故、發明說明： 【發明所屬之技術領域】 本發明係關於麵聚合物二次電池及其製造方法。更詳細 之本务明係關於車父先别充放電周期特性及低溫特性卓越 之鐘聚合物二次電池及其製造方法。 【先前技術】 伴隨著IT技術之進步作為手機、攜帶式數據終端機、筆 型電腦、個人電腦等電源，鋰離子二次電池大量被使用。 近年來，替代鋰離子二次電池之有機電解液而使用之固 =電解質層之麵聚合物二次電池之開發積極進行，將有機 兒~液藉由面分子之物理交聯而使用矩陣化固體電解質層 之被稱為Bellcore型之鋰聚合物二次電池市場來臨。 +然而利則㈣交敎麵聚合物二次電池彡高溫環境下或 電池 < 異常發熱時，於固體電解質層之矩陣中發生相分 離，有機電解液滲出之可能性很高，#電池之可靠性方面 仍殘留著問題。再者發生相分離之鐘聚合物二次電池一反 覆充放電周期，則有可能發生突然急遽電容降低，周期特 性亦殘留問題。 因此針對物理交聯，開發利用因化學鍵結而交聯，使用 ::機電解液矩陣化之高分子固體電解質層之鋰聚合物二 次電池。該高分子固體電解質層，將混合具至少丨以上不飽 和雙鍵之交聯前之前驅體及含有鋰鹽之有機電解液之溶 液，精由熱及光等能源交聯（聚合）。因此，—度交聯之高分 子固體電解質層，即使高溫環境下或電池之異常發散時麵 84453 1222232 陣很少發生相分離。所以可靠性很高，有望作為充放電周 期特性亦優越之鋰聚合物二次電池。 根據熱及光等能源而交聯被得到使用高分子固體電解質 層义鋰聚合物二次電池，儘管高溫環境下或電池之異常發 熱時亦很難發生因液體滲出而液體漏出等，反覆充放電周 期時具有不發生急遽電容降低之優點。但因為高分子固體 f解質層以化學交聯形成堅固之網目構造，故較利用物理 人如 < 鋰聚合物二次電池離子之移動度變低，特別如 所謂如此之低溫下殘留放電電容變低之課題。 再者，鋰聚合物二次電池於正極及負極之間將高分子固 ^私解貝層作為電解質層而介入，因為該電解質層係含有 機電解液之矩陣，故預防電池内部之短路其強度並=充 足。因此，隔板隨著有機電解液一體化作為高分子固體電 ::貝層而使用《係為一般。然而一旦使用隔板，例如根據 紫外線照射等交聯而欲得到高分子固體電解質層之情況， π殘留其光因隔板而被遮掩，交聯將成為不充分而損害電 池之可靠性之課題。 且例如於特開平9-7577號公報中，於電池内利用光之穿 透率測量合物電解質相變化之程度之技術；於特開平 11-121003號公報中利用光之穿透率判斷製❹二次電池 用負極之碳材料時之原料之調製標準之技術被應用。但改 善鋰聚合物二次電池之高分子固體電解質層之性能通常相 關於透光率而應用，其至現今未被明確揭示。 【發明内容】 84453 1222232 本發明係以上述之課題引以鑒戒而做出之成果，以提供 不損害充放電周期特性、低溫特性卓越之鋰聚合物二次電 池及其製造方法為目的。 如此根據本發明提供鋰聚合物二次電池，其包含於有機 電解液及活性物質之存在下含有交聯之高分子之正極及負 極，且於有機電解液及隔板（未含不織布）之存在下，位於兩 極端間含有交聯之高分子之高分子固體電解質層，其特徵 為上述有機電解液含有γ-丁内酯，且上述高分子固體電解 質層具50%以上之透光率。 再者，若根據本發明，上述鋰聚合物二次電池之製造方 法，其特徵為調整有機電解液及交聯前高分子之存在下之 隔板之透光率成為如同50%以上後，包含使交聯前之高分 子交聯而得到高分子固體電解質層之步騾而提供鋰聚合物 二次電池之製造方法。 【實施方式】 於本發明，高分子固體電解質層之製造之際，調整有機 電解液及交聯前高分子之存在下之隔板之透光率成為如同 5 0%以上作為特徵之一。藉由測量透光率，可確認於隔板 上與含有交聯前之前驅體（以下簡稱前驅體）及混合含有鋰 鹽之有機電解液之溶液是否充分滲透。 於本發明中，以調製50%以上之穿透率，可製造簡便且 高性能之鋰聚合物二次電池。 透光率係例如照射波長365 nm之紫外線於對象物測量隔 著隔板之該照度，可根據下述公式算出。 84453 1222232 牙透率二（隔著隔板之光度）/(未隔隔板之光度）x 100 (% ) 隔板於落液注入前為白色，光之穿透率幾乎為〇%，然而 一 >王入溶液半透明溶液就變為透明。因此，可根據上述公 式以光之穿透率對隔板之溶液之注入程度定量化。此時， 穿透率因一旦未滿50%對隔板之溶液之注入不充足，不僅 提高電池之内部電阻，亦因形成以光交聯之情況之交聯反 應不充分而不理想。較理想之穿透率為6〇%以上，更理想 為7〇%以上’特別理想為80%以上，最理想為90%以上。（上 限為100%) 再者’因於交聯後高分子固體電解質層之透光率與交聯 岫隔板之透光率大致同等或1〜2%之低下程度，於交聯之 後測里亦可。且若於交聯後測量，就可預先選擇只限於優 越特性之高分子固體電解質層。 於圖1表示本發明鋰聚合物二次電池一例之概況剖面 圖。圖1中之1係隔板、2係高分子固體電解質層、3係正極 /舌性物貝、4係負極活性物質、5係集電體。 於本發明之高分子固體電解質層中之隔板若為不織布以 外’則無特別限定，可使用習知之隔板。 隔板之厚度理想為5〜30 μϊη，特別理想為8〜25 。因 旦薄於5 μηι機械式之強度即變低，電池之正極及負極具 短路之情況不為理想。一旦厚於30 μϊη電極間距離變長不僅 電池内部之電阻變高，目注入與含有至少W以上不飽和雙 鍵之前驅體及鋰鹽之有機電解液混合溶液時之透光率變低 之情況，其不為理想。 84453 -9 1222232 此外，作為隔板可舉例微小多孔質膜等。作為隔板，可 用不織布，然而其較微小多孔質膜之細孔之直徑大，正極 及/或負極活性物質貫穿不織布，發生電池之短路之可能性 很问。因此，使用微小多孔質膜為理想。特別係從包含聚 乙烯、聚丙烯或聚乙烯及聚丙烯之複合體之聚晞烴系而成 之微小多孔質膜強度及成本方面為理想。於此，所謂微小 多孔質膜係0.01〜ίο μηι之孔，含有1〇2〜⑺^個^一之膜。 再者於如γ-丁内酯（GBL)一般之聚烯烴系膜上使用難以 冷透之溶劑之情況，提高膜之溶劑親和性者為理想。作為 提高方法，可舉例以氧氣電漿處理膜之表面之方法、以表 面活性劑垔層膜之方法等，然而並未被限定於該等。 於本發明之鬲分子固體電解質層之有機電解液係使用於 含有GBL之有機溶劑以規定之濃度溶解鋰鹽之溶液。有機 電解液中之水分量係50 ppm以下為理想，特別理想係2〇 ppm以下。一旦水分量多，電池之充電時，因發生水之電解， 充放電效率低下而不理想。 鋰鹽濃度係0.5〜2.5 mol/Ι為理想。於較〇·5 mol/1低濃度 中，高分子固體電解質層之電荷之濃度變低，具電池内部 足阻抗變高之情況不為理想。於較2·5 m〇1/1高濃度中，發 生麵離子及陰離子之重新鍵結，離子傳導率低下、具電池 内部之阻抗變高之情況不為理想。 麵鹽之種類未特別被限定，可使用LiPF6、LiBF4、 LiN(CF3S02)2 等。 有機溶劑中之必要成分之GBL，係對其他溶劑以體積比 84453 -10- 1222232 包含60%以上為理想。一旦GBL少於60%，因於-20°c —般 之低溫中離子傳導率變低，電池之低溫特性惡化不為理 想。作為其他之溶劑，係例如丙烯碳酸酯（PC)、乙烯碳酸 酯（EC)等之環狀碳酸酯類，二乙基碳酸酯（DEC)、二甲基碳 酸酯（DMC)、乙基甲基碳酸酯（EMC)等之鏈狀碳酸酯類，四 氫呋喃、2-甲基四氫呋喃等之環狀乙醚類，二乙醚、二甲 氧乙烷、二乙氧乙烷、乙氧基甲氧基乙烷等之鏈狀乙醚類， 醋酸甲酯、乙醋酸乙酯、丙酸甲酯、丙酸乙酯等之酯類， 其他乙、環丁嗎、N-甲基-2-吡咯啶等可舉例。其他該等之 溶劑，亦可使用複數種類。 更具體之係例如使用黑錯系材料於負極活性物質之情 況，因於GBL混合EC之溶劑，未使充放電效率低下亦可提 高低溫特性，所以合適。特別係GBL : EC之體積比60 : 40 〜80 : 20為理想。因一旦GBL變為較60 : 40少，-20°C之低 溫之離子傳導率變低，電池之性能亦有變低之情況不為理 想。因GBL變為較80 : 20高電池之充放電效率低下，一旦 反覆充放電周期即發生電池電容之惡化之情況不為理想。 作為高分子固體電解質層交聯（聚合）前之高分子（前驅 體）分子内含環氧乙烷單元及氧化乙烯單元之任意共聚物 或嵌段聚合物，對該末端具丙烯基或甲基丙烯醯基等之不 飽和鍵結之多官能性化合物為理想。其係因為即使於如 GBL—般之高分子等溶解能力高之溶劑之存在下亦能以末 端交聯。又根據混合具單機能性之前驅體及多官能性之前 驅體，可製造各式各樣交聯構造之固體電解質層。 -11 - 84453 1222232 對於含前驅體之鋰鹽之有機電解液之量係，前驅體：有 機電解液之重量比係7 : 93〜3 : 97為理想。前驅體之量因 為一旦變為較7: 93多，即具高分子固體電解質層之離子傳 導率變低之情況不為理想。因前驅體之量一旦較3 ·· 97變 少，即具交聯反應充份完成之情況不為理想。 為促進交聯（聚合）反應，亦可使用起發劑。作為由光能起 發劑反應之起發劑，可舉例磷化氫系、乙驢苯系、二苯甲 酮系、α-羥基酮系、米謝（Michler)酮系、苯甲基系、苯偶 姻系、苯偶姻乙醚系、苯甲基甲基縮酮系化合物等。該起 發劑，亦可混合1種或2種以上使用。 根據熱能反應作為起發劑而開始反應，有機過氧化物系 化合物為合適。作為其具體例，可舉例異丁基過氧化氫、 α，α’-雙（新癸醯基過氧化）二異丙基苯、異丙苯基過氧化癸 酸酯、二-η-丙基過氧化二碳酸鹽、二異丙基過氧化二碳酸 鹽、1，1，3,3-四甲基丁基過氧化新癸酸酯、雙（4-t-丁基環己 基）過氧化二碳酸鹽、1_環己基-1-甲基乙基過氧化新癸酸 酯、二-2-乙氧基乙基過氧化二碳酸鹽、二（2-乙基己基過氧 化）二碳酸鹽、t-己基過氧化新癸酸酯、二甲氧基丁基過氧 化二碳酸鹽、二（3-甲基-3-甲氧基丁基過氧化）二碳酸鹽、卜 丁基過氧化新癸酸酯、t-過氧化特戊酯等。該起發劑，亦可 以混合1種或2種以上使用。 該起發劑係對於與含有前驅體及經鹽之有機電解液混合 之溶液之總重量以100〜5000 ppm之比率添加為理想。 作為具體之高分子固體電解質層之製造法，首先混合含 -12- 84453 1222232 有七驅體及4里鹽之有機電解液之溶液（依據情況亦添加起 發劑）預先注入於隔板。其次，光交聯之情況，以波長3〇〇 〜800 nm範圍之光5〜500 mw/cm2之光度使用1〜1200秒照 射’熱交聯之情況能以30〜8(rc熱處理〇.5〜1〇〇小時而後 製造高分子固體電解質層。 以光交聯之時，一旦波長變為較300 nm短，具發生前驅 體本身分解及鋰鹽之分解之情況不為理想。一旦變為較8〇〇 nm長’具交聯反應變為不充分之情況不為理想。以熱交聯 之時，因為一旦溫度變為較3〇。〇低，即具交聯反應成為不 充分 < 情況不為理想。因為一旦變為較8(rc高，·該溶液發 生包含有機溶劑之揮發及鋰鹽之分解之情況不為理想。 於本發明之高分子固體電解質層係注入含鋰鹽之有機電 解液或使其保持。如同該層之巨大固體狀態，然而微小之 鋰鹽溶液連續相形成，亦顯示較未使用溶劑之高分子固體 電解質層高之離子傳導率。 作為正極活性物質，並未特別限定，亦可使用於該領域 中任-習知之物。例如於本發明，可作為正極活性物質而 使用含有鋰之金屬氧化物。特別以Lia(A)b(B)e〇2 (於此，A 係過渡金屬元素之i種或2種以上之元素。則系周期表副、 IVB及VB族之非金屬元素及半金屬元素、驗土族類金屬， 從Zn’ Cu，Ti等金屬元素之中選擇丨種或2種以上之元素 b ’ C係各自為〇<d.15、0.85$b+cm 〇<c。）顯示 t層狀構造之複合氧化物或含尖晶石構造之複合氧化物二 少選擇1個為理想。此外’該等金屬氧化物因亦具促進有： 84453 -13、 1222232 過氧化物熱起發劑聚合之反應之效果為理想。 作為代表之複合氧化物可舉例Μ。：、L漏2、Therefore, the description of the invention: [Technical field to which the invention belongs] The present invention relates to a surface polymer secondary battery and a method for manufacturing the same. In more detail, the subject matter is about a bell polymer secondary battery with superior charge and discharge cycle characteristics and low temperature characteristics, and a method for manufacturing the same. [Previous technology] With the advancement of IT technology, lithium ion secondary batteries have been widely used as power sources for mobile phones, portable data terminals, pen computers, and personal computers. In recent years, the development of solid polymer secondary batteries using solid = electrolyte layers instead of organic electrolytes for lithium ion secondary batteries has been actively carried out. Matrix organic solids are used to physically crosslink surface molecules and use matrix solids. The market for lithium polymer secondary batteries called Bellcore type electrolytes is coming. + However, Lithium-Ion-Polymer secondary battery, high temperature environment or battery < abnormal