201027821 六、發明說明： 【發明所屬之技術領域】 本專利申請案係關於一種薄膜電池，其包括至少一作為 組件（A)之片狀負極、至少一作為組件（B)之片狀正極、至 少一作為組件（C)之電解質及至少一作為組件（D)之設置於 該至少一負極（A)與該至少一正極（B)之間之片狀分隔器， 其中該至少一分隔器包括至少一經陰離子基團官能化之聚 合物；本專利申請案亦關於以經陰離子基團官能化之聚合 物作為薄臈電池中之分隔器之用途及該薄膜電池於電子組 件中之用途。 【先前技術】 薄膜電池已為熟悉此項技術者知曉多年，特定言之係其 等在智慧卡、活性RFID標籤、感應器、智慧化妝品中或^ 醫療部門（如晶片實驗室（lapia_ehip))中之料。薄膜電 池尤其被使用作為主電池（即非可充電電池），其利用廉 價、對環境無害之起始物質及非高成本之製程製造，例如 藉由網版印刷自溶液塗佈。通f所知詩該等薄膜電池之 系統係基於使用水性（通常為驗性）電解f及多孔分隔器之 Zn/Mn〇2及鋅/空氣。先前技術中已知薄膜電池。 US 2003/0219648 A1揭示一種藉由印刷技術製得之薄膜 ，池。其包括—其上印刷有—第—導電層之可換性背概薄 。-第-電極層印刷於此第一導電層上。一第二電極層 印刷於此第一電極層上。一第__ 弟一導電層印刷於此第二電極201027821 VI. Description of the Invention: [Technical Field] The present patent application relates to a thin film battery comprising at least one sheet-shaped negative electrode as component (A) and at least one sheet-shaped positive electrode as component (B), at least An electrolyte as the component (C) and at least one sheet separator disposed between the at least one negative electrode (A) and the at least one positive electrode (B) as the component (D), wherein the at least one separator includes at least one separator A polymer functionalized with an anionic group; the present patent application also relates to the use of a polymer functionalized with an anionic group as a separator in a thin tantalum battery and to the use of the thin film battery in an electronic component. [Prior Art] Thin film batteries have been known to those skilled in the art for many years, in particular in smart cards, active RFID tags, sensors, smart cosmetics or in medical departments (such as wafer labs (lapia_ehip)). The material. Thin film batteries are especially used as primary batteries (i.e., non-rechargeable batteries), which are fabricated using inexpensive, environmentally friendly starting materials and non-high cost processes, such as by solution printing from screen printing. The systems of such thin film batteries are based on the use of aqueous (usually anatory) electrolysis f and porous separators of Zn/Mn〇2 and zinc/air. Thin film batteries are known in the prior art. US 2003/0219648 A1 discloses a film, cell made by printing technology. It includes - the exchangeability of the first conductive layer printed thereon. The first electrode layer is printed on the first conductive layer. A second electrode layer is printed on the first electrode layer. a first __ a conductive layer printed on the second electrode
上。該第二導電層藉由另一保護層與外部隔離。上述US 144644.doc 201027821 文件卞揭示之另一替代方案中，該二電極之間存在一分隔 器/電解質層。該分隔器在陽極與陰極之間傳導離子並使 該陽極與該陰極間在電學上分隔，從而不產生電流。根據 - US 2003/0219648 A1之分隔器包括一多孔或經薄印之基質 材料，其選自高度填充之聚丙烯酸水溶液、聚二氟亞乙烯on. The second conductive layer is isolated from the outside by another protective layer. In another alternative disclosed in the above-mentioned U.S. Patent No. 144,644, the disclosure of which is incorporated herein by reference. The separator conducts ions between the anode and the cathode and electrically separates the anode from the cathode so that no current is generated. The separator according to US Pat. No. 2003/0219648 A1 comprises a porous or thin printed substrate material selected from the group consisting of highly filled polyacrylic acid aqueous solutions, polydifluoroethylene
W 均聚物與共聚物及聚丙烯腈均聚物與共聚物。所提及之US 文件未揭示其中存在經陰離子基團官能化之聚合物的薄膜 電池。 ® WO 97/22466揭示一種可撓性薄膜電池，其包括一電解 質水溶液、一負極、一正極及一作為所提及電極之間之分 隔器且可包括濾紙、塑膠膜、纖維素膜、紡織物等的多孔 層。此文件並未揭示用於薄膜電池之包括至少一經陰離子 基團官能化的聚合物的分隔器。 WO 03/069700 A2揭示一種可撓性薄膜電池，其中一陽 極印刷於一支撐材料上且一陰極印刷於一第二支撐材料 ^ 上。陽極與陰極係放置在一起，且在陽極與陰極之間具有 一紙層、一膠層或印製分隔器作為分隔器。WO 03/069700 未揭示其中使用陰離子官能化聚合物作為分隔器之薄膜電 ' 池。 . WO 2005/106990 A2揭示一種包括一負極與一正極之可 撓性薄膜電池。該薄膜電池外部係由聚合物膜包纏。在所 闡述之薄膜電池中，存在經澱粉塗覆之紙作為該二電極之 間之分隔器層。WO 2005/106990 A2未揭示其中使用陰離 子官能化聚合物作為分隔器之薄膜電池。 144644.doc 201027821 先則技術中所提及薄媒電池中所包括之分隔器對於對抗 氧自該薄膜電池正極侧擴散至負極側僅具有無法令人滿意 的障壁功能。此點對該種薄膜電池(特定言之鋅/空氣薄膜 電）之壽命具有不利影響。再者，自先前技術所知用於 薄膜電池之分隔器具有無法令人滿意的機械穩定性及，或 離子滲透性。 【發明内容】 因此，本發明之-目的係提供—種具有非多孔性分隔器 之薄膜電池，該分隔器對於對抗氧自該電池之正極擴散至 負極顯示改良的障壁作用。本發明之另一目的係依此方法 改良薄膜電池壽命。再者，儘管所用分隔器之非多孔性結 構二本發明之薄膜電池亦應埃保充足的離子流。本發明之 另—目的係為薄媒電池提供改善機械穩定性之薄膜電池用 的分隔器。 根據本發明，該等目的係藉由一種薄膜電池而達成，該 電池包括： (A) 至少一作為組件（A)之片狀負極， (B) 至少一作為組件（B)之片狀正極， (C) 至少一作為組件之電解質，及 (D) 至少一作為組件（D)之設置於至少一第一電極與至少 —第二電極之間之片狀分隔器， 其中該至少一分隔器包括至少一陰離子官能化聚合物。 人本發明該等目㈣係透過使用經陰離子基團官能化的聚 合物作為薄膜電池中之分隔器，及於電子組件中使用根據 144644.doc 201027821 本發明之薄膜電池而達成。 【實施方式】 1下更詳細說明本發明之薄膜電池·· 本『明之薄膜電池包括至少一作為組件⑷之片狀負 = 為組物之片狀正極、至少-作為組件(〇 質及至少一作為組件（D)之設置於該至 該至少-正極之間之片狀分隔器。 、W homopolymers and copolymers and polyacrylonitrile homopolymers and copolymers. The mentioned US document does not disclose a thin film battery in which a polymer functionalized with an anionic group is present. ® WO 97/22466 discloses a flexible thin film battery comprising an aqueous electrolyte solution, a negative electrode, a positive electrode and a separator between the electrodes mentioned and which may comprise filter paper, plastic film, cellulose film, textile A porous layer of the same. This document does not disclose a separator for a thin film battery comprising at least one polymer functionalized with an anionic group. WO 03/069700 A2 discloses a flexible thin film battery in which an anode is printed on a support material and a cathode is printed on a second support material ^. The anode and cathode are placed together with a paper layer, a glue layer or a printed separator between the anode and cathode as a separator. WO 03/069700 does not disclose a thin film electrical cell in which an anionic functionalized polymer is used as a separator. WO 2005/106990 A2 discloses a flexible thin film battery comprising a negative electrode and a positive electrode. The exterior of the thin film battery is wrapped by a polymer film. In the illustrated thin film battery, starch coated paper is present as a separator layer between the two electrodes. WO 2005/106990 A2 does not disclose a thin film battery in which an anion functionalized polymer is used as a separator. 