201145660 六、發明說明： 【發明所屬之技術領域】 本發明係關於非水溶媒二次電池的負極集電體用銅箔 與其裝k方法。更詳而言之，本發明係關於使用作為鋰 離子一次電池的負極集電體的情況時，與該電池的負極活 性物質的黏著性優異，且可提升充放電特性之銅落與該銅 箔的製造方法。 、再者’本發明關於非水溶媒二次電池負極電極的製造 方法β特別是關於與m負極活性物質的黏著性優異， 且可提升充放電特性的負極電極的製造方法。 L无珂技術】 使用非水電解液之-呤雪 人電池業經使用作為各種電、電 千機益的驅動電源。使用非 之用非水電解液之二次電池（後文，稱 ::容媒二次電池)，已知具備電動勢(― :電:M’且能量密度也高的特徵，其代表例為u離子二 L i離子二次電池，係經由 _ t '止極與負極之間設置且備 電，··邑緣性與保液性之間隔件 、 ^ # „ε , ^ 成之電極群，於兼具負極端 子的電池瓶中與預定量的非 瓶的開口部係以具備正極端子^液一起收納’前述電池 以密閉所成構造。料的封口板經由絕緣性塾片予 在此，正極係如下所述方式製造。 首先’將作為正極活性物暂 物質，例如LiCo〇2粉末，與碳 201145660 導電劑、多氟化乙烯等之黏著劑， W 甲基。比洛哈酿|耸夕 非水溶媒混練而調製規定組成的正極漿體。 其次，將該聚體之規定量，塗布：正極 的兩面，乾燥之後壓製成形，作為 之、 /6 %疋厚度之正極片，於 該正極片之規定位置附裝導線架而作為正極。 、 另外，已知於負極的製造中係 τ係使用水溶液系漿體的情 況與使用溶劑系漿體的情況。 製造水溶液系漿體的情況’首 , 百先，製作羧曱基纖維素 (CMC)的水溶液’於該水溶液中 .A T成13石墨粉末或非晶形碳粉 末，追加苯乙稀丁二稀橡膠(SBR)，調製負極聚體。 製造溶劑系毁體的情況，於溶劑之N_甲基心各炫嗣 中，混合石墨粉末或非晶形碳粉末，追加作為點著劑之之 聚氟化偏乙烯，調製負極漿體。 其次，將規定量的任一製體塗布於負極集電體的銅羯 兩面，乾料壓製成形為規定厚度的負㈣，於其規定位 置附裝導線架而作為負極。 負極漿體如上述方式，雖有水作為溶媒的負極毁體與 有機溶劑作為溶媒的負極聚體的二種類，但近來由環境問 題、防爆性的觀點’以水作為溶媒的負極製體的使用逐漸 成為主流。 此處，作為負極的集電體，一般而言採用銅箔係如下 述的理由。 由於銅箔導電性優異，且其機械強度亦高，故製造時 的操作容易。 201145660[Technical Field] The present invention relates to a copper foil for a negative electrode current collector of a nonaqueous solvent secondary battery and a method for mounting the same. More specifically, the present invention relates to a case where a negative electrode current collector as a lithium ion primary battery is used, and the adhesion to the negative electrode active material of the battery is excellent, and the copper drop and the copper foil which can improve the charge and discharge characteristics are obtained. Manufacturing method. Further, the method for producing a negative electrode for a nonaqueous solvent secondary battery of the present invention is a method for producing a negative electrode which is excellent in adhesion to an m negative electrode active material and which can improve charge and discharge characteristics. L flawless technology] The non-aqueous electrolyte is used. The battery is used as a driving power source for various electric and electric machines. A secondary battery using a non-aqueous electrolyte (hereinafter, referred to as: a secondary secondary battery) is known to have an electromotive force (-: electricity: M' and a high energy density, and a representative example thereof is u. The ion-ion Li-ion secondary battery is formed by _t' between the terminal and the negative electrode, and is provided with a separator, a separator of the rim property and the liquid retention property, and an electrode group of ^ # ε, ^ In the battery bottle having the negative electrode terminal, the opening portion of the predetermined amount of the non-bottle is housed with the positive electrode terminal liquid, and the battery is sealed. The sealing plate of the material is provided here via the insulating sheet. It is manufactured as follows. First, 'will be used as a positive electrode active material, for example, LiCo〇2 powder, with carbon 201145660 conductive agent, polyfluorinated ethylene, etc., W methyl. Biloha brewing | The solvent is kneaded to prepare a positive electrode slurry having a predetermined composition. Next, a predetermined amount of the polymer is applied to both surfaces of the positive electrode, dried, and then press-formed, and a positive electrode sheet having a thickness of /6 % is used for the positive electrode sheet. The lead frame is attached to the position as a positive electrode. It is known that in the production of a negative electrode, a case where an aqueous solution is used as a slurry and a case where a solvent-based slurry is used. In the case of producing an aqueous slurry, the first solution is to prepare an aqueous solution of carboxymethyl cellulose (CMC). 'In this aqueous solution, AT is 13 graphite powder or amorphous carbon powder, and styrene butadiene rubber (SBR) is added to prepare a negative electrode polymer. In the case where the solvent is destroyed, the solvent is N-methyl. In each of the hearts, a graphite powder or an amorphous carbon powder is mixed, and a polyfluorinated vinyl group as a dot additive is added to prepare a negative electrode slurry. Next, a predetermined amount of any body is applied to the negative electrode current collector. On both sides of the copper plaque, the dry material is press-formed into a negative (four) of a predetermined thickness, and a lead frame is attached at a predetermined position as a negative electrode. The negative electrode slurry has the negative electrode of water as a solvent and the organic solvent as a solvent as described above. There are two types of negative electrode aggregates, but recently, the use of a negative electrode body using water as a solvent has gradually become the mainstream from the viewpoint of environmental problems and explosion-proof properties. Here, as the current collector of the negative electrode, copper foil is generally used as follows.Reasons for the description Since the copper foil is excellent in electrical conductivity and high in mechanical strength, it is easy to handle at the time of manufacture.
