound (sputtered silicon film plus adhesive) was removed from the copper foil using acetone, and then it was scraped off from the foil. The scraped material is pulverized and sieved to form a powder. The x-ray diffraction pattern of the powder is shown in FIG. 4. It is characterized by the absence of crystalline stones. The powder was combined with the binder according to the procedure of Example 2 and applied on a second copper foil to form an electrode. The final dry coating contains 50% by weight of canonical silicon, 35% by weight of Super-P carbon, and 15% by weight of polyvinylidene fluoride, of which the amount of Super-p carbon and polyvinylidene fluoride Presentation-17- This paper size is applicable to Zhongguanjia Standard (CNS) A4 specification (210 X 297 public love) -------- (Please read the precautions on the back before filling this page) ~ j ^ ---- --- ^ --------------------------------- 501299 The Intellectual Property Bureau of the Ministry of Economic Affairs printed a description of inventions for consumer cooperatives ( 15. The sum of these materials in both the layer on the silicon-tin-steel particles and the dispersion used to form the final electrode. As explained in Example 2, the electrode was used to construct a 2325 coin cell and tested. In addition to discharging the battery to a fixed capacity of 1400 milliamp-hours / gram, instead of 700 milliamp-hours / gram, to lithify the electrode. Figure 5 shows the results of the cyclic action expressed in trickle charge capacity and charge stop voltage. For comparison, 0.5 g of amorphous silicon (Iowa TMn FUms, Ames, IA) was compared with 30% by weight of polyvinylidene fluoride and 70% by weight. The electrode of Super P carbon is combined with tromethamine_2_pyrrolidone to form a dispersion to prepare an electrode. The dispersion is coated on a copper foil lining (0.5 mil) using a 20 mil blade coater. And dried in the air for 4 hours. The final dry coating contains 50% by weight of amorphous silicon, 35% by weight of Super P carbon, and 15% by weight of polyvinylidene fluoride. It is then assembled and tested in accordance with the aforementioned procedures. 2325 coin-shaped battery. Figure 5 shows the results expressed in terms of the charge capacity and charge stop voltage. Samples prepared to have a conductive layer of carbon dispersed in polyvinylidene fluoride show higher charge in most cycles The resting voltage and the low trickle charge capacity show that partially covering the amorphous silicon core with the conductive layer can improve the charging efficiency of the electrode. Example 4 By using a silicon target and a chromium target in accordance with the sputtering procedure # 3 sputtering deposition, and A layered film containing 82.0 weight percent amorphous silicon and 18 weight percent network was prepared. The silicon system was rotated at a rate of 3 · 8 rpmi under a pressure of 13 Torr of argon and 40.10 Angstroms per watt minute Rate sputtered on copper foil. Power is 5 5 shi, and total time is 2 hours. Cheap money deposited dream film has one of 265 microns 18-This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm) I -------- install * ------- ^ ---------- ^ IAWI (Please read the precautions on the back before filling this page ) 501299

