JP4803550B2 - Composition for electrolytic formation of silver oxide film - Google Patents
Composition for electrolytic formation of silver oxide film Download PDFInfo
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本発明は、銀酸化物膜を電解法によって形成するために使用できる組成物及び銀酸化物膜の形成方法に関する。 The present invention relates to a composition that can be used for forming a silver oxide film by an electrolytic method and a method for forming a silver oxide film.
酸化銀（Ａｇ２Ｏ）、過酸化銀（ＡｇＯ）等の銀酸化物は、禁制帯幅が結晶性Ｓｉと同程度の１．１〜１．５ｅＶの酸化物半導体であり、吸収係数の大きい物質である。この様な特性を利用して、銀酸化物は、太陽電池の光吸収層としての利用が期待されており、更に、粉末状、粒子状などの銀酸化物は、酸化銀電池の正極活物質としても利用されている。 Silver oxides such as silver oxide (Ag 2 O) and silver peroxide (AgO) are 1.1 to 1.5 eV oxide semiconductors having a forbidden band width similar to that of crystalline Si and have a large absorption coefficient. It is a substance. Utilizing such characteristics, silver oxide is expected to be used as a light-absorbing layer in solar cells. Further, silver oxide in powder form, particulate form, etc. is used as a positive electrode active material for silver oxide batteries. It is also used as.
酸化銀（Ａｇ２Ｏ）の製造方法としては、例えば、加圧加熱下において、銀塩をアルカリ液で加水分解する方法（下記特許文献１参照）、陽極室と中間室の間の隔膜として陰イオン交換膜を設置し、陰極室と中間室の間の隔膜として陽イオン交換膜を設置した三室電解槽において中間室に塩水溶液をアノードに銀電極を用い、電解で得られる陽極室からの銀水溶液と陰極室からの苛性アルカリ溶液を反応させる方法（下記特許文献２）等が知られている。 As a method for producing silver oxide (Ag 2 O), for example, a method in which a silver salt is hydrolyzed with an alkaline solution under pressure and heating (see Patent Document 1 below), and a negative electrode is used as a diaphragm between an anode chamber and an intermediate chamber. In a three-chamber electrolytic cell in which an ion exchange membrane is installed and a cation exchange membrane is installed as a diaphragm between the cathode chamber and the intermediate chamber, a salt solution is used in the intermediate chamber and a silver electrode is used as the anode. A method of reacting an aqueous solution with a caustic solution from a cathode chamber (Patent Document 2 below) is known.
また、過酸化銀（ＡｇＯ）については、酢酸銀などの水溶液銀塩を含む水溶液中で陽極電解反応を行うことによって、基板上に過酸化銀膜が形成されることが報告されている（下記非特許文献１）。 As for silver peroxide (AgO), it is reported that a silver peroxide film is formed on a substrate by performing an anodic electrolysis reaction in an aqueous solution containing an aqueous silver salt such as silver acetate (described below). Non-patent document 1).
更に、膜状の酸化銀については、反応性スパッタリング法によって形成できることが知られている。 Furthermore, it is known that film-like silver oxide can be formed by a reactive sputtering method.
以上のように、銀酸化物の製造方法として各種の方法が知られているが、酸化銀（Ag2O）、過酸化銀（AgO）等の銀酸化物を幅広い用途に適用可能とするためには、真空排気装置や加熱装置などの大規模装置を必要とすることなく、比較的容易な方法によって各種用途に使用し得る銀酸化物を製造可能な方法が望まれている。
本発明は、上記した従来技術の現状に鑑みてなされたものであり、その主な目的は、大規模装置を必要とすることなく、簡単な製造方法によって、良好な銀酸化物を得ることができる、新規な銀酸化物の製造方法を提供することである。 The present invention has been made in view of the current state of the prior art described above, and its main object is to obtain a good silver oxide by a simple manufacturing method without requiring a large-scale apparatus. It is to provide a novel method for producing silver oxide.
本発明者は、上記した目的を達成すべく鋭意研究を重ねてきた。その結果、銀化合物と錯化剤を含有するｐＨ５以上の水溶液中での陽極電解という簡単な方法によって、大規模な装置を用いることなく、水溶液中における電解各種の基材上に膜厚、組成などの均一性に優れた良好な銀酸化物膜を形成できることを見出し、ここに本発明を完成するに至った。 The present inventor has intensively studied to achieve the above-described object. As a result, film thickness, composition on various substrates of electrolysis in aqueous solution by simple method of anodic electrolysis in aqueous solution of pH 5 or higher containing silver compound and complexing agent without using large-scale equipment The present inventors have found that it is possible to form a good silver oxide film having excellent uniformity such as the above, and have completed the present invention.
