JP2016184494A - Tab lead material for film exterior package battery and manufacturing method for the same - Google Patents
Tab lead material for film exterior package battery and manufacturing method for the same Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
Description
本発明は、リチウムイオンポリマー電池や電気二重層キャパシタ等に好適に用いられるフィルム外装電池用タブリード材料及びその製造方法に関する。 The present invention relates to a tab lead material for a film-clad battery that is suitably used for a lithium ion polymer battery, an electric double layer capacitor, and the like, and a method for producing the same.
携帯機器等の電源として、リチウムイオン二次電池や電気二重層キャパシタ等（以下、これらをまとめて「電池」と称する）が用いられているが、これら電池の軽量化や薄型化がますます要望されている。このようなことから、電池の外装体として、金属ケースよりも軽量で薄いラミネートフィルムが用いられてきている。
このフィルム外装電池は、電極及び電解質を含む電池本体をフィルム外装体で密封して包装した構造になっている。そして、電池内部の電極（正極及び負極）に導電性のタブリードが接続され、この一対のタブリードがフィルム外装体の合わせ目のシール部から外部に露出して外部と電気的接続が可能となっている。
Lithium ion secondary batteries, electric double layer capacitors, etc. (hereinafter collectively referred to as “batteries”) are used as power sources for portable devices, etc., but these batteries are becoming increasingly lighter and thinner. Has been. For this reason, a laminate film that is lighter and thinner than a metal case has been used as a battery outer package.
This film-clad battery has a structure in which a battery body including an electrode and an electrolyte is sealed and packaged with a film-clad body. Then, conductive tab leads are connected to the electrodes (positive electrode and negative electrode) inside the battery, and the pair of tab leads are exposed to the outside from the sealing portion of the joint of the film outer package so that they can be electrically connected to the outside. Yes.
ところで、フィルム外装体の密封を維持するため、タブリードはフィルム外装体と隙間なく密着する必要があり、例えばタブリードとフィルム外装体の内面とは接着テープによって接着されている。また、タブリードは、電池内部で電解質に接触するため、電解質に対する耐食性が求められる。
このようなことから、リード線金属の表面に樹脂成分と金属塩とを含む処理液を噴霧して複合皮膜層を形成し、さらにその上に絶縁体を貼り合わせ、耐フッ酸性を向上させた技術が開示されている（特許文献１）。
By the way, in order to maintain the sealing of the film outer package, the tab lead needs to be in close contact with the film outer package without any gap. For example, the tab lead and the inner surface of the film outer package are bonded by an adhesive tape. Moreover, since the tab lead contacts the electrolyte inside the battery, corrosion resistance to the electrolyte is required.
For this reason, a treatment liquid containing a resin component and a metal salt is sprayed on the surface of the lead wire metal to form a composite coating layer, and an insulator is further bonded thereon to improve hydrofluoric acid resistance. A technique is disclosed (Patent Document 1).
しかしながら、特許文献１記載の技術の場合、樹脂を含んだ処理液を噴霧する工程や、その後に乾燥硬化する工程などが必要となり、生産性が低下したり製造工程が複雑になるという問題がある。また、樹脂を含む複合皮膜層がリード線金属の接点部や端子部に塗着すると、接点部の電気接続性や端子部の溶接性が低下する。このため、接点部や端子部をマスキングしたり、余分な皮膜を剥離、研磨する必要が生じ、生産性がさらに低下するおそれがある。
さらに、タブリードを電池内部に引き回したり、電池を携帯機器内に収容する際に電池外部のタブリードを曲げることがあり、タブリードにはある程度の曲げ性が要求されるが、特許文献１記載の技術の場合、リードを曲げると複合皮膜層がひび割れたり脱落する可能性がある。
一方、タブリードとしてＮｉが用いられているが、Ｎｉは高価であるため、Ｃｕ又はＣｕ合金に代替することが考えられる。しかしながら、Ｃｕ又はＣｕ合金はＮｉに比べて溶接性が劣ることが判明した。
However, in the case of the technique described in Patent Document 1, there is a problem that a step of spraying a treatment liquid containing a resin, a step of drying and curing after that, and the like are required, resulting in a decrease in productivity and a complicated manufacturing process. . Moreover, when the composite coating layer containing resin is applied to the contact portion or terminal portion of the lead wire metal, the electrical connectivity of the contact portion and the weldability of the terminal portion are reduced. For this reason, it is necessary to mask the contact portion and the terminal portion, or to peel off and polish an excessive film, which may further reduce the productivity.
Further, the tab lead may be routed inside the battery or the tab lead outside the battery may be bent when the battery is accommodated in the portable device. The tab lead is required to have a certain degree of bendability. In this case, bending the lead may cause the composite coating layer to crack or fall off.
On the other hand, Ni is used as the tab lead. However, since Ni is expensive, it is conceivable to replace it with Cu or a Cu alloy. However, it has been found that Cu or Cu alloys have poor weldability compared to Ni.
従って、本発明の目的は、フィルム外装体との密着性、耐食性、溶接性及び曲げ性に優れると共に、生産性にも優れたフィルム外装電池用タブリード材料及びその製造方法を提供することにある。 Accordingly, an object of the present invention is to provide a tab lead material for a film-clad battery and a method for producing the same, which are excellent in adhesion with a film outer package, corrosion resistance, weldability, and bendability and also in productivity.
本発明者らは種々検討した結果、Ｃｕ又はＣｕ合金からなる基材の表面にＮｉめっき層を２層めっきし、そのうち上層側のＮｉめっき層中のＳ濃度を高くすることで、上層側のＮｉめっき層が優先的に腐食され、下層側のＮｉめっき層の耐食性を確保できることを見出した。
上記の目的を達成するために、本発明のフィルム外装電池用タブリード材料は、フィルム外装電池の内部の電極に接続されると共に該フィルム外装電池の外部に取り出されるフィルム外装電池用タブリード材料であって、Ｃｕ又はＣｕ合金からなる基材の表面に第１Ｎｉめっき層が形成され、その上に第２Ｎｉめっき層が形成されてなり、前記第１Ｎｉめっき層が８００質量ｐｐｍ以下のＳを含み、かつ前記第２Ｎｉめっき層が１０００〜２５０００質量ｐｐｍのＳを含む。
As a result of various studies, the present inventors have plated the surface of the substrate made of Cu or Cu alloy with two Ni plating layers, and by increasing the S concentration in the upper Ni plating layer, the upper layer side It has been found that the Ni plating layer is preferentially corroded and the corrosion resistance of the lower Ni plating layer can be secured.
