JP2016152068A - Positive electrode, air secondary battery using the same, and method for manufacturing positive electrode - Google Patents
Positive electrode, air secondary battery using the same, and method for manufacturing positive electrode 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
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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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
Description
本発明は、アルカリ性水溶液を電解質とし、正極では放電時に酸素が還元され、充電時には酸素が発生する空気二次電池の正極およびその製造方法、並びにその正極を用いた空気二次電池に関する。 The present invention relates to a positive electrode of an air secondary battery in which an alkaline aqueous solution is used as an electrolyte, oxygen is reduced during discharge and oxygen is generated during charging, a method for manufacturing the same, and an air secondary battery using the positive electrode.
空気電池は、空気中の酸素を正極活物質とする電池であり、市販されている亜鉛／空気一次電池がよく知られている。亜鉛／空気一次電池と類似な構造を有する空気電池には、負極活物質にアルミニウムや鉄を用いる電池がある。また、空気電池は、機械式充電型の亜鉛／空気二次電池を除いて、二次電池としてはいまだ実用化されていない。機械式充電型の亜鉛／空気二次電池とは、電池の反応としては放電だけを行うもので、放電後の亜鉛負極を電池外に取り出し、新しい亜鉛負極と取り替えることで電池を再び放電できるようにしたものである。したがって、一般に知られる二次電池のように、電池で生じる充電反応により蓄電して、繰り返し利用できるものではない。なお、上記のような亜鉛、アルミニウム、鉄などを負極活物質に用いる空気電池は、通常、ＫＯＨ溶液やＮａＯＨ溶液のようなアルカリ性水溶液を電解質として用いている。 The air battery is a battery using oxygen in the air as a positive electrode active material, and a commercially available zinc / air primary battery is well known. Among air batteries having a structure similar to that of a zinc / air primary battery, there are batteries using aluminum or iron as a negative electrode active material. Air batteries are not yet put into practical use as secondary batteries except for mechanically charged zinc / air secondary batteries. The mechanical rechargeable zinc / air secondary battery only discharges as a battery reaction, and the battery can be discharged again by taking out the discharged zinc negative electrode and replacing it with a new zinc negative electrode. It is a thing. Therefore, unlike a generally known secondary battery, it cannot be stored repeatedly by charging reaction generated in the battery. Note that an air battery using zinc, aluminum, iron, or the like as described above as a negative electrode active material usually uses an alkaline aqueous solution such as a KOH solution or an NaOH solution as an electrolyte.
一方、アルカリ性水溶液を電解質とする空気二次電池として、本発明者は特許文献１および特許文献２に、水素吸蔵合金を負極に用いる空気二次電池を開示した。以下、これを水素／空気二次電池と称する。この電池では、放電と充電の際に、それぞれ以下のような式で表される電池反応が生じる。
放電：４ＭＨ＋Ｏ２→４Ｍ＋２Ｈ２Ｏ
充電：４Ｍ＋２Ｈ２Ｏ→４ＭＨ＋Ｏ２
なお、式中のＭは水素吸蔵合金を示し、ＭＨは水素を吸蔵した状態の水素吸蔵合金を意味する。また、負極に亜鉛を用いる空気二次電池（亜鉛／空気二次電池）は前述の通り実用化されていないが、その電池反応は以下の式で示される。
放電：２Ｚｎ＋Ｏ２→２ＺｎＯ
充電：２ＺｎＯ→２Ｚｎ＋Ｏ２
これらの電池では、正極で起こる反応は同じで、以下の式で示される。
放電：Ｏ２＋２Ｈ２Ｏ＋４ｅ−→４ＯＨ−
充電：４ＯＨ−→Ｏ２＋２Ｈ２Ｏ＋４ｅ−
すなわち、アルカリ性水溶液を電解質とする空気二次電池の正極では、放電時に空気中の酸素が還元されてＯＨ−がアルカリ性水溶液中に生成され、充電時にアルカリ性水溶液中のＯＨ−が酸化されてＯ２とＨ２Ｏとが生成される。
On the other hand, as an air secondary battery using an alkaline aqueous solution as an electrolyte, the present inventor disclosed in Patent Document 1 and Patent Document 2 an air secondary battery using a hydrogen storage alloy as a negative electrode. Hereinafter, this is referred to as a hydrogen / air secondary battery. In this battery, a battery reaction represented by the following equation occurs during discharging and charging.
Discharge: 4MH + O 2 → 4M + 2H 2 O
Charging: 4M + 2H 2 O → 4MH + O 2
In the formula, M represents a hydrogen storage alloy, and MH represents a hydrogen storage alloy in a state of storing hydrogen. Moreover, although the air secondary battery (zinc / air secondary battery) which uses zinc for a negative electrode is not put into practical use as above-mentioned, the battery reaction is shown by the following formula | equation.
Discharge: 2Zn + O 2 → 2ZnO
Charging: 2ZnO → 2Zn + O 2
In these batteries, the reaction occurring at the positive electrode is the same, and is represented by the following formula.
Discharge: O 2 + 2H 2 O + 4e − → 4OH −
Charging: 4OH − → O 2 + 2H 2 O + 4e −
That is, in the positive electrode of an air secondary battery using an alkaline aqueous solution as the electrolyte, when oxygen in the air is reduced to discharge OH - are generated in an alkaline aqueous solution, OH alkaline aqueous solution during charge - is oxidized O 2 And H 2 O are produced.
このような放電と充電の反応が正極で起こるためには、
１）放電の際に、空気中の酸素が正極内部に侵入して反応サイトまで到達可能であり、かつ、充電の際に、正極内部で発生した酸素が空気中に放出され得ること、
２）放電および充電の両方において、ＯＨ−とＯ２、Ｈ２Ｏの間で円滑な電子の受け渡しができるような反応サイトが提供されること、
３）電気化学的な酸化や還元が生じ、かつアルカリ性水溶液に接する雰囲気でも正極材料が安定であり、また酸素の発生に対して耐性がある（耐アルカリ性や耐酸化性に優れる）こと
などの条件を正極が満足する必要がある。
In order for such a discharge and charge reaction to occur at the positive electrode,
1) Oxygen in the air can penetrate into the positive electrode during discharge and reach the reaction site, and oxygen generated in the positive electrode during charging can be released into the air.
2) To provide a reaction site capable of smoothly transferring electrons between OH − and O 2 , H 2 O in both discharging and charging;
3) Conditions such as electrochemical oxidation and reduction, and the cathode material is stable even in an atmosphere in contact with an alkaline aqueous solution and resistant to oxygen generation (excellent alkali resistance and oxidation resistance). The positive electrode must be satisfied.
アルカリ性水溶液を電解質とする空気一次電池や空気二次電池の正極には、これまで、正極全体の導電性を保つための導電材として、様々な種類の炭素材料が用いられることが多く、例えば粉末状、粒子状、ファイバー状、チューブ状などの炭素材料が使用されている。また、その炭素材料には金属、酸化物、硫化物などの材料からなる触媒が担持されており、さらに導電材同士が接している部分の隙間などに入り込み、正極内部を結着させる作用と、正極内部に空気中の酸素が円滑に取り込まれ、または正極内部で発生する酸素が円滑に空気中に放出されるために、正極内部が電解質であるアルカリ性水溶液で完全に満たされないように、正極内部に撥水性を付与する撥水剤も正極を構成する材料として用いられ、例えば耐アルカリ性や耐酸化性に優れるポリテトラフルオロエチレンなどがその代表である。なお、撥水剤は上記に述べた役割からわかるように、結着剤とも称される。また、特許文献１および特許文献２で開示されているように、導電材にはニッケル粉末やニッケル粒子が用いられることも知られている。 For positive electrodes of air primary batteries and air secondary batteries that use an alkaline aqueous solution as an electrolyte, various types of carbon materials have often been used as conductive materials for maintaining the conductivity of the entire positive electrode. , Particulates, fibers, tubes, and other carbon materials are used. In addition, the carbon material carries a catalyst made of a material such as a metal, oxide, sulfide, etc., and further enters the gap between the portions where the conductive materials are in contact with each other, and binds the inside of the positive electrode, The oxygen inside the positive electrode is smoothly taken in or the oxygen generated inside the positive electrode is smoothly released into the air, so that the inside of the positive electrode is not completely filled with an alkaline aqueous solution that is an electrolyte. Water repellents that impart water repellency are also used as materials constituting the positive electrode, such as polytetrafluoroethylene having excellent alkali resistance and oxidation resistance. The water repellent is also referred to as a binder, as can be seen from the above-described role. In addition, as disclosed in Patent Document 1 and Patent Document 2, it is also known that nickel powder or nickel particles are used for the conductive material.
アルカリ性水溶液を電解質とする空気二次電池では、正極が前述の１）〜３）の条件を満たすことが望まれる一方、正極が可能な限り軽いことも望まれる。空気電池以外の他の形式の電池では正極活物質が正極内にあるが、空気二次電池では正極活物質が空気中の酸素であるため、正極内に貯蔵しておく必要がなく、理論的には空気二次電池の電池容量を増やすために、正極の重量をそれに伴って増やす必要はないからである。言い換えれば、正極の重量は可能な限り軽くした状態で、その重量を変えることなく、電池容量を増加させることができるのが、空気二次電池である。したがって、正極が軽くなれば、その分だけ電池全体の重量は小さくなり、放電容量と放電電圧から求められる放電エネルギー（放電容量×放電電圧）に対して、電池全体の重量の減少によって、電池重量当たりのエネルギーである重量エネルギー密度（Ｗｈ／ｋｇ）を高くすることができる。空気二次電池は、この重量エネルギー密度や、体積当たりの放電エネルギーである体積エネルギー密度（Ｗｈ／Ｌ）が、既存のリチウムイオン二次電池の理論値を上回る値を発揮できる可能性を持つことから、次世代の高エネルギー密度二次電池として期待されている。 In an air secondary battery using an alkaline aqueous solution as an electrolyte, the positive electrode is desired to satisfy the above-mentioned conditions 1) to 3), while the positive electrode is also desired to be as light as possible. In other types of batteries other than air batteries, the positive electrode active material is in the positive electrode. However, in the air secondary battery, the positive electrode active material is oxygen in the air, so there is no need to store it in the positive electrode. This is because, in order to increase the battery capacity of the air secondary battery, it is not necessary to increase the weight of the positive electrode accordingly. In other words, an air secondary battery can increase the battery capacity without changing the weight while keeping the weight of the positive electrode as light as possible. Therefore, if the positive electrode becomes lighter, the weight of the entire battery decreases accordingly, and the weight of the battery is reduced by the decrease in the weight of the entire battery with respect to the discharge energy (discharge capacity × discharge voltage) obtained from the discharge capacity and the discharge voltage. It is possible to increase the weight energy density (Wh / kg), which is the hit energy. The air secondary battery has the possibility that the weight energy density and the volume energy density (Wh / L), which is discharge energy per volume, can exceed the theoretical value of the existing lithium ion secondary battery. Therefore, it is expected as a next-generation high energy density secondary battery.
