JP2016204713A - Aluminum alloy for anode material and manufacturing method therefor and brine aluminum cell having anode containing the aluminum alloy - Google Patents
Aluminum alloy for anode material and manufacturing method therefor and brine aluminum cell having anode containing the aluminum alloy Download PDFInfo
- Publication number
- JP2016204713A JP2016204713A JP2015088841A JP2015088841A JP2016204713A JP 2016204713 A JP2016204713 A JP 2016204713A JP 2015088841 A JP2015088841 A JP 2015088841A JP 2015088841 A JP2015088841 A JP 2015088841A JP 2016204713 A JP2016204713 A JP 2016204713A
- Authority
- JP
- Japan
- Prior art keywords
- aluminum alloy
- aluminum
- negative electrode
- intermetallic compound
- salt water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Continuous Casting (AREA)
- Hybrid Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
本発明は、塩水アルミニウム空気電池の負極材として用いられるアルミニウム合金及びその製造方法、ならびに、このアルミニウム合金を含む負極を備える塩水アルミニウム空気電池に関する。 The present invention relates to an aluminum alloy used as a negative electrode material for a salt water aluminum air battery, a method for producing the same, and a salt water aluminum air battery including a negative electrode containing the aluminum alloy.
塩水アルミニウム空気電池は、下記式（１）で示す負極におけるアルミニウム溶解反応と、下記式（２）で示す正極における空気中の酸素を活物質とした反応によって表される一次電池である。負極材に用いられる金属としては、アルミニウムの他、亜鉛、マグネシウム、リチウムなどが知られている。これらの金属のうち、加工性が良好であること、軽量であること、３価の軽金属元素なので単位重量当たりの電流効率が高いことから、アルミニウム材が注目されている。
（１）負極（アノード）反応：Ａｌ → Ａｌ３＋＋３ｅ
（２）正極（カソード）反応：Ｏ２＋２Ｈ２Ｏ＋４ｅ → ４ＯＨ−
The salt water aluminum-air battery is a primary battery represented by an aluminum dissolution reaction in the negative electrode represented by the following formula (1) and a reaction using oxygen in the air in the positive electrode represented by the following formula (2) as an active material. As a metal used for the negative electrode material, zinc, magnesium, lithium and the like are known in addition to aluminum. Of these metals, aluminum materials are attracting attention because of their good workability, light weight, and high current efficiency per unit weight because they are trivalent light metal elements.
(1) Negative electrode (anode) reaction: Al → Al 3+ + 3e
(2) Positive electrode (cathode) reaction: O 2 + 2H 2 O + 4e → 4OH −
このように、塩水アルミニウム空気電池では、負極活物質としてアルミニウム又はアルミニウム合金を用い、正極活物質として空気中の酸素を用い、電解液としてはＮａＣｌ水溶液などが用いられる。 Thus, in the salt water aluminum air battery, aluminum or an aluminum alloy is used as the negative electrode active material, oxygen in the air is used as the positive electrode active material, and an aqueous NaCl solution is used as the electrolyte.
このようなアルミニウム空気電池には、軽量且つ高い電気容量が求められる。塩水アルミニウム空気電池用の負極材として、これまでに種々のアルミニウム合金が開発されている。例えば、特許文献１には、Ｍｎ：０．０１〜０．５％、Ｍｇ：０．１〜２．０％、Ｓｎ０．０３〜１．０％を含有するアルミニウム合金が記載されている。また、特許文献２には、Ｍｇ：０〜０．１％、Ｚｎ：０．５〜１．０％、Ｓｎ：０．０４〜１．０％、Ｇａ：０．００３〜１．０％、Ｂｉ：０．００５〜１．０％を含有するアルミニウム合金が記載されている。更に、特許文献３には、Ｍｎ：０．０１〜３０％、Ｚｎ：０．０１〜２０％、Ｓｎ：０〜０．０１％を含有するアルミニウム合金が記載されている。 Such an aluminum air battery is required to be lightweight and have a high electric capacity. Various aluminum alloys have been developed so far as negative electrode materials for brine aluminum air batteries. For example, Patent Document 1 describes an aluminum alloy containing Mn: 0.01 to 0.5%, Mg: 0.1 to 2.0%, and Sn 0.03 to 1.0%. Patent Document 2 includes Mg: 0 to 0.1%, Zn: 0.5 to 1.0%, Sn: 0.04 to 1.0%, Ga: 0.003 to 1.0%, An aluminum alloy containing Bi: 0.005 to 1.0% is described. Furthermore, Patent Document 3 describes an aluminum alloy containing Mn: 0.01 to 30%, Zn: 0.01 to 20%, and Sn: 0 to 0.01%.
