201205920 六、發明說明： 【發明所屬之技術領域】 本發明係關於壽命特性及安全性佳之鋰離子蓄電池。 【先前技術】 電池，是藉由電化學氧化還原反應將裝入於內部之化 學物質的化學能轉換爲電能之裝置。近年來，電池係以電 子、通訊、電腦等之可攜式電子機器爲中心爲全球各地所 使用，並且可預測到的是今後將作爲電動車等之移動體或 是電力負荷平準系統等之大型電池而達實用化，乃曰益成 爲重要的關鍵裝置。 當中，鋰離子蓄電池已大幅地達到普及化。該鋰離子 蓄電池是以：含鋰的過渡金屬複合氧化物作爲活性物質之 正極，以鋰金屬、鋰合金、如金屬氧化物或碳般之可吸存 /釋出鋰之材料作爲活性物質之負極，以及非水電解液與 分隔片或是固體電解質，作爲主要構成要素。 在此，例子之一，鋰離子蓄電池中，從初期充電時用 作爲正極之鋰金屬複合氧化物所釋出之鋰離子，在用作爲 負極之石墨電極中移動並***於石墨電極間。此時，由於 鋰的反應性高，所以在石墨負極表面形成薄膜的被膜層。 將該層稱爲SEI( Solid Electrolyte Interface:固態電解質 界面）層。上述SEI層，一旦形成時乃具有離子穿隧之功 用，而僅讓鋰離子通過。藉由具有此般離子穿隧效果之保 護膜，可防止電解液等對石墨負極的結構所造成之破壞。 -5- 201205920 當一旦形成SEI層時，鋰離子不會再次與石墨負極或 其他物質進行副反應，而能夠可逆地維持電解質中的鋰離 子的量並確保安定的充放電。 該SEI層對於正極亦相同，藉由對正極形成保護膜， 使正極不易產生電位崩潰。 鋰離子蓄電池中，該SEI層，以往係在初期充放電時 形成於電極活性物質材料表面》藉此可抑制活性物質被腐 蝕。然而，形成該SEI層（保護膜）時，至膜形成爲止之 間，由於化學反應所形成之氣體化而使電池的內壓上升， 導致電池厚度的增加或是依據反應所形成之容量的降低， 且更存在有均一性和因膜厚增加所造成之電阻增加之課題 ，而成爲在不均一部分上的腐蝕所造成之壽命降低，以及 因電阻增加所造成之壽命降低之結果。 此外，在使用電極層與集電體之密著性不充分的電極 之蓄電池中，乃存在有以充放電循環特性爲首之電極特性 的課題。 相關的先前技術，係揭示有一種將於二烯系聚合物中 使用羧基等的官能基之改質聚合物，用作爲黏結劑之技術 (例如參照專利文獻1 )。然而，即使是此般黏結劑，亦 無法充分提升密著性，在急速充電時或循環特性上，仍無 法消除課題。 [先前技術文獻] [專利文獻] [專利文獻1]日本特開平1〇_17714號公報 -6- 201205920 【發明內容】 (發明所欲解決之課題） 本發明係爲了解決此等課題而創作出之發明，其課題 在於提供一種安全性佳且循環壽命特性佳之電池。 此外，在於提供一種可一邊抑制電池內部的瞬間溫度 上升並同時達成高容量與高輸出之組裝電池。 (用以解決課題之手段） 爲了解決上述課題而進行精心探討，結果發現到藉由 在正極中設置含有特定金屬元素之丙烯酸層，可解決上述 課題，因而完成本發明。 根據本發明，係提供下列所示之本電池中所使用之電 極用黏結劑組成物、電極用膏及電極。 亦即爲一種本電池中所使用之電極用黏結劑組成物， 其係含有：具有可與特定金屬元素鍵結之丙烯酸基的聚合 物材料、與特定金屬元素：以及與電極活性物質混合之電 極用塗料。 一種電池，其係具備有電極，該電極係使用此等組成 物及塗料，將前述電極用塗料塗佈於集電體金屬箔並進行 乾燥所形成。 發明之效果： 根據本發明之電池，是一種急速放電下的容量降低亦 201205920 少’且循環特性佳之電池，亦可抑制急速充電時之電池內 的溘度上升和金屬枝狀結晶，再者，即使夾持金屬片以強 制產生內部短路，其溫度上升亦小，而成爲安全的鋰離子 蓄電池。 【實施方式】 以下係顯示本發明之較佳型態。 首先，關於作爲本發明的支柱之電極用黏結劑，在釘 刺或碰撞試驗中，因試驗條件的不同，有時內部短路時的 發熱溫度會局部性的到達數百°c，若爲結晶性且結晶熔點 低者、或是即使是非結晶性但分解起始溫度低者，則會伴 隨著因樹脂的軟化或燒結損失所造成之變形，尤其爲正極 時，會由於活性物質的崩落使集電體剝離，使激烈的過剩 電流流動而引起異常過熱。因此，電極內的黏結劑，必須 至少使用1種非結晶性且耐熱性高，並且具有橡膠彈性之 具有丙烯酸基之橡膠性狀高分子。將此般材料用作爲電極 用黏結劑之鋰離子蓄電池，與具有結晶性且膜質硬之電極 不同，當於正負極夾介分隔片來進行電池組裝構成時，不 會因電極產生龜裂等而造成損失，所以具有可維持高良率 來生產之優點》 關於正極，活性物質可列舉出鎳錳酸鋰、錳酸鋰、鎳 酸鋰、鎳鈷錳酸鋰及此等的改質體（使鋁或鎂等金屬進行 共結晶者）等之複合氧化物。黏結劑，可將經改質的丙烯 腈橡膠粒子黏合劑（日本Zeon股份有限公司製BM-520等 201205920 )與具有增黏效果之羧甲基纖維素（CMC ) /可溶性經改 質的丙稀腈橡膠（日本Zeon股份有限公司製BM-720H等） 組合來作爲基礎材料。導電劑，可單獨或組合使用乙炔黑 /科琴黑/各種石墨。 關於負極’活性物質可使用各種天然石墨及人造石墨 /砂化物等之砂系複合材料、氧化砂系材料、鈦合金系材 料、及各種合金組成材料。黏結劑，就鋰離子接受性提升 的觀點來看’可將SBR及其改質體與以CMC爲首之纖維素 樹脂倂用或少量添加’並且與正極相同，尤佳爲丙烯酸系 樹脂。 關於電解液，鹽類可使用選自由LiPF6、LiBF4、 LiCl〇4、LiSbF6、LiAsF6、LiCF3S03、LiN(S02CF3)2、LiN (S02C2F5)2、LiC(S02CF3)3、LiN(S03CF3)2、LiC4F9S03、 LiA104、LiAlCl4、LiCl、Lil、LiBETI、LiTFS 所組成之群 組之1種或混合2種以上來使用。此外，溶劑可單獨或組合 使用碳酸乙烯酯（EC)、碳酸二甲酯（DMC)、碳酸二乙 酯（DEC)、碳酸甲基乙酯（MEC)。爲了保證過充電時 的安定性，亦可使用碳酸伸乙烯酯（VC)、環己基苯（ CHB )、丙烷磺內酯（PS)、丙烯亞硫酸（PRS )、乙烯 亞硫酸（E S )等。 關於分隔片，只要在可承受鋰離子蓄電池的使用範圍 之組成即可，並無特別限定，一般而言可單一或複合使用 聚乙烯/聚丙烯等之烯烴系樹脂的微多孔薄膜，且其爲較 佳型態。該分隔片的厚度並無特別限定，可在得到設計容 -9- 201205920 量之膜厚內設計。亦即，尤佳爲6μπι〜2 5μιη。 此外，正極中所用之丙烯酸黏合劑內，可含有本發明 所示之金屬元素，藉此可得到下列作用及效果。 在正極電解質至少與丙烯酸層接觸之環境，或是在構 成爲丙烯酸層包覆活性物質之狀態的環境下，當下列金屬 元素存在於丙烯酸層時，可得知鋰的解離反應和擴散增快 。在不含此等金屬元素之狀態下，丙烯酸層的黏結劑中所 使用之高分子爲絕緣體，其電阻較高，若無法包覆活性物 質來形成保護膜（SEI)，則會於活性物質與電解液的界 面引起化學反應，而產生以往所具有之氣體化等課題。然 而，藉由含有此等金屬元素，可藉由丙烯酸層來包覆活性 物質，而能夠消除活性物質與電解液產生反應之課題。此 外，本發明所示之丙烯酸，其耐電壓性佳，且當丙烯酸層 內含有本發明所示之金屬元素時，可使電位緩和，降低到 達活性物質之氧化電位。惟由於鋰未被緩衝而能夠移動， 所以可得到一種實現高電壓規格的高容量、高輸出之離子 傳導機構。 可有效地獲得本發明的效果之金屬，較佳者可列舉出 Mn、Ni、鹵化金屬（F、I等）、鹼金屬（Na、K、Li ) '201205920 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a lithium ion secondary battery having excellent life characteristics and safety. [Prior Art] A battery is a device that converts chemical energy of a chemical substance charged therein into electric energy by an electrochemical redox reaction. In recent years, the battery is used in the world for portable electronic devices such as electronics, communication, and computers. It is predicted that it will be used as a mobile body such as an electric vehicle or a power load leveling system. The practical use of the battery has become an important key device. Among them, lithium ion batteries have been greatly popularized. The lithium ion battery is a cathode containing a lithium-containing transition metal composite oxide as an active material, and a lithium metal, a lithium alloy, a material such as a metal oxide or carbon capable of absorbing/releasing lithium as a negative electrode of an active material. And a non-aqueous electrolyte and a separator or a solid electrolyte as a main component. Here, in one of the examples, in the lithium ion secondary battery, lithium ions released from the lithium metal composite oxide as the positive electrode at the time of initial charging are moved and inserted between the graphite electrodes in the graphite electrode as the negative electrode. At this time, since the reactivity of lithium is high, a film layer of a thin film is formed on the surface of the graphite negative electrode. This layer is referred