TW201248974A - Copper alloy bar used for battery tab material for charging - Google Patents

Abstract

The purpose of the present invention is to provide a copper alloy bar suitable for a battery connection tab material, which has a good balance among good tensile strength, electrical conductivity, repeated bendability and weldability. The present invention relates to an Sn-plated copper alloy bar for a battery tab for charging, which contains 2-12% by mass of Zn and 0.1-1.5% by mass of Sn with the balance made up of copper and unavoidable impurities. The Sn-plated copper alloy bar for a battery tab for charging has an aspect ratio of crystal grains in the thickness direction and in a direction parallel to the rolling direction of 0.1 or more, and is provided with a reflow Sn plating wherein the thickness of the Sn layer after reflow is 0.10-1.60 [mu]m and the thickness of the Cu-Sn compound after reflow is 0.10-1.90 [mu]m. This copper alloy bar is preferably provided with an Ni/Cu base plating or a Cu base plating, and has an electrical conductivity of 31-70% IACS, a number of bending repetitions of 2.5 or more in a 180 DEG bending and bend-back test, and a tensile strength of 300-610 MPa.

Description

201248974 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種用於充電用電池標記材、詳細而言 用於連接Li離子電池等高性能充電用電池之標記材的銅合 金條。 【先前技術】 攝像機或膝上型電腦等攜帶用電子機器中會使用鎖鑛 電池或Li離子電池等充電式電池。又，受到近年來環境負 荷降低之動向之影響，電動汽車或混合動力汽車之需求亦 增加，亦推進車載用Li離子二次電池之開發。為確保必要 之電容，該等充電式電池將複數個單體構造之電池以複數 條彼此接近之狀態電性連接而使用。用於電池之連接之金 屬引線材料被稱為集電標記或標記，為確實地連接，大多 情形下藉由利用電阻造成之發熱的電阻熔接而與電池之電 極熔著。對電極熔接有標記之複數個電池雖被收納於緊密 之盒體内’但向小龍、複雜化之盒體等中收納失敗之情 形等時，自盒體取出並放入電池時，必須再次進行標記之 •f曲恢復及彎曲加卫，對用於標記之材料不僅要求有與電 極材料之良好熔接性，而且亦要求有反覆彎曲性。 電池電極材料中通常使用有經链鎳之不鏽鋼板或軟鋼 板、或者錦板。於使用電阻熔接機連接由該等材料板所構 成之電池電極與標記時，鋼之導電率過高，故具有過大之 電流流通於標記中而導致熔損之缺點，因此無法實用化， 而-直將㈣㈣性相對較佳之鎮條用於先前之標記材 201248974 = 而，錦為稀有金屬’價格非常高且亦存在供給不穩 U "^性°又’錦之導電率相對較低為21.5%IACS (實 :值），故存在較易於高容量電池中之使用中發熱之缺點。 此’為課求成本之降低及電池高性能化，要求以其他金 屬材料代替錦。目前，銅原料金屬之價格為錄之約3分之1 左右而具有吸5丨力’但即便將各種公知之銅合金用作標記 材料亦難以進行熔接，故實際上幾乎未被利用。又，雖曾 嘗4使用銅或耐熱銅合金基層、與由…等所構成之炼接層 的包層（clad )進行熔接性之改良（曰本特開平^ — 297300 )’但鋼之強度較低且上述耐熱銅合金亦反覆彎曲加 工性較差，無法應對小型化之需求。 口 [專利文獻1]曰本特開平丨丨—2973〇〇號公報 【發明内容】 本發明之目的在於提供-種對平衡性良好地兼且有？ :之拉伸強度、導電率、反覆弯曲性及溶接性之電池連‘ 標記材而言較佳之銅合金條。 本發明係發現以下情況而完成者，即經回焊鑛以之 -Zn系銅合金對具有良好之拉伸強度、導電率、反覆彎： 性及炼接性之電池用標記材而言較佳，具體而言，如下所 述。 (1) 一種充電用電池標記用之鍍Sn鋼合金條，係含 有2〜12質量％之Zn且含有〇1〜15質量％之Sn，剩餘= 分由銅及不可避免之雜質構成的鋼合金條，其板厚方向及 壓延平行方向之結晶粒的縱橫比為〇1以上，並實施有如下 4 201248974 回焊（reflow)鍍Sn :回焊後之Sn層的厚度為〇 1〇〜 1_60μπι ’且Cu — Sn化合物之厚度為〇 1〇〜丨9〇_。 (2) 如上述（1)之鑛Sn銅合金條，其實施有Ni/Cu 基底鍍敷或Cu基底鍍敷。 (3) 如上述（1)或（2)之銅合金條，其導電率為η 〜70%IACS。 (4) 如上述（1)至（3)中任一項之銅合金條，其⑽。 密接彎曲及彎曲恢復試驗中之反覆弯曲次數為2 5次以上。 (5) 如上述（1)至 )中任項之銅合金條，其拉 伸強度為300〜61〇MPa » 【實施方式】 (銅合金） 本發明係關於一種Cu—Zn—Sn系合金1 c — :系合金以外，作為具有高強度、高導電性之銅合金而有 .± 牛寻扪又馱1之段落「0021」中作 為較佳之組成而列舉之。 〜4人人 ir糸、Cu—Be — 系&金、或其他之c Ni ^Ν· ς . η Nl Sl 系、Cu - Mg-P 系、Cu[Technical Field] The present invention relates to a copper alloy strip for use in a battery marking material for charging, and in particular to a marking material for connecting a high performance charging battery such as a Li ion battery. [Prior Art] A portable battery such as a lock-up battery or a Li-ion battery is used in a portable electronic device such as a video camera or a laptop computer. In addition, the demand for electric vehicles or hybrid vehicles has also increased due to the trend of lowering the environmental load in recent years, and the development of Li-ion secondary batteries for vehicles has also been promoted. In order to secure the necessary capacitance, the rechargeable battery is used by electrically connecting a plurality of cells of a single structure in a state in which a plurality of batteries are in close proximity to each other. The metal lead material used for the connection of the battery is called a collector mark or a mark, and is connected in a sure manner. In many cases, the electrode of the battery is fused by resistance welding by heat generated by a resistor. When a plurality of batteries in which the electrodes are welded and spliced are housed in a close-packed case, when the storage fails in a compact or complicated box, etc., when the battery is taken out of the case and the battery is placed, it must be performed again. The mark is restored and bent, and the material used for marking is required to have good weldability with the electrode material, and also requires repeated bending. A stainless steel plate or a mild steel plate of a chain nickel or a slab is usually used for the battery electrode material. When a battery electrode and a mark composed of the material plates are connected by a resistance welding machine, the electrical conductivity of the steel is too high, so that an excessive current flows in the mark and causes a melt loss, so that it cannot be put to practical use, and - Straight (4) (four) relatively better strips used in the previous marking material 201248974 = And, Jin is rare metal 'price is very high and there is also supply instability U " ^ ° ° and 'Jin' conductivity is relatively low is 21.5 %IACS (real: value), so there is a disadvantage that it is easier to use heat in a high-capacity battery. In order to reduce the cost and improve the performance of the battery, it is required to replace the brocade with other metal materials. At present, the price of the copper raw material metal is about one-third of that recorded and has a suction force of 5 volts. However, even if various known copper alloys are used as a marking material, it is difficult to weld, and thus it is practically used. Moreover, although the copper or the heat-resistant copper alloy base layer was used, and the cladding layer of the kneading layer composed of, etc., was used for the improvement of the weldability (曰本特平平^297370), the strength of the steel was compared. The heat-resistant copper alloy described above is also inferior in bending workability, and cannot meet the demand for miniaturization. [Patent Document 1] 曰本特开平丨丨—2973〇〇号 SUMMARY OF THE INVENTION [The present invention] It is an object of the present invention to provide a good balance of balance. : The battery of tensile strength, electrical conductivity, reversibility of bending and compatibility is better than the copper alloy strip of the 'marker. The present invention has been found to be successful in the case of a remelted ore-Zn-based copper alloy for a battery marking material having good tensile strength, electrical conductivity, reverse bending, and refining properties. Specifically, it is as follows. (1) A Sn-plated steel alloy strip for marking a battery for charging, comprising 2 to 12% by mass of Zn and containing 1 to 15% by mass of Sn, and the remaining = a steel alloy composed of copper and unavoidable impurities In the strip, the aspect ratio of the crystal grain in the direction of the plate thickness and the direction parallel to the calendering is 〇1 or more, and the following is performed. 4 201248974 Reflow plating Sn: The thickness of the Sn layer after reflow is 〇1〇~1_60μπι ' And the thickness of the Cu—Sn compound is 〇1〇~丨9〇_. (2) The Sn copper alloy strip of the above (1), which is subjected to Ni/Cu base plating or Cu base plating. (3) The copper alloy strip according to (1) or (2) above, which has a conductivity of η to 70% IACS. (4) A copper alloy strip according to any one of the above (1) to (3), wherein (10). The number of times of repeated bending in the close bending and bending recovery test was 25 or more. (5) The copper alloy strip according to any one of the above (1) to (3), which has a tensile strength of 300 to 61 MPa (Embodiment) (Copper alloy) The present invention relates to a Cu-Zn-Sn-based alloy 1 In the paragraph "0021" which is a copper alloy having high strength and high electrical conductivity, which is a high-strength, high-conductivity alloy, is listed as a preferable composition. ~4 people ir糸, Cu-Be — system & gold, or other c Ni ^Ν·ς . η Nl Sl system, Cu - Mg-P system, Cu

