575973575973
發明領域 本發明係關於膠態叙電池及其製作方法 種將乳化聚合反應應用於膠態電解液之合成 發明背景 ，特別係關於一 目前隨著使用者對於可攜式電子設備（例如：手機、個 人數位助理器及筆記型電腦等）#、薄、短、小的要求愈 來愈嚴格，故電子設備的每一摄杜壬曰 ^ 構件的重量及尺寸亦被嚴格 限制’其中’影響可攜式電子机供 s 私卞叹備的重I及外觀最大者就 疋其電源供應為’也就是麵電池。 經電池不但料體積、重量的限制愈來愈嚴格，其對於 電性安全、機械強度及耐環境變異性亦有很高之檢驗標 準。尤其在機械強度方面需要通過衝擊實驗（_act test)、碌壓實驗（erushtest)及摔时驗（dn)ptest)等嚴格 的考驗，即在規足足測試條件下受到外力的破壞仍不會使 内容物外漏或造成短路而著火。 白知之鋰電池的製備方法，、係先分別於導電材上塗佈正 極活性物質及負極活性物質以製備正負極板，再將上述正 負極板以隔離膜加以隔離後形成鋰電池的核心素子^。上述 電池的核心素子及液態之電解液需要共置於一容器内，最 後進行封裝即可形成鋰電池早期常見之鋰電池係以金屬 入罐方式封裝，可將電池之核心素子緊密包覆。但是因金 屬罐厚、重、不易封口且僅能製成方形，使得以金屬罐為 封裝材的鋰電池的外觀缺乏變化。即使金屬罐漸漸由原來 的厚度8mm改良為4mm，但仍難使電池達到真正薄形且輕 裝 ijFIELD OF THE INVENTION The present invention relates to a colloidal battery and a method for manufacturing the same. The invention relates to the background of synthesizing emulsification polymerization applied to a colloidal electrolyte. In particular, the present invention relates to a method for carrying portable electronic devices such as Personal digital assistants and notebook computers, etc.) #, thin, short, small requirements are becoming more and more stringent, so each shot of the electronic device is not limited ^ The weight and size of the components are also strictly restricted 'where' affects portable For electronic devices, the most important ones are the ones with the biggest appearance and the largest appearance, and their power supply is 'surface batteries'. The battery not only has stricter restrictions on the volume and weight of the battery, it also has high test standards for electrical safety, mechanical strength and resistance to environmental variability. Especially in terms of mechanical strength, it is necessary to pass rigorous tests such as _act test, erushtest, and dn ptest, that is, the damage caused by external forces under full test conditions will not cause the The contents leaked out or caused a short circuit and caught fire. Bai Zhizhi's method for preparing lithium batteries consists of first coating a positive active material and a negative active material on a conductive material to prepare positive and negative plates, and then isolating the positive and negative plates with a separator to form the core element of a lithium battery ^ . The core cells and the liquid electrolyte of the above-mentioned battery need to be co-located in a container, and then finally sealed to form a lithium battery. The lithium batteries commonly used in the early days are packaged in metal cans, which can tightly cover the core cells of the battery. However, because the metal can is thick, heavy, difficult to seal, and can only be made into a square shape, the appearance of lithium batteries using metal cans as packaging materials is lacking. Even if the metal can is gradually improved from the original thickness of 8mm to 4mm, it is still difficult to make the battery truly thin and lightweight ij
能高台灣專利\78〇5〇如 0973 A7Noble Taiwan patent \ 78〇50, such as 0973 A7
