TW550848B - Multi-layered electrode structural body, cell using same, dual-layer capacitor and manufacturing method for same - Google Patents
Multi-layered electrode structural body, cell using same, dual-layer capacitor and manufacturing method for same Download PDFInfo
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- TW550848B TW550848B TW091102319A TW91102319A TW550848B TW 550848 B TW550848 B TW 550848B TW 091102319 A TW091102319 A TW 091102319A TW 91102319 A TW91102319 A TW 91102319A TW 550848 B TW550848 B TW 550848B
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- 239000003990 capacitor Substances 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 239000002355 dual-layer Substances 0.000 title abstract description 3
- 239000010410 layer Substances 0.000 claims abstract description 238
- 239000000463 material Substances 0.000 claims abstract description 55
- 239000000203 mixture Substances 0.000 claims abstract description 45
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Classifications
-
- 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
-
- 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
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/04—Construction or manufacture in general
- H01M10/0436—Small-sized flat cells or batteries for portable equipment
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
550848 五、發明說明（1) 技術領域 利用該構造體的電 本發明涉及一種多層電極構造體 池或電氣雙層電容器的製造方法。 背景技術 迄今，製造電極構造體時，都在集電材料面上塗布包 括電極材料、粉狀導電物質、钻合劑和溶劑的混合物，附 著一層電極層製成電極構造體。 〈一〉本發明是以製造具有多層電極層的多層電極構 造體為目的。 〈二〉本發明是以獲得附著性良好的多層電極構造體 為目的。 〈三〉本發明是以獲得電阻低的多層電極構造體為目 的。 〈四〉本發明是以獲得具有附著性良好並且電阻低的 多層電極構造體的電池或電氣雙層電容器為目的。 發明内容 本發明的一種多層電極構造體，是一種在集電材料上 多層疊層具有至少由高分子物質構成的粘合劑和電極材料 的電極層的多層電極構造體，其特徵是接連集電材料配置 的第1電極層和配置於第1電極層上的第2電極層是由不 同的物質組成或不同的配合比形成；或者 一種多層電極構造體，是在集電材料上多層疊層具有550848 V. Description of the invention (1) TECHNICAL FIELD The present invention relates to a method for manufacturing a multilayer electrode structure cell or an electric double-layer capacitor. BACKGROUND ART Heretofore, when an electrode structure is manufactured, a surface of a current collecting material is coated with a mixture of an electrode material, a powdery conductive material, a drilling compound, and a solvent, and an electrode layer is attached to form an electrode structure. (1) The present invention aims to produce a multilayer electrode structure having a multilayer electrode layer. <2> The present invention aims to obtain a multilayer electrode structure having good adhesion. <3> The present invention aims to obtain a multilayer electrode structure having low resistance. (4) The present invention aims to obtain a battery or an electric double-layer capacitor having a multilayer electrode structure having good adhesion and low resistance. SUMMARY OF THE INVENTION A multilayer electrode structure according to the present invention is a multilayer electrode structure in which an electrode layer having a binder composed of at least a polymer substance and an electrode material is laminated in multiple layers on a current collecting material. The first electrode layer and the second electrode layer disposed on the first electrode layer are formed of different materials or different mixture ratios; or a multilayer electrode structure is a multilayer electrode structure on a current collecting material.
第4頁 550848 五、發明說明（2) 至少由高分子物質組成的粘合 層電極構造體，其特徵是接連 粘合劑比第1電極層上配置的 強；或者 一種多層電極構造體，是 至少 質的 置的 導電 中， 蓋； 中， 用容 子物 的多 池， 極層 電率 由高分子物質組成 電極層的多層電極 第1電極層與在第1 率高；或者 一種多 至少一 或者 一種多 第1電 易原纖 一種電 質組成 層電極 其特徵 上配置 高；或 一種電 層電極構造 層電極層的 電解質相同 一種電 層電極 極層以 化的粘池，是 的粘合 構造體 是接連 的第2 者 池，其 的或親 氣雙層 構造 外的 合劑 將集 劑和 作為 集電 電極 特徵 和性 電容 的粘合 構造體 電極層 體，其 電極材 體，其 至少一 聚合物 電材料 電極材 電極並 材料配 層相比 是在接 高的粘 器，是 劑和電極材料的電 集電材料配置的第 第2電極層相比， 在集電材料上多層 劑和電極材料及粉 ，其特徵是接連集 上配置的第2電極 特徵是上述多層電 料用離子導電性聚 特徵是上述多層電 層電極層的高分子 ;或者 上多層疊層具有至 料及粉狀導電物質 且在電極間配置電 置的第1電極層與 ，粘合劑的粘合力 極層的多 1電極層 粘合力 疊層具有 狀導電物 電材料配 層相比， 極構造體 合物覆 極構造體 粘合劑使 少由高分 的電極層 解質的電 在第1電 強並且導 連電解質的電極層上使用跟 合劑；或者 將集電材料上多層疊層具有Page 4 550848 V. Description of the invention (2) An adhesive layer electrode structure composed of at least a polymer substance, characterized in that the successive adhesive is stronger than the first electrode layer; or a multilayer electrode structure, is At least the quality of the conductive medium and cover; in the use of multi-cells, the electrode layer of the multi-layer electrode composed of polymer material electrode layer and the first electrode layer with a high rate; or at least one or more A multi-first electric easy fibril, an electric component layer electrode, which is characterized by high configuration; or an electric layer electrode structure layer, the electrode layer of the electrolyte is the same, an electric layer electrode layer, and a sticky pool, which is an adhesive structure It is a second consecutive pool. The mixture outside its or double-layer structure is a current collector and an adhesive structure that is a characteristic and capacitance of the collector electrode. The electrode layer body, its electrode material, and its at least one polymer. Compared with the second electrode layer of the electrode material and the electrode layer, the second electrode layer of the electrode material and the electrode material is higher in the current collector. The multi-layer agent and electrode material and powder on the material are characterized in that the second electrode disposed on the successive set is characterized by the above-mentioned ion-conducting polymer for the multi-layer electrical material is a polymer of the above-mentioned multi-layer electrical layer electrode layer; Compared with the first electrode layer which is electrically conductive and is disposed between the electrodes and the powdery conductive substance, the electrode layer has a layer of a conductive material and an electric material with a layer of an adhesive layer having more adhesive layer than an adhesive layer. Electrode structured electrode structure electrode structured electrode adhesive used to decompose the electrode layer with less high-density electricity. Use a follower on the electrode layer with the first electric strength and conductive electrolyte; have
