JP6803566B2 - Manufacturing method of copper three-dimensional nanostructures - Google Patents
Manufacturing method of copper three-dimensional nanostructures Download PDFInfo
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Description
本発明は、銅三次元ナノ構造体の製造方法に関し、より詳細にはスズを担持した銅三次元ナノ構造体を容易に製造することができる銅三次元ナノ構造体の製造方法に関する。 The present invention relates to a method for producing a copper three-dimensional nanostructure, and more particularly to a method for producing a copper three-dimensional nanostructure capable of easily producing a copper three-dimensional nanostructure carrying tin.
本発明者は、電解銅めっき法により、銅からなる薄い板状の析出物が基板上にランダムに交錯した形態の銅三次元ナノ構造体を形成する方法を提案した（特許文献１）。この銅三次元ナノ構造体は、薄い板状の析出物がランダムに交錯した形態となることから、きわめて比表面積が大きく、さまざまな用途に利用することが可能である。たとえば、銅三次元ナノ構造体にSnやSiといった活物質を取り込むことにより、リチウムイオン電池の負極材料として利用することができる。SnやSiはグラファイトと比較して理論容量が３倍以上もあり、活物質として実用することができれば、グラファイトを活物質としている従来の電池の充放電特性を上回る充放電特性を得ることが可能である。 The present inventor has proposed a method of forming a copper three-dimensional nanostructure in a form in which thin plate-shaped precipitates made of copper are randomly interlaced on a substrate by an electrolytic copper plating method (Patent Document 1). Since this copper three-dimensional nanostructure has a form in which thin plate-shaped precipitates are randomly interlaced, it has an extremely large specific surface area and can be used for various purposes. For example, by incorporating an active material such as Sn or Si into a copper three-dimensional nanostructure, it can be used as a negative electrode material for a lithium ion battery. Sn and Si have a theoretical capacity more than three times that of graphite, and if they can be put to practical use as active materials, it is possible to obtain charge / discharge characteristics that exceed the charge / discharge characteristics of conventional batteries that use graphite as the active material. Is.
スズを負極に使用する例としては、リチウムの吸排時のスズの形状変化を安定化させる金属を活物質の粒界に析出、結合させるといった方法（特許文献２）や、Sn−Cu、Sn−Ni、Sn-AgといったSn合金を使用する例が報告されている（非特許文献１、２）。 Examples of using tin as a negative electrode include a method of precipitating and binding a metal that stabilizes the shape change of tin during absorption and exhaustion of lithium at the grain boundary of an active material (Patent Document 2), Sn-Cu, Sn- Examples of using Sn alloys such as Ni and Sn-Ag have been reported (Non-Patent Documents 1 and 2).
本発明者は、銅三次元ナノ構造体にSnを取り込む方法として、めっき法により銅三次元ナノ構造体にスズを担持する方法を検討している。無電解スズめっきは、薄板状の析出物がランダムに交錯した複雑な形態を備える銅三次元ナノ構造体の内部にまでめっき液が行き渡ることで、銅三次元ナノ構造体の内部の析出物の表面にも均一にスズめっきを施すことができる。 The present inventor is studying a method of supporting tin in a copper three-dimensional nanostructure by a plating method as a method of incorporating Sn into the copper three-dimensional nanostructure. In electrolytic tin plating, the plating solution spreads to the inside of a copper three-dimensional nanostructure having a complicated morphology in which thin plate-like precipitates are randomly interlaced, so that the precipitate inside the copper three-dimensional nanostructure is deposited. The surface can also be uniformly tin-plated.
しかしながら、銅三次元ナノ構造体に無電解スズめっきを施すと、銅三次元ナノ構造体を支持している基板である銅板がめっき時に溶解するという問題が生じた。銅三次元ナノ構造体は、銅の薄板の基部部分で基板と連結するから、基板が溶融すると銅三次元ナノ構造体と基板との密着性が損なわれ、銅三次元ナノ構造体の構造も損なわれてしまうという問題がある。 However, when electroless tin plating is applied to the copper three-dimensional nanostructures, there is a problem that the copper plate, which is the substrate supporting the copper three-dimensional nanostructures, melts during plating. Since the copper three-dimensional nanostructure is connected to the substrate at the base of the thin copper plate, when the substrate melts, the adhesion between the copper three-dimensional nanostructure and the substrate is impaired, and the structure of the copper three-dimensional nanostructure also becomes. There is a problem that it is damaged.
本発明は銅三次元ナノ構造体を形成した被めっき物に対し無電解スズめっきを施した際に基板を溶解したりすることなく、三次元ナノ構造体の形態を保持して確実にスズめっきを施すことができる銅三次元ナノ構造体の製造方法を提供することを目的とする。 The present invention retains the morphology of the three-dimensional nanostructures and ensures tin plating without melting the substrate when electroless tin plating is applied to the object to be plated on which the copper three-dimensional nanostructures are formed. It is an object of the present invention to provide a method for producing a copper three-dimensional nanostructure which can be subjected to plating.