即ち、本発明は、下記の銀酸化物膜電解形成用組成物及び銀酸化物膜の形成方法を提供するものである。
１． 銀化合物及び錯化剤を含有するｐＨ５以上の水溶液からなる銀酸化物膜電解形成用組成物。
２． 錯化剤が、ｐＨ５以上の水溶液中において銀イオンを錯化して水溶性銀化合物を形成できる化合物である上記項１に記載の銀酸化物膜電解形成用組成物。
３． 上記項１又は２に記載の組成物中において、銀酸化物形成用基材を陽極として電解を行うことを特徴とする銀酸化物膜の形成方法。
That is, the present invention provides the following silver oxide film electroforming composition and silver oxide film forming method.
1. A composition for electroforming a silver oxide film, comprising an aqueous solution containing a silver compound and a complexing agent and having a pH of 5 or more.
2. Item 2. The composition for electrolytic formation of a silver oxide film according to Item 1, wherein the complexing agent is a compound capable of complexing silver ions to form a water-soluble silver compound in an aqueous solution having a pH of 5 or higher.
3. Item 3. The method for forming a silver oxide film according to item 1 or 2, wherein electrolysis is performed using the substrate for forming silver oxide as an anode.
以下、本発明の銀酸化物膜電解形成用組成物について具体的に説明する。 Hereinafter, the composition for electrolytic formation of a silver oxide film of the present invention will be specifically described.
銀酸化物膜電解形成用組成物
本発明の銀酸化物膜電解形成用組成物は、銀化合物及び錯化剤を含有する水溶液からなるものである。以下、該組成物について具体的に説明する。
Silver oxide film electroforming composition The silver oxide film electroforming composition of the present invention comprises an aqueous solution containing a silver compound and a complexing agent. Hereinafter, the composition will be specifically described.
（ｉ）銀化合物：
本発明の組成物では、銀化合物としては、後述する錯化剤と同時に用いた場合に、水溶液中で安定に存在でき、水溶液中において銀イオンを遊離する化合物であればよい。例えば、硝酸銀、酢酸銀、炭酸銀などの水溶液銀塩の他、塩化銀、酸化銀（Ａｇ２Ｏ）、過酸化銀（ＡｇＯ）等のそれ自体では不溶性及び難溶性の銀化合物も使用できる。
(I) Silver compound:
In the composition of the present invention, the silver compound may be any compound that can be stably present in an aqueous solution and liberates silver ions in the aqueous solution when used together with the complexing agent described later. For example, in addition to aqueous silver salts such as silver nitrate, silver acetate and silver carbonate, silver compounds which are insoluble and hardly soluble in themselves such as silver chloride, silver oxide (Ag 2 O), silver peroxide (AgO) and the like can be used.
銀化合物の濃度については特に限定的ではないが、銀化合物の濃度が低すぎると銀酸化物を析出させることが困難となり、一方、濃度が高くなりすぎると爆発性の窒化銀を生成する傾向にある。このための、通常、銀化合物中の銀金属量として、０．０００１ｍｏｌ／Ｌ〜２ｍｏｌ／Ｌ程度とすることが好ましく、０．００１ｍｏｌ／Ｌ〜１ｍｏｌ／Ｌ程度とすることがより好ましい。特に、銀化合物として硝酸銀を用いる場合には、通常、銀金属量として、０．０２ｍｏｌ／Ｌ〜０．５ｍｏｌ／Ｌ程度とすることが好ましい。 The concentration of the silver compound is not particularly limited. However, if the concentration of the silver compound is too low, it is difficult to precipitate silver oxide. On the other hand, if the concentration is too high, explosive silver nitride tends to be generated. is there. For this purpose, the amount of silver metal in the silver compound is usually preferably about 0.0001 mol / L to 2 mol / L, and more preferably about 0.001 mol / L to 1 mol / L. In particular, when silver nitrate is used as the silver compound, the amount of silver metal is usually preferably about 0.02 mol / L to 0.5 mol / L.
（ii）錯化剤：
錯化剤としては、ｐＨ５以上の水溶液中において銀イオンを錯化して水溶性銀化合物を形成できるものであれば特に限定なく使用できる。
(Ii) Complexing agent:
Any complexing agent can be used without particular limitation as long as it can complex silver ions in an aqueous solution having a pH of 5 or higher to form a water-soluble silver compound.