上記のようなエネルギー密度の観点からは、アルカリ性水溶液を電解質とする空気二次電池の正極の導電材としての炭素材料は、導電性がよく、比表面積を大きくすることにより触媒を高分散で担持することができ、しかも密度も小さいので、軽量な正極を作製するための材料として優れているが、耐酸化性では非常に大きな問題がある。すなわち、炭素材料は、正極で充電時に酸素が発生すると、同時に酸化されて二酸化炭素となって消耗する。このような二酸化炭素への酸化が起こって導電材である炭素が消耗すると、正極は導電性のない部分が生じて反応が起こらなくなり、炭素が消耗した部分からアルカリ性水溶液が電池外部に漏れる漏液が起こり、電池として作動できなくなる。 From the viewpoint of energy density as described above, the carbon material as the conductive material of the positive electrode of the air secondary battery using an alkaline aqueous solution as the electrolyte is highly conductive and supports the catalyst in a highly dispersed manner by increasing the specific surface area. In addition, since the density is small, it is excellent as a material for producing a light-weight positive electrode, but there is a very big problem in oxidation resistance. That is, when oxygen is generated during charging at the positive electrode, the carbon material is simultaneously oxidized and consumed as carbon dioxide. When the carbon, which is a conductive material, is consumed due to such oxidation to carbon dioxide, a non-conductive part is generated in the positive electrode, the reaction does not occur, and the alkaline aqueous solution leaks from the exhausted part of the carbon to the outside of the battery. Will occur and will not work as a battery.
これに対して、本発明者が特許文献１や特許文献２などで開示した空気二次電池の正極は、導電材としてニッケル粉末を用いたものである。アルカリ性水溶液を電解質とするニッケル水素二次電池の正極活物質がニッケルであることからも明らかなように、ニッケルはアルカリ性水溶液中で安定であり、さらに非特許文献１で開示しているように、アルカリ性水溶液を電解質とする空気二次電池の正極の導電材として用いた場合も、充電時の酸素発生に対して炭素材料のように消耗することはなく、安定性が高いことが判っている。 On the other hand, the positive electrode of the air secondary battery disclosed by the inventor in Patent Document 1 and Patent Document 2 uses nickel powder as a conductive material. As is clear from the fact that the positive electrode active material of the nickel-metal hydride secondary battery using an alkaline aqueous solution as an electrolyte is nickel, nickel is stable in an alkaline aqueous solution, and as disclosed in Non-Patent Document 1, Even when used as a positive electrode conductive material of an air secondary battery using an alkaline aqueous solution as an electrolyte, it has been found that it is not consumed like a carbon material with respect to the generation of oxygen during charging, and is highly stable.
前述のように、ニッケルは、アルカリ性水溶液中で安定であり、アルカリ性水溶液を電解質とする空気二次電池の正極の導電材として使用しても炭素材料のように酸素発生とともに消耗することはなく、高い耐アルカリ性と耐酸化性を持つ。その一方で、ニッケルは炭素に比べて密度が大きいため、ニッケルを導電材とする空気二次電池の正極は、炭素材料を導電材に用いた同じ体積の正極に比べて重くなり、その結果、空気二次電池の重量エネルギー密度が小さくなるという課題があった。 As described above, nickel is stable in an alkaline aqueous solution, and even if it is used as a conductive material for a positive electrode of an air secondary battery using an alkaline aqueous solution as an electrolyte, it is not consumed with oxygen generation like a carbon material. High alkali resistance and oxidation resistance. On the other hand, since nickel has a higher density than carbon, the positive electrode of the air secondary battery using nickel as a conductive material is heavier than the positive electrode of the same volume using a carbon material as a conductive material. There existed a subject that the weight energy density of an air secondary battery became small.
また、炭素材料などの他の導電性の非金属材料に比べてニッケルは高価であることから、ニッケルを正極の導電材に用いる場合にも、ニッケルの使用量はできるだけ少ないほうが良い。また、アルカリ性水溶液を電解質に用いる空気二次電池において、ニッケルは導電材であり、正極の活物質ではないため、導電材として使用されるニッケルは正極全体の導電性を保つことができる量があれば十分である。このような観点からは、例えばニッケル粒子を正極の導電材として用いる場合、ニッケル粒子は正極全体に導電性を付与し、かつ正極に必要な形状と機械的強度を持つことができるのであれば、中空状であってもよいと言える。言い換えると、ニッケル粒子は高い耐アルカリ性と耐酸化性を有するが、重量からはその中心部分（コア部分）が正極全体を重くする要因となり、同時に正極に使用されるニッケルのコストが大きくなる要因にもなるという課題があった。 Further, since nickel is more expensive than other conductive non-metallic materials such as a carbon material, the amount of nickel used should be as small as possible even when nickel is used for the conductive material of the positive electrode. In addition, in an air secondary battery using an alkaline aqueous solution as an electrolyte, nickel is a conductive material and not an active material for the positive electrode. Therefore, there is an amount of nickel used as the conductive material that can maintain the conductivity of the entire positive electrode. It is enough. From such a viewpoint, for example, when nickel particles are used as a conductive material for the positive electrode, the nickel particles can impart conductivity to the entire positive electrode and have the shape and mechanical strength necessary for the positive electrode. It can be said that it may be hollow. In other words, the nickel particles have high alkali resistance and oxidation resistance, but the weight increases the weight of the central part (core part), and at the same time increases the cost of nickel used for the positive electrode. There was a problem of becoming.
すなわち、従来のアルカリ性水溶液を電解質に用いる空気二次電池では、重量エネルギー密度や重量出力密度を向上させる上で、正極の軽量化が重要かつ不可欠であるのに対して、前述のような正極に求められる１）〜３）の条件を満たしながら、軽量化を可能にするような導電材がなかったため、これらを可能とする新たな正極、さらにこれらを可能とする正極の新たな製造方法、並びにその正極を用いることでエネルギー密度を向上させることができる空気二次電池が要望されていた。 That is, in the conventional air secondary battery using an alkaline aqueous solution as an electrolyte, the weight reduction of the positive electrode is important and indispensable for improving the weight energy density and the weight output density. Since there was no conductive material that can reduce the weight while satisfying the required conditions 1) to 3), a new positive electrode that enables these, a new method for manufacturing a positive electrode that enables these, and There has been a demand for an air secondary battery that can improve the energy density by using the positive electrode.
本発明は、アルカリ性水溶液を電解質に用いる空気二次電池において放電時には酸素の還元、充電時には酸素の発生を生じさせる正極であって、放電の際には正極内部に酸素が侵入して反応サイトまで到達可能であり、充電の際には正極内部で発生した酸素が空気中に放出され、かつ放電・充電ともにアルカリ性水溶液中のＯＨ−とＯ２、Ｈ２Ｏとの間で円滑な電子の受け渡しができるような反応サイトが提供されるとともに、電気化学的な酸化や還元が生じ、かつアルカリ性水溶液に接する雰囲気でも耐アルカリ性や耐酸化性に優れるとともに、従来のニッケル粉末やニッケル粒子を導電材に用いる場合に比べて軽量である正極とその製造方法を提供することを課題とする。また、本発明は、ニッケル粉末やニッケル粒子を導電材とする正極を用いた場合に比べて、重量エネルギー密度が高い空気二次電池を提供することを課題とする。 The present invention relates to a positive electrode that causes reduction of oxygen during discharge and generation of oxygen during charge in an air secondary battery using an alkaline aqueous solution as an electrolyte. During discharge, oxygen penetrates into the positive electrode and reaches the reaction site. Reachable, oxygen generated inside the positive electrode is released into the air when charging, and smooth electron transfer between OH − and O 2 , H 2 O in alkaline aqueous solution for both discharging and charging In addition to providing a reaction site that enables electrochemical oxidation and reduction, and excellent resistance to alkalis and oxidation even in an atmosphere in contact with an alkaline aqueous solution, conventional nickel powder and nickel particles can be used as a conductive material. It is an object of the present invention to provide a positive electrode that is lighter than the case of use and a method for manufacturing the same. Moreover, this invention makes it a subject to provide an air secondary battery with a high weight energy density compared with the case where the positive electrode which uses nickel powder or nickel particle as a electrically conductive material is used.
上記の課題を解決するために本発明の正極は、以下の構成を有している。
本発明の正極は、アルカリ性水溶液を電解質に用いる空気二次電池の正極であって、ニッケルよりも密度の小さいコア材料と、コア材料を被覆するニッケルおよび／またはニッケル合金からなる被覆層とを含むニッケル被覆材料を備えたことを特徴とする。この構成により、正極に必要な導電性がコア材料表面に形成されたニッケルおよび／またはニッケル合金からなる被覆層によって保たれるともに、ニッケル自身が有する耐アルカリ性および耐酸化性が正極に付与され、かつニッケルからなる導電材に比べて正極が軽くなり、ニッケルの使用量が減ることから正極のコストが低減されるという作用が生じる。
In order to solve the above problems, the positive electrode of the present invention has the following configuration.
The positive electrode of the present invention is a positive electrode of an air secondary battery using an alkaline aqueous solution as an electrolyte, and includes a core material having a density lower than that of nickel and a coating layer made of nickel and / or a nickel alloy covering the core material. A nickel coating material is provided. With this configuration, the conductivity necessary for the positive electrode is maintained by the coating layer made of nickel and / or nickel alloy formed on the surface of the core material, and the alkali resistance and oxidation resistance of nickel itself are imparted to the positive electrode. In addition, the positive electrode is lighter than the conductive material made of nickel, and the amount of nickel used is reduced, so that the cost of the positive electrode is reduced.
ここで、アルカリ性水溶液としては、ＫＯＨ溶液やＮａＯＨ溶液が挙げられるが、これに限定されるものではない。また、アルカリ性水溶液のｐＨは少なくとも１０以上であり、このようなｐＨとなるのに適したＫＯＨやＮａＯＨの濃度が選択される。ｐＨが１０よりも小さくなると、正極での酸素還元や酸素発生に対する過電圧がＯＨ−の活量低下のために大きくなり、またアルカリ性水溶液の導電率が低くなって空気二次電池全体での抵抗を増加させる要因となるため好ましくない。 Here, examples of the alkaline aqueous solution include, but are not limited to, a KOH solution and a NaOH solution. Further, the pH of the alkaline aqueous solution is at least 10 or more, and a concentration of KOH or NaOH suitable for achieving such a pH is selected. When the pH is less than 10, the overvoltage for oxygen reduction and oxygen generation at the positive electrode increases due to a decrease in the activity of OH − , and the conductivity of the alkaline aqueous solution decreases to reduce the resistance of the entire air secondary battery. This is not preferable because it causes an increase.