本発明に係る銅三次元ナノ構造体の製造方法は、銅からなる基板の表面に、無電解スズめっきにより溶解しない金属からなるバリア層を形成する工程と、前記バリア層を形成した基板に電解銅めっきを施し、前記バリア層の表面に、銅からなる薄板状の析出物がランダムに交錯して形成された銅三次元ナノ構造体を形成する工程と、前記銅三次元ナノ構造体を形成した基板に無電解スズめっきを施し、前記銅三次元ナノ構造体にスズを担持させる工程とを備え、前記バリア層を形成する工程においては、バリア層としてニッケル層を形成し、前記銅三次元ナノ構造体を形成する工程においては、ポリアクリル酸を添加剤とし、ポリアクリル酸の添加濃度ｃを2×10 -5 M＜ｃ＜2×10 -3 Mの範囲に設定した銅めっき浴を使用して銅三次元ナノ構造体を形成し、前記銅三次元ナノ構造体にスズを担持させる工程においては、添加剤としてチオ尿素を使用するめっき浴を用いて銅三次元ナノ構造体にスズを担持することを特徴とする。
銅三次元ナノ構造体を形成した基板に無電解スズめっきを施し、銅三次元ナノ構造体にスズを担持させる工程を備えることにより、スズを担持した銅三次元ナノ構造体を製造することができる。無電解スズめっきを利用することにより、銅三次元ナノ構造体の内部まで均一にスズめっきが施され、きわめて比表面積の大きな銅三次元ナノ構造体にスズが担持された三次元ナノ構造体を得ることができる。
銅三次元ナノ構造体に均一に活物質のスズを担持したことにより、リチウムイオンの吸排効率が極めて高く、優れた電気容量特性を備えるリチウムイオン電池の負極材料として利用することができる。
The method for producing a copper three-dimensional nanostructure according to the present invention includes a step of forming a barrier layer made of a metal that does not dissolve by electrolytic tin plating on the surface of a substrate made of copper , and electrolysis on the substrate on which the barrier layer is formed. A step of forming a copper three-dimensional nanostructure formed by randomly interlacing thin plate-like precipitates made of copper on the surface of the barrier layer by copper plating, and forming the copper three-dimensional nanostructure. In the step of forming the barrier layer, a nickel layer is formed as the barrier layer, and the copper three-dimensional structure is provided, which comprises a step of subjecting the prepared substrate to electroless tin plating and supporting tin on the copper three-dimensional nanostructure. In the process of forming the nanostructure, a copper plating bath in which polyacrylic acid is used as an additive and the concentration c of polyacrylic acid is set in the range of 2 × 10 -5 M <c <2 × 10 -3 M is used. In the step of forming a copper three-dimensional nanostructure using the copper three-dimensional nanostructure and supporting tin on the copper three-dimensional nanostructure, tin is applied to the copper three-dimensional nanostructure using a plating bath using thiourea as an additive. It is characterized by carrying .
Subjected to electroless tin plating on the substrate formed with copper three-dimensional nano-structures, by providing a step of carrying a tin copper three-dimensional nano-structures, it is possible to manufacture a copper three-dimensional nano-structure supporting tin it can. By using electroless tin plating, tin plating is uniformly applied to the inside of the copper three-dimensional nanostructure, and a three-dimensional nanostructure in which tin is supported on a copper three-dimensional nanostructure having an extremely large specific surface area is formed. Obtainable.
Since the active material tin is uniformly supported on the copper three-dimensional nanostructure, it can be used as a negative electrode material for a lithium ion battery having extremely high lithium ion absorption / exhaust efficiency and excellent electric capacity characteristics.
基板に形成するバリア層は、銅三次元ナノ構造体を形成した基板に無電解スズめっきを施す際に、銅基板が無電解スズめっき液により溶解することを防止する目的で設ける。したがって、バリア層には無電解スズめっきの際に溶解しない金属であれば適宜金属を用いることができる。無電解スズめっきにおいては添加剤としてチオ尿素を使用する。銅と比較してこのチオ尿素（またはその誘導体）と錯イオンを形成しにくい金属であればバリア層の金属として用いることができる。
バリア層としてニッケル層を設ける方法は、めっき法により簡単にバリア層を設けることができること、ニッケル層が無電解スズめっきを施す際に基板が溶解することを防止するバリア層として確実に作用する点で有効である。
なお、電解めっきにより銅三次元ナノ構造体を形成する場合の下地層は銅に限定されるものではなく、ニッケル層等のバリア層を下地層として銅三次元ナノ構造体を形成することが可能である。
The barrier layer formed on the substrate is provided for the purpose of preventing the copper substrate from being dissolved by the electroless tin plating solution when electroless tin plating is applied to the substrate on which the copper three-dimensional nanostructure is formed. Therefore, any metal that does not dissolve during electroless tin plating can be appropriately used for the barrier layer. Thiourea is used as an additive in electroless tin plating. Any metal that is less likely to form complex ions with this thiourea (or a derivative thereof) than copper can be used as a metal for the barrier layer.
The method of providing the nickel layer as the barrier layer is that the barrier layer can be easily provided by the plating method, and that the nickel layer surely acts as a barrier layer that prevents the substrate from melting when electroless tin plating is performed. It is effective in.
When forming a copper three-dimensional nanostructure by electroplating, the base layer is not limited to copper, and it is possible to form a copper three-dimensional nanostructure using a barrier layer such as a nickel layer as a base layer. Is.
電解銅めっきにより基板のバリア層上に銅三次元ナノ構造体を形成する際には、ポリアクリル酸を添加剤とする銅めっき浴を用いることにより銅三次元ナノ構造体を形成することができる。銅めっき浴に添加するポリアクリル酸の添加濃度ｃを、2×10 -5 M＜ｃ＜2×10 -3 Mの範囲に設定した銅めっき浴を使用することにより、銅が薄板状にランダムに交錯して析出した銅三次元ナノ構造体を形成することができる。
When forming a copper three-dimensional nanostructure on the barrier layer of a substrate by electrolytic copper plating, the copper three-dimensional nanostructure can be formed by using a copper plating bath containing polyacrylic acid as an additive. .. By using a copper plating bath in which the concentration c of polyacrylic acid added to the copper plating bath is set in the range of 2 × 10 -5 M <c <2 × 10 -3 M, copper is randomly formed into a thin plate. Ru can be formed of copper three-dimensional nano-structure precipitated interlaced to.
また、銅三次元ナノ構造体にスズを担持させた銅三次元ナノ構造体を製造する他の方法として、銅三次元ナノ構造体を形成する基板そのものを無電解スズめっきにより溶解しない金属により作製し、この基板に銅三次元ナノ構造体を形成し、次いで無電解スズめっきを施すことにより銅三次元ナノ構造体にスズを担持させた銅三次元ナノ構造体を製造することが可能である。 In addition, as another method for producing a copper three-dimensional nanostructure in which tin is supported on a copper three-dimensional nanostructure, the substrate itself forming the copper three-dimensional nanostructure is made of a metal that does not dissolve by electroless tin plating. Then, by forming a copper three-dimensional nanostructure on this substrate and then subjecting it to electroless tin plating, it is possible to manufacture a copper three-dimensional nanostructure in which tin is supported on the copper three-dimensional nanostructure. ..