この様な錯化剤の具体例としては、アンモニア；硝酸アンモニウム、硫酸アンモニウム、炭酸アンモニウムなどの水溶性アンモニウム化合物等を使用できる。更に、アミノ基等の窒素系官能基、カルボキシル基等の酸素系官能基等の官能基を一種又は二種以上含む、銀イオンと水溶性錯体を形成し得る有機化合物も錯化剤として使用できる。この様な有機化合物の具体例としては、リシン等のアミノ酸を例示できる。 Specific examples of such complexing agents include ammonia; water-soluble ammonium compounds such as ammonium nitrate, ammonium sulfate, and ammonium carbonate. Furthermore, organic compounds that can form a water-soluble complex with silver ions, which contain one or more functional groups such as nitrogen-based functional groups such as amino groups and oxygen-based functional groups such as carboxyl groups, can also be used as complexing agents. . Specific examples of such organic compounds include amino acids such as lysine.
錯化剤の使用量は、特に限定的ではなく、添加した銀化合物の少なくとも一部が水溶液中において錯体として存在できる量であればよく、添加した銀化合物の全てが錯体を形成する量より少ない量であっても良い。例えば、不溶性の銀化合物を用いる場合には、錯化剤が不足すると一部の銀化合物が沈殿することがあるが、この場合にも、溶液中に銀錯体が飽和して存在するので、陽極酸化によって銀酸化物を析出させることができる。 The amount of the complexing agent used is not particularly limited as long as at least a part of the added silver compound can exist as a complex in the aqueous solution, and the amount of the added silver compound is less than the amount that forms a complex. It may be an amount. For example, when an insoluble silver compound is used, a part of the silver compound may precipitate if the complexing agent is insufficient. In this case, too, the silver complex is saturated and exists in the solution. Silver oxide can be deposited by oxidation.
通常、錯化剤の使用量は、銀化合物中の銀金属量に対して、錯化剤中の配位子が０．５倍当量程度以上となる量とすればよく、１倍当量以上となる量とすることが好ましい。尚、銀化合物を完全に錯体とするには、通常、銀化合物中の銀金属量に対して、錯化剤中の配位子が２．５倍当量程度以上となる量の錯化剤を添加すればよい。 Usually, the amount of complexing agent used may be an amount such that the ligand in the complexing agent is about 0.5 times equivalent or more with respect to the amount of silver metal in the silver compound. It is preferable to make it an amount. In order to completely convert the silver compound into a complex, the complexing agent is usually used in an amount such that the ligand in the complexing agent is about 2.5 times equivalent or more with respect to the amount of silver metal in the silver compound. What is necessary is just to add.
錯化剤の添加量の上限についても特に限定的ではないが、錯化剤の量が多くなりすぎると、析出した銀酸化物が再溶解し易くなる。このために、錯化剤の添加量は、銀化合物中の銀金属量に対して、錯化剤中の配位子が６倍当量程度以下となる量とすることが好ましく、５倍当量以下となる量とすることがより好ましい。 The upper limit of the addition amount of the complexing agent is not particularly limited, but when the amount of the complexing agent is excessive, the precipitated silver oxide is easily dissolved again. For this reason, the addition amount of the complexing agent is preferably such that the ligand in the complexing agent is about 6 times equivalent or less with respect to the amount of silver metal in the silver compound, and is 5 times equivalent or less. It is more preferable to set the amount to be.
尚、本願明細書において、錯化剤の配位子とは、銀イオンに配位子し得る錯化剤中に含まれる基又は原子団を意味し、例えば、水溶性アンモニウム化合物では、ＮＨ４基一個が配位子一個に相当する。 In the present specification, the ligand of the complexing agent means a group or an atomic group contained in a complexing agent capable of liganding to silver ions. For example, in a water-soluble ammonium compound, NH 4 One group corresponds to one ligand.
銀酸化物膜の形成方法
本発明の銀酸化物膜電解形成用組成物を用いて銀酸化物を形成するには、該組成物中において、銀酸化物形成用基材を陽極として電解を行えばよい。これにより、陽極において該基材上に銀酸化物膜を形成することができる。
Method for Forming Silver Oxide Film In order to form silver oxide using the composition for electrolytic formation of silver oxide film of the present invention, electrolysis is carried out in the composition using the substrate for forming silver oxide as an anode. Just do it. Thereby, a silver oxide film can be formed on the substrate at the anode.