heating, phase separation occurs in the matrix of solid electrolyte layer, the possibility of organic electrolyte seepage is high, # battery reliability Problems remain. Furthermore, if the phase-separated bell polymer secondary battery is repeatedly charged and discharged, there may be a sudden sudden decrease in capacitance, and the cycle characteristics may remain. Therefore, for physical cross-linking, a lithium polymer secondary battery that uses cross-linking due to chemical bonding and uses a polymer solid electrolyte layer matrixed with :: organic electrolyte matrix has been developed. The polymer solid electrolyte layer mixes a solution of a precursor having at least one or more unsaturated double bonds before crosslinking and an organic electrolyte solution containing a lithium salt, and is crosslinked (polymerized) by energy such as heat and light. Therefore, the phase-crosslinked high-molecular-weight solid electrolyte layer rarely undergoes phase separation even in high-temperature environments or when the battery diverges abnormally. Therefore, it has high reliability and is expected to be a lithium polymer secondary battery with excellent charge-discharge cycle characteristics. Lithium polymer secondary batteries using polymer solid electrolyte layers are cross-linked based on heat, light and other energy sources. Despite the high temperature environment or abnormal heating of the battery, liquid leakage due to liquid leakage is difficult to occur, and it is repeatedly charged and discharged. There is an advantage that no sudden capacitance reduction occurs during the cycle. However, because the polymer solid f decomposition layer is chemically cross-linked to form a solid mesh structure, the mobility of ions is lower than that of a physical person such as < lithium polymer secondary battery, especially the so-called residual discharge capacitor at such a low temperature. The issue of getting lower. In addition, lithium polymer secondary batteries use a polymer solid electrolyte layer between the positive electrode and the negative electrode as an electrolyte layer. Because the electrolyte layer contains a matrix of organic electrolytes, the strength of the battery is prevented from being short-circuited inside the battery. And = sufficient. Therefore, the separator is generally used as a polymer solid electrolyte :: shell layer with the integration of an organic electrolyte. However, once a separator is used, for example, when a polymer solid electrolyte layer is desired to be obtained by cross-linking such as ultraviolet radiation, the residual π light is masked by the separator, and cross-linking becomes a problem that impairs the reliability of the battery. For example, in Japanese Patent Application Laid-Open No. 9-7577, a technique for measuring the degree of phase change of a compound electrolyte in a battery by using light transmittance in a battery; in Japanese Patent Application Laid-Open No. 11-121003, a system using light transmittance judgment A standard technology for preparing raw materials for a carbon material of a negative electrode for a secondary battery is applied. However, improving the performance of the polymer solid electrolyte layer of a lithium polymer secondary battery is usually applied in relation to light transmittance, which has not been clearly disclosed to date. [Summary of the Invention] 84453 1222232 The present invention is based on the above-mentioned problems, and aims to provide a lithium polymer secondary battery that does not impair the charge and discharge cycle characteristics and has excellent low temperature characteristics, and a method for manufacturing the same. Thus, according to the present invention, there is provided a lithium polymer secondary battery including a positive electrode and a negative electrode containing a crosslinked polymer in the presence of an organic electrolyte and an active material, and the presence of an organic electrolyte and a separator (excluding a non-woven fabric). Next, a polymer solid electrolyte layer containing a cross-linked polymer between the extremes is characterized in that the organic electrolyte contains γ-butyrolactone, and the polymer solid electrolyte layer has a light transmittance of more than 50%. Furthermore, according to the present invention, the above-mentioned method for manufacturing a lithium polymer secondary battery is characterized in that after adjusting the light transmittance of the separator in the presence of the organic electrolyte and the polymer before crosslinking to be 50% or more, The step of cross-linking a polymer before crosslinking to obtain a polymer solid electrolyte layer provides a method for manufacturing a lithium polymer secondary battery. [Embodiment] In the present invention, when manufacturing a polymer solid electrolyte layer, adjusting the light transmittance of a separator in the presence of an organic electrolyte and a polymer before crosslinking becomes one of the characteristics as above 50%. By measuring the light transmittance, it can be confirmed whether a solution containing a precursor before crosslinking (hereinafter referred to as a precursor) and an organic electrolyte solution containing a lithium salt is sufficiently permeated on the separator. In the present invention, a lithium polymer secondary battery with simple and high performance can be manufactured by adjusting a transmittance of 50% or more. The light transmittance is measured by irradiating ultraviolet rays with a wavelength of 365 nm on the object, and the illuminance across the separator can be calculated according to the following formula. 