Sn系、Cu—Fe—p系笼。妙工 6Jr » _ , 而，由本發明人研究之 、、·。果可知，該等鋼合金雖 接性、反覆管曲性之任導電性’但溶 已知本發二2差，不適合用作標記。 h含量以外亦h系合金藉由除適當之- 強声日日粒偟之縱橫比進行管理，而且備除高 強度、尚導電性以外之作 U除间 (A)Zn漠度乍為U用材料之特性’從而最佳。 201248974 本發明之合金係含有2〜12質量％ (以下以％表示）、 較佳為2〜9/。之Zn’且剩餘部分由銅及不可避免之雜質所 構成之銅合金。若Zn濃度未達2%，則料標記所必需之 強度不充分，並且導電率變得過高而使標記於熔接時熔 才貝，或者藉由通過銅合金條之電流所產生之發熱量較少， 電流難以流通於電池電極側之不鏽鋼板或軟鋼板，故炫接 性劣化。若Zn濃度超過12%，則不但於熔接時zn發生氣Sn-based, Cu-Fe-p-based cages. Wonderful work 6Jr » _ , and, by the inventors, research. It can be seen that these steel alloys are inferior in conductivity and reversal of the pipe bendability, but they are known to be inferior in the present invention and are not suitable for use as a mark. In addition to the h content, the h-based alloy is managed by the aspect ratio of the appropriate-strong sound-day granules, and the high-strength, yet conductive, U-division (A) Zn-moisture 乍 is used for U. The properties of the material 'are optimal. 201248974 The alloy of the present invention contains 2 to 12% by mass (hereinafter referred to as %), preferably 2 to 9/. The copper alloy of Zn' and the remainder consisting of copper and unavoidable impurities. If the Zn concentration is less than 2%, the strength necessary for the marking of the material is insufficient, and the electrical conductivity becomes too high to cause the mark to be melted when welded, or the amount of heat generated by the current passing through the copper alloy strip is higher. Since the electric current is hard to flow to the stainless steel plate or the soft steel plate on the battery electrode side, the bridging property is deteriorated. If the Zn concentration exceeds 12%, the gas is not only generated when zn is welded.

化使材料脆化而使炫接神沈儿 —Q 峪按性$化，而且導電率變低而難以達 成電池之高性能化。進而’-般而言，Zn之價格為Cu之價 格之-半以下’故可以說是亦對成本削減有效之添加元素。 (B) Sn濃度 丹有促進壓延時 --------叩，负助；yj：、5至度 昇。本發明之銅合金條經问捏你c 俅1 口焊鍍Sn ’因此於鍍Sn後之步 中產生之邊角材料令必缺全古 T…、3有Sn成分。然而，本發明之 合金條於上述範園内合古ς 固内3有Sn，因此存在即便為鍍Sn後之 角材料亦可簡單地㈣再利作為本發明之銅合金料: 優點。另一方面，於為了實現強度提昇而採用Sn以外之》 加元素以形成不含Sn之銅合金細士 』Q鱼組成之情形時，為了回收^ 利用鍍Sn後之邊自好钮而v U ^ ^The material makes the material embrittlement and makes the sleek and sleek--Q 峪 峪 , , , , , , , , , , , , , , , 。 。 。 。 。 。 Furthermore, the price of Zn is generally - half or less of the price of Cu, so it can be said that it is also an additive element that is effective for cost reduction. (B) Sn concentration Dan has a promotion of pressure delay -------- 叩, negative help; yj:, 5 to degrees liter. The copper alloy strip of the present invention is pinched by your c 俅1 port for Sn ’ so that the corner material produced in the step after the Sn plating is indispensable for the entire T... and 3 Sn components. However, the alloy strip of the present invention has Sn in the above-mentioned vane, and therefore there is an advantage that even if it is a corner material after Sn plating, it can be simply used as the copper alloy material of the present invention. On the other hand, in order to achieve the strength improvement, when adding an element other than Sn to form a composition of a copper alloy without Sn, the Q fish composition is used, in order to recover the use of the Sn-plated edge after the Sn button ^ ^

角材科而必須進行精煉步驟。然而，於S 濃度較低之情形時，當將鍍Sn 'The angle section must be refined. However, when the S concentration is low, when the Sn will be plated

^ ^ -Λ & ^ 引屋生之邊角材料與鍍S 後之邊角材料一併作為本發 銅合金原料用碎屑時，韻^ ^ -Λ & ^ The corner material of the lead house and the corner material after the S plating are used together as the raw material for the copper alloy.

Sn後之邊角材料之使用 … 艮制故難以取得質吾斗 衡，回收再利用性較差。反之， .,A """Sn濃度較向’則 則產生之邊角材料之僅用詈典 彳銀Si 又艮制，故依然難以取得質 6 201248974The use of the corner material after Sn... It is difficult to obtain the quality and balance, and the recycling is poor. On the other hand, ., A """Sn concentration is better than the 'the corner material produced by the ’ 彳 彳 Si Si Si Si , , , , , 6 6 6 6 6 6 6 6 6 2012 2012 2012 2012 2012 2012