次に、ニッケル（密度：８．９ｇ／ｃｍ３）よりも密度の小さいコア材料としては、シリカ（密度：２．２ｇ／ｃｍ３）、アルミナ（密度：４．０ｇ／ｃｍ３）、黒鉛（密度：２．３ｇ／ｃｍ３）、非晶質炭素（密度：１．８〜２．１ｇ／ｃｍ３）、下記に記載のフッ素樹脂、重合体、有機無機混成材料などが挙げられるが、これに限定されるものではない。また、シリカやアルミナのような酸化物以外にも、ニッケルよりも密度の小さい金属、合金、金属硫化物、金属窒化物、金属炭化物、金属酸化物や金属硫化物や金属炭化物や金属炭化酸化物などの一部を窒素置換したもの、金属と酸素と窒素と炭素の複合酸化物などを用いてもよい。なお、密度が小さいこととともに耐アルカリ性、耐酸化性も備えている材料としては、シリカやアルミナなどがより好ましい。 Next, as a core material having a density lower than that of nickel (density: 8.9 g / cm 3 ), silica (density: 2.2 g / cm 3 ), alumina (density: 4.0 g / cm 3 ), graphite ( density: 2.3g / cm 3), amorphous carbon (density: 1.8~2.1g / cm 3), fluorocarbon resin described below, the polymer, but such an organic inorganic hybrid material and the like, which It is not limited to. In addition to oxides such as silica and alumina, metals, alloys, metal sulfides, metal nitrides, metal carbides, metal oxides, metal sulfides, metal carbides and metal carbide oxides having a density lower than that of nickel A part of which is substituted with nitrogen, a composite oxide of metal, oxygen, nitrogen, and carbon may be used. In addition, as a material having a low density and alkali resistance and oxidation resistance, silica, alumina and the like are more preferable.
また、空気二次電池の正極に用いられる撥水剤としては、従来から用いられているポリテトラフルオロエチレン（略称：ＰＴＦＥ，密度：２．１〜２．２ｇ／ｃｍ３）をはじめとして、テトラフルオロエチレン・パーフルオロアルキルビニルエーテル共重合体（略称：ＰＦＡ，密度：２．１〜２．２ｇ／ｃｍ３）、テトラフルオロエチレン・ヘキサフルオロプロピレン共重合体（略称：ＦＥＰ，密度：２．１〜２．２ｇ／ｃｍ３）、ポリクロロトリフルオロエチレン（略称：ＰＣＴＦＥ，密度：２．１〜２．２ｇ／ｃｍ３）、テトラフルオロエチレン・エチレン共重合体（略称：ＥＴＦＥ，密度：１．７ｇ／ｃｍ３）、クロロトリフルオエチレン・エチレン共重合体（略称：ＥＣＴＦＥ，密度：１．７ｇ／ｃｍ３）、ポリビニリデンフルオライド（略称：ＰＶＤＦ，密度：１．７〜１．８ｇ／ｃｍ３）などのフッ素樹脂材料が挙げられるが、これに限定されるものではない。なお、上記のコア材料や撥水剤の材料の密度はいずれも室温付近での値である。 Moreover, as a water repellent used for the positive electrode of an air secondary battery, the polytetrafluoroethylene (abbreviation: PTFE, density: 2.1-2.2 g / cm < 3 >) used conventionally, tetra, etc. are used. Fluoroethylene / perfluoroalkyl vinyl ether copolymer (abbreviation: PFA, density: 2.1 to 2.2 g / cm 3 ), tetrafluoroethylene / hexafluoropropylene copolymer (abbreviation: FEP, density: 2.1 to 2.2g / cm 3), polychlorotrifluoroethylene (abbreviation: PCTFE, density: 2.1~2.2g / cm 3), tetrafluoroethylene-ethylene copolymer (abbreviation: ETFE, density: 1.7 g / cm 3), chlorotrifluoroethylene-ethylene copolymer (abbreviation: ECTFE, density: 1.7g / cm 3), polyvinylidene Ruoraido (abbreviation: PVDF, Density: 1.7~1.8g / cm 3) can be mentioned fluorine resin material such as is, but is not limited thereto. Note that the densities of the core material and the water repellent material are values around room temperature.
さらに、本発明では、上記以外の重合体や、有機無機混成材料などを撥水剤として使用することもできる。使用可能な重合体としては、ポリスチレン、ポリメチルメタクリレート、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、ポリブチレンテレフタレート、ポリスルホン、ポリカーボネート、ポリアミドなどの線状重合体；ジビニルベンゼン、ヘキサトリエン、ジビニルエーテル、ジビニルスルホン、ジアリルカルビノール、アルキレンジアクリレート、オリゴまたはポリアルキレングリコールジアクリレート、アルキレントリアクリレート、アルキレンテトラアクリレート、アルキレントリメタクリレート、アルキレンテトラメタクリレート、アルキレンビスアクリルアミド、アルキレンビスメタクリルアミド、両末端アクリル変性ポリブタジエンオリゴマーなどを単独または他の重合性単量体と重合させて得られる網状重合体；フェノールホルムアルデヒド樹脂、メラミンホルムアルデヒド樹脂、ベンゾグアナミンホルムアルデヒド樹脂、尿素ホルムアルデヒド樹脂などの熱硬化性樹脂、γ−（メタ）アクリロキシプロピルトリメトキシシラン、トリメトキシシリルスチレン、ビニルトリメトキシシランなどのシラン含有単量体の単独または他の重合性単量体と共重合させて得られる樹脂やそれら加水分解性シリル基を加水分解後架橋させた重合体微粒子、ジメチルポリシロキサンなどのオルガノポリシロキサン樹脂などが挙げられるが、これに限定されるものではない。 Furthermore, in the present invention, polymers other than those described above, organic-inorganic hybrid materials, and the like can also be used as the water repellent. Polymers that can be used include linear polymers such as polystyrene, polymethyl methacrylate, polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, polysulfone, polycarbonate, and polyamide; divinylbenzene, hexatriene, divinyl ether, divinylsulfone, diallyl Carbinol, alkylene diacrylate, oligo or polyalkylene glycol diacrylate, alkylene triacrylate, alkylene tetraacrylate, alkylene trimethacrylate, alkylene tetramethacrylate, alkylene bisacrylamide, alkylene bis methacrylamide, both end acrylic modified polybutadiene oligomers alone or Network polymerization obtained by polymerization with other polymerizable monomers Silane-containing single quantity such as phenol formaldehyde resin, melamine formaldehyde resin, benzoguanamine formaldehyde resin, urea formaldehyde resin, thermosetting resin, γ- (meth) acryloxypropyltrimethoxysilane, trimethoxysilylstyrene, vinyltrimethoxysilane Resin obtained by copolymerization of the polymer alone or with other polymerizable monomers, polymer fine particles obtained by crosslinking these hydrolyzable silyl groups after hydrolysis, organopolysiloxane resins such as dimethylpolysiloxane, etc. However, the present invention is not limited to this.
コア材料は、それ自身で導電性があってもなくてもよく、真球状、楕円体状、多面体状、針状、ファイバー状、チューブ状、ウイスカー状、柱状、筒状、不定形状などの様々な形状が可能である。なお、真球状、楕円体状、多面体状、針状、粒子状、粉末状などの場合、内部が中空であってもよい。ただし、ニッケルおよび／またはニッケル合金で十分に被覆することが難しいような形状、例えば激しい突起や凹凸の繰り返しを含んだ形状は望ましくない。コア材料の導電性および形状は、ニッケルおよび／またはニッケル合金からなる被覆層の形成が可能であるかどうかにも関係するため、被覆層の形成方法も考慮して選択する必要がある。なお、空気二次電池の正極の厚みは一般に１００μｍ〜１ｍｍ程度であることから、このような厚みの中で利用可能な形状・サイズの導電材であることが必要である。コア材料の表面にニッケルおよび／またはニッケル合金を被覆する方法としては、電気めっき法、無電解めっき法、溶融めっき法、物理蒸着法、化学蒸着法、電気泳動法のほか、加圧または減圧または静電的に表面を被覆する方法や、コア材料の表面に前駆体を塗布した後、これを所定の温度で還元して金属または合金で被覆する方法など、被覆層を形成する様々な方法を用いることが可能であり、上記に示した方法に限定されるものではない。なお、このような被覆層を形成する方法は、文献Ａ〜文献Ｉに開示されている。
文献Ａ：特開２００１−２３４３５号公報
文献Ｂ：特開２００３−２１２５３４号公報
文献Ｃ：特開２００９−１４３７５４号公報
文献Ｄ：特開２００９−９６６６１号公報
文献Ｅ：特開２０１１−１７５９５１号公報
文献Ｆ：特開２０１２−１６０４６０号公報
文献Ｇ：特開２０１２−３６３１３号公報
文献Ｈ：特開２０１４−２２０６５号公報
文献Ｉ：特開２０１４−１３２５４２号公報
The core material may or may not be conductive on its own, and includes various shapes such as spherical, ellipsoidal, polyhedral, needle, fiber, tube, whisker, columnar, cylindrical, and irregular shapes. Various shapes are possible. In the case of a true sphere, ellipsoid, polyhedron, needle, particle, powder, etc., the inside may be hollow. However, a shape that is difficult to sufficiently cover with nickel and / or a nickel alloy, for example, a shape including repeated severe protrusions and unevenness is not desirable. The conductivity and shape of the core material are also related to whether or not a coating layer made of nickel and / or a nickel alloy can be formed. Therefore, the method for forming the coating layer must also be selected. In addition, since the thickness of the positive electrode of an air secondary battery is generally about 100 micrometers-1 mm, it is necessary to be a conductive material of the shape and size which can be utilized in such thickness. The method of coating the surface of the core material with nickel and / or nickel alloy includes electroplating method, electroless plating method, hot dipping method, physical vapor deposition method, chemical vapor deposition method, electrophoresis method, pressurization or reduced pressure or Various methods of forming a coating layer, such as a method of electrostatically coating the surface or a method of applying a precursor to the surface of the core material and then reducing it at a predetermined temperature and coating it with a metal or alloy. It can be used and is not limited to the method described above. In addition, the method of forming such a coating layer is disclosed in Documents A to I.