84453 1222232 Permeability rate 2 (photographed through a separator) / (photographed without a separator) x 100 (%) The separator was white before the liquid was injected, and the light transmittance was almost 0%, but one > Wangru solution The translucent solution becomes transparent. Therefore, it is possible to quantify the degree of injection of the solution of the separator with the light transmittance according to the above formula. At this time, the transmittance is not sufficient because the injection of the separator solution is less than 50%, which not only increases the internal resistance of the battery, but also causes insufficient cross-linking reaction in the case of photo-crosslinking. A more desirable transmittance is 60% or more, more preferably 70% or more ', particularly preferably 80% or more, and most preferably 90% or more. (The upper limit is 100%.) Furthermore, because the light transmittance of the polymer solid electrolyte layer after cross-linking and the light transmittance of the cross-linked 岫 separator are approximately the same or 1 to 2%, it is measured after the cross-linking. Yes. And if measured after cross-linking, a polymer solid electrolyte layer limited to superior characteristics can be selected in advance. An outline sectional view of an example of the lithium polymer secondary battery of the present invention is shown in Fig. 1. In Fig. 1, the 1-series separator, the 2-series polymer solid electrolyte layer, the 3-series positive electrode / tongue shell, the 4-series negative electrode active material, and the 5-series current collector. The separator in the polymer solid electrolyte layer of the present invention is not particularly limited as long as it is made of a non-woven fabric, and a conventional separator can be used. The thickness of the separator is preferably 5 to 30 μϊη, and particularly preferably 8 to 25. Since the mechanical strength becomes thinner than 5 μηι, the situation that the positive and negative electrodes of the battery are short-circuited is not ideal. Once the distance between the electrodes is longer than 30 μϊη, not only the internal resistance of the battery becomes higher, but also the transmittance when the solution is mixed with an organic electrolyte solution containing at least W or more of unsaturated double bond precursors and lithium salts. It's not ideal. 84453 -9 1222232 In addition, examples of the separator include a minute porous membrane. As the separator, a non-woven fabric may be used. However, the diameter of the pores of the microporous membrane is large, and the positive electrode and / or negative electrode active material penetrates through the non-woven fabric, and the possibility of short circuit of the battery is very questionable. Therefore, it is desirable to use a minute porous film. In particular, it is desirable from the viewpoint of strength and cost of a microporous film composed of polyethylene, polypropylene, or a polyfluorene based on a composite of polyethylene and polypropylene. Here, the so-called microporous membrane is a pore having a diameter of 0.01 to Ιο μηι, and contains 102 to ^^^ 1 membranes. Furthermore, in the case of using a solvent that is difficult to cool through on a polyolefin film such as γ-butyrolactone (GBL), it is desirable to improve the solvent affinity of the film. Examples of the improvement method include a method of treating the surface of the film with an oxygen plasma, and a method of applying a surfactant to the film, but the method is not limited thereto. The organic electrolytic solution used in the amidine molecular solid electrolyte layer of the present invention is a solution in which a lithium salt is dissolved in an organic solvent containing GBL at a predetermined concentration. The water content in the organic electrolyte is preferably 50 ppm or less, and particularly preferably 20 ppm or less. Once the water content is large, the battery is not fully charged due to the electrolysis of water and the charge and discharge efficiency is low. The lithium salt concentration is preferably 0.5 to 2.5 mol / I. At a lower concentration than 0.5 mol / 1, the charge concentration of the polymer solid electrolyte layer becomes lower, and it is not ideal that the internal battery's foot impedance becomes higher. At a higher concentration than 2.5 m0 / 1/1, re-bonding of surface ions and anions occurs, the ion conductivity is low, and the internal impedance of the battery is not ideal. The type of the surface salt is not particularly limited, and LiPF6, LiBF4, LiN (CF3S02) 2, and the like can be used. The GBL of essential components in organic solvents is ideal for other solvents with a volume ratio of 84453 -10- 1222232 containing more than 60%. Once the GBL is less than 60%, the low-temperature characteristics of the battery are not ideal because the ionic conductivity becomes low at -20 ° c, which is generally low temperature. Examples of other solvents include cyclic carbonates such as propylene carbonate (PC) and ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), and ethylmethyl. Chain carbonates such as carbonates (EMC), cyclic ethers such as tetrahydrofuran and 2-methyltetrahydrofuran, diethyl ether, dimethoxyethane, diethoxyethane, and ethoxymethoxyethane Ethyl chain ethers, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate and other esters, other ethyl, cyclamidine, N-methyl-2-pyrrolidine and the like can be exemplified. For these other solvents, plural types may be used. More specifically, for example, the case where a black-type material is used for the negative electrode active material is suitable because GBL is mixed with a solvent of EC, and low-temperature characteristics can be improved without lowering charge and discharge efficiency. Especially, the volume ratio of GBL: EC is preferably 60: 40 ~ 80: 20. Because once the GBL becomes less than 60:40, the low-temperature ionic conductivity of -20 ° C becomes lower, and the performance of the battery may become lower. As GBL becomes lower than 80:20, the charge and discharge efficiency of the battery is low, and once the charge and discharge cycle is repeated, the deterioration of the battery capacitance is not ideal. As a polymer (precursor) before the polymer solid electrolyte layer is crosslinked (polymerized), any copolymer or block polymer containing ethylene oxide units and ethylene oxide units in the molecule has a propylene group or a methyl group at the end An unsaturated-bonded polyfunctional compound such as an acrylic fluorenyl group is preferable. This is because it can be