第5頁 550848 五、發明說明（3) 至少由高分 質的電極層 電解質的電 第1電極層 比，粘合劑 一種電 層上使用跟 一種多 層具有 層的多 包括高 第1電 電極物 層電極 第2電 一種多 層具有 導電物 集電材 狀導電 層上塗 物質的 混合粉 導電率 層疊 電極 塗布 形成 劑、 層疊 力比 層疊 粉狀 徵是 和粉 電極 導電 層， 層的 子物質組成的粘合劑和電極材料及粉狀導電物 的多層電極構造體作為電極並且在電極間配置 氣雙層電容器，其特徵是接連集電材料配置的 粘合劑與在第1電極層上配置的第2電極層相 的粘合力強並且導電率高；或者 氣雙層電容器，其特徵是在接連電解質的電極 電解質相同的或親和性高的粘合劑；或者 層電極構造體的製造方法，是在集電材料上多 至少由高分子物質組成的钻合劑和電極材料的 層電極構造體製造方法，其特徵是集電材料上 分子钻合劑、電極物質和溶劑的混合物並乾燥 極層，在第1電極層上塗布包括高分子枯合 質和溶劑的混合物並乾燥形成第2電極層，多 層，混合高分子粘合劑使得第1電極層的結合 極層的結合力強；或者 層電極構造體的製造方法，是在集電材料上多 至少由高分子物質組成的枯合劑和電極材料及 質的電極層的多層電極構造體製造方法，其特 料上塗布包括高分子粘合劑、電極物質、溶劑 物質的混合物並乾燥形成第1電極層，在第1 布包括高分子粘合劑、電極物質、溶劑和粉狀 混合物並乾燥形成第2電極層，多層疊層電極 狀導電物質使得第1電極層的導電率比第2電極 變成高導電率；或者Page 5 550848 V. Description of the invention (3) At least the first electrode layer ratio of the electrolyte with at least a high-quality electrode layer electrolyte, the use of an adhesive on an electrical layer, and the use of a multi-layered layer including a high first electrical electrode Layer electrode 2nd type A multi-layer mixed powder having a conductive material, a collector material, a conductive layer, and a layer of mixed powder conductivity. A layered electrode coating forming agent, a layering force ratio, a layered powdery sign, and a powder electrode conductive layer. A multilayer electrode structure including an electrode material, an electrode material, and a powdery conductive material is used as an electrode, and an air double-layer capacitor is arranged between the electrodes, which is characterized in that an adhesive disposed on the current collecting material and a second electrode disposed on the first electrode layer are connected. Layered layers have strong adhesion and high electrical conductivity; or gas double-layer capacitors, which are characterized by the same or high-affinity binders in the electrode and electrolyte connected to the electrolyte; or the method of manufacturing the layered electrode structure, A method for manufacturing a layered electrode structure consisting of a biting agent composed of at least a polymer material and an electrode material on an electric material is characterized in that A mixture of a cementing agent, an electrode substance, and a solvent is used to dry the electrode layer. The first electrode layer is coated with a mixture of a polymer compound and a solvent and dried to form a second electrode layer. The multilayer is mixed with a polymer binder to make the first electrode layer 1 The bonding strength of the electrode layer is strong; or the manufacturing method of the layered electrode structure is to manufacture a multilayered electrode structure with a current collector composed of at least a polymeric compound, an electrode material, and a quality electrode layer. A method in which a special material is coated with a mixture including a polymer binder, an electrode substance, and a solvent substance and dried to form a first electrode layer, and a first cloth includes a polymer binder, an electrode substance, a solvent, and a powdery mixture and dried. Forming a second electrode layer, and multilayering an electrode-shaped conductive substance so that the conductivity of the first electrode layer becomes higher than that of the second electrode; or
第6頁 550848 五、發明說明（4) 一種多層電極構造體的製 極層上塗布高分子枯合劑、電 物，使其結合力比第2電極層高 第3電極層，並多層疊層電極 一種多層電極構造體的製 電極構造體的製造方法中，至 離子導電性聚合物覆蓋；或者 一種多層電極構造體的製 電極構造體的製造方法中，第 極層的高分子粘合劑使用容易 者 一種多層電極構造體的製 層的粉狀導電物質含有支援電 一種電池製造方法，是將 至少由高分子物質組成的粘合 質的電極層的多層電極構造體 電解質的電池製造方法，其特 高分子粘合劑、電極物質、溶 並乾燥形成第1電極層，在第 粘合劑、電極物質、溶劑和粉 形成第2電極層，多層疊層電 得第1電極層的結合力比第2 狀導電物質使得第1電極層的 率變成高導電率；或者 造方法，其特徵是在第2電 極物質和溶劑混合後的混合 分子粘合劑強，乾燥後製成 層；或者 造方法，其特徵是上述多層 少一層電極層的電極材料用 造方法，其特徵是上述多層 1電極層以外的至少一層電 原纖化的粘合劑聚合物；或 其特徵 質；或 料上多 材料及 並且在 電材料 導電物 上塗布 質的混 合高分 結合力 第2電 是第1 者 層疊層 粉狀導 電極間 上塗布 質的混 包括高 合物並 子粘合 強’混 極層的 電極 具有 電物 配置 包括 合物 分子 乾燥 劑使 合粉 導電 造方 解鹽 在集 劑和 作為 徵是 劑和 1電 狀導 極層 電極 導電 法， 的物 電材 電極 電極 在集 粉狀 極層 電物 ，混 層的 率比Page 6 550848 V. Description of the invention (4) A polymer electrode and an electric substance are coated on the electrode layer of a multilayer electrode structure to make the binding force higher than that of the second electrode layer. The third electrode layer is a multilayer electrode. In a method for manufacturing an electrode structure of a multilayer electrode structure, covering with an ion conductive polymer; or in a method for manufacturing an electrode structure of a multilayer electrode structure, the polymer binder of the first electrode layer is easy to use A method for manufacturing a battery including a powdery conductive material for forming a multilayer electrode structure and a battery supporting method is a method for manufacturing a multilayer electrode structure electrolyte using a binder electrode layer composed of at least a polymer substance. The polymer binder and electrode substance are dissolved and dried to form a first electrode layer. The second electrode layer is formed on the first binder, electrode substance, solvent, and powder. The two-shaped conductive substance makes the rate of the first electrode layer become high; or the manufacturing method is characterized by a mixed molecular binder after the second electrode substance and the solvent are mixed. It is strong and dried to form a layer; or a manufacturing method, characterized in that the method for manufacturing an electrode material for the above-mentioned multilayer electrode layer and one less electrode layer is characterized in that at least one layer of the electrofibrillated binder polymer other than the above-mentioned multilayer 1 electrode layer is used Or its characteristic properties; or a mixture of multiple materials on the material and a coating material on the conductive material of the conductive material with a high binding force. The second electricity is the first one. Electrodes with a strong mixed electrode layer of the nucleophilic bond have an electrical configuration including a molecular desiccant to desalinate the powdered conductive formula in a collector and as a characteristic agent and a conductive method for the conductive layer electrode. The ratio of the electric material electrode to the electrode material in the powdery electrode layer and the mixed layer
第7頁 550848 五、發明說明（5) 層疊層 粉狀導 電極間 集電材 狀導電 極層上 電物質 層，混 極層的 電率比 種電 具有 電物 配置 料上 物質 塗布 的混 合高 結合 第2 氣雙層 至少由 質的電 電解質 塗布包 的混合 包括高 合物並 分子粘 力強， 電極層 電容器 高分子 極層的 的電氣 括南分 物並乾 分子枯 乾燥後 合劑使 混合粉 的導電 製造 物質 多層 雙層 子粘 燥後 合劑 形成 得第 狀導 率變 方法， 組成的 電極構 電容器 合劑、 形成第 、電極 第2電 1電極 電物質 成南導 是將在集 枯合劑和 造體作為 製造方法 電極物質 1電極層 物質、溶 極層，多 層的結合 使得第1 電率。 電材料 電極材 電極並 ，其特 、溶劑 ，在第 劑和粉 層疊層 力比第 電極層 上多 料及 且在 徵是 和粉 1電 狀導 電極 2電 的導 具體實施例 以下，用附圖說明本發明的實施例。 《一》 多層電極構造體 多層電極構造體使用在將電解質介於電極間的電氣構 件電極中。電氣部件是電池的情況下，多層電極構造體可 與電解質的離子之間進行電交接。電氣部件是電氣雙層電 容器的情況下，多層電極構造體是在表面積大的高表面積 材料與電解質之間形成電氣雙層電容器的。 圖1表示幾個多層電極構造體的例子。圖1 ( A )是 用作電池正電極使用的，是集電材料1 3表面上附著由作 為電極材料1 1的粉狀電極活性物質、粉狀導電物質1 4Page 7 550848 V. Description of the invention (5) The electric material layer on the current collector electrode layer between the powdery conductive electrodes in the laminated layer, the electric conductivity of the mixed electrode layer is higher than that of the kind of electric material which has the material coating on the electrical material configuration material. The second gas double layer is composed of at least a high-quality electro-electrolyte coating. The mixture includes a high compound and has strong molecular adhesion. The electrical layer of the electrode layer capacitor and the polymer electrode layer is dried and the mixture is dried to dry the mixture. The conductive manufacturing material is a multi-layered and double-layered mixture. The mixture is formed to form a first conductivity change method. The composition of the electrode-capacitor mixture, the second electrode, the second electrode, the first electrode, and the south electrode are used to collect the mixture and the body. As the manufacturing method of the electrode substance 1, the electrode