上記各特許文献に記載されているアルミニウム合金は、常温における通電時の電流密度がいずれも１０〜１００ｍＡ／ｃｍ２程度であり、電池としての出力が小さいという問題があった。これらのアルミニウム合金を用いて大きな電池出力を得るには、電池の使用温度を例えば６０℃以上と高温にしたり、電池セルを大きくする必要があった。しかしながら、近年はエネルギー消費に伴う環境負荷削減の観点から、軽量且つ常温でも使用可能な空気電池の要求が多くなっている。そのため、常温において高い電流密度が得られることが必要となる。 The aluminum alloys described in each of the above patent documents have a problem that the current density when energized at room temperature is about 10 to 100 mA / cm 2 and the output as a battery is small. In order to obtain a large battery output using these aluminum alloys, it has been necessary to increase the battery operating temperature to, for example, 60 ° C. or higher, or to increase the battery cell. However, in recent years, from the viewpoint of reducing the environmental load accompanying energy consumption, there is an increasing demand for air batteries that are lightweight and can be used at room temperature. Therefore, it is necessary to obtain a high current density at room temperature.
また、電池の電圧（起電力）とは正極と負極との電位差であり、この電位差が大きいほど電池性能が高くなる。通常、負極の電位については、電流を流さない状態で最も卑となり、電流を流す状態で貴に変化するという分極現象が発生する。このような分極現象が強く発生すると、正極と負極との電位差を大きく取れない。そのため、アルミニウム空気電池には、電流を流しても負極の電位が卑のままの状態が維持されるように、分極現象が発生し難い特性が要求される。 The battery voltage (electromotive force) is the potential difference between the positive electrode and the negative electrode, and the larger the potential difference, the higher the battery performance. In general, the potential of the negative electrode is lowest when no current is passed, and a polarization phenomenon occurs that changes noblely when current is passed. When such a polarization phenomenon occurs strongly, the potential difference between the positive electrode and the negative electrode cannot be made large. For this reason, the aluminum-air battery is required to have a characteristic that the polarization phenomenon is unlikely to occur so that the negative electrode potential remains unchanged even when a current is passed.
また、アルミニウム空気電池では、長時間通電すると、負極（アノード）反応によって生成したＡｌ３＋が水和酸化物を形成し電極間に蓄積されて電気抵抗となり、正極と負極との電位差が低減する。この現象は、塩水環境において起こる局所的なアノード反応の進行によって大きく影響を受け、アノード反応が局所的であるほどＡｌ３＋水和酸化物の形成が集中して正極と負極との電位差が著しく低下してしまう。このため、アルミニウム空気電池の負極用アルミニウム合金には、塩水環境においても均一にアノード反応が進行することも要求される。 In an aluminum air battery, when energized for a long time, Al 3+ generated by the negative electrode (anode) reaction forms a hydrated oxide and accumulates between the electrodes, resulting in an electrical resistance, and the potential difference between the positive electrode and the negative electrode is reduced. This phenomenon is greatly influenced by the progress of the local anodic reaction that occurs in a salt water environment. The more the local anodic reaction is, the more concentrated the formation of Al 3+ hydrated oxides, and the potential difference between the positive and negative electrodes decreases significantly. Resulting in. For this reason, the aluminum alloy for the negative electrode of an aluminum air battery is also required to allow the anode reaction to proceed uniformly even in a salt water environment.
更に、アルミニウム合金の負極を電解質に晒すと自己腐食が発生する。このような自己腐食によるアルミニウム合金の消耗は、電流を得ることには寄与しない。従って、自己腐食量が多いと、負極の単位重量当たりに得られる電流、すなわち電流効率を低下させる。なお、電流効率とは、通電後に消耗したアルミニウム合金の質量減少に対する、得られた電気量から算出されるアルミニウム合金の溶解量の割合として定義される。従って、電流効率が高いほど、同じ質量のアルミニウム合金から取り出される電流が多いことになる。 Furthermore, when an aluminum alloy negative electrode is exposed to an electrolyte, self-corrosion occurs. Such consumption of the aluminum alloy due to self-corrosion does not contribute to obtaining an electric current. Therefore, when the amount of self-corrosion is large, the current obtained per unit weight of the negative electrode, that is, the current efficiency is lowered. The current efficiency is defined as the ratio of the dissolved amount of the aluminum alloy calculated from the obtained electric quantity to the mass decrease of the aluminum alloy consumed after energization. Therefore, the higher the current efficiency, the more current is drawn from the same mass of aluminum alloy.
また、ＳｎやＧａのような低融点元素は、鋳造工程において最終凝固部に偏析し易く、材料中にＡｌ−Ｓｎ系金属間化合物やＡｌ−Ｓｎ−Ｇａ系金属間化合物として粗大に晶出するため、微細に分散させることが困難である。従って、材料中のＳｎ系金属間化合物をマトリクス中に再固溶させた後に、微細に析出させる熱処理工程が必須となる。また、粗大化した上記金属間化合物は、熱間圧延を施すと、それらを取り囲むα−Ａｌ母相と共に部分的に溶融してしまう。溶融して液相として繋がった領域は、再び凝固する際に最終凝固部にて粗大な晶出物が生成され、且つ微細な析出物が消失する。すなわち、組織制御を行うための熱処理工程は、熱間圧延の後に必ず実施しなければならず、製造コストが高くなるという問題があった。 In addition, low melting point elements such as Sn and Ga are easily segregated in the final solidified portion in the casting process, and crystallize coarsely as an Al—Sn intermetallic compound or Al—Sn—Ga intermetallic compound in the material. Therefore, it is difficult to finely disperse. Therefore, a heat treatment step is required for finely depositing the Sn-based intermetallic compound in the material after re-dissolving in the matrix. Moreover, when the above-mentioned coarsened intermetallic compound is hot-rolled, it partially melts together with the α-Al matrix surrounding it. In the melted region connected as a liquid phase, when the solidification is performed again, coarse crystallized products are generated in the final solidified portion, and fine precipitates disappear. That is, the heat treatment process for controlling the structure must be performed after the hot rolling, which increases the manufacturing cost.