Literature A: JP 2001-23435 A Literature B: JP 2003-21534 A Literature C: JP 2009-143754 A Literature D: JP 2009-96661 A Literature E: JP 2011-175951 A Literature F: JP 2012-160460 A Literature G: JP 2012-36313 A Literature H: JP 2014-22065 A Literature I: JP 2014-132542 A
ニッケルおよび／またはニッケル合金からなる被覆層の厚みは、コア材料のサイズや形状によって適切な範囲が異なるが、例えばコア材料が粒子の場合には１０ｎｍ〜１μｍの範囲が望ましい。被覆層がこの範囲よりも小さくなると被覆層の電気抵抗が大きくなって導電性を保つことが難しくなり、またこの範囲よりも大きくなると被覆層の重量が大きくなって軽量化の効果が得られにくくなり、いずれの場合も好ましくない。 The appropriate thickness of the coating layer made of nickel and / or nickel alloy varies depending on the size and shape of the core material. For example, when the core material is particles, the thickness is preferably in the range of 10 nm to 1 μm. If the coating layer is smaller than this range, the electrical resistance of the coating layer will increase and it will be difficult to maintain conductivity. If the coating layer is larger than this range, the weight of the coating layer will increase and it will be difficult to achieve the effect of weight reduction. In either case, it is not preferable.
本発明の正極には、導電材とともに、すでに述べたように酸素発生と酸素還元に対する触媒を用いることができる。触媒は導電材上に担持される。このような触媒としては、例えば、白金や銀のような貴金属、その他の金属、合金、金属酸化物、金属硫化物、金属窒化物、金属炭化物、金属酸化物や金属硫化物や金属炭化物や金属炭化酸化物などの一部を窒素置換したもの、金属と酸素と窒素と炭素の複合酸化物（ＭｅＣｘＮｙＯｚ：ただし、Ｍｅは金属または合金、Ｃは炭素、Ｎは窒素、Ｏは酸素で、ｘ、ｙ、ｚは組成比を示す）や、構造的な分類からは、少なくとも２種類以上の酸素以外の元素を含み、それらが酸素とともに原子レベルで固溶した状態である複合酸化物、２種類以上の金属酸化物または金属酸化物と非金属酸化物が混合された混合酸化物などが挙げられるが、これらに限定されるものではない。例えば、複合酸化物としては、パイロクロア型、ペロブスカイト型、スピネル型などに分類されるものが挙げられ、パイロクロア型酸化物としてはビスマスイリジウム酸化物、ビスマスルテニウム酸化物などが挙げられる。さらに、混合酸化物としては酸化イリジウム−酸化タンタル混合酸化物や酸化ルテニウム−酸化タンタル混合酸化物などが挙げられる。 In the positive electrode of the present invention, a catalyst for oxygen generation and oxygen reduction can be used together with the conductive material as described above. The catalyst is supported on the conductive material. Examples of such catalysts include noble metals such as platinum and silver, other metals, alloys, metal oxides, metal sulfides, metal nitrides, metal carbides, metal oxides, metal sulfides, metal carbides and metals. Carbon oxide partially substituted with nitrogen, metal, oxygen, nitrogen and carbon composite oxide (MeC x N y O z : Me is a metal or alloy, C is carbon, N is nitrogen, O is Oxygen, x, y, and z indicate composition ratios) and structurally, it contains at least two kinds of elements other than oxygen, and they are in a state of solid solution with oxygen at the atomic level. And two or more kinds of metal oxides or mixed oxides in which metal oxides and nonmetal oxides are mixed, but are not limited thereto. For example, examples of the composite oxide include those classified into a pyrochlore type, a perovskite type, and a spinel type. Examples of the pyrochlore type oxide include bismuth iridium oxide and bismuth ruthenium oxide. Furthermore, examples of the mixed oxide include iridium oxide-tantalum oxide mixed oxide and ruthenium oxide-tantalum oxide mixed oxide.
本発明の正極には、導電材、触媒とともに、すでに述べたような撥水剤を用いることもできる。このような撥水剤としては、前述のフッ素樹脂材料などが挙げられるが、これに限定されるものではない。また、一般に知られている方法であるが、導電材、触媒、撥水剤を混合して一体に形成することにより正極を製造する場合は、撥水剤の出発物質として、撥水剤を適当な溶液中に分散させた撥水剤分散溶液を用いることもできる。 In the positive electrode of the present invention, a water repellent as described above can be used together with a conductive material and a catalyst. Examples of such a water repellent include, but are not limited to, the aforementioned fluororesin material. In addition, although it is a generally known method, when a positive electrode is manufactured by mixing and integrally forming a conductive material, a catalyst, and a water repellent, a water repellent is appropriately used as a starting material for the water repellent. It is also possible to use a water repellent dispersed solution dispersed in a simple solution.
さらに、本発明の正極は、上記の導電材、触媒、撥水剤とともに、外部端子へ接続される集電体と一体に形成された構造体でもよい。このような集電体には、網状、繊維状、多孔質体などの種々の形状の金属や導電性有機物などを用いることができるが、空気に接する側に集電体が配置される場合には、空気中の酸素を取り込むための開口部を集電体が有することが必要である。集電体の材料としてはニッケルなどが好ましいが、これに限定されるものではない。 Furthermore, the positive electrode of the present invention may be a structure formed integrally with a current collector connected to an external terminal together with the above-described conductive material, catalyst, and water repellent. For such a current collector, various shapes of metal such as mesh, fiber, porous body, and conductive organic materials can be used. However, when the current collector is disposed on the side in contact with air, The current collector needs to have an opening for taking in oxygen in the air. The material for the current collector is preferably nickel or the like, but is not limited thereto.
導電材と触媒と撥水剤とを一体とする方法には、プレス法や押し出し法などの一般に空気電池用の正極を作製する際に用いられる方法が利用できる。例えば、導電材、触媒、撥水剤が粉末状または粒子状であれば、これらを乾式または湿式で混合した後、ロールプレス機を用いて薄板状に成形することで作製できる。また、特定の型に混合物を入れて成型加工により作製することができる。また、集電体は、上記に述べた正極の成形工程で一体としても、導電材、触媒、撥水剤を一体に形成した後に、さらにこれを集電体と一体としてもよい。さらに、正極を作製する際には、上記のような成形もしくは一体化の工程の後に、加熱処理を行ってもよい。 As a method for integrating the conductive material, the catalyst, and the water repellent, a method generally used for producing a positive electrode for an air battery, such as a press method or an extrusion method, can be used. For example, if the conductive material, the catalyst, and the water repellent are in the form of powder or particles, they can be produced by mixing them in a dry or wet manner and then forming them into a thin plate using a roll press. Moreover, it can be produced by putting a mixture in a specific mold and molding it. The current collector may be integrated in the positive electrode molding step described above, or may be further integrated with the current collector after the conductive material, the catalyst, and the water repellent are integrally formed. Furthermore, when producing a positive electrode, you may heat-process after the above shaping | molding or integration processes.
また、本発明の正極は、コア材料がシリカ粒子であることを特徴とする。シリカは耐アルカリ性と耐酸化性に優れている。このため、この構成により、空気二次電池の電解質であるアルカリ性水溶液への溶解によるニッケル被覆材料および正極の形状変化、正極からのアルカリ性水溶液の漏洩、電解質の導電率の低下や粘性の増加などの、正極での酸素還元・酸素発生に悪影響を及ぼす各種現象が防がれるという作用が生じる。また、シリカはコア材料候補の中でも特に比重が小さい。このため、この構成により、正極を軽くすることができるという作用が生じる。なお、シリカ粒子の粒径は５０ｎｍ〜１００μｍの範囲が望ましいが、これに限定されるものではない。この範囲よりも小さくなると、シリカ粒子が凝集しやすくなるため、ニッケルおよび／またはニッケル合金で各粒子を被覆することが難しくなり、この範囲よりも大きくなると、均一な厚みの被覆層を形成することが難しくなったり、正極が厚くなりすぎて正極内で酸素が反応サイトへ至る移動の抵抗が大きくなることがあるため、いずれも好ましくない。 The positive electrode of the present invention is characterized in that the core material is silica particles. Silica is excellent in alkali resistance and oxidation resistance. For this reason, with this configuration, the shape of the nickel coating material and the positive electrode due to dissolution in the alkaline aqueous solution that is the electrolyte of the air secondary battery, leakage of the alkaline aqueous solution from the positive electrode, decrease in the conductivity of the electrolyte, increase in viscosity, etc. In addition, various effects that adversely affect oxygen reduction and oxygen generation at the positive electrode are prevented. Silica has a particularly low specific gravity among the core material candidates. For this reason, this structure produces the effect | action that a positive electrode can be lightened. The particle size of the silica particles is preferably in the range of 50 nm to 100 μm, but is not limited thereto. If it is smaller than this range, the silica particles tend to aggregate, so that it is difficult to coat each particle with nickel and / or a nickel alloy, and if it is larger than this range, a coating layer having a uniform thickness is formed. This is not preferable because it may become difficult, or the positive electrode may become too thick and resistance to movement of oxygen to the reaction site in the positive electrode may increase.
また、本発明の正極は、被覆層がニッケル−リン合金であることを特徴とする。この構成により、まずコア材料がシリカ粒子のような非導電性である場合、導電材に必要な電気伝導性が付与されるという作用が生じる。また、コア材料が導電性、非導電性のいずれであるかに関わらず、ニッケル−リン合金は、耐アルカリ性と耐酸化性に優れ、かつ無電解めっき法などにより、組成が均一で、緻密な被覆層を形成することができるので、被覆層上へ担持される触媒に対する良好な電気的接続が可能になるとともに、触媒が被覆層上で安定に保持されるという作用が生じる。さらに、ニッケル−リン合金からなる被覆層は、厚みを制御することが容易であり、必要な厚みの被覆層を一般に知られる方法によって形成することが可能である。このため、この構成により、任意の粒径を有するコア材料に対して、導電性、触媒の保持性、耐アルカリ性、耐酸化性を良好に保つために必要で、かつ適した厚みの被覆層の形成が可能になるという作用が生じる。ニッケル−リン合金を形成する方法としては、例えば、文献Ｅ、文献Ｈ、文献Ｊに開示されているような方法を用いることができるが、これらに限定されるものではない。
文献Ｊ：特開２０１４−１９４０６３号公報
The positive electrode of the present invention is characterized in that the coating layer is a nickel-phosphorus alloy. With this configuration, first, when the core material is non-conductive such as silica particles, there is an effect that necessary electrical conductivity is imparted to the conductive material. Regardless of whether the core material is conductive or non-conductive, the nickel-phosphorus alloy is excellent in alkali resistance and oxidation resistance, and has a uniform and dense composition by electroless plating. Since the coating layer can be formed, an excellent electrical connection to the catalyst supported on the coating layer is possible, and the catalyst is stably held on the coating layer. Furthermore, the thickness of the coating layer made of a nickel-phosphorus alloy can be easily controlled, and a coating layer having a required thickness can be formed by a generally known method. For this reason, with this configuration, the core material having an arbitrary particle size is required to maintain good conductivity, catalyst retention, alkali resistance, and oxidation resistance, and a coating layer having a suitable thickness. The effect that the formation becomes possible occurs. As a method for forming the nickel-phosphorus alloy, for example, methods disclosed in Document E, Document H, and Document J can be used, but the method is not limited to these.