144644.doc 201027821 The separator included in the thin-film battery mentioned in the prior art has only an unsatisfactory barrier function for the diffusion of oxygen against the anode side of the thin film battery to the negative electrode side. This has an adverse effect on the lifetime of such a thin film battery (specifically, zinc/air film electricity). Furthermore, separators for thin film batteries known from the prior art have unsatisfactory mechanical stability and/or ion permeability. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a thin film battery having a non-porous separator which exhibits an improved barrier effect against oxygen diffusion from the positive electrode of the battery to the negative electrode. Another object of the invention is to improve the life of a thin film battery in accordance with this method. Further, in spite of the non-porous structure of the separator used, the thin film battery of the present invention should also have sufficient ion current. Another object of the present invention is to provide a separator for a thin film battery which improves mechanical stability for a thin dielectric battery. According to the present invention, the objects are achieved by a thin film battery comprising: (A) at least one sheet-shaped negative electrode as component (A), and (B) at least one sheet-shaped positive electrode as component (B), (C) at least one electrolyte as a component, and (D) at least one sheet separator disposed between the at least one first electrode and the at least a second electrode as the component (D), wherein the at least one separator comprises At least one anionically functionalized polymer. These objects (4) of the present invention are achieved by using a polymer functionalized with an anionic group as a separator in a thin film battery, and using a thin film battery according to the invention according to 144644.doc 201027821 in an electronic component. [Embodiment] 1 Hereinafter, a thin film battery of the present invention will be described in more detail. The thin film battery of the present invention includes at least one sheet-like positive electrode as a component (4), a sheet-shaped positive electrode as a group, and at least a component (a enamel and at least one). As the component (D), the sheet separator is disposed between the at least the positive electrode.
膜電池個別組件之厚度 ，對於本發明之目❾，「片狀」意指本發明薄膜電池中之 5亥等電極或至少—分隔器之寬度與長度顯著切本發明薄 :夕負極、該至少一正極及該至少一分隔器在彼等 平面延伸方向上可具有任何規則或不規則形狀，如四邊 形(例如正方形、長方形)、三角形、多邊形、圓形、概圓 形等。較佳根據設計用途決定該等至少三層之形狀。 在-較佳實施例中，本發明之薄膜電池_存在—作為組 件(A)之片狀負極、一作為組件(B)之片狀正極、一作為組 件（C)之電解質及一作為組件（D)之設置於一負極與一正極 之間之分隔器。 另較佳實施例中，設置組件（A)至（D)，以致所存在 兩電極之一者形成其上施加至少一分隔器之下層。隨後將 第一電極施加於該分隔器上。依此方式，可配置本發明之 薄膜電、池，以致至少一作為組件（A)之片&負極形成一其 上細加作為組件（D)之至少一分隔器之下方區域。隨後將 作為組件（B)之至少—片狀正極施加至此至少一分隔器。 144644.doc 201027821 在此配置中，該電解質（組件（c))較佳亦存在於該至少兩電 極（組件（A)與組件（B))之間，如透過使分隔器中充滿電解 質。 在本發明薄膜電池之一較佳實施例中，在該至少一片狀 負極之背對該至少一分隔器之侧上存在至少一保護膜。 在另一較佳實施例中，在該至少—片狀正極之背對該至 少一分隔器之侧上存在至少一保護膜。 在一特佳實施例中，在該至少—片狀負極之#對該至少 一分隔器之側上及在該至少一片狀正極之背對該至少一分 隔器之側上均存在—保護膜。根據本發明，可钱材料及 /或配置而言相同類型之保護膜存在於電極兩側上，但根 據本發明，亦可使不同類型保護膜存在於負極與正極上。 以下詳述本發明薄臈電池之各個組件： 組件（A): 在本發明薄膜電池中’存在至少一片狀負極作為組件 ._ ......^川〜-碍犋1：池負 (亦即陽極）之活性物質均可使用在本發明薄膜電池之至 一片狀負極中。 通常可在薄膜電池之陽極使用之活性物質係（例如）呈 ^及/或部份氧化形式之金屬，較佳係呈元素形式，例: 自由鋅、鎖、鐵及其混合物组成之群之金屬。可 ^薄膜電池之陽極中使用之其他適宜的金屬係、例如 呈元素或部份氧化形式之㉝、銀、鈦絲。在本發明^ 144644.doc 201027821 電池之較佳實施例中，該至少一片狀負極（A)包括呈元素 形式之辞。 在本發明薄膜電池中，作為組件（A)存在之該至少一負 極了包括所有為彼等熟悉此項技術者所知之添加劑，且可 藉由熟悉此項技術者所知之方法製得。 s亥至少一負極（A)可（例如）藉由在適當的基材上印刷適當 的油墨而獲得。適當的油墨及製程為熟悉此項技術者所 知。製造該至少一負極（A)之其他製程同樣為熟悉此項技 術者所知。 存在於印刷油墨中的組分較佳係以存在可塗佈或可印刷 糊料的量添加。 組件（B): 在本發明薄膜電池中，存在至少一片狀正極作為組件 (B)。 本發明薄膜電池中之至少一片狀正極（組件（B))係作為電 ❷ 池中之陰極。本發明薄膜電池中之組件（B)包括至少一種 活性物質。根據本發明，可使用熟悉此項技術者所知之所 有物質，特定言之係適用於薄膜電池正極之金屬氧化物。 用於根據本發明之至少一正極之適宜活性物質之實例係 選自由二氧化錳（Mn〇2)、氧化銀（丨）(Ag2〇)及其混合物組 成之群之金屬化合物。在本發明薄膜電池之一較佳實施例 中’該至少一片狀正極（B)包括Mn〇2。 根據本發明之至少一正極較佳包括作為活性物質之二氧 化錳（Mn〇2)、作為導電物質之里碳黑形式之碳及作為黏合 144644.doc 201027821 劑之聚稀烴（如聚異丁稀）、或鐵氟龍（Tefi(m)，及使用芳族 化〇物（如甲笨）作為電極油墨之懸浮介質。 、 組件（c): 存在至j 一電解質作為本發明薄膜電池中之組件（〇。 在本發明薄膜電池中，該至少—電解質可在該電池 現離子傳導。為此目的，在-較佳實施例中，該至少一負 極（，.且件A) a至少一正極（組件B)及該至少一分隔器（組件 D)係經液體電解質含浸。因此，在—較佳實施例中，該至 少一液體電解質係存在於該至少一負極（組件A)、該至少 一正極（組件B)及該至少一分隔器（組件D)中。 在本發明薄膜電池中，較佳使用至少一離子化合物之水 溶液作為組件（C)。適宜的離子化合物係（例如）無機鹽。在 一較佳實施例中，該至少一電解質（c)係鹼性水溶液。 電解質（組件（C))中存在之尤佳化合物係（例如）選自由氣 化辞（ZnCh) '氣化銨（ΝΗπΐ)、醋酸銨（nj^-Ac)、醋酸鋅 (Zn(OCOCH3)2)、溴化辞（ZnBr2)、氟化鋅（znF2) ' 峨化鋅 (Znl2)、酒石酸鋅（ZnC4H406.H20)、過氣酸辞（zn(ci〇4)2.6H20；) 、氫氧化鉀（KOH)、氫氧化鈉（NaOH)及其混合物組成之 群，較佳為氫氧化鉀（KOH)及其混合物。 在存在氫氧化鉀（KOH)作為電解質中之離子化合物之較 佳情形中，使用（例如）包括20重量％至40重量％之氫氧化 鉀’較佳25重量％至35重量％之氫氧化鉀的水溶液。 