In order to achieve the above object, a tab lead material for a film-clad battery according to the present invention is a tab lead material for a film-clad battery that is connected to an electrode inside the film-clad battery and taken out of the film-clad battery. A first Ni plating layer is formed on the surface of a substrate made of Cu or Cu alloy, a second Ni plating layer is formed thereon, the first Ni plating layer contains 800 ppm by mass or less of S, and The second Ni plating layer contains 1000 to 25000 mass ppm of S.
前記第１Ｎｉめっき層の厚みが０．２〜７．０μｍ、かつ前記第２Ｎｉめっき層の厚みが０．２〜２．０μｍであることが好ましい。
前記第２Ｎｉめっき層の表面に、厚みが１〜１０ｎｍの３価Ｃｒの化成処理膜が形成されてなることが好ましい。
It is preferable that the thickness of the first Ni plating layer is 0.2 to 7.0 μm and the thickness of the second Ni plating layer is 0.2 to 2.0 μm.
Preferably, a trivalent Cr chemical conversion film having a thickness of 1 to 10 nm is formed on the surface of the second Ni plating layer.
本発明のフィルム外装電池用タブリード材料の製造方法は、フィルム外装電池の内部の電極に接続されると共に該フィルム外装電池の外部に取り出されるフィルム外装電池用タブリード材料の製造方法であって、Ｃｕ又はＣｕ合金からなる基材の表面に、８００質量ｐｐｍ以下のＳを含む第１Ｎｉめっき層をめっきした後、１０００〜２５０００質量ｐｐｍのＳを含む第２Ｎｉめっき層をめっきする。 The method for producing a tab lead material for a film-clad battery according to the present invention is a method for producing a tab lead material for a film-clad battery that is connected to an electrode inside the film-clad battery and is taken out of the film-clad battery, After plating the surface of the base material made of Cu alloy with the first Ni plating layer containing 800 mass ppm or less of S, the second Ni plating layer containing 1000 to 25000 mass ppm of S is plated.
本発明のフィルム外装電池用タブリード材料の製造方法において、前記第１Ｎｉめっき層の厚みを０．２〜７．０μｍ、かつ前記第２Ｎｉめっき層の厚みを０．２〜２．０μｍとすることが好ましい。
前記第２Ｎｉめっき層の表面に、厚みが１〜１０ｎｍの３価Ｃｒの化成処理膜を形成することが好ましい。
In the method for producing a tab lead material for a film-clad battery according to the present invention, the thickness of the first Ni plating layer may be 0.2 to 7.0 μm, and the thickness of the second Ni plating layer may be 0.2 to 2.0 μm. preferable.
It is preferable to form a trivalent Cr chemical conversion film having a thickness of 1 to 10 nm on the surface of the second Ni plating layer.
本発明によれば、フィルム外装体との密着性、耐食性、溶接性及び曲げ性に優れると共に、生産性にも優れたフィルム外装電池用タブリード材料が得られる。 ADVANTAGE OF THE INVENTION According to this invention, while being excellent in adhesiveness with a film exterior body, corrosion resistance, weldability, and bendability, the tab lead material for film exterior batteries excellent in productivity is obtained.
以下、本発明の実施形態について説明する。
図１は、タブリード１を備えたフィルム外装電池１００を示す斜視図、図２は図１のＡ−Ａ線に沿う断面図である。
図１に示すように、フィルム外装電池１００は、電極及び電解質を含む電池本体（図示せず）をフィルム外装体５で熱融着等により密封して包装した構造になっている。そして、電池内部の電極（正極及び負極）に導電性の一対のタブリード１が接続され、各タブリード１がフィルム外装体５の合わせ目のシール部５ａから外部に露出して外部と電気的接続が可能となっている。又、図１のフィルム外装電池１００は、非水電解質と、所定の活物質が塗布された正極及び負極と、セパレータとを電池本体とするリチウムイオン電池となっているが、電解質及び一対の電極を有し、電気エネルギーを蓄えて放出できるものであれば良く、電気二重層キャパシタ等を用いることもできる。
Hereinafter, embodiments of the present invention will be described.
FIG. 1 is a perspective view showing a film-clad battery 100 having a tab lead 1, and FIG. 2 is a cross-sectional view taken along the line AA in FIG.
As shown in FIG. 1, the film-clad battery 100 has a structure in which a battery body (not shown) including an electrode and an electrolyte is sealed and packaged with a film-clad body 5 by heat fusion or the like. Then, a pair of conductive tab leads 1 are connected to the electrodes (positive electrode and negative electrode) inside the battery, and each tab lead 1 is exposed to the outside from the seam seal portion 5a of the film outer package 5 to be electrically connected to the outside. It is possible. 1 is a lithium ion battery having a non-aqueous electrolyte, a positive electrode and a negative electrode coated with a predetermined active material, and a separator as a battery main body. The electrolyte and the pair of electrodes In other words, an electric double layer capacitor or the like can be used.
正極としては、例えば正極活性物質をアルミニウム等の正極集電材に塗布したものを用いることができる。負極としては、例えば負極活性物質をＣｕ等の負極集電材に塗布したものを用いることができる。
電解質としては、例えば有機溶媒等の非水溶媒にリチウム塩を配合した、液状、ゲル状および高分子ポリマー状の各種非水電解質を用いることができる。
フィルム外装体５としては、例えば金属箔の少なくとも片面に樹脂フィルムを積層したラミネートフィルムを用いることができる。金属箔としては、水を透過しないニッケル、銅、アルミニウム、ステンレス等の箔を用いることができる。樹脂フィルムとしては、ナイロン、ポリエチレン、ポリプロピレン、ポリエチレンテレフタレートなどの熱融着フィルムを用いることができる。なお、少なくともタブリード１側のフィルム外装体５は、タブリード１と絶縁を図るために金属箔が露出していない樹脂フィルム側とする必要がある。通常は、金属箔の両面に樹脂フィルムを積層する。
As the positive electrode, for example, a positive electrode active material coated on a positive electrode current collector such as aluminum can be used. As the negative electrode, for example, a negative electrode active material coated on a negative electrode current collector such as Cu can be used.