Document J: Japanese Patent Application Laid-Open No. 2014-194063
また、本発明の正極は、ニッケル被覆材料と混合された、ビスマスイリジウム酸化物および／またはビスマスルテニウム酸化物からなる触媒をさらに備えたことを特徴とする。ビスマスイリジウム酸化物とビスマスルテニウム酸化物はパイロクロア型の複合酸化物であり、その一般式はＢｉ２Ｉｒ２Ｏ７±ｚ、Ｂｉ２Ｒｕ２Ｏ７±ｚで表記される。これらの酸化物を触媒とすることによって、以下の作用が得られる。
（Ａ）この触媒と導電材のニッケルとの間における電子的および化学的な相互作用によって、酸素発生と酸素還元に対する高い触媒活性が得られ、正極内部における酸素発生と酸素還元をいずれも円滑に進行させることができる。
（Ｂ）この触媒と導電材のニッケルとの組み合わせによって、正極で副反応として生じる可能性があるニッケル自身の酸化や還元が抑制されることで、酸素発生・還元サイクルに対する耐久性を向上させることができる。
（Ｃ）この触媒と導電材は、湿式または乾式のいずれの方法でも撥水剤との混合、成形が容易であり、特別な装置を用いず正極を製造することができる。
（Ｄ）白金などの高価な貴金属を触媒に用いないことから、これらに対して正極のコストを低減できる。
（Ｅ）鉛イリジウム酸化物のような他のパイロクロア型酸化物に対して、鉛のような有毒成分を含まないため、空気二次電池の製造・使用・廃棄・処分において安全性が高くなる。
（Ｆ）ビスマスイリジウム酸化物やビスマスルテニウム酸化物は、硝酸ビスマスのようなビスマス化合物と塩化イリジウム酸または塩化ルテニウムのような化合物を出発原料とし、共沈法、逆均一沈殿法、逆ミセル法などのような、前駆体物質を合成してから加熱処理するという簡単な方法で得られることから、正極を構成する活性の高い触媒を容易に得ることができる。なお、ビスマスイリジウム酸化物やビスマスルテニウム酸化物には、ビスマス、イリジウム、ルテニウムの一部を他の元素で部分的に置換したものも当然ながら含まれる。
The positive electrode of the present invention is further characterized by further comprising a catalyst made of bismuth iridium oxide and / or bismuth ruthenium oxide mixed with a nickel coating material. Bismuth iridium oxide and bismuth ruthenium oxide are pyrochlore type composite oxides, and their general formulas are represented by Bi 2 Ir 2 O 7 ± z and Bi 2 Ru 2 O 7 ± z . By using these oxides as catalysts, the following effects can be obtained.
(A) High catalytic activity for oxygen generation and oxygen reduction is obtained by electronic and chemical interaction between the catalyst and nickel of the conductive material, and both oxygen generation and oxygen reduction inside the positive electrode are smoothly performed. Can be advanced.
(B) The combination of the catalyst and nickel as a conductive material suppresses oxidation and reduction of nickel that may occur as a side reaction at the positive electrode, thereby improving durability against oxygen generation / reduction cycles. Can do.
(C) The catalyst and the conductive material can be easily mixed and molded with a water repellent by either a wet method or a dry method, and a positive electrode can be produced without using a special apparatus.
(D) Since expensive noble metals such as platinum are not used for the catalyst, the cost of the positive electrode can be reduced.
(E) Compared to other pyrochlore type oxides such as lead iridium oxide, since it does not contain toxic components such as lead, safety is enhanced in the manufacture, use, disposal, and disposal of air secondary batteries.
(F) Bismuth iridium oxide and bismuth ruthenium oxide are prepared by using a bismuth compound such as bismuth nitrate and a compound such as iridium chlorate or ruthenium chloride as a starting material. Thus, a highly active catalyst constituting the positive electrode can be easily obtained because the precursor material is obtained by a simple method of synthesizing the precursor material and then heat-treating it. The bismuth iridium oxide and bismuth ruthenium oxide naturally include those in which a part of bismuth, iridium, and ruthenium is partially substituted with other elements.
また、本発明の正極は、ニッケル被覆材料と混合された、ポリテトラフルオロエチレンからなる撥水剤をさらに備えたことを特徴とする。ポリテトラフルオロエチレンは、良好な撥水性を有するとともに、３７０℃程度の比較的低い温度で軟化して形状を変化させることができる。このため、この構成により、正極が複雑な内部構造を有する場合でも、空気中の酸素が侵入して反応の活性点までに到達できるような良好な経路が正極に付与されるとともに、正極の作製時に触媒を担持した導電材同士が部分的に結着するという作用が生じる。また、ポリテトラフルオロエチレンは、高濃度のアルカリ性水溶液や酸素発生反応に対して極めて安定であり、耐アルカリ性や耐酸化性に優れている。このため、この構成により、正極の充放電を繰り返した場合にも上記のような機能が保持されるという作用が生じる。 The positive electrode of the present invention is further characterized by further comprising a water repellent agent made of polytetrafluoroethylene mixed with a nickel coating material. Polytetrafluoroethylene has good water repellency and can be softened at a relatively low temperature of about 370 ° C. to change its shape. For this reason, even if the positive electrode has a complicated internal structure, this structure provides the positive electrode with a good path through which oxygen in the air can penetrate and reach the active point of the reaction, and the positive electrode is manufactured. Occasionally, the conductive material carrying the catalyst partially binds. In addition, polytetrafluoroethylene is extremely stable against a high concentration alkaline aqueous solution and oxygen generation reaction, and is excellent in alkali resistance and oxidation resistance. For this reason, by this structure, the effect | action that the above functions are hold | maintained also when charging / discharging of a positive electrode is repeated arises.
また、本発明の正極の製造方法は、アルカリ性水溶液を電解質に用いる空気二次電池の正極の製造方法であって、ニッケルよりも密度の小さいコア材料にニッケルおよび／またはニッケル合金からなる被覆層を形成する被覆工程と、被覆工程で得られたニッケル被覆材料と触媒と撥水剤とを混合する混合工程と、混合工程で得られた混合物を成形する成形工程と、成形工程で得られた成形体を加熱する加熱工程とを備え、混合工程において、撥水剤と同じ材料からなる混練具で混合することを特徴とする。この構成により、ニッケル被覆材料を導電材とし、この導電材上に触媒が担持され、これらが撥水剤とともに一体に成形された空気二次電池用の正極を作製することができるとともに、混合時の圧力によりニッケル被覆材料の被覆層が割れる、はがれる、クラックが入るなどして正極内で導電性がない部分が生じるのを防止することができる。また、この構成により、ニッケル被覆材料上に触媒を高分散で担持することが可能となり、さらに混合工程において混練具から混練具の一部が混入したとしても、これが撥水剤と同じ材料であることで、正極で生じる酸素の還元や酸素の発生が阻害されたり、触媒の活性が低下させられないという作用が生じる。 The positive electrode manufacturing method of the present invention is a method of manufacturing a positive electrode of an air secondary battery using an alkaline aqueous solution as an electrolyte, and a coating layer made of nickel and / or a nickel alloy is formed on a core material having a density lower than that of nickel. The coating process to be formed, the mixing process for mixing the nickel coating material obtained in the coating process, the catalyst and the water repellent, the molding process for molding the mixture obtained in the mixing process, and the molding obtained in the molding process A heating step of heating the body, and mixing in a kneading tool made of the same material as the water repellent in the mixing step. With this configuration, it is possible to produce a positive electrode for an air secondary battery in which a nickel coating material is used as a conductive material, a catalyst is supported on the conductive material, and these are integrally molded together with a water repellent. It is possible to prevent the non-conductive portion from being formed in the positive electrode by cracking, peeling off or cracking of the coating layer of the nickel coating material. In addition, this configuration makes it possible to carry the catalyst in a highly dispersed manner on the nickel coating material, and even if a part of the kneading tool is mixed from the kneading tool in the mixing step, this is the same material as the water repellent. As a result, there is an effect that the reduction of oxygen generated at the positive electrode and the generation of oxygen are inhibited, and the activity of the catalyst cannot be lowered.
また、本発明の正極の製造方法は、撥水剤がポリテトラフルオロエチレンであることを特徴とする。さらに、本発明の正極の製造方法は、混合工程が、ニッケル被覆材料と触媒とを混合する第１混合工程と、第１混合工程で得られた一次混合物と撥水剤とを混合する第２混合工程とを含むことを特徴とする。さらに、本発明の正極の製造方法は、コア材料がシリカ粒子であり、被覆層がニッケル−リン合金であることを特徴とする。 The positive electrode manufacturing method of the present invention is characterized in that the water repellent is polytetrafluoroethylene. Furthermore, in the method for producing a positive electrode of the present invention, the mixing step includes a first mixing step in which the nickel coating material and the catalyst are mixed, and a second mixture in which the primary mixture obtained in the first mixing step and the water repellent are mixed. And a mixing step. Furthermore, the method for producing a positive electrode of the present invention is characterized in that the core material is silica particles and the coating layer is a nickel-phosphorus alloy.
また、本発明の空気二次電池は、アルカリ性水溶液を電解質に用いる空気二次電池であって、正極と負極とを備え、正極が、前述の本発明のいずれかの正極であることを特徴とする。また、本発明の空気二次電池は、負極が、水素吸蔵合金、亜鉛、アルミニウム、鉄、リチウム、マグネシウム、ナトリウムのいずれかを含むことを特徴とする。この構成により、正極はニッケルのみを成分とする導電材を用いた場合に比べて軽量でありながら、前述のようなニッケルが有する優れた特性を付与したものとなり、これによって正極が軽くなることで重量エネルギー密度が向上するとともに、正極のニッケル使用量が低減されることでコストが抑制され、空気二次電池のコストが低減されるという作用が生じる。また、この構成により、正極が軽量化されることで、空気二次電池の出力密度も向上するという作用が生じる。 The air secondary battery of the present invention is an air secondary battery using an alkaline aqueous solution as an electrolyte, comprising a positive electrode and a negative electrode, wherein the positive electrode is any one of the positive electrodes of the present invention described above. To do. In the air secondary battery of the present invention, the negative electrode contains any one of a hydrogen storage alloy, zinc, aluminum, iron, lithium, magnesium, and sodium. With this configuration, the positive electrode is lighter than the case where a conductive material containing only nickel is used, but it has the above-mentioned excellent characteristics of nickel, thereby reducing the weight of the positive electrode. The weight energy density is improved and the amount of nickel used in the positive electrode is reduced, so that the cost is suppressed and the cost of the air secondary battery is reduced. Moreover, this structure produces the effect | action that the output density of an air secondary battery also improves because a positive electrode is reduced in weight.