crosslinked at the end even in the presence of a solvent with high solubility such as GBL-like polymers. In addition, a solid electrolyte layer having various crosslinked structures can be produced by mixing a single functional precursor and a multifunctional precursor. -11-84453 1222232 For the amount of organic electrolyte containing precursor lithium salt, the weight ratio of precursor: organic electrolyte is 7: 93 ~ 3: 97. Because the amount of precursor is more than 7:93, it is not ideal that the ion conductivity of the polymer solid electrolyte layer becomes low. If the amount of precursor is smaller than 3.97, it is not ideal that the crosslinking reaction is fully completed. To promote the cross-linking (polymerization) reaction, a hair starter may also be used. Examples of the hair starting agent which reacts with a light energy starting agent include phosphine-based, ethyl donkey benzene-based, benzophenone-based, α-hydroxyketone-based, Michler ketone-based, benzyl-based, Benzoin-based, benzoin-ether-based, benzylmethylketal-based compounds, and the like. This hair-starting agent may be used singly or in combination of two or more. An organic peroxide-based compound is suitable as a starter based on the thermal energy reaction. Specific examples thereof include isobutyl hydroperoxide, α, α′-bis (neodecanyl peroxide) diisopropylbenzene, cumyl peroxydecanoate, and di-η-propyl Peroxydicarbonate, diisopropylperoxydicarbonate, 1,1,3,3-tetramethylbutylperoxy neodecanoate, bis (4-t-butylcyclohexyl) peroxide Carbonate, 1-cyclohexyl-1-methylethyl peroxyneodecanate, di-2-ethoxyethyl peroxydicarbonate, bis (2-ethylhexyl peroxy) dicarbonate, t-hexyl peroxy neodecanoate, dimethoxybutyl peroxydicarbonate, bis (3-methyl-3-methoxybutyl peroxy) dicarbonate, butyl peroxy neodecanoate , T-tamyl peroxide and the like. The hair restorer may be used in combination of one kind or two or more kinds. It is desirable to add the hair-generating agent at a ratio of 100 to 5000 ppm based on the total weight of the solution mixed with the organic electrolyte containing the precursor and the salt. As a specific method for manufacturing a polymer solid electrolyte layer, first, a solution containing an organic electrolyte solution containing -12-84453 1222232 seven-flood body and four miles of salt (an initiator is also added according to the situation) is injected into the separator in advance. Secondly, in the case of photo-crosslinking, light with a wavelength of 300 to 800 nm in the range of 5 to 500 mw / cm2 can be irradiated for 1 to 1200 seconds. In the case of thermal crosslinking, heat treatment can be performed at 30 to 8 (rc 0.5 ~ 100 hours, and then manufacture a polymer solid electrolyte layer. When photocrosslinking, once the wavelength becomes shorter than 300 nm, it is not ideal that the precursor itself decomposes and the lithium salt is decomposed. The 800nm length is not ideal when the crosslinking reaction becomes insufficient. In the case of thermal crosslinking, once the temperature becomes lower than 30 °, the crosslinking reaction becomes insufficient < Not ideal. Once it becomes higher than 8 (rc), it is not ideal that the solution contains volatilization of organic solvents and decomposition of lithium salts. The polymer solid electrolyte layer of the present invention is injected with organic compounds containing lithium salts. The electrolyte may keep it. Like the huge solid state of this layer, but the continuous formation of a tiny lithium salt solution also shows a higher ionic conductivity than a polymer solid electrolyte layer without a solvent. As a positive electrode active material, Specially limited, also It is used in any field in this field. For example, in the present invention, a lithium-containing metal oxide can be used as a positive electrode active material. In particular, Lia (A) b (B) e02 (here, A is a transition Type i or more than two types of metal elements. They are non-metallic elements and semi-metallic elements of the Periodic Table, Group IVB and VB, and metals of the soil test group. Select from Zn 'Cu, Ti and other metal elements. Or two or more kinds of elements b'C are each ＜ d.15, 0.85 $ b + cm 〇 < c.) A composite oxide showing a t-layer structure or a composite oxide containing a spinel structure. It is ideal to choose less. In addition, 'these metal oxides also have the effect of promoting the polymerization reaction of 84453 -13, 1222232 peroxide thermal hair starter. The representative composite oxide can be exemplified. :, L leak 2,
LiCoxNi“x〇2 (〇<χ< 1)等。讀莓笳 仏所 )Ψ褒寺子夂合氧化物係於負極活性 斗貝上使用碳質材料之情況，具所謂其利益· ⑴即使發生伴隨後質材料本身之充電、：電之電壓變化 (大約1 Vvs. Ll/Ll+)亦顯示充足實用之作動電壓， 一⑺電池之充電、放電反應必要之_子，從組合電池之 則，已以例如LiC〇〇2、UNi〇2等形式包含於電池内。 作為負極活性物質，並㈣職定，亦可使用於該領域 中任-習知《物。例如作為負極活性物質，可使用碳質材 枓。碳質材料係插人/脫附電化學41所得之材料為理想。插 =/脫㈣之電位係因近於金屬鐘之析出/溶解電位，可構成 高能源密度之電池。其典型例係粒子狀（鱗片狀、塊狀、纖 維狀、晶鬚狀、球狀、粉碎粒子狀等)之天然或人造里鉛。 ，用可得到黑純内消旋碳微玻璃珠、介晶相瀝青粉末、 等向性瀝:青粉末等之人造黑錯可。 作為較理想之破質材料，可舉例於表面附著非晶暂碳之 黑錯粒子。作為附著之方法係黑錯粒子於焦油、遊青粉末 等煤系重油或重油等之石油系重質油浸潰提起，可以向碳 化溫度以上加熱分解重質油而得到。再者，亦可粉碎回應 必要而被得到之瑷質材料。根據如該處理’因充電時於畲 2發生之有機溶劑、鋰鹽之分解反應有意制止，改善充放 電周期壽命，且制止根據該分解反應之氣體之發生成為可 ^Γι 月匕° 84453 -14- 1222232 此外’碳質材料係關於根據bet法被測量之比表面積之 、、、田孔，其根據非晶質碳之附著而有某程度堵塞。具體之比 表面％於1〜5 m2/g範圍為理想。一旦比表面積變為較該範 圍大，與於有機溶劑溶解鋰鹽之有機電解液之接觸面積亦 夂大 口 &等之分解反應更易發生並不理想。且因增加為 义負極上形成高分子固體電解質層之起發劑之吸著量，因 月U驅體〈叉聯被妨礙並不理想。一旦比表面積變為較該範 圍J因包解質之接觸面積亦變小，電氣化學之反應速度 變fe，因具電池之負荷特性變低之情況不為理想。 、正極、負極係基本上以接合劑目定正極、負極活性物質 《各自〈活性物質層變為集電體而於金屬上形成者。作 為成為上述集電體之金屬箔之材料可舉例銘、不銹鋼、欽、 、,；、木等於其中，一旦考慮電化學之安定性、延伸性及 、、二w性，於正極使用鋁箔、負極用銅箔為理想。 一再者’作為箔以外之正極、負極集電體之形態，可舉例 篩目、柔性金屬、板條體、多孔體或於樹 子傳導材料等，然而不應限定於該者。 復μ 與若相當於正極、負極之製造必要之黑鉛、碳黑、乙块 黑、導電性碳黑、碳纖維、導電性金屬氧化物等化學 足之活性物質配合導電材料使用，可使電子傳導提高。心 且相當於正極、g極之制珠 &人二， 、、…、 /、 I仏，接&劑係於化學上穩定、 通當〈溶劑溶解，從不侵害有機電解液之樹脂之中選擇為 :想。眾多之樹脂被習知，例如可選擇融化於 = 84453 N-甲基〜峨（腑），而於有機電解液安定之聚偏= -15- 1222232 晞ll化（PVDF)偏好被使用。再者，未溶解於溶劑之接合劑， 亦可作為分散液而使用。 其他可使用之樹脂，例如可舉例丙婦、甲基丙烯醯、乙 烯基氟化、氯丁二晞、乙婦基啶、苯乙烯丁二烯橡膠（SBR)、 羥甲基纖維素（CMC)及該謗導體、乙烯叉二氯、乙烯、丙 烯、環狀二烯（例如，環戊二烯、1，3-環己二烯等）。 電極係混合活性物質及若必要之時用導電材料混合劑樹 脂之溶液做糊，將該者用適當覆蓋塗抹均等之厚度於金屬 箔上，可根據乾燥後按壓而製造。電極中之接合劑之比率 係作為必要最低限度為理想，將電極作為100重量部，而一 般1〜1 5重量部為充分。導電材料係將電極作為1 00重量 部，一般係為2〜15重量部。 