layer substance and the electrode solution layer, a combination of a plurality of layers results in a first electrical conductivity. Electrical materials, electrode materials, electrodes, and solvents have more force on the layer of the first agent and powder than on the first electrode layer, and the specific embodiment of the electrical conductivity of the conductive electrode 2 of the powder and the powder 1 is described below with reference to the drawings. Examples of the present invention will be described. << 1 >> Multi-layer electrode structure The multi-layer electrode structure is used for an electrical component electrode in which an electrolyte is interposed between electrodes. When the electrical component is a battery, the multilayer electrode structure and the ions of the electrolyte can be electrically transferred. When the electric component is an electric double-layer capacitor, the multilayer electrode structure forms an electric double-layer capacitor between a high surface area material having a large surface area and an electrolyte. FIG. 1 shows examples of several multilayer electrode structures. Figure 1 (A) is used as the positive electrode of a battery, and a powdery electrode active material and a powdery conductive material 14 are attached to the surface of a current collecting material 1 3 as an electrode material 1 1
第8頁 550848 五、發明說明（6) 和粘合劑1 7 (即，粘合劑、結合劑）構成電極層18的電 極構造體1 。電極層1 8成為多層，附圖中由第1電極層 181和第2電極層182構成，第1電極層181比第 . 2電極層1 8 2增加了粉狀導電物質1 4和粘合劑1 7的濃 度。作為粉狀電極活性物質，例如使用L i C 〇〇2。圖1 ' (B) 是已用離子導電性聚合物12覆蓋著圖1(A)的 、 電極材料1 1的電極構造體。離子導電性聚合物1 2雖然 / 也具有粘合劑的功能，但是在第1電極層1 8 1上，為了 提高粘結性，混合有粘合劑1 7 。第1電極層1 8 1比第 2電極層1 8 2增加了粉狀導電物質1 4的濃度。圖1 (C) 是用作電池的負電極的，是集電材料1 3的表面上 φ 附著由作為電極材料1 1的粉狀電極活性物質和粘合劑1 7構成的電極層1 8的電極構造體1 。作為粉狀電極活性 物質，例如使用石墨粉末。第1電極層1 8 1比第2電極 層1 8 2增加了粘合劑1 7的濃度。圖1 ( D )是用離子 導電性聚合物1 2覆蓋圖1 ( C )的電極材料的電極構造 體。離子導電性聚合物1 2雖然也具有粘合劑的功能，但 是在第1電極層1 8 1上，為了提高粘結性，混合了粘合 劑1 7 。圖1 ( E )是用作電氣雙層電容器的電極構造 體，是集電材料1 3的表面上附著由作為電極材料1 1的 高表面積材料和粘合劑1 7構成的電極層1 8的電極構造 體1 。作為高表面積材料，例如使用活性碳。第1電極層鲁 1 8 1比第2電極層1 8 2增加了粘合劑1 7的濃度。圖 1(F)是用離子導電性聚合物1 2覆蓋圖1 (E)的粉狀 〃Page 8 550848 V. Description of the invention (6) and a binder 17 (ie, a binder, a binder) constitute the electrode structure 1 of the electrode layer 18. The electrode layer 18 is multi-layered, and is composed of a first electrode layer 181 and a second electrode layer 182 in the drawing. The first electrode layer 181 adds a powdery conductive substance 14 and a binder than the second electrode layer 1 8 2 1 to 7 concentration. As the powdery electrode active material, for example, L i C 002 is used. FIG. 1 ′ (B) shows the electrode structure of FIG. 1 (A) with the electrode material 11 covered with the ion conductive polymer 12. Although the ion conductive polymer 12 also has a function of a binder, a binder 17 is mixed with the first electrode layer 1 8 1 to improve adhesion. The first electrode layer 1 8 1 has a higher concentration of the powdery conductive substance 14 than the second electrode layer 1 8 2. Fig. 1 (C) is used as the negative electrode of the battery, and the electrode layer 18 composed of the powdery electrode active material as the electrode material 11 and the binder 17 is attached to the surface φ of the current collecting material 13 Electrode structure 1. As the powdery electrode active material, for example, graphite powder is used. The first electrode layer 1 8 1 has a higher concentration of the binder 17 than the second electrode layer 1 8 2. Fig. 1 (D) is an electrode structure in which the electrode material of Fig. 1 (C) is covered with an ion conductive polymer 12. Although the ion-conductive polymer 12 also has a function of a binder, the first electrode layer 1 8 1 is mixed with a binder 17 to improve adhesion. FIG. 1 (E) is an electrode structure used as an electric double-layer capacitor. An electrode layer 18 composed of a high surface area material as an electrode material 11 and a binder 17 is attached to the surface of a current collecting material 13. Electrode structure 1. As the high surface area material, for example, activated carbon is used. The first electrode layer Lu 1 8 1 has a higher concentration of the binder 17 than the second electrode layer 1 8 2. Figure 1 (F) is a powdery coating of Figure 1 (E) with an ion conductive polymer 12
第9頁 550848 五、發明說明（7) 活性炭的電極構造體。離子導電性聚合物1 2雖然也具有 粘合劑的功能，但是在第1電極層1 8 1上，為了提高粘 結性，混合了粘合劑1 7 。另外，用離子導電性聚合物覆 蓋的電極材料以後再詳細敘述。 《二》 多層電極 多層電極是不同特性多層重疊的。使特性不同的方法 有多種，除圖1 ( A )〜（F )以外，改變配合物質的配 合比或種類。 圖2 ( A )〜（B )是使用粉狀電極活性物質作為電Page 9 550848 V. Description of the invention (7) Electrode structure of activated carbon. Although the ion conductive polymer 12 also has a function of a binder, a binder 17 is mixed with the first electrode layer 1 8 1 to improve adhesion. The electrode material covered with an ion conductive polymer will be described in detail later. "Two" Multi-layer electrode Multi-layer electrode is a multilayer of different characteristics. There are various methods to make the characteristics different. In addition to Fig. 1 (A) to (F), the ratio or type of the compounding substance is changed. Figures 2 (A) ~ (B) are using powdered electrode active material as electricity
極材料，並將以離子導電性聚合物1 2覆蓋粉狀電極活性 物質的和不覆蓋的電極構造體用於第1電極層和第2電極 層的例子。圖2 ( C )〜（D )是使用活性炭作為電極材 料，並將以離子導電性聚合物1 2覆蓋活性炭的和不覆蓋 的電極構造體用於第1電極層和第2電極層的例子。 並且，在第2電極層上作為粘合劑，如使用原纖化容 易的枯合劑聚合物，就可以用少量枯合劑結合電極材料或 粉狀導電物質。但是，原纖化容易的粘合劑聚合物跟集電 材料結合力弱，因而使用於第1電極層以外。As an example of the first electrode layer and the second electrode layer, an electrode structure in which a powdery electrode active material is covered with an ion conductive polymer 12 and an uncovered electrode structure is used. Figs. 2 (C) to (D) are examples in which activated carbon is used as an electrode material, and an electrode structure in which an activated carbon is covered with an ion conductive polymer 12 and an uncovered electrode structure are used for the first electrode layer and the second electrode layer. In addition, if a desiccant polymer that is easily fibrillated is used as a binder on the second electrode layer, a small amount of the desiccant can be used to bind the electrode material or the powdery conductive material. However, since a binder polymer that is easy to fibrillate has a weak binding force to a current collector, it is used outside the first electrode layer.
並且，要是電極層中含有支持電解鹽，Li離子密度 將提高，L i離子的傳遞速度會加快。特別是，若進入第 1電極層，則第1電極層L i離子的移動容易傳遞到第2 電極層去。 並且，把多層電極構造體使用於電池或電氣雙層電容 器等上時，在連接電解質的電極層中，可以使用跟該電解In addition, if the electrode layer contains a supporting electrolytic salt, the density of Li ions will increase and the transfer rate of Li ions will increase. In particular, when entering the first electrode layer, the movement of the first electrode layer Li ions is easily transmitted to the second electrode layer. In addition, when a multilayer electrode structure is used in a battery, an electric double-layer capacitor, or the like, the electrode layer connected to the electrolyte can be used in conjunction with the electrolysis.