一方、アルミニウム合金は、使用するアルミニウム地金中にＦｅ、Ｓｉ等の不可避的不純物が多量に含まれていると、Ａｌ−Ｆｅ系金属間化合物やＡｌ−Ｆｅ−Ｓｉ系金属間化合物が粗大化する。粗大化した金属間化合物は、材料の自己腐食速度を増大させる。そのため、従来のアルミニウム空気電池には、Ｆｅ、Ｓｉ等の不可避的不純物濃度の低い、高価な高純度アルミニウム地金を使用する必要があり、原料コストが高くなるという問題があった。 On the other hand, when an aluminum alloy contains a large amount of inevitable impurities such as Fe and Si, the aluminum alloy used in the aluminum alloy coarsens the Al-Fe intermetallic compound and the Al-Fe-Si intermetallic compound. To do. The coarsened intermetallic compound increases the self-corrosion rate of the material. For this reason, the conventional aluminum air battery needs to use an expensive high-purity aluminum ingot having a low concentration of inevitable impurities such as Fe and Si, resulting in a problem that the raw material cost increases.
本発明は上記事情に鑑みてなされてものであり、常温でも電流密度が高く、通電を続けても負極の電位が卑のままの状態が維持され、塩水環境においても均一にアノード反応が進行し、自己腐食が少なく、且つ原料コスト及び製造コストが安価な塩水アルミニウム空気電池の負極材用アルミニウム合金及びその製造方法、ならびに、当該アルミニウム合金を含む負極を備える塩水アルミニウム空気電池を提供することを目的とする。 The present invention has been made in view of the above circumstances, and the current density is high even at room temperature, the negative electrode potential is maintained even when energization is continued, and the anode reaction proceeds uniformly even in a salt water environment. An object of the present invention is to provide an aluminum alloy for a negative electrode material of a salt water aluminum air battery with low self-corrosion and low raw material costs and manufacturing costs, a method for manufacturing the same, and a salt water aluminum air battery including a negative electrode containing the aluminum alloy. And
発明者らは、上記課題を解決すべく鋭意研究を重ねた結果、アルミニウム合金のＳｉ、Ｆｅ、Ｍｇ、Ｓｎ、Ｇａの含有量と、合金マトリックス中のＳｎ系金属間化合物粒子の大きさ及びその存在密度とを調節することにより本発明を完成させるに至った。 As a result of intensive studies to solve the above problems, the inventors have found that the content of Si, Fe, Mg, Sn, Ga in the aluminum alloy, the size of the Sn-based intermetallic compound particles in the alloy matrix, and its The present invention has been completed by adjusting the abundance density.
本発明は請求項１において、Ｓｉ：０．０００１〜０．７０００ｍａｓｓ％、Ｆｅ：０．０００１〜０．７０００ｍａｓｓ％、Ｍｇ：０．０５〜２．００ｍａｓｓ％、Ｓｎ：０．０１〜１．００ｍａｓｓ％、Ｇａ：０．００５〜１．０００ｍａｓｓ％を含有し、残部Ａｌ及び不可避的不純物からなるアルミニウム合金であり、マトリクス中に存在する０．２μｍ以下の円相当直径を有するＳｎ系金属間化合物粒子の密度が１０６個／ｍｍ２以上であることを特徴とするアルミニウム塩水電池の負極材用アルミニウム合金とした。 The present invention relates to claim 1, wherein Si: 0.0001 to 0.7000 mass%, Fe: 0.0001 to 0.7000 mass%, Mg: 0.05 to 2.00 mass%, Sn: 0.01 to 1.00 mass% %, Ga: 0.005 to 1.000 mass%, an aluminum alloy composed of the balance Al and unavoidable impurities, and having an equivalent circle diameter of 0.2 μm or less present in the matrix The aluminum alloy for the negative electrode material of the aluminum salt water battery is characterized by having a density of 10 6 / mm 2 or more.
本発明は請求項２では請求項１において、前記アルミニウム合金が、Ｍｎ：０．０５〜０．３０ｍａｓｓ％を更に含有するものとした。 According to a second aspect of the present invention, in the first aspect, the aluminum alloy further contains Mn: 0.05 to 0.30 mass%.
本発明は請求項３では、請求項１又は２に記載のアルミニウム塩水電池の負極材用アルミニウム合金の製造方法において、前記アルミニウム合金の鋳造工程での板厚中央における冷却速度が２００℃／秒以上であることを特徴とするアルミニウム塩水電池の負極材用アルミニウム合金の製造方法とした。 According to a third aspect of the present invention, in the method for producing an aluminum alloy for an anode material of an aluminum salt water battery according to the first or second aspect, the cooling rate at the center of the plate thickness in the casting step of the aluminum alloy is 200 ° C./second or more. It was set as the manufacturing method of the aluminum alloy for negative electrode materials of the aluminum salt water battery characterized by the above-mentioned.