本發明之鋰聚合物二次電池，例如根據以下之方法可製 造° (1) 預先將各個之正極、負極及隔板含浸於與含有至少1 個以上之不飽和雙键之前驅體及含有鋰鹽之有機電解液混 合之溶液，對各個照射熱或光或雙方之能源交聯而貼合所 得物之製造電池方法。 (2) 預先於任一之電極上裝載隔板及於另一之電極含浸於 與含有至少1個以上之不飽和雙鍵之前驅體及含有鋰鹽之 有機電解液混合之溶液，對雙方照射熱或光或雙方之能源 交聯而貼合所得物之製造電池方法。 (3) 預先於正極及負極之間上夾隔板，含浸於與含有至少1 個以上之不飽和雙键之前驅體及含有鋰鹽之有機電解液混 -16- 84453 1222232 合之溶液，對雙方照射熱或光或雙方之能源交聯而貼合所 得物之製造電池方法。 若根據上述本發明，可提供未損害充放電周期特性，於 低溫卓越特性之鋰聚合物二次電池。 包含正極、隔板及負極之單位可構成重疊或捲轉之層積 型或捲轉型之鋰聚合物二次電池。 製造電池係於鐵使用鎳鍍及鋁製之圓柱裝罐、正方罐或 作為包裝材料可於鋁箔上使用薄片覆蓋樹脂，然而未被限 _ 定於該等。 該等電池製造步騾係為預防水分之浸入氬氣及氮氣體等 之惰性氣體環境下或於乾燥之空氣中實行為理想。 實施例 以下根據實施例具體說明本發明，然而本發明絲毫未被 限制於該等。再者，製造之電池之電容係作為如20mAh — 般。 (實施例1) · 於以下之步騾製造實施例1之電池。 a)正極之製造 混合100重量部之平均粒子直徑7 μιη之LiCo02、5重量部 之導電材料之乙炔黑及5重量部之接合劑之PVDF，作為溶 劑添加適量NMP混合而得正極材料糊。將該者塗抹於20 μιη 之Α1箔上乾燥後壓得正極薄片。將該正極薄片切下為30x30 mm，焊接Α1集電襻得正極。 b)負極之製造 84453 -17- 1222232 將非晶質碳附著於黑鉛粒子之表面之碳材料粉末（平均 粒子直徑12 μπι，比表面積2 m2/g)100重量部與接合劑之 PVDF混合，其重量比為100 : 9，作為溶劑添加適量NMP混 合而得負極材料糊。將該者塗抹於1 8 μιη之Cu箔上乾燥後壓 得負極薄片。將該負極薄片切下為30x30 mm，焊接Ni集電 襻得負極。 c) 調製高分子固體電解質層之前驅體溶液 於GBL及EC之80 ·· 20之體積比混合溶劑中溶解LiBF4，其 濃度為2 mol/1，得到有機電解液。 於該重量95%有機電解液上混合重量3.5 %之分子量 75 00〜9000之3機能聚醚多元醇丙烯酸乙酯酯及重量1.5% 之分子量2800〜3000之單機能聚醚多元醇丙婦酸乙酯酯。 再者，對上述溶液添加2000 ppm光聚合起發劑之2,4,6-三甲 基-苯甲醯苯基磷化氫氧化而得到前驅體溶液。 d) 電池之組合 於上述所得之正極上，裝上以聚氧丙烯二醇處理表面之 聚丙烯製隔板（厚度24 μιη)，注入前驅體溶液。以2張石英 玻璃板（厚度500 μιη)爽該者，以波長365 nm之紫外線之20 mW/cm2之照度下照射2分鐘。其次，於負極注入前驅體溶 液，與正極同樣照射紫外線。如同正極及負極相向一般貼 合該等者，插入於包裝材料之鋁箔薄片覆蓋樹脂膜製之 袋，以熱封缝料封閉。使該者以6(TC 24小時加熱處理完成 電池。且僅高分子固體電解質層之波長365 nm之透光率為 87%(紫外線照射前係89%)。 -18- 84453 1222232 (實施例2) 以以下之步騾製造實施例2之電池。 a) 正極之製造 與實施例1同樣重覆操作而得到正極。 b) 負極之製造 與實施例1同樣重覆操作而得到負極。 c) 調製高分子固體電解質層之前驅體溶液 於GBL及EC之60 ·· 40之體積比混合溶上LiBF4溶解為如 1 mol/1之濃度。 於該有機電解液重量80%混合重量12%分子量7500〜 9000之3機能聚醚多元醇丙烯酸乙酯及重量8%分子量220 〜3 0 0之單機能聚醚多元醇丙烯酸乙酿，再者對上述溶液添 加3000 ppm光起發劑之雙（2,6-二甲氧基苯甲醯）-2,4,4-三甲 基-戊基鱗化氮氧化而得到前驅體溶液。 d) 電池之組合 於以上述得到之正極上，載著以聚氧乙烯二醇處理表面 之聚乙烯製品隔板（厚度9 μπι)，注入前驅體溶液。以2張石 英玻璃板（厚度500 μιη)夾該者，以波長365 nm之紫外線20 mW/cm2之光度2分鐘照射。其次，於負極注入前驅體溶液 及與正極同樣以紫外線照射。如同正極及負極相向一般貼 合並插入該等者於包裝材料之鋁箔薄片覆蓋樹脂膜製之 袋，以熱封缝料封閉。以8 0 °C加熱2小時處理使電池完成。 且僅高分子固體電解質層之波長365 nm之透光率為92% (紫外線照射前係93%)。 -19- 84453 1222232 (實施例3) 以以下之步驟製造實施例3之電池。 a) 正極之製造 與實施例1同樣重覆操作而得到正極。 b) 負極之製造 以如重量比100: 9混合100重量部_般，將黑錯粒子粉末 (平均粒子直徑12岬，比表面積5 m2/g)及接合劑之pvDF , 作為溶劑添加適量NMP混合而得負極材料糊。將該者塗抹 於18 μιη之Cu箔上乾燥後壓得負極薄片。將該負極薄片=下 為3 0 X 3 0 mm，焊接Ni集電襻得負極。 c)調製高分子固體電解質層之前驅體溶液 於GBL及EC之75: 25體積比混合溶劑中溶解1汨1?4為如濃 度0.8 mo 1/1 —般而得到有機電解液。 於該有機電解液重量97%混合重量2.4%分子量75〇〇〜 9000之3機能聚醚多元醇丙婦酸乙g旨及重量〇·6%分子量 220〜300之單機能聚醚多元醇丙晞酸乙酯，再者對上述溶 液添加1000 ppm熱起發劑之t-丁基過氧化新癸酸醋而得到 别驅體溶液。 d)電池之組合 以上述得到之負極及正極之間，夾以氧氣電漿表處理面 之聚乙烯製品隔板（厚度1 3 μπι)，插入該等於包裝材料之鋁 荡薄片覆蓋樹脂膜製之袋，於c)注入前驅體溶液而封閉該 袋。以60°C加熱72小時處理使電池完成。且僅測量高分子 固體電解質層之波長760 nm之透光率。透光率為59%(加熱 84453 -20- 1222232 前係60%)。 (比較例1) 以以下之步驟製造比較例丨之電池。 a) 正極之製造 與實施例1同樣重覆操作而得到正極。 b) 負極之製造 與貫施例1同樣重覆操作而得到負極。 c) 調製高分子固體電解質層之前驅體溶液 於EC及DMC之30 : 70體積比混合溶劑上溶*LiBF4為如 辰度1.5 mol/1—般而得到有機電解液。 其他與貫施例1同樣重覆操作而得到前驅體溶液。 d) 電池之組合 於以上述得到之正極上載放聚丙晞製品隔板（厚度24 μηι)，〉王入前驅體溶液。以2張石英玻璃板（厚度5〇〇叫幻夾 咸者以波長365 nm之紫外線2〇 mw/cm2之光度照射2分 知。其次，於負極注入前驅體溶液及與正極同樣以紫外線 照射。如同正極及負極相向一般貼合並插入該等者於包裝 材料之鋁强薄片覆蓋樹脂膜製之袋，以熱封縫料封閉。以 6〇°C加熱24小時處理使電池完成。且僅高分子固體電解質 層之波長365 nm之透光率為80%(加熱前係82%)。 (比較例2) 以以下之步驟製造比較例2之電池。 a)正極之製造 與實施例1同樣重覆操作而得到正極。 84453 -21 - 1222232 b) 負極之製造 與實施例1同樣重覆操作而得到正杯。 c) 鬲分子固體電解質層之前驅體溶液調製 與實施例1同樣重覆操作而得到前驅體溶液 d) 電池之組合 於以上返得到 w衣口口隔板（厚度30 ㈣’注入前驅體溶液。其他與實施⑴同樣重覆 作 而使電池完成。且僅測量高分子固體電解質層之波二 1^111之透光率為48%(紫外線照射前係49%)。 (比較例3) 以以下之步驟製造比較例3之電池。 a) 正極之製造 與實施例1同樣重覆操作而得到正極。 b) 負極之製造 與實施例1同樣重覆操作而得到正極。 C)調製高分子固體電解質層之前驅體溶液 與實施例1同樣重覆操作而得到前驅體溶液。 d)電池之組合 糸以上述得到之正極上載放聚酯製品不織布（厚度 μιη)，注入可驅體溶液。其他與實施例i同樣重覆一般操作 而使電池完成。且僅測量高分子固體電解質層之波長 nm之透光率為73% (紫外線照射前係乃％ )。 上述製k之各電池以定電流4㈤入至4·2 v為止充電，到達 4·2 V後以定電壓充電直至電流衰減至} mA (以下稱為ο』。 84453 -22- 1222232 充電）。測定以定電流20 mA，25°C至-20°C中至3 V為止放 電時之低溫電容維持率、以25°C至500次為止0.2C充電及定 電流20 mA重覆放電至3 V時之周期維持率。該等定義於以 下之公式表示。 低溫電谷維持率（％) = (-20 C放電電答）/(25 C之放電電答） X 100LiCoxNi "x〇2 (〇 < χ < 1), etc .. Reading the berry 笳 仏 Ψ 褒) The use of carbonaceous materials on the anode active bucket is a so-called benefit. ⑴ Even if it occurs Along with the charging of the aftermath material itself: the voltage change of electricity (approximately 1 Vvs. Ll / Ll +) also shows a sufficient practical operating voltage. Once the battery is required for charging and discharging reactions, from the assembled battery, it has been It is included in the battery in the form of, for example, LiC002, UNi02, and the like. As a negative electrode active material, it can also be used in any field in the field-the conventional material. For example, as a negative electrode active material, carbon can be used. The material is ideal. The carbonaceous material is ideally obtained by inserting / desorbing electrochemical 41. The potential of the insert = / desorb is close to the precipitation / dissolution potential of the metal clock, which can constitute a high energy density battery. Its Typical examples are particle-like (scaly, lumpy, fibrous, whisker-like, spheroidal, pulverized particles, etc.) natural or artificial lead. It can be used to obtain black pure meso-carbon micro glass beads and mesogens. Phase asphalt powder, isotropic bitumen: green powder, etc. As an ideal destructive material, black staggered particles of amorphous temporary carbon are adhered on the surface. As a method of attachment, black streak particles are immersed in coal-based heavy oil such as tar and blue powder or heavy oil such as heavy oil. It can be obtained by heating and decomposing heavy oil to a temperature above the carbonization temperature. In addition, it can also pulverize the high-quality materials obtained in response to the need. According to this treatment, organic solvents and lithium salts that occur in 畲 2 due to charging The decomposition reaction is intentionally stopped, the charge-discharge cycle life is improved, and the occurrence of gas based on the decomposition reaction can be prevented. ^ Γ 月 月 ° 84453 -14-1222232 In addition, the carbonaceous material is about the specific surface area measured by the bet method. The pores are blocked to some extent due to the adhesion of amorphous carbon. The specific surface area is preferably in the range of 1 to 5 m2 / g. Once the specific surface area becomes larger than this range, it is compatible with organic solvents. The contact area of the organic electrolyte that dissolves the lithium salt is also