As the electrolyte, for example, various non-aqueous electrolytes in a liquid, gel-like, or polymer-like form in which a lithium salt is blended with a non-aqueous solvent such as an organic solvent can be used.
As the film outer package 5, for example, a laminate film in which a resin film is laminated on at least one surface of a metal foil can be used. As the metal foil, a foil made of nickel, copper, aluminum, stainless steel or the like that does not transmit water can be used. As the resin film, a heat-sealing film such as nylon, polyethylene, polypropylene, or polyethylene terephthalate can be used. Note that at least the film outer package 5 on the tab lead 1 side needs to be on the resin film side where the metal foil is not exposed in order to insulate the tab lead 1. Usually, a resin film is laminated on both surfaces of a metal foil.
又、図２に示すように、フィルム外装体５のシール部５ａは、一枚のフィルム外装体５を折り返した外縁部の合わせ目に形成され、タブリード１が電池の内部からシール部５ａを通って外部に取り出されている。
タブリード１は、Ｃｕ又はＣｕ合金からなる基材１ａと、基材１ａの両面にそれぞれ形成された第１Ｎｉめっき層１ｂと、各第１Ｎｉめっき層１ｂ上にそれぞれ形成された第２Ｎｉめっき層１ｃを有している。そして、シール部５ａ近傍のフィルム外装体５の内面と、タブリード１の表裏面との間は、それぞれ接着層３で隙間なく密封されている。接着層３としては、例えばポリエチレンやポリプロピレン等の粘着テープを用いることができる。
一方、フィルム外装体５の内部には電解質９及び図示しない電極（正極及び負極）が収容されている。そして、フィルム外装体５の内部で、タブリード１は、電解質９に接触すると共に、各電極のうち活物質が塗布されていない集電材露出部７に溶接等により接続されている。
なお、本実施形態では、各第２Ｎｉめっき層１ｃの表面に３価Ｃｒの化成処理膜２が形成されているが、この化成処理膜２は必須ではない。
Further, as shown in FIG. 2, the seal portion 5a of the film outer package 5 is formed at the joint of the outer edge portion of the folded film outer package 5, and the tab lead 1 passes through the seal portion 5a from the inside of the battery. Has been taken out.
The tab lead 1 includes a base 1a made of Cu or a Cu alloy, a first Ni plating layer 1b formed on each side of the base 1a, and a second Ni plating layer 1c formed on each first Ni plating layer 1b. Have. And between the inner surface of the film exterior body 5 in the vicinity of the seal portion 5a and the front and back surfaces of the tab lead 1 are sealed without gaps by the adhesive layer 3, respectively. As the adhesive layer 3, for example, an adhesive tape such as polyethylene or polypropylene can be used.
On the other hand, an electrolyte 9 and electrodes (not shown) (positive electrode and negative electrode) are accommodated inside the film outer package 5. The tab lead 1 is in contact with the electrolyte 9 inside the film outer package 5 and is connected to the current collector exposed portion 7 to which no active material is applied among the electrodes by welding or the like.
In the present embodiment, the trivalent Cr chemical conversion film 2 is formed on the surface of each second Ni plating layer 1c, but this chemical conversion film 2 is not essential.
次に、本発明の実施形態に係るフィルム外装電池用タブリード材料について詳細に説明する。図２に示すように、フィルム外装電池用タブリード材料は、Ｃｕ又はＣｕ合金からなる基材１ａの表面に第１Ｎｉめっき層１ｂが形成され、その上に第２Ｎｉめっき層１ｃが形成されてなる。 Next, the tab lead material for a film-clad battery according to the embodiment of the present invention will be described in detail. As shown in FIG. 2, the tab lead material for a film-clad battery has a first Ni plating layer 1b formed on the surface of a substrate 1a made of Cu or a Cu alloy, and a second Ni plating layer 1c formed thereon.
＜基材＞
ＣｕおよびＣｕ合金は導電性に優れ、かつ耐食性も比較的良好であるため、基材としてＣｕ又はＣｕ合金を用いる。Ｃｕ又はＣｕ合金は、例えば、ＪＩＳ−Ｈ３１００（Ｃ１０２０）に規格する無酸素銅、ＪＩＳ−Ｈ３１００（Ｃ１１００）に規格するタフピッチ銅、ＪＩＳ−Ｈ３１００（Ｃ２２００）に規格する丹銅、ＪＩＳ−Ｈ３１１０（５１９１）に規格するリン青銅、ＪＩＳ−Ｈ３１００（Ｃ２６００）に規格する黄銅、ＣＤＡ掲載合金（Ｃ７０２５）に規格するコルソン銅などが挙げられる。
特に、比較的大電流を流すタイプの電池のタブリードには、無酸素銅やタフピッチ銅などの高導電材料が好ましい。
基材の厚みは特に限定されないが、好ましくは０．１〜０．８ｍｍ、より好ましくは０．１〜０．６、さらに好ましくは０．１〜０．４ｍｍである。基材の幅は特に限定されないが、例えば幅３〜１００ｍｍ程度である。
基材は、インゴットを圧延し、さらにスリット加工して所定幅の条として製造できる。さらに必要に応じ、連続プレスにより所定形状（例えば、部分的に穴が開いた形状）の条に加工してもよい。Ｎｉめっき後のタブリードをプレス等で加工すると、加工部のめっき層が薄くなったりクラックが生じる可能性があるが、予め基材を加工した後にＮｉめっきを施すと、耐食性がより向上する。従って、耐食性をより一層向上させたい場合は、基材を加工後にＮｉめっきを施すとよい。
<Base material>
Since Cu and Cu alloy are excellent in conductivity and relatively good in corrosion resistance, Cu or Cu alloy is used as a base material. Cu or Cu alloy is, for example, oxygen-free copper standardized to JIS-H3100 (C1020), tough pitch copper standardized to JIS-H3100 (C1100), red copper standardized to JIS-H3100 (C2200), JIS-H3110 (5191). ), Phosphor bronze standardized to JIS-H3100 (C2600), corson copper standardized to CDA listed alloy (C7025), and the like.
In particular, a highly conductive material such as oxygen-free copper or tough pitch copper is preferable for the tab lead of a battery of a type in which a relatively large current flows.