本発明に係る銅三次元ナノ構造体の製造方法によれば、無電解スズめっきを利用して銅三次元ナノ構造体に確実にスズを担持させることができ、リチウムイオン電池の負極材料等として好適に利用できる銅三次元ナノ構造体を製造することができる。 According to the method for producing a copper three-dimensional nanostructure according to the present invention, tin can be reliably supported on the copper three-dimensional nanostructure by utilizing electroless tin plating, and it can be used as a negative electrode material for a lithium ion battery or the like. Copper three-dimensional nanostructures that can be suitably used can be produced.
本発明に係る銅三次元ナノ構造体の製造方法は、銅三次元ナノ構造体に無電解スズめっきを施す際に、銅三次元ナノ構造体を支持する基板が溶解することを防止し、銅三次元ナノ構造体の特徴的な構造が阻害されないように無電解スズめっきを施すことができる銅三次元ナノ構造体を提供するものである。
銅三次元ナノ構造体を支持する基板が無電解スズめっき液によって溶解されないようにし、銅三次元ナノ構造体の構造を維持する方法として、本発明では、基板の表面に無電解スズめっきによって基板が侵されることを防止するバリア層を設け、バリア層上に銅三次元ナノ構造体を形成する。
The method for producing a copper three-dimensional nanostructure according to the present invention prevents the substrate supporting the copper three-dimensional nanostructure from melting when the copper three-dimensional nanostructure is subjected to electroless tin plating, and copper. It is an object of the present invention to provide a copper three-dimensional nanostructure that can be subjected to electrolytic tin plating so that the characteristic structure of the three-dimensional nanostructure is not disturbed.
In the present invention, as a method of preventing the substrate supporting the copper three-dimensional nanostructure from being dissolved by the electroless tin plating solution and maintaining the structure of the copper three-dimensional nanostructure, the substrate is subjected to electroless tin plating on the surface of the substrate. A barrier layer is provided to prevent the coating from being attacked, and a copper three-dimensional nanostructure is formed on the barrier layer.
バリア層は、無電解スズめっきの際に基板が溶解することを防止するための層であり、無電解スズめっきによって侵されない金属、たとえばニッケルを用いることができる。バリア層は、無電解スズめっきによって侵されないバリア機能を基板に付与するためのものであり、バリア機能を備えるものであればニッケル以外の金属を用いることができる。
バリア層を形成する方法にはめっき等の適宜成膜方法を利用することができる。
基板に設けるバリア層の厚さも、無電解スズめっきの際に基板が侵されることが防止できる厚さであればよい。ニッケルめっきによってバリア層を形成した実験例では、ニッケルめっき層の厚さを0.15μm〜1.5μmとすることでバリア層として機能する実験結果が得られている。
The barrier layer is a layer for preventing the substrate from melting during electroless tin plating, and a metal that is not attacked by electroless tin plating, such as nickel, can be used. The barrier layer is for imparting a barrier function to the substrate that is not affected by electroless tin plating, and a metal other than nickel can be used as long as it has a barrier function.
As a method for forming the barrier layer, an appropriate film forming method such as plating can be used.
The thickness of the barrier layer provided on the substrate may be a thickness that can prevent the substrate from being attacked during electroless tin plating. In the experimental example in which the barrier layer was formed by nickel plating, the experimental result of functioning as a barrier layer was obtained by setting the thickness of the nickel plating layer to 0.15 μm to 1.5 μm.
基板にバリア層を形成し、バリア層の上に電解銅めっきを施して銅三次元ナノ構造体を形成する。実験によれば、バリア層としてニッケル層を設け、電解銅めっきによりこのニッケル層を下地層として銅三次元ナノ構造体が得られることを確認している。すなわち、銅三次元ナノ構造体は基板（下地層）を銅以外の金属を使用しても形成することができる。
銅三次元ナノ構造体を形成する際のめっき条件として、銅めっき浴に添加剤としてポリアクリル酸を使用し、ポリアクリル酸の添加濃度ｃを2×10-5 M＜ｃ＜2×10-3 Mの範囲に設定することで銅三次元ナノ構造体を形成することができること、とくに好適な範囲ｃが、1×10-4 M＜ｃ＜5×10-4 Mであることが知られている（特許文献１）。銅以外の下地層を利用する場合も、銅めっき浴に添加するポリアクリル酸の濃度をこれらの範囲内に設定することにより銅三次元ナノ構造体を形成することができる。
A barrier layer is formed on the substrate, and electrolytic copper plating is applied on the barrier layer to form a copper three-dimensional nanostructure. According to the experiment, it has been confirmed that a nickel layer is provided as a barrier layer, and that a copper three-dimensional nanostructure can be obtained by electrolytic copper plating using this nickel layer as a base layer. That is, the copper three-dimensional nanostructure can be formed by using a metal other than copper for the substrate (underlayer).
As the plating conditions for forming a copper three-dimensional nano-structures, using a polyacrylic acid as an additive to a copper plating bath, the addition concentration c of polyacrylic acid 2 × 10 -5 M <c < 2 × 10 - It is known that copper three-dimensional nanostructures can be formed by setting the range to 3 M, and that a particularly suitable range c is 1 × 10 -4 M <c <5 × 10 -4 M. (Patent Document 1). Even when a base layer other than copper is used, a copper three-dimensional nanostructure can be formed by setting the concentration of polyacrylic acid added to the copper plating bath within these ranges.
（銅三次元ナノ構造体の作製例：基板 銅板）
基板に銅板を使用し、基板にバリア層を形成せずに電解銅めっき法により、基板上に銅三次元ナノ構造体を形成した。めっき浴として下記のめっき浴を使用した。
CuSO4・5H2O ：0.85M
H2SO4 ：0.55M
添加剤 ポリアクリル酸（分子量：5000) ：3×10-4 M
電解銅めっきにより銅三次元ナノ構造体を形成する場合に、添加剤としてポリアクリル酸を特定の範囲で添加することが有効である。ここでは銅三次元ナノ構造体を形成するためのポリアクリル酸の添加量をとくに好適な範囲内に設定した。
(Example of manufacturing copper three-dimensional nanostructure: substrate copper plate)
A copper plate was used for the substrate, and a copper three-dimensional nanostructure was formed on the substrate by an electrolytic copper plating method without forming a barrier layer on the substrate. The following plating bath was used as the plating bath.