量平衡。因此’本發明之合金含有〇 i〜1 5%、較佳為〇 J 〜0.8%、進而較佳為ο 2〜0 6%之Sn。若Sn濃度未達ο 1% 則無法獲得所期望之效果’若Sn濃度超過丨.5%則導電率降 低。 (C )其他元素 為了對上述既存之高強度、高導電性銅合金改良除強 度以外之特性，大多情形下添加Mg、Fe、Si。然而，根據 以下理由’本發明之合金中含有該等元素之情形時需要謹 慎。 於本發明之銅合金中含有作為活性金屬之之情形 時’ Mg容易於熔接時發生氣化並產生火花而難以進行熔 接，並且材料發生脆化。因此，Mg濃度較佳為0.3。/。以下， 進而較佳為0·〗。/。以下。 於本發明之銅合金中含有Fe之情形時，與熔接機之電 極材（熔接棒）反應而腐蝕熔接棒熔接性及生產性較差❶ 並且，Fe幾乎不會固溶於銅基質中，故即便Fe含量為微量 亦於母相中局部存在富Fe相，故而產生上述問題。因此， Fe濃度較佳為0.05%以下。 於作為含有Si及Ni之析出型銅合金之卡遜合金之情形 :^法進行點電阻炼接，溶接性較差。隸並非根據理 ’限疋本發明’但亦認為因炼接時產生之焦耳熱導致析出 物固/谷導電率急遽降低而難以進行熔接。 (D)合金條之特性 本發明之合金條之導電率（JIS Η 0505 )通常為31〜 201248974 70%IACS ’較佳為35〜70%IACS，進而較伟 1主為 40〜 60°/〇IACS，若為該範圍則可適當地用作標記材料。从 3 1%IACS ’則較易於充電池使用時產生熱。— 万面，若 超過70%IACS，則於電阻熔接時發生熔損，亦 ^ 4考於電池電 極側之金屬板中未流通充分之電流，熔接性降低。 關於本發明之合金條之反覆彎曲性，當於18〇〇U字彎 曲或密接彎曲後進行彎曲恢復而作為1次循環之情形時 使至少10mm寬度之試樣斷裂為止之反覆彎曲次^通常為 2.5次以上，較佳為3.〇次以上，進而較佳為3 5次以上。 若未達2.5二欠，則很有可能於將電池收納於盒❹之__ 破損，生產效率降低》 若本發明之合金條之拉伸強度（JISZ 224l)通常為 〜6H)MPa、較佳為39〇〜6〇〇MPa、進而較佳為Μ卜 540MPa’則可較佳地用作標記材料。於㈣6i〇Mpa之十 形時，通常反覆彎曲性較差。又，若拉伸強度未達3〇〇Mpa 則通常不滿足Li離子電池用標記所要求之耐振動性基準 本發明之合金條之厚度並無特別限定，較佳為〇〇3一 1.〇〇麵，更佳為〇.12〜。.6mm，例如為〇 15随，若為該肩 度，則滿足作為充電池連接用標記材料之強度、溶接性。 (E- 1 ) Cu基底回焊鍍Sn 對本發明之銅合金條實施HU—(回焊處理後 之Sn層及Cu-Sn化合物層之合計厚度）之回谭鍍h，達 成優異之炫接性。回㈣如係於銅合金母材上，藉由電鍵 等在CU基底㈣層上形成鐘Sn層，進行回焊處理而形成。 8 201248974 藉由該回焊處理，銅合金母材及Cu基底鍍敷層與錄s 反應而形成Cu-Sn化合物層（Cu向鍍Sn層擴散而形成 故亦稱為擴散層鑛敷層構造係自表面側起形成純㈣ Cu-Sn化合物層、錄Cu層、母材層（參照圖〇。又，鍵 Cu層可於回焊後完全轉換為Cu—Sn化合物，亦可_ f 再者’於本發明中幾乎看不韻^層之厚度對溶接性之与 響，回焊處理前之Cu基底鍍敷層之厚度並無特別限定，： 佳為0_05〜3.0μηι’更佳為ο.Μ 〇μιη。又，亦可 Cu基底鍍敷。 订 層之合計厚度與熔 為目的而於進行上 (E-2) Ni/Cu基底回焊鍍Sn Cu—Sn化合物層及回焊後之純Sn 接性相關，故亦可以提高鍍敷之耐熱性 述鍵Cu之前實施鑛犯。 /Cu基底回焊鑛Sn係於母材上，藉由電鍍依序形成 鐘Ni層、鍵Cu層及錄“層，其後進行回焊處理。藉由該 回焊處理，鑛敷層間之Cu# Sn反應而形成Cu_sn化合物 層。另一方面，鍍Ni層以大致剛完成電鍍之狀態（厚度） 殘留。回焊處理後之鑛敷層之構造係自表面側起形成鍍Sn 層、CU—Sn化合物層、鍍Ni層。Ni基底鍍敷層之厚度並 無特別限& ’較佳為〇」〜〇 8μιη，更佳為〇」〜〇 3㈣。其 他鍍敷條件與（Ε — 1)同等。 ' 圖2係：將具有「自下方起為純Sn層、^一“化合物 層銅0金母材層之構成」的本發明之銅合金條配置在於 上表面叹置有鍍Ni層之Fe板上，並受到熔著後之剖面照 201248974 片（FE-SEM像）。炼著部位（圖2之x)如下所示般，即 殘留於周圍R (右）及L (左）之純^層變薄或消失且 存在於銅合金條之下部之Cu_Sn化合物層與電池電極表面 之鍍川層被直接熔著（參照圖2)。並非根據理論限制本發 明，但關於本發明之銅合金條之熔著機制，首先，存在於 標記之銅合金表面與電池電極表面之Ni面間的鍍以之純 Sn層（熔點230。。）因藉由電阻熔接產生之焦耳熱而熔融， 於熔接用電極棒之加壓下㈣Sn自加壓部移動至非加壓 部。因此可認為’較之純Sn層，存在於内部之〜化 合物層（炫點戰以上）t傾向作為活性之新生面而與 沁接觸’進而藉由受到加熱加壓而使各成分（a— h化合 物及Ni元素）相互擴散並牢固地接合。因此可以說於： 接後之標記中，合金條表面之Cu_Sn化合物層與電池電極 表面之Nl層進行反應而炫著’為了達成優異之炼接性而必 須存在回焊鍍Sn之Cu — Sn化合物層。 又，若探討上述機制與Zn之添加效果，則為了於溶接 步驟前保護Cu-Sn化合物層之新生面，較理想為：於鍛& Μ在不使擴散層成長至表層之情況下儘可能長時間存在 表面純Sn層。而且，本申請案發明之銅合金中含有Zn，故 Cu之擴散速度較低，純Sn層可長時間存在。 對本發明之銅合金實施有厚度〇·2〇〜3.50叫之回焊鍍 Sn。所謂厚度0.20〜3.50_之回焊鑛Sn，係指如下鍍敷： 回焊處理後殘存之Sn層及藉由回焊處理所形成之Cu_Sn 化合物層的厚度合計為0.20〜3.5— Sn層之厚度為〇·ι〇 10 201248974 〜較佳為0.30〜，2—，進而較佳為〇5〇Balanced. Therefore, the alloy of the present invention contains 〇 i 〜 1 5%, preferably 〇 J 〜 0.8%, and more preferably ο 2 〜 0 6% of Sn. If the Sn concentration is less than ο 1%, the desired effect cannot be obtained. If the Sn concentration exceeds 丨.5%, the conductivity is lowered. (C) Other elements In order to improve the characteristics other than the strength of the above-mentioned high-strength, high-conductivity copper alloy, Mg, Fe, and Si are often added. However, care must be taken in the case where the alloy of the present invention contains such elements for the following reasons. In the case where the copper alloy of the present invention contains the active metal, 'Mg is easily vaporized at the time of welding and generates a spark to make it difficult to weld, and the material is embrittled. Therefore, the Mg concentration is preferably 0.3. /. Hereinafter, it is more preferably 0·〗. /. the following. When the copper alloy of the present invention contains Fe, it reacts with the electrode material (welding rod) of the fusion splicer to corrode the fusion rod and has poor weldability and productivity, and Fe is hardly dissolved in the copper matrix, so even The above problem is caused by the fact that the Fe content is a trace amount and the Fe-rich phase is locally present in the matrix phase. Therefore, the Fe concentration is preferably 0.05% or less. In the case of a Carson alloy which is a precipitation type copper alloy containing Si and Ni: the point resistance welding is performed, and the fusion property is inferior. It is not intended to limit the invention to the present invention. However, it is also considered that the Joule heat generated during the refining causes the solid/valley conductivity of the precipitate to be lowered rapidly and it is difficult to weld. (D) Characteristics of the alloy strip The conductivity of the alloy strip of the present invention (JIS Η 0505 ) is usually 31 to 201248974 70% IACS 'preferably 35 to 70% IACS, and further the main 1 is 40 to 60 ° / 〇 IACS, if it is this range, can be suitably used as a marking material. From 3 1% IACS ' it is easier to generate heat when using the battery. —When the surface is over 70% IACS, the fuse is melted at the time of resistance welding. Also, the sufficient current is not circulated in the metal plate on the battery electrode side, and the weldability is lowered. The reverse bending property of the alloy strip of the present invention is a bending correction after bending at 18 〇〇 U-shape or after bending and bending, and in the case of a single cycle, the repeated bending of the sample having a width of at least 10 mm is usually 2.5 times or more, preferably 3. times or more, more preferably 35 times or more. If it is less than 2.5 owed, it is very likely that the battery is stored in the cassette, and the production efficiency is lowered. If the tensile strength (JISZ 224l) of the alloy strip of the present invention is usually ～6H) MPa, preferably It is preferably used as a marking material of 39 〇 to 6 MPa, and more preferably 540 MPa'. In the case of (4) 6i〇Mpa, the bending is usually poor. Further, if the tensile strength is less than 3 〇〇Mpa, the vibration resistance of the Li ion battery is generally not required. The thickness of the alloy strip of the present invention is not particularly limited, and is preferably 〇〇3 to 1. Noodles, better for 〇.12~. .6 mm, for example, 〇15, and if it is the shoulder, it satisfies the strength and the solubility as a marking material for charging the battery. (E-1) Cu base reflow plating Sn The copper alloy strip of the present invention is subjected to HU-(the total thickness of the Sn layer and the Cu-Sn compound layer after the reflow treatment), and the excellent tandem property is achieved. . The back (4) is formed on a copper alloy base material by forming a clock Sn layer on a CU base (four) layer by a key or the like, and performing a reflow process. 8 201248974 By the reflow process, the copper alloy base material and the Cu-based plating layer react with the s to form a Cu-Sn compound layer (Cu is diffused into the Sn-plated layer, so it is also called a diffusion layer ore layer structure system). A pure (tetra) Cu-Sn compound layer, a Cu layer, and a base material layer are formed from the surface side (see FIG. 又. Further, the bond Cu layer can be completely converted into a Cu-Sn compound after reflow, or _f again) In the present invention, the thickness of the layer is almost invisible, and the thickness of the Cu-based plating layer before the reflow process is not particularly limited. Preferably, the thickness is 0_05 to 3.0μηι'. 〇μιη. Also, Cu substrate plating. The total thickness of the layer and the purpose of melting are performed on the upper (E-2) Ni/Cu substrate reflow-plated Sn Cu-Sn compound layer and pure Sn after reflow The connection is related, so it is also possible to improve the heat resistance of the plating before the implementation of the bond Cu. /Cu base reflow ore Sn is attached to the base metal, and the clock Ni layer and the key Cu layer are sequentially formed by electroplating. The layer is thereafter subjected to a reflow process. By the reflow process, the Cu# Sn reaction between the mineral deposits forms a Cu_sn compound layer. The Ni layer remains in a state (thickness) which is almost just completed. The structure of the ore layer after the reflow process is to form a Sn-plated layer, a CU-Sn compound layer, and a Ni-plated layer from the surface side. The thickness is not particularly limited to & 'preferably 〇'~〇8μιη, more preferably 〇"~〇3(4). Other plating conditions are equivalent to (Ε-1). 'Figure 2 series: will have "from below The copper alloy strip of the present invention in which the pure Sn layer and the "compound layer copper 0 gold base material layer are formed" is disposed on the upper surface of the Fe plate with the Ni layer coated thereon, and is subjected to the cross section after the fusion. 201248974 (FE-SEM image). The refining part (x in Fig. 2) is as follows, that is, the pure layer remaining in the surrounding R (right) and L (left) becomes thin or disappears and exists in the lower part of the copper alloy strip. The Cu_Sn compound layer and the plated layer on the surface of the battery electrode are directly fused (refer to FIG. 2). The present invention is not limited by theory, but the melting mechanism of the copper alloy strip of the present invention is firstly present in the marked copper alloy. The pure Sn layer (melting point 230.) is plated between the surface and the Ni surface of the battery electrode surface. The Joule heat generated by the resistance welding is melted, and under the pressure of the electrode rod for welding (4) Sn is moved from the pressurizing portion to the non-pressurizing portion. Therefore, it can be considered that the 'compound layer is present in the interior than the pure Sn layer. In the war, it is inclined to contact the ruthenium as a new surface of the activity. Further, by heating and pressurizing, the components (a-h compound and Ni element) are mutually diffused and firmly bonded. Therefore, it can be said that: In the middle, the Cu_Sn compound layer on the surface of the alloy strip reacts with the N1 layer on the surface of the battery electrode to sleek. In order to achieve excellent refining properties, a Cu-Sn compound layer of Sn-plated Sn must be present. Further, in order to investigate the effect of the above mechanism and the addition of Zn, in order to protect the newly formed surface of the Cu-Sn compound layer before the melting step, it is preferable that the forging & 尽可能 is as long as possible without growing the diffusion layer to the surface layer. There is a surface pure Sn layer at the time. Further, since the copper alloy of the invention of the present application contains Zn, the diffusion rate of Cu is low, and the pure Sn layer can exist for a long time. The copper alloy of the present invention is provided with a thickness of 〇·2〇~3.50 called reflow-plated Sn. The reflowed Sn of thickness 0.20 to 3.50_ refers to the following plating: the thickness of the Sn layer remaining after the reflow process and the Cu_Sn compound layer formed by the reflow process is 0.20 to 3.5 - the thickness of the Sn layer 〇·ι〇10 201248974~ preferably 0.30~, 2—, and further preferably 〇5〇