Although the thickness of a base material is not specifically limited, Preferably it is 0.1-0.8 mm, More preferably, it is 0.1-0.6, More preferably, it is 0.1-0.4 mm. Although the width | variety of a base material is not specifically limited, For example, it is about 3-100 mm in width.
The base material can be manufactured as a strip having a predetermined width by rolling an ingot and further slitting the ingot. Further, if necessary, it may be processed into a strip having a predetermined shape (for example, a shape having a partially opened hole) by continuous pressing. When the tab lead after Ni plating is processed with a press or the like, the plating layer in the processed portion may be thinned or cracks may occur. However, if Ni plating is performed after the substrate is processed in advance, the corrosion resistance is further improved. Therefore, when it is desired to further improve the corrosion resistance, Ni plating may be performed after the base material is processed.
＜第１Ｎｉめっき層＞
本発明においては、基材の表面にＮｉめっき層を２層めっきし、そのうち上層側のＮｉめっき層中のＳ濃度を高くすることで、上層側のＮｉめっき層が優先的に腐食され、下層側のＮｉめっき層の耐食性を確保できる。又、Ｎｉめっき層はタブリードの溶接性を向上させる。
このうち、第１Ｎｉめっき層は、基材を保護する下地めっき層として機能し、８００質量ｐｐｍ以下のＳを含む。第１Ｎｉめっき層のＳの濃度は好ましくは６００質量ｐｐｍ以下である。なお、後述するウッド浴やスルファミン酸浴など工業的に公知のＮｉめっき液には硫酸塩やスルファミン酸塩が含有され、これらの成分がめっき過程において不可避的にめっき皮膜中に微量取り込まれるため、Ｓ濃度の下限は２０〜３０質量ｐｐｍである。
Ｎｉめっき層中のＳ濃度が高くなるほど腐食し易くなる。このため、第１Ｎｉめっき層のＳの濃度が８００質量ｐｐｍを超えると、第１Ｎｉめっき層の耐食性が低下し、その下層の基材の腐食を抑制することが困難となる。
<First Ni plating layer>
In the present invention, two Ni plating layers are plated on the surface of the substrate, and by increasing the S concentration in the upper Ni plating layer, the upper Ni plating layer is preferentially corroded, and the lower layer The corrosion resistance of the Ni plating layer on the side can be ensured. Moreover, the Ni plating layer improves the weldability of the tab lead.
Among these, a 1st Ni plating layer functions as a base plating layer which protects a base material, and contains 800 mass ppm or less of S. The concentration of S in the first Ni plating layer is preferably 600 ppm by mass or less. In addition, industrially known Ni plating solutions such as a wood bath and a sulfamic acid bath, which will be described later, contain sulfates and sulfamic acid salts, and these components are inevitably incorporated in the plating film in the plating process, The lower limit of the S concentration is 20 to 30 ppm by mass.
The higher the S concentration in the Ni plating layer, the easier it is to corrode. For this reason, when the concentration of S in the first Ni plating layer exceeds 800 mass ppm, the corrosion resistance of the first Ni plating layer is lowered, and it becomes difficult to suppress corrosion of the underlying substrate.
第１Ｎｉめっき層の厚みは、０．２〜７．０μｍが好ましく、０．５〜５．０μｍがより好ましく、０．７〜２．０μｍが最も好ましい。
第１Ｎｉめっき層の厚みが０．２μｍ未満であると、めっき層のピンホールが多くなって耐食性が低下する場合がある。第１Ｎｉめっき層の厚みが７．０μｍを超えると耐食性の効果が飽和すると共に、曲げ性が低下する場合がある。
The thickness of the first Ni plating layer is preferably 0.2 to 7.0 μm, more preferably 0.5 to 5.0 μm, and most preferably 0.7 to 2.0 μm.
If the thickness of the first Ni plating layer is less than 0.2 μm, the pinholes in the plating layer may increase and the corrosion resistance may decrease. When the thickness of the first Ni plating layer exceeds 7.0 μm, the corrosion resistance effect is saturated and the bendability may be reduced.
第１Ｎｉめっき層及び第２Ｎｉめっき層の境界は、フィルム外装電池用タブリード材料の断面をＦＩＢ（Focused Ion Beam；集束イオンビーム）により観察して区別することができる。
又、第１Ｎｉめっき層及び第２Ｎｉめっき層中のＳ濃度は、グロー放電質量分析法（ＧＤ−ＭＳ法）により、深さ方向にＳ濃度を測定することで求める。
具体的には、グロー放電質量分析法（ＧＤ−ＭＳ法）により、第２Ｎｉめっき層の表面から深さ方向にアルゴンスパッタし、厚さ方向の中央部まで削ったときのＳ濃度と、Ｃ（炭素）濃度を測定した。さらに、第２Ｎｉめっき層をアルゴンスパッタで除去した後、第１Ｎｉめっき層を深さ方向にアルゴンスパッタし、厚さ方向の中央部まで削ったときのＳ，Ｃ濃度を同様に測定した。
The boundary between the first Ni plating layer and the second Ni plating layer can be distinguished by observing the cross section of the tab lead material for a film-clad battery with a focused ion beam (FIB).
Further, the S concentration in the first Ni plating layer and the second Ni plating layer is obtained by measuring the S concentration in the depth direction by glow discharge mass spectrometry (GD-MS method).
Specifically, by glow discharge mass spectrometry (GD-MS method), argon concentration is sputtered in the depth direction from the surface of the second Ni plating layer, and the S concentration and the C ( Carbon) concentration was measured. Further, after removing the second Ni plating layer by argon sputtering, the S and C concentrations when the first Ni plating layer was argon sputtered in the depth direction and cut to the center in the thickness direction were similarly measured.