第10頁 550848 五、發明說明（8) 質相同的聚合物或親和性高的粘合劑聚合物。例如，第2 電極層上配置第3電極層，在第3電極層上也可以使用跟 電解質相同的聚合物或親和性高的粘合劑聚合物。 並且，或者使用牢固粘結集電材料的粘合劑聚合物、 或者改變每個層中粉狀導電物質的種類、或者改變粉狀電 極活性物質的平均粒徑、或者使用離子導電性的粘合劑聚 合物、或者使用作為電解質使用的離子導電性聚合物，用 以上各種方法都可以改變多層的特性。 《三》多層電極構造體製造方法Page 10 550848 V. Description of the invention (8) Polymers of the same quality or binder polymers with high affinity. For example, a third electrode layer is disposed on the second electrode layer, and the same polymer as the electrolyte or a high affinity binder polymer may be used on the third electrode layer. In addition, either a binder polymer that firmly adheres to the current collecting material, or the type of powdery conductive material in each layer, or the average particle diameter of the powdery electrode active material, or an ion-conductive binder is used. A polymer or an ion-conducting polymer used as an electrolyte can change the characteristics of multiple layers by various methods described above. "Three" multilayer electrode structure manufacturing method
圖3表示多層電極構造體製造方法的例子。多層電極 構造體1是用混合器3混合電極材料1 1 、粉狀導電物質 1 4、枯合劑1 7和溶劑1 9 ，使其變成泥漿成為混合物 3 1 。將混合物3 1薄薄地塗布到集電材料1 3的表面 上。塗布的裝置有刮刀敷料器等。從塗布後的混合物中蒸 發溶劑，使之乾燥，作為第1電極層1 8 1附著於集電材 料1 3而製成。在這裏，蒸發溶劑使其乾燥之際，利用熱 風加熱裝置或紅外線照射裝置對集電材料上的混合物3 1 吹熱風或照射紅外線。接著，在第1電極層1 8 1上同樣 形成第2電極層1 82 。另外，形成第2電極層時，也可 以在第1電極層乾燥處理之前進行。FIG. 3 shows an example of a method for manufacturing a multilayer electrode structure. The multilayer electrode structure 1 is a mixture of an electrode material 1 1, a powdery conductive material 14, a desiccant 17, and a solvent 1 9 with a mixer 3 to make a slurry into a mixture 3 1. The mixture 31 was thinly applied to the surface of the current collector 13. The coating device includes a doctor blade applicator. The solvent is evaporated from the applied mixture, dried, and it is produced as a first electrode layer 1 8 1 attached to a current collector 13. Here, when the solvent is evaporated and dried, a hot air heating device or an infrared irradiation device is used to blow hot air or infrared rays to the mixture 3 1 on the current collector. Next, a second electrode layer 1 82 is formed on the first electrode layer 1 81 in the same manner. When the second electrode layer is formed, it may be performed before the first electrode layer is dried.
熱風加熱裝置6 ，例如圖4的樣子，用傳送帶6 3把 由在集電材料13上塗布了電極層18構成的電極構造體 移動到筐體6 2内，從熱風吹出口 6 1向電極層18吹出 熱風6 5 ，使電極層1 8裏含有的溶劑蒸發。熱風通過筐體The hot air heating device 6 is, for example, as shown in FIG. 4. The conveyor structure 63 is used to move the electrode structure formed by coating the electrode layer 18 on the current collector 13 into the housing 6 2, and from the hot air outlet 61 to the electrode layer. 18 blows hot air 6 5 to evaporate the solvent contained in the electrode layer 18. Hot air through the casing
第11頁 550848 五、發明說明（9) 的出口 6 4向外部移送溶劑。 紅外線照射裝置5 ，例如圖5的樣子，用傳送帶5 8 把在集電材料1 3塗布了電極層1 8移動到筐體5 4内， 照射由紅外線發生器5 1發生的紅外線5 2。在筐體5 4 與紅外線發生器5 1之間配置透射紅外線的紅外線透射隔 壁5 3 。並且，在因蒸發的氣體種類或濃度等對紅外線發 生器5 1不會發生問題時，就不用配置紅外線透射隔壁5 3 。從電極層1 8蒸發出的溶劑1 9 ，用紅外線透射隔壁Page 11 550848 V. Outlet of Description (9) 6 4 Transfer solvent to the outside. The infrared irradiation device 5, for example, as shown in FIG. 5, moves the collector layer 13 coated with the electrode layer 18 on the conveyor 5 8 into the housing 5 4, and irradiates the infrared 5 2 generated by the infrared generator 51. An infrared transmitting partition 5 3 that transmits infrared rays is arranged between the housing 5 4 and the infrared generator 51. In addition, when there is no problem with the infrared generator 51 due to the type or concentration of the vaporized gas, it is not necessary to arrange the infrared transmitting partition 5 3. The solvent 19 evaporated from the electrode layer 18 is transmitted through the partition wall with infrared rays.
5 3跟紅外線發生器5 1隔斷。筐體5 4内充滿的溶劑1 9濃度一升高到平衡濃度，就限制蒸發，因此用風扇5 6 從筐體5 4内向溶劑回收器5 5吸引，進行回收。此時， 為了使筐體5 4内的氣壓跟外面氣壓平衡，向筐體5 4内供應 外氣5 7，可是該外氣5 7通過送風不是用於蒸發溶劑1 9 ，而是在打破溶劑濃度平衡的程度就可以。流速也取 決於筐體5 4的大小，因而例如0. 5 m /分以下就行。另 外，集電材料1 3的兩面都塗布電極層1 8時，可以從電 極構造體1的兩面照射紅外線。5 3 is separated from the infrared generator 5 1. As soon as the concentration of the solvent 19 filled in the casing 5 4 rises to an equilibrium concentration, evaporation is restricted. Therefore, the fan 5 6 is sucked from the inside of the casing 5 4 to the solvent recovery device 5 5 and recovered. At this time, in order to balance the air pressure inside the casing 54 with the outside air pressure, the outside air 5 7 is supplied to the inside of the casing 54, but the outside air 5 7 is not used to evaporate the solvent 19 by supplying air, but to break the solvent. The degree of concentration balance is sufficient. The flow velocity also depends on the size of the housing 54, so for example 0.5 m / min or less is sufficient. When the electrode layers 18 are coated on both sides of the current collector 13, infrared rays can be irradiated from both sides of the electrode structure 1.
紅外線包括從接近可見光的近紅外線到中紅外線進而 直至接近電波的遠紅外線，然而若不是由空氣的熱傳播加 熱混合物，而是可以幾乎不通過空氣相距遙遠地加熱混合 物，也可以使用任何的紅外線。由於遠紅外線比近紅外線 透過混合物内部的比率高，所以能夠加熱内部。 作為蒸發溶劑1 9並使混合物3 1乾燥的方法如果使 用紅外線，混合物3 1乾燥起來的電極層1 8跟電極材料Infrared rays include near-infrared rays that are close to visible light, medium-infrared rays, and far-infrared rays that are close to radio waves. However, if the mixture is not heated by the heat of the air, the mixture may be heated remotely by almost no air. Any infrared rays may be used. Since far infrared rays penetrate the interior of the mixture more than near infrared rays, they can heat the interior. As a method of evaporating the solvent 19 and drying the mixture 31, if infrared rays are used, the electrode layer 1 8 and the electrode material dried by the mixture 3 1
第12頁 550848 五、發明說明（ίο) 1 1良好附著，而且，電極層1 8的電阻會降低。圖6強 調地表示使覆蓋於集電材料1 3的混合物中溶劑1 9蒸發 時的混合物3 1内狀態。 圖6 ( A )的情況下，可以認為溶劑蒸發的機理如Page 12 550848 V. Description of the Invention (1) The 1 1 adheres well, and the resistance of the electrode layer 18 will decrease. Fig. 6 highlights the internal state of the mixture 31 when the solvent 19 is evaporated from the mixture covering the current collector 13. In the case of Fig. 6 (A), the mechanism of solvent evaporation can be considered as
下。首先，熱風6 5衝撞混合物表面，混合物3 1表面附近 受熱風迅速變暖，使表面附近的溶劑活躍蒸發，同時隨熱 風6 5飛去。因此，表面附近的溶劑迅速蒸發，混合物内 部或集電材料附近的溶劑向表面附近移動，使其補充。此 時，溶劑中混合著的粘合劑或粉狀導電物質跟溶劑一起向 混合物3 1的表面附近運動。其結果，混合物的集電材料 侧的粘合劑或粉狀導電物質濃度變薄。under. First, the hot air 65 hits the surface of the mixture, and the heated air near the surface of the mixture 3 1 rapidly warms up, so that the solvent near the surface actively evaporates, and at the same time it flies away with the hot air 65. Therefore, the solvent near the surface evaporates quickly, and the solvent inside the mixture or near the current collecting material moves toward the surface to replenish it. At this time, the adhesive or powdery conductive substance mixed in the solvent moves toward the vicinity of the surface of the mixture 31 together with the solvent. As a result, the concentration of the binder or the powdery conductive material on the current collector side of the mixture becomes thin.