經濟部智慧財產局員工消費合作社印製 厚度。 路係在3¾耗爾之氬下使用3.8 rpm之基材旋轉速率及5 5埃 /什瓦分鐘之速率濺鍍於矽薄膜上。功率爲55仟瓦，及總賤 鏡時間爲10分鐘。濺鍍沈積鉻薄膜具有〇 3微米之厚度。因 此’鉻之量爲複合物薄膜之10體積百分比。濺鍍複合物薄 膜之組合物係使用珀金埃爾曼Optima 3300 DV利用感應偶 合電漿測定。 於賤鍍後，經由將複合物薄膜自箔刮除，而將其自銅簿 移除。將經刮除的材料粉碎並過篩，而形成粉末。粉末之 射線繞射圖案示於圖6。其之特徵爲不存在結晶矽。尖銳 的波峰僅係由於鉻所產生。 依照實施例2之程序將粉末與黏合劑結合，並塗布於第二 銅’4上，而形成電極。最終的乾燥塗層包含5 〇重量百分比 之矽-鉻、35重量百分比之Super-P碳、及15重量百分比之聚 偏二氟乙烯。如實施例2所説明，使用電極於構造2325幣形 呢池並進行測試，除了使電池放電至丨4〇〇毫安培小時/克之 固足容量，而非700毫安培小時/克，以將電極鋰化。圖7顯 示以涓滴充電容量及充電休止電壓表示的循環作用結果， 其並顯示如實施例3之説明所製備得之無定形矽電極的結果 供比較用。經製備成具有鉻層之樣品在多數循環中展現較 高的充電休止電壓及較低的渭滴充電容量，其顯示以鉻之 導電性層部分覆蓋無定形矽顆粒可改良電極的充電效率。 實施例5 經由使用矽靶及銅靶依照濺鍍程序#3濺鍍沈積，而製備 裝·-------訂---------線 (請先閱讀背面之注意事項再填寫本頁) -19· 501299 A7 B7 17 五、發明說明（ 得包含75.3重量百分比無定形梦及24· 7重量百分比銅之層狀 薄膜。；?夕係在13毫托爾之氬下使用3 · 8 rpm之基材旋轉速率 及40.10埃/仟瓦分鐘之速率濺鍍於銅箔上。功率爲5.5仟瓦 ，及總濺鍍時間爲3小時又2分鐘。濺鍍沈積矽薄膜具有4微 米之厚度。 銅係在13毫托爾之氬下使用3.8 rpin之基材旋轉速率及250 埃/仟瓦分鐘之速率濺鍍於矽薄膜上。功率爲2·〇仟瓦，及總 濺鍍時間爲10分鐘。濺鍍沈積銅薄膜具有5微米之厚度。因 此，銅之量爲複合物薄膜之56體積百分比。濺鍍複合物薄 膜之組合物係使用珀金埃爾曼〇ptima 3300 DV利用感應偶 合電漿測定。 於賤鍍後，經由將複合物薄膜自箔刮除，而將其自銅猪 移除。將經刮除的材料粉碎並過篩，而形成粉末。粉末之 X-射線繞射圖案示於圖8。其之特徵爲不存在結晶矽。 依照實施例2之程序將粉末與黏合劑結合，並塗布於第二 銅箔上，而形成電極。最終的乾燥塗層包含5〇重量百分比 之矽-銅、35重量百分比之Super_P碳、及15重量百分比之聚 偏二氟乙烯。如實施例4所説明，使用電極於構造2325幣形 電池並進行測試。圖9顯示以涓滴充電容量及充電休止電壓 表示的循環作用結果，其並顯示如實施例3之說明所製備得 I無定形矽電極的結果供比較用。經製備成具有鋼層之樣 品在多數循環中展現較高的充電休止電壓及較低的涓滴充 電容量，其顯示以銅之導電性層部分覆蓋無定形矽顆粒可 改良電極的充電效率。 -20- (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 —— — — — —II ^ — — — — — — — — — I ΙΙΙΙΙΙΙΙΙΙΙ1ΙΙΙΙΙΙΙΙΙ — , 501299 A7 B7 五、發明說明（18 如實施例2所説明製備得具有及不具有導電性層之樣品。 製備以此等樣品爲主的電極，並使其在1毫安培/平方公分 下循環作用至700亳安培小時/克之固定容量。在循環作用 前後攝取電極的光學顯微照片。結果示於圖1〇。顯微照片 顯示在沒有導電性層的情況下，活性金屬顆粒可容易地被 推動通過聚偏二氟乙烯黏合劑，幾乎不受黏合劑影響地移 動，以致循環作用後的顯微照片看來與循環作用前的顯微 片相當不同。然而，在具有導電性層的樣〇 J俅Ρ口中，循環作 用前後的顯微照片非常相似，其顯示由於活性6 至屬顆當 猶環作用時係實質上均勻地膨脹及收縮，因 , 阳稍粒相對於^ 彼此的移動非常小。此行爲依序造成改良的電植性处 ' 其他具體實例係在以下之申請專利範園的範園内匕 (請先閱讀背面之注意事項再填寫本頁)Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. The system was sputtered on a silicon film using a substrate rotation rate of 3.8 rpm and a rate of 55 Angstroms per minute under a ¾ argon argon. The power is 55 watts, and the total mirror time is 10 minutes. The sputter deposited chromium film has a thickness of 0.3 micron. Therefore, the amount of 'Cr is 10% by volume of the composite film. The composition of the sputtered composite film was determined using a PerkinElman Optima 3300 DV using an inductive coupling plasma. After the base plating, the composite film was removed from the copper book by scraping the composite film from the foil. The scraped material is crushed and sieved to form a powder. The powder diffraction pattern is shown in FIG. It is characterized by the absence of crystalline silicon. The sharp peaks are only due to chromium. The powder was combined with a binder in accordance with the procedure of Example 2 and coated on a second copper'4 to form an electrode. The final dry coating contained 50 weight percent silicon-chromium, 35 weight percent Super-P carbon, and 15 weight percent polyvinylidene fluoride. As described in Example 2, the electrode was used to construct a 2325 coin-shaped felt cell and tested, except that the battery was discharged to a solid capacity of 4,000 mAh / g, rather than 700 mAh / g to charge the electrode. Lithification. Fig. 7 shows the results of the cyclic action in terms of trickle charge capacity and charge rest voltage, and also shows the results of the amorphous silicon electrode prepared as described in Example 3 for comparison. Samples prepared with a chromium layer exhibit higher charging rest voltage and lower Wei drop charging capacity in most cycles, which shows that partially covering amorphous silicon particles with a conductive layer of chromium can improve the charging efficiency of the electrode. Example 5 Prepared by using a silicon target and a copper target in accordance with the sputtering procedure # 3 sputtering deposition. --------- Order --------- line (Please read the precautions on the back first (Fill in this page again) -19 · 501299 A7 B7 17 V. Description of the invention (A layered film containing 75.3% by weight of amorphous dreams and 24.7% by weight of copper may be used. It is used under argon of 13 mTorr 3 · 8 rpm substrate rotation rate and 40.10 Angstroms per watt minute sputtering on copper foil. Power is 5.5 watts and total sputtering time is 3 