＜第２Ｎｉめっき層＞
第２Ｎｉめっき層は第１Ｎｉめっき層の表面に形成されている。上記したように第２Ｎｉめっき層中のＳ濃度を１０００〜２５０００質量ｐｐｍに高くすることで、第２Ｎｉめっき層が優先的に腐食され、下層側の第１Ｎｉめっき層の耐食性を確保できる。又、第２Ｎｉめっき層を介して相手材と溶接が行われる。
ここで、例えば第２Ｎｉめっき層に微細なピンホールが存在する場合に、第２Ｎｉめっき層より第１Ｎｉめっき層が腐食し易いと、ピンホールを介して下地の第１Ｎｉめっき層が集中的に腐食し、基材に達すると考えられる。一方、第２Ｎｉめっき層が第１Ｎｉめっき層より腐食し易いと、上記ピンホールが存在しても、ピンホール周囲で第２Ｎｉめっき層が優先的に腐食し、第１Ｎｉめっき層の腐食を抑制できると考えられる。
<Second Ni plating layer>
The second Ni plating layer is formed on the surface of the first Ni plating layer. As described above, by increasing the S concentration in the second Ni plating layer to 1000 to 25000 mass ppm, the second Ni plating layer is preferentially corroded, and the corrosion resistance of the first Ni plating layer on the lower layer side can be ensured. Further, welding with the counterpart material is performed via the second Ni plating layer.
Here, for example, when a fine pinhole exists in the second Ni plating layer, if the first Ni plating layer is more easily corroded than the second Ni plating layer, the underlying first Ni plating layer corrodes intensively through the pinhole. It is thought that the base material is reached. On the other hand, if the second Ni plating layer is more easily corroded than the first Ni plating layer, even if the pinhole exists, the second Ni plating layer corrodes preferentially around the pinhole, and the corrosion of the first Ni plating layer can be suppressed. it is conceivable that.
第２Ｎｉめっき層のＳの濃度が１０００ｐｐｍ未満であると、第２Ｎｉめっき層が第１Ｎｉめっき層に比べて優先的に腐食し難くなり、上記しためっき層全体の耐食性が低下する。一方、第２Ｎｉめっき層のＳの濃度が２５０００ｐｐｍを超えると、曲げ性が低下すると共に、めっき層が割れやすくなって耐食性も低下する。
第２Ｎｉめっき層のＳの濃度は、好ましくは１０００〜１５０００ｐｐｍである。
If the concentration of S in the second Ni plating layer is less than 1000 ppm, the second Ni plating layer is less likely to corrode preferentially than the first Ni plating layer, and the corrosion resistance of the entire plating layer described above is reduced. On the other hand, when the concentration of S in the second Ni plating layer exceeds 25000 ppm, the bendability is deteriorated, the plating layer is easily broken, and the corrosion resistance is also reduced.
The concentration of S in the second Ni plating layer is preferably 1000 to 15000 ppm.
第２Ｎｉめっき層の厚みは、０．２〜３．０μｍが好ましく、０．３〜２．０μｍがより好ましく、０．５〜１．０μｍが最も好ましい。
第２Ｎｉめっき層の厚みが０．２μｍ未満であると、第２Ｎｉめっき層が第１Ｎｉめっき層に比べて優先的に腐食し難くなり、上記しためっき層全体の耐食性が低下する場合がある。第２Ｎｉめっき層の厚みが３．０μｍを超えると、曲げ性が低下する場合がある。
The thickness of the second Ni plating layer is preferably 0.2 to 3.0 μm, more preferably 0.3 to 2.0 μm, and most preferably 0.5 to 1.0 μm.
If the thickness of the second Ni plating layer is less than 0.2 μm, the second Ni plating layer is less likely to corrode preferentially than the first Ni plating layer, and the corrosion resistance of the entire plating layer described above may be reduced. If the thickness of the second Ni plating layer exceeds 3.0 μm, the bendability may be reduced.
第１Ｎｉめっき層及び第２Ｎｉめっき層は、例えばウッド浴やスルファミン酸浴など工業的に公知のＮｉめっき液を用いた電解Ｎｉめっきで形成することができる。めっき条件も公知の条件を適用できる。
ここで、第１Ｎｉめっき層用のめっき液と、第２Ｎｉめっき層用のめっき液とに、それぞれ異なる濃度でＳ含有化合物からなる光沢剤を添加することで、各Ｎｉめっき層にＳが取り込まれ、各Ｎｉめっき層中のＳ濃度を調整することができる。Ｓ含有化合物からなる光沢剤としては、例えばスルフォン酸塩（飽和または不飽和の脂肪族のスルフォン酸塩、芳香族のスルフォン酸塩等）が挙げられ、具体的にはサッカリン、クマリン、ブチンジオール等が挙げられる。
The first Ni plating layer and the second Ni plating layer can be formed by electrolytic Ni plating using an industrially known Ni plating solution such as a wood bath or a sulfamic acid bath. Known conditions can be applied to the plating conditions.
Here, S is taken into each Ni plating layer by adding brighteners made of S-containing compounds at different concentrations to the plating solution for the first Ni plating layer and the plating solution for the second Ni plating layer. The S concentration in each Ni plating layer can be adjusted. Examples of brighteners comprising S-containing compounds include sulfonates (saturated or unsaturated aliphatic sulfonates, aromatic sulfonates, etc.), and specific examples include saccharin, coumarin, and butynediol. Is mentioned.
本発明の実施形態に係るフィルム外装電池用タブリード材料は、例えば基材の条を連続めっきライン（フープめっきライン）で、電解脱脂、酸洗等の前処理に続いて電解Ｎｉめっきして工業的に製造することができる。ここで、最初にめっきする第１Ｎｉめっき層用のめっき漕のめっき液には少ない量の上記光沢剤を添加し、次にめっきする第２Ｎｉめっき層用のめっき漕のめっき液にはこれより多い量の上記光沢剤を添加すればよい。 The tab lead material for a film-clad battery according to an embodiment of the present invention is industrially produced by, for example, subjecting a strip of a base material to a continuous plating line (hoop plating line) and electrolytic Ni plating following pretreatment such as electrolytic degreasing and pickling. Can be manufactured. Here, a small amount of the brightener is added to the plating solution for the first Ni plating layer to be plated first, and more than this to the plating solution for the second Ni plating layer to be plated next. An amount of the brightener may be added.