large, and the decomposition reaction is more likely to occur, which is not ideal. And because of the increase, the formation of a polymer solid electrolyte layer on the negative electrode is initiated. The amount of adsorption is not ideal because the U-disc body is blocked. Once the specific surface area becomes larger than this range, the contact area due to encapsulation is also reduced, and the reaction speed of electrochemistry becomes fe. It is not ideal when the load characteristics become low. The positive electrode and negative electrode are basically the positive electrode and negative electrode active materials based on the binder. Each active material layer becomes a current collector and is formed on a metal. The material of the metal foil of the electrical body can be exemplified by stainless steel, stainless steel, copper, copper, copper, etc. Once the stability, elongation, and stability of the electrochemical are considered, aluminum foil for the positive electrode and copper foil for the negative electrode are Ideally, as the form of the positive and negative electrode current collectors other than the foil, sieves, flexible metals, slatted bodies, porous bodies, or conductive materials for the tree can be exemplified, but they should not be limited to those. Compound μ If used with conductive materials such as black lead, carbon black, block black, conductive carbon black, carbon fiber, conductive metal oxide and other chemically sufficient active materials that are necessary for the production of positive and negative electrodes, it can conduct electrons. improve. It is equivalent to the positive electrode and the g electrode, and the beads are made of & human II, ,, ..., /, I 、, and the agent is chemically stable and generally soluble in the solvent, and will never harm the resin of the organic electrolyte. The choice is: think. Numerous resins are known. For example, they can be melted at = 84453 N-methyl ~ E (腑), and the stability of the organic electrolyte = -15-1222232 PVDF (PVDF) is preferred. Moreover, a bonding agent which is not dissolved in a solvent can also be used as a dispersion liquid. Other resins that can be used include, for example, acrylic acid, methacrylic acid, vinyl fluoride, chloroprene, ethynidine, styrene butadiene rubber (SBR), hydroxymethyl cellulose (CMC), and the like. Conductor, vinylidene chloride, ethylene, propylene, cyclic diene (eg, cyclopentadiene, 1,3-cyclohexadiene, etc.). The electrode system is mixed with an active material, and if necessary, a solution of a conductive material mixture resin is used as a paste, and this is coated with an appropriate thickness on a metal foil, and can be manufactured by pressing after drying. The ratio of the bonding agent in the electrode is preferably the minimum necessary, and the electrode is 100 parts by weight, and generally 1 to 15 parts by weight is sufficient. The conductive material uses an electrode as 100 parts by weight, and generally uses 2 to 15 parts by weight. The lithium polymer secondary battery of the present invention can be manufactured by, for example, the following methods: (1) Impregnate each positive electrode, negative electrode, and separator with a precursor containing at least one unsaturated double bond and contain lithium in advance A method of manufacturing a battery by mixing a solution of a salt with an organic electrolytic solution and irradiating heat or light or the energy of both sides to cross-link them. (2) A separator is mounted on one of the electrodes in advance and the other electrode is impregnated with a solution mixed with a precursor containing at least one unsaturated double bond and an organic electrolyte containing a lithium salt, and irradiated to both sides A method of manufacturing a battery by cross-linking heat or light or energy from both sides and bonding the resultant. (3) Put a separator between the positive electrode and the negative electrode in advance, and impregnate a solution mixed with a precursor containing at least one unsaturated double bond and an organic electrolyte containing a lithium salt. A method for manufacturing a battery by bonding heat and light to both sides or cross-linking energy from both sides and bonding the resultant. According to the present invention as described above, a lithium polymer secondary battery having excellent characteristics at low temperatures without impairing charge-discharge cycle characteristics can be provided. A unit including a positive electrode, a separator, and a negative electrode may constitute a laminated or rolled lithium polymer secondary battery that is overlapped or rolled. The manufacturing of batteries is based on cylindrical cans, square cans made of nickel-plated and aluminum made of iron, or as a packaging material. Aluminum foil can be used to cover the resin, but it is not limited to these. These battery manufacturing steps are ideal to prevent moisture from immersing in an inert gas environment such as argon and nitrogen gas or in dry air. Examples The present invention will be specifically described below based on examples, but the present invention is not limited to these in any way. In addition, the capacity of the manufactured battery is as 20mAh. (Example 1) The battery of Example 1 was manufactured in the following steps. a) Manufacture of positive electrode Mix 100 parts by weight of LiCo02 with an average particle diameter of 7 μm, 5 parts by weight of conductive material acetylene black, and 5 parts by weight of PVDF binder, and add an appropriate amount of NMP as a solvent to obtain a positive electrode material paste. This was applied to 20 μm of A1 foil, dried, and pressed to obtain a positive electrode sheet. The positive electrode sheet was cut into 30x30 mm, and the A1 current collector was welded to obtain a positive electrode. b) Manufacturing of negative electrode 84453 -17-1222232 100 parts by weight of carbon material powder (average particle diameter 12 μm, specific surface area 2 m2 / g) with amorphous carbon attached to the surface of black lead particles, and PVDF of the binder, Its weight