ここで、負極に水素吸蔵合金を用いる空気二次電池では、水素吸蔵合金として、Ｌａ−Ｎｉ系合金、Ｌａ−Ｎｄ−Ｎｉ系合金、Ｌａ−Ｇｄ−Ｎｉ系合金、Ｌａ−Ｙ−Ｎｉ系合金、Ｌａ−Ｃｏ−Ｎｉ系合金、Ｌａ−Ｃｅ−Ｎｉ系合金、Ｌａ−Ｎｉ−Ａｇ系合金、Ｌａ−Ｎｉ−Ｆｅ系合金、Ｌａ−Ｎｉ−Ｃｒ系合金、Ｌａ−Ｎｉ−Ｐｄ系合金、Ｌａ−Ｎｉ−Ｃｕ系合金、Ｌａ−Ｎｉ−Ａｌ系合金、Ｌａ−Ｎｉ−Ｍｎ系合金、Ｌａ−Ｎｉ−Ｉｎ系合金、Ｌａ−Ｎｉ−Ｓｎ系合金、Ｌａ−Ｎｉ−Ｇａ系合金、Ｌａ−Ｎｉ−Ｓｉ系合金、Ｌａ−Ｎｉ−Ｇｅ系合金、Ｌａ−Ｎｉ−Ａｌ−Ｃｏ系合金、Ｌａ−Ｎｉ−Ａｌ−Ｍｎ系合金、Ｌａ−Ｎｉ−Ａｌ−Ｃｒ系合金、Ｌａ−Ｎｉ−Ａｌ−Ｃｕ系合金、Ｌａ−Ｎｉ−Ａｌ−Ｓｉ系合金、Ｌａ−Ｎｉ−Ａｌ−Ｔｉ系合金、Ｌａ−Ｎｉ−Ａｌ−Ｚｒ系合金、Ｌａ−Ｎｉ−Ｍｎ−Ｚｒ系合金、Ｌａ−Ｎｉ−Ｍｎ−Ｔｉ系合金、Ｌａ−Ｎｉ−Ｍｎ−Ｖ系合金、Ｌａ−Ｎｉ−Ｃｒ−Ｍｎ系合金、Ｌａ−Ｎｉ−Ｃｒ−Ｚｒ系合金、Ｌａ−Ｎｉ−Ｆｅ−Ｚｒ系合金、Ｌａ−Ｎｉ−Ｃｕ−Ｚｒ系合金、Ｔｉ−Ｖ−Ｃｒ合金、Ｔｉ−Ｖ−Ｃｒ−Ｎｉ合金、並びに、上記合金中のＬａ元素をミッシュメタルで置き換えた合金、また、Ｔｉ−Ｚｒ−Ｍｎ−Ｍｏ系合金やＺｒ−Ｆｅ−Ｍｎ系合金、Ｍｇ−Ｎｉ系合金などのＴｉ、Ｆｅ、Ｍｎ、Ａｌ、Ｃｅ、Ｃａ、Ｍｇ、Ｚｒ、Ｎｂ、Ｖ、Ｃｏ、Ｎｉ、Ｃｒ元素の２組以上の組合せからなる合金などの水素吸蔵合金、さらには、Ｔｉ、Ｖ、Ｚｒ、Ｌａ、Ｐｄ、Ｐｔなどの水素化物を形成する（水素吸蔵性を有する）金属、または上記合金や金属の水素化物（水素を吸蔵した物質）、さらに構造的な分類からは、水素吸蔵合金に対して一般に使われるＡＢ５構造、Ａ２Ｂ７構造、ＡＢ２構造、ＢＣＣ構造、超格子構造などの各構造で表記される合金などを用いることができるが、水素の吸蔵と放出が可能な材料であれば、特に上記の組成に限定されるものではない。 Here, in an air secondary battery using a hydrogen storage alloy for the negative electrode, as the hydrogen storage alloy, a La—Ni alloy, a La—Nd—Ni alloy, a La—Gd—Ni alloy, or a La—Y—Ni alloy is used. La-Co-Ni alloy, La-Ce-Ni alloy, La-Ni-Ag alloy, La-Ni-Fe alloy, La-Ni-Cr alloy, La-Ni-Pd alloy, La -Ni-Cu alloy, La-Ni-Al alloy, La-Ni-Mn alloy, La-Ni-In alloy, La-Ni-Sn alloy, La-Ni-Ga alloy, La-Ni -Si alloy, La-Ni-Ge alloy, La-Ni-Al-Co alloy, La-Ni-Al-Mn alloy, La-Ni-Al-Cr alloy, La-Ni-Al-Cu alloy Alloy, La-Ni-Al-Si alloy, La-Ni-Al-T Alloy, La-Ni-Al-Zr alloy, La-Ni-Mn-Zr alloy, La-Ni-Mn-Ti alloy, La-Ni-Mn-V alloy, La-Ni-Cr-Mn Alloy, La-Ni-Cr-Zr alloy, La-Ni-Fe-Zr alloy, La-Ni-Cu-Zr alloy, Ti-V-Cr alloy, Ti-V-Cr-Ni alloy, and An alloy in which the La element in the above alloy is replaced with misch metal, and Ti, Fe, Mn, Al, such as Ti—Zr—Mn—Mo alloy, Zr—Fe—Mn alloy, Mg—Ni alloy, Hydrogen storage alloys such as alloys composed of two or more combinations of Ce, Ca, Mg, Zr, Nb, V, Co, Ni, and Cr elements, and hydrogen such as Ti, V, Zr, La, Pd, and Pt A metal that forms a fluoride (having hydrogen storage), or Serial alloy or a metal hydride (substance absorbing hydrogen), the more structural classification, AB 5 structure commonly used with respect to the hydrogen storage alloy, A 2 B 7 structure, AB 2 structure, BCC structure, super An alloy or the like represented by each structure such as a lattice structure can be used, but the material is not particularly limited to the above composition as long as it can absorb and release hydrogen.
また、水素吸蔵合金、亜鉛、アルミニウム、鉄は、アルカリ性水溶液中でそのまま使用することができる。一方、リチウム、マグネシウム、ナトリウムは水と激しく反応するため、これらの金属を負極に用いる場合は、それぞれの金属のイオンに対してイオン伝導性を有する固体膜などを用いることにより、これらの金属とアルカリ性水溶液が直接接触しない構造とすることによって使用することができる。例えば、リチウムを負極に用いる場合は、リチウムとアルカリ性水溶液に特許文献Ｋなどに開示されているようなリチウムイオン伝導性の固体膜などを用いることができる。
文献Ｋ：特開２０１４−２２９５７９号公報
Moreover, hydrogen storage alloy, zinc, aluminum, and iron can be used as they are in an alkaline aqueous solution. On the other hand, since lithium, magnesium and sodium react violently with water, when these metals are used for the negative electrode, by using a solid film having ion conductivity with respect to the ions of each metal, It can be used by setting it as the structure where an alkaline aqueous solution does not contact directly. For example, when lithium is used for the negative electrode, a lithium ion conductive solid film as disclosed in Patent Document K can be used for lithium and an alkaline aqueous solution.
Document K: Japanese Patent Application Laid-Open No. 2014-229579
さらに、本発明の空気二次電池では、アルカリ性水溶液を保持し、かつ正極と負極の短絡を防止する機能を有する電解質保持体をさらに用いてもよい。このような電解質保持体としては、アルカリ性水溶液を電解液に用いる電池、例えば、亜鉛／空気一次電池、ニッケル／水素二次電池、アルカリ電池、アルカリマンガン電池、ニッケル／カドミウム電池などで利用されている様々な電池セパレータの材料などを用いることができる。このような材料は、例えば、文献Ｋ、文献Ｌ、文献Ｍ、文献Ｎ、文献Ｏ、文献Ｐ、文献Ｑなどに開示されている。具体的な例としては、セロハンなどのイオン透過性フィルム、ポリプロピレンやポリエチレンなどのフィルム、ポリビニルアルコール系繊維、セルロース系繊維、ポリアミド系繊維、ポリオレフィン系繊維、エチレン−ビニルアルコール系共重合体繊維を、単独、または混合、または積層してなる不織布、ＴｉＯ２、Ｋ２Ｔｉ６Ｏ１３、ＺｒＯ２、Ａｌ２Ｏ３、ＳｉＯ２またはＢＮなどの無機化合物を多孔性樹脂シートに充填した複合膜、などが挙げられる。また、これらの材料については、極細繊維、芯鞘型複合繊維、親水化処理を施したものなども用いられる。電解質保持体は、正極と負極を隔離し、電解液を保持できる機能を有していればよく、したがってアルカリ性水溶液を保持した状態でイオン伝導性またはイオン透過性を持ち、耐アルカリ性とアルカリ性水溶液に対する吸液性を有するものであれば、特に上記に限定されるものではない。
文献Ｋ：特開平７−２７２７７１号公報
文献Ｌ：特開平１１−２９３５６４号公報
文献Ｍ：特開２００７−１５４４０２号公報
文献Ｎ：特開２００７−２８４８４５号公報
文献Ｏ：特開２００９−２２４１００号公報
文献Ｐ：特公表２００９−５１６７８１号公報
文献Ｑ：特開２０１０−７０８７０号公報
Furthermore, in the air secondary battery of the present invention, an electrolyte holding body that holds an alkaline aqueous solution and has a function of preventing a short circuit between the positive electrode and the negative electrode may be further used. As such an electrolyte holder, a battery using an alkaline aqueous solution as an electrolyte, for example, a zinc / air primary battery, a nickel / hydrogen secondary battery, an alkaline battery, an alkaline manganese battery, or a nickel / cadmium battery is used. Various battery separator materials can be used. Such materials are disclosed in, for example, Document K, Document L, Document M, Document N, Document O, Document P, Document Q, and the like. Specific examples include ion permeable films such as cellophane, films such as polypropylene and polyethylene, polyvinyl alcohol fibers, cellulose fibers, polyamide fibers, polyolefin fibers, and ethylene-vinyl alcohol copolymer fibers. Non-woven fabric formed by singly or mixed or laminated, a composite film in which a porous resin sheet is filled with an inorganic compound such as TiO 2 , K 2 Ti 6 O 13 , ZrO 2 , Al 2 O 3 , SiO 2 or BN, etc. Is mentioned. Further, for these materials, ultrafine fibers, core-sheath type composite fibers, those subjected to hydrophilic treatment, and the like are also used. The electrolyte holding body only needs to have a function of isolating the positive electrode and the negative electrode and holding the electrolytic solution. Therefore, the electrolyte holding body has ion conductivity or ion permeability while holding the alkaline aqueous solution, and is resistant to alkali resistance and alkaline aqueous solution. As long as it has liquid absorbency, it is not limited to the above.