T化的目的。 取而代之的，是以銘羯愿膜的鐘電池封裝方法。近日銘 落軟包裝方式之先進鐘電池製程繼之興起，然其機械強度 逐不如金屬罐之強度，故在前述各項機械強度實驗時容易 有漏液之問題產生。近日鋰電池業界嘗試研發膠態鋰電 池，將液態之電解液密封於膠態之高分子塑材中以避免漏 液問題。 在使用鋁络封裝袋的電池中，高分子電池在薄型化上佔 了優勢，使用高分子電解質可以解決漏液之問題及提高其 文全性前已有Sony公司成功地推出該種產品，以調製 <電解液與高分子塑材精細地塗佈於極板上，再與隔離膜 捲繞成核心素子，並直接置入鋁箔袋中，而不需再注入電 解液，經封裝活化後即成為電池。然該種電池需要精密的 叹備才能生產；除極板製作外，其餘相關製程尚得在全乾 燥室中完成，故其製程複雜且成本高昂。、 曼之簡要說明 ’ 本發明之第一目的係提供一種膠態鋰電池及其製作方 法’其將乳化聚合反應應用於膠態電解液之合成，提昇相 關製程之可靠度及結構之安全性。: 本發明之弟一目的係提供一種簡化製程及不需要高精密 之生產設備的膠態鋰電池，與習知液態魏電池之製造程序 近似，僅需增加熱烘熟成之步驟。） 本發明之弟二目的係提供一種裡電池具微孔洞之膠態電 解液’其高分子塑材經乳化聚合反應後產生整齊良好的微 H:\Hu\lgc^能高台灣專利\78050d〇c _ 5 _ t紙張尺度適财國B家標準(CNS) M規格(21QX 297公着） —--- A7 五、發明説明（3 孔洞結構，故電性之均一性較佳，並可有效增進鋰電池的 循環壽命與放電效能。 為達成上述目的並避免先前技藝所面臨的缺點，本發明 <膠態鋰電池及其製作方法係利用電解液、聚合單體及起 士口劑配方混合而成之溶液，再經由乳化聚合作用形成微孔 洞構造之膠態電解液的前驅物。取現有鋰電池通用之核心 素子兀件放入一鋁箔袋中，及將該膠態電解液的前驅物注 入其内並密封，經加熱熟成即為具孔洞且以高導電度之膠 怨電解液包覆在核心素子的内外。該鋁箔袋已形成硬實之 外型，再經活化後就完成為具有高可靠度、抑制膨脹、安 全及不漏電解液之麵電池。 1式之簡軍說1 本發明將依照後附圖式來說明，其中： 圖1係本發明膠態電解液應用乳化作用的原理示意圖； 圖2係本發明之第一具體實施例之加熱前導電度測試結 果圖； 圖3係本發明之第一具體實施例之加熱後導電度測試結 果圖； 圖4係本發明之第二/具體實施例之放電效率圖；及 圖5係本發明之第二具體實施例之充放電循環壽命圖。 ϋ牛符號說明 11 電解液之微液滴 13 而分子單體 10 微胞單元 12 具界面活性之單體 發明詳細翰昍 H:\Hu\lgc\興能高台灣專利\78〇5〇d〇c 本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐） 575973The purpose of Tization. Instead, the bell cell packaging method with Mingxuan film is used. In recent days, the advanced bell battery manufacturing process in which the flexible packaging method has been developed has continued, but its mechanical strength is not as strong as that of metal cans, so it is easy to have the problem of liquid leakage during the aforementioned mechanical strength experiments. Recently, the lithium battery industry has tried to develop colloidal lithium batteries. The liquid electrolyte is sealed in a colloidal polymer plastic material to avoid leakage. Among batteries using aluminum-encapsulated bags, polymer batteries have an advantage in thinness. The use of polymer electrolytes can solve the problem of liquid leakage and improve its integrity. Sony Corporation has successfully launched this product before. Preparation < Electrolyte and polymer plastic material are finely coated on the electrode plate, and then wound into a core element with an insulation film, and placed directly into the aluminum foil bag without the need to inject the electrolyte. Become a battery. However, this type of battery requires precise preparation to produce; apart from the production of the electrode plates, the other related processes have to be completed in a fully dry room, so the process is complicated and costly. Brief description of Mann's first object of the present invention is to provide a colloidal lithium battery and a method for manufacturing the same. The application of the emulsion polymerization reaction to the synthesis of a colloidal electrolyte improves the reliability of related processes and the safety of the structure. : One of the objectives of the present invention is to provide a colloidal lithium battery that simplifies the manufacturing process and does not require high-precision production equipment. It is similar to the manufacturing process of the conventional liquid Wei battery, and only requires additional steps of thermal curing. The second purpose of the present invention