to as an SEI (Solid Electrolyte Interface) layer. The above SEI layer, once formed, has the function of ion tunneling, and only allows lithium ions to pass. By the protective film having such an ion tunneling effect, it is possible to prevent damage to the structure of the graphite negative electrode caused by an electrolyte or the like. -5- 201205920 When the SEI layer is formed, lithium ions are not side-reacted with the graphite negative electrode or other substances, and the amount of lithium ions in the electrolyte can be reversibly maintained and a stable charge and discharge can be ensured. The SEI layer is also the same for the positive electrode, and by forming a protective film on the positive electrode, the positive electrode is less likely to cause potential collapse. In the lithium ion secondary battery, the SEI layer is conventionally formed on the surface of the electrode active material at the time of initial charge and discharge, whereby the active material can be suppressed from being corroded. However, when the SEI layer (protective film) is formed, the internal pressure of the battery rises due to the gasification of the chemical reaction between the formation of the film, resulting in an increase in the thickness of the battery or a decrease in the capacity formed by the reaction. Further, there is a problem of uniformity and an increase in resistance due to an increase in film thickness, which is a result of a decrease in life due to corrosion in a part of unevenness and a decrease in life due to an increase in resistance. Further, in a battery using an electrode having insufficient adhesion between the electrode layer and the current collector, there is a problem in that the electrode characteristics including the charge and discharge cycle characteristics are the first. In the related art, a modified polymer using a functional group such as a carboxyl group in a diene polymer is disclosed as a binder (see, for example, Patent Document 1). However, even with such a binder, the adhesion cannot be sufficiently improved, and the problem cannot be solved in the case of rapid charging or cycle characteristics. [PRIOR ART DOCUMENT] [Patent Document 1] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. 177-2012. The present invention has been made to solve such problems. The object of the invention is to provide a battery which is excellent in safety and has excellent cycle life characteristics. Further, it is to provide an assembled battery which can suppress an instantaneous temperature rise inside the battery while achieving high capacity and high output. (Means for Solving the Problem) In order to solve the above problems, it has been found that the above problem can be solved by providing an acrylic layer containing a specific metal element in the positive electrode, and thus the present invention has been completed. According to the present invention, there are provided a binder composition for an electrode, an electrode paste and an electrode used in the battery shown below. That is, a composition for an electrode for use in the battery, which comprises: a polymer material having an acrylic group bondable to a specific metal element, a specific metal element: and an electrode mixed with the electrode active material Use paint. A battery comprising an electrode formed by applying the electrode coating material to a current collector metal foil and drying the composition using the composition and the coating material. Advantageous Effects of Invention: The battery according to the present invention is a battery having a reduced capacity under rapid discharge and having a low 201205920 and excellent cycle characteristics, and can also suppress the increase in temperature and metal dendrite in the battery during rapid charging, and further, Even if the metal piece is clamped to force an internal short circuit, its temperature rise is small, and it becomes a safe lithium ion battery. [Embodiment] The following shows a preferred form of the invention. First, in the nail bonding test which is the pillar of the present invention, in the nailing or impact test, the heat generation temperature at the time of internal short-circuit may locally reach several hundred ° C depending on the test conditions, and if it is crystallinity If the crystal melting point is low, or even if it is amorphous, the decomposition initiation temperature is low, which is accompanied by deformation due to softening or sintering loss of the resin. Especially in the case of the positive electrode, the electricity is collected due to the collapse of the active material. The body is peeled off, causing a drastic excess current