CuSO 4 · 5H 2 O: 0.85M
H 2 SO 4 : 0.55M
Additive Polyacrylic acid (Molecular weight: 5000): 3 x 10 -4 M
When forming a three-dimensional copper nanostructure by electrolytic copper plating, it is effective to add polyacrylic acid as an additive in a specific range. Here, the amount of polyacrylic acid added to form the copper three-dimensional nanostructure was set within a particularly suitable range.
めっき膜作製条件は下記のように設定した。
カソード ：銅板
アノード ：含リン銅板
電流規制法 電流密度 ：1.0 Adm-2
通電量 :30C (膜厚約3〜4μm)
液温 : 25℃±0.5℃
撹拌 ：なし
時間 :300sec
The plating film preparation conditions were set as follows.
Cathode: Copper plate Anode: Phosphorus-containing copper plate Current regulation law Current density: 1.0 Adm -2
Energization amount: 30C (film thickness about 3-4μm)
Liquid temperature: 25 ° C ± 0.5 ° C
Stirring: None Time: 300sec
図１に、銅三次元ナノ構造体を形成した銅板の外観写真を示す。図１で黒色に見える部分が銅三次元ナノ構造体が形成されている領域である。銅三次元ナノ構造体は光を反射しないため、黒色に見える。
図２に銅三次元ナノ構造体の表面SEM像を示す。図２からわかるように、銅三次元ナノ構造体は銅の薄い板状体（厚さ数十nm）が交錯してランダムに入り組んだ形態となる。板状体がランダムに交錯した形態となることから、構造体の内部に複雑な空隙が形成され、比表面積がきわめて大きな構造体となる。
FIG. 1 shows an external photograph of a copper plate on which a copper three-dimensional nanostructure is formed. The part that looks black in FIG. 1 is the region where the copper three-dimensional nanostructure is formed. Copper three-dimensional nanostructures do not reflect light and therefore appear black.
FIG. 2 shows a surface SEM image of a copper three-dimensional nanostructure. As can be seen from FIG. 2, the copper three-dimensional nanostructure has a form in which thin copper plates (thickness of several tens of nm) are interlaced and randomly intertwined. Since the plate-like bodies are randomly interlaced, complex voids are formed inside the structure, resulting in a structure having an extremely large specific surface area.
（銅三次元ナノ構造体の作製例：基板 銅板に光沢ニッケルめっき）
銅板にバリア層として光沢ニッケルめっきを施し、電解銅めっきにより、バリア層の上に銅三次元ナノ構造体を形成した。
光沢ニッケルめっきとして、下記の光沢ワット浴を使用した。
NiSO4・6H2O ：1M
NiCl2・6H2O ：0.2M
H3BO3 ：0.5M
サッカリンNa ：0.01M
ブチンジオール ：0.0025M
(Example of manufacturing copper three-dimensional nanostructure: glossy nickel plating on substrate copper plate)
A copper plate was plated with bright nickel as a barrier layer, and a copper three-dimensional nanostructure was formed on the barrier layer by electrolytic copper plating.
The following glossy watt bath was used as the glossy nickel plating.
NiSO 4・ 6H 2 O: 1M
NiCl 2 · 6H 2 O: 0.2M
H 3 BO 3 : 0.5M
Saccharin Na: 0.01M
Butindiol: 0.0025M
光沢ニッケルめっきのめっき膜作製条件を以下に示す。
カソード : Cu板
アノード : Ni板
電流規制法 電流密度 ：3.0 Adm-2
通電量 :30C、15C、6C、3C
液温 : 25℃±0.5℃
撹拌 ：なし
時間 : 100sec、50sec、20sec、10sec
The conditions for producing a plating film for bright nickel plating are shown below.
Cathode: Cu plate Anode: Ni plate Current regulation law Current density: 3.0 Adm -2
Energization amount: 30C, 15C, 6C, 3C
Liquid temperature: 25 ° C ± 0.5 ° C
Stirring: None Time: 100sec, 50sec, 20sec, 10sec
めっき時間を変えて銅板上にめっき厚が1.5μm、0.7μm、0.3μm、0.15μmのニッケルめっきを施した４種のサンプルを作製した後、電解銅めっきにより、バリア層の上に銅三次元ナノ構造体を形成した。
銅三次元ナノ構造体を形成するめっき浴及び電析条件は、上述した銅板上に銅三次元ナノ構造体を形成しためっき条件と同一である。
Four types of samples were prepared by nickel-plating 1.5 μm, 0.7 μm, 0.3 μm, and 0.15 μm on a copper plate with different plating times, and then electrolytic copper plating was performed to create three-dimensional copper on the barrier layer. A nanostructure was formed.
The plating bath and electrodeposition conditions for forming the copper three-dimensional nanostructures are the same as the plating conditions for forming the copper three-dimensional nanostructures on the copper plate described above.
図３に、銅板に光沢ニッケルめっきをし、さらに電解銅めっきを施して銅三次元ナノ構造体を形成したサンプルの外観写真を示す。図３(a)、(b)、(c)、(d)は、それぞれ厚さ1.5μm、0.7μm、0.3μm、0.15μmの光沢ニッケルめっき膜を施したサンプルの表面に、銅三次元ナノ構造体を形成したものである。図３に示すサンプルの外観からは、ニッケルめっきの厚さによる差異はほとんど見られない。 FIG. 3 shows an external photograph of a sample in which a copper plate is plated with bright nickel and then electrolytic copper is plated to form a copper three-dimensional nanostructure. Figures 3 (a), (b), (c), and (d) show three-dimensional copper nanostructures on the surface of a sample coated with a bright nickel-plated film having thicknesses of 1.5 μm, 0.7 μm, 0.3 μm, and 0.15 μm, respectively. It forms a structure. From the appearance of the sample shown in FIG. 3, there is almost no difference due to the thickness of the nickel plating.