is to provide a colloidal electrolyte with micropores in the inner battery. Its polymer plastic material produces neat and fine micro-particles after emulsification polymerization. H: \ Hu \ lgc ^ Energy Taiwan Patent \ 78050d 〇c _ 5 _t Paper Standard Applicable Country B Standard (CNS) M Specification (21QX 297) ----- A7 5. Description of the invention (3 hole structure, so the uniformity of electrical properties is better, and Effectively improve the cycle life and discharge efficiency of lithium batteries. In order to achieve the above objectives and avoid the disadvantages faced by the prior art, the present invention < colloidal lithium battery and manufacturing method thereof utilize the electrolyte, polymerized monomer and cheese mouthpiece formula The mixed solution is used to form a precursor of a colloidal electrolyte with a microporous structure through emulsification polymerization. A core element element commonly used in existing lithium batteries is placed in an aluminum foil bag, and the colloidal electrolyte is The precursor is injected into it and sealed. After heating and curing, it will be porous and covered with high conductivity gel electrolyte inside and outside the core element. The aluminum foil bag has formed a hard solid shape, and it is completed after activation. With high reliability and suppression Expansion, safety, and electrolyte-free surface battery. Type 1 Jianjun said 1 The present invention will be described in accordance with the following drawings, in which: Figure 1 is a schematic diagram of the emulsification principle of the colloidal electrolyte of the present invention; Figure 2 FIG. 3 is a diagram of the conductivity test result before heating of the first embodiment of the present invention; FIG. 3 is a diagram of the conductivity test result after heating of the first embodiment of the present invention; FIG. 4 is the second / specific embodiment of the present invention Figure 5 shows the discharge efficiency diagram; and Figure 5 is the charge-discharge cycle life diagram of the second embodiment of the present invention. Yak symbol description 11 Micro droplets of the electrolyte 13 and molecular monomers 10 microcells 12 with interfacial activity Detailed inventions: Han Hu: \ Hu \ lgc \ Xingneng High Taiwan Patent \ 78〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇４〇 The paper size is applicable to China National Standard (CNS) A4 specification (210X 297 mm) 575973
本發明藉由乳化聚合作用之觀念調製電解液、聚合單體 及起始劑之配方，以形成微孔洞架構之膠態電解液的前驅 物’其中聚合單體會形成將電解液之微液滴之微液滴i i包 覆的微胞早兀1 〇，如圖i所示。電解液之微液滴丨丨是屬極 性化合物，所以具界面活性之單體丨2之非極性基向外而極 性基向内，再與電解液之微液滴丨丨形成基本的微胞結構 1 〇。若再與另-高分子單體i 3混合，可將孔洞撐大形成有 利於離子進出的結構。可利用烘烤加熱或紫外光照射加速 乳化聚合作用，使其中化學反應的比例更高，並鬆開各個 微胞結構再重新排列整齊。若加入適當之催化劑 (accelerator)甚至可在室溫靜置下完成反應，自然形成微 孔洞膠態電解液。 如下所述’將更完整地說明以上述膠態電解液完成本發 明之麵電池的步驟與元件。前述之核心素子仍採用一般鋰 電池的製作方法，無論是捲繞型式或堆疊形式皆可適用於 本發明。將該核心素子置入成型之鋁箔袋中，並注入電解 液、高分子單體及起始劑之定量混合而成之溶液，該溶液 或稱之為膠態電解液前趨物。電解液係採用習用鋰離子二 次電池用之電解液，如EC/DMC/EMC/lMliPF6，使用 量佔配方之9 5〜5 0 % (重量百分比）。而高分子單體係採 用採用亞克力系列單體，又細分為單官能基及多官能基型 單體（二雙官能基以上者），使用量為配方之5〜50 %，單 /多官能基單體比例為5 / 9 5〜9 5 / 5 (重量比）。