本発明は請求項４では請求項３において、鋳造工程後に、前記アルミニウム合金の板材が４８０℃未満の圧延工程において所定厚さまで圧延されるものとした。 According to a fourth aspect of the present invention, in the third aspect, after the casting process, the aluminum alloy plate is rolled to a predetermined thickness in a rolling process at less than 480 ° C.
本発明は請求項５において、正極と、負極と、前記正極と負極との間に介在し、１．０〜４．０ｍｏｌ／リットルのＮａＣｌを含有する電解水溶液とを備え、前記負極が、請求項１又は２に記載のアルミニウム塩水電池の負極材用アルミニウム合金を含むことを特徴とするアルミニウム塩水電池とした。 The present invention according to claim 5 is provided with a positive electrode, a negative electrode, and an electrolytic aqueous solution interposed between the positive electrode and the negative electrode and containing 1.0 to 4.0 mol / liter NaCl, and the negative electrode is The aluminum salt water battery characterized by including the aluminum alloy for negative electrode materials of the aluminum salt water battery according to Item 1 or 2.
本発明に係わる塩水アルミニウム空気電池の負極材用アルミニウム合金は、常温でも電流密度が高く、通電を続けても負極の電位が卑のままの状態が維持され、塩水環境においても均一にアノード反応が進行し、自己腐食が少なく、且つ原料コスト及び製造コストを安価とすることができる。 The aluminum alloy for negative electrode material of the salt water aluminum air battery according to the present invention has a high current density even at room temperature, and the negative electrode potential is maintained even when energization is continued, and the anode reaction is uniformly performed even in a salt water environment. It progresses, there is little self-corrosion, and raw material cost and manufacturing cost can be made low.
［合金組成］
１．アルミニウム合金の組成
本発明に係る塩水アルミニウム空気電池の負極材用アルミニウム合金の組成は、Ｓｉ：０．０００１〜０．７０００ｍａｓｓ％（以下、単に「％」と記す）、Ｆｅ：０．０００１〜０．７０００％、Ｍｇ：０．０５〜２．００％、Ｓｎ：０．０１〜１．００％、Ｇａ：０．００５〜１．０００％を含有し、残部Ａｌ及び不可避的不純物からなる。更に、選択的添加元素として、Ｍｎ：０．０５〜０．３０％を含有してもよい。
[Alloy composition]
1. Composition of Aluminum Alloy The composition of the aluminum alloy for the negative electrode material of the salt water aluminum air battery according to the present invention is as follows: Si: 0.0001 to 0.7000 mass% (hereinafter, simply referred to as “%”), Fe: 0.0001 to 0 .7000%, Mg: 0.05 to 2.00%, Sn: 0.01 to 1.00%, Ga: 0.005 to 1.000%, with the balance being Al and inevitable impurities. Furthermore, you may contain Mn: 0.05-0.30% as a selective addition element.
〔Ｓｉ：０．０００１〜０．７０００％、Ｆｅ：０．０００１〜０．７０００％〕
Ｓｉ及びＦｅはアルミニウム合金マトリクス中において、Ａｌ−Ｆｅ系金属間化合物、Ａｌ−Ｆｅ−Ｓｉ系金属間化合物及び金属Ｓｉ等からなるＦｅやＳｉを含有する粒子として晶出又は析出する。これらの金属間化合物は、アルミニウム母相に対してカソード反応を生起し、自己腐食速度を増大させる。自己腐食速度が大きくなると、アルミニウムの消耗が速くなるだけでなく、同じ電流を取り出すためにはより多くのアノード反応が必要となる。その結果、負極の電位が貴化してしまい、正極との大きな電位差の確保が困難になる。そのためには、ＳｉとＦｅはそれぞれ、０．７０００％以下とする必要がある。一方、Ｓｉ及びＦｅは、アルミニウム材の不可避不純物として知られており、それぞれの含有量を０．０００１％未満にすることは工業生産上困難である。このように、アルミニウム合金中のＳｉ含有量及びＦｅ含有量は共に、０．０００１〜０．７０００％と規定する。なお、好ましいＳｉ含有量及びＦｅ含有量は共に、０．０００１〜０．０２００％である。
[Si: 0.0001 to 0.7000%, Fe: 0.0001 to 0.7000%]
Si and Fe crystallize or precipitate as particles containing Fe or Si made of Al—Fe intermetallic compound, Al—Fe—Si intermetallic compound, metal Si, or the like in the aluminum alloy matrix. These intermetallic compounds cause a cathodic reaction on the aluminum matrix and increase the self-corrosion rate. As the self-corrosion rate increases, not only is aluminum consumed faster, but more anodic reactions are required to extract the same current. As a result, the potential of the negative electrode becomes noble and it becomes difficult to ensure a large potential difference from the positive electrode. For that purpose, Si and Fe must each be 0.7000% or less. On the other hand, Si and Fe are known as inevitable impurities of the aluminum material, and it is difficult for industrial production to make each content less than 0.0001%. Thus, both the Si content and the Fe content in the aluminum alloy are defined as 0.0001 to 0.7000%. In addition, both preferable Si content and Fe content are 0.0001 to 0.0200%.