電解方法としては、定電位電解及び定電流電解のいずれの方法も採用できる。定電位電解によって電解酸化を行う場合には、陽極電位は電解液の濃度などに応じて適宜設定すればよいが、通常、Ｐｔ参照電極基準で0mV〜2500mV程度が適当であり、200mV〜2000mV程度が好ましく、300mV〜1600mV程度が特に望ましい。この電位範囲での陽極電流密度は、基材の種類によって異なるが、通常、0.05 mA/cm2 〜100 mA/cm2 程度となる。また、定電流電解では陽極電流密度は、電解液の濃度などに応じて適宜設定すればよいが、通常、0.05 mA/cm2 〜100 mA/cm2程度が適当であり、0.1 mA/cm2 〜50 mA/cm2程度が好ましく、0.5 mA/cm2 〜35 mA/cm2程度が特に望ましい。この電流密度範囲での陽極電位は、用いる基材の種類によって異なるが、通常、0 mV〜2500mV 程度となる。銀酸化物膜の析出速度は、陽極電位が貴になるほど、言い換えれば陽極電流密度が大きいほど速くなる。
As an electrolysis method, any method of constant potential electrolysis and constant current electrolysis can be adopted. When electrolytic oxidation is performed by constant potential electrolysis, the anodic potential may be appropriately set according to the concentration of the electrolytic solution, etc., but usually 0 mV to 2500 mV is appropriate based on the Pt reference electrode, and about 200 mV to 2000 mV Is preferably about 300 mV to 1600 mV. The anode current density in this potential range varies depending on the type of substrate, but is usually about 0.05 mA / cm 2 to 100 mA / cm 2 . In constant current electrolysis, the anode current density may be set as appropriate according to the concentration of the electrolytic solution, etc., but generally 0.05 mA / cm 2 to 100 mA / cm 2 is appropriate, and 0.1 mA / cm 2 About 50 mA / cm 2 is preferable, and about 0.5 mA /
尚、陰極電解では金属銀が析出して、銀酸化物を形成することができない。 In cathodic electrolysis, metallic silver precipitates and silver oxide cannot be formed.
陰極については特に限定的ではないが、通常、カーボン、白金、白金めっきチタン等の不溶性材料を用いることができる。 Although it does not specifically limit about a cathode, Usually, insoluble materials, such as carbon, platinum, platinum plating titanium, can be used.
本発明組成物の温度は広い範囲で設定できるが、通常は、5℃〜60℃程度とすればよく、10℃〜30℃程度が好ましい。 Although the temperature of the composition of the present invention can be set in a wide range, it is usually about 5 ° C to 60 ° C, preferably about 10 ° C to 30 ° C.
本発明組成物のｐＨは５程度以上とすればよく、上限は特に限定されない。この範囲においてｐＨが高くなると酸化銀（Ａｇ２Ｏ）が形成され易くなり、ｐＨが低くなると過酸化銀（ＡｇＯ）が形成され易くなる傾向がある。形成される銀酸化物の具体的な種類は、電解液の濃度や陽極電位等にも影響されるので一概に規定できないが、通常、ｐＨが１１程度以下では過酸化銀（ＡｇＯ）が形成され易い。また、ｐＨ１２．８程度以上、例えば、１２．８〜１４程度では、酸化銀（Ａｇ２Ｏ）が形成され易くなるが、この場合には陽極電位又は電流密度を高くすることによって、過酸化銀（ＡｇＯ）を形成することができる。上記したｐＨ範囲の中間、即ち、ｐＨ１１〜１２．８程度の範囲では、酸化銀（Ａｇ２Ｏ）と過酸化銀（ＡｇＯ）が同時に形成され易くなる。 The pH of the composition of the present invention may be about 5 or more, and the upper limit is not particularly limited. If the pH is higher in this range, silver oxide (Ag 2 O) tends to be formed, and if the pH is lowered, silver peroxide (AgO) tends to be formed. The specific type of silver oxide to be formed is uncertain because it is affected by the concentration of the electrolytic solution, the anode potential, etc. Usually, silver peroxide (AgO) is formed at a pH of about 11 or less. easy. Further, when the pH is about 12.8 or more, for example, about 12.8 to 14, silver oxide (Ag 2 O) is easily formed. In this case, silver peroxide is increased by increasing the anode potential or current density. (AgO) can be formed. In the middle of the above pH range, that is, in the range of about pH 11 to 12.8, silver oxide (Ag 2 O) and silver peroxide (AgO) are easily formed simultaneously.
前述した組成及び電解条件の範囲内において、上記した傾向に基づいて条件を適宜調節することによって、目的とする銀酸化物膜を形成することができる。 The intended silver oxide film can be formed by appropriately adjusting the conditions based on the above-mentioned tendency within the range of the composition and the electrolysis conditions described above.