組件（D): 在本發明之薄層電池中’存在至少一片狀分隔器作為位 144644.doc -10- 201027821 於該至少一負極與該至少-正極之間的組件(D)，且該至 少-分隔器包括至少一經陰離子基團官能化之聚合物。 在根據本發明之分隔器中，可使用為熟悉此項技術者所 知且經陰離子基團官能化之所有聚合物。可根據本發明使 用之聚合物可為有孔或非多孔性，較佳為使用非多孔性聚 合物。The thickness of the individual components of the membrane battery, for the purpose of the present invention, "sheet" means that the width and length of the electrode of the 5th electrode or at least the separator in the thin film battery of the present invention are significantly thinner than the present invention: the negative electrode, the at least A positive electrode and the at least one separator may have any regular or irregular shape in the direction in which they extend in a plane, such as a quadrilateral (e.g., square, rectangular), triangular, polygonal, circular, circular, and the like. Preferably, the shape of the at least three layers is determined according to the design use. In a preferred embodiment, the thin film battery of the present invention is present as a sheet-like negative electrode of the assembly (A), a sheet-like positive electrode as the component (B), an electrolyte as the component (C), and a component ( D) is a separator disposed between a negative electrode and a positive electrode. In a further preferred embodiment, components (A) through (D) are provided such that one of the two electrodes is present to form at least one lower layer of the separator thereon. A first electrode is then applied to the separator. In this manner, the thin film electric and cell of the present invention can be configured such that at least one of the sheets & the negative electrode as the component (A) forms a lower region on which at least one separator is finely added as the component (D). At least one sheet-like positive electrode as component (B) is then applied to the at least one separator. 144644.doc 201027821 In this configuration, the electrolyte (component (c)) is preferably also present between the at least two electrodes (component (A) and component (B)), such as by passing the separator full of electrolyte. In a preferred embodiment of the thin film battery of the present invention, at least one protective film is present on the side of the at least one separator opposite the at least one separator. In another preferred embodiment, at least one protective film is present on the side of the at least one sheet-shaped positive electrode that faces away from at least one of the separators. In a particularly preferred embodiment, a protective film is present on the side of the at least one separator on the at least one separator and on the side of the at least one separator on the back of the at least one positive electrode. . According to the present invention, the same type of protective film is present on both sides of the electrode in the form of a usable material and/or configuration, but according to the present invention, different types of protective films may be present on the negative electrode and the positive electrode. The components of the thin tantalum battery of the present invention are detailed below: Component (A): In the thin film battery of the present invention, 'at least one negative electrode is present as a component. _ ...... ^川~- 犋 : 1: Pool negative The active material (i.e., the anode) can be used in the sheet-like negative electrode of the thin film battery of the present invention. The active material which can usually be used at the anode of a thin film battery is, for example, a metal in the form of a oxidized form, preferably in the form of an element, for example: a metal of a group consisting of free zinc, locks, iron and mixtures thereof. . Other suitable metal systems for use in the anode of the thin film battery, such as 33, silver or titanium wire in elemental or partially oxidized form. In a preferred embodiment of the battery of the invention, the at least one piece of the negative electrode (A) comprises the element in the form of an element. In the thin film battery of the present invention, the at least one negative electrode present as the component (A) includes all additives known to those skilled in the art, and can be obtained by a method known to those skilled in the art. At least one negative electrode (A) can be obtained, for example, by printing a suitable ink on a suitable substrate. Suitable inks and processes are known to those skilled in the art. Other processes for making the at least one negative electrode (A) are also known to those skilled in the art. The components present in the printing ink are preferably added in an amount in which a coatable or printable paste is present. Component (B): In the thin film battery of the present invention, at least one sheet of the positive electrode was present as the component (B). At least one of the positive electrodes (component (B)) in the thin film battery of the present invention serves as a cathode in the battery. The component (B) in the thin film battery of the present invention comprises at least one active material. In accordance with the present invention, it is possible to use all materials known to those skilled in the art, in particular for metal oxides of positive electrodes of thin film batteries. Examples of suitable active