〔Ｍｇ：０．０５〜２．００％〕
ＭｇはＳｎ系粒子に固溶することでアルミニウムの酸化皮膜の破壊を促進させ、アノード反応の分極を小さくする。このような効果を得るためには、０．０５％以上のＭｇを含有させることが必要である。一方、過剰にＭｇが含有されれば、Ｍｇを含有する酸化皮膜が形成されるため、アノード反応の分極が大きくなってしまう。この過剰Ｍｇの含有によるアノード反応の分極の増大を回避するには、Ｍｇ含有量の上限は２．００％とする必要がある。このように、Ｍｇ含有量は０．０５〜２．００％と規定する。なお、好ましいＭｇ含有量は、０．２０〜１．００％である。
[Mg: 0.05-2.00%]
Mg dissolves in Sn-based particles, thereby promoting the destruction of the oxide film of aluminum and reducing the polarization of the anode reaction. In order to obtain such an effect, it is necessary to contain 0.05% or more of Mg. On the other hand, if Mg is contained excessively, an oxide film containing Mg is formed, and thus the polarization of the anode reaction is increased. In order to avoid an increase in the polarization of the anode reaction due to the excessive Mg content, the upper limit of the Mg content needs to be 2.00%. Thus, the Mg content is defined as 0.05 to 2.00%. A preferable Mg content is 0.20 to 1.00%.
〔Ｓｎ：０．０１〜１．００％〕
Ｓｎはマトリクス中にＳｎ系粒子として存在することにより、アルミニウムの酸化皮膜の破壊を促進させてアノード反応の分極を小さくする。このＳｎ添加の効果を得るためには、０．０１％以上のＳｎの含有が必要である。一方、過剰にＳｎが含有されれば、耐自己腐食性が低下するとともに、鋳造中に粗大なＳｎ粒子が晶出してしまい、製造性を著しく損なう。この過剰なＳｎの含有による製造性や耐自己腐食性への悪影響を回避するためには、Ｓｎ量の上限は１．００％とする必要がある。このように、Ｓｎ含有量は０．０１〜１．００％と規定する。なお、好ましいＳｎ含有量は、０．０５〜０．３０％である。
[Sn: 0.01 to 1.00%]
Sn is present as Sn-based particles in the matrix, thereby promoting the destruction of the aluminum oxide film and reducing the polarization of the anode reaction. In order to obtain the effect of adding Sn, it is necessary to contain 0.01% or more of Sn. On the other hand, if Sn is contained excessively, the self-corrosion resistance is lowered, and coarse Sn particles are crystallized during casting, which impairs the productivity. In order to avoid the adverse effects on manufacturability and self-corrosion resistance due to the excessive Sn content, the upper limit of the Sn content needs to be 1.00%. Thus, the Sn content is defined as 0.01 to 1.00%. In addition, preferable Sn content is 0.05 to 0.30%.
〔Ｇａ：０．００５〜１．０００％〕
Ｇａは結晶粒界やＳｎ系粒子の周囲に存在し、アルミニウムの酸化皮膜の破壊を促進させ、アノード反応の分極を小さくする。このＧａ添加の効果を得るためには、後述するように０．２μｍ以下の円相当直径を有するＳｎ系金属間化合物粒子密度を１０６個／ｍｍ２以上とする必要がある。そのためには、０．００５％以上のＧａの含有が必要である。一方、過剰にＧａが含有されれば、耐自己腐食性が低下する。この過剰なＧａの含有による耐自己腐食性への悪影響を回避するためには、Ｇａ量の上限は１．０００％とする必要がある。このように、Ｇａ含有量は０．００５〜１．０００％と規定する。なお、好ましいＧａ含有量は、０．０１〜０．２０％である。
[Ga: 0.005 to 1.000%]
Ga exists around crystal grain boundaries and Sn-based particles, promotes the destruction of the oxide film of aluminum, and reduces the polarization of the anode reaction. In order to obtain the effect of Ga addition, it is necessary that the density of Sn-based intermetallic compound particles having a circle-equivalent diameter of 0.2 μm or less be 10 6 particles / mm 2 or more as described later. For that purpose, it is necessary to contain 0.005% or more of Ga. On the other hand, if Ga is excessively contained, the self-corrosion resistance is lowered. In order to avoid the adverse effect on the self-corrosion resistance due to the excessive Ga content, the upper limit of the Ga amount needs to be 1.000%. Thus, the Ga content is defined as 0.005 to 1.000%. In addition, preferable Ga content is 0.01 to 0.20%.