該高分子 單體之化學結構式表示如下·· 能高台溥專利V78050.doc - 7 - 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐)The invention uses the concept of emulsion polymerization to modulate the formulation of electrolyte, polymerized monomer and initiator to form a precursor of a colloidal electrolyte of a microporous structure, wherein the polymerized monomer will form a microliquid of the electrolyte. The microcells coated by the droplet ii are as early as 10, as shown in Fig. I. Electrolyte microdroplets are polar compounds, so interfacial active monomers, 2 non-polar groups are outward and polar groups are inward, and then they form basic microcellular structures with the microdroplets of the electrolyte. 1 〇. If it is mixed with another polymer monomer i 3, the holes can be enlarged to form a structure which is favorable for the ion to enter and exit. Baking heating or ultraviolet light irradiation can be used to accelerate the emulsification polymerization, so that the proportion of chemical reactions therein is higher, and the individual cell structures are loosened and then rearranged. If an appropriate catalyst is added, the reaction can be completed even at room temperature, and a microporous colloidal electrolyte is formed naturally. As described below, the steps and components for completing the face cell of the present invention using the above-mentioned colloidal electrolyte will be more fully explained. The aforementioned core element is still made by the general lithium battery, and it can be applied to the present invention regardless of the winding type or the stacking type. The core element is put into a formed aluminum foil bag, and a solution obtained by quantitatively mixing an electrolytic solution, a polymer monomer, and an initiator is injected. This solution is also called a colloidal electrolyte precursor. The electrolyte is an electrolyte for a conventional lithium ion secondary battery, such as EC / DMC / EMC / lMliPF6, and the amount used is 95 to 50% (weight percent) of the formula. The single polymer system uses acrylic monomers, which are subdivided into monofunctional and polyfunctional monomers (the ones with more than two difunctional groups). The usage amount is 5-50% of the formula. Mono / multifunctional groups The monomer ratio is 5/9 5 to 9 5/5 (weight ratio). The chemical structural formula of the polymer monomer is shown as follows: Nogaotai Patent V78050.doc-7-This paper size applies to China National Standard (CNS) A4 (210X297 mm)
裝 訂Binding
575973 A7 B7 五、發明説明（5 ) vA〇.ri v^〇-R2.bA/ V^〇-f.〇A/ °J° 其中R1可為Η、 烷基、乙晞氧基、矽烷或矽氧基等， R2及R3則可為烷基、乙烯氧基、矽烷或矽氧基等。起始 劑是採用自由基起始劑如Β Ρ 0，A I Β Ν或過氧化氫物，使 用量為高分子單體之0.1〜5 %。 該鋁箔袋内已置有核心素子及注入的膠態電解液前趨 物，此時需要再使用特殊之夾製具以確保内容積之間隙， 並加壓定型完成封合的步驟。為能加快膠態電解液前趨物 之乳化聚合作用之反應速度，再將封合定型完之鋰電池置 於循環烤箱中以4 0〜1 0 0 °C加熱1〜1 2小時，此一加熱的 步驟稱為熟成。熟成後的鋰電池還要完成活化步驟，也就 可以得到最終之全膠態之鋰電池的成品。 第一具體實施例之說明 膠態電解液使用 EC/ DMC/EMC (1/1/1) 1M LiPF6 重量百分比90 %，與高分子單體重量百分比10 %製成配方 1〜3之樣品，如表1所示為電解液及與此三種配方混合前後 之導電度數據。高分子單體採用界面活性之單體（3-methacryloxypropyltris(trimethylsilane) silane) 15% 與多官能基 亞克力單體（polyethylene glycol 200 diacrylate)、（tetraethylene glycol diacrylate)或（highly ethoxylated TMPTA) 85%混合。