materials for at least one positive electrode according to the present invention are selected from the group consisting of manganese dioxide (Mn 2 ), silver oxide (Ag 2 ), and mixtures thereof. In a preferred embodiment of the thin film battery of the present invention, the at least one sheet-shaped positive electrode (B) comprises Mn〇2. The at least one positive electrode according to the present invention preferably comprises manganese dioxide (Mn〇2) as an active material, carbon in the form of carbon black as a conductive substance, and a polyhydrocarbon (such as polyisobutylene) as a binder 144644.doc 201027821 Diluted), or Teflon (Tefi (m), and the use of aromatic sputum (such as a stupid) as a suspension medium for electrode ink., component (c): exists to j-electrolyte as the thin film battery of the present invention Component (〇. In the thin film battery of the present invention, the at least-electrolyte can be ionically conducted in the battery. For this purpose, in the preferred embodiment, the at least one negative electrode (, and A) is at least one positive electrode. (Component B) and the at least one separator (component D) are impregnated with a liquid electrolyte. Thus, in a preferred embodiment, the at least one liquid electrolyte is present in the at least one negative electrode (component A), the at least one In the positive electrode (component B) and the at least one separator (component D), in the thin film battery of the present invention, an aqueous solution of at least one ionic compound is preferably used as the component (C). Suitable ionic compounds are, for example, inorganic salts. In a better In the embodiment, the at least one electrolyte (c) is an alkaline aqueous solution. The preferred compound present in the electrolyte (component (C)) is, for example, selected from the group consisting of gasification (ZnCh) 'vaporized ammonium (ΝΗπΐ), acetic acid Ammonium (nj^-Ac), zinc acetate (Zn(OCOCH3)2), brominated (ZnBr2), zinc fluoride (znF2) 'zinc telluride (Znl2), zinc tartrate (ZnC4H406.H20), peroxy acid a group consisting of zn(ci〇4)2.6H20;), potassium hydroxide (KOH), sodium hydroxide (NaOH) and mixtures thereof, preferably potassium hydroxide (KOH) and mixtures thereof. In the preferred case of potassium (KOH) as the ionic compound in the electrolyte, for example, an aqueous solution comprising 20% by weight to 40% by weight of potassium hydroxide, preferably 25% by weight to 35% by weight, of potassium hydroxide is used. (D): in the thin-layer battery of the present invention, there is at least one sheet-shaped separator as a component (D) between the at least one negative electrode and the at least-positive electrode as the bit 144644.doc -10- 201027821, and the at least The separator comprises at least one polymer functionalized with an anionic group. In the separator according to the invention, it can be used as a cooked Known in the art and by the anionic groups of the functionalized polymers all may be may be a porous or non-porous, non-porous is preferably used according to the present invention, the polymer of the polymer used.
在一較佳實施例巾，所使用之經陰離子基團官能化的聚 合物係選自由聚砜、聚醚碾 '鐵氟龍、聚二氟亞乙烯 (PVDF)、聚（二氟亞乙稀_六氣丙烯）共聚物（pvdF_聊共聚 物）、聚芳基醚酮（如聚醚醚鲖（PEEK)、聚醚酮（ρΕκ)、聚 賴嗣（ΡΕΚΚ))、聚苯并咪哇（ΡΒΙ)、聚酿亞胺、聚苯乙 婦、聚醯胺、聚丙賴自旨及其共聚物及混合物組成之群。 根據本發明，陰離子基團對聚合物之官能化可存在於所 述聚合物之主鏈及/或側鏈上。官能化較佳發生於所述聚 合物之側鏈上。根據本發明，首先可使用在聚合物製備中 經預先官能化之單體，其次亦可隨後在聚合物_類似物反 應中於先前製得的聚合物上進行適當的官能化。 存在於分隔器（D)之陰離子官能化聚合物中之陰離子基 團可選自熟悉此項技術者所知之所有陰離子官能團，如磺 酸根-S03-、羧酸根-C〇2-、-Ρ〇(〇Η)〇-或ρ〇32_。特佳係存 在磺酸根-S〇3_基團。 在本發明薄膜電池中尤佳使用磺化聚芳基醚酮，如選自 由磺化聚醚醚酮（PEEK)、磺化聚醚酮（pEK)、磺化聚醚醚 酮酮（PEKK)及其混合物組成之群之磺化聚芳基醚酮，極佳 144644.doc 201027821 係磺化聚醚醚酮。 因此，本發明較佳提供一種根據本發明之薄膜電池，其 中該至少一陰離子官能化聚合物係磺化聚芳基醚酮，尤佳 係選自由磺化聚醚醚酮（PEEK)、磺化聚醚酮（PEK)、磺化 聚醚酮酮（PEKK)及其混合物組成之群之磺化聚芳基醚酮， 極佳係磺化聚醚醚酮。 根據本發明，可使用為熟悉此項技術者所知之所有磺化 聚芳基醚酮，特定言之係聚醚醚酮（PEEK)、磺化聚醚酮 (PEK)、磺化聚醚酮酮（PEKK)或其混合物。 該等磺化聚合物係（例如）藉由利用適宜的磺化劑，如發 煙硫酸、濃硫酸、高濃度（即98%強度）硫酸、三氧化硫或 氣磺酸在至少一適宜的有機溶劑中或丁基鋰連同二氧化硫 將適宜的前體化合物磺化，隨後再利用（例如）過錳酸鉀氧 化而製得。適宜的聚醚醚酮、聚醚酮、聚醚酮酮為熟悉此 項技術者已知。極佳使用PEEK與PEK聚合物等級（自 Victrex pic.購得），特定言之為 PEEKtm 450P、PEEKtm 150P與 PEKtm P22 ° 特定言之，根據本發明尤佳使用作為陰離子官能化聚合 物之磺化聚芳基醚酮係透過包括以下步驟之製程製得： 使至少一聚芳基醚酮與至少一烷磺酸反應產生含硫的聚 芳基醚酮（I)，及使根據⑴製得之含硫聚芳基醚酮與至少一 磺化劑反應產生磺化聚芳基醚酮（II)。 根據本發明較佳用於製備磺化聚芳基醚酮之此製程為熟 悉此項技術者已知且發表於WO 2004/076530中。 144644.doc •12- 201027821 在步驟⑴巾’脂族韻通常適於作為院姐。較佳使用 以下通式之烷磺酸： r-so3h 、 系刀支鏈或無分支鏈之烴基且含有1至12個碳原子， 較佳1至6個碳原子，尤佳係具有1至3個碳原子之無分支鍵 的达基，極佳係具有1個碳原子，即曱續酸。 ⑴中反應物之莫耳比較佳係在通常為1:1至1:1000之範圍 ❿ 更佳為1,2至1:500且特佳為1:10至1:300。通常，該至 V院續酸係以過量使用。若該烧續酸同時用作溶劑，則 其係以對聚芳基醚酮之莫耳過量存在。 就本發明之目的而言，「含硫聚芳基醚酮」係包含鍵結 硫之聚芳基越酮。其非必要或非完全必要以績酸基團形式 存在。 藉由元素分析測定，較佳為PEEKTM與PEKTM聚合物等級 (自Victrex plc.購得）之含硫聚芳基醚酮之含硫量通常係自 # 〇‘1〇重量％至8.7重量％’較佳自4重量％至5.7重量％。 步驟⑴之後進行磺化步驟（ii)，其中使根據⑴製得之含 硫聚芳基醚酮之磺化程度固定。 用與（η)中烷磺酸不同之至少一烷磺酸或磺化劑將自（^) 製得之含硫聚芳基醚酮處理一次或二次。原則上可使用先 則技術所知之所有磺化劑，如發煙硫酸、濃硫酸、高濃度 (即98%強度）硫酸、三氧化硫或氯磺酸在至少一適宜的有 機溶劑十或丁基鋰連同二氧化硫且隨後利用（例如）過錳酸 钟氧化。 144644.doc -13· 201027821 可尤佳使用之續化聚芳基喊嗣（特定言之為績化聚趟醚 嗣。)之「續化程度」通常為⑽至90%，較佳自35%至 8〇%。特定言之，可經由步驟⑼中之磺化劑濃度控制聚芳 基=之不同「績化程度」。可根據本發明較佳使用之磺 化聚芳基醚_較佳具有窄幅分佈之「磺化程度」。 尤佳使用已根據本發明續化且具有低「續化程度」之聚 芳基㈣’尤佳的「續化程度」通常自1〇%至55%，較佳 自35%至55%，尤佳自辦。至55%或自35%至40%。 根據本發明所用之陰離子官能化聚合物係不可溶於本發_ 明薄膜電池所用之電解質’且在操作條件下（特定言之在 高溫下在阳值>13之驗性條件下）具有高電荷載體密度及 聚口物差。構之長期穩定性。此外，根據本發明之水不溶性 聚合物在電解質溶液令(特定言之在水中或水與醇(如甲醇） 之混合物中）顯示低膨脹。 