hours and 2 minutes. Sputtered deposited silicon film has 4 Thickness of micron. Copper was sputtered on a silicon film using a substrate rotation rate of 3.8 rpin and a rate of 250 Angstroms per kilowatt-minute under argon of 13 mTorr. The power was 2.0 watts and total sputtering The time is 10 minutes. The sputter-deposited copper film has a thickness of 5 micrometers. Therefore, the amount of copper is 56% by volume of the composite film. The composition of the sputtered composite film is using PerkinElman Optima 3300 DV Inductively coupled plasma measurement. After base plating, the composite film was removed from the copper pig by scraping it away from the foil. The scraped material is pulverized and sieved to form a powder. The X-ray diffraction pattern of the powder is shown in Figure 8. It is characterized by the absence of crystalline silicon. The powder is combined with the binder according to the procedure of Example 2. And coated on a second copper foil to form an electrode. The final dry coating comprises 50 weight percent silicon-copper, 35 weight percent Super_P carbon, and 15 weight percent polyvinylidene fluoride. As in Example 4 Illustrated, the electrode was used to construct a 2325 coin cell and tested. Figure 9 shows the results of the cyclic action expressed in trickle charge capacity and charge rest voltage, and it also shows the I amorphous silicon electrode prepared as described in Example 3. The results are for comparison. Samples prepared with a steel layer exhibit higher charging rest voltage and lower trickle charging capacity in most cycles, which shows that partially covering amorphous silicon particles with a conductive layer of copper can improve the electrode's performance. Charging efficiency. -20- (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs — — — — — II ^ — — — — — — — — — I ΙΙΙΙΙΙΙΙΙΙΙΙΙΙΙΙΙΙΙΙΙΙΙΙΙΙ — 501299 A7 B7 V. Description of the invention (18 Samples with and without a conductive layer were prepared as described in Example 2. Electrodes based on these samples were prepared and placed on Cyclic action at 1 milliampere / cm 2 to a fixed capacity of 700 ampere-hours / gram. Optical micrographs of the electrodes were taken before and after cycling. The results are shown in Figure 10. The micrographs show the absence of a conductive layer The active metal particles can be easily pushed through the polyvinylidene fluoride adhesive and can be moved almost without being affected by the adhesive, so that the photomicrograph after the cycling action looks quite different from the micrograph before the cycling action. However, in the sample with a conductive layer, the photomicrographs before and after the cyclic action are very similar, which shows that due to the activity of the 6 particles, it expands and contracts substantially uniformly when the ring is acting. The movement of the slightly grains relative to each other is very small. This behavior sequentially leads to improved electrophysiology. '' Other specific examples are in the following patent application parks (please read the precautions on the back before filling this page)

• I I n I I I I I I 經濟部智慧財產局員工消費合作社印製 21 _線丨-- 本紙張尺度適用中國國家標準（CNS)A4規格（210 χ 297公釐）• I I n I I I I I I Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 21 _ 线 丨-This paper size applies to China National Standard (CNS) A4 (210 χ 297 mm)

Claims (1)