電解は、無攪拌または攪拌下で行なうことができ、攪拌法としては公知の方法をいずれも使用できる。 The electrolysis can be performed without stirring or with stirring, and any known method can be used as the stirring method.
本発明では、上記した条件で陽極電解を行うことによって、基材上に銀酸化物膜を形成することができる。 In the present invention, a silver oxide film can be formed on a substrate by performing anodic electrolysis under the above-described conditions.
基材の種類については特に限定されず、銀酸化物膜の使用目的に応じて適宜決めればよい。例えば、通常の電気めっきの対象となる全ての材料を基材とすることができ、銅、鉄等の金属材料、ＮＥＳＡガラス、ＩＴＯガラス等のガラス材料、セラミックス材料、プラスチックス材料等を基材とすることができる。セラミックス材料、プラスチックス材料等の非導電性材料に対しては、常法に従って、無電解めっき法等の湿式処理、ＰＶＤ法等の乾式処理等によって、導電化処理を施せばよい。基材には、上記電解を行う前に、常法に従って、前処理を施してもよい。また、電解後には、水洗、乾燥など通常行われている操作を行ってもよい。 The type of the substrate is not particularly limited, and may be appropriately determined according to the purpose of use of the silver oxide film. For example, all materials that are subject to normal electroplating can be used as a base material, and metal materials such as copper and iron, glass materials such as NESA glass and ITO glass, ceramic materials, plastics materials, etc. are used as base materials. It can be. A non-conductive material such as a ceramic material or a plastics material may be subjected to a conductive treatment by a wet process such as an electroless plating method or a dry process such as a PVD method according to a conventional method. The substrate may be pretreated according to a conventional method before the above electrolysis. Moreover, you may perform operation normally performed, such as washing with water and drying, after electrolysis.
本発明の銀酸化物膜電解形成用組成物によれば、水溶液からの陽極電解によって酸化銀膜、過酸化銀膜等の銀酸化物膜を形成することができる。この様な水溶液からの電解法によれば、真空排気装置や加熱炉などの大規模設備を必要とせず、工業的に用いられている電気めっき装置を使用でき、しかも、膜厚および組成の均一な銀酸化物膜を形成可能であって、膜厚および組成を電解条件により容易に制御できる等の各種の利点がある。 According to the composition for electrolytic formation of silver oxide film of the present invention, a silver oxide film such as a silver oxide film or a silver peroxide film can be formed by anodic electrolysis from an aqueous solution. According to the electrolytic method from such an aqueous solution, an electroplating apparatus used in industry can be used without requiring large-scale equipment such as a vacuum exhaust apparatus or a heating furnace, and the film thickness and composition are uniform. It is possible to form a simple silver oxide film, and there are various advantages such that the film thickness and composition can be easily controlled by electrolysis conditions.
以下に実施例および比較例を示し、本発明の特徴を一層明らかにする
実施例１
下記表１に記載の各成分を含有する水溶液からなる銀酸化物電解形成用組成物を調製した。
Examples and Comparative Examples are shown below to further clarify the features of the present invention.
The composition for silver oxide electrolysis formation which consists of the aqueous solution containing each component of following Table 1 was prepared.
得られた各組成物について、陽極としてＮＥＳＡガラス、陰極として白金板を使用して下記表１に示す電解条件で電解を行うことによって、ＮＥＳＡガラス上に電析膜を析出させた。形成された電析膜について、Ｘ線回折法によって電析膜の種類を調べた結果も表１示す。尚、実施例１と実施例８で得られた電析膜のＸ線回折パターンをそれぞれ図１と図２に示す。 About each obtained composition, the electrodeposition film was deposited on NESA glass by performing electrolysis on the electrolysis conditions shown in following Table 1 using NESA glass as an anode and a platinum plate as a cathode. Table 1 also shows the results of examining the types of deposited films by X-ray diffraction method. The X-ray diffraction patterns of the electrodeposited films obtained in Example 1 and Example 8 are shown in FIGS. 1 and 2, respectively.
以上の結果から明らかなように、銀化合物及び錯化剤を含む溶液中で陽極酸化を行うことによって、酸化銀（Ａｇ２Ｏ）又は過酸化銀（ＡｇＯ）の電析膜を形成できることが判る。 As is apparent from the above results, it can be seen that an electrodeposited film of silver oxide (Ag 2 O) or silver peroxide (AgO) can be formed by anodizing in a solution containing a silver compound and a complexing agent. .
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