存在於本發明薄膜電池中之分隔器（組件（D))包括至少一 種上述經陰離子基團官能化之聚合物。 自該等聚合物製備用作分隔器之膜係藉由熟悉此項技術❿ 者已知之慣用製程實行。 通常藉由施加鑄膜溶液或鑄膜分散液至至少一適宜的支 撐材料上而製得該膜。鑄膜溶液或鑄膜分散液可係在所述 聚合物之製備中得到的溶液。然而，亦可分離所述聚合物 且將其再溶解於適宜溶劑或溶劑混合物中以製得該鑄膜溶 液。適宜的溶劑或溶劑混合物係（例如）DMF、dms〇、 MP DMAc、甲齡、丁内醋、環戊鲷或上述二種或多 144644.doc • 14- 201027821 種溶劑之混合物。為製得該等膜，根據本發明較佳使用上 述陰離子官能化聚合物之驗金屬鹽，如納鹽。 鑄膜溶液或鑄膜分散液中聚合物之濃度通常為2重量％ 至30重量％，較佳為5重量％至15重量％。根據本發明較佳 係獲得高黏度的可成膜溶液。 適宜的支撐物係（例如）玻璃片或塑料臈，如由聚酯或聚 烯烴構成之膜。較佳使用聚對苯二甲酸乙二酯膜作為支撐 物。 ❹ 可藉由熟悉此項技術者所知之任何製程實行該铸膜溶液 或鑄膜分散液之施用。如，可藉由鑄膜、到刀塗佈、浸 塗、旋塗、滾筒塗佈、喷塗、凸版印刷、凹版印刷、平版 印刷或網版印刷製程或（如適當）藉由擠壓完成該施用。施 用後之濕膜厚度通常自0 01 mm至2 mm，較佳自〇 〇5瓜瓜 至1 mm ’尤佳自〇 2 mm至1 mm。 其他製備該膜之製程可藉由熟悉此項技術者已知之方法 參 實订’如藉由移除所用溶劑。移除溶劑通常係在2〇。〇至 l2〇°C之溫度下進行，較佳係40°C至120。(：，尤佳係6(rC至 在母清形中之壓力通常係自100 mbar至1 〇〇〇 mbar ° 該等膜顯不高離子導電性。因此，可獲得通常高達O.i S/Cm ’較佳面達〇.〇80 S/cm，尤佳高達0.07 S/cm，極佳 〇.02 〜⑽至0.07 S/cm’ 特定言之 0.02 S/cm 至 〇.〇6 S/cm 之 離子導電性。 …、該/谷液層以去除存在的溶劑。使用（如）30°C至 144644.doc -15- 201027821 150°C，較佳4〇艺至12〇它’如6〇£)(：至9〇。(：之溫度實行此操 作。實施乾燥直至所有溶劑自獲得膜中去除為止。就本發 明目的而言，此意謂最終膜中存在較佳不多於〇 5重量％， 尤佳不多於0.3重量％之溶劑。 所得膜較佳具有與亦可在本發明薄膜電池中用作分隔器 之膜相同之厚度。該厚度係（例如）1〇 0111至1〇〇 μιη，如邨 μηι至 60 μπι 〇 在將依此方法獲得之膜用作本發明薄膜電池中之分隔器 前，需使該膜活化。此可藉由熟悉此項技術者所知之所有 方法實行。 在一較佳實施例中，陰離子官能化聚合物之活化係藉由 將其浸入適當的電解質中而完成。在—較佳實施例中，使 用與亦存在於本發明薄膜電池中之相同的電解質。 因此，較佳將獲得之聚合物膜浸入一上述離子化合物之 水溶液中，尤佳為氫氧化鉀（K〇H)、ZnCl2&/或醋酸銨。 分隔器之活化可於分隔器中建立離子導電性。 在藉由浸入適當的電解質中而活化聚合物膜後，可將該 膜用作分隔器。 本發明薄膜電池中之個別組件，即如上述之至少一負 極、至少-正極、至少-電解f及至少—分隔器，可_ 熟悉此項技術者所知之方法結合在一起而製得本發明之薄 膜電池。 此係藉由（例如）層合或黏著結合個別層，即至少一負 極、至少一正極及至少一分隔器，而達成。在一實施例 l446U.doc • J6- 201027821 中’使用自活化步驟存在於分隔器中之水溶液作為本發明 薄膜電池之電解質。在另一實施例中，在結合個別層過程 中加入額外的電解質。 本發明亦提供一種藉由使至少一作為組件（A)之負極、 至少一作為組件（B)之正極、作為組件（c)之電解質及至少 一作為組件（D)之分隔器結合在一起而製備本發明薄膜電 池之製程’其中該至少一分隔器包括至少一種經陰離子基 團B月包化的聚合物。 ❹ 在一較佳實施例中’本發明薄膜電池在二電極之背離分 隔器之側上具有保護膜。 該等保護膜可包括為熟悉此項技術者已知且可選自由金 屬箔（如鋁箔）、紙、聚酯、聚碳酸酯、聚醯胺、聚醯亞 胺、聚醚、酮、聚醚醚酮、聚醚砜、聚苯硫醚、聚烯烴 (如聚乙烯及聚丙烯）、聚苯乙烯、聚二氣亞乙烯纖維素 及其衍生物及該等聚合物之混合物組成之群之所有材料物 ❹質。 此外’本發明薄膜電池可在外部具有電接點，如至少一 連接至該至少一負極之接點及至少一連接至該至少一正極 之接點。接點可引出於薄膜電池中產生之電流。 本發明亦提供經陰離子基團官能化之聚合物於薄膜電池 中作為分隔器之用途。關於經陰離子基團官能化之聚合物 及薄膜電池之内容已如上所述。 本發明亦提供根據本發明之薄膜電池在電子組件中之用 途。電子組件之實例係RFID標籤、感應器、智慧卡。 144644.doc -17- 201027821 圖： 圖1顯示在Zn作為陽極及Mn〇2作為陰極之實例中，根據 本發明之夾層電池之結構。 此處’參考符號A、B、C及D具有以下定義： A :外部保護膜：铭箔/pe B: PET膜上之陽極材料 C :分隔器’經電解質活化的陰離子官能化聚合物 D : PET膜上之陰極材料 圖2、3及4顯示每一實例中在i 乂電壓下根據本發明薄膜 @ 電池之恒電壓放電。在每一情形中，電流以μ A計繪於y 轴，且時間以秒計繪於x軸。圖2顯示根據本發明藉由 KOH(30%)活化之薄膜電池之放電曲線。圖3顯示根據本發 明藉由ZnCl2(l M)活化之薄膜電池之放電曲線。圖4顯示根 據本發明藉由NH4·Ac( 1 M)活化之薄膜電池之放電曲線。 實例： 實例1 :根據本發明陽極之製造 將NMP緩慢逐滴加入97重量。鋅粉與3重量。粉® 中同時授拌直至形成可塗佈或可印刷的糊料。使用pet 膜作為基材。 實例2 :根據本發明陰極之製造 將 0·4 g 氧化錳（iv)、〇·31 g碳黑（Super p u)及 〇 〇8 g Oppanol B 200®(分子量約4〇〇〇〇之聚異丁烯）一起放於一容 器中且隨後將甲苯緩慢逐滴加入其中，同時並授拌直至 形成蜜樣糊料。使用PET膜作為基材。 144644.doc 18· 201027821 實例3 :根據本發明之Na-sPEEK膜之製造 將100 g N-甲基吡咯啶酮（NMP)置於一反應容器中且邊 擾拌邊缓慢滴入16.5 g之Na sPEEK(續化聚醚醚_之納 .鹽）。室溫下過夜後完全溶解。將部份此高黏性聚合物溶 液傾倒於作為基材之PET膜上且藉由電動刮刀分佈於大約 DIN A4尺寸上。設定層厚度以使乾膜厚度約5 0 μηι。經2 小時逐步進行乾燥至終溫為約80°C。 實例4 :在30%強度KOH溶液中活化 ® 將實例3中所得之Na-sPEEK膜置於30%強度KOH水溶液 中過夜，隨後以蒸餾水清洗及作為分隔器安裝於夾層電池 中〇 實例5 :在1 M ZnCl2中活化 將實例3中所得之Na-sPEEK膜置於1 M ZnCl2水溶液中過 夜，隨後以蒸餾水清洗及作為分隔器安裝於夾層電池中。 實例6 :在1 M NH4-Ac中活化 ^ 將實例3中所得之Na-sPEEK膜置於1 M NH4-Ac水溶液中 過夜，隨後以蒸餾水清洗及作為分隔器安裝於夾層電池 中〇 - 【圖式簡單說明】 . 圖1顯示在Zn作為陽極及Μη02作為陰極之實例中，根據 本發明之夾層電池之結構； 圖2顯示根據本發明藉由KOH(30%)活化之薄膜電池之放 電曲線， 圖3顯示根據本發明藉由ZnCl2(l M)活化之薄膜電池之 144644.doc -19- 201027821 放電曲線，及 圖4顯示根據本發明藉由NH4-Ac(l M)活化之薄膜電池之 放電曲線。 144644.doc 20-In a preferred embodiment, the anionic group-functionalized polymer used is selected from the group consisting of polysulfone, polyether-rolled Teflon, polydifluoroethylene (PVDF), and poly(difluoroethylene). _6-gas propylene) copolymer (pvdF_Liao copolymer), polyaryl ether ketone (such as polyether ether oxime (PEEK), polyether ketone (ρΕκ), poly lye (ΡΕΚΚ)), polybenzopyrene (ΡΒΙ), a mixture of polyamidiamine, polystyrene, polyamide, polypropylene, and its copolymers and mixtures. According to the invention, the functionalization of the anionic groups to the polymer may be present on the backbone and/or side chains of the polymer. Functionalization preferably occurs on the side chains of the polymer. According to the present invention, a monomer which has been previously functionalized in the preparation of the polymer can be used first, and then a suitable functionalization can be subsequently carried out on the previously prepared polymer in the polymer-analog reaction. The anionic group present in the anionically functionalized polymer of the separator (D) may be selected from all anionic functional groups known to those skilled in the art, such as sulfonate-S03-, carboxylate-C〇2-, -Ρ 〇(〇Η)〇- or ρ〇32_. The genus is in the sulfonate-S〇3_ group. Sulfonated polyaryl ether ketones, such as those selected from the group consisting of sulfonated polyetheretherketone (PEEK), sulfonated polyether ketone (pEK), sulfonated polyetheretherketone ketone (PEKK), are particularly preferred for use in the thin film battery of the present invention. A sulfonated polyaryl ether ketone of the group consisting of a mixture of 144644.doc 201027821 is a sulfonated polyetheretherketone. Accordingly, the present invention preferably provides a thin film battery according to the present invention, wherein the at least one anionic functionalized polymer is a sulfonated polyaryl ether ketone, preferably selected from the group consisting