〔Ｍｎ：０．０５〜０．３０％〕
本発明の塩水アルミニウム空気電池の負極材用アルミニウム合金において、選択的添加元素としてＭｎを０．０５〜０．３０％更に含有することが好ましい。アルミニウム合金にＭｎが添加されることにより、上述のＡｌ−Ｆｅ系金属間化合物はＡｌ−Ｆｅ−Ｍｎ系金属間化合物として、また上述のＡｌ−Ｆｅ−Ｓｉ系金属間化合物はＡｌ−Ｆｅ−Ｓｉ−Ｍｎ系金属間化合物として晶出又は析出する。Ａｌ−Ｆｅ−Ｍｎ系金属間化合物は、Ａｌ−Ｆｅ系金属間化合物に比べ、またＡｌ−Ｆｅ−Ｓｉ−Ｍｎ系金属間化合物は、Ａｌ−Ｆｅ−Ｓｉ系金属間化合物に比べ、アルミニウム合金の耐自己腐食性を大幅に向上させる効果を有しており、自己腐食速度を大幅に低減させることができる。その結果、負極の単位重量当たりに得られる電流、すなわち電流効率が向上する。このＭｎ添加の効果を得るためには、０．０５％以上のＭｎの含有させることが好ましい。一方、過剰にＭｎが含有されれば、マトリックス中のＭｎ固溶量が増大し、負極の電位が上昇し、正極との電位差が小さくなってしまう。この過剰Ｍｎの含有による電位の上昇を回避するには、Ｍｎ含有量の上限は０．３０％とすることが好まましい。なお、さらに好ましいＭｎ含有量は、０．１０〜０．２０％である。
[Mn: 0.05 to 0.30%]
In the aluminum alloy for negative electrode material of the salt water aluminum air battery of the present invention, it is preferable to further contain 0.05 to 0.30% of Mn as a selective additive element. By adding Mn to the aluminum alloy, the above-described Al—Fe-based intermetallic compound is used as an Al—Fe—Mn-based intermetallic compound, and the above-described Al—Fe—Si-based intermetallic compound is Al—Fe—Si. -Crystallized or precipitated as a Mn-based intermetallic compound. The Al—Fe—Mn intermetallic compound is compared with the Al—Fe intermetallic compound, and the Al—Fe—Si—Mn intermetallic compound is compared with the Al—Fe—Si intermetallic compound. It has the effect of greatly improving the self-corrosion resistance, and the self-corrosion rate can be greatly reduced. As a result, the current obtained per unit weight of the negative electrode, that is, current efficiency is improved. In order to obtain the effect of this Mn addition, it is preferable to contain 0.05% or more of Mn. On the other hand, if Mn is excessively contained, the amount of Mn solid solution in the matrix increases, the potential of the negative electrode increases, and the potential difference from the positive electrode becomes small. In order to avoid the potential increase due to the excessive Mn content, the upper limit of the Mn content is preferably 0.30%. A more preferable Mn content is 0.10 to 0.20%.
Ｓｉ及びＦｅの他の不可避的不純物として、Ｃｕ、Ｚｎなどを各々０．０２％以下、全体で０．０５％以下が含んでいても、本発明の効果を損なわない。 As other inevitable impurities of Si and Fe, even if Cu, Zn, etc. are contained in 0.02% or less and 0.05% or less in total, the effect of the present invention is not impaired.
２．アルミニウム合金の金属組織（Ｓｎ系金属間化合物粒子）
〔０．２μｍ以下の円相当直径を有するＳｎ系金属間化合物粒子が１０６個／ｍｍ２以上〕
本発明の塩水アルミニウム空気電池の負極材用アルミニウム合金の金属組織は、そのマトリクスにおいては、０．２μｍ以下の円相当直径を有するＳｎ系金属間化合物粒子の密度を１０６個／ｍｍ２以上とする。ここで、Ｓｎ系金属間化合物には、Ａｌ−Ｓｎ系金属間化合物、Ａｌ−Ｓｎ―Ｇａ系金属間化合物、Ａｌ−Ｍｇ−Ｓｉ−Ｓｎ系金属間化合物、Ａｌ−Ｍｇ−Ｓｎ−Ｇａ系金属間化合物が含まれ、アルミニウム合金にＭｎが含有される場合には、これら金属間化合物に加えてＡｌ−Ｓｎ−Ｍｎ系金属間化合物、Ａｌ−Ｍｇ−Ｓｉ−Ｓｎ−Ｍｎ系金属間化合物、Ａｌ−Ｍｇ−Ｓｎ−Ｇａ−Ｍｎ系金属間化合物が含まれる。
2. Metal structure of aluminum alloy (Sn-based intermetallic compound particles)
[10 6 / mm 2 or more of Sn-based intermetallic compound particles having a circle-equivalent diameter of 0.2 μm or less]
The metal structure of the aluminum alloy for negative electrode material of the salt water aluminum air battery of the present invention has a density of 10 6 particles / mm 2 or more of Sn-based intermetallic compound particles having a circle-equivalent diameter of 0.2 μm or less in the matrix. To do. Here, the Sn-based intermetallic compound includes Al-Sn based intermetallic compound, Al-Sn-Ga based intermetallic compound, Al-Mg-Si-Sn based intermetallic compound, Al-Mg-Sn-Ga based metal. When intermetallic compounds are included and the aluminum alloy contains Mn, in addition to these intermetallic compounds, Al-Sn-Mn intermetallic compounds, Al-Mg-Si-Sn-Mn intermetallic compounds, Al -An Mg-Sn-Ga-Mn intermetallic compound is included.