＜３価Ｃｒ（クロム）の化成処理膜＞
第２Ｎｉめっき層の表面に、厚みが１〜１０ｎｍの３価Ｃｒの化成処理膜が形成されていてもよい。化成処理膜は、フィルム外装体５との密着性を向上させる。
化成処理膜の厚みが１ｎｍ未満であると、密着性が低いフィルムと積層した場合の浸漬試験後の密着強度が低くなる場合がある。化成処理膜の厚みが１０ｎｍを超えると、接触抵抗が大きくなって溶接性が低下する場合がある。密着性が低いフィルムとしては、例えば市販のポリエチレン系低粘性圧着フィルムが挙げられる。
化成処理膜の厚みは、ＸＰＳ（Ｘ線光電子分光分析）により、アルゴンスパッタしながら深さ方向に成分分析を行ってＣｒ濃度が２％以上の領域を化成膜厚さとした。なおＸＰＳでは３価Ｃｒと６価Ｃｒを区別可能である。
化成処理膜の厚みが１．５〜５ｎｍであるとより好ましい。
<Chemical conversion film of trivalent Cr (chromium)>
A trivalent Cr chemical conversion film having a thickness of 1 to 10 nm may be formed on the surface of the second Ni plating layer. The chemical conversion treatment film improves the adhesion with the film outer package 5.
When the thickness of the chemical conversion treatment film is less than 1 nm, the adhesion strength after the immersion test when laminated with a film having low adhesion may be lowered. If the thickness of the chemical conversion film exceeds 10 nm, the contact resistance may increase and the weldability may decrease. Examples of the film having low adhesion include a commercially available polyethylene-based low-viscosity pressure-bonding film.
The thickness of the chemical conversion treatment film was analyzed by XPS (X-ray photoelectron spectroscopic analysis) in the depth direction while performing argon sputtering, and the region having a Cr concentration of 2% or more was defined as the chemical film thickness. In XPS, trivalent Cr and hexavalent Cr can be distinguished.
The thickness of the chemical conversion film is more preferably 1.5 to 5 nm.
化成処理膜は、例えば３価クロムを含有する溶液中に、第２Ｎｉめっき層を形成したタブリード材料を浸漬した後、乾燥して形成することができる。
３価クロムを含有する溶液としては、主成分の３価クロムの他に、亜鉛、ニッケルなどを含有する水溶性化合物を溶解した水溶液を使用することができる。水溶性の３価クロム化合物としては、例えば、硝酸クロム、硫酸クロム、塩化クロム、燐酸クロム、酢酸クロム等の塩類の他、クロム酸や重クロム酸塩等の六価クロム化合物を還元剤により３価に還元した化合物を使用することも可能である。また、これらを複数併用することもできる。
化成処理膜は、例えば上述の連続めっきラインのＮｉめっき、その後の水洗処理の工程の後に３価クロム処理槽を設け、連続的に形成する方法が効率的であり好ましい。又、めっきラインと別個に３価クロム処理ラインを設けてもよい。化成処理膜の形成は、３価クロム処理に通常使用される条件で行うことができ、処理温度、処理ｐＨ、処理時間、任意の添加剤などについて、当業者が通常行う通りに、具体的な実施の態様に応じた処理条件の変更を行うことができる。
The chemical conversion treatment film can be formed, for example, by immersing the tab lead material on which the second Ni plating layer is formed in a solution containing trivalent chromium and then drying.
As the solution containing trivalent chromium, an aqueous solution in which a water-soluble compound containing zinc, nickel or the like is dissolved in addition to the main component trivalent chromium can be used. Examples of water-soluble trivalent chromium compounds include salts of chromium nitrate, chromium sulfate, chromium chloride, chromium phosphate, chromium acetate, and hexavalent chromium compounds such as chromic acid and dichromate with a reducing agent. It is also possible to use a compound reduced to a valence. A plurality of these can also be used in combination.
For example, the chemical conversion treatment film is preferably formed by providing a trivalent chromium treatment tank after the above-described steps of Ni plating in the continuous plating line and the subsequent water washing treatment, so that it is efficient. Further, a trivalent chromium treatment line may be provided separately from the plating line. The formation of the chemical conversion treatment film can be performed under the conditions normally used for the trivalent chromium treatment, and the treatment temperature, treatment pH, treatment time, optional additives, etc. The processing conditions can be changed according to the embodiment.
以下に実施例をあげて、本発明を詳細に説明するが、本発明は以下の実施例に限定されるものではない。 EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples.
＜タブリード材の製造＞
基材となるＣｕおよびＣｕ合金として、それぞれタフピッチ銅（ＪＩＳ−Ｃ１１００）、リン青銅（ＪＩＳ−Ｃ５２００）、コルソン銅（ＪＩＳ−Ｃ７０２５）を用いた。これらの厚さ０．２ｍｍの銅合金板を、幅３０ｍｍ、長さ１００ｍｍの短冊状に切断した。
基材の両面に、第１Ｎｉめっき層と第２Ｎｉめっき層をこの順でめっきしてタブリード材料を製造した。又、一部の試料については、第２Ｎｉめっき層の表面にクロム化成処理を行って３価Ｃｒの化成処理膜を形成した。
第１Ｎｉめっき層及びの第２Ｎｉめっき層のめっき浴は、スルファミン酸浴（スルファミン酸ニッケルとホウ酸を含有、液温５５℃）に、光沢剤としてサッカリンを０〜２０ｇ/Ｌの間で種々調整し、１，４ブチンジオールを０〜５ｇ/Ｌの間で種々調整したものを用いた。これにより、各Ｎｉめっき層中のＳ濃度を調整した。
クロム化成処理は市販の３価Ｃｒ含有処理液（４０℃，ｐＨ４．５）を用い、処理液中に第２Ｎｉめっき層をめっきした後の試料を浸漬させて行った。化成処理膜の厚さは、処理液への浸漬時間を変えることで調整した。このようにして短冊状のタブリード材を製造した。
<Manufacture of tab lead materials>
Tough pitch copper (JIS-C1100), phosphor bronze (JIS-C5200), and Corson copper (JIS-C7025) were used as Cu and Cu alloy as the base material, respectively. These copper alloy plates having a thickness of 0.2 mm were cut into strips having a width of 30 mm and a length of 100 mm.
A tab lead material was produced by plating a first Ni plating layer and a second Ni plating layer in this order on both surfaces of the substrate. Moreover, about some samples, the chemical conversion treatment film of trivalent Cr was formed by performing chromium chemical conversion treatment on the surface of the second Ni plating layer.