of sulfonated polyetheretherketone (PEEK), sulfonated. A sulfonated polyaryl ether ketone of a group consisting of polyetherketone (PEK), sulfonated polyetherketoneketone (PEKK), and mixtures thereof, which is excellently a sulfonated polyetheretherketone. According to the present invention, all sulfonated polyaryl ether ketones known to those skilled in the art can be used, in particular polyetheretherketone (PEEK), sulfonated polyether ketone (PEK), sulfonated polyether ketone. Ketone (PEKK) or a mixture thereof. Such sulfonated polymers are, for example, by using a suitable sulfonating agent such as fuming sulfuric acid, concentrated sulfuric acid, high concentration (i.e., 98% strength) sulfuric acid, sulfur trioxide or gas sulfonic acid in at least one suitable organic A suitable precursor compound is sulfonated in a solvent or butyllithium together with sulfur dioxide, followed by oxidation with, for example, potassium permanganate. Suitable polyetheretherketones, polyetherketones, polyetherketoneketones are known to those skilled in the art. Excellent use of PEEK and PEK polymer grades (available from Victrex pic.), specifically PEEKtm 450P, PEEKtm 150P and PEKtm P22 °. In particular, sulfonation as an anionic functionalized polymer is particularly preferred according to the invention. The polyaryl ether ketone is obtained by a process comprising the steps of: reacting at least one polyaryl ether ketone with at least one alkane sulfonic acid to produce a sulfur-containing polyaryl ether ketone (I), and obtaining the compound according to (1) The sulfur-containing polyaryl ether ketone is reacted with at least one sulfonating agent to produce a sulfonated polyaryl ether ketone (II). This process, which is preferred for the preparation of sulfonated polyaryl ether ketones in accordance with the present invention, is known to those skilled in the art and is disclosed in WO 2004/076530. 144644.doc •12- 201027821 In the step (1) towel, the fat rhyme is usually suitable as a sister. It is preferred to use an alkanesulfonic acid of the formula: r-so3h, a branched or unbranched hydrocarbon group and having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 One of the carbon atoms has no branching bond, and it is excellent to have one carbon atom, that is, a tannic acid. The molar ratio of the reactants in (1) is preferably in the range of usually 1:1 to 1:1000 ❿ more preferably 1,2 to 1:500 and particularly preferably 1:10 to 1:300. Usually, the V-house acid is used in excess. If the calcined acid is used as a solvent at the same time, it is present in a molar excess of the polyaryl ether ketone. For the purposes of the present invention, "sulfur-containing polyaryl ether ketone" is a polyaryl ketone which is bonded to sulfur. It is not necessary or necessary to exist in the form of a acid group. The sulphur content of the sulfur-containing polyaryl ether ketone, preferably PEEKTM and PEKTM polymer grade (available from Victrex plc.), is usually determined from elemental analysis, from #〇'1〇% by weight to 8.7% by weight. It is preferably from 4% by weight to 5.7% by weight. The step (1) is followed by a sulfonation step (ii) in which the degree of sulfonation of the sulfur-containing polyaryl ether ketone prepared according to (1) is fixed. The sulfur-containing polyaryl ether ketone prepared from (^) is treated once or twice with at least one alkanesulfonic acid or sulfonating agent different from the alkanesulfonic acid in (η). In principle, all sulfonating agents known in the art can be used, such as fuming sulfuric acid, concentrated sulfuric acid, high concentration (ie 98% strength) sulfuric acid, sulfur trioxide or chlorosulfonic acid in at least one suitable organic solvent ten or The base lithium is combined with sulfur dioxide and then oxidized using, for example, permanganic acid. 144644.doc -13· 201027821 The “continuation degree” of the continuation of the polyaryl screaming (specifically, the polyunion ether oxime) is usually (10) to 90%, preferably from 35%. Up to 8〇%. Specifically, the degree of "probability" of the polyaryl group = can be controlled via the concentration of the sulfonating agent in the step (9). The sulfonated polyaryl ether which can be preferably used in accordance with the present invention preferably has a "degree of sulfonation" of a narrow distribution. It is preferred to use a polyaryl group (four) which has been renewed according to the present invention and has a low degree of "continuation". The degree of "continuation" is generally from 1% to 55%, preferably from 35% to 55%, especially Good to do it. Up to 55% or from 35% to 40%. The anionic functionalized polymer used in accordance with the present invention is insoluble in the electrolyte used in the thin film battery of the present invention and has a high operating condition (specifically, under high temperature conditions under the conditions of positive value > 13) The charge carrier density and the agglomerate are poor. Long-term stability of the structure. Furthermore, the water-insoluble polymer according to the present invention exhibits low expansion in an electrolyte solution (specifically