六、 申請專利範圍 2. 經濟部智慧財產局員工消費合作社印製 Ί. —種電極組合物，包括· (a) 多數複合物顆粒， ，乃广、、、薇 其各包括（1)電化學活性全屦 及⑻邵分覆蓋該顆粒之導電性層， “屬 其中該層係以不大於該複合物4 存在；及 (b) 與孩複合物顆粒混 —種電極組合物，包括：數導'性稀釋劑顆粒。 (a)多數複合物顆粒，並久勹 ，zw.·、、 其各包括（1)電化學活性金屬顆 及（11)邵为覆蓋該顆粒之導電性層， 4 存ί 2層係以不大於該複合物之约75體積百分比之量 與該複合物顆粒混合之多數導電性稀釋劑顆粒。 Π:專利範圍第1或2項之電極組合物，其中該金屬顆 :包含選自由銘1、錫、銻'錯、鍺、鎂、辞 鉍、及銦所組成之群之金屬。 如申4專利範圍第i或2項之電極組合物，其中該層包括 分散於聚合黏合劑中之導電性碳顆粒。 如申請專利範園第4項之電極組合物，其中該聚合黏合劑 包括聚偏二氟乙烯。 申叩專利範圍第1或2項之電極組合物，其中該層包括 金屬。 如申請專利範圍第！或2項之電極組合物，其中該層係非 石墨。 - 如申請專利範圍第1或2項之電極组合物，其更包括使該 顒粒 之约75重量百分比之量 f 歷 I訂 線 22-6. Scope of patent application 2. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. —A kind of electrode composition, including: (a) most of the composite particles, Nai Guang ,, and Wei each include (1) electrochemical The active layer and the sulphur compound cover the conductive layer of the particle, "being in which the layer exists with no more than the composite 4; and (b) mixed with the child composite particles-an electrode composition, including: 'Analytical diluent particles. (A) Most composite particles, and long time, zw .. ,, each of which includes (1) electrochemically active metal particles and (11) Shao is a conductive layer covering the particles, 4 The two layers are the majority of the conductive diluent particles mixed with the composite particles in an amount not greater than about 75% by volume of the composite. Π: The electrode composition of the patent scope item 1 or 2, wherein the metal particles: Contains a metal selected from the group consisting of Ming 1, tin, antimony, germanium, magnesium, bismuth, and indium. The electrode composition of item i or 2 of the patent scope of claim 4, wherein the layer includes a polymer dispersed in a polymer. Conductive carbon particles in the adhesive, such as patent application No. 4 An electrode composition, wherein the polymer binder includes polyvinylidene fluoride. The electrode composition of claim 1 or 2 in the patent scope, wherein the layer includes a metal. For example, the electrode composition of the scope of patent application! Or 2 Wherein the layer is non-graphite.-For example, the electrode composition of the scope of patent application No. 1 or 2, it further includes an amount of about 75% by weight of the granule f. 9.如中稀釋劑顆粒分散於其中的聚合黏合劑。 包括之電極組合物，其中該聚合黏㈡多Li專利氣園弟1或2项之電極組合物，其中該層係^ 一種鋰離子電池，包括： (A)弟一電極，包括： r，及「、复口物顆粒’其各包括⑴電化學活性金屬f 粒，及⑻郅分覆蓋該顒粒之導電性層， 屬’ 其中該層係以不大於^ 存在；及 大於舔複合物之約75重量百分比之』 11 I.------------丨| (請先閱讀背面之注意事項再填寫本頁) 經 濟 部 智 慧 財 產 局 員 (b)與該複合物顆粒 (B) 相對電極；及 户数導-性稀釋劑顆粒; (C) 分離該電極與該相對電極的電解質。 12· —種鋰離子電池，包括： (A) 弟一電極，包括·· (a) 多數複合物顆粒，並 、 其各包括⑴電化學活性金屬 粒，及（11)郅为覆蓋該顆粒之導電性層， 存=層係以不大於該複合物之约;5體積百分比之 (b) 與該複合物顆粒 (B) 相對電極;及 ，數導“生稀釋劑顆粒; (C) 分離該電極與該相對電極的電解質。 訂 顆 量 社 印 製 ________ -23- 本紙張尺度適用中國國家標準（CNS)A4 ^格（21〇 x 297公爱）9. A polymeric binder in which the diluent particles are dispersed. Included electrode composition, wherein the polymer is an electrode composition of item 1 or 2 of the patented Li gas patent, wherein the layer is a lithium ion battery, including: (A) an electrode, including: r, and ", Complex mouth particles', each of which includes tritium electrochemically active metal f particles, and a conductive layer that covers the tritium particles, and belongs to the group of" where the layer exists with no more than ^; 75% by weight ”11 I .------------ 丨 | (Please read the precautions on the back before filling this page) Member of the Intellectual Property Bureau of the Ministry of Economic Affairs (b) and the composite particles (B (C) Separating the electrode from the electrolyte of the opposite electrode. 12 · —a lithium ion battery, including: (A) a primary electrode, including ... (a) Most composite particles, each of which includes ⑴electrochemically active metal particles, and (11) 郅 is a conductive layer covering the particles, and the layer is not more than about the composite; 5 vol% (b ) An electrode opposite to the composite particle (B); and, a "derived diluent particle"; (C) separating the electrode from the Electrolyte of the opposite electrode. Printed by Quantitative Corporation ________ -23- This paper size applies to China National Standard (CNS) A4 ^ grid (21〇 x 297 public love)