The plating bath of the first Ni plating layer and the second Ni plating layer is variously adjusted between 0 and 20 g / L of saccharin as a brightener in a sulfamic acid bath (containing nickel sulfamate and boric acid, liquid temperature 55 ° C.). In addition, 1,4-butynediol was variously adjusted between 0 and 5 g / L. Thereby, the S concentration in each Ni plating layer was adjusted.
The chromium chemical conversion treatment was performed by using a commercially available trivalent Cr-containing treatment solution (40 ° C., pH 4.5) and immersing the sample after plating the second Ni plating layer in the treatment solution. The thickness of the chemical conversion treatment film was adjusted by changing the immersion time in the treatment liquid. In this way, a strip-shaped tab lead material was produced.
各Ｎｉめっき層の厚さはＦＩＢ（ＳＩＩナノテクノノジー社製 ＳＭＩ−３０５０ＳＥ）での断面像で各Ｎｉめっき層の境界を識別して測定した。
各Ｎｉめっき層中のＳとＣ濃度はグロー放電質量分析計（VG マイクロトレース社製 VG 9000）を用いて、上述のように測定した。
化成処理膜（クロメート層）の厚さは、ＸＰＳ（アルバックファイ社製 ＰＨＩ-５０００）による深さ方向分析を行って、上述のように測定した。
The thickness of each Ni plating layer was measured by identifying the boundary of each Ni plating layer by a cross-sectional image using FIB (SMI-3050SE, manufactured by SII Nanotechnology).
The S and C concentrations in each Ni plating layer were measured as described above using a glow discharge mass spectrometer (VG 9000 manufactured by VG Microtrace).
The thickness of the chemical conversion treatment film (chromate layer) was measured as described above by performing a depth direction analysis by XPS (PHI-5000 manufactured by ULVAC-PHI).
得られた試料につき、以下の評価を行った。
＜耐食性（腐食試験）＞
リチウムイオン電池の電解液として一般的に使用されているエチレンカーボネート＋ジメチルカーボネート＋ジエチルカーボネート液（１：１：１（モル比））にＬｉＰＦ６を１ｍｏｌ／Ｌ添加し、次に純水を電解液に対して１０００質量ｐｐｍ添加した腐食液を準備した。この腐食液に各試料を浸漬して６０℃の恒温槽の中に７２時間放置した。なお、上述のように試料は短冊形状であり、Ｎｉめっきの際にめっきセルに保持した一方の端面がめっきされずに基材が露出しているため、この露出部を腐食液に浸漬させないようにして試験を行った。
腐食試験後の試料を取出して洗浄、乾燥した後、試料表面の外観を光学顕微鏡（２０〜２００倍）で観察し、以下の基準で耐食性を評価した。評価が○、△であれば実用上問題はない。
○：腐食が観察されなかった
△：腐食点の数が１〜２個／ｍｍ２
×：腐食点の数が３個／ｍｍ２以上
なお、腐食の有無は、図４に示すようにめっき面の色調と異なる基材の銅のスポット状の色味（図４の暗部）が出たか否かで判定した。
The following evaluation was performed about the obtained sample.
<Corrosion resistance (corrosion test)>
1 mol / L of LiPF6 is added to ethylene carbonate + dimethyl carbonate + diethyl carbonate solution (1: 1: 1 (molar ratio)) generally used as an electrolyte for lithium ion batteries, and then pure water is added to the electrolyte. A corrosive solution added with 1000 ppm by mass was prepared. Each sample was immersed in this corrosive solution and left in a constant temperature bath at 60 ° C. for 72 hours. As mentioned above, the sample has a strip shape, and one end face held in the plating cell at the time of Ni plating is not plated and the base material is exposed, so that this exposed portion is not immersed in the corrosive liquid. The test was conducted.
After the sample after the corrosion test was taken out, washed and dried, the appearance of the sample surface was observed with an optical microscope (20 to 200 times), and the corrosion resistance was evaluated according to the following criteria. If evaluation is (circle) and (triangle | delta), there is no problem practically.
○: Corrosion was not observed Δ: Number of corrosion points was 1 to 2 / mm 2
×: The number of corrosion points is 3 / mm 2 or more Note that the presence or absence of corrosion produces a spot-like color of copper (dark part in FIG. 4) of the base material different from the color tone of the plating surface as shown in FIG. Judged by whether or not.
＜溶接性（接触抵抗）＞
ＪＩＳ−Ｃ５４０２（５．３）に準拠して、各試料の接触抵抗を測定した。接触抵抗は、ロレスタ２端子法ＡＰプローブを使用し、直流抵抗として測定した。
＜曲げ性（曲げ試験）＞
日本伸銅協会技術標準ＪＣＢＡ Ｔ３０７に従い、Ｗ型の金型を用いて各試料を曲げ半径Ｒ＝１．０ｍｍで曲げた。曲げ部のＮｉめっき層の割れの有無、割れの大きさを光学顕微鏡（５００倍）で観察し、以下の基準で曲げ性を評価した。評価が○、△であれば実用上問題はない。
○：Ｎｉめっき層の割れが観察されなかった
△：Ｎｉめっき層が割れたが基材は観察されなかった
×：Ｎｉめっき層が割れ、基材が観察された
なお、基材は、Ｎｉめっき層と色調と異なるので識別可能である。
<Weldability (contact resistance)>
The contact resistance of each sample was measured according to JIS-C5402 (5.3). The contact resistance was measured as a direct current resistance using a Loresta two-terminal AP probe.
<Bendability (bending test)>
Each sample was bent at a bending radius R = 1.0 mm using a W-shaped mold in accordance with Japan Copper and Brass Association Technical Standard JCBA T307. The presence or absence of cracks in the Ni plating layer at the bent part and the size of the cracks were observed with an optical microscope (500 times), and the bendability was evaluated according to the following criteria. If evaluation is (circle) and (triangle | delta), there is no problem practically.
○: Ni plating layer was not cracked Δ: Ni plating layer was cracked but the substrate was not observed ×: Ni plating layer was cracked and the substrate was observed Note that the substrate was Ni plated It can be distinguished because it is different in color from layer.