図４は、図３に示した下地層のニッケルめっきの厚さが異なる４種のサンプルの表面SEM像である。ニッケルめっきの厚さに関わらず、４種のサンプルとも同様の形態の銅三次元ナノ構造体が形成されている。図５は、図４のSEM像をより高倍率にしたものである。
図５に示すSEM像からも、図２に示したと同様に、すなわち銅板上にじかに銅三次元ナノ構造体を形成した場合と同様な、銅三次元ナノ構造体が形成されていることがわかる。
FIG. 4 is a surface SEM image of four types of samples having different nickel plating thicknesses of the base layer shown in FIG. Regardless of the thickness of the nickel plating, copper three-dimensional nanostructures having the same shape are formed in all four types of samples. FIG. 5 is a higher magnification of the SEM image of FIG.
From the SEM image shown in FIG. 5, it can be seen that the copper three-dimensional nanostructures are formed in the same manner as in FIG. 2, that is, similar to the case where the copper three-dimensional nanostructures are directly formed on the copper plate. ..
（銅三次元ナノ構造体の作製例：基板 銅板に無光沢ニッケルめっき）
銅板に無光沢ニッケルめっきを施し、電解銅めっきにより、銅三次元ナノ構造体を形成した。
無光沢ニッケルめっきとして、下記の無光沢ワット浴を使用した。
NiSO4・6H2O ：1M
NiCl2・6H2O ：0.2M
H3BO3 ：0.5M
(Example of manufacturing copper three-dimensional nanostructure: matte nickel plating on substrate copper plate)
A copper plate was plated with matte nickel, and a copper three-dimensional nanostructure was formed by electrolytic copper plating.
The following matte watt bath was used as the matte nickel plating.
NiSO 4・ 6H 2 O: 1M
NiCl 2 · 6H 2 O: 0.2M
H 3 BO 3 : 0.5M
無光沢ニッケルめっきによるめっき膜作製条件は、上述した光沢ニッケルめっきによるめっき膜作製条件と同一とした。
図６に、銅板に無光沢ニッケルめっきをし、さらに電解銅めっきを施して銅三次元ナノ構造体を形成したサンプルの外観写真を示す。図６(a)、(b)、(c)、(d)は、それぞれ厚さ1.5μm、0.7μm、0.3μm、0.15μmの無光沢ニッケルめっき膜を施したサンプルの表面に、銅三次元ナノ構造体を形成したものである。
図６に示すサンプルの外観と図３に示すサンプルの外観を比較すると、無光沢ニッケルめっきを施したものの方が、光沢ニッケルめっきを施したものよりも、若干むらがある（不均一）ように見える。
The conditions for producing a plating film by matte nickel plating were the same as the conditions for producing a plating film by bright nickel plating described above.
FIG. 6 shows an external photograph of a sample in which a copper plate is plated with matte nickel and further plated with electrolytic copper to form a copper three-dimensional nanostructure. Figures 6 (a), (b), (c), and (d) show three-dimensional copper on the surface of a sample coated with a matte nickel-plated film having thicknesses of 1.5 μm, 0.7 μm, 0.3 μm, and 0.15 μm, respectively. It forms a nanostructure.
Comparing the appearance of the sample shown in FIG. 6 with the appearance of the sample shown in FIG. 3, it seems that the matte nickel-plated one is slightly uneven (non-uniform) than the glossy nickel-plated one. appear.
図７は、図６のニッケルめっきの厚さが異なる４種のサンプルについての表面SEM像、図８は図７よりも高倍率とした表面SEM像である。
これらの表面SEM像と、図２の銅板上に銅三次元ナノ構造体を形成したサンプルの表面SEM像とを比較すると、銅三次元ナノ構造体の構造にはほとんど差異がみられない。すなわち、銅板に無光沢ニッケルめっきを施し、電解銅めっきにより銅三次元ナノ構造体を形成した場合も、銅板にじかに銅三次元ナノ構造体を形成した場合と同様の銅三次元ナノ構造体が形成される。すなわち、銅三次元ナノ構造体を形成する下地層は銅に限定されるものではなく、ニッケル層を下地層として銅三次元ナノ構造体を形成することができる。
FIG. 7 is a surface SEM image of four types of samples having different nickel plating thicknesses in FIG. 6, and FIG. 8 is a surface SEM image at a higher magnification than that of FIG.
Comparing these surface SEM images with the surface SEM images of the sample in which the copper three-dimensional nanostructures are formed on the copper plate of FIG. 2, there is almost no difference in the structure of the copper three-dimensional nanostructures. That is, even when the copper plate is plated with matte nickel and the copper three-dimensional nanostructure is formed by electrolytic copper plating, the same copper three-dimensional nanostructure as when the copper three-dimensional nanostructure is directly formed on the copper plate is obtained. It is formed. That is, the base layer for forming the copper three-dimensional nanostructure is not limited to copper, and the copper three-dimensional nanostructure can be formed by using the nickel layer as the base layer.
（銅三次元ナノ構造体：無電解スズめっき）
銅板の表面にバリア層としてニッケルめっきを施し、次いで電解銅めっきにより銅三次元ナノ構造体を形成し、さらに無電解スズめっき（置換スズめっき）を施す実験を行った。
銅板の基板にはバリア層として光沢ニッケルめっきを施した。光沢ニッケルめっきに用いためっき浴、めっき膜作製条件は前述した光沢ニッケルめっきと同一である。また、バリア層上に電解めっきにより銅三次元ナノ構造体を形成するためのめっき浴及びめっき膜作製条件は下記のとおりである。
めっき浴
CuSO4・5H2O ：0.85M H2SO4 ：0.55M
ポリアクリル酸（分子量：5000) ：2.5×10-4 M
めっき膜作製条件
カソード ：光沢ニッケルめっき銅板 アノード ：含リン銅板
電流規制法 電流密度 ：1.2 Adm-2 通電量 :90C
液温 : 25℃±1℃ 撹拌 ：なし 時間 :750sec
(Copper three-dimensional nanostructure: electroless tin plating)
An experiment was conducted in which nickel plating was applied to the surface of a copper plate as a barrier layer, then a copper three-dimensional nanostructure was formed by electrolytic copper plating, and electroless tin plating (substitution tin plating) was further applied.
The copper plate substrate was plated with bright nickel as a barrier layer. The plating bath and plating film preparation conditions used for bright nickel plating are the same as those for bright nickel plating described above. The plating bath and plating film preparation conditions for forming a copper three-dimensional nanostructure on the barrier layer by electrolytic plating are as follows.