對此，在本發明圖6 ( B )的情況下，可以認為溶劑蒸 發的機理如下。首先，向混合物表面照射紅外線5 2，紅外 線5 2透入到混合物内部，加熱整個混合物。與此同時， 由於沒有吹出熱風，所以溶劑徐徐從混合物表面蒸發。因 此，粘合劑、粉狀導電物質1 4的濃度全體變得均勾起 來。其結果，混合物3 1乾燥起來的電極層中，因為集 電材料附近的粘合劑濃度不變薄，使電極層跟集電材料1 3附著良好。並且，集電材料附近的粉狀導電物質濃度也 不變薄，因而電極層的整個電阻降低。利用這種紅外線的 效果，在多層整個厚度厚時是特別有效的。 《四》 集電材料 集電材料1 3只要是容易導電的物質即可，根據電氣 部件選擇形狀和材料為例，把鋁、銅等導電物質形成板On the other hand, in the case of FIG. 6 (B) of the present invention, the mechanism of solvent evaporation can be considered as follows. First, the surface of the mixture is irradiated with infrared rays 52, and infrared rays 52 are penetrated into the mixture to heat the entire mixture. At the same time, since no hot air was blown out, the solvent slowly evaporated from the surface of the mixture. As a result, the concentration of the binder and the powdery conductive material 14 becomes uniform as a whole. As a result, in the dried electrode layer of the mixture 31, the concentration of the binder in the vicinity of the current collector does not become thin, so that the electrode layer and the current collector 13 adhere well. In addition, the concentration of the powdery conductive material near the current collector does not become thin, so the overall resistance of the electrode layer is reduced. This infrared effect is particularly effective when the entire multilayer is thick. "IV" Current collector materials The current collector materials 1 and 3 are only required to be easily conductive. Selecting shapes and materials according to electrical components is taken as an example. A conductive material such as aluminum or copper is formed into a plate.
第13頁 550848 電 據 根 下 況 情 料 材 一£一&0 集 的。 箔面 或兩 體或 狀面 板單 在用 。使 狀造 ⑻網構 或的 明 說箔件 明 P 發 立口 、」狀氣 五 料 材 電靠 集更 貼其 緊使 上 料 緊 8 1± 層 極 ^¾ 的 3 材 集 到 緊 壓 以 可 這 的 2 1± 圖 用 如 例 貼 緊 之 使 了 為 成置 構裝 料力 材壓 電用 集過 的通 後， 物間 合之 混1 布4 塗筒 由滾 把力 。壓 行到 進夾 來1 4體 置造 裝構 緊極 貼電 種的 層 極 把 夠 能 就 轉 旋 其 使 力 壓 加 施 2 0 4上 筒料 滾材 轉電 倒集 給到 3貼 4緊 池 ^¾ 1 圖 圖或 或 幻C /(V 1± 1± 圖圖 將將 是， 池極 >電電 五 正 {為 作 體 造 構 極 電 層 多 的 ΒPage 13 550848 Electricity is based on information from the £ 1 & 0 episode. Foil or two- or double-sided sheets are in use. Make the shape of the net structure or the plain foils, make the openings, and the shape of the five materials is closer to the material, so that the material is tighter and the material is tighter. This 2 1 ± figure is used as an example to make the piezoelectric material used as a material for the structure. After the material has been collected, the material is mixed together. 1 The cloth 4 is coated by a roller. Press it into the clamp. 1 4 body is placed on the poles that are close to the electrode type. Turn it enough to apply the force. 2 0 4 The upper roll material is transferred to the 3 pieces. 4 Tight cell ^ ¾ 1 picture or or magic C / (V 1 ± 1 ± picture will be, the cell electrode > electricity and electricity five positive
體 造 構 極 電 層 多 的 D Γν IX 將} 示D 表C 7 1 圖圖 。將 構和 結極 一 fv6- 質正 物為 解作 電體 置造 配構 間極 其電 成層 形多 ，的 極} 電B 負C 為1 作圖 是 。2 x\y -Ιο 1± A 1物 {板合 7隔聚 圖有性 。置電 子配導 例間子 池極離 ^¾ #^ν 的，體 極況固 電情為 負的質 為6物 作1解 體液電 造解示 構電表 極為} 電質B 層物C 多解7 的電圖 配 而。 1用 體使 造以 構加 極要 ^¾^¾ ^H^¾ 層據 多根 對可 一也 開， 分等 了體 為固 是是 5質 1物 板解 隔電 。使 況即 情， 的置 六 口少口 容 層 雙 氣 ι^βο 層 雙 氣 電 圖 等 是 器 容D Γν IX with many electrode layers in the body structure will be shown in D Table C 7 1. The structure and junction pole fv6-mass positive substance is used as an electrical body to construct the configuration pole. The electrode layer has many layers, the pole} electricity B negative C is 1, and the drawing is. 2 x \ y -Ιο 1 ± A 1 物 {板 合 7 聚聚 图 sexual. If the electronic pilot is placed between the electrode and the electrode, ^ ¾ # ^ ν, the solid state of the body is negative, the mass is 6 substances, and the disassembly is performed. Figure 7 shows. 1 It is very important to use the structure to build the structure. ^ ¾ ^ ¾ ^ H ^ ¾ The layers can be opened according to the number of pairs, and the grade is solid. It is a 5 quality 1-material board to de-isolate. To put it in context, the dual-layer dual-gas ι ^ βο-layer dual-electrogram for the six-port, low-capacity layer is a container.
作 體 造 構 極 1^80 T^or 層 多 的 E ，其 極成 電形 對， 一極 為電 對出 1 示 為} 作A 體C 造8 構 tal 極以 電。 層成 多構 λ、4 白 白 3質 F物 C解 L^6- u 圖置 將配 電或間 以氣 ，電 器的 容體 電造 層構 雙極 氣電 電層 的多 體的 造} 構F 極C 一&J ^Bu 層圖 多用 的採 }出 E示 () 1 B 圖 用8 採圖The body constructs E with many layers of 1 ^ 80 T ^ or layers. Its poles form an electrical pair. One pole is an electrical pair. 1 is shown as}. A body C is used to make 8 tal electrodes. Multi-layered λ, 4 white and white matter F matter C solution L ^ 6- u maps the distribution of electricity or gas, electrical appliances to build a multilayer structure of bipolar gas-electricity layer multi-body structure} structure F pole C_ & J ^ Bu layer map multi-purpose mining} E shows () 1 B diagram with 8 mining
第14頁 550848 五、發明說明（12) 雙層電容器 況’電極間 固體的離子 開一對多層 等，也可根 以下， 《一》多層 對4種 紅外線加熱 電阻。各試 溶劑的材料 出剝離強度 。圖8 (A)是電解物質為電解液1 6的情 配置有隔板1 5 。圖8 (B)表示電解物質為 導電性聚合物1 2的情況。隔板1 5是為了分 電極構造體1而配置，即使電解物質是固體 據需要加以使用。 說明多層電極構造體的實施例。 電極構造體試料的製造 多層電極構造體的試料1〜4 ，用熱風加熱和 的二種加熱方法使其乾燥，測定其剝離強度和 料的多層電極材料、粉狀導電物質、粘合劑、 以及比例都在表1裏表示出來。試料的測定測 和電阻。表2裏示出其結果。 表 1Page 14 550848 V. Description of the invention (12) Double-layer capacitors ’Between the electrodes, solid ions, open a pair of multilayers, etc., it can also be as follows," 一 "multilayers for 4 kinds of infrared heating resistors. The material of each test solvent showed peel strength. Fig. 8 (A) shows the case where the electrolytic substance is the electrolytic solution 16 and the separator 15 is arranged. Fig. 8 (B) shows a case where the electrolytic substance is a conductive polymer 12. The separator 15 is disposed to separate the electrode structure 1, and it is used as necessary even if the electrolytic substance is solid. Examples of the multilayer electrode structure will be described. Preparation of electrode structure sample Samples 1 to 4 of multilayer electrode structure are dried by two methods of heating with hot air and multi-layer electrode material, powdery conductive material, adhesive, and the peel strength of the material, and The proportions are shown in Table 1. The measurement of the sample and the resistance. Table 2 shows the results. Table 1