to flow and causing abnormal overheating. Therefore, at least one type of rubber-like polymer having an acrylic group which is non-crystalline and has high heat resistance and has rubber elasticity must be used as the binder in the electrode. A lithium ion secondary battery using the same as a bonding agent for an electrode is different from an electrode having a crystalline and hard film. When the separator is sandwiched between positive and negative electrodes to form a battery assembly, cracks or the like are not generated by the electrode. The loss is caused, so it has the advantage of maintaining high yield to produce. For the positive electrode, the active material may include lithium nickel manganese oxide, lithium manganate, lithium nickelate, lithium nickel cobalt manganese oxide, and the like (made of aluminum). A composite oxide such as a metal such as magnesium which is co-crystallized. Adhesive, modified acrylonitrile rubber particle binder (201205920, manufactured by Zeon Co., Ltd., Japan, etc.) and carboxymethyl cellulose (CMC)/soluble modified propylene with viscosity increasing effect Nitrile rubber (BM-720H, manufactured by Zeon Co., Ltd., Japan) is used as a base material. Conductive agent, acetylene black / ketjen black / various graphites may be used singly or in combination. As the negative electrode, various kinds of natural graphite, sand-based composite materials such as artificial graphite/sand, sand oxide-based materials, titanium alloy-based materials, and various alloy constituent materials can be used. The binder can be used for the purpose of improving the acceptability of lithium ions, and the SBR and its modified body can be used in the same manner as the positive electrode of the cellulose resin such as CMC, and it is preferably an acrylic resin. As the electrolyte, the salt may be selected from the group consisting of LiPF6, LiBF4, LiCl〇4, LiSbF6, LiAsF6, LiCF3S03, LiN(S02CF3)2, LiN(S02C2F5)2, LiC(S02CF3)3, LiN(S03CF3)2, LiC4F9S03, One or a mixture of two or more of LiA104, LiAlCl4, LiCl, Lil, LiBETI, and LiTFS is used. Further, the solvent may be used alone or in combination of ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), and methyl ethyl carbonate (MEC). In order to ensure the stability at the time of overcharge, a vinyl carbonate (VC), cyclohexylbenzene (CHB), propane sultone (PS), propylene sulfite (PRS), ethylene sulfite (E S ) or the like can also be used. The separator is not particularly limited as long as it can withstand the range of use of the lithium ion secondary battery, and generally, a microporous film of an olefin resin such as polyethylene/polypropylene can be used singly or in combination, and The preferred form. The thickness of the separator is not particularly limited, and it can be designed in a film thickness of a design amount of -9 - 201205920. That is, it is particularly preferably 6 μπι to 2 5 μιη. Further, the acrylic binder used in the positive electrode may contain the metal element shown in the present invention, whereby the following actions and effects can be obtained. In the environment where the positive electrode electrolyte is in contact with at least the acrylic layer, or in the environment in which the acrylic layer is coated with the active material, when the following metal element is present in the acrylic layer, the dissociation reaction and diffusion of lithium are known to increase. In the state where the metal element is not contained, the polymer used in the binder of the acrylic layer is an insulator, and the electric resistance thereof is high. If the active material cannot be coated to form a protective film (SEI), the active material and the active material are The interface between the electrolytes causes a chemical reaction, which causes problems such as gasification in the past. However, by containing such a metal element, the active material can be coated with an acrylic layer, and the problem that the active material reacts with the electrolytic solution can be eliminated. Further, the acrylic acid of the present invention has excellent voltage resistance, and when the metal element represented by the present invention is contained in the acrylic layer, the potential can be relaxed and lowered to the oxidation potential of the active material. However, since lithium can be moved without being buffered, a high-capacity, high-output ion transmission mechanism that realizes a high voltage specification can be obtained. A metal which can effectively obtain the effects of the present invention is preferably Mn, Ni, a metal halide (F, I, etc.), or an alkali metal (Na, K, Li) '