Cu-Sn化合物層之厚度為〇心…9〇_，較佳： 0.20 〜1.50μπι ’ 進而較佳為 〇 4〇 〜〇 9〇_。 ·‘、 右Sn層厚度未達Q，則於與電池電極板之 =獲得广-Sn化合物層之新生面而熔接性較差。 私圮熔著之複數個電池成為由複數個電池所構成之、 組’標記部進而與底座溶接（通孔構裝），# Sn層較薄， 則與底絲接時之焊料潤濕性亦變差。另-方面，若超過 1柳爪，則於熔接時大量Sn熔融，故Cu_sn化合物層與 經鍍Ni之電池電極或Ni電池電極之熔著於通常採用之 定條件下變得困難。 若Cu—Sn化合物層厚度未達〇 1〇μπι，則與電極表面之 均勻之熔著較為困冑，故難以獲得目標熔接強度。另一方 面，若Cu—Sn化合物層之厚度超過i 9〇μηι，則鍍sn之厚 度容易變得不均勻，於製造上產生障礙。又，由於鍍〜之 厚度變得不均勻，Cu-Sn化合物層與經賴之電池電極或 Ni電池電極之熔著於通常採用之特定條件下變得困難。 為形成0.20〜3.50μΓη之回焊鍍Sn，通常以成為〇〇5〜 3·〇μηι、較佳為〇.丨〜之厚度之方式於銅合金上進行鍍 Cu其後，以成為0.20〜3.00pm、較佳為〇 23〜2 6〇μπι之 厚度之方式進行鍍Sn後，進行回焊處理。通常之回焊處理 係於溫度為300〜60(TC且為氮（氧lv〇1%以下）環境之加 熱爐中***試樣5〜1 5秒後進行水冷。 (F )結晶粒之縱橫比 201248974 若調整結晶粒之縱橫比，則可進一步 性。最終製品中之妬盾士 a l ^ € φ 之板厚方向b及壓延平行方向3之 縱橫比f為(M以上，較佳為〇.17,，進而較佳為 0.30〜0.7G。圖3係於試樣剖面觀察到之結晶粒之模式圖。 若板厚方向及壓延平行方向之結晶粒之縱橫比“a未 達0.1 ’則雖然材料之強度較高，但於反覆 集中而容易形成剪切帶，反覆㈣性較差。若二變= 0.80,則雖然反覆彎曲性良好，㈣於讀低之加工度製 造’故強度較低，於作為標記材料而使用中存在因振動或 衝擊而斷裂之虞。 本發明之平均結晶粒徑較佳為i2μπ1以下進而較佳為 7μηι以下。若為12,以下’則可預料強度之增加故而較 佳0 (G)製造方法 本發明之銅合金之製造步驟基本上與通常之合金條相 同，於熔解鑄造、均質化退火及熱壓延、面削之後，反覆 進行複數次冷壓延、退火而製造。 藉由調整以下之製造條件可進一步改善反覆彎曲性。 熱壓延之結束溫度較佳為600〜750。(：，製品之最終退 火後之冷壓延之加工度通常為1〇〜7〇%，較佳為1〇〜6〇%。 若該等為上述範圍外，則結晶粒之縱橫比處於本發明中較 佳之範圍外’反覆彎曲性劣化，強度亦不足。 關於中間退火溫度，較佳為於680〜780°C進行5〜20 秒’若退火條件為上述範圍外，則縱橫比處於本發明中較 12 201248974 佳之範圍外，反覆-曲性劣化。 (H)熔接條件 若為通常使用之充電池 金條可與任意材料炼接，較“材料，則本發明之銅合 板，例如可列舉經鑛錦之=:表面具有鑛錄層之金屬 再者，、 ，板或軟鋼板，進而鎳板。 丹考於將鎳板用於電極之愔拟盹& ^ 度通常為(Μ〜〇3_… 員錄錄。電極材料厚 光“ 贿可根據實際使用之充電池而變動， 並無特別限制。 標記材之熔接係以來自標記板與電極間之電阻之發熱 進行炼接σα質受到溶接電流、通電時間、壓下壓力之 影響。溶接電流根據熔接之構件之材質及表面狀態、以及 ，極壓下壓力而變化。並且，考慮到防止熔接機電極之熔 著等各種要素，可於通常進行之範圍内適當調整電流或電 極之壓下壓力等。 [實施例] 實施例中進行之測定之條件如下所述。 [利用電解式膜厚計之鍍敷厚度測定] 使用CT — 1型電解式膜厚計（電測股份有限公司製 造），依據JIS Η8501，對回焊後之試樣測定鍍Sn層、Cu —Sn化合物層及鍍Ni層之厚度。對鍍Sn層及Cu- Sn化 合物層之電解液係使用Kocour公司製之電解液R — 50 (商 品名）。又，對鍍Ni層使用Kocour公司製電解液R— 54(商 品名）。 [導電率] 13 201248974 對於各銅合金板’依據JISH0505,由藉由使用雙電橋 裝置之四端子法求出之體積電阻率算出％IACS。若導電率 為40%以上，則將導電性評價為「良好」〇，若為η%以 上且未達40%，則評價為「規格内」△，於未達3ι%之情 形時評價為「不良」X。 [拉伸強度] 對於各銅合金板，於與壓延方向平行之方向上進行拉 伸試驗，依據JIS Z2241求出拉伸強度。 [反覆彎曲性] μ π運万向興 .u〜々八装忭 4 個厚 〇·15随'寬10mm、長4〇職之最終品試驗片，以與試驗片 2長邊方向呈直角之方向作為彎曲轴，進行刚。密接彎曲 後，恢復彎曲。以此作為丨 2, . L 1 人進仃反覆考曲直至試樣斷 平均斷二出4個試樣之平均斷裂（反覆弯曲）次數。若 =^人為2.5次以上，則將反覆彎曲性評價為「良好」 右為1.5次以上且去；去t 於夹.查“ 且未達2.5次，則評價為「規格内」△， 於未達1.5次之情形時評價為「不良」X。The thickness of the Cu-Sn compound layer is 〇... 9 〇 _, preferably: 0.20 〜 1.50 μπι ‘ and further preferably 〇 4 〇 〇 〇 9 〇 _. · When the thickness of the right Sn layer is less than Q, the new surface of the wide-Sn compound layer is obtained with the battery electrode plate, and the weldability is poor. The plurality of batteries that are fused by the private cells are formed by a plurality of batteries, and the group 'marking portion is further fused with the base (through-hole structure), and the #Sn layer is thinner, and the solder wettability when connected with the bottom wire is also Getting worse. On the other hand, when it exceeds one of the claws, a large amount of Sn is melted at the time of welding, so that it becomes difficult to fuse the Cu_sn compound layer with the Ni-plated battery electrode or the Ni battery electrode under the usual conditions. If the thickness of the Cu-Sn compound layer is less than 〇 1 〇 μm, the uniform fusion with the electrode surface is difficult, so that it is difficult to obtain the target fusion strength. On the other hand, if the thickness of the Cu-Sn compound layer exceeds i 9 〇 μη, the thickness of the plating Sn tends to be uneven, which causes an obstacle in manufacturing. Further, since the thickness of the plating layer becomes uneven, it becomes difficult to fuse the Cu-Sn compound layer with the battery electrode or the Ni battery electrode which is usually used. In order to form a reflow-plated Sn of 0.20 to 3.50 μm, Cu is usually plated on the copper alloy so as to have a thickness of 〇〇5 to 3·〇μηι, preferably 〇.丨, to become 0.20 to 3.00. The reflow process is performed after plating Sn in a manner of pm, preferably 〇23 to 2 6 〇μπι. The usual reflow treatment is carried out by inserting a sample into a heating furnace having a temperature of 300 to 60 (TC and nitrogen (oxygen lv〇1% or less) for 5 to 15 seconds, and then performing water cooling. (F) Aspect ratio of crystal grains 201248974 If the aspect ratio of the crystal grain is adjusted, it can be further improved. The aspect ratio f of the plate thickness direction b and the rolling parallel direction 3 of the 妒 士 al al al ^ ^ φ in the final product is (M or more, preferably 〇.17 Further, it is preferably 0.30 to 0.7 G. Fig. 3 is a schematic view of the crystal grains observed in the cross section of the sample. If the aspect ratio of the crystal grain in the direction of the thickness direction and the parallel direction of the calendering is "a not as 0.1", the material is The strength is high, but the shear band is easily formed in the reverse concentration, and the reverse (four) property is poor. If the second change is 0.80, the reverse bending property is good, and (4) the low degree of processing is produced, so the strength is low. The marking material is used for rupture due to vibration or impact. The average crystal grain size of the present invention is preferably i2 μπ 1 or less, more preferably 7 μηι or less. If it is 12, the following is expected to increase the strength, and thus preferably 0. (G) Manufacturing Method Manufacturing Step of Copper Alloy of the Present Invention Basically, in the same manner as a normal alloy strip, after melt casting, homogenization annealing, hot rolling, and surface cutting, it is repeatedly produced by performing multiple cold rolling and annealing. The reverse bending property can be further improved by adjusting the following manufacturing conditions. The end temperature of the hot calendering is preferably from 600 to 750. (: The degree of cold rolling after the final annealing of the product is usually from 1 〇 to 7 〇%, preferably from 1 〇 to 6 〇 %. Outside the above range, the aspect ratio of the crystal grains is outside the preferred range of the present invention, and the repeated bending property is deteriorated and the strength is insufficient. Regarding the intermediate annealing temperature, it is preferably carried out at 680 to 780 ° C for 5 to 20 seconds. When the condition is outside the above range, the aspect ratio is outside the range of 12 201248974 in the present invention, and the over-elasticity is deteriorated. (H) If the welding condition is a commonly used rechargeable battery gold strip, it can be rectified with any material, compared with "material, For example, the copper plate of the present invention may be exemplified by a metal having a mineral layer on the surface, a plate or a soft steel plate, and further a nickel plate. Dan Kao uses a nickel plate for the electrode. & ^ degrees usually (Μ~〇3_... member record. Electrode material thick light" Bribe can be changed according to the actual rechargeable battery, and there is no particular limitation. The welding of the marking material is performed by heating from the resistance between the marking plate and the electrode. The σα quality is affected by the welding current, the energization time, and the pressing pressure. The welding current varies depending on the material and surface state of the welded member, and the pressure under the extreme pressure. Further, various factors such as prevention of fusion of the electrode of the fusion splicer are considered. The current, the pressure of the electrode, and the like can be appropriately adjusted within the range normally performed. [Examples] The conditions of the measurement performed in the examples are as follows. [Measurement of Plating Thickness by Electrolytic Thickness Gauge] Using CT — A type 1 electrolytic film thickness meter (manufactured by Electric Co., Ltd.), in accordance with JIS Η 8501, measures the thickness of the Sn plating layer, the Cu—Sn compound layer, and the Ni plating layer on the reflowed sample. For the electrolyte solution on which the Sn layer and the Cu-Sn compound layer were plated, an electrolyte R-50 (trade name) manufactured by Kocour Co., Ltd. was used. Further, an electrolyte R-54 (trade name) manufactured by Kocour Co., Ltd. was used for the Ni plating layer. [Electrical conductivity] 13 201248974 For each copper alloy plate, % IACS was calculated from the volume resistivity obtained by the four-terminal method using a double bridge device in accordance with JISH0505. When the conductivity is 40% or more, the conductivity is evaluated as "good", and if it is η% or more and less than 40%, it is evaluated as "in specification" △, and when it is less than 3 %, it is evaluated as " Bad "X. [Tensile Strength] For each copper alloy sheet, a tensile test was conducted in a direction parallel to the rolling direction, and tensile strength was determined in accordance with JIS Z2241. [Reverse bending] μ π Yun Wan Xiangxing.u~々八装忭4 thick 〇·15 with 'width 10mm, length 4 之 之 final test piece, at right angle to the test piece 2 long side direction The direction is taken as the bending axis, and the straight is performed. After the bending is tight, the bending is resumed. This is used as the 丨 2, . L 1 person to repeat the test until the sample breaks the average number of breaks (repeated bending) of the four samples. If the =^ person is 2.5 or more times, the repeated bending property is evaluated as "good". The right is 1.5 times or more and goes; when t is checked in the folder. If it is less than 2.5 times, the evaluation is "in specification" △, in the absence When it was 1.5 times, it was evaluated as "bad" X.