配 方1〜3皆採用自由基起始劑AI Β Ν ( 1 %相對於單體含 量），於循環烘箱6 0 ° C中加熱8小時。圖2所示為配方3於 托\^\18〇\興能高台灣專利\78050.doc - 8 _ 本紙張尺度適用中國國家標準(CNS) A4規格(21〇X 297公釐） 575973 A7 — ___ B7 五、發明説明（6 ) 加熱前導電度之測試結果；圖3所示為配方3於加熱熟成 後之導境度測滅結果。该兩個圖式係在改變交流電頻率之 條件下測得之交流阻抗值，導電度與阻抗值互為倒數。如 圖2所示，加熱前因有一界面存在，故導電度在低頻測試 下很低。如圖3所示，加熱後因膠態電解液之微胞排列整 齊與大小均勻，故導電度表現遠較未加熱之對照組為佳。 表1 習用電解液 樣品1 樣品2 樣品3 組成 物質 EC/DMC/EMC/ 1M LiPF6 EC/DMC/ EMC/ 1M LiPF6+ PEG200+ S i - s i 1 a n e (配方1 ) EC/DMC/ EMC/ 1M LiPF6 + TTEGDA+ S i - s i 1 a n e (配方2 ) EC/DMC/ EMC/ 1M LiPF6+ HEOTMPTA + S i - s i 1 a n e (配方3 ) 未混 合導 電度 7.6 X 1 0'3 S / c m X X X 已混 合導 電度 2.7x10-3 S / c m 2.4x10-3 S / c m 3.22x10-3 S / c m 第二具體實施例之說明 將鐘電池做成5.0(t)X30(w)X48(l) mm尺寸之長方 體外型，核心素子之正極片材料為L i C 〇 0 2，及負極片材 料為人造石墨，電池之設計容量6 5 0 m A h。膠態電解液使 用 EC/ DMC/EMC (1/1/1) 1M LiPF6 (90%)與配方3 (10% )之物質製成，並採用自由基起始劑AI B N ( 1 %相 H:\Hu\lgcV興能高台灣專利\78050.(^ - 9 ~ 本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐) 575973 A7 B7 五 發明説明（7 ) 對於單體含量），於循環烘箱6 0 Q C中加熱8小時。樣品所 呈現不同之放電效率如圖4所示，而樣品之充放電循環壽 命如圖5所示，其顯示當充放電條件為1 C時經5 0 0次循環後 後，本發明仍保有原電容量之60%以上。 本發明之技術内容及技術特點巳揭示如上，然而熟悉本 項技術之人士仍可能基於本發明之教示及揭示而作種種不 背離本發明精神之替換及修飾。因此，本發明之保護範圍 應不限於具體實施例所揭示者，而應包括各種不背離本發 明之替換及修飾，並為以下之申請專利範圍所涵蓋。 -10- H:\Hu\lgc\興能高台灣專利\78050.(1(^ 本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐)575973 A7 B7 V. Description of the invention (5) vA〇.ri v ^ 〇-R2.bA / V ^ 〇-f.〇A / ° J ° where R1 can be fluorene, alkyl, ethoxy, silane or Silyl and the like, R2 and R3 may be alkyl, vinyloxy, silane, or siloxy. The initiator is a radical initiator such as Β 0, Α Β Ν or hydrogen peroxide, so that the amount is 0.1 to 5% of the polymer monomer. The aluminum foil bag has the core element and the injected precursor of the colloidal electrolyte. At this time, special clamps are needed to ensure the gap between the internal volume, and the sealing step is completed by pressure setting. In order to accelerate the reaction speed of the emulsification polymerization of the precursor of the colloidal electrolyte, the sealed lithium battery is placed in a circulating oven and heated at 40 ~ 100 ° C for 1 ~ 12 hours. The step of heating is called maturation. After the mature lithium battery has completed the activation step, the final product of the fully colloidal lithium battery can be obtained. The description of the first specific embodiment uses colloidal electrolyte EC / DMC / EMC (1/1/1) 1M LiPF6 90% by weight, and polymer monomer 10% by weight to make samples of formulas 1 to 3, such as Table 1 shows the conductivity data of the electrolyte and before and after mixing with these three formulations. The polymer monomer is mixed with 15% of 3-methacryloxypropyltris (trimethylsilane) silane and 85% of polyfunctional acrylic monomer (polyethylene glycol 200 diacrylate), (tetraethylene glycol diacrylate) or (highly ethoxylated TMPTA). Formulations 1 to 3 all use the radical initiator AI Β Ν (1% relative to the monomer content), and heat in a circulating oven at 60 ° C for 8 hours. Figure 2 shows the formula 3 