試料 1 i極物質組成（重量份） 電極 層 電極 材料 粉狀導電 物質 (碳黑） 粘合劑 電極 厚度 溶劑 (重量份） 聚合物 A1 聚四氟X 乙烯 PVDF 1 第1 (活性炭） 18 2 0.8 75 NMPC30) 第2 (活性炭） 18 2 0.6 250 NMPC34) 2 第1 (活性炭） 18 2 1.2 75 NMP(30) 第2 (活性炭） 18 2 0.8 0. 24 250 NMPC34) 第15頁 550848 五、發明說明（13) 3 第1 (活^生炭） 20 1 50 NMP(30) 第2 (活性炭） 20 0.5 250 NMP(34) 4 第1 (LiCo02) 91 6 8 20 NMP(30) 第2 (LiCo02) 91 6 3 60 NEK(20)+NMP (10) 比較例 1 第1 (活性炭） 18 2 0.8 0. 24 330 NMP(34) 比較例 2 第1 (LiCo02) 91 6 3 80 NEK(20)+NMP (10)Sample 1 Composition of electrode material (parts by weight) Electrode layer electrode material Powdery conductive substance (carbon black) Binder electrode thickness solvent (parts by weight) Polymer A1 PTFE X ethylene PVDF 1 1st (activated carbon) 18 2 0.8 75 NMPC30) No. 2 (activated carbon) 18 2 0.6 250 NMPC34) 2 No. 1 (activated carbon) 18 2 1.2 75 NMP (30) No. 2 (activated carbon) 18 2 0.8 0. 24 250 NMPC34) Page 15 550848 5. Description of the invention (13) 3 No. 1 (living carbon) 20 1 50 NMP (30) No. 2 (activated carbon) 20 0.5 250 NMP (34) 4 No. 1 (LiCo02) 91 6 8 20 NMP (30) No. 2 (LiCo02) 91 6 3 60 NEK (20) + NMP (10) Comparative Example 1 First (activated carbon) 18 2 0.8 0. 24 330 NMP (34) Comparative Example 2 First (LiCo02) 91 6 3 80 NEK (20) + NMP (10)
表 一· 試料 紅外線加熱 紅外線加熱 乾燥強度 剝離強度 阻抗 剝離強度 阻抗 1 30V 、 Ihr A 0.1 b 0.5 2 30V 、 Ihr A 0.15 b 0.7 3 30V 、 Ihr A 0.7 b 6 4 30V 、 Ihr A 0.9 b 2.3 比較例1 30V 、 Ihr B 0.2 c 1.2 比較例2 30V 、 Ihr B 2 c 6Table 1 Samples Infrared heating Infrared heating Drying strength Peeling strength Resistance Peeling strength resistance 1 30V, Ihr A 0.1 b 0.5 2 30V, Ihr A 0.15 b 0.7 3 30V, Ihr A 0.7 b 6 4 30V, Ihr A 0.9 b 2.3 Comparative example 1 30V, Ihr B 0.2 c 1.2 Comparative Example 2 30V, Ihr B 2 c 6
imi 第16頁 550848 五、發明說明（14) 熱風加熱裝置使熱風從熱風吹出口吹向混合物的表 面。熱風被控制在大約8 0〜2 0 0 ° C的溫度下，約1 5〜2 5 m/分的流速。 ^ 紅外線照射裝置使用遠紅外線陶瓷板加熱器P Η — 1 00、iPHl 00C (阪口電熱株式會社製造）全部試料 ' 的紅外線乾燥條件是3 0 V，1小時。 ' 試料1是電容器用電極，第1電極層在作為電極材料 _ 原來酚醛的活性炭（關西化學（株）製造）中作為粉狀導 ％ 電物質添加碳黑，利用混合器進行幹式混合。而後，作為 粘合劑添加聚合物A1進行混合。進而，作為溶劑加上N Μ P ( N甲基吣ti咯烷酮）進行混合。混合以後，用刮刀 φ 敷料器塗布到集電體上。用紅外線或熱風乾燥試料。電極 厚度為7 5仁m。第2電極層，減少聚合物A1的比例，增 加稀釋溶劑的比例，在第1電極層上邊大致用同樣的方法 形成。電極厚度為250 /zm。 試料2跟試料1大致同樣製造5試料2的弟2電極 層，作為枯合劑加入聚合物A1並添加聚四氟乙烯。聚四 氟乙烯是原纖化容易的聚合物。 試料3是電容器用電極，跟試料1或試料2大致同樣 製造，試料3的多層電極，第1電極層和第2電極層哪一 層也不添加碳黑。並且，第1電極層添加聚合物A1作為 粘合劑，第2電極層添加聚四氟乙烯。另外，聚合物A 1 _ 是離子導電性聚合物原料，如表3所示。imi page 16 550848 V. Description of the invention (14) The hot air heating device makes the hot air blow from the hot air blowing outlet to the surface of the mixture. The hot air is controlled at a temperature of about 80 ~ 200 ° C and a flow rate of about 15 ~ 25 m / min. ^ The infrared irradiation device uses a far-infrared ceramic plate heater P Η — 1 00, iPHl 00C (manufactured by Sakaguchi Electric Heating Co., Ltd.) All samples ′ The infrared drying conditions are 30 V, 1 hour. '' Sample 1 is an electrode for a capacitor. The first electrode layer is carbon powder which is used as an electrode material _ original phenolic activated carbon (manufactured by Kansai Chemical Co., Ltd.) to add carbon black as a powdery conductive material, and dry-mixed with a mixer. Then, polymer A1 was added as a binder and mixed. Furthermore, as a solvent, N M P (N methylpyrrolidone) was added and mixed. After mixing, apply to the current collector with a spatula φ applicator. Dry the sample with infrared or hot air. The thickness of the electrode is 75 mm. The second electrode layer is formed by reducing the proportion of the polymer A1 and increasing the proportion of the diluting solvent, and is formed on the first electrode layer in substantially the same manner. The electrode thickness is 250 / zm. Sample 2 produced the electrode layer of sample 2 of sample 5 in approximately the same manner as sample 1, and polymer A1 was added as a desiccant and polytetrafluoroethylene was added. Polytetrafluoroethylene is a polymer that is easy to fibrillate. Sample 3 is an electrode for a capacitor, and is manufactured in substantially the same manner as Sample 1 or Sample 2. In the multilayer electrode of Sample 3, no carbon black is added to either the first electrode layer or the second electrode layer. A polymer A1 was added to the first electrode layer as a binder, and a polytetrafluoroethylene was added to the second electrode layer. The polymer A 1 _ is an ion-conductive polymer raw material, as shown in Table 3.
第17頁 550848 五、發明說明（15) 表3 離子導電性聚合物原料（Al) San Nics 物質名稱 混合比（重量部分） 三官能團（丙二醇·乙二醇）無序共聚物 Sannics FA—103 (PO/EO—2/ 8，Mw= 3 2 8 2，三洋化成工業（株） 製造） 8.3 6 二官能團多元醇的1，4 —丁二醇 0. 34 乙撐氰醇 1.2 7 反應催化劑N C —I Μ (三共Airproductz (株）製造） 0. 03 合計 10 試料4是電池正電極用的電極構造體，第1電極層和 第2電極層的哪一層都使用LiC〇〇2作為電極材料並使 用碳黑作為粉狀導電物質。第1電極層添加聚合物A 1作 為粘合劑，第2電極層添加P V D F 。另外，P V D F (聚偏二氟乙烯）是原纖化容易的聚合物。作為溶劑，1第 1電極層使用Ν Μ P ( N甲基讣匕咯烷酮），第2電極層使 用Ν Μ P ( Ν曱基蛇匕咯烷酮）和Μ Ε Κ (丁酮）。 表1的比較例1是省去試料2的第1電極層，加厚第 2電極層製成一層的例子，表1的比較例2是省去試料4Page 17 550848 V. Description of the invention (15) Table 3 Ionic conductive polymer raw materials (Al) San Nics Substance name mixing ratio (weight part) Trifunctional (propylene glycol · ethylene glycol) disordered copolymer Sannics FA—103 ( PO / EO—2 / 8, Mw = 3 2 8 2, manufactured by Sanyo Chemical Industry Co., Ltd. 8.3 6 1,4-butanediol of difunctional polyol 0.34 ethylene cyanohydrin 1.2 7 reaction catalyst NC — I Μ (manufactured by Sankyo Airproductz Co., Ltd.) 0. 03 Total 10 Sample 4 is an electrode structure for a battery positive electrode, and LiC〇02 is used as an electrode material for both the first electrode layer and the second electrode layer. Carbon black is used as a powdery conductive substance. Polymer A 1 was added to the first electrode layer as a binder, and P V D F was added to the second electrode layer. P V D F (polyvinylidene fluoride) is a polymer that is easy to fibrillate. As a solvent, NM P (N methylpyrrolidone) was used as the first electrode layer, and NM P (N-methylpyrrolidone) and MES (butanone) were used as the second electrode layer. Comparative example 1 in Table 1 is an example in which the first electrode layer of sample 2 is omitted, and the second electrode layer is thickened to make one layer. Comparative example 2 in Table 1 is an example in which sample 4 is omitted.