[熔接性;I 利用串聯點焊機（例如Mi 體式電_ _ lyachi c卿oration製之電晶 頭ZH—32(Mm (製时名）及空氣驅動式 熔接時Η1Λ 於加壓力20Ν、熔接電流3.0kA、 驗片於2點進行點禪( =)與本發明之銅合金試 1隔右為10〜50mm之範圍内， 14 201248974 則可同樣進行熔接而無特別問題）。以Ajk〇h ⑻公 司製之精密荷重測定機（m〇del_13igvr:製品幻進行 拉伸試驗（試驗速度為1Gmm/min)，測定料強度。若炫 接強度為35N以上’則將炼接性判斷為「最良好」（幻，若 炫接強度未達35N且為25N以上，則評價為「更良好」（B)， 若熔接強度未達25N且為肅以上，則評價為「良好」（c)， 若熔接強度未達20N，則評價為「不良」（D)，於無法熔接 或者無法預料穩定之製造之情形時評價為「無法 (E)。 、 讶」 [回收再利用容易性] 於回焊後之材料未進行精煉而容易回收再利用作為鋼 合金之原材料之情形時判斷為「良好」Q，於根據鋼合金 之組成必須進行精煉以用作原材料之情形或者冑sn後之邊 角材料之回收再利用中存在限制之情形時評價為「一部分 不良」△，若必須精煉，則評價為「不良」χ。再者，於^ / Cu基底回焊鍍Sn之情形時，雖鍍敷層中含有，但通 常實施之鍍Ni厚度較薄，故未精煉便可回收再利用。 [結晶粒之縱橫比] 依照JIS H050 1之切斷法，對各銅合金板測定並算出與 壓延方向平行之剖面及垂直之剖面之結晶粒徑。於圖3所 示之與壓延方向平行之剖面中，測定相對於壓延面平行之 方向之結晶粒徑，將平行方向之測定值設為長徑a，將板厚 方向之測定值設為短徑b。 (試樣製備） 15 201248974 ，以高頻感應㈣解電解銅，利用木炭被㈣液表面 後添力s金元素將溶液調整為所期望之組成。再者，下 述表1表2中§己載有銅以外之合金元素之組成。合金之剩 餘4刀為銅。以堯鎢溫& i 2Q(rc進行鑄造，將獲得之铸錢 乂 850 C加熱3小時後，以熱壓延將其壓延至板厚8mm為 止，將熱壓延結束溫度調整至65(^以上。以面削去除表面 產生之氧化皮°其後’以冷壓延將其加工至板厚1.5_為 止，以7〇〇〇C進行12秒之中間退火，it而適當進行冷壓延 直至達到特定板厚為止，以68〇<>c進行丨〇秒之最終退火， 對最終退火後之銅合金板進行冷壓延，加工成〇 15mm之 板。中間退火及最終退火係於氨分解氣體環境中以連續線 進行。 藉由改變最終退火後之冷壓延之加工度而獲得拉伸強 度不同之銅合金條。一般而言，若加工度變高，則拉伸強 度及0.2。/。耐力增大，伸長率減少，反覆彎曲性降低。又， 若加工度變高’則結晶粒之縱橫比降低。另一方面，若加 工度較低，則製品之拉伸強度變低，縱橫比依舊較大。 利用10質量％硫酸一1質量％過氧化氫溶液對獲得之銅 合金條進行酸洗’去除表面氧化膜。於鹼水溶液中以試樣 作為陰極進行電解脫脂（電流密度：7.5 A/ dm2。脫脂劑： 氫氧化鈉10g/L、破酸鈉30g/ L、偏矽酸鈉7g/ L、及剩 餘部分之水。溫度：80°C »時間60秒）。使用1〇質量％硫 酸水溶液進行酸洗。於實施鍍Cu(鍍浴組成：硫酸60g/ L、 硫酸銅200g/ L、及剩餘部分之水。鍍浴溫度：25°C »電流 201248974 密度.5.0A/dm2)後’進而實施鍍Sn (鑛浴組成：硫酸亞 錫40g/L、硫酸60g/L、甲酚磺酸4〇g/L、明膠、 /3 _萘酚1 g/ L、及剩餘部分之水。鍍浴溫度：2〇。〇。電流 密度.1.5A/dm2)。其中，鍍Sn厚度係藉由電沈積時間（於 電沈積時間為2分鐘之情形時’回焊處理前之“層之厚度 、’勺為1 μηι )進行調整。作為回焊處理，於將溫度調整為 400 C、環境氣體調整為氡1ν()ι%以下）之加熱爐中插 入試樣5〜30秒並進行水冷。表丨中表示試驗結果。 再者，實施例7及1 〇係以如下條件於鍍Cu之前實施 鍍Nil鍍浴組成：硫酸鎳25〇g/L、氯化鎳45g/L、硼酸 3〇g/L。鍍浴溫度：5〇〇c。電流密度：5八/如2。其中鍍 Νι厚度係藉由電沈積時間進行調整而設為〇.3叫⑺。 又，關於實施例11，除未進行鍍Cu以外於與實施例9 相同之條件下進行製備。 表1中之實施例1〜25為本發明之範圍内，因此為具 有良好或規格内之拉伸強度、導電性、反覆彎曲性、熔接 性及回收再利用容易性之合金條。於未鑛Cu之實施例11 中，藉由回焊處理而使銅合金母材與鍍Sn層反應，形成厚 度〇.70μηι之Cu_ Sn化合物層。又實施例22〜之a 濃度約為10% ’ Sn濃度約為〇 5%，均稍高故導電率相對 較低...勺為32%IACS。於實施例3 +，最終退火後之冷壓延 加工度超過7〇%，縱橫比於本發明之範圍内變低，但反覆 f曲性為規格内。於實施例U中，加工度未達1G%且縱橫 比為0.78，但看不到強度之明顯降低。於加工度為1 5%之 17 201248974 實施例19中，縱橫比為〇 71，維持充分之強度。 比較例26為市售純銅，故拉伸強度較差，由於導電率 極尚，故熔接時之發熱量較少而無法熔接。又，必須進行 精煉步驟以回收再利用鑛Snif角材料作為原材料，故回收 再利用性亦較差。 比較例27及28為先前使用之Ni板，未進行鍍Sn，m 板自身之回收再利用性良好，但導電率較差，故無法實現 電池之高性能化。而且’於經鑛Sn之情形時回收再利用性 不良。再者，比較例27之加工度較低，故縱橫比較高，與 比較例28相比強度較低。 、比較例29〜31為不含Zn之卡遜合金系銅合金，均無 法熔接，比較例29不含Sn，故與比較例30相比強度較低， 回收再利用性較差，比較例3 i使拉伸強度增大，結果導致 反覆彎曲性較差。 比較例32不含Zn及Sn而含Mg，故強度不會降低但 無法熔接，回收再利用性亦較差。 ^比較例33不含Zn且Sn濃度超過本發明之上限，導電 率較低，反覆彎曲性亦不良。 幸交例34係Zn為少量，不含sη而含有Fe及少量之ρ 之析出硬化型銅合金之例，雖然強度不會降低但熔接棒受 】腐蝕而無法熔接，回收再利用性亦較差。 比較例35及36之Zn濃度未達2%，因此強度相對較 •導電率過南而導致熔接不良。又，比較例35由於Sn 濃度較低，故回收再利用性亦較差。 18 201248974 比較例3 7之s η濃度未達〇. 1 %，因此強度更低，導電 率過高而導致熔接性不良，回收性亦較差。 比較例38、40及41之Zn量及Sn濃度為本發明之範 圍内，但鍍Sn中之純Sn層厚度較小，熔接不良。另一方 面，於比較例39中，純Sn層厚度較大，於熔接時Sn大量 炼融故無法溶接。 比較例42之Zn濃度及Sn濃度為本發明之範圍内，但 Cu — Sn化合物層之厚度較小，拉伸強度較小，熔接不良。 比較例43之Zn濃度及Sn濃度、回焊後之層厚度為本 發明之範圍内’ ^拉伸強度增大，但加卫度較高且結晶粒 之縱橫比為本發明之範圍外，故強度雖高但反覆彎曲性較 比較例44之Sn濃度超過〇.8。/。，因此導電率較低，反 覆彎曲性及回收再利用性較差。 比較例45〜48之Zn濃度超過12%，故導電率較低， 於熔接時Zn發生氣化，產生熔接部之脆化，故導致熔接不 良或者無法熔接。再者’比較例48為Zn濃度較高之一般 之市售κ銅，加工度相對較低，故縱橫比 較Sr 丄 7 Ί-田於為 仃加工硬化之組成之材料，故而強度得到保證。然 而由於不含sn，故而回收再利用性較差。 反覆彎曲性、 目的，但比較 以上，本發明係以於拉伸強度、導電率、 熔接性之所有項目中取得平衡之優異效果為 例無法達成該效果。 201248974 回收再利 用容易性 評價 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 o w>.l K? 喊 3 u 熔接性 評價 < < < U U 0Q CQ u < < < CQ u Ο < < < < < < < < < < < 反覆彎曲性 評價 〇 〇 < 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 拉伸強度 MPa 340 1552_I S v〇 420 420 420 420 420 420 420 420 420 420 420 443 Ο 599 346 410 555 607 寸 556I 607 縱橫比 丨 b/a | 1 0-55 | | 0.22 | | 0.16 | 0.49 | 0.49 | 0.49 0.49 | 0.49 | 0.49 I 0.49 | 0.49 0.49 0.49 0.49 1 0.61 1 1 0.35 1 1 0.26 1 | 0.78 | ! 0.71 0.41 i 0.21 0.68 0.51 0.43 0.55 加工度 CN ΓΟ \Τί cn in to IT) (N s Ό 00 o 導電率 評價 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 < <1 < <1 | %IACS | | 68.9 | i 1 59.9 1 1 59.4 | 1 59.4 | 1 59.4 1 1 59.4 | 1 59.4 | 1 59.4 | 1 59.4 | 1 59.4 1 1 59.4 | 1 59.4 | 1 59.4 1 丨 49.6 1 1 51.6 1 | 40.9 | I 40.9 | 41.2 | 40.1 <N 31.6 | 31.8 | 31.1 回焊後之厚度（“m) | 1.55 | 1 ι·4ΐ 1 5 | 0.22 | | 0.93 | 1 0.65 1 0.96 0.78 | 1.55 | 1 1.84 | (N in | 2.30 | 1 2.31 1 1 3.40 1 η LLioJ 5 1-25 | 1 1-51 1 1-52 | 1.51 | 1.55 | Ni層 1 1 1 1 1 1 | 0.30 | 1 I | 0.30 | 1 1 1 1 1 1 1 1 1 1 1 1 t 1 1 1 Sn-Cu 層 0.81 0.73 0.68 0.10 0.81 0.30 0.28 0.10 0.81 0.78 0.70 f—N 0.81 0.68 0.64 0.71 0.73 I 0.73 | 0.74 0.79 0.81 0.83 0.67 0.67 璨 4 < -1 η Ο ~Ί 书· < Sn層 1 0.74 | | 0.68 | 1 0-75 | 丨 0-12 1 丨 0-12 1 1 0.35 1 I 0.38 | I 0.68 | 1 0-74 | | 0.76 | | 0.82 | o 1 0.66 1 1 0.76 1 | 0.78 | | 0.61 | | 0.61 | 051 1 | 0.72 | 0-71 1 | 0.68 | | 0.88 | | 0.88 | 組成（mass%) Cu • 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 I ( I 1 1 < 1 1 1 ίΛ • 1 1 • 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 I 1 1 1 1 1 1 • 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 t 1 1 1 碧 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 t 1 1 1 1 ζ 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 L〇〇2| L〇J9| 0.18 0.18 0.18 0.18 0.18 0.18 0.18 0.18 0.18 0.18 0.18 0.28 0.29 0.28 0.29 0.29 0.27 0.29 0.45 0.51 0.49 ilAU 12.101 | 2.89 | 1 2.98 | 1 3-12 | 1 3-12 1 1 3·12 1 1 3-12 | 丨 3.12 1 1 3.12 | 1 3.12 1 1 3.12 | 1 3.12 | 1 3.12 | 1 3.12 1 1 4.87 1 1 4-95 1 | 4.80 | | 7.98 1 I 7.98 | 1 7-81 | | 8.06 | | 9.84 | 1 9.95 1 I 9.89 | I 11.20 | 1實施例1 實施例2 I實施例3 實施例4 1實施例5 實施例6 1實施例7 1實施例8 實施例9 1實施例io 實施例11* I實施例12 丨實施例13 實施例14 實施例15 1實施例16 1實施例17 實施例18 I實施例19 I實施例20 實施例21 實施例22 1實施例23 I實施例24 實施例25 201248974 回收再利用容易性 評價 X 〇 〇 X 〇 〇 X 〇 X <1 〇 < 〇 〇 〇 〇 〇 〇 < 〇 〇 〇 X 表中之「-」表示未添加。 熔接性 評價 U u UQ P-1 UJ u Q Q Q Q Q Q Q < U Q Q Q ω 反覆彎曲性 評價 〇 〇 〇 〇 <1 X 〇 X 〇 〇 〇 〇 〇 〇 〇 〇 〇 X X 〇 〇 〇 〇 拉伸強度 MPa 279 346 546 495 v〇 yn 1 745 丨 462 丨仍 1 340 1 347 1 290 440 546 420 420 420 650 547 V£> o m 488 縱橫比 b/a 0.72 ： 1 °·91 1 0.49 1 | 0.67 | \ 〇·71 1 1 〇·43 1 1 0.61 1 1 0.36 1 1 0.51 1 1 0.49 1 1 0.48 1 | 0.49 | 〇_5i 1 | 0.26 | 0.49 0.49 0.49 0.05 0.35 0.71 0.43 0.51 0.81 加工度 ο 5 § 00 o o ο 導電率 評價 〇 X X 〇 〇 < 〇 X 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 X X X X· X |%IACS| | 97.0 1 <N (N 1 22.1 59.8 1 51-4 1 1 37.5 1 1 28.9 1 1 69.5 1 1 75·3 1 71.0 74.0 60.0 ON 59.4 1 59.4 1 59.4 1 1 50.9 <D\ cs 30.6 30.5 30.3 28.2 回焊後之厚度（//m) 1合計 (N ΓΛ 1 146 ^Ti 1.41 ν〇 〇 2·51 1 1 o.io 1 1 0.86 1 1 0.56 1 Ό 1.40 1.42 a； 1.53 1.45 Sn-Cu 層 0.61 0.67 0.81 0.74 0.81 0.68 0.82 0.70 0.91 0.80 0.79 0.78 1.31 0.71 0.05 0.81 0.05 0.69 0.64 0.68 0.81 0.81 0.63 Sn層| 0.71 1 0.79 1 1 0-74 | 0.68 | | 0.69 | 丨 0.78 1 0.73 0.71 1 0.65 1 0.73 1 0.75 1 | 0.72 | 0.09 g 1 0.05 1 1 0.05 1 1 0.51 1 0.67 | 0.76 | 0.74 | 0.68 | | 0.72 0.82 組成（mass%) CU 1 1 1 1 1 0.01 Ο 1 1 1 1 1 1 1 1 0.49 0.46 0.58 1 I 1 1 1 1 1 1 £ 1 1 1 1 1 1 1 Μ 1 1 1 1 1 1 1 1 1 1 0.49 1 1 1 1 1 1 1 z ο r-N 〇 M ㈣ 1 Μ I I 1 1 1 1 eg 1 1 1 M 0.49 1 Μ 1 0.05 0.18 0.05 0.18 Μ 0.18 0.18 0.28 0.17 0.17 0.15 1 1 1 1 1 1 1 Ο *—Η 2.00 ㈣ 3.00 Μ μ 4-87 4.95 12.7 12.8 13.1 29.8 比較例26 比較例27 比較例28 比較例29 比較例30 比較例31 比較例32 比較例33 比較例34 比較例35 比較例36 比較例37 比較例38 比較例39 比較例40 比較例41 比較例42 比較例43 比較例44 比較例45 比較例46 比較例47 比較例48 201248974 [產業上之可利用性] 本發明之銅合金條平衡性良好地兼具有良好之拉伸強 度、導電率、反覆彎曲性及熔接性，可較佳地用於充電用 電池標記材、詳細而言可較佳地用於連接Li離子電池等高 性能充電用電池之標記材。 【圖式簡單說明】 圖1A係本發明之銅合金條（Cu—8Zn—〇.3Sn)之熔接 步驟前的表面附近之剖面照片（FE— SEM像）。 圖1B係圖1A照片之概略圖。 圖2係將圖丨a之銅合金條與電池電極（經鍍川之軟 鋼）熔著後之剖面照片。自中水 ^目甲央X之上部以熔接用電極棒 加壓而進行電阻熔接。 曰曰 圖3係於本發明之銅纟金條之試樣剖面觀察到之妹 粒之模式圖。 ° 【主要元件符號說明】 純Sn層 2 3 L X R 10 20[Fusibility; I use a tandem spot welder (for example, the electric crystal head ZH-32 (Mm (time) and air-driven welding) made by the Mi-type electric _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 3.0kA, the test piece is punctured at 2 o'clock (=) and the copper alloy test 1 of the present invention is within the range of 10 to 50 mm, and 14 201248974 can be welded without any special problem.) Ajk〇h (8) The company's precision load measuring machine (m〇del_13igvr: the product is subjected to tensile test (test speed is 1Gmm/min), and the material strength is measured. If the splicing strength is 35N or more, the refining property is judged as "the best". (Imaginary, if the strength of the splicing is less than 35N and is 25N or more, the evaluation is "better" (B). If the welding strength is less than 25N and is above, the evaluation is "good" (c), if the welding strength If it is less than 20N, it is evaluated as "defective" (D). When it is impossible to weld or cannot be expected to be stable, it is evaluated as "unable (E). Surprise" [Ease of recycling] Material after reflow The case where it is easy to recycle and reuse as a raw material of steel alloy without refining When it is judged as "good" Q, it is evaluated as "partially defective" when the composition of the steel alloy has to be refined for use as a raw material or when there is a restriction in the recycling of the corner material after 胄sn. If it is necessary to refine it, it is evaluated as "bad". In addition, in the case of Sn/Cu substrate reflow soldering, although it is contained in the plating layer, the thickness of Ni plating usually performed is thin, so it can be recovered without refining. [Using the aspect ratio of crystal grains] According to the cutting method of JIS H050 1, the crystal grain size of the cross section parallel to the rolling direction and the cross section perpendicular to each other is measured and calculated for each copper alloy sheet. In the cross section in which the directions are parallel, the crystal grain size in the direction parallel to the rolling surface is measured, and the measured value in the parallel direction is the long diameter a, and the measured value in the thickness direction is the short diameter b. (Sample preparation) 15 201248974, using high frequency induction (4) to decompose copper, using charcoal to adjust the solution to the desired composition by adding the gold element to the surface of the liquid. Furthermore, the alloys other than copper are contained in Table 2 of Table 1 below. The composition of the elements. Alloy The remaining 4 knives are made of copper. The casting is carried out with 尧tungsten temperature & i 2Q (rc), and the obtained MG 850 C is heated for 3 hours, and then calendered to a thickness of 8 mm by hot rolling, and the hot rolling is finished. The temperature is adjusted to 65 (^ or more. The surface is peeled off to remove the oxide scale produced by the surface. Then it is processed by cold rolling to a thickness of 1.5 mm, and an intermediate annealing is performed at 7 ° C for 12 seconds. The cold rolling was carried out until a specific thickness was reached, and final annealing of leap seconds was performed at 68 Å >>, and the copper alloy sheet after the final annealing was cold-rolled and processed into a 〇15 mm plate. The intermediate annealing and final annealing are carried out in a continuous line in an ammonia decomposition gas atmosphere. A copper alloy strip having different tensile strengths is obtained by changing the degree of cold rolling after final annealing. In general, if the degree of work becomes high, the tensile strength is 0.2. /. The endurance is increased, the elongation is reduced, and the repeated bending property is lowered. Further, if the degree of work becomes high, the aspect ratio of the crystal grains is lowered. On the other hand, if the degree of processing is low, the tensile strength of the product becomes low and the aspect ratio is still large. The obtained copper alloy strip was pickled with 10% by mass of sulfuric acid to 1% by mass of hydrogen peroxide solution to remove the surface oxide film. Electrolytic degreasing with a sample as a cathode in an aqueous alkali solution (current density: 7.5 A/dm2. Degreaser: 10 g/L sodium hydroxide, 30 g/L sodium sulphate, 7 g/L sodium metasilicate, and the remainder) Water. Temperature: 80 ° C » Time 60 seconds). The acid was washed with a 1% by mass aqueous sulfuric acid solution. After performing Cu plating (plating bath composition: sulfuric acid 60g / L, copper sulfate 200g / L, and the remaining part of the water. plating bath temperature: 25 ° C » current 201248974 density. 5.0A / dm2) after the implementation of plating Sn ( Mineral bath composition: stannous sulfate 40g / L, sulfuric acid 60g / L, cresol sulfonic acid 4 〇 g / L, gelatin, / 3 - naphthol 1 g / L, and the remaining part of the water. Bath temperature: 2 〇 〇. Current density. 1.5A/dm2). Among them, the thickness of the Sn plating is adjusted by the electrodeposition time (the thickness of the layer before the reflow process, the 'spoon is 1 μηι) when the electrodeposition time is 2 minutes. The sample was inserted into the heating furnace adjusted to 400 C and the ambient gas was adjusted to 氡1 ν (1% by weight or less) for 5 to 30 seconds and water-cooled. The test results are shown in Table 。. Further, Examples 7 and 1 are The following conditions were applied to the plating of Nil plating bath before Cu plating: nickel sulfate 25 〇 g / L, nickel chloride 45 g / L, boric acid 3 〇 g / L. plating bath temperature: 5 〇〇 c. Current density: 5 八 / For example, the thickness of the ruthenium plating is adjusted by the electrodeposition time to be 〇.3 (7). Further, with respect to Example 11, the preparation was carried out under the same conditions as in Example 9 except that Cu plating was not performed. In the first embodiment, the examples 1 to 25 are within the scope of the present invention, and therefore are alloy strips having good tensile strength, electrical conductivity, reversibility of bending, weldability, and ease of recycling. In the eleventh embodiment, the copper alloy base material is reacted with the Sn-plated layer by a reflow process to form a thick layer. The layer of Cu_Sn. 70μηι. The concentration of Example 22~a is about 10%. The concentration of Sn is about 〇5%, which is slightly higher, so the conductivity is relatively low... The spoon is 32% IACS. Example 3 +, the cold rolling degree after the final annealing exceeds 7〇%, and the aspect ratio becomes lower within the range of the present invention, but the inverse f curvature is within the specification. In the example U, the degree of processing is less than 1 G%. Further, the aspect ratio was 0.78, but no significant decrease in strength was observed. In the case of the processing degree of 15%, in the case of the embodiment 19, the aspect ratio was 〇71, and the sufficient strength was maintained. Comparative Example 26 is commercially available pure copper. The tensile strength is poor, and since the electrical conductivity is extremely high, the amount of heat generated during welding is small and cannot be welded. Further, the refining step must be performed to recover and reuse the Snif horn material as a raw material, so that the recycling property is also poor. 27 and 28 are the previously used Ni plates, and the Sn plate is not plated. The m plate itself has good recycling and recyclability, but the conductivity is poor, so that the battery cannot be improved in performance, and it is recovered in the case of the mine Sn. Poor utilization. Furthermore, the processing degree of Comparative Example 27 is low. Therefore, the aspect ratio was relatively high, and the strength was lower than that of Comparative Example 28. The comparative examples 29 to 31 were all Zn-free Carson-based alloy copper alloys, and were not welded, and Comparative Example 29 did not contain Sn, so that it was in comparison with Comparative Example 30. The specific strength was low, and the recycling property was inferior, and in Comparative Example 3, the tensile strength was increased, and as a result, the reverse bending property was inferior. In Comparative Example 32, since Zn and Sn were not contained and Mg was contained, the strength was not lowered but the welding could not be performed. The recovery and recyclability were also inferior. ^Comparative Example 33 contained no Zn and the Sn concentration exceeded the upper limit of the present invention, and the conductivity was low, and the repeated bending property was also poor. Fortunately, 34 is a small amount of Zn, and does not contain sη but contains Fe and In the case of a small amount of ρ precipitation hardening type copper alloy, although the strength is not lowered, the fusion rod is corroded and cannot be welded, and the recycling property is also inferior. The Zn concentrations of Comparative Examples 35 and 36 were less than 2%, so the strength was relatively higher. • The conductivity was too south and the fusion was poor. Further, in Comparative Example 35, since the Sn concentration was low, the recycling property was also inferior. 