in water or a mixture of water and an alcohol such as methanol). The separator (component (D)) present in the thin film battery of the present invention comprises at least one of the above-described anionic group-functionalized polymers. The preparation of membranes for use as separators from such polymers is carried out by conventional processes known to those skilled in the art. The film is typically prepared by applying a casting solution or cast film dispersion to at least one suitable support material. The casting solution or the cast film dispersion may be a solution obtained in the preparation of the polymer. However, the polymer can also be isolated and redissolved in a suitable solvent or solvent mixture to produce the cast film solution. Suitable solvents or solvent mixtures are, for example, DMF, dms(R), MP DMAc, Ageing, Butyrate, Cyclopentanyl or a mixture of two or more of the above 144644.doc • 14-201027821 solvents. To make such films, it is preferred according to the invention to use a metal salt of an anionic functionalized polymer such as a sodium salt. The concentration of the polymer in the casting solution or the cast film dispersion is usually from 2% by weight to 30% by weight, preferably from 5% by weight to 15% by weight. It is preferred according to the invention to obtain a high viscosity film-forming solution. Suitable supports are, for example, glass flakes or plastic crucibles, such as films composed of polyester or polyolefin. A polyethylene terephthalate film is preferably used as a support. The application of the casting solution or cast film dispersion can be carried out by any process known to those skilled in the art. For example, by casting, knife coating, dip coating, spin coating, roller coating, spray coating, letterpress printing, gravure printing, lithography or screen printing, or (if appropriate) by extrusion Apply. The wet film thickness after application is usually from 0 01 mm to 2 mm, preferably from 〇5 瓜 melon to 1 mm ‘especially from 2 mm to 1 mm. Other processes for preparing the film can be accomplished by methods known to those skilled in the art, such as by removing the solvent used. The solvent is usually removed at 2 Torr. It is carried out at a temperature of l2 〇 ° C, preferably 40 ° C to 120 ° C. (:, especially good 6 (rC to the pressure in the mother clear is usually from 100 mbar to 1 〇〇〇 mbar ° These films show no high ionic conductivity. Therefore, usually up to Oi S / Cm can be obtained The preferred surface is 〇80〇/cm, especially up to 0.07 S/cm, excellent 〇.02 ~(10) to 0.07 S/cm' 0.02 S/cm to 〇.〇6 S/cm Conductivity. ..., the / liquid layer to remove the solvent present. Use (for example) 30 ° C to 144644.doc -15 - 201027821 150 ° C, preferably 4 〇 to 12 〇 it '如 6 〇 £) (: to 9 〇. (: The temperature is carried out. The drying is carried out until all the solvent is removed from the obtained film. For the purposes of the present invention, this means that preferably no more than 5% by weight of the final film is present, More preferably, it is not more than 0.3% by weight of the solvent. The obtained film preferably has the same thickness as the film which can also be used as a separator in the thin film battery of the present invention. The thickness is, for example, 1〇0111 to 1〇〇μηη, Such as the village μηι to 60 μπι 〇 Before the film obtained by this method is used as a separator in the thin film battery of the present invention, the film needs to be activated. All methods known to those skilled in the art are practiced. In a preferred embodiment, activation of the anionic functionalized polymer is accomplished by immersing it in a suitable electrolyte. In the preferred embodiment, the use and presence are also present. The same electrolyte in the thin film battery of the present invention. Therefore, it is preferred to immerse the obtained polymer film in an aqueous solution of the above ionic compound, particularly preferably potassium hydroxide (K〇H), ZnCl2&/or ammonium acetate. Activation of the device can establish ionic conductivity in the separator. After activation of the polymer film by immersion in a suitable electrolyte, the film can be used as a separator. The individual components of the thin film battery of the present invention, ie, as described above At least one of a negative electrode, at least a positive electrode, at least an electrolysis f, and at least a separator, the thin film battery of the present invention can be obtained by a method known to those skilled in the art. This is by, for example, lamination. Or bonding the individual layers, ie, at least one negative electrode, at least one positive electrode, and at least one separator, is achieved. In an embodiment, l446U.doc • J6-201027821, the use of a self-activation step exists. The aqueous solution in the separator serves as the electrolyte of the thin film battery of the present invention. In another embodiment, an additional electrolyte is added during the bonding of the individual layers. The present invention also provides at least one of the negative electrodes as component (A), at least A process for preparing a thin film battery of the present