Document K: Japanese Patent Laid-Open No. 7-272771 Document L: Japanese Patent Laid-Open No. 11-293564 Document M: Japanese Patent Laid-Open No. 2007-154402 Document N: Japanese Patent Laid-Open No. 2007-284845 Document O: Japanese Patent Laid-Open No. 2009-224100 Document P: JP 2009-516781 A Document Q: JP 2010-70870 A
本発明によれば、アルカリ性水溶液を電解質に用いる空気二次電池において放電時には酸素の還元、充電時には酸素の発生を生じさせる正極であって、放電の際には正極内部に酸素が侵入して反応サイトまで到達可能であり、充電の際には正極内部で発生した酸素が空気中に放出され、かつ放電・充電ともにアルカリ性水溶液中のＯＨ−とＯ２、Ｈ２Ｏとの間で円滑な電子の受け渡しができるような反応サイトが提供されるとともに、電気化学的な酸化や還元が生じ、かつアルカリ性水溶液に接する雰囲気でも耐アルカリ性や耐酸化性に優れるとともに、従来のニッケル粉末やニッケル粒子を導電材に用いる場合に比べて軽量である正極とその製造方法を提供することができることによって、正極が優れた充放電サイクル特性を発揮し、電池全体の重量を軽量化することが可能となり、正極において高い導電性と酸素還元・酸素発生に対する高い触媒性を同時に達成し、さらに任意の形状の正極を低コストで得ることが可能になるという効果を有する。また、本発明によれば、ニッケル粉末やニッケル粒子を導電材とする正極を用いた場合に比べて、重量エネルギー密度が向上し、さらに電池重量が軽くなることで単位重量当たりの出力である出力密度も向上し、同じ電池容量の組電池や電池パックにおいて、より軽量でエネルギー密度や出力密度の高く、かつ可燃性の有機電解液を持ちないことから安全性も高い組電池や電池パックが可能になるという効果を有する。 According to the present invention, in an air secondary battery using an alkaline aqueous solution as an electrolyte, the positive electrode causes reduction of oxygen during discharge and generation of oxygen during charge. During discharge, oxygen enters the positive electrode and reacts. It is possible to reach the site. During charging, oxygen generated inside the positive electrode is released into the air, and both discharge and charging are smooth electrons between OH − and O 2 , H 2 O in the alkaline aqueous solution. Provides a reaction site that can deliver and deliver electrochemically oxidized and reduced materials, and is excellent in alkali resistance and oxidation resistance even in an atmosphere in contact with an alkaline aqueous solution. By providing a positive electrode that is lighter than when used for the material and its manufacturing method, the positive electrode exhibits excellent charge / discharge cycle characteristics, It is possible to reduce the weight of the entire pond, and simultaneously achieve high conductivity and high catalytic properties for oxygen reduction / oxygen generation in the positive electrode, and it is possible to obtain a positive electrode of any shape at low cost. Has an effect. In addition, according to the present invention, the weight energy density is improved as compared with the case where a positive electrode using nickel powder or nickel particles as a conductive material is used, and the output per unit weight is reduced by reducing the battery weight. Density is improved, and assembled batteries and battery packs with the same battery capacity are lighter, have higher energy density and output density, and do not have flammable organic electrolytes. It has the effect of becoming.
以下、本発明を実施例により具体的に説明する。なお、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be specifically described by way of examples. The present invention is not limited to these examples.
（実施例１）
Ｂｉ（ＮＯ３）３・５Ｈ２ＯとＨ２ＩｒＣｌ６・６Ｈ２Ｏを同じ濃度となるように７５℃の蒸留水に溶解した後、攪拌・混合した。この溶液に７５℃で、１ｍｏｌ／ＬのＮａＯＨ水溶液を所定量滴下し、その後、酸素でバブリングしながら３日間攪拌した。これによって生じた沈殿物を含む溶液を８５℃で保持することにより蒸発・乾固させてペースト状とした。このペースト状のものを蒸発皿に移し、１２０℃、１２時間乾燥させてから乳鉢で粉砕した後に、空気雰囲気中で６００℃、２時間焼成した。次に、焼成物中に含まれる副生成物を除去するために、７０℃の蒸留水を用いて吸引ろ過し、パイロクロア型のビスマスイリジウム酸化物を単離した。さらに、これを１２０℃、１２時間乾燥させた後に、乳鉢を用いて粉砕してビスマスイリジウム酸化物粒子を得た。Ｘ線回折法により分析した結果、得られた酸化物は、Ｂｉ２Ｉｒ２Ｏ７−ｚで示される酸素欠損型ビスマスイリジウム酸化物であり、ＳＥＭによる観察から粒径は２０ｎｍ〜１００ｎｍであった。これを触媒として用いた。
Example 1
Bi (NO 3 ) 3 · 5H 2 O and H 2 IrCl 6 · 6H 2 O were dissolved in distilled water at 75 ° C. to the same concentration, and then stirred and mixed. To this solution, a predetermined amount of 1 mol / L NaOH aqueous solution was dropped at 75 ° C., and then stirred for 3 days while bubbling with oxygen. The solution containing the precipitate formed thereby was kept at 85 ° C. to evaporate and dry to form a paste. The paste-like material was transferred to an evaporating dish, dried at 120 ° C. for 12 hours, pulverized in a mortar, and then baked in an air atmosphere at 600 ° C. for 2 hours. Next, in order to remove by-products contained in the fired product, suction filtration was performed using distilled water at 70 ° C. to isolate pyrochlore-type bismuth iridium oxide. Furthermore, after drying this at 120 degreeC for 12 hours, it grind | pulverized using the mortar and obtained the bismuth iridium oxide particle. As a result of analysis by an X-ray diffraction method, the obtained oxide was an oxygen-deficient bismuth iridium oxide represented by Bi 2 Ir 2 O 7-z , and the particle size was 20 nm to 100 nm from observation by SEM. . This was used as a catalyst.
無電解めっき法により、シリカ粒子（粒径：４μｍ〜４０μｍ，平均粒径約１１μｍ）の表面をニッケル−リン合金（ニッケル：リンの平均組成７９：２１ａｔ．％，厚さ１５０ｎｍ〜２５０ｎｍ）で被覆した材料を導電材とした。この導電材の表面を走査型電子顕微鏡で観察したところ図１の結果が得られた。 The surface of silica particles (particle size: 4 μm to 40 μm, average particle size of about 11 μm) is coated with a nickel-phosphorus alloy (nickel: phosphorus average composition 79:21 at.%, Thickness 150 nm to 250 nm) by electroless plating. The obtained material was used as a conductive material. When the surface of this conductive material was observed with a scanning electron microscope, the result of FIG. 1 was obtained.
上記の導電材と触媒をポリテトラフルオロエチレン（ＰＴＦＥ）製の乳鉢と乳棒を用いて混合した。この混合物に撥水剤となるＰＴＦＥの懸濁液（ダイキン工業製，Ｄ−２１０Ｃ，ＰＴＦＥ粒子の平均粒径２２０ｎｍ）を加えて、ＰＴＦＥ製の乳鉢と乳棒でさらに混合した混合物を得た。この際、混合物中の導電材と触媒とＰＴＦＥ粒子の重量比は４４：３７：１９であった。この混合物をロールプレス機で薄板状に伸ばしたのち、集電体となるニッケル網とともに再びロールプレス機で成形した。その後、窒素雰囲気中３７０℃で１３分間熱処理して正極を作製した。得られた正極の寸法は４３ｍｍ×４５ｍｍ×０．２７ｍｍであり、重量はニッケル網を含む全重量で１．７９ｇ、ニッケル網を除いた重量で０．７４ｇであった。このようにして得られた正極は図２に示したような外観であり、走査型電子顕微鏡でその表面を観察したところ、導電材上に担持された触媒の様子が図３のように見られた。このように触媒は、導電材のニッケル−リン合金からなる被覆層の上に分散して担持されていた。また、この正極の導通を市販のテスターで調べた結果、良好な導通があることを確認した。 The conductive material and the catalyst were mixed using a mortar and pestle made of polytetrafluoroethylene (PTFE). To this mixture, a suspension of PTFE serving as a water repellent (Daikin Industries, D-210C, average particle diameter of PTFE particles 220 nm) was added, and a mixture further mixed with a PTFE mortar and pestle was obtained. At this time, the weight ratio of the conductive material, the catalyst, and the PTFE particles in the mixture was 44:37:19. This mixture was stretched into a thin plate with a roll press and then molded again with a roll press with a nickel mesh as a current collector. Then, it heat-processed for 13 minutes at 370 degreeC in nitrogen atmosphere, and produced the positive electrode. The dimensions of the obtained positive electrode were 43 mm × 45 mm × 0.27 mm, and the weight was 1.79 g in total weight including the nickel net, and 0.74 g in weight excluding the nickel net. The positive electrode thus obtained has an appearance as shown in FIG. 2, and when the surface is observed with a scanning electron microscope, the state of the catalyst supported on the conductive material is seen as shown in FIG. It was. Thus, the catalyst was dispersed and supported on the coating layer made of a nickel-phosphorus alloy as a conductive material. Moreover, as a result of investigating the conduction | electrical_connection of this positive electrode with the commercially available tester, it confirmed that there existed favorable continuity.
この正極の特性を３電極式電気化学セルと電気化学測定装置を用いて評価した。電気化学セルでは、正極を所定のＰＴＦＥ製ホルダーに配置し、ニッケル網の側が空気に接するように、反対側はアルカリ性水溶液に接するように配置した。アルカリ性水溶液には６ｍｏｌ／ＬのＫＯＨ水溶液を用いた。また、この水溶液には対極として白金板を浸漬した。さらに６ｍｏｌ／ＬのＫＯＨ水溶液の水銀／酸化水銀電極を参照電極として使用し、この参照電極と正極が接しているＫＯＨ溶液とは、液絡によって接続した。参照電極に対する正極の電位を５ｍＶ／ｓの走査速度で変えながら電流を測定するサイクリックボルタメトリーで、酸素還元電流と正極の電極電位の関係を室温で測定した。その結果、図４に示したような酸素還元電流と電位の関係が得られた。 The characteristics of the positive electrode were evaluated using a three-electrode electrochemical cell and an electrochemical measurement device. In the electrochemical cell, the positive electrode was arranged in a predetermined PTFE holder, and the nickel net side was in contact with air, and the other side was arranged in contact with the alkaline aqueous solution. A 6 mol / L KOH aqueous solution was used as the alkaline aqueous solution. Further, a platinum plate was immersed in this aqueous solution as a counter electrode. Furthermore, a mercury / mercury oxide electrode of a 6 mol / L KOH aqueous solution was used as a reference electrode, and the reference electrode and the KOH solution in contact with the positive electrode were connected by a liquid junction. The relationship between the oxygen reduction current and the electrode potential of the positive electrode was measured at room temperature by cyclic voltammetry in which the current was measured while changing the potential of the positive electrode with respect to the reference electrode at a scanning speed of 5 mV / s. As a result, the relationship between the oxygen reduction current and the potential as shown in FIG. 4 was obtained.