18 201248974 Comparative Example 3 7 s η concentration does not reach 〇 1 %, so the strength is lower, the conductivity is too high, resulting in poor weldability and poor recovery. The Zn amount and the Sn concentration of Comparative Examples 38, 40 and 41 were within the scope of the present invention, but the thickness of the pure Sn layer in the Sn plating was small and the fusion was poor. On the other hand, in Comparative Example 39, the thickness of the pure Sn layer was large, and Sn was not fused at the time of welding and could not be melted. The Zn concentration and the Sn concentration of Comparative Example 42 were within the range of the present invention, but the thickness of the Cu-Sn compound layer was small, the tensile strength was small, and the fusion was poor. The Zn concentration and the Sn concentration of Comparative Example 43 and the layer thickness after reflowing are within the range of the present invention, and the tensile strength is increased, but the degree of reinforcement is high and the aspect ratio of the crystal grains is outside the range of the present invention. Although the strength was high, the reverse bending property was higher than that of Comparative Example 44 by more than 〇.8. /. Therefore, the electrical conductivity is low, the reverse bending property and the recycling property are poor. In Comparative Examples 45 to 48, the Zn concentration was more than 12%, so that the electrical conductivity was low, and Zn was vaporized during welding, which caused embrittlement of the welded portion, resulting in poor welding or fusion. Further, Comparative Example 48 is a general commercially available κ copper having a high Zn concentration, and the degree of processing is relatively low. Therefore, the aspect ratio is higher than that of Sr 丄 7 Ί-Tian, which is a composition of work hardening, so that the strength is secured. However, since it does not contain sn, the recycling is poor. The present invention is not able to achieve this effect by taking the excellent effect of achieving balance in all items of tensile strength, electrical conductivity, and weldability. 201248974 Ease of recycling easy evaluation wo w>.l K? Shout 3 u fusion evaluation<< &lt UU 0Q CQ u <<< CQ u Ο <<<<<<<<<<<<<>> 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇 Tensile strength MPa 340 1552_I S v〇420 420 420 420 420 420 420 420 420 420 420 443 Ο 599 346 410 555 607 inch 556I 607 Aspect ratio 丨b /a | 1 0-55 | | 0.22 | | 0.16 | 0.49 | 0.49 | 0.49 0.49 | 0.49 | 0.49 I 0.49 | 0.49 0.49 0.49 0.49 1 0.61 1 1 0.35 1 1 0.26 1 | 0.78 | ! 0.71 0.41 i 0.21 0.68 0.51 0.43 0.55 Machining degree CN ΓΟ \Τί cn in to IT) (N s Ό 00 o Conductivity evaluation 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇 <<1<<1 | %IACS | | 68.9 | i 1 59.9 1 1 59.4 | 1 59.4 | 1 59.4 1 1 59.4 | 1 59.4 | 1 59.4 | 59.4 | 1 59.4 1 1 59.4 | 1 59.4 | 1 59.4 1 丨49.6 1 1 51.6 1 | 40.9 | I 40.9 | 41.2 | 40.1 <N 31.6 | 31.8 | 31.1 Thickness after reflow ("m) | 1.55 | 1 ι·4ΐ 1 5 | 0.22 | | 0.93 | 1 0.65 1 0.96 0.78 | 1.55 | 1 1.84 | (N in | 2.30 | 1 2.31 1 1 3.40 1 η LLioJ 5 1-25 | 1 1-51 1 1-52 | 1.51 | 1.55 | Ni layer 1 1 1 1 1 1 | 0.30 | 1 I | 0.30 | 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Sn-Cu layer 0.81 0.73 0.68 0.10 0.81 0.30 0.28 0.10 0.81 0.78 0.70 f—N 0.81 0.68 0.64 0.71 0.73 I 0.73 | 0.74 0.79 0.81 0.83 0.67 0.67 璨4 < -1 η Ο ~Ί Book · < Sn layer 1 0.74 | | 0.68 | 1 0-75 | 丨0-12 1丨0-12 1 1 0.35 1 I 0.38 | I 0.68 | 1 0-74 | | 0.76 | | 0.82 | o 1 0.66 1 1 0.76 1 | 0.78 | | 0.61 | | 0.61 | 051 1 | 0.72 | 0-71 1 0.68 | | 0.88 | | 0.88 | Composition (mass%) Cu • 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 I ( I 1 1 < 1 1 1 ίΛ • 1 1 • 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 I 1 1 1 1 1 1 • 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 t 1 1 1 Bi 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 t 1 1 1 1 ζ 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 L〇〇2| L〇J9| 0.18 0.18 0.18 0.18 0.18 0.18 0.18 0.18 0.18 0.18 0.18 0.28 0.29 0.28 0.29 0.29 0.27 0.29 0.45 0.51 0.49 ilAU 12.101 | 2.89 | 1 2.98 | 1 3-12 | 1 3-12 1 1 3·12 1 1 3-12 | 丨3.12 1 1 3.12 | 1 3.12 1 1 3.12 | 1 3.12 | 1 3.12 | 1 3.12 1 1 4.87 1 1 4-95 1 | 4.80 | | 7.98 1 I 7.98 | 1 7-81 | | 8.06 | | 9.84 | 1 9.95 1 I 9.89 | I 11.20 | 1 Example 1 Embodiment 2 I Embodiment 3 Embodiment 4 1 Embodiment 5 Embodiment 6 1 Embodiment 7 1 Embodiment 8 Embodiment 9 1 Embodiment io Example 11 * I Embodiment 12 丨 Embodiment 13 Example 14 Example 15 1 Embodiment 16 1 Embodiment 17 Embodiment 18 I Embodiment 19 I Embodiment 20 Embodiment 21 Example 22 1 Example 23 I Example 24 Example 25 201248974 Evaluation of ease of recycling and reuse X 〇〇X 〇〇X 〇X <1 〇<〇〇〇〇〇〇< 〇〇〇X The "-" in the table indicates that it has not been added. Fusion property evaluation U u UQ P-1 UJ u QQQQQQQ < UQQQ ω Repetitive bending evaluation 〇〇〇〇 <1 X 〇X 〇〇〇〇〇〇〇〇〇XX 〇〇〇〇 Tensile strength MPa 279 346 546 495 v〇yn 1 745 丨462 丨 still 1 340 1 347 1 290 440 546 420 420 420 650 547 V £ om 488 aspect ratio b/a 0.72 : 1 °·91 1 0.49 1 | 0.67 | \ 〇· 71 1 1 〇·43 1 1 0.61 1 1 0.36 1 1 0.51 1 1 0.49 1 1 0.48 1 | 0.49 | 〇_5i 1 | 0.26 | 0.49 0.49 0.49 0.05 0.35 0.71 0.43 0.51 0.81 Machining degree ο 5 § 00 oo ο Conductive Rate evaluation 〇 XX 〇〇 < 〇X 〇〇〇〇〇〇〇〇〇〇XXXX· X |%IACS| | 97.0 1 <N (N 1 22.1 59.8 1 51-4 1 1 37.5 1 1 28.9 1 1 69.5 1 1 75·3 1 71.0 74.0 60.0 ON 59.4 1 59.4 1 59.4 1 1 50.9 <D\ cs 30.6 30.5 30.3 28.2 Thickness after reflow (//m) 1 total (N ΓΛ 1 146 ^Ti 1.41 ν〇 〇2·51 1 1 o.io 1 1 0.86 1 1 0.56 1 Ό 1.40 1.42 a; 1.53 1.45 Sn-Cu layer 0.61 0.67 0.81 0.74 0.81 0.68 0.82 0.70 0.91 0.80 0 .79 0.78 1.31 0.71 0.05 0.81 0.05 0.69 0.64 0.68 0.81 0.81 0.63 Sn layer | 0.71 1 0.79 1 1 0-74 | 0.68 | | 0.69 | 丨0.78 1 0.73 0.71 1 0.65 1 0.73 1 0.75 1 | 0.72 | 0.09 g 1 0.05 1 1 0.05 1 1 0.51 1 0.67 | 0.76 | 0.74 | 0.68 | | 0.72 0.82 Composition (mass%) CU 1 1 1 1 1 0.01 Ο 1 1 1 1 1 1 1 1 0.49 0.46 0.58 1 I 1 1 1 1 1 1 £ 1 1 1 1 1 1 1 Μ 1 1 1 1 1 1 1 1 1 1 0.49 1 1 1 1 1 1 1 z ο rN 〇M (4) 1 Μ II 1 1 1 1 eg 1 1 1 M 0.49 1 Μ 1 0.05 0.18 0.05 0.18 Μ 0.18 0.18 0.28 0.17 0.17 0.15 1 1 1 1 1 1 1 Ο *—Η 2.00 (4) 3.00 Μ μ 4-87 4.95 12.7 12.8 13.1 29.8 Comparative Example 26 Comparative Example 27 Comparative Example 28 Comparative Example 29 Comparative Example 30 Comparison Example 31 Comparative Example 32 Comparative Example 33 Comparative Example 34 Comparative Example 35 Comparative Example 36 Comparative Example 37 Comparative Example 38 Comparative Example 39 Comparative Example 40 Comparative Example 41 Comparative Example 42 Comparative Example 43 Comparative Example 44 Comparative Example 45 Comparative Example 46 Comparative Example 47 Comparative Example 48 201248974 [Industrial Applicability] The copper alloy strip of the present invention has good balance Good tensile strength, electrical conductivity, reversibility and weldability, and can be preferably used for a battery marking material for charging, and in detail, a marking material for connecting a high-performance rechargeable battery such as a Li ion battery. . BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1A is a cross-sectional photograph (FE-SEM image) near the surface before the welding step of the copper alloy strip (Cu-8Zn-〇.3Sn) of the present invention. Fig. 1B is a schematic view of the photograph of Fig. 1A. Fig. 2 is a cross-sectional photograph showing the copper alloy strip of Fig. a and the battery electrode (soft steel plated with galvanized steel). The upper part of the water is compressed by the electrode rod for welding, and the electric resistance is welded. Figure 3 is a schematic view of the sister particles observed in the cross section of the sample of the copper beryllium gold strip of the present invention. ° [Main component symbol description] Pure Sn layer 2 3 L X R 10 20