Ll離子之間不生成 再者’具有充放電的過程中進出的 合金的性質。 此汁，銅箔可低成本 J馬電池的大量 生產所必需的寬銅箔，故可容易地製造 因此，對於Li離子二次電池所代表 池，近來更強烈地對於更高能量密度化與充放電 的長期化的期冑，而對應料的研究正進行中。2 = 向中’關於使用銅箱作為負極集電體時的電池特性了 ： 有下述各點的指摘。 來 由於二次電池的最重要特性之充放電循環壽命 Γ電池容量’已知受到負極集電體之鋼箱表面狀態(例如 表面粗糙度、表面皮膜的種類等)的左右。亦即，已知根據 銅羯表面狀態而有設置於該㈣表面的負極活性物質 著性的問題。 作為負極集電體的銅箔為電解銅箔與壓延銅箔。 電解銅箔係於回轉的鈦滾筒（titanium drum)上藉由 銅硫馱作為主成分之電鍍液進行銅電鍍，將該鍍銅拉 剝成為箔狀的銅經由連續地捲取而製造。 相對於此，壓延銅箔係熔解銅而鑄造錠塊（ingot)，進 y于…、乳’之後重複進行冷軋（cold roll)、製程退火 bmeess annealing) ’進行最終冷軋而製造銅箔。 製羯後的銅箔’其表面係施行例如笨并三唑皮膜或鉻 酉文鹽皮膜等作為防鏽處理（參照專利文獻1及2)。 電池的負極製造時，覆蓋有防鏽皮膜的銅箔作為負極 201145660 集電體而供給至塗布負極活性物質之負極漿體塗布線，於 其表面塗布負極漿體。根據該防鏽皮膜的種類或生成方法 而與負極活性物質的黏著性不同，黏著性越佳者，重複充 放電循環後的容量降低有越小的傾向。 用於提高負極集電體之銅箔與負 有如專利文獻1及2 的表面處理 皮膜或鉻酸鹽皮膜。再者， 系負極漿體的沾濕性之處理 皮膜（參照專利文獻3)。 極活性物質的黏著性 所揭示方式之苯并三唑 已有提案作為提高銅箔與溶劑 之含有具羰基之噁唑化合物之 【先前專利文獻】 【專利文獻】 【專利文獻丨】曰本特開平1 1-273683號公報 【專利文獻2】日本特開2008-226800號公報 【專利文獻3】日本特開2〇〇8_251 469號公報 【發明内容】 【發明欲解決之課題】 jl rr\ 只川H、j氷瓶1乐便用水 作為溶媒。水作為溶媒之負極活性物質係以專利文獻丄所 揭示之皮膜的種類及皮膜厚度而銅箱與負極活性物質的黏 著性難謂充分，而在mi表面的耐防鏽性方面亦有問題。 再者，專利文獻3所揭示之皮膜，於塗布以有機㈣ 作為溶媒之負極Μ時，鋼落與負極㈣的沾㈣雖然良 好’但沾濕性良好的銅羯與負極活性物質的黏著性不必然 145660 為一致的 分者。 對於銅落與負極活 性物質的黏著性難謂 其為 充 因此’期望作為非水溶姐_ 4 箔睥，、—-人電池的負極用而使用銅 /白時，解決電池的充 電循h命與充電初期❸電池容量 又到銅、治的表面狀態左右的 象可保持優異的充放電循 衣/、间的電池容量的非水，玄# /媒—二人電池負極集電體用銅箔 與其製造方法。 【用於解決課題之手段】 ，本發明之非水溶媒二次電池負極集電體用銅猪，其特 徵係於該銅箱的表面形成有機化合物皮媒，且該銅笛的至 少-面的電雙層電容的倒數（1/0為G. 3pG. w/ # F。 前述有機化合物皮膜較佳為含有三唑化合物之皮膜， 成3有一嗤化合物及胺化合物之皮膜。 本發明之非水溶媒二次電池負極集電體用銅羯的製造 方法’其特徵係使銅箔表面與包含有機化合物的溶液接 觸，於銅猪的至少一面形成電雙層電容的倒數（1/0為 〇. 31 〜〇. 9cm2/ // F 的皮膜。 前述有機化合物皮膜較佳為含有三唑化合物之皮膜， 或含有三唾化合物及胺化合物之皮膜。 本發明之非水溶媒二次電池負極電極的製造方法，其 特徵係於銅箔的至少一面形成電雙層電容的倒數（1/c)為 〇. 3卜0. 9cm2/ μ F的有機化合物皮膜的鋼箱表面，塗布水作 為溶媒之負極活性物質漿體，使其乾燥。 【發明效果】 201145660 本發明之作為非水溶媒二次電池的負極用的銅箱，與 負極活性物質的黏著性優異，具有可保持非水溶媒二 池的充放電循環壽命與高的電池容量的優異效果。 =本發明之非水溶媒二次電池負極集電體用㈣ 製法’係可容易地提供可優異地保持非水溶媒二土 電池的充放電循環及高的電池容量的優異的非水溶媒二： 電池的負極用銅箔的優異的製造方法。 進-步地，根據本發明之非水溶媒二次電池負極電極 的製造方法’料與負極活性物質_著性優異， 充放電特性提升的負極電極。 八 【實施方式] 本發明者們係於銅落表面上形成一定厚度的有機化合 物皮膜’進行與負極活性物f的”性提高的^離子二次 電池的負極集電體用銅箔的開發。 近年來，例如作為電動車用之電池而開發之u 二 次電池等，更期望性能提升。 於1^離子二次電池等更為提升性能方面，上述有機化 ^物皮膜的厚度成為提高負極活性物質的㈣性對於銅 箔表面的耐鞋性為重要因素。 專利文獻1所揭示之介電體層的厚度表示電雙層電容 的倒數U/O為G.H.W/W，由於有機化合物皮膜的厚 度薄而使提高銅羯與負極活性物質的黏著性的效果不充 份’且關於銅落的防鏽亦不充份。特別是將水作為溶媒之 201145660 作為，體之負極活性物質塗布於㈣表面的製法中 的黏者性、銅_表面的耐#性皆不充份。 因此’本發明者研究關於比專利文獻i所揭示 體層的厚度更後的介電體層為皮膜 ： 皙玷办益& ，曰興負極活性物 、著性、銅箔表面的财钱性的έ士果，媒，θ 士时二 果獲得結論為具有 皮膜的1/C值為〇 31〜〇 9cm2/ " F的如# 把、 .9cm / /z F的銅箔，提升銅箔與負 活性物質間的黏著性’亦提升銅箱的耐飯性。 、 又，有機化合物皮膜的厚度’係以市售之直接檢測式 又s電谷測定儀測定同鉑表面的電雙層電容 (capacitance，C:以 F) , w m, 以式（1)所不方式，算出其倒數 值（1/C)。 l/C = A*d + B · · . *(1) 惟’ d為形成於銅箔表面之電雙層的厚度，A、b為定數。The properties of the alloy that enters and exits during the charging and discharging process are not generated between the L1 ions. This juice, copper foil can be easily produced in a large-volume copper foil which is required for mass production of a low-cost J-horse battery. Therefore, for a pool represented by a Li-ion secondary battery, more recently, for higher energy density and charge The period of long-term discharge is expected, and research on the corresponding materials is underway. 2 = "In the middle" regarding the battery characteristics when using a copper box as a negative current collector: There are indications of the following points. The charge/discharge cycle life of the most important characteristics of the secondary battery Γ the battery capacity is known to be affected by the surface condition of the steel box of the negative electrode current collector (for example, the surface roughness, the type of the surface film, and the like). That is, it is known that there is a problem that the negative electrode active material is provided on the surface of the (four) depending on the surface state of the matte. The copper foil as the negative electrode current collector is an electrolytic copper foil and a rolled copper foil. The electrolytic copper foil is subjected to copper plating on a rotating titanium drum by a plating solution containing copper sulphide as a main component, and the copper which is stripped into a foil shape is continuously wound up. On the other hand, in the rolled copper foil, copper is melted and an ingot is cast, and after the milk is pressed, cold rolling (cold roll, process annealing) is repeated to perform final cold rolling to produce a copper foil. The surface of the copper foil after the tamping is subjected to, for example, a ruthenium-triazole film or a chrome-based salt film as a rust-preventing treatment (see Patent Documents 1 and 2). In the production of the negative electrode of the battery, the copper foil covered with the anti-rust film is supplied as a negative electrode 201145660 current collector to