（比較例１）
ＰＴＦＥ製の乳鉢と乳棒ではなく、メノウ製の乳鉢と乳棒を用いたことを除いて、実施例１と同じ方法で比較例１の正極を作製した。比較例１の正極は、図１と同様に薄板状に形成されたものであったが、テスターで調べた結果、導通がないことが判った。また、正極の表面を走査型電子顕微鏡で観察したが、導通がないため、電子顕微鏡写真を得ることはできなかった。また、実施例１と同じ方法で特性の評価を試みたが、正極の抵抗が大きく、測定自体ができなかった。これらの理由として、正極を作製している過程で、ニッケル−リン合金からなる被覆層が割れたり、はがれたり、クラックが入るなどして、導電材の間で電気的な接触ができなかったことが推察される。
(Comparative Example 1)
A positive electrode of Comparative Example 1 was produced in the same manner as in Example 1 except that an agate mortar and pestle were used instead of the PTFE mortar and pestle. The positive electrode of Comparative Example 1 was formed in a thin plate shape as in FIG. 1, but as a result of examination with a tester, it was found that there was no conduction. Moreover, although the surface of the positive electrode was observed with a scanning electron microscope, since there was no conduction, an electron micrograph could not be obtained. Further, evaluation of characteristics was attempted by the same method as in Example 1, but the resistance of the positive electrode was large and measurement itself was not possible. For these reasons, in the process of producing the positive electrode, the coating layer made of the nickel-phosphorus alloy was broken, peeled off, or cracked, and electrical contact between the conductive materials was not possible. Is inferred.
実施例１と比較例１の比較から、本発明の正極の製造方法によって、ニッケル被覆材料からなる導電材と、その表面に担持された触媒粒子と、これらと混合された撥水剤とを備えた、空気二次電池用の正極が作製できることが判った。 From the comparison between Example 1 and Comparative Example 1, the method for producing a positive electrode of the present invention comprises a conductive material made of a nickel coating material, catalyst particles supported on the surface thereof, and a water repellent mixed with these. It was also found that a positive electrode for an air secondary battery can be produced.
（比較例２）
導電材にニッケル粉末（粒径：１０μｍ〜２０μｍ）を用いたことと、導電材と触媒とＰＴＦＥの重量比を７０：２０：１０にしたことを除いて、実施例１と同じ方法で比較例２の正極を作製した。得られた正極の寸法は４３ｍｍ×４５ｍｍ×０．２５ｍｍであり、重量はニッケル網を含む全重量で２．４４ｇ、ニッケル網を除いた重量で１．４１ｇであった。比較例２の正極は、図１と同様に薄板状に形成されたものであり、テスターで調べた結果、良好な導通があることを確認した。この正極の特性を実施例１と同じ方法で評価した。その結果、図４に示したような酸素還元電流と電位の関係が得られた。
(Comparative Example 2)
Comparative Example in the same manner as in Example 1 except that nickel powder (particle size: 10 μm to 20 μm) was used as the conductive material and that the weight ratio of the conductive material, the catalyst, and PTFE was 70:20:10. No. 2 positive electrode was produced. The dimensions of the positive electrode obtained were 43 mm × 45 mm × 0.25 mm, and the weight was 2.44 g in terms of the total weight including the nickel mesh and 1.41 g in terms of the weight excluding the nickel mesh. The positive electrode of Comparative Example 2 was formed in a thin plate shape as in FIG. 1, and as a result of examination with a tester, it was confirmed that there was good conduction. The characteristics of this positive electrode were evaluated in the same manner as in Example 1. As a result, the relationship between the oxygen reduction current and the potential as shown in FIG. 4 was obtained.
実施例１と比較例２の正極を比較すると、実施例１は比較例２に対して全重量が２７％小さくなり、集電体であるニッケル網を除いた重量では４８％小さくなり、本発明のニッケル被覆材料を導電材に用いることで正極が軽量化できることが判った。また、図４の結果から、実施例１の正極は比較例２の正極に比べて同じ電位での酸素還元電流が大きく、触媒活性が高いことも判った。 Comparing the positive electrode of Example 1 and Comparative Example 2, the total weight of Example 1 is 27% smaller than that of Comparative Example 2, and 48% is smaller by weight excluding the nickel net as a current collector. It was found that the positive electrode can be reduced in weight by using the nickel coating material for the conductive material. From the results of FIG. 4, it was also found that the positive electrode of Example 1 had a larger oxygen reduction current at the same potential than the positive electrode of Comparative Example 2, and high catalytic activity.
（実施例２）
実施例１の正極と、この正極とほぼ同じサイズの水素吸蔵合金負極（容量約１．７Ａｈ）と、電解質保持体であるポリプロピレン製不織布に６ｍｏｌ／ＬのＫＯＨ水溶液を含浸させたものを、ＰＴＦＥ製容器の下から負極、不織布、正極の順に配置し、正極は集電体側を空気に接するようにして水素／空気二次電池を作製した。この二次電池は充放電が可能であり、室温において１００ｍＡでの放電における重量エネルギー密度は１２６Ｗｈ／ｋｇであった。
(Example 2)
A positive electrode of Example 1, a hydrogen storage alloy negative electrode (capacity: about 1.7 Ah) having approximately the same size as this positive electrode, and a polypropylene nonwoven fabric impregnated with 6 mol / L KOH aqueous solution as an electrolyte holder were obtained by PTFE. A hydrogen / air secondary battery was prepared by arranging a negative electrode, a non-woven fabric, and a positive electrode in this order from the bottom of the container, and the positive electrode was in contact with air on the collector side. This secondary battery was chargeable / dischargeable, and the weight energy density at discharge at 100 mA at room temperature was 126 Wh / kg.
（比較例３）
比較例２の正極を用いたことを除いて、実施例２と同じように水素／空気二次電池を作製した。この二次電池は充放電が可能であり、１００ｍＡの放電における重量エネルギー密度は１０６Ｗｈ／ｋｇであった。
(Comparative Example 3)
A hydrogen / air secondary battery was produced in the same manner as in Example 2 except that the positive electrode of Comparative Example 2 was used. This secondary battery was chargeable / dischargeable, and the weight energy density at a discharge of 100 mA was 106 Wh / kg.
実施例２と比較例３の比較から、本発明の水素／空気二次電池では、本発明の正極を用いたことによって、約１９％も重量エネルギー密度を向上できることが判った。 From comparison between Example 2 and Comparative Example 3, it was found that the hydrogen / air secondary battery of the present invention can improve the weight energy density by about 19% by using the positive electrode of the present invention.
本発明の空気二次電池用の正極および空気二次電池は、充放電特性に優れ、エネルギー密度が高く、電解質に水溶液を用いることから安全性も高いことから、パソコン、携帯電話、携帯音楽プレーヤー、携帯ビデオプレーヤー、携帯書籍端末などのモバイル機器の電源、電気自動車、ハイブリッド自動車、電動バイク、電動自転車、ショベルカーなどの電動作業機械や電動建設機械などの動力用または補助用電池、自動車用、家庭用、業務用、産業用の燃料電池の電力貯蔵用・出力調整用電池、太陽光発電、風力発電、水力発電、原子力発電などの電力貯蔵・出力調整用電池などに用いることができる。 The positive electrode for an air secondary battery and the air secondary battery of the present invention have excellent charge / discharge characteristics, high energy density, and high safety because an aqueous solution is used as an electrolyte. , Power supplies for mobile devices such as portable video players, portable book terminals, electric cars, hybrid cars, electric bikes, electric bicycles, excavator cars, etc. It can be used for power storage and output adjustment batteries for fuel cells for home use, business use, and industrial use, and batteries for power storage and output adjustment such as solar power generation, wind power generation, hydroelectric power generation, and nuclear power generation.
Claims (11)
ニッケルよりも密度の小さいコア材料と、前記コア材料を被覆するニッケルおよび／またはニッケル合金からなる被覆層とを含むニッケル被覆材料を備えたことを特徴とする正極。 A positive electrode of an air secondary battery using an alkaline aqueous solution as an electrolyte,
A positive electrode comprising a nickel coating material including a core material having a density lower than that of nickel and a coating layer made of nickel and / or a nickel alloy that covers the core material.
ニッケルよりも密度の小さいコア材料にニッケルおよび／またはニッケル合金からなる被覆層を形成する被覆工程と、
前記被覆工程で得られたニッケル被覆材料と触媒と撥水剤とを混合する混合工程と、
前記混合工程で得られた混合物を成形する成形工程と、
前記成形工程で得られた成形体を加熱する加熱工程と、
を備え、前記混合工程において、前記撥水剤と同じ材料からなる混練具で混合することを特徴とする正極の製造方法。 A method for producing a positive electrode of an air secondary battery using an alkaline aqueous solution as an electrolyte,
A coating step of forming a coating layer made of nickel and / or a nickel alloy on a core material having a density lower than that of nickel;
A mixing step of mixing the nickel coating material, catalyst and water repellent obtained in the coating step;
A molding step of molding the mixture obtained in the mixing step;
A heating step of heating the molded body obtained in the molding step;
And mixing in a kneading tool made of the same material as the water repellent in the mixing step.
前記ニッケル被覆材料と前記触媒とを混合する第１混合工程と、
前記第１混合工程で得られた一次混合物と前記撥水剤とを混合する第２混合工程と、
を含むことを特徴とする請求項６または７に記載の正極の製造方法。 The mixing step is
A first mixing step of mixing the nickel coating material and the catalyst;
A second mixing step of mixing the primary mixture obtained in the first mixing step and the water repellent;
The manufacturing method of the positive electrode of Claim 6 or 7 characterized by the above-mentioned.
正極と負極とを備え、
前記正極が、請求項１から５のいずれか１項に記載の正極であることを特徴とする空気二次電池。 An air secondary battery using an alkaline aqueous solution as an electrolyte,
A positive electrode and a negative electrode,
The air secondary battery, wherein the positive electrode is the positive electrode according to any one of claims 1 to 5.
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| JP2018055810A (en) * | 2016-09-26 | 2018-04-05 | Fdk株式会社 | Air electrode for air secondary battery and air-hydrogen secondary battery including the air electrode |
| WO2019189014A1 (en) | 2018-03-30 | 2019-10-03 | Fdk株式会社 | Method for producing catalyst for air secondary batteries, method for producing air secondary battery, catalyst for air secondary batteries, and air secondary battery |
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