第18頁 550848 五、發明說明（16) 的第1電極層，加厚第2電極層製成一層的例子。比較例 1的情況，如表2所示，與試料2比較，無論用紅外線加 熱還是用熱風加熱，剝離強度都小，並且，電阻將增大。. 比較例2的情況，如表2所示，與試料4比較，無論用紅 外線加熱還是用熱風加熱，剝離強度都小，並且，電阻將 ' 增大。這樣，在多層電極構造體中，可以獲得既剝離強度 ’ 又電阻都比單層優良的特性。 - 《二》 層電極構造體的試料測定結果 ~ 剝離強度的測定方法是：把纖維帶粘貼到集電材料表 面製成的電極層上，採用撕下來的辦法，電極層粘附於纖 維帶從集電材料剝離。按照該剝離量就可以給剝離強度分 φ 等級。圖9顯示電極層粘附於纖維帶上的狀態（從照片發 生的圖）。圖9 ( A )是描繪電極層的上層部分僅僅薄薄 剝去一部的狀態圖（黑色部分為電極層剝去部分），並作 為等級a。圖9 ( B )是描繪從電極層中層部分薄薄剝去 的狀態圖（黑色部分為電極層剝去部分），並作為等級 b。圖9 ( C )是描繪電極層從集電材料上完全剝離的狀 態圖（黑色部分為電極層剝去部分），並作為等級c。 電阻測定法是：將集電體上形成的電極夾到直徑 2cm、厚度5mm的銅板間，從上下加4. 5kg/cm2壓力壓 緊，利用電阻分析器，測定交流1 0 Κ Η z的電阻值。 如果用同一試料批號對比紅外線加熱和熱風加熱的試馨 料，無論哪一種試料，用紅外線照射，剝離強度也全部是 等級a，用溫風加熱全部是等級b，紅外線照射一方具有 /Page 18 550848 V. Example of the invention (16) The first electrode layer is made by thickening the second electrode layer. In the case of Comparative Example 1, as shown in Table 2, in comparison with Sample 2, the peeling strength was small regardless of heating by infrared rays or hot air, and resistance was increased. In the case of Comparative Example 2, as shown in Table 2, compared with Sample 4, the peeling strength was small regardless of whether it was heated by infrared rays or hot air, and the resistance was increased. In this way, in the multilayer electrode structure, both the peeling strength and the resistance are better than those of a single layer. -"Second" layer electrode structure measurement results ~ The measurement method of peeling strength is: the fiber layer is adhered to the electrode layer made of the surface of the current collecting material, and the electrode layer is adhered to the fiber layer from The current collecting material is peeled. According to this peeling amount, the peeling strength can be graded by φ. Fig. 9 shows a state where an electrode layer is adhered to a fiber tape (a picture taken from a photograph). FIG. 9 (A) is a state diagram depicting a state where the upper part of the electrode layer is only thinly peeled off (the black part is the electrode layer peeled part), and it is regarded as level a. Fig. 9 (B) is a state diagram depicting a thin stripped state from the middle layer portion of the electrode layer (the black portion is the stripped portion of the electrode layer), and it is taken as the level b. Fig. 9 (C) is a state diagram depicting the state where the electrode layer is completely peeled from the current collector (the black part is the electrode layer peeled part), and it is taken as the level c. The resistance measurement method is: sandwiching an electrode formed on a current collector between a copper plate having a diameter of 2 cm and a thickness of 5 mm, and pressing the pressure of 4.5 kg / cm2 from above and below, and using a resistance analyzer to measure the resistance of the AC 1 0 κ Η z value. If the same sample batch number is used to compare the infrared heating and hot air heating test samples, no matter which sample is irradiated with infrared light, the peel strength is all grade a, and warm air heating is all grade b. The infrared irradiation side has /
第19頁 550848 五、發明說明（17) 1級上的剝離強度。並且，電阻也是用紅外線照射的一方 電阻小，特別，顯示試料2用紅外線照射一方，電阻值小 2個數量級。 . 以下，說明有關用離子導電性聚合物覆蓋的電極材 料。 · · 《一》 用離子導電性聚合物覆蓋電極層 ％ 圖1中，粉狀電極活性物質1 1具有如L i C 〇〇2由 · 結合粒構成粒子的形狀，並顯示用離子導電性聚合物1 2 覆蓋的過程。所謂覆蓋，就是在離子導電性聚合物1 2與 粉狀電極活性物質1 1整個表面之間處於接連著的狀態使 離子能夠充分移動，離子導電性聚合物1 2覆蓋在粉狀電鲁 極活性物質1 1的表面，用離子導電性聚合物1 2掩蓋。粉 狀電極活性物質1 1雖然粒子變成越細越有活性，可是因 為用離子導電性聚合物1 2覆蓋會抑制活性並成為穩定。 如果覆蓋的離子導電性聚合物1 2的厚度厚的話，導電率 將降低，集電效率就會惡化，因而以較薄為佳。另外，有 關用離子導電性聚合物覆泛的電極構造體的發明，在本申 請人在先申請的發明（特願平1 1 — 2 5 0 1號、特願平 11 一 262502號）中已有記載。 另外，所謂粉狀電極活性物質1 1 、粉狀導電物質1 4等的粉狀是指細小粒狀物質。又叫做集聚許多物質的集 合狀態。按照不同情況，也稱為細小粒狀物質許多集合的 ® 狀態。 《二》 粉狀電極活性物質 /Page 19 550848 V. Description of the invention (17) Peel strength on level 1. In addition, the resistance is also irradiated with infrared rays. The resistance is small. In particular, the display sample 2 is irradiated with infrared rays, and the resistance value is two orders of magnitude smaller. The following describes electrode materials covered with ion-conductive polymers. "I" Covering the electrode layer with an ion conductive polymer% In Fig. 1, the powdery electrode active material 11 has the shape of a particle composed of a binding particle such as L i C 〇02, and shows ion conductive polymerization. Object 1 2 process. The so-called covering means that the entire surface of the ion conductive polymer 12 and the powdery electrode active material 1 1 are in a continuous state so that the ions can move sufficiently, and the ion conductive polymer 12 is covered with the powdery electrode. The surface of the substance 11 is covered with an ion conductive polymer 12. Although the powdery electrode active material 1 1 becomes finer, the particles become more active. However, coating with the ion conductive polymer 1 2 suppresses the activity and stabilizes it. If the thickness of the ion-conducting polymer 12 to be covered is thick, the conductivity will be lowered, and the current collection efficiency will be deteriorated. In addition, the invention of an electrode structure covered with an ion-conducting polymer is disclosed in the invention previously applied by the applicant (Japanese Patent Application Nos. 1 1 to 2 5 0 1 and Japanese Patent Application Nos. 11 to 262502). Documented. The powders such as the powdery electrode active material 1 1 and the powdery conductive material 14 refer to fine granular materials. It is also called an aggregate state where many substances are gathered. Depending on the situation, it is also called the ® state of many collections of fine particulate matter. 《二》 Powder electrode active material /