Ti等。此外、金屬之外，亦可列舉出含有鹵素者。 此外，由於擴散速度增快且電阻降低，所以亦可抑制 高輸出時的溫度上升，而提高壽命和安全性。 此外，亦發現到可藉由在電極上設置陶瓷層，提高正 極-負極間之鋰離子的移動速度，而能夠實現急速充電及 -10- 201205920 更高輸出。此外，亦可抑制內部短路而提升安全性。 在此，丙烯酸層較佳爲含有聚丙烯酸單位之橡膠性狀 高分子，如此更具效果。 電極上的陶瓷層爲Al2〇3與Zr02-P205，更可得到本效 果，故較佳。 再者，藉由使正極與負極之黏合劑高分子的分子量成 爲不同，係發現到除了可緩和電池內部應力外，更可控制 解離反應與脫溶劑和反應、溶劑和反應之均衡而控制離子 擴散，故可提升充放電效率。如此，亦可抑制熱化、熱產 生量，而能夠提升安全性、壽命。 尤其當使用碳（carbon )電極作爲負極時，碳，對於 鋰的接受存在有Li C6的關係，若無法將鋰的移動控制在大 約1/6的速度，則會產生鋰的枝狀結晶（相對於充電時鋰 的移動從正極高速移動至負極，鋰暫時成爲過剩（飽和） 狀態）。此控制在本發明之具有SEI功能之黏合劑系統中 ，可藉由改變黏合劑的分子量控制。 陶瓷層的膜厚d相對於正極膜厚a位於0.03a$ dS 0.3a 的範圍內時，最能夠獲得本效果，較0.03 a更薄時，內部 短路抑制效果會有所變動。較〇.3 a更厚時，由於電極之罐 內***量的減少或電極極間距離的擴大，會使電池容量降 低。 正極的膜厚較佳亦爲50μιη以上150μηι以下，較50μιη更 薄時，電池罐內的活性物質塡充量減少，難以得到期望容 量，導致容量降低，使容量性能上的變動極端地增大。較 -11 - 201205920 1 5 Ομιη更厚時，電阻增高，導致輸出特性降低，使輸出性 能的變動極端地增大。 分隔片的厚度較佳爲6μιη以上30μιη以下，較6μιη更薄 時，難以確保正極與負極間的絕緣性，使電池性能降低， 使用中可能會產生劣化而短路。較30μιη更厚時，電池內部 電阻增高，導致性能降低。 此外，正極材料，尤其若是含有錬及錳元素之系列時 ，更可顯現本發明之效果。 例如可確認有 LiMn204、LiMnP04、LiNixMny04、 LiFexMny04、LiXMnyTi(i y)O2、Li2MnSi04、Li2Mn03 ' LiNixCoyMnz02、LiNi02、LiNixCoyAlz02之系列。 [實施例] 本發明並不限定於下列例子。 此外，下列電池係構成爲在乾空氣環境下注入電解液 後，放置一定時間後以相當於0.1 C之電流進行約20分鐘的 預充電步驟，然後封口並完成電池後，進行在60°C的環境 下放置1曰的老化之步驟。 (比較例1 ) 以3/1/0.09的重量比率，將Sumitomo 3M股份有限公司 製的鎳錳鈷酸鋰BC-618、吳羽化學股份有限公司製的 PVDF#1320 (固形份12重量份的N·甲基吡咯啶酮（NMP)溶 液）、及乙炔黑，與NMP—同以雙臂式捏合機予以攪拌， -12- 201205920 而製作出正極膏》將該膏塗佈於13.3 μπι厚的鋁箔並乾燥， 壓延成總厚度爲155μιη後，裁切成特定大小而得正極電極 〇 另一方面，以100/2.5/1的重量比率，將人造石墨與曰 本Zeon股份有限公司製的苯乙烯-丁二烯共聚物橡膠粒子 黏結劑BM-400B (固形份40重量份）與CMC，與適量的水 一同以雙臂式捏合機予以攪拌，而製作出負極塗料。將該 塗料塗佈於1〇μιη厚的銅箔並乾燥，壓延成總厚度爲180μιη 後，裁切成特定大小而得負極電極。 以20μπι厚的聚丙烯微多孔薄膜作爲分隔片，將此等正 負極夾持該分隔片而層合構成，並切斷爲既定大小***於 電槽罐內，使用將LiPF6溶解1Μ於EC/DMC/MEC混合溶劑 之電解液，來製作出層合型鋰離子蓄電池。將此設爲比較 例1。 以下所示之金屬元素粉末對黏合劑之添加，爲了防止 氧化，係採用以溶液狀來添加經分散於NMP溶劑者之方法 (實施例1 ) 以固形份量比〇.〇4重量％，將60nm〜Ο.ίμιη粒徑的Μη ( 和光純藥工業股份有限公司製）添加於Sumitomo 3Μ股份 有限公司製的鎳錳鈷酸鋰BC-618、與聚丙烯酸系橡膠之曰 本Zeori股份有限公司製的BM-520B (固形份8重量份的N-甲基吡咯啶酮溶液）中，並以固形份比94/3/3的重量比率 -13- 201205920 將乙炔黑與NMP—同攪拌，而製作出與比較例1相同之電 池。 此外，此時於負極的黏合劑中，係採用相對於正極所 使用之丙烯酸黏合劑的單體分子量爲10倍者。 (實施例2 ) 實施例1中，將Μη取代爲同樣大小的Ni而構成電池。 (實施例3 ) 實施例1中，不添加Μη而在黏合劑中使氟氣起泡並封 閉，使用經摻雜者來構成電池。 (實施例4 ) 實施例1中，將Μη取代爲碘粉末而製作出電池。 (實施例5 ) 實施例4中，使用鈉粉末來取代碘粉末而製作出電池 (實施例6 ) 實施例5中，使用鉀粉末來取代鈉粉末而製作出電池 (實施例7 ) -14- 201205920 實施例6中 ，使用鋰粉末來取代鉀粉末而製作出電池 (實施例8 ) 實施例7中 ，使用鈦粉末來取代鋰粉末而製作出電池 (實施例9 ) 實施例8中 ，使用鋁粉末來取代鈦粉末而製作出電池 (實施例1 〇 ) 實施例9中 ，使用鋅粉末來取代鋁粉末而製作出電池 (實施例Π ) 實施例1中 ，更在黏合劑內使氟氣起泡，以使氟的比 率相對於含有Μη之黏合劑溶液成爲〇.〇〇3wt%而封閉，然 後以相對於該溶液使固形份重量比率成爲〇 . 〇 5 wt°/。之方式 混合鋁粉末來進行電池的製作。 (實施例1 2 ) 實施例11中，使用鋅粉末來取代鋁粉末而製作出電池 -15- 201205920 (實施例1 3 ) 實施例1中，將正極取代爲錳酸鋰之日本電工股份有 限公司製的type-A而構成電池。 (實施例1 4 ) 實施例13中，將正極取代爲鎳鈷酸鋰（戶田工業股份 有限公司製）而構成電池。 (實施例1 5 ) 實施例1中，以重量比96/4wt%，混合中位徑約0.3μπι 的α-Α1203與ΒΜ520Β黏合劑並塗佈形成於負極表面，而構 成在負極表面形成6μιη膜厚的陶瓷層之電池。 (實施例1 6 ) 實施例15中，將陶瓷層的膜厚形成爲正極膜厚的〇.〇3 倍之2.1μιη而構成電池。 (比較例2 ) 實施例15中，將陶瓷層的膜厚形成爲正極膜厚的〇.〇2 倍之1·4μηι而構成電池。 (實施例1 7 ) 實施例15中，將陶瓷層的膜厚形成爲正極膜厚的〇.3 -16- 201205920 倍之21μιη而構成電池。 (比較例3 ) 實施例15中，將陶瓷層的膜厚形成爲正極膜厚的〇.4 倍之28μιη而構成電池。 (實施例1 8 ) 實施例15中，以相對於α-Α1203爲5wt°/。的比率將Zr02-P2〇5添加於陶瓷層形成塗料中而構成電池。 (實施例1 9 ) 相對於實施例1之正極單面電極膜厚70.85 μιη，係形成 爲50μιη而構成電池。 (比較例4 ) 相對於實施例1之正極單面電極膜厚70.8 5 μιη，係形成 爲49μιη而構成電池》 (實施例20 ) 相對於實施例1之正極單面電極膜厚70.8 5 μιη，係形$ 爲150μιη而構成電池。 (比較例5 ) 相對於實施例1之正極單面電極膜厚70.8 5 μιη，係形成 201205920 爲151μιη而構成電池。 (實施例2 1 ) 實施例15中，將分隔片的膜厚20μηι變更爲6μιη，且爲 了確保正極與負極之絕緣性，將陶瓷層的膜厚形成爲2 2 μπι 而構成電池（未形成陶瓷層時爲絕緣不良）。 (比較例6 ) 將實施例21之分隔片變更爲5 μιη的膜厚者而構成電池 (實施例22 ) 實施例1中，將分隔片的膜厚20μηι變更爲30μιη而構成 電池。由於電池群的膜厚增加而難以***於電池罐內，所 以使用電池罐增厚爲1 . 5 5倍，且電解液量亦增加爲1 . 5 5倍 者而構成電池。 (比較例7 ) 將實施例22之分隔片的膜厚變更爲31μιη而構成電池。 (比較例8 ) 實施例1中，將負極的黏合劑採用爲與正極者相同（ 正負極均爲相同黏合齊！J (相同分子量））而構成電池。 藉由下列所示之方法來評估此等電池。第1圖爲彙總 -18- 201205920 顯示各實施例中的電池條件之表。第2圖爲彙總顯示各比 較例中的電池條件之表。第3圖爲彙總顯示各實施例及各 比較例中的評估結果之表。 (電池初期容量評估） 將比較例1的規格電位範圍3V-4.15V中之1C放電容量 設爲100，來進行各實施例的容量比較性能評估。此外， 電池形態’此次係使用方型電池罐並構成爲層合電池。 此外，容量評估亦在2.5V-4.6V的電位範圍內進行。 (釘刺安全性） 在常溫環境下以5mm/秒的速度將2.7mm直徑的鐵製圓 釘貫通充滿電的電池，並觀測此時的發熱狀態及外觀。 (過充電安全性） 將電流維持在充電率200%，經過15分鐘以上若未引起 外觀異常，則表示爲「OK」，若有變化（膨脹、破裂等 )，則表示爲「NG」。 (常溫壽命特性） 在將藉由實施例1~22及比較例1〜3所製造之電池設爲 規格電位範圍3V-4.15V的規格時，實施2000循環之在25°C 下以1C/4.15V進行充電後再以1C/3V進行放電，並且比較 相對於初次容量之容量的降低。 -19- 201205920 以下依序記載評估結果。 將多孔膜層接著形成於正負極上之實施例，可得知其 大幅地抑制釘刺後的過熱。將此等試驗後的電池分解並進 行調査時，可得知在全部電池中，分隔片廣範圍地熔融， 但在實施例中，多孔膜層仍保留其原先形狀》從該內容中 ，可考量爲當多孔膜層的耐熱性爲充分時，即使因釘刺後 所引起的短路而產生發熱，膜構造亦未被破壞，可抑制短 路場所的擴大而防止大幅的過熱。 在此，當多孔膜層接著形成於分隔片上時，可得知在 釘刺速度較慢時會引起過熱。將電池分解並進行調査時， 可確認到伴隨著前述分隔片的熔融，多孔膜層亦會變形。 該原因可視爲下列結果，亦即本發明之多孔膜層，其水平 方向的構造是由接著形成之基板（正負極及分隔片）所保 持，不論多孔膜層本身的耐熱性爲何，其不得不跟隨產生 收縮或熔融之基板（分隔片）的形狀變化而反映該變化之 結果。 接著詳述作爲內部短路的替代評估之釘刺試驗的特徵 與數據之解釋。釘刺所造成之過熱，從過去的試驗結果中 可說明如下。亦即，由於正負極的接觸（短路）而產生焦 耳熱，由於該熱的存在使耐熱性低的材料（分隔片）的熔 融擴大，而形成堅固的短路部。藉此使焦耳熱持續產生， 甚至到達正極的熱不安定區（160 °C以上）而導致過熱崩 潰。 在各種先例中，即使在未確認到過熱崩潰之規格中， -20- 201205920 在本次確認中乃觀察到一部分過熱的促進。 目前，鋰離子蓄電池的安全規格在各種用途中變得更 加嚴格下，藉由運用多孔膜層的耐熱性，不論釘刺速度（ 短路狀態）爲何均可抑制過熱崩潰之本發明，可說是已達 更具實用性之技術。 接著，關於多孔膜層的厚度可確認如下，當膜厚過小 時，耐熱性無法充分發揮而無法抑制過熱（比較例2)， 相反的，當膜厚過大時（較正極的0.3倍更大），罐*** 量縮小或是活性物質量減少，使得設計容量大幅降低，並 且導致高速率放電容量的降低（比較例3)。