the negative electrode slurry coating line to which the negative electrode active material is applied, and the negative electrode slurry is applied to the surface. Depending on the type or method of formation of the anticorrosive film, the adhesion to the negative electrode active material is different, and the better the adhesion, the smaller the capacity reduction after repeating the charge and discharge cycle. A copper foil for improving the anode current collector and a surface treatment film or a chromate film of Patent Documents 1 and 2 are used. In addition, the film of the wetness of the negative electrode slurry is treated (see Patent Document 3). A benzotriazole having a carbonyl group-containing compound in a copper foil and a solvent has been proposed as a method for improving the adhesion of a polar active material. [Patent Literature] [Patent Document] 曰本特开平[Patent Document 2] Japanese Patent Laid-Open Publication No. 2008-226800 (Patent Document 3) Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. H, j ice bottle 1 will use water as a solvent. The negative electrode active material of water as a solvent is difficult to adhere to the copper case and the negative electrode active material by the type of the film disclosed in the patent document and the film thickness, and there is a problem in the rust resistance of the mi surface. Further, in the film disclosed in Patent Document 3, when the negative electrode of the organic (four) solvent is applied, the adhesion between the steel falling and the negative electrode (four) is good, but the adhesion of the copper ruthenium having good wettability to the negative electrode active material is not good. Inevitably 145,660 is a consistent score. It is difficult to say that the adhesion between the copper drop and the negative electrode active material is such that it is expected to be used as a non-water-soluble sister _ 4 foil 睥, and the use of copper/white for the negative electrode of the human battery, thereby solving the charging behavior of the battery. At the beginning of charging, the battery capacity is up to the surface of the copper and the surface of the treatment, and the battery can maintain excellent charge and discharge, and the battery capacity of the non-water, Xuan #/media-two-cell battery negative electrode collector copper foil and Production method. [Means for Solving the Problem] The copper pig for a non-aqueous solvent secondary battery negative electrode current collector of the present invention is characterized in that an organic compound skin medium is formed on the surface of the copper box, and at least the surface of the copper flute is The reciprocal of the electric double layer capacitor (1/0 is G.3pG.w/#F. The organic compound film is preferably a film containing a triazole compound, and has a film of a ruthenium compound and an amine compound. The method for producing a copper crucible for a secondary battery of a negative electrode current collector is characterized in that the surface of the copper foil is brought into contact with a solution containing an organic compound, and the reciprocal of the electric double layer capacitance is formed on at least one side of the copper pig (1/0 is 〇. 31. The film of the organic compound film is preferably a film containing a triazole compound or a film containing a trisal compound and an amine compound. The nonaqueous solvent secondary battery negative electrode of the present invention is produced. The method is characterized in that the reciprocal (1/c) of the electric double layer capacitance is formed on at least one side of the copper foil to be the surface of the steel box of the organic compound film of 〇3. 0cm 2 / μ F, and the coating liquid is used as the negative electrode activity of the solvent. Material slurry, [Effect of the invention] 201145660 The copper box for the negative electrode of the nonaqueous solvent secondary battery of the present invention is excellent in adhesion to the negative electrode active material, and has a high charge/discharge cycle life and a high retention of the nonaqueous solvent. Excellent effect of the battery capacity. The method for the non-aqueous solvent secondary battery negative electrode current collector of the present invention can easily provide excellent charge and discharge cycles and high battery capacity of the nonaqueous solvent-containing two-earth battery. Non-aqueous solvent 2: an excellent method for producing a copper foil for a negative electrode of a battery. Further, the method for producing a negative electrode for a non-aqueous solvent secondary battery according to the present invention is excellent in the material and the negative electrode active material. In the present invention, the present inventors have formed a negative