in the tray \ ^ \ 18〇 \ Xingneng High Taiwan Patent \ 78050.doc-8 _ This paper size is applicable to the Chinese National Standard (CNS) A4 specification (21〇X 297 mm) 575973 A7 — ___ B7 V. Description of the invention (6) Test results of electrical conductivity before heating; Figure 3 shows the results of the conductivity measurement of formula 3 after heating and maturation. These two diagrams are the AC impedance values measured under the condition of changing the frequency of AC power, and the conductivity and impedance values are mutually inverse. As shown in Figure 2, there is an interface before heating, so the conductivity is very low under the low frequency test. As shown in Figure 3, after the heating, the cells of the colloidal electrolyte are arranged and uniform in size, so the conductivity performance is much better than the unheated control group. Table 1 Conventional electrolyte sample 1 Sample 2 Sample 3 Component EC / DMC / EMC / 1M LiPF6 EC / DMC / EMC / 1M LiPF6 + PEG200 + S i-si 1 ane (Recipe 1) EC / DMC / EMC / 1M LiPF6 + TTEGDA + S i-si 1 ane (formulation 2) EC / DMC / EMC / 1M LiPF6 + HEOTMPTA + S i-si 1 ane (formulation 3) Unmixed conductivity 7.6 X 1 0'3 S / cm XXX Mixed conductivity 2.7x10 -3 S / cm 2.4x10-3 S / cm 3.22x10-3 S / cm Description of the second embodiment The bell battery is made into a rectangular external shape with a size of 5.0 (t) X30 (w) X48 (l) mm. The material of the positive electrode sheet of the core element is L i C 0 02, and the material of the negative electrode sheet is artificial graphite. The design capacity of the battery is 650 m Ah. The colloidal electrolyte is made of EC / DMC / EMC (1/1/1) 1M LiPF6 (90%) and formulation 3 (10%), and uses the radical initiator AI BN (1% phase H: \ Hu \ lgcV Xingneng High Taiwan Patent \ 78050. (^-9 ~ This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) 575973 A7 B7 Five invention instructions (7) for monomer content), Heating in a circulating oven at 6 0 QC for 8 hours. The different discharge efficiency shown by the sample is shown in Figure 4, and the charge and discharge cycle life of the sample is shown in Figure 5, which shows that when the charge and discharge condition is 1 C, the battery passes 5 0 After 0 cycles, the present invention still retains more than 60% of the original electric capacity. The technical content and technical characteristics of the present invention are disclosed above, but those familiar with this technology may still make various departures based on the teaching and disclosure of the present invention. The substitution and modification of the spirit of the present invention. Therefore, the protection scope of the present invention should not be limited to those disclosed in the specific embodiments, but should include various substitutions and modifications that do not depart from the present invention, and are covered by the following patent application scope. -H: \ Hu \ lgc \ Xingneng High Taiwan Patent \ 78050. (1 (^ paper size With China National Standard (CNS) A4 size (210X 297 mm)