因此，可具 體實現本發明的效果之範圍，較佳者係多孔膜層的膜厚d 相對於正極膜厚&具有0.03£»$(1$0.33之關係。 此外，關於分隔片（聚乙烯微多孔薄膜）的厚度可確 認如下，厚度過薄時，伴隨著分隔片熔融的加速而無法抑 制過熱（比較例6 )，相反的，過厚時，捲取完成品的電 極板長度縮短，使得設計容量大幅降低，並且導致高速率 放電容量的降低（比較例7)。因此，可具體實現本發明 的效果之範圍，較佳者係分隔片的厚度爲6~3 0μιη之範圍內 〇 再者，關於多孔膜層中的黏結劑，必須至少使用1種 不易引起本身的燒結損失或熔融者，具體而言爲結晶熔點 及分解起始溫度爲220 °C以上者。作爲該具體例，較佳者 爲非結晶性且耐熱性高（3 2 0 °C )之含有聚丙烯腈單位之 橡膠性狀高分子。此黏結劑具有橡膠彈性，該性質對本實 -21 - 201205920 施例之鋰離子蓄電池而言，可發揮極佳的效果》 此外，藉由在陶瓷層中的塡充材添加Zr02-P205，可 提升速率性能，抑制電池內的發熱，安定地顯現高輸出性 能，並抑制熱劣化，而提升壽命特性。此外，當使用基本 上僅具有與分隔片的微多孔性薄膜相同程度的耐熱性之塡 充材時，可得知其無法發揮本發明之功能。因而考量塡充 材必須選擇無機氧化物。 產業上之可利用性： 本發明之鋰離子蓄電池，係有用於作爲具有較佳安全 性與壽命特性及高輸出特性之蓄電池電源。 【圖式簡單說明】 第1圖爲彙總顯示各實施例中的電池條件之表。 第2圖爲彙總顯示各比較例中的電池條件之表。 第3圖爲彙總顯示各實施例及各比較例中的評估結果 之表® -22-Ti et al. Further, in addition to the metal, those containing a halogen may also be mentioned. Further, since the diffusion speed is increased and the electric resistance is lowered, the temperature rise at the time of high output can be suppressed, and the life and safety can be improved. In addition, it has been found that by providing a ceramic layer on the electrode and increasing the moving speed of lithium ions between the positive electrode and the negative electrode, it is possible to achieve rapid charging and a higher output of -10-201205920. In addition, internal short circuits can be suppressed to improve safety. Here, the acrylic layer is preferably a rubbery polymer containing a polyacrylic acid unit, which is more effective. The ceramic layer on the electrode is Al2〇3 and Zr02-P205, and the present effect is obtained, which is preferable. Furthermore, by making the molecular weight of the binder polymer of the positive electrode and the negative electrode different, it is found that in addition to mitigating the internal stress of the battery, the dissociation reaction can be controlled to balance the solvent and reaction, the solvent and the reaction, and the ion diffusion can be controlled. Therefore, the charging and discharging efficiency can be improved. In this way, heat generation and heat generation can be suppressed, and safety and life can be improved. In particular, when a carbon electrode is used as the negative electrode, carbon has a relationship of Li C6 for the acceptance of lithium, and if the movement of lithium cannot be controlled at a rate of about 1/6, a dendrite of lithium is generated (relatively During the charging, the movement of lithium moves from the positive electrode to the negative electrode at a high speed, and the lithium temporarily becomes an excessive (saturated) state. This control can be controlled by changing the molecular weight of the binder in the SEI-functional adhesive system of the present invention. When the film thickness d of the ceramic layer is in the range of 0.03a$dS 0.3a with respect to the film thickness a of the positive electrode, the effect can be most obtained, and when it is thinner than 0.03 a, the effect of suppressing the internal short circuit changes. When it is thicker than .3 a, the battery capacity is lowered due to a decrease in the insertion amount of the electrode in the tank or an increase in the distance between the electrodes. The film thickness of the positive electrode is preferably 50 μm or more and 150 μm or less, and when it is thinner than 50 μm, the amount of active material in the battery can is reduced, and it is difficult to obtain a desired capacity, resulting in a decrease in capacity and an extremely large variation in capacity performance. -11 - 201205920 1 5 When Ομιη is thicker, the resistance is increased, resulting in a decrease in output characteristics and an extremely large increase in output performance. When the thickness of the separator is preferably 6 μm or more and 30 μm or less, and it is thinner than 6 μm, it is difficult to ensure insulation between the positive electrode and the negative electrode, and battery performance is lowered, which may cause deterioration and short circuit during use. When the thickness is thicker than 30 μm, the internal resistance of the battery is increased, resulting in a decrease in performance. Further, the positive electrode material, particularly if it contains a series of cerium and manganese elements, can further exhibit the effects of the present invention. For example, a series of LiMn204, LiMnP04, LiNixMny04, LiFexMny04, LiXMnyTi(i y)O2, Li2MnSi04, Li2Mn03 'LiNixCoyMnz02, LiNi02, LiNixCoyAlz02 can be confirmed. [Examples] The present invention is not limited to the following examples. In addition, the following battery system is configured to perform a pre-charging step of about 20 minutes after a certain period of time after injecting the electrolyte in a dry air environment, and then sealing