electrode current collector of an organic compound film having a certain thickness on the surface of the copper drop to improve the positive electrode active material f. Development of a copper foil for use in the body. In recent years, for example, a secondary battery developed as a battery for electric vehicles is expected to have improved performance. In terms of improving the performance of the cell, etc., the thickness of the above-mentioned organic film is an important factor for improving the (four) property of the negative electrode active material on the surface of the copper foil. The thickness of the dielectric layer disclosed in Patent Document 1 indicates the electric double. The reciprocal U/O of the layer capacitance is GHW/W, and the effect of improving the adhesion between the copper ruthenium and the negative electrode active material is not sufficient due to the thin thickness of the organic compound film, and the rust prevention of the copper drop is not sufficient. In the method of applying the water as a solvent to the 201145660, the negative electrode active material applied to the surface of the (4) surface is not sufficient for the adhesion and the copper-surface resistance. Therefore, the inventors studied the patent document i. The thickness of the dielectric layer revealing the thickness of the body layer is the film: 皙玷 益 & & 、, 曰 负极 负极 负极 活性 活性 负极 负极 负极 负极 负极 负极 负极 负极 负极 负极 负极 负极 负极 负极 负极 负极 负极 负极 负极 负极 负极 负极 负极 负极 负极 负极 负极 负极 负极 负极 负极 负极 负极In order to have a film with a 1/C value of 〇31~〇9cm2/ " F such as #把, .9cm / /z F copper foil, enhance the adhesion between the copper foil and the negative active material' also enhances the copper box Resistance to rice. Further, the thickness of the organic compound film is measured by a direct detection type and a sigmatometer of a commercially available platinum electric double layer capacitor (capacitance, C: F), wm, which is not in the formula (1). In the way, calculate the reciprocal value (1/C). l/C = A*d + B · · . *(1) Only 'd is the thickness of the electric double layer formed on the surface of the copper foil, and A and b are constant numbers.
本發明實施態樣的銅羯，1/C值係設定於 〇. 3卜0. 9cm2/ // F的範圍。形成1/c值測量為比〇. 3icm2/以F 更小值時之有機皮膜層的銅落時，與活性物質的黏著性變 低，耐蝕性也有變差的傾向。而1/c值為比〇.9cmV"F更 大的銅箔，即便提高為其以上（皮膜更厚），黏著性飽和而 無改善效果。 首先’說明本發明實施態樣的銅羯。 用於製造銅箔的材料，可為電解銅箔、壓延銅箔之任 一種。電解銅箔的情況中，由於可低成本的製箔寬者，適 合於提尚生產性之大量生產為必要之例如作為電動車用電 201145660 池的負極集電體使用。 再者，本發明實 爪_，規定的1〇點;…’以 α T 〇 tl· -V ^ 勺粗‘度（Rz)較佳為 2. m 以下。此方式之鋼箔可以 μ 古膜，日立*且均—的厚度形成有機化合物 皮膜’且其上所载持的負極活 活性物質的黏著性優異 = 升與負極 、的電池的充放電循環壽命特性與充 電初期的電池容量。 興 由於銅羯的厚度越薄作 溥作為全體的電極面積就越大，且 表面粗糙度可變小，對於高 门把篁在度化或充放電循環壽命 特性為有利的。例如，摁 揭▼用的電性、電子機器用的小型 電池，或電動車用算的士】 1電池的情況中，銅箔的厚度較 佳為2 0以m以下。 …'而銅泊的厚度過薄時，由於其機械強度降低，且 針孔等亦變多，作為實際使用上可耐受的㈣厚度的下限 為6以m左右》 依此方式，較佳的銅箔厚度為20〜6以m。 於該銅落表面所形成之有機化合物皮m，為含有三嗤 化合物的皮膜。或者為含有三唑化合物及胺化合物的皮膜。 二唑化合物，或三唑化合物及胺化合物，藉由溶解於 水或有機溶劑，保持一定的溶液溫度，將銅箔浸潰一定時 間’之後將其乾燥，使銅箔表面形成有機化合物皮膜。 二。坐化合物溶液的濃度’或三唑化合物及胺化合物溶 液的濃度宜為10〜1〇, 000ppm。 低於1 Oppm時’可保持與負極活性物質的黏著性程度 10 201145660 的有機化合物皮膜厚度不万， 而超過l〇,〇〇〇ppm時有機化 合物皮膜厚度飽和，亦盔法如 、 …、法期待黏著性提升的效果。 進一步較佳為50〜5, 〇〇〇ppm。 再者，溶液的溫度雖可為 π i皿’根據需要亦可加溫使 用。 三嗤化合物中進-步添加胺化合物之溶液塗布於㈣ 二，㈣化合物單獨的情況相&，銅箱與負極活性物質 的黏者f生更佳良好的同時，翻炫& 1 __ 銅泊的耐蝕性亦提升而更較佳。 三吐化合物與胺化合物的 初的6周配比例，以重量計，對於 三唑化合物，胺化合物為 . . 2倍為有效。添加2倍以 上胺化合物也已經無法期 ^ π _ U黏者性、耐㈣的提升，而低 於0. 5倍時，黏著性、 j蚀改的效果無法表現。 於溶液之銅箔的浸潰時間， 一 』根據二β坐化合物、二 唑化合物及胺化合物的溶 一 么物皮膜的厘^ 解，晨度、洛液溫度或形成有機化 口物皮膜的厚度的關係 n c qn ^ 、且决疋，一般而言，只要為 (J.5〜<30秒左右即可。 作為二唑化合物，可列一 « ^ ^ ^ 本开二唑、甲苯基三唑、羧 基本开二唑、虱笨并三 異去^. 乙基本开三唑、萘并三唑等。 再者’作為胺化合物’可為 梡某脸、SPA 平況基胺、二烧基胺、三 烷基胺早％烷基胺、二環烷基胺等單脸# 美敢捭夕-的丄 敗寺早胺類，經卜4個烧 基取代之一胺類，烷基之至 Μ Μ 個為具有羥基或環氧乙烷 基4親水性基的烷基單胺 舉單乙胺等。其等之中，可列 舉早乙醇胺、二乙醇胺、三乙醇胺、二 基乙醇胺、罝田甘 甲基乙醇胺、一乙 签呼胺早曱基乙醇胺、 基乙醇胺、單丁基乙醇胺 201145660 等。 該有機化合物皮膜 难市成於銅箔的兩面， 但依電池的製造步驟、作為負極的形態或與使用目地的關 係，亦可只為單面。然而，通常的_子二次電池的正極、 負極的情況中，由於任一者皆成為於各集電體的兩面載持 有活性物質的構造，以具有於㈣的兩面於上述方式 有機皮膜層為較佳。 根據本發明實施態樣之用於非水溶媒二次電池的負極 及電體用銅箔，係如第丨圖所示製程製造。 步驟1:你丨如製造/準備厚度6，“，表面粗糙度 (Rz)2. 5 μ m以下的銅羯。 步驟2:冑銅羯浸潰於含有有機化合物的水溶液 其與水溶液接觸。 步驟3:使其乾燥。 如以上所述’形成1/Cm0 9為F的 電體用mg。ϋ由於該負極集電體用銅箱實施下述處理了 形成非水溶媒二次電池用負極電極。 步驟4:塗布負極活性物質漿體。 步驟5:使其乾燥。 以下，根據本發明實施態樣，說明實施例。 【實施例】 70〜130 g/1 [銅箔的製造：步驟1 J 電解液 銅： 201145660 硫酸： 80〜140 g/i 添加劑： 3-疏基1 —丙烧績酸鈉=1〜1 Oppm 羥基乙基纖維素=l~100ppm 低分子量膠（分子量3,000) = 1〜50ppm 氣化物離子濃度=10〜50ppm 溫度： 5 0〜6 〇度 使用該電解液，陽極為貴金屬氧化物被覆鈦電極，陰 極係使用鈦製回轉滾筒，以電流密度=5(M〇〇A/dm2製造 厚度6〜20#m、兩面的表面粗糙度（Rz)為2.5//in以下的電 解銅箔。 [被膜形成用有機化合物] 1 .—唑化合物（作為其中之一種的BTA) 2.—唑化合物（作為其中之一種的ΒΤΑ) +胺化合物（作為 其中之一種的TEA) BTA :苯并三。坐 單乙醇胺鹽 TEA :三乙醇胺 四唑：1H-四唾 [鉻酸鹽處理] 之後、v 1經洛解於水溶液中，將銅箔浸潰（步 之後進行乾燥（步驟3)。 於上述鋼箔，以# 合物、、 所示條件塗布被膜形成用有機 13 201145660 【表1】 种哼平i用有機化合物的与布條立 編號 BTA 濃度（ppm) TEA 濃度（ppm) 液溫 浸潰時間 1 带施例1 50 一_ 0 50°C 10秒 2 奢施例2 250 _ 〇 5〇°C 10秒 3 赍施例3 500 0 50°c 10秒 4 實施例4 500 0 20°c 10秒 5 f施例5 1000 〇 5〇°C 10秒 6 f施例6 2000 0 5〇°c 10秒 7 f施例7 50 60 5〇°c 10秒 8 f施例8 250 300 50°C 10秒 9 f施例9 500 600 50°C 10秒 10 f施例10 500 600 2〇°c 10秒 11 f施例11 1000 1200 50°C 10秒 12 實施例12 2000 2400 5〇°c 10秒 【表 2】 編號 四0坐濃度（ppm) TEA 濃度（ppm) ---- 液溫 浸潰時間 13 比較例1 500 600 50°C 10秒 【表3】 編號 鉻酸鹽濃度（ppm) 液溫 ----^ 浸潰時間 14 比較例2 1000 20°C 10秒 於所作成之14種類的電極上，塗覆下述活性物質（步 驟4 )，進行黏著性的評估。 [負極活性物質層的製作] 首先，使用PRIMIX製造之均質機’藉由使致甲基纖維 素（CMC) [DAICEL化學工業製造之#1380)溶解於去離子水， 可得濃度1. 0質量％的CMC水溶液。 14 201145660 其次，科量該CMC水溶液loo〇g，以及人造石墨（爭均 粒徑21"m，表面積4.0 m2/g)980g，使用PRIMIX製造之 均質機混合後，追加笨乙烯丁二烯橡膠（SBR)(固形分濃度 50質量°/〇)20g’調製負極漿體。 又’人造石墨、CMC與SBR的質量比為人造石 墨：CMC:SBR = 98. 0:1.〇:1. 〇 。 上述負極名體’使用逆塗（1_6代1^6〇〇3^(：)方式，由兩面 經塗布有機化合物的銅箔所成之負極集電體的兩面予以塗 覆，進一步經由乾燥、壓延（壓製成形），於負極集電體的 兩面形成負極活性物質層。又，負極活性物質的塗布量為 226 mg/lOcm2，負極填充密度為i 6〇 g/cc。 [負極活性物質黏著性的測定] 集電體與有機化合物皮膜之間的黏著強冑，根據以下方 式藉由9G度剝離試驗法而評估。具體而言，使用7〇随X 2〇_尺寸的兩面膠帶（Nichiban股份有限公司製造之 「NAISTAK® NW-20」），於！9η ΟΛ 」J於12〇mm x 30mm尺寸的壓克力板 貼附負極’經貼附有負極的端部以日本電產如卿股份有 限公司製造之小型桌上試驗機（「m_Tv」及「心5」卜 對有機化合物皮膜於9〇产的古a — 川度的方向，以一定速度（5〇mm/min) 於上方55mm拉伸，測定剝離時的強度。 叱運仃3 -人’ 3次的測定結果的平均 為90度剝離強度示於表4之測定結果。 由表4，各貫施例顯示盘作 /、怍為輮準之比較例2為 同的黏著性。 略相 15 201145660 【表4】 活性物質的黏著性 編號 活性物質黏著性 1 實施例1 102 2 賁施例2 109 3 實施例3 123 4 實施例4 114 5 實施例5 128 6 實施例6 130 7 實施例7 122 8 實施例8 139 9 實施例9 150 10 實施例10 140 11 實施例11 153 12 實施例12 158 13 比較例1 100 14 比較例2 119 比較例1作為1 〇 〇時的相對值 [於表面形成有有機化合物被膜的介電體層的厚度] 如上述方式，於表面形成有有機化合物皮膜的銅箔表 面的介電體層的厚度，係測定電雙層電容（C: // F)，根據 下式確認厚度。 ..(1)The copper beryllium according to the embodiment of the present invention has a 1/C value set in the range of 卜.3b.0cm2/ //F. When the 1/c value is measured to be smaller than the value of ic. 3icm2 / when the copper film of the organic film layer is smaller than F, the adhesion to the active material is lowered, and the corrosion resistance tends to be deteriorated. The 1/c value is larger than 〇.9cmV"F, and even if it is increased above (the film is thicker), the adhesion is saturated and there is no improvement. First, the copper beryllium of the embodiment of the present invention will be described. The material for producing the copper foil may be either an electrolytic copper foil or a rolled copper foil. In the case of the electrolytic copper foil, it is necessary to use it as a negative electrode current collector for the electric battery for use in the 201145660 pool, because it is suitable for mass production with high productivity. Further, in the present invention, the actual claw _, the predetermined one point; ...' is α 2 〇 tl · -V ^ scoop coarse ‘degree (Rz) is preferably 2. m or less. The steel foil of this type can be formed into an organic film by the thickness of the ancient film, Hitachi* and the thickness of the film, and the adhesive activity of the negative electrode active material carried thereon is excellent. The charge and discharge cycle life characteristics of the battery with the negative electrode and the negative electrode are obtained. The battery capacity at the beginning of charging. The thinner the thickness of the copper ruthenium, the larger the electrode area as a whole, and the smaller the surface roughness, which is advantageous for the high door handle enthalpy or the charge/discharge cycle life characteristics. For example, in the case of a battery, a small battery for electrical or electronic equipment, or a taxi for an electric vehicle is used. In the case of a battery, the thickness of the copper foil is preferably 20 or less. When the thickness of the copper boll is too thin, the mechanical strength is lowered, and the pinholes and the like are also increased. As a practical use, the lower limit of the thickness of (4) is about 6 m. In this manner, preferably The thickness of the copper foil is 20 to 6 m. The organic compound skin m formed on the surface of the copper drop is a film containing a triterpene compound. Or a film containing a triazole compound and an amine compound. The oxadiazole compound, or the triazole compound and the amine compound, are dissolved in water or an organic solvent to maintain a certain solution temperature, and the copper foil is immersed for a certain period of time, and then dried to form an organic compound film on the surface of the copper foil. two. The concentration of the compound solution or the concentration of the triazole compound and the amine compound solution is preferably 10 to 1 000 000 ppm. When the amount is less than 1 Oppm, the degree of adhesion to the negative electrode active material can be maintained. The thickness of the organic compound film is less than 10, and the thickness of the organic compound film is saturated at 〇〇〇ppm, and the method is as follows. Look forward to the effect of adhesion improvement. Further preferably, it is 50 to 5, 〇〇〇ppm. Further, the temperature of the solution may be π i dish, and may be heated as needed. A solution of a further addition of an amine compound in a triterpenoid compound is applied to (iv) two, (iv) a compound in a single phase &, a copper box and a negative active material are better