Plating bath
CuSO 4 · 5H 2 O: 0.85MH 2 SO 4: 0.55M
Polyacrylic acid (molecular weight: 5000): 2.5 x 10 -4 M
Plating film preparation conditions Cathode: Glossy nickel-plated copper plate Anode: Phosphorus-containing copper plate Current regulation law Current density: 1.2 Adm -2 Energization amount: 90C
Liquid temperature: 25 ° C ± 1 ° C Stirring: None Time: 750sec
無電解スズめっきに用いためっき浴とめっき膜作製条件は下記のとおりである。
めっき浴
K4P2O7 ：0.5M
Sn2P2O7 ：0.15M
チオ尿素 ：3M
HCl 適量（pH 5に調整）
PEG600（ポリエチレングリコール） ：0.002M
次亜リン酸Na ：0.005M
SDS（ドデシル硫酸ナトリウム） ：0.1g/L
めっき膜作製条件
基板 ：ニッケルめっき上に銅三次元ナノ構造体を形成
セル ：500mLビーカー
液量 ：300mL
温度 ：85℃
時間 ：15sec
攪拌 ：カソードロッカー
The plating bath and plating film preparation conditions used for electroless tin plating are as follows.
Plating bath
K 4 P 2 O 7 : 0.5M
Sn 2 P 2 O 7 : 0.15M
Thiourea: 3M
Appropriate amount of HCl (adjusted to pH 5)
PEG600 (polyethylene glycol): 0.002M
Na hypophosphate: 0.005M
SDS (sodium dodecyl sulfate): 0.1 g / L
Plating film preparation conditions Substrate: Copper three-dimensional nanostructure formed on nickel plating Cell: 500 mL Beaker Liquid volume: 300 mL
Temperature: 85 ℃
Time: 15sec
Stirring: Cathode rocker
図９は、基板に光沢ニッケルめっきを施し、銅三次元ナノ構造体を形成したサンプルに無電解スズめっきを施す前後における表面SEM像である。スズめっきを施す前と、スズめっきを施した後のそれぞれについて、低倍率と高倍率の像を示す。
無電解スズめっきを施した前後で銅三次元ナノ構造体の構造はほとんど変わらない。図９の表面SEM像から、無電解スズめっきを施したことにより、銅三次元ナノ構造体の構造に変化が生じないことがわかる。
FIG. 9 is a surface SEM image before and after electroless tin plating is applied to a sample in which a substrate is plated with bright nickel and a copper three-dimensional nanostructure is formed. Images of low magnification and high magnification are shown before tin plating and after tin plating, respectively.
The structure of the copper three-dimensional nanostructure is almost the same before and after electroless tin plating. From the surface SEM image of FIG. 9, it can be seen that the structure of the copper three-dimensional nanostructure does not change due to the electroless tin plating.
図１０は、無電解スズめっきを施す前後における断面SEM像である。それぞれ低倍率と高倍率の像を示す。この断面SEM像からも、無電解スズめっきを施した前後における銅三次元ナノ構造体の構造について明らかな変化は見られない。すなわち、無電解スズめっきを施しても銅三次元ナノ構造体の構造はそのまま維持されている。 FIG. 10 is a cross-sectional SEM image before and after electroless tin plating. Images with low magnification and high magnification are shown, respectively. From this cross-sectional SEM image, there is no clear change in the structure of the copper three-dimensional nanostructure before and after electroless tin plating. That is, the structure of the copper three-dimensional nanostructure is maintained as it is even if electroless tin plating is applied.
図１１は、無電解スズめっきを施したサンプルの断面SEM像とEPMA像（電子線マイクロアナライザによる像）である。EPMA像から、銅三次元ナノ構造体の全体にわたってCu(銅）が分布していること、また銅三次元ナノ構造体の厚さ方向の全体にわたってSn(スズ）が分布していることがわかる。すなわち、無電解スズめっきにより、銅三次元ナノ構造体の内部にまで均等にスズめっきが施されている。 FIG. 11 is a cross-sectional SEM image and an EPMA image (image by an electron probe microanalyzer) of the sample subjected to electroless tin plating. From the EPMA image, it can be seen that Cu (copper) is distributed throughout the copper three-dimensional nanostructure, and Sn (tin) is distributed throughout the thickness direction of the copper three-dimensional nanostructure. .. That is, by electroless tin plating, tin plating is evenly applied to the inside of the copper three-dimensional nanostructure.
図１２は、バリア層としてのニッケルめっき層の作用を示す。図１２(a)は、銅板上にニッケルめっきを施した後に、銅三次元ナノ構造体を形成し、さらに無電解スズめっきを施したサンプル、図１２(b)は、銅板にニッケルめっきを施さずに銅三次元ナノ構造体を形成し、無電解スズめっきを施したサンプルの断面SEM像を示す。
銅板にあらかじめニッケルめっきを施したもの（図１２(a)）では、無電解スズめっきを施しても、銅板の表面が溶解せず、銅三次元ナノ構造体は当初の構造を維持している。
一方、銅板にニッケルめっきを施さずに無電解スズめっきを施したものでは（図１２(b)）、基板の表面が溶解して侵食され銅三次元ナノ構造体の構造が崩れてしまっている。
この図１２に示す実験結果は、銅板の表面にニッケルめっきを施す方法が、銅三次元ナノ構造体の構造を損なうことなく、無電解スズめっきにより銅三次元ナノ構造体の表面にスズを担持させる方法として有効であることを示す。
FIG. 12 shows the action of the nickel plating layer as the barrier layer. FIG. 12 (a) shows a sample in which a copper three-dimensional nanostructure is formed after nickel plating on a copper plate and then electroless tin plating is performed. FIG. 12 (b) shows a sample in which a copper plate is nickel plated. A cross-sectional SEM image of a sample obtained by forming a copper three-dimensional nanostructure without electroless tin plating is shown.
In the case where the copper plate is nickel-plated in advance (Fig. 12 (a)), the surface of the copper plate does not melt even if electroless tin plating is applied, and the copper three-dimensional nanostructure maintains its original structure. ..