invention as a positive electrode of the component (B), an electrolyte as the component (c), and at least one separator as the component (D), wherein the at least one separator includes at least one anion The group B monthly polymerized polymer. In a preferred embodiment, the thin film battery of the present invention has a protective film on the side of the two electrodes facing away from the separator. The protective films may comprise metal foils (such as aluminum foil), paper, polyester, polycarbonate, polyamide, polyimine, polyether, ketone, polyether known to those skilled in the art and optionally free. All of the group consisting of ether ketone, polyether sulfone, polyphenylene sulfide, polyolefin (such as polyethylene and polypropylene), polystyrene, polydiethylene vinyl cellulose and its derivatives, and mixtures of such polymers Material enamel. Further, the thin film battery of the present invention may have an electrical contact externally, such as at least one contact connected to the at least one negative electrode and at least one contact connected to the at least one positive electrode. The contacts can be drawn from the current generated in the thin film battery. The invention also provides the use of an anionic group-functionalized polymer as a separator in a thin film battery. The contents of polymers and thin film batteries functionalized with anionic groups have been described above. The invention also provides for the use of a thin film battery in accordance with the present invention in an electronic component. Examples of electronic components are RFID tags, sensors, smart cards. 144644.doc -17- 201027821 Fig. 1 shows the structure of a sandwich battery according to the present invention in an example in which Zn is used as an anode and Mn〇2 is used as a cathode. Here, 'reference symbols A, B, C and D have the following definitions: A: outer protective film: ingot foil / pe B: anode material on PET film C: separator 'electrolyte activated anion functionalized polymer D: Cathode Materials on PET Film Figures 2, 3 and 4 show the constant voltage discharge of the film @cell according to the invention at i 乂 voltage in each example. In each case, the current is plotted on the y-axis in μA and the time is plotted on the x-axis in seconds. Figure 2 shows the discharge curve of a thin film battery activated by KOH (30%) according to the present invention. Figure 3 shows the discharge curve of a thin film battery activated by ZnCl2(l M) according to the present invention. Figure 4 shows the discharge curve of a thin film battery activated by NH4·Ac (1 M) according to the present invention. EXAMPLES Example 1: Manufacture of an anode according to the invention NMP was slowly added dropwise to 97 weights. Zinc powder with 3 weights. Mix in Powder® until a coatable or printable paste is formed. A pet film was used as the substrate. Example 2: Manufacture of a cathode according to the present invention: 0.4 g of manganese oxide (iv), 〇 31 g of carbon black (Super pu) and 〇〇 8 g of Oppanol B 200® (polyisobutylene having a molecular weight of about 4 Å) The two were placed together in a container and then toluene was slowly added dropwise thereto while being mixed until a honey-like paste was formed. A PET film was used as the substrate. 144644.doc 18· 201027821 Example 3: Manufacture of Na-sPEEK film according to the invention 100 g of N-methylpyrrolidone (NMP) was placed in a reaction vessel and slowly dropped into 16.5 g of Na while stirring sPEEK (continued polyether ether _ nat. salt). Completely dissolved overnight at room temperature. A portion of this highly viscous polymer solution was poured onto a PET film as a substrate and distributed by an electric doctor blade to a size of about DIN A4. The layer thickness was set so that the dry film thickness was about 50 μm. Drying was gradually carried out over 2 hours to a final temperature of about 80 °C. Example 4: Activation in a 30% strength KOH solution The Na-sPEEK film obtained in Example 3 was placed in a 30% strength KOH aqueous solution overnight, then rinsed with distilled water and installed as a separator in a sandwich cell. Example 5: Activation in 1 M ZnCl 2 The Na-sPEEK film obtained in Example 3 was placed in a 1 M ZnCl 2 aqueous solution overnight, then washed with distilled water and mounted as a separator in a sandwich battery. Example 6: Activation in 1 M NH4-Ac ^ The Na-sPEEK film obtained in Example 3 was placed in a 1 M NH4-Ac aqueous solution overnight, then washed with distilled water and mounted as a separator in a sandwich cell. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows the structure of a sandwich battery according to the present invention in an example in which Zn is used as an anode and Μ?02 as a cathode; and Fig. 2 shows a discharge curve of a thin film battery activated by KOH (30%) according to the present invention, 3 shows a discharge curve of 144644.doc -19-201027821 of a thin film battery activated by ZnCl 2 (l M) according to the present invention, and FIG. 4 shows a discharge of a thin film battery activated by NH4-Ac (l M) according to the present invention. curve. 144644.doc 20-