Cu — Sn化合物層 母材層 炫者部位之左側 熔著部位 熔著部位之右側 壓延面 板厚方向 壓延方向（壓延平行方面） 22 30 201248974 a 長徑 b 短徑Cu — Sn compound layer Base material layer Left side of the bright part Melting part Right side of the fusion part Calendering surface Thickness direction Calendering direction (rolling parallel) 22 30 201248974 a Long diameter b Short diameter

Claims (1)

201248974 七、申請專利範圍： 1. 一種充電用電池標記用之鍍811銅合金條，係含有2 〜12質量％之Zn且含有（M〜h5 f量％之Sn，剩餘部分由 銅及不可避免之雜質構成的銅合金條，其板厚方向及壓延 平行方向之結晶粒的縱橫比為〇.丨以上，並實施有如下回焊 (reflow)鍍Sn:回焊後之811層的厚度為〇 io'j 6〇μΐΏ， 且Cu- Sn化合物之厚度為〇1〇〜丨9〇μιη。 2. 如申請專利範圍第i項之鍍Sn銅合金條，其實施有 Ni/Cu基底錢敷或Cu基底鑛敷。 3. 如申請專利範圍第丨或2項之銅合金條，其導電率為 31 〜70%IACS » 4. 如申請專利範圍第丨或2項之銅合金條，其18〇。密接 彎曲及脊曲恢復試驗中之反覆彎曲次數為25次以上。 5. 如申請專利範圍第丨或2項之銅合金條，其拉伸強度 為 300〜610MPa ° 24201248974 VII. Patent application scope: 1. A plated 811 copper alloy strip for charging battery marking, containing 2~12% by mass of Zn and containing (M~h5 f%% of Sn, the remaining part is made of copper and inevitable In the copper alloy strip composed of the impurities, the aspect ratio of the crystal grains in the thickness direction and the parallel direction of the rolling is 〇.丨 or more, and the following reflow plating is performed: the thickness of the 811 layer after the reflow is 〇 Io'j 6〇μΐΏ, and the thickness of the Cu-Sn compound is 〇1〇~丨9〇μιη. 2. The Sn-plated copper alloy strip according to item i of the patent application is implemented with a Ni/Cu substrate or Cu base mineral deposit 3. If the copper alloy strip of the second or second patent application scope, the conductivity is 31 ~ 70% IACS » 4. For the copper alloy strip of the second or second patent application, 18〇 The number of times of repeated bending in the tight bending and spine recovery test is 25 or more. 5. The copper alloy strip of the second or second patent application has a tensile strength of 300 to 610 MPa ° 24