０．２μｍ以下の円相当直径を有するＳｎ系金属間化合物の粒子密度を１０６個／ｍｍ２以上と限定したのは、０．２μｍ以下の円相当直径を有するＳｎ系金属間化合物は、負極の電位を低くすることに寄与し、電池特性としての有効時間の向上に寄与するためである。Ｓｎ系金属間化合物の円相当直径の下限を限定しないのは、０．０１μｍ未満の円相当直径を有するＳｎ系金属間化合物はＳＥＭで観察できず、上記効果が明確でないためである。従って、Ｓｎ系金属間化合物の円相当直径の下限は実質的に０．０１μｍである。そして、その密度を１０６個／ｍｍ２以上に限定したのは、１０６個／ｍｍ２未満では電池特性の向上への寄与が不十分なためである。なお、この密度は、好ましくは２×１０６個／ｍｍ２以上である。また、この密度は、アルミニウム合金の組成や製造条件に依存するものであるため、上限は特に規定しないが、測定可能な範囲として、１０１０個／ｍｍ２とする。 The reason why the particle density of the Sn-based intermetallic compound having an equivalent circle diameter of 0.2 μm or less is limited to 10 6 particles / mm 2 or more is that the Sn-based intermetallic compound having an equivalent circle diameter of 0.2 μm or less is a negative electrode This is because it contributes to lowering the potential of the battery and contributes to improvement of the effective time as battery characteristics. The reason why the lower limit of the equivalent circle diameter of the Sn-based intermetallic compound is not limited is that the Sn-based intermetallic compound having an equivalent circle diameter of less than 0.01 μm cannot be observed by SEM, and the above effect is not clear. Therefore, the lower limit of the equivalent circle diameter of the Sn-based intermetallic compound is substantially 0.01 μm. The reason why the density is limited to 10 6 pieces / mm 2 or more is that if it is less than 10 6 pieces / mm 2 , the contribution to the improvement of battery characteristics is insufficient. The density is preferably 2 × 10 6 pieces / mm 2 or more. Moreover, since this density depends on the composition of aluminum alloy and the manufacturing conditions, the upper limit is not particularly defined, but is 10 10 pieces / mm 2 as a measurable range.
３．アルミニウム合金の製造方法
次に、本発明の塩水アルミニウム空気電池の負極材用アルミニウム合金の製造方法について説明する。
3. Next, the manufacturing method of the aluminum alloy for negative electrode materials of the salt water aluminum air battery of this invention is demonstrated.
３−１．鋳造工程
本発明の塩水アルミニウム空気電池の負極材用アルミニウム合金は、アルミニウム合金の鋳造工程での板厚中央における冷却速度が２００℃／秒以上であることが求められる。
3-1. Casting process The aluminum alloy for the negative electrode material of the salt water aluminum-air battery of the present invention is required to have a cooling rate of 200 ° C./second or more at the center of the plate thickness in the casting process of the aluminum alloy.
〔鋳造工程での板厚中央において２００℃／秒以上の冷却速度〕
２００℃／秒以上の冷却速度は、Ｇａ及びＳｎの最終凝固部への偏析を抑制できるため、Ａｌ−Ｓｎ系、Ａｌ−Ｓｎ−Ｇａ系金属間化合物を微細に晶出させることが可能となり、上述のＳｎ系金属間化合物の粒子密度を確保できる。また、同時に固溶限の低いＳｎを代表とする低融点元素を過飽和に固溶させることも可能となり、過飽和に固溶したＳｎを、後述する圧延工程においてＡｌ−Ｓｎ系金属間化合物として微細に析出させることが可能となる。さらに、固溶限の低いＦｅを代表とする不可避的不純物も鋳造工程において過飽和に固溶させることが可能となり、不可避的不純物として存在するＦｅの固溶量を大幅に増大させることができ、Ａｌ−Ｆｅ系金属間化合物、Ａｌ−Ｆｅ−Ｓｉ系金属間化合物の粗大化を抑制することができる。また、アルミニウム合金にＭｎが含有される場合には、Ａｌ−Ｆｅ−Ｍｎ系金属間化合物、Ａｌ−Ｆｅ−Ｓｉ−Ｍｎ系金属間化合物の粗大化を抑制することができる。一方、板厚中央における冷却速度が２００℃／秒より低い場合は、Ｇａ及びＳｎが最終凝固部に偏析するため、Ａｌ−Ｓｎ系、Ａｌ−Ｓｎ−Ｍｇ−Ｇａ系析出物の放電特性に有効な面密度が得られない。また、低融点元素であるＳｎや、不可避的不純物として添加されているＦｅのような、固溶限以上に添加された溶質元素が最終凝固部に偏析し、粗大な晶出物が形成される。Ａｌ−Ｆｅ系金属間化合物とＡｌ−Ｆｅ−Ｓｉ系金属間化合物、及び、アルミニウム合金にＭｎが含有される場合には、Ａｌ−Ｆｅ−Ｍｎ系金属間化合物とＡｌ−Ｆｅ−Ｓｉ−Ｍｎ系金属間化合物、ならびに、金属Ｓｉ等からなるＦｅやＳｉを含有する粒子は、粗大化すると自己腐食速度を増大させる。なお、上記冷却速度は、好ましくは２３０℃／秒以上である。
[Cooling rate of 200 ° C / second or more at the center of the plate thickness in the casting process]