and completing the battery, and then performing the charging at 60 ° C. Place 1 aging step in the environment. (Comparative Example 1) Lithium nickel manganese cobalt oxide BC-618 manufactured by Sumitomo 3M Co., Ltd., PVDF #1320 manufactured by Kureha Chemical Co., Ltd. (12 parts by weight of solid content) was added at a weight ratio of 3/1/0.09. N·methylpyrrolidone (NMP) solution, and acetylene black, and NMP—with a double-arm kneader, -12-201205920 to make a positive paste”, the paste is applied to 13.3 μπ thick The aluminum foil is dried and calendered to a total thickness of 155 μm, and then cut into a specific size to obtain a positive electrode. On the other hand, artificial graphite and styrene manufactured by Sakamoto Zeon Co., Ltd. are added at a weight ratio of 100/2.5/1. - Butadiene copolymer rubber particle binder BM-400B (solid content: 40 parts by weight) and CMC were stirred with a suitable amount of water by a two-arm kneader to prepare a negative electrode coating. This coating material was applied to a copper foil having a thickness of 1 μm and dried, rolled to a total thickness of 180 μm, and cut into a specific size to obtain a negative electrode. A polypropylene microporous film having a thickness of 20 μm was used as a separator, and the positive and negative electrodes were sandwiched between the positive and negative electrodes to be laminated, and cut into a predetermined size and inserted into a pot, and LiPF6 was dissolved in an EC/DMC. /MEC mixed solvent electrolyte to make a laminated lithium ion battery. This was set as Comparative Example 1. The addition of the metal element powder shown below to the binder, in order to prevent oxidation, is carried out by adding a solution dispersed in a NMP solvent (Example 1) in a solid form ratio of 〇.〇4% by weight, 60 nm. Ο ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί BM-520B (8 parts by weight of a solid solution of N-methylpyrrolidone) was stirred at a weight ratio of 94/3/3 to 13-201205920 to produce acetylene black and NMP. The same battery as in Comparative Example 1. Further, at this time, in the binder of the negative electrode, the molecular weight of the monomer of the acrylic adhesive used for the positive electrode was 10 times. (Example 2) In Example 1, a battery was formed by substituting Μn with Ni of the same size. (Example 3) In Example 1, a fluorine gas was bubbled and sealed in a binder without adding Μη, and a battery was formed using a dopant. (Example 4) In Example 1, a battery was produced by substituting Μn with iodine powder. (Example 5) In Example 4, a battery was produced by using sodium powder instead of iodine powder (Example 6). In Example 5, a battery was produced by using potassium powder instead of sodium powder (Example 7) -14- 201205920 In Example 6, a lithium battery was used instead of potassium powder to prepare a battery (Example 8). In Example 7, a battery was produced by using titanium powder instead of lithium powder (Example 9). In Example 8, aluminum was used. A battery was prepared by substituting a powder of titanium powder (Example 1 〇) In Example 9, a battery was produced by using zinc powder instead of aluminum powder (Example Π) In Example 1, the fluorine gas was further generated in the binder. Soaking, so that the ratio of fluorine is blocked with respect to the binder solution containing Μ 〇 3 wt%, and then the solid weight ratio with respect to the solution is 〇. 5 wt ° /. The method is to mix aluminum powder for battery production. (Example 1 2) In Example 11, a battery was produced by using zinc powder instead of aluminum powder. -15-201205920 (Example 13) In Example 1, Japan Electric Co., Ltd. was replaced with lithium manganese oxide by a positive electrode. The type-A system constitutes a battery. (Example 1 4) In Example 13, a positive electrode was replaced with lithium nickel cobaltate (manufactured by Toda Industries Co., Ltd.) to constitute a battery. (Example 1 5) In Example 1, a weight ratio of 96/4 wt% was mixed with α-Α1203 and ΒΜ520Β adhesive having a median diameter of about 0.3 μm and coated on the surface of the negative electrode to form a film of 6 μm on the surface of the negative electrode. A battery with a thick ceramic layer. (Example 1 6) In Example 15, the film thickness of the ceramic layer was set to 2.1 μm which is 3 times the thickness of the positive electrode film to constitute a battery. (Comparative Example 2) In the fifteenth embodiment, the thickness of the ceramic layer was formed into a battery of a positive electrode film thickness of ·2〇1·4μηι. (Example 1 7) In Example 15, the film thickness of the ceramic layer was set to 21 μm of 正极.3 -16 - 201205920 of the positive electrode film thickness to constitute a battery. (Comparative Example 3) In Example 15, the thickness of the ceramic layer was formed to be 28 μm of the positive electrode film thickness to constitute a battery. (Example 1 8) In Example 15, it was 5 wt% with respect to α-Α1203. The ratio of Zr02-P2〇5 is added to the ceramic layer forming coating to form a battery. (Example 1 9) The positive electrode single-sided electrode film of Example 1 was formed to have a thickness of 70.85 μm to form a battery. (Comparative Example 4) The positive electrode single-sided electrode film of Example 1 was 70.8 5 μm thick, and was formed into a battery of 49 μm to form a battery. (Example 20) The positive electrode single-sided electrode film of Example 1 was 70.8 5 μm thick. The line $ is 150 μm to form a battery. (Comparative Example 5) A battery was formed by forming a thickness of 70.8 5 μm with respect to the positive electrode single-sided electrode film of Example 1 to form 151 μm at 201205920. (Example 2 1) In Example 15, the film thickness 20 μm of the separator was changed to 6 μm, and in order to ensure the insulation between the positive electrode and the negative electrode, the thickness of the ceramic layer was set to 2 2 μm to form a battery (the ceramic was not formed). The layer is poorly insulated). (Comparative Example 6) A battery was formed by changing the separator of Example 21 to a film thickness of 5 μm (Example 22) In Example 1, the film thickness of the separator was changed to 30 μm to form a battery. Since the film thickness of the battery group is increased and it is difficult to insert it into the battery can, the battery can be thickened to 1.5 times and the amount of the electrolyte is increased to 1.5 times. (Comparative Example 7) A battery was formed by changing the film thickness of the separator of Example 22 to 31 μm. (Comparative Example 8) In Example 1, the binder of the negative electrode was used in the same manner as in the case of the positive electrode (both positive and negative electrodes were bonded in the same manner! J (same molecular weight)) to constitute a battery. These batteries were evaluated by the methods shown below. Fig. 1 is a table showing the battery conditions in the respective examples in the summary -18-201205920. Figure 2 is a table summarizing the battery conditions in each comparative example. Fig. 3 is a table summarizing the evaluation results in the respective examples and comparative examples. (Evaluation of Battery Initial Capacity) The capacity comparison performance evaluation of each example was performed by setting the 1 C discharge capacity of the specification potential range 3V - 4.15 V of Comparative Example 1 to 100. In addition, the battery form was used as a laminated battery. In addition, the capacity evaluation is also performed in the potential range of 2.5V-4.6V. (Snail safety) A 2.7 mm diameter iron nail was passed through a fully charged battery at a speed of 5 mm/sec under a normal temperature environment, and the heat generation state and appearance at this time were observed. (Overcharge safety) The current is maintained at 200% of the charge rate. If the appearance is abnormal for 15 minutes or longer, it is indicated as "OK". If there is a change (expansion, crack, etc.), it is indicated as "NG". (Normal Temperature Life Characteristics) When the batteries manufactured in Examples 1 to 22 and Comparative Examples 1 to 3 were set to the specifications of the potential range of 3 V to 4.15 V, 2000 cycles were performed at 25 ° C at 1 ° C / 4.15. After V is charged, discharge is performed at 1 C/3 V, and the decrease in capacity with respect to the initial capacity is compared. -19- 201205920 The results of the evaluation are recorded in the following order. The example in which the porous film layer was formed on the positive and negative electrodes was found to greatly suppress overheating after nailing. When the batteries after the tests were decomposed and investigated, it was found that the separator was widely melted in all the batteries, but in the examples, the porous film layer retained its original shape. From this content, it is considered When the heat resistance of the porous film layer is sufficient, even if heat is generated by a short circuit caused by nailing, the film structure is not broken, and the expansion of the short-circuited place can be suppressed to prevent a large overheating. Here, when the porous film layer is subsequently formed on the separator, it is known that overheating is caused when the nailing speed is slow. When the battery was decomposed and investigated, it was