ratio is 100: 9, and an appropriate amount of NMP is added as a solvent and mixed to obtain a negative electrode material paste. This was applied to a 18 μm Cu foil, dried, and pressed to obtain a negative electrode sheet. The negative electrode sheet was cut into 30 × 30 mm, and Ni collector was welded to obtain a negative electrode. c) Preparing the polymer solid electrolyte layer precursor solution Dissolve LiBF4 in a mixed solvent with a volume ratio of 80 ·· 20 in GBL and EC to a concentration of 2 mol / 1 to obtain an organic electrolyte. On this 95% organic electrolyte, 3.5% by weight of a functional polyether polyol ethyl acrylate having a molecular weight of 75 00 to 9000 and 1.5% by weight of a single-functional polyether polyol ethyl methacrylate having a molecular weight of 2800 to 3000 are mixed. Ester. In addition, to the above solution, 2000 ppm of 2,4,6-trimethyl-benzylphenylphosphine phosphine hydroxide as a photopolymerization initiator was added to obtain a precursor solution. d) Battery assembly On the positive electrode obtained above, a polypropylene separator (thickness: 24 μm) with a surface treated with polyoxypropylene glycol was attached, and a precursor solution was injected. This was refreshed with two quartz glass plates (thickness: 500 μιη), and irradiated with ultraviolet light at a wavelength of 365 nm at 20 mW / cm2 for 2 minutes. Next, a precursor solution was injected into the negative electrode, and ultraviolet rays were irradiated in the same manner as in the positive electrode. The positive electrode and the negative electrode are generally adhered to each other, and the aluminum foil sheet inserted into the packaging material is covered with a resin film bag and closed with a heat-sealing compound. This person completed the battery with a heating treatment of 6 (TC for 24 hours. Only the polymer solid electrolyte layer had a light transmittance of 87% at a wavelength of 365 nm (89% before UV irradiation). -18- 84453 1222232 (Example 2 ) Manufacture the battery of Example 2 in the following steps: a) Manufacture of the positive electrode The same operation as in Example 1 was repeated to obtain a positive electrode. b) Production of negative electrode The same operation as in Example 1 was repeated to obtain a negative electrode. c) Preparing polymer solution for polymer solid electrolyte layer. LiBF4 was mixed and dissolved at a volume ratio of 60 ·· 40 in GBL and EC to a concentration of 1 mol / 1. 80% of the weight of the organic electrolyte is mixed with 12% of the molecular weight of 7500 ~ 9000, 3 functional polyether polyol ethyl acrylate and 8% by weight of the single-functional polyether polyol acrylic acid, and then The above solution was oxidized with 3000 ppm of bis (2,6-dimethoxybenzidine) -2,4,4-trimethyl-pentyl squamous nitrogen to obtain a precursor solution. d) Battery assembly On the positive electrode obtained as described above, a polyethylene product separator (thickness: 9 μm) with a surface treated with polyoxyethylene glycol was loaded, and a precursor solution was injected. This was sandwiched between two quartz glass plates (thickness: 500 μιη), and irradiated with ultraviolet light at a wavelength of 365 nm and a light intensity of 20 mW / cm2 for 2 minutes. Next, a precursor solution was injected into the negative electrode and irradiated with ultraviolet rays as in the positive electrode. As the positive and negative electrodes face each other, insert the aluminum foil sheet into the packaging material to cover the bag made of resin film and seal it with heat-sealing compound. Heat at 80 ° C for 2 hours to complete the battery. And only the polymer solid electrolyte layer has a light transmittance of 92% at a wavelength of 365 nm (93% before ultraviolet irradiation). -19- 84453 1222232 (Example 3) The battery of Example 3 was manufactured by the following steps. a) Production of positive electrode The same operation as in Example 1 was repeated to obtain a positive electrode. b) For the production of the negative electrode, black miscellaneous particle powder (average particle diameter of 12 points, specific surface area of 5 m2 / g) and pvDF of the binder are added as a solvent, and an appropriate amount of NMP is mixed as a solvent. Thus, a negative electrode material paste was obtained. This was applied to a 18 μm Cu foil, dried, and pressed to obtain a negative electrode sheet. The negative electrode sheet = 30 x 3 0 mm, and Ni collector was welded to obtain a negative electrode. c) Preparing a polymer solid electrolyte layer precursor solution. Dissolve 1 汨 1 ~ 4 in a mixed solvent with a volume ratio of 75:25 in GBL and EC to obtain an organic electrolyte solution at a concentration of 0.8 mo 1/1. Based on the weight of the organic electrolytic solution, 97% by weight, 2.4% by weight, and a molecular weight of 7500 to 9000 with 3 functional polyether polypropionate and a weight of 0.6% and a molecular weight of 220 to 300 are single-functional polyether polyols. Ethyl acetate, and t-butyl peroxyneodecanoate vinegar was added to the above solution at 1000 ppm to obtain an allophore solution. d) The combination of the battery is a polyethylene product separator (thickness: 13 μm) sandwiched between the negative electrode and the positive electrode obtained above, with an oxygen plasma surface treated, and the aluminum foil sheet equal to the packaging material is covered with a resin film. The bag is filled with the precursor solution at c) to close the bag. The battery was completed by heating at 60 ° C for 72 hours. And only the light transmittance of the polymer solid electrolyte layer with a wavelength of 760 nm was measured. Light transmittance is 59% (60% before heating 84453 -20-1222232). (Comparative Example 1) The battery of Comparative Example 1 was manufactured by the following steps. a) Production of positive electrode The same operation as in Example 1 was repeated to obtain a positive electrode. b) Production of negative electrode The same operation as in Example 1 was repeated to obtain a negative electrode. c) Preparing a polymer solid electrolyte