第20頁 550848 五、發明說明（18) 粉狀電極活性物質可以使用離子可插入脫離的材料或 7Γ共軛導電性高分子材料等。例如，作為非水電解液電池 的正電極使用的電極活性物質雖然沒有特別限定，但是在 可充電電池的情況下，可以使用鋰離子可插入脫離的硫族 化合物或含有經的複合硫族化合物。 作為上述硫族化合物，可以舉出FeS2、Ti S2、Mo S2、V2〇5、 V6〇i3、Mn〇2等。作為含有上述鋰的 複合硫族化合物，可以舉出用LiCo〇2 'LixNiyl^—y〇 2 (其中，Μ表示從過渡金屬或A1中選擇的至少一種以 上的金屬元素，最好表示從Co、Mn、Ti、Cr、V、A 1中選擇的至少一種以上的金屬元素，而且是0.05SxS 1. 10、0. 0)表示的鋰複合氧化物、Li N i Ο L i Μ η Ο L i Μη9 〇 4 這些是把鋰 鈷 鎳、錳等的氧化物、鹽類、或氫氧化物等作為初始原料， 根據組成混合這些初始原料，在氧氣氛下6 0 0 ° C〜1 0 0 0 ° C的溫度範圍内通過燒結而獲得。 並且，作為水電解液電池的負電極使用的電極活性物 質雖然沒有特別限定，但是可以使用鋰離子可插入脫離的 枋料，可以使用鐘金屬、鋰合金（經與銘、錯、銦等的合 金）、碳質材料等。 並且，作為7Γ共軛導電性高分子材料，可以舉出聚乙 炔類、聚苯胺類、聚咯類、聚專吩類、聚一p ( para ) —苯撐類、聚4唑類、聚氮烯類、硫磺聚合物類等。 特別，在非水電解液一次電池中，如果鋰金屬使用於Page 20 550848 V. Description of the invention (18) The powdery electrode active material can use ion-insertable or detachable materials or 7Γ conjugated conductive polymer materials. For example, although the electrode active material used as the positive electrode of a non-aqueous electrolyte battery is not particularly limited, in the case of a rechargeable battery, a chalcogen compound capable of intercalating and detaching lithium ions or a complex chalcogen compound containing lithium ion can be used. Examples of the chalcogen compound include FeS2, TiS2, MoS2, V205, V60i3, and Mn02. Examples of the complex chalcogen compound containing lithium include LiCo〇2 'LixNiyl ^ -y〇2 (where M represents at least one or more metal elements selected from transition metals or A1, and preferably from Co, Mn, Ti, Cr, V, A 1 selected from at least one metal element, and is a lithium composite oxide represented by 0.05SxS 1.10, 0.0), Li N i Ο L i Μ η Ο L i Μη9 〇4 These are lithium cobalt nickel, manganese and other oxides, salts, or hydroxides as the initial raw materials, these initial raw materials are mixed according to the composition, in an oxygen atmosphere 6 0 0 ° C ~ 1 0 0 0 ° The temperature range of C is obtained by sintering. In addition, although the electrode active material used as the negative electrode of the water electrolyte battery is not particularly limited, a lithium ion insertable and detachable material can be used, and a bell metal, a lithium alloy (alloys such as metal, aluminum, and indium) can be used. ), Carbonaceous materials, etc. Examples of the 7Γ conjugated conductive polymer materials include polyacetylenes, polyanilines, polyrolees, polyphenylenes, poly (p-para) phenylenes, poly4azoles, and polynitrogens. Olefins, sulfur polymers, etc. In particular, in non-aqueous electrolyte primary batteries, if lithium metal is used in
第21頁 550848 五、發明說明（19) 負電極，就可獲得大的電池容量。 並且，在非水電解液電池中，如果把可插入脫離鋰的 碳材料用於負電極，就可獲得優良的循環壽命。作為碳材 . 料雖然沒有特別限定，但是可以舉出熱分解碳類、焦碳類 (瀝青焦碳、針狀焦碳、石油焦碳等）、石墨類、玻璃狀 ' 碳類、有機高分子化合物燒結體（在適當溫度燒結酚醛樹 ~ 脂、 喃樹脂等碳化物）、碳纖維、活性炭等。 · 《三》粉狀導電物質 粉狀導電物質是提高電極構造體導電性的物質，雖然 沒有特別限定，但是可使用金屬粉末、碳粉末等。特別， 就碳粉末而言，碳黑等的熱分解碳、以及其石墨化產品、_ 人造和天然的鱗片狀石墨粉、碳纖維及其石墨化產品等都 適合。並且，也使用這些碳粉末的混合品。 《四》 離子導電性聚合物 離子導電性聚合物能在0 . 1 Μ (摩爾/ 1 )以上濃度 可以溶解以下舉出的至少鋰鹽，而且，溶解了 〇. 1Μ以 上濃度鋰鹽的聚合物是在室溫下顯示1 0 — 8 S (西門子） /cm電傳導性的聚合物。另外，特別理想的是，離子導電 性聚合物是至少溶解鋰鹽成0 . 8 Μ〜1 . 5 Μ的濃度，並 顯示1 0 一 3 S / cm〜1 〇 - 5 S / cm電傳導性。 所謂鋰鹽，使用將Cl〇4—、CF3S〇3—、B F4—、P F6— 、AsF6_、 SbF6— 、CF3C〇2-、 ( C F 3 S 0 · 3 - ) 2 N —等作為陰離子的鋰鹽任一種以上。 離子導電性聚合物原料是從外部給予能量，通過聚 /Page 21 550848 V. Description of the invention (19) The negative electrode can obtain a large battery capacity. In addition, in a non-aqueous electrolyte battery, if a carbon material that can be inserted and detached from lithium is used for the negative electrode, excellent cycle life can be obtained. The carbon material is not particularly limited, but examples include pyrolytic carbons, cokes (asphalt coke, needle coke, petroleum coke, etc.), graphites, glassy carbons, and organic polymers. Compound sintered body (sintering of phenolic resins, resins such as phenols, urethane resins, etc.), carbon fibers, activated carbon, etc. · "Three" Powdery Conductive Substances Powdery conductive substances are substances that increase the conductivity of the electrode structure. Although not particularly limited, metal powders and carbon powders can be used. In particular, as the carbon powder, thermally decomposed carbon such as carbon black, and its graphitized products, artificial and natural flaky graphite powder, carbon fiber and its graphitized products are suitable. A mixture of these carbon powders is also used. "Four" Ion-conductive polymer Ion-conductive polymer can dissolve at least the lithium salt listed below at a concentration of 0.1 M (mol / 1) or more, and a polymer having a lithium salt of 0.1 M or more dissolved It is a polymer that shows 10-8 S (Siemens) / cm electrical conductivity at room temperature. In addition, it is particularly desirable that the ion-conducting polymer dissolves at least a lithium salt to a concentration of 0.8 M to 1.5 M, and exhibits an electrical conductivity of 10 to 3 S / cm to 1 0 to 5 S / cm. . The so-called lithium salt uses ClO4—, CF3S〇3—, B F4—, P F6—, AsF6_, SbF6—, CF3C〇2-, (CF 3 S 0 · 3-) 2 N — and the like as anions. Any one or more of lithium salts. Ion-conductive polymer raw materials are
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| JP4415673B2 (en) * | 2003-12-26 | 2010-02-17 | Ｔｄｋ株式会社 | Capacitor electrode manufacturing method |
| CA2535064A1 (en) * | 2006-02-01 | 2007-08-01 | Hydro Quebec | Multi-layer material, production and use thereof as an electrode |
| CN102237199A (en) * | 2010-04-21 | 2011-11-09 | 财团法人金属工业研究发展中心 | Electric storage device, electrode group of electric storage device and method for manufacturing electrode group |
| CN103647039A (en) * | 2010-12-06 | 2014-03-19 | 丰田自动车株式会社 | Lithium ion secondary battery |
| JP5699858B2 (en) * | 2011-08-23 | 2015-04-15 | 日産自動車株式会社 | Electrodes and electrical devices |
| CN102427124A (en) * | 2011-12-05 | 2012-04-25 | 深圳市中星动力电池技术有限公司 | Positive plate of multi-element nano vanadium power battery |
| CN102683637A (en) * | 2012-05-28 | 2012-09-19 | 东莞新能源科技有限公司 | Lithium ion battery electrode plate |
| CN103779569A (en) * | 2012-10-23 | 2014-05-07 | 海洋王照明科技股份有限公司 | Lithium ion battery anode sheet and preparation method thereof |
| JP6052083B2 (en) * | 2013-07-12 | 2016-12-27 | トヨタ自動車株式会社 | Drying apparatus, drying method, and battery manufacturing method |
| CN104715932A (en) * | 2013-12-11 | 2015-06-17 | 财团法人工业技术研究院 | Energy storage element and super capacitor element |
| TWI570752B (en) * | 2013-12-11 | 2017-02-11 | 財團法人工業技術研究院 | Power storage device and super capacitor device |
| CN107464916B (en) * | 2017-08-31 | 2020-05-15 | 柔电（武汉）科技有限公司 | Laminated flexible electrode plate and preparation method thereof |
| CN109546080B (en) * | 2018-11-29 | 2020-09-29 | 中国科学院过程工程研究所 | Positive pole piece, and preparation method and application thereof |
| CN111755733B (en) * | 2019-03-28 | 2024-07-26 | 揖斐电株式会社 | All-solid-state battery and method for manufacturing same |
| WO2021192541A1 (en) * | 2020-03-24 | 2021-09-30 | パナソニックＩｐマネジメント株式会社 | Electrode for secondary batteries and method for producing same |
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| TWI622070B (en) * | 2013-08-06 | 2018-04-21 | 日本華爾卡工業股份有限公司 | Method of manufacturing an electrode film for electrically double layers capacitor |
| US10373768B2 (en) | 2013-08-06 | 2019-08-06 | Valqua, Ltd. | Method for producing electrode film for electric double layer capacitors |
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