confirmed that the porous film layer was also deformed accompanying the melting of the separator. This reason can be regarded as the following result, that is, the porous film layer of the present invention, whose horizontal structure is held by the subsequently formed substrate (positive and negative electrode and separator), regardless of the heat resistance of the porous film layer itself, The result of the change is reflected by the shape change of the substrate (separator) which causes shrinkage or melting. Next, the characteristics and data interpretation of the nail test as an alternative evaluation of the internal short circuit will be detailed. The overheating caused by nail penetration can be explained from the past test results. That is, the Joule heat is generated due to the contact (short circuit) between the positive and negative electrodes, and the heat of the material (separator) having a low heat resistance is expanded by the presence of the heat to form a strong short-circuit portion. Thereby, the Joule heat is continuously generated, even reaching the thermal unstable zone (above 160 °C) of the positive electrode, resulting in overheat collapse. In various precedents, even in the specification that the overheat collapse was not confirmed, -20-201205920 observed a part of the overheating promotion in this confirmation. At present, the safety specifications of lithium ion batteries have become more stringent in various applications. By utilizing the heat resistance of the porous film layer, the present invention can suppress the collapse of overheating regardless of the nailing speed (short circuit state), and it can be said that A more practical technology. Next, the thickness of the porous film layer was confirmed as follows. When the film thickness was too small, heat resistance could not be sufficiently exhibited, and overheating could not be suppressed (Comparative Example 2). Conversely, when the film thickness was too large (greater than 0.3 times of the positive electrode) The reduction in the amount of can insertion or the decrease in the mass of the active material greatly reduced the design capacity and resulted in a decrease in the high rate discharge capacity (Comparative Example 3). Therefore, the range of effects of the present invention can be specifically achieved, and it is preferable that the film thickness d of the porous film layer has a relationship of 0.03 £»$ (1$0.33) with respect to the film thickness of the positive electrode. Further, regarding the separator (polyethylene micro The thickness of the porous film was confirmed as follows. When the thickness was too thin, overheating could not be suppressed with the acceleration of the melting of the separator (Comparative Example 6). Conversely, when the thickness was too thick, the length of the electrode plate of the finished product was shortened, resulting in design. The capacity is greatly reduced, and the high rate discharge capacity is lowered (Comparative Example 7). Therefore, the range of effects of the present invention can be specifically achieved, and it is preferable that the thickness of the separator is in the range of 6 to 30 μm. Regarding the binder in the porous film layer, it is necessary to use at least one type of sintering loss or melting which is not likely to cause itself, and specifically, the crystal melting point and the decomposition initiation temperature are 220 ° C or more. It is a rubber-like polymer containing polyacrylonitrile units which is non-crystalline and has high heat resistance (30 ° C). The binder has rubber elasticity, and this property is related to the lithium ion of the embodiment of the present invention. In addition, Zr02-P205 can be used to increase the rate performance, suppress the heat generation in the battery, stabilize the high output performance, and suppress the heat. It is deteriorated to improve the life characteristics. Further, when a crucible having substantially the same heat resistance as that of the microporous film of the separator is used, it is known that the function of the present invention cannot be exerted. Industrial oxides must be selected. Industrial Applicability: The lithium ion secondary battery of the present invention is used as a battery power source having better safety and life characteristics and high output characteristics. [Simplified Schematic] FIG. A table showing the battery conditions in each of the examples is collectively shown in Fig. 2. Fig. 2 is a table summarizing the battery conditions in the respective comparative examples. Fig. 3 is a table summarizing the evaluation results in the respective examples and comparative examples. -