layer precursor solution Dissolved in a mixed solvent of 30:70 volume ratio of EC and DMC. * LiBF4 is as high as 1.5 mol / 1 to obtain an organic electrolyte. Other operations were repeated in the same manner as in Example 1 to obtain a precursor solution. d) Combination of battery Put a polypropylene separator (thickness: 24 μm) on the positive electrode obtained above, and then enter the precursor solution. Two pieces of quartz glass plate (thickness of 500) were irradiated for 2 minutes with ultraviolet light at a wavelength of 365 nm and ultraviolet light of 20 mw / cm2. Secondly, the precursor solution was injected into the negative electrode and the same as the positive electrode was irradiated with ultraviolet light. As the positive electrode and the negative electrode face each other, insert and insert the aluminum strong sheet of the packaging material into the bag made of resin film and seal it with heat-sealing material. Heat it at 60 ° C for 24 hours to complete the battery. And only the polymer The light transmittance of the solid electrolyte layer at a wavelength of 365 nm was 80% (82% before heating). (Comparative Example 2) The battery of Comparative Example 2 was manufactured by the following steps. A) The fabrication of the positive electrode was the same as in Example 1. Operation to obtain a positive electrode. 84453 -21-1222232 b) Manufacture of negative electrode The same operation as in Example 1 was repeated to obtain a positive cup. c) The precursor solution of the tritium molecular solid electrolyte layer was prepared in the same manner as in Example 1 to obtain the precursor solution. d) The battery assembly was obtained in the above manner to obtain a precursor solution (thickness: 30 ㈣). The rest of the battery was completed in the same way as the implementation of the test. The light transmittance of Wave 2 1 111 of the polymer solid electrolyte layer was measured only at 48% (49% before UV irradiation). (Comparative Example 3) The following This step produced the battery of Comparative Example 3. a) The production of the positive electrode was repeated in the same manner as in Example 1 to obtain a positive electrode. b) Production of negative electrode The same operation as in Example 1 was repeated to obtain a positive electrode. C) Preparing a polymer solid electrolyte layer precursor solution Repeat the same operation as in Example 1 to obtain a precursor solution. d) Combination of batteries 糸 Put the polyester fabric nonwoven fabric (thickness μm) on the positive electrode obtained above, and inject the drive solution. Otherwise, the same operation as in Example i is repeated to complete the battery. And only measure the light transmittance of the polymer solid electrolyte layer at a wavelength of nm (73% (before UV irradiation)). Each battery made by the above k is charged at a constant current of 4 至 to 4 · 2 v. After reaching 4 · 2 V, the battery is charged at a constant voltage until the current decays to} mA (hereinafter referred to as ο ′). Measure the low-temperature capacitance retention rate at a constant current of 20 mA and discharge at 25 ° C to -20 ° C to 3 V, charge at 0.2C at 25 ° C to 500 times, and repeat discharge to 20 V at a constant current of 20 mA Time cycle maintenance rate. These definitions are expressed in the following formulas. Low-temperature electricity valley maintenance rate (%) = (-20 C discharge electricity answer) / (25 C discharge electricity answer) X 100
周期維持率（％ )=(第500次放電電容）/(初次之放電電容）X 100 於以下之表1顯示上述實施例及比較例結果。 表1 透光率(％) 低溫電容維持率(％) 周期維持率(％) 實施例1 87 68 80 實施例2 92 50 86 實施例3 59 38 88 比較例1 80 3 82 比較例2 48 9 38 比較例3 73 55 33 如顯示於表1一般，從實施例1及比較例1之結果，為提高 維持電池之周期特性及低溫特性，即使高分子固體電解質 層之透光率具50%以上，判明有必要使用含有GBL之高分 子固體電解質層之事。 且從實施例1及比較例2之結果，一旦高分子固體電解質 層之透光率未滿50%，判明電池之低溫特性及周期特性低 -23- 84453 落之事。 再者，從實施例1及比較 上，並非隔板而係於不織布：、去果’即使透光率具5°%以 未能維持周期特性之事。”起電池内部之短路’判明 提“能維持如孩-般之低溫之 政之周期特性’亦不發生性能惡化之鐘聚合物二次電池。Cycle maintenance rate (%) = (500th discharge capacity) / (first discharge capacity) X 100 The results of the above examples and comparative examples are shown in Table 1 below. Table 1 Light transmittance (%) Low-temperature capacitance retention rate (%) Cycle retention rate (%) Example 1 87 68 80 Example 2 92 50 86 Example 3 59 38 88 Comparative Example 1 80 3 82 Comparative Example 2 48 9 38 Comparative Example 3 73 55 33 As shown in Table 1, from the results of Example 1 and Comparative Example 1, in order to improve the cycle characteristics and low temperature characteristics of the battery, even if the light transmittance of the polymer solid electrolyte layer is 50% or more It was found necessary to use a polymer solid electrolyte layer containing GBL. And from the results of Example 1 and Comparative Example 2, once the light transmittance of the polymer solid electrolyte layer is less than 50%, it is determined that the low-temperature characteristics and cycle characteristics of the battery are low -23-84453. In addition, from Example 1 and comparison, it was tied to a non-woven fabric instead of a separator: even if the light transmittance was 5%, the cycle characteristics could not be maintained. "A short circuit inside the battery" was identified as "a clock polymer secondary battery capable of maintaining cycle characteristics such as child-like low temperature" without degradation of performance.
、：：，判明以透光率測量對高分子固體電解質層交聯前 之冋刀子及γ- 丁内酯之隔板之滲透性之所謂製造方法係簡 便且高性能之鍾聚合物二次電池之製造方法之事。 5 【圖式簡單說明】 圖1係本發明鋰聚合物二次電池之概略剖面圖。 【圖式代表符號說明】 1 隔板:: It is clear that the so-called manufacturing method for measuring the permeability of the trowel and the separator of γ-butyrolactone before cross-linking the polymer solid electrolyte layer by light transmittance is a simple and high-performance bell polymer secondary battery. Of manufacturing methods. 5 [Brief description of the drawings] FIG. 1 is a schematic cross-sectional view of a lithium polymer secondary battery of the present invention. [Schematic representation of symbols] 1 Partition
向分子固体電解質層 正極活性物質 負極活性物質 集電體 84453 -24-Molecular solid electrolyte layer Positive active material Negative active material Current collector 84453 -24-