and better, and a blush & 1 __ copper The corrosion resistance of the mooring is also improved and more preferably. The initial 6-week ratio of the three-oxygen compound to the amine compound is, for weight, the amine compound is .2 times effective. The addition of 2 times of the above-mentioned amine compound has also been unable to improve the adhesion of π _ U and the resistance of (4), and less than 0.5 times, the effect of adhesion and j alteration cannot be expressed. The immersion time of the copper foil in the solution, the crystallization of the film of the bismuth compound, the diazole compound and the amine compound, the morning temperature, the temperature of the lyophobic solution or the thickness of the organic film formed. The relationship nc qn ^ , and 疋 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Carboxy-opened oxadiazole, oxime and tri-isolation. Ethyl-opened triazole, naphtho-triazole, etc. In addition, 'as an amine compound' can be a face, a SPA, a diamine, a dialkylamine , trialkylamine, early % alkylamine, dicycloalkylamine, etc. single face #美敢捭夕- 丄 寺 早 早 早 早 早 早 早 早 早 早 早 早 早 早 早 早 早 早 早 早 早 早 早 早 早 早 早 早 早 早 早The alkyl monoamine having a hydrophilic group of a hydroxyl group or an oxiranyl group is monoethylamine, etc. Among them, examples thereof include early ethanolamine, diethanolamine, triethanolamine, diethanolamine, and cineatin. , E-labeled oxamine decylethanolamine, hydrylethanolamine, monobutylethanolamine 201145660, etc. The organic compound film Difficult to be formed on both sides of the copper foil, but depending on the manufacturing steps of the battery, the form of the negative electrode, or the relationship with the purpose of use, it may be a single surface. However, in the case of the positive electrode and the negative electrode of a normal sub-secondary battery, Any of them is a structure in which an active material is carried on both sides of each current collector, and it is preferable to have the organic film layer having the both sides of (4) in the above-described manner. The non-aqueous solvent is used according to an embodiment of the present invention. The negative electrode of the secondary battery and the copper foil for the electric body are manufactured as shown in the figure. Step 1: For example, if you manufacture/prepare the thickness 6, ", the surface roughness (Rz) is less than 2.5 μm. Step 2: The copper ruthenium is immersed in an aqueous solution containing an organic compound and it is contacted with the aqueous solution. Step 3: It is dried. As described above, 'the formation of 1/Cm0 9 is F for the electric body with mg. ϋ due to the negative electrode The current collector is subjected to the following treatment to form a negative electrode for a non-aqueous solvent secondary battery. Step 4: Coating a negative electrode active material slurry Step 5: Drying. Hereinafter, the embodiment will be described based on the embodiment of the present invention. [Examples] 70~130 g/1 [Copper Manufacturing: Step 1 J Electrolyte Copper: 201145660 Sulfuric Acid: 80~140 g/i Additives: 3-Siliary 1 - Propane Sodium Sodium = 1 to 1 Oppm Hydroxyethyl Cellulose = 1~100ppm Low Molecular Weight Glue ( Molecular weight 3,000) = 1~50ppm Vapor ion concentration = 10~50ppm Temperature: 5 0~6 The electrolyte is used, the anode is a noble metal oxide coated titanium electrode, and the cathode is made of a titanium rotary drum with a current density = 5 (M〇〇A/dm2 is an electrolytic copper foil having a thickness of 6 to 20 #m and a surface roughness (Rz) of 2.5//in or less on both sides. [Organic compound for film formation] 1. - azole compound (BTA as one of them) 2. - azole compound (as one of them) + amine compound (TEA as one of them) BTA: benzotriene. Sitting monoethanolamine salt TEA: triethanolamine tetrazole: 1H-tetrasodium [chromate treatment], v 1 is dissolved in an aqueous solution, and the copper foil is impregnated (step and then dried (step 3). Foil, coating organic film for film formation under the conditions indicated by #合合,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, 1 with application 1 50 _ 0 50 ° C 10 seconds 2 extravagant application 2 250 _ 〇 5 〇 ° C 10 seconds 3 赍 Example 3 500 0 50 ° c 10 seconds 4 Example 4 500 0 20 ° c 10 Second 5 f Example 5 1000 〇 5 〇 ° C 10 sec 6 f Example 6 2000 0 5 〇 ° c 10 sec 7 f Example 7 50 60 5 〇 ° c 10 sec 8 f Example 8 250 300 50 ° C 10 sec 9 f Example 9 500 600 50 ° C 10 sec 10 f Example 10 500 600 2 〇 ° c 10 sec 11 f Example 11 1000 1200 50 ° C 10 sec 12 Example 12 2000 2400 5 〇 ° c 10 Seconds [Table 2] No. 4 0 Sitting concentration (ppm) TEA concentration (ppm) ---- Liquid temperature immersion time 13 Comparative example 1 500 600 50 ° C 10 seconds [Table 3] No. Chromate concentration (ppm) Liquid temperature -----^ Immersion time 14 Comparative example 2 1 000 at 20 ° C for 10 seconds, the following active materials were applied to the prepared 14 kinds of electrodes (Step 4), and the adhesion was evaluated. [Preparation of Negative Electrode Active Material Layer] First, a homogenizer manufactured by PRIMIX was used. The CMC aqueous solution having a concentration of 1.0% by mass was obtained by dissolving methyl cellulose (CMC) [#1380 manufactured by DAICEL Chemical Industry Co., Ltd.) in deionized water. 