On the other hand, in the case where the copper plate is electroless tin-plated without nickel plating (Fig. 12 (b)), the surface of the substrate is melted and eroded, and the structure of the copper three-dimensional nanostructure is destroyed. ..
The experimental results shown in FIG. 12 show that the method of nickel plating the surface of the copper plate supports tin on the surface of the copper three-dimensional nanostructure by electroless tin plating without damaging the structure of the copper three-dimensional nanostructure. It is shown that it is effective as a method of making it.
（銅三次元ナノ構造体：無電解スズめっき方法）
銅板にバリア層と銅三次元ナノ構造体を形成した後、無電解スズめっきを施す際に用いるめっき浴の添加剤による作用を調べた結果について説明する。
バリア層として光沢ニッケルめっきを施した。光沢ニッケルめっきのめっき条件は前述した光沢ニッケルめっきと同一である。バリア層上に形成する銅三次元ナノ構造体のめっき条件も上述した無電解スズめっきのめっき条件と同一である。
(Copper three-dimensional nanostructure: electroless tin plating method)
After forming a barrier layer and a copper three-dimensional nanostructure on a copper plate, the results of investigating the action of the additives in the plating bath used when performing electroless tin plating will be described.
Glossy nickel plating was applied as a barrier layer. The plating conditions for bright nickel plating are the same as those for bright nickel plating described above. The plating conditions for the copper three-dimensional nanostructures formed on the barrier layer are also the same as the plating conditions for electroless tin plating described above.
無電解スズめっきには下記の基本浴と光沢浴の２種類を使用した。それぞれのめっき浴の組成と無電解スズめっき条件を以下に示す。
基本浴
K4P2O7 ：0.5M Sn2P2O7 ：0.15M チオ尿素 ：3M
光沢浴
K4P2O7 ：0.5M Sn2P2O7 ：0.15M チオ尿素 ：3M
PEG600 ：0.003M
ベンズアルデヒド ：0.1g/L
基本浴、光沢浴ともに、HClを用いてめっき浴をｐH=5に調整した。基本浴は添加剤PEG600とベンズアルデヒドを添加していないものである。
無電解スズめっき条件
基板 ：銅板、光沢ニッケルめっき、銅三次元ナノ構造体
液量 ：300mL
液温 ：85℃
攪拌 ：なし
時間 ：15sec
The following two types of basic bath and gloss bath were used for electroless tin plating. The composition of each plating bath and electroless tin plating conditions are shown below.
Basic bath
K 4 P 2 O 7 : 0.5M Sn 2 P 2 O 7 : 0.15M Thiourea: 3M
Glossy bath
K 4 P 2 O 7 : 0.5M Sn 2 P 2 O 7 : 0.15M Thiourea: 3M
PEG600: 0.003M
Benzaldehyde: 0.1 g / L
In both the basic bath and the gloss bath, the plating bath was adjusted to pH = 5 using HCl. The basic bath is one without the additives PEG600 and benzaldehyde.
Electroless tin plating conditions Substrate: Copper plate, bright nickel plating, copper three-dimensional nanostructure Liquid volume: 300 mL
Liquid temperature: 85 ° C
Stirring: None Time: 15sec
図１３は、めっき浴に添加した添加剤の作用を調べるため、銅三次元ナノ構造体を形成していない銅板に上記めっき条件で無電解スズめっきを施したサンプルの表面SEM像である。図１３で基本浴とあるのは、上記基本浴を用いてめっきしたもの、光沢浴とあるのは上記光沢浴を用いてめっきしたものである。
図１３から、添加剤を加えない場合には、銅板の表面に析出するSn粒子の大きさが数μｍ程度であるのに対し、添加剤を加えためっき浴を用いるとSn粒子の粒径がはるかに小さくなることがわかる。
FIG. 13 is a surface SEM image of a sample obtained by electroless tin plating on a copper plate on which a copper three-dimensional nanostructure is not formed in order to investigate the action of the additive added to the plating bath. In FIG. 13, the basic bath is plated using the basic bath, and the gloss bath is plated using the gloss bath.
From FIG. 13, when no additive is added, the size of the Sn particles precipitated on the surface of the copper plate is about several μm, whereas when the plating bath with the additive is used, the particle size of the Sn particles becomes large. It turns out that it is much smaller.
図１４は、銅三次元ナノ構造体を形成した基板に基本浴と光沢浴を用いて無電解スズめっきを施したサンプルの表面SEM像、図１５は断面SEM像である。断面SEM像には銅基板の表面位置（ニッケルめっきのよるバリア層の位置）を示す。
図１４のSEM像から、無電解スズめっきにより銅三次元ナノ構造体を構成する銅の薄板の表面に微細なSn粒子が均一に析出していることがわかる。図１５の断面SEM像からは、無電解スズめっきにより銅基板が侵食されていないことがわかる。
FIG. 14 is a surface SEM image of a sample obtained by electroless tin plating on a substrate on which a copper three-dimensional nanostructure is formed using a basic bath and a gloss bath, and FIG. 15 is a cross-sectional SEM image. The cross-sectional SEM image shows the surface position of the copper substrate (the position of the barrier layer by nickel plating).
From the SEM image of FIG. 14, it can be seen that fine Sn particles are uniformly deposited on the surface of the thin copper plate constituting the copper three-dimensional nanostructure by electroless tin plating. From the cross-sectional SEM image of FIG. 15, it can be seen that the copper substrate is not eroded by electroless tin plating.
図１６は、基本浴と光沢浴を用いて無電解スズめっきを施したサンプルの断面における元素マッピング像である。図１６から、銅基板の表面位置に薄くニッケル層からなるバリア層が形成され、バリア層の上に銅三次元ナノ構造体が形成されていること、Snが銅三次元ナノ構造体の全体に均一に析出していることがわかる。この実験結果は、銅三次元ナノ構造体の内部にまで均一にSnを析出させる方法として無電解スズめっき方法が有効であることを示す。 FIG. 16 is an element mapping image of a cross section of an electroless tin-plated sample using a basic bath and a gloss bath. From FIG. 16, a barrier layer composed of a thin nickel layer is formed at the surface position of the copper substrate, a copper three-dimensional nanostructure is formed on the barrier layer, and Sn is applied to the entire copper three-dimensional nanostructure. It can be seen that the precipitation is uniform. This experimental result shows that the electroless tin plating method is effective as a method for uniformly depositing Sn even inside the copper three-dimensional nanostructure.