＜フィルムとの密着性＞
タブリード材の片面に、メタロセン系ポリプロピレンからなる市販のシーラントフィルム（日本ポリプロ社製、ＷＩＮＴＥＣ）を重ね、１３０℃で５秒間熱圧着させた。この試験片につき、ＪＩＳ−Ｃ５０１６に従う１８０°ピール試験を行って密着性を評価した。
○：ピール強度が５Ｎ／１０ｍｍ以上
×：ピール強度が５Ｎ／１０ｍｍ未満
<Adhesion with film>
On one side of the tab lead material, a commercially available sealant film made of metallocene polypropylene (manufactured by Nippon Polypro Co., Ltd., WINTEC) was layered and thermocompression bonded at 130 ° C. for 5 seconds. About this test piece, the 180 degree peel test according to JIS-C5016 was done, and adhesiveness was evaluated.
○: Peel strength is 5 N / 10 mm or more ×: Peel strength is less than 5 N / 10 mm
得られた結果を表１、表２に示す。 The obtained results are shown in Tables 1 and 2.
表１、表２から明らかなように、各実施例の場合、フィルムとの密着性、耐食性、溶接性及び曲げ性に優れていた。
なお、実施例１７は、第１Ｎｉめっき層をめっきする際、めっき浴中の光沢剤（サッカリン）濃度を０としたものである。
As is clear from Tables 1 and 2, in each case, the adhesion to the film, the corrosion resistance, the weldability and the bendability were excellent.
In Example 17, when the first Ni plating layer was plated, the brightener (saccharin) concentration in the plating bath was set to zero.
一方、第１Ｎｉめっき層を形成しなかった比較例１の場合、第２Ｎｉめっき層が腐食し易いために下地の基材が露出して腐食し、耐食性が劣った。
第２Ｎｉめっき層を形成しなかった比較例２の場合、第２Ｎｉめっき層が優先的に腐食されることによる下層側の第１Ｎｉめっき層の保護が実現されず、下地の基材が露出して腐食し、耐食性が劣った。これは、第１Ｎｉめっき層の微細なピンホールやめっき欠陥を通して下地の基材が直接腐食したためと考えられる。
第１Ｎｉめっき層のＳの濃度が８００質量ｐｐｍを超えた比較例３の場合、第１Ｎｉめっき層の耐食性が低下し、その下層の基材が露出して腐食し、耐食性が劣った。
第２Ｎｉめっき層のＳの濃度が１０００ｐｐｍ未満である比較例４の場合、第２Ｎｉめっき層が優先的に腐食し難くなり、下層側の第１Ｎｉめっき層の保護が十分でなくなったため、下地の基材が露出して腐食し、耐食性が劣った。
第２Ｎｉめっき層のＳの濃度が２５０００ｐｐｍを超えた比較例５の場合、曲げ性が劣ったと共に、第２Ｎｉめっき層が割れて耐食性も劣った。
On the other hand, in Comparative Example 1 in which the first Ni plating layer was not formed, the second Ni plating layer was easily corroded, so that the underlying base material was exposed and corroded, resulting in poor corrosion resistance.
In the case of Comparative Example 2 in which the second Ni plating layer was not formed, the protection of the first Ni plating layer on the lower layer side due to the preferential corrosion of the second Ni plating layer was not realized, and the underlying base material was exposed. Corroded and inferior in corrosion resistance. This is presumably because the underlying substrate was directly corroded through fine pinholes and plating defects in the first Ni plating layer.
In the case of Comparative Example 3 in which the concentration of S in the first Ni plating layer exceeded 800 ppm by mass, the corrosion resistance of the first Ni plating layer was lowered, the underlying base material was exposed and corroded, and the corrosion resistance was inferior.
In the case of Comparative Example 4 in which the concentration of S in the second Ni plating layer is less than 1000 ppm, the second Ni plating layer is not easily corroded preferentially, and the protection of the first Ni plating layer on the lower layer side is not sufficient. The material was exposed and corroded, resulting in poor corrosion resistance.
In the case of Comparative Example 5 in which the concentration of S in the second Ni plating layer exceeded 25000 ppm, the bendability was inferior, and the second Ni plating layer was cracked and the corrosion resistance was also inferior.
なお、図３、図４は、それぞれ実施例１、比較例１の試料の腐食試験後の外観を示す。実施例１の場合、試料の表面に腐食点が観察されなかったが、比較例１の場合、濃色の腐食点が観察された。 3 and 4 show the appearances of the samples of Example 1 and Comparative Example 1 after the corrosion test, respectively. In the case of Example 1, no corrosion point was observed on the surface of the sample, but in the case of Comparative Example 1, a dark color corrosion point was observed.
１ タブリード
１ａ 基材
１ｂ 第１Ｎｉめっき層
１ｃ 第２Ｎｉめっき層
１００ フィルム外装電池
DESCRIPTION OF SYMBOLS 1 Tab lead 1a Base material 1b 1st Ni plating layer 1c 2nd Ni plating layer 100 Film exterior battery
Claims (6)
Ｃｕ又はＣｕ合金からなる基材の表面に第１Ｎｉめっき層が形成され、その上に第２Ｎｉめっき層が形成されてなり、
前記第１Ｎｉめっき層が８００質量ｐｐｍ以下のＳを含み、かつ前記第２Ｎｉめっき層が１０００〜２５０００質量ｐｐｍのＳを含むフィルム外装電池用タブリード材料。 A tab lead material for a film-clad battery that is connected to an electrode inside the film-clad battery and taken out of the film-clad battery,
A first Ni plating layer is formed on the surface of a base material made of Cu or Cu alloy, and a second Ni plating layer is formed thereon,
A tab lead material for a film-clad battery, wherein the first Ni plating layer contains 800 ppm by mass or less of S, and the second Ni plating layer contains 1000 to 25000 ppm by mass of S.
Ｃｕ又はＣｕ合金からなる基材の表面に、８００質量ｐｐｍ以下のＳを含む第１Ｎｉめっき層をめっきした後、１０００〜２５０００質量ｐｐｍのＳを含む第２Ｎｉめっき層をめっきするフィルム外装電池用タブリード材料の製造方法。 A method for producing a tab lead material for a film-clad battery that is connected to an electrode inside the film-clad battery and is taken out of the film-clad battery,
Tab lead for film-clad battery, in which a surface of a base material made of Cu or Cu alloy is plated with a first Ni plating layer containing 800 mass ppm or less of S and then a second Ni plating layer containing 1000 to 25000 mass ppm of S is plated Material manufacturing method.
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