14 201145660 Secondly, the amount of the CMC aqueous solution loo〇g, and artificial graphite (average particle size 21 " m, surface area 4.0 m2 / g) 980g, mixed with a homogenizer manufactured by PRIMIX, add a stupid vinyl butadiene rubber ( SBR) (solid content concentration 50 mass ° / 〇) 20 g 'modulation of the negative electrode slurry. Further, the mass ratio of artificial graphite, CMC and SBR is artificial graphite: CMC: SBR = 98. 0: 1. 〇: 1. 〇 . The above-mentioned negative electrode name 'is coated on both sides of the negative electrode current collector formed of a copper foil coated with an organic compound on both sides by reverse coating (1_6 generation 1^6〇〇3^(:)), and further dried and calendered. (Pressure molding), a negative electrode active material layer was formed on both surfaces of the negative electrode current collector. Further, the coating amount of the negative electrode active material was 226 mg/lOcm2, and the negative electrode packing density was i6〇g/cc. [Negative electrode active material adhesion property Measurement] The adhesion between the current collector and the organic compound film was evaluated by the 9G peel test method in the following manner. Specifically, a double-sided tape of 7 〇 with X 2 〇 _ size (Nichiban Co., Ltd.) was used. "NAISTAK® NW-20" manufactured by @9η ΟΛ ”J on a 12〇mm x 30mm size acrylic plate with a negative electrode attached to the end of the negative electrode to Nippon Electric Co., Ltd. The small table-top tester ("m_Tv" and "Heart 5") was applied to the organic compound film at a speed of 5 mm at a constant speed (5 〇mm/min) at a speed of 55 mm. Determine the strength at the time of peeling. 叱运仃3 -人' 3 The average of the measurement results is a 90-degree peel strength as shown in Table 4. From Table 4, each of the examples shows that the disk is the same as that of Comparative Example 2, which is the same as the adhesion. Table 4] Adhesiveness of Active Material No. Active Material Adhesion 1 Example 1 102 2 贲 Example 2 109 3 Example 3 123 4 Example 4 114 5 Example 5 128 6 Example 6 130 7 Example 7 122 8 Example 8 139 9 Example 9 150 10 Example 10 140 11 Example 11 153 12 Example 12 158 13 Comparative Example 1 100 14 Comparative Example 2 119 Comparative Example 1 as a relative value of 1 [ [formed on the surface Thickness of dielectric layer of organic compound film] As described above, the thickness of the dielectric layer on the surface of the copper foil on which the organic compound film is formed on the surface is measured by electric double layer capacitance (C: //F), and is confirmed by the following formula Thickness. ..(1)
1/C 惟， d為形成於銅箔表面之電雙層的厚度，a、b為定數。 又1/C的測定係使用曰置電機（股份有限公司）製造1/C However, d is the thickness of the electric double layer formed on the surface of the copper foil, and a and b are constant numbers. The measurement of 1/C is also made by 曰置电机 (股份有限公司)
S 16 201145660 之化學阻抗計 ΗΙΟΚΙ 3532-80。1/C的測定值示於表5。 再者，鉻酸鹽皮膜由於無法以1/C評估而以鉻酸鹽附著 量示於表6。 【表5】 1 / C的測定值 1/C值 編號 Μ面 S面 1 實施例1 0. 450 0. 333 2 實施例2 0. 542 0. 390 3 實施例3 0. 524 0. 413 4 實施例4 0. 422 0. 384 5 實施例5 0. 488 0. 583 6 實施例6 0. 722 0. 735 7 實施例7 0. 338 0. 493 8 實施例8 0. 416 0. 613 9 實施例9 0. 559 0. 854 10 實施例10 0. 447 0. 608 11 實施例11 0. 520 0. 670 12 實施例12 0. 795 0. 814 13 比較例1 0. 862 1. 390 【表6】 鉻酸鹽附著量 鉻酸鹽量（mg/dm2) 編號 Μ面 S面 14 比較例2 0. 02 0. 02 17 201145660 [耐氧化性比較]The chemical impedance meter of S 16 201145660 ΗΙΟΚΙ 3532-80. The measured value of 1/C is shown in Table 5. Further, the chromate film was shown in Table 6 as a chromate adhesion amount because it could not be evaluated by 1/C. [Table 5] 1 / C measured value 1 / C value number Μ face S surface 1 Example 1 0. 450 0. 333 2 Example 2 0. 542 0. 390 3 Example 3 0. 524 0. 413 4 Example 4 0. 422 0. 384 5 Example 5 0. 488 0. 583 6 Example 6 0. 722 0. 735 7 Example 7 0. 338 0. 493 8 Example 8 0. 416 0. 613 9 Example 9 0. 559 0. 854 10 Example 10 0. 447 0. 608 11 Example 11 0. 520 0. 670 12 Example 12 0. 795 0. 814 13 Comparative Example 1 0. 862 1. 390 [ Table 6] Chromate adhesion amount Chromate amount (mg/dm2) No. No. S surface 14 Comparative example 2 0. 02 0. 02 17 201145660 [Comparison of oxidation resistance]