（コインセルを用いた充放電試験）
銅三次元ナノ構造体に無電解スズめっきを施した銅板の充放電特性を調べるため、下記の構成を備える二電極式コインセルを用いて充放電試験を行った。
セル ：２電極式コインセル（2032型）
負極 ：作製試料（銅三次元ナノ構造体に無電解スズめっき）
電解液 ：1 M LiPF6 (EC:DEC＝ 1:1 vol %)
測定電位範囲 ：0.02 −1.5 V
電流密度 ：200mA/g
(Charge / discharge test using coin cell)
In order to investigate the charge / discharge characteristics of a copper plate in which an electroless tin plating is applied to a copper three-dimensional nanostructure, a charge / discharge test was conducted using a two-electrode coin cell having the following configuration.
Cell: 2-electrode coin cell (2032 type)
Negative electrode: Fabrication sample (electroless tin plating on copper three-dimensional nanostructures)
Electrolyte: 1 M LiPF 6 (EC: DEC = 1: 1 vol%)
Measurement potential range: 0.02 −1.5 V
Current density: 200mA / g
図１７に、銅三次元ナノ構造体を形成していない銅板に無電解スズめっきを施したサンプル（Cu基板）と、銅板に銅三次元ナノ構造体を形成し無電解スズめっきを施したサンプル（三次元銅）について充放電特性を測定した結果を示す。いずれのサンプルも無電解スズめっきには上記基本浴を用いた。
図１７は、充放電サイクル３０回行った結果である。図１７から、銅板に単に無電解スズめっきを施した場合と、銅三次元ナノ構造体に無電解スズめっきを施した場合とでは、充電量、放電量に大きな差があることがわかる。
FIG. 17 shows a sample (Cu substrate) in which a copper plate on which a copper three-dimensional nanostructure is not formed is electroless tin-plated, and a sample in which a copper three-dimensional nanostructure is formed on a copper plate and electroless tin-plated. The results of measuring the charge / discharge characteristics of (three-dimensional copper) are shown. In each sample, the above basic bath was used for electroless tin plating.
FIG. 17 shows the results of 30 charge / discharge cycles. From FIG. 17, it can be seen that there is a large difference in the amount of charge and the amount of discharge between the case where the copper plate is simply electroless tin-plated and the case where the copper three-dimensional nanostructure is electroless tin-plated.
図１８は電池のサイクル特性（サイクル数30）を示す。「Cu基板」とあるのは銅基板に銅三次元ナノ構造体を形成せずに無電解スズめっきを施したサンプル、「三次元銅」とあるのは、銅基板に銅三次元ナノ構造体を形成し無電解スズめっきを施したサンプルである。図１８には、無電解スズめっきを施すめっき浴として基本浴を使用した場合と、光沢浴を使用した場合について示す。
銅三次元ナノ構造体に無電解スズめっきを施したサンプルについては、30サイクル経過後の状態で、グラファイトの理論容量（375mAh/g）の約２倍の放電容量が得られている。なお、無電解スズめっきに基本浴を使用したサンプルと光沢浴を使用したサンプルとで明確な差異は見られない。
FIG. 18 shows the cycle characteristics of the battery (number of cycles: 30). "Cu substrate" is a sample obtained by electroless tin plating without forming a copper three-dimensional nanostructure on a copper substrate, and "three-dimensional copper" is a copper three-dimensional nanostructure on a copper substrate. This is a sample formed by electroless tin plating. FIG. 18 shows a case where a basic bath is used as a plating bath for electroless tin plating and a case where a gloss bath is used.
For the sample in which the copper three-dimensional nanostructure is electroless tin-plated, a discharge capacity about twice the theoretical capacity (375 mAh / g) of graphite is obtained after 30 cycles. There is no clear difference between the sample using the basic bath for electroless tin plating and the sample using the gloss bath.
Claims (2)
前記バリア層を形成した基板に電解銅めっきを施し、前記バリア層の表面に、銅からなる薄板状の析出物がランダムに交錯して形成された銅三次元ナノ構造体を形成する工程と、
前記銅三次元ナノ構造体を形成した基板に無電解スズめっきを施し、前記銅三次元ナノ構造体にスズを担持させる工程とを備え、
前記バリア層を形成する工程においては、バリア層としてニッケル層を形成し、
前記銅三次元ナノ構造体を形成する工程においては、ポリアクリル酸を添加剤とし、ポリアクリル酸の添加濃度ｃを2×10 -5 M＜ｃ＜2×10 -3 Mの範囲に設定した銅めっき浴を使用して銅三次元ナノ構造体を形成し、
前記銅三次元ナノ構造体にスズを担持させる工程においては、添加剤としてチオ尿素を使用するめっき浴を用いて銅三次元ナノ構造体にスズを担持することを特徴とする銅三次元ナノ構造体の製造方法。 A process of forming a barrier layer made of metal that does not dissolve by electroless tin plating on the surface of a substrate made of copper , and
A step of subjecting a substrate on which the barrier layer is formed to electrolytic copper plating, and forming a copper three-dimensional nanostructure formed by randomly interlacing thin plate-like precipitates made of copper on the surface of the barrier layer.
The substrate on which the copper three-dimensional nanostructure is formed is subjected to electroless tin plating, and the copper three-dimensional nanostructure is provided with a step of supporting tin.
In the step of forming the barrier layer, a nickel layer is formed as the barrier layer, and the nickel layer is formed.
In the step of forming the copper three-dimensional nanostructure, polyacrylic acid was used as an additive, and the addition concentration c of polyacrylic acid was set in the range of 2 × 10 -5 M <c <2 × 10 -3 M. A copper plating bath is used to form copper three-dimensional nanostructures,
In the step of supporting tin on the copper three-dimensional nanostructure, the copper three-dimensional nanostructure is characterized in that tin is supported on the copper three-dimensional nanostructure by using a plating bath using thiourea as an additive. How to make a body.
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