Li離子二次電池的電極製造步驟中，乾燥為重要的（步 驟5)。該乾燥不充分而水分帶人以離子二次電池時，對 於電池的循環特性及充放電容量有大的影響。 必需為難以氧化。此處測 經以鉻酸鹽防鏽處理之銅 因此，銅箔於該乾燥步驟中 定經以三唑化合物處理之銅落與 箱的耐氧化性。 後 又’測定係將銅箔於大氣洪 使用陰極還原法測定 【表7】In the electrode manufacturing step of the Li ion secondary battery, drying is important (step 5). When the drying is insufficient and the water is brought to an ion secondary battery, it has a large influence on the cycle characteristics and the charge and discharge capacity of the battery. It must be difficult to oxidize. Here, the chromate-treated rust-treated copper is used. Therefore, the copper foil is subjected to the oxidation resistance of the copper drop and the box treated with the triazole compound in the drying step. After the measurement, the copper foil was subjected to atmospheric reduction using a cathodic reduction method [Table 7].
箱中，150°C X 測定結果示於表7。 lHr加熱 銅箔的耐氧化性 -------- 氧化备 編號 Μ面 S而 1 實施例1 189. 1 258 7 2 實施例2 175. 9 189 7 3 實施例3 _ ----- 160.8 191. 3 4 實施例4 158.8 _^86. 5 5 實施例5 151. 1 177. 9 6 實施例6 147.3 185. 2 7 實施例7 186.1 21? 1 8 實施例8 175.2 上 21 1 c 9 實施例9 159. 1 D 222 7 10 實施例10 157.4 18〇 a 11 實施例11 --- 149.3 — 191. 5 12 實施例12 142. 6 163. 5 13 比較例1 99. 25 135.2 14 比較例2 456.71 18 201145660 由該數據可知， 合物與胺化合物之 異。 含有三唑化合物之皮膜以及含有三唑化 皮膜經由鉻酸鹽防鏽’耐氧化性亦為優 [恆溫恆濕試驗及其結果] 於60 C X 90%的環境下進行恆溫恆濕評估。評估結果 不於表8。 平4 、5階奴進行，評估3以下為有茶色點及變色而作 為電池的使用有困難。 【表8】 編號 目視評估（1<<5) 經過曰數 起始時 2曰 9曰 3 S面 5 5 4 Μ面 - ——— 5 5 4 9 S面 Μ面 ------- 5 5 --------- 5 5 5 5 10 S面 5 5 5 Μ面 5 5 5 14 S面 5 5 4 Μ面 5 3 1 比較例2(編號14)的μ面係於第9日為茶色點變色而作 為電池的使用成為困難的狀態，而根據苯發明知各實施例 成乎〉又有變色，可知可充份地使用作為電池用銅箔。 [測定氧化量] 又，測定此時的氧化量。測定結果示於表9。 19 201145660 【表9】 氧化量（Α) 編號 經過曰數 起始時 2曰 9曰 3 S面 32. 8 55. 2 128. 0 Μ面 33.2 48. 6 522. 5 9 S面 33.0 44. 9 59. 3 Μ面 31.8 44. 9 308. 3 10 — 一 S面 32.7 46.4 71. 1 ---- Μ面 32. 5 42.8 112. 3 14 S面 33. 2 72. 9 1185. 0 一 一' Μ面 33. 0 74. 7 1384. 8 各實施例之氧化速度與比較例2 (編號14)相比較明顯為 慢，可知充分地可使用作為電池用電極。 如上所述’本發明之實施態樣以及實施例之非水溶媒二 次電池負極用銅箔’係與負極活性物質的黏著性、耐氧化 性優異，於尚溫、兩濕的環境下亦不變色，為且有可保持 非水溶媒二次電池的充放電循環壽命與高的電池溶量的優 異效果者。 【圖式簡單說明】 圖 第1 圖為本發明實施態樣的 I造方法之處理 的示意 【主要元件符號說明】 M. 20The results of the measurement at 150 ° C in the box are shown in Table 7. Oxidation resistance of lHr heated copper foil -------- Oxidation number No. S and 1 Example 1 189. 1 258 7 2 Example 2 175. 9 189 7 3 Example 3 _ ---- - 160.8 191. 3 4 Example 4 158.8 _^86. 5 5 Example 5 151. 1 177. 9 6 Example 6 147.3 185. 2 7 Example 7 186.1 21? 1 8 Example 8 175.2 Upper 21 1 c 9 Example 9 159. 1 D 222 7 10 Example 10 157.4 18〇a 11 Example 11 --- 149.3 — 191. 5 12 Example 12 142. 6 163. 5 13 Comparative Example 1 99. 25 135.2 14 Comparison Example 2 456.71 18 201145660 It is known from the data that the compound is different from the amine compound. The film containing the triazole compound and the triazole-containing film were also excellent in oxidation resistance by chromate rust resistance [constant temperature and humidity test and results], and constant temperature and humidity evaluation was carried out in an environment of 60 C X 90%. The evaluation results are not in Table 8. The 4th and 5th order slaves were evaluated. It is difficult to evaluate the use of the battery as a brown point and discoloration. [Table 8] No. Visual evaluation (1<<5) 2曰9曰3 S face 5 5 4 face after the number of turns - 5 5 4 9 S face ------ - 5 5 --------- 5 5 5 5 10 S surface 5 5 5 Μ surface 5 5 5 14 S surface 5 5 4 Μ surface 5 3 1 The μ surface of Comparative Example 2 (No. 14) is attached to The ninth day is a state in which the brown point is discolored, and it is difficult to use it as a battery. According to the benzene invention, it is known that the respective embodiments are discolored, and it is known that the copper foil for a battery can be sufficiently used. [Measurement of Oxidation Amount] Further, the amount of oxidation at this time was measured. The measurement results are shown in Table 9. 19 201145660 [Table 9] Oxidation amount (Α) No. 2曰9曰3 S surface 32. 2 55. 0 Μ面33.2 48. 6 522. 5 9 S surface 33.0 44. 9 59. 3 Μ 31.8 44. 9 308. 3 10 — an S surface 32.7 46.4 71. 1 ---- Μ 32. 5 42.8 112. 3 14 S surface 33. 2 72. 9 1185. 0 one by one Μ面33. 0 74. 7 1384. 8 The oxidation rate of each of the examples was significantly slower than that of Comparative Example 2 (No. 14), and it was found that it was sufficiently used as a battery electrode. As described above, the embodiment of the present invention and the copper foil for a non-aqueous solvent secondary battery negative electrode of the embodiment are excellent in adhesion to the negative electrode active material and oxidation resistance, and are not in an environment of temperature and humidity. The color change is excellent in that the charge/discharge cycle life of the nonaqueous solvent secondary battery and the high battery amount can be maintained. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view showing the processing of the I manufacturing method according to an embodiment of the present invention. [Main component symbol description] M. 20