Since the cooling rate of 200 ° C./second or more can suppress segregation of Ga and Sn to the final solidified portion, it becomes possible to finely crystallize Al—Sn-based and Al—Sn—Ga-based intermetallic compounds, The particle density of the Sn-based intermetallic compound can be ensured. At the same time, a low melting point element represented by Sn having a low solid solubility limit can be dissolved in supersaturation, and the supersaturated Sn is finely formed as an Al-Sn intermetallic compound in a rolling process described later. It can be deposited. Furthermore, inevitable impurities represented by Fe with a low solid solubility limit can be dissolved in supersaturation in the casting process, and the amount of Fe dissolved as inevitable impurities can be greatly increased. The coarsening of the -Fe intermetallic compound and the Al-Fe-Si intermetallic compound can be suppressed. Further, when Mn is contained in the aluminum alloy, it is possible to suppress the coarsening of the Al—Fe—Mn intermetallic compound and the Al—Fe—Si—Mn intermetallic compound. On the other hand, when the cooling rate at the center of the plate thickness is lower than 200 ° C./sec, Ga and Sn are segregated in the final solidified portion, which is effective for the discharge characteristics of Al—Sn and Al—Sn—Mg—Ga precipitates. A high surface density cannot be obtained. In addition, solute elements added beyond the solid solubility limit, such as Sn, which is a low melting point element, and Fe, which is added as an inevitable impurity, segregate in the final solidified portion, and a coarse crystallized product is formed. . Al-Fe-Mn intermetallic compound and Al-Fe-Si-based intermetallic compound, and Al-Fe-Mn-based intermetallic compound and Al-Fe-Si-Mn-based when Mn is contained in the aluminum alloy Particles containing Fe or Si made of an intermetallic compound and metal Si or the like increase the self-corrosion rate when coarsened. The cooling rate is preferably 230 ° C./second or more.
上記板厚中央とは、両板表面から等距離の、板表面と平行な面を示す。例えば、板厚８ｍｍの場合は、板両面から板厚方向に４ｍｍの位置にあって、板両面に平行な面である。この位置における冷却速度は、板厚に依らず最も低い。 The center of the plate thickness means a plane parallel to the plate surface that is equidistant from both plate surfaces. For example, in the case of a plate thickness of 8 mm, the surface is located at a position of 4 mm in the plate thickness direction from both sides of the plate and is parallel to both sides of the plate. The cooling rate at this position is the lowest regardless of the plate thickness.
〔薄板連続鋳造〕
本発明に係るアルミニウム合金材が、板厚中央において２００℃／秒以上の冷却速度で鋳造されるためには、薄板連続鋳造法を用いることが望ましい。薄板連続鋳造は、ＤＣ鋳造と比較して鋳造板厚を小さくでき、且つ鋳造時に鋳型と鋳塊の接触時間を長く取れるため、板表面から板厚中央までの凝固を短時間で完了させることが可能である。そのため、薄板連続鋳造法は、凝固時の冷却速度がＤＣ鋳造法に比べて数倍〜数百倍高い。ＤＣ鋳造法の場合の冷却速度が０．５〜２０℃／秒であるのに対し、例えば、双ロール式薄板連続鋳造法の場合は１００〜１０００℃／秒である。
[Thin plate continuous casting]
In order for the aluminum alloy material according to the present invention to be cast at a cooling rate of 200 ° C./second or more in the center of the plate thickness, it is desirable to use a thin plate continuous casting method. Thin plate continuous casting can reduce the cast plate thickness compared to DC casting and can take longer contact time between the mold and the ingot at the time of casting. Is possible. Therefore, the thin plate continuous casting method has a cooling rate during solidification several times to several hundred times higher than the DC casting method. The cooling rate in the case of the DC casting method is 0.5 to 20 ° C./second, whereas, for example, in the case of the twin roll thin plate continuous casting method, it is 100 to 1000 ° C./second.
このように、板厚中央において２００℃／秒以上の冷却速度で鋳造することにより、粗大なＡｌ−Ｓｎ系金属間化合物の晶出が抑制され、Ａｌ−Ｓｎ系、Ａｌ−Ｓｎ−Ｇａ系金属間化合物を微細に晶出させることが可能になる。また、同時にＳｎのような最大固溶量の低い添加元素を過飽和に固溶させることが可能となるため、後述する圧延工程で、Ａｌ−Ｓｎ系金属間化合物の微細析出が促進される。また、固溶限の低いＦｅを代表とする不可避的不純物も鋳造工程において過飽和に固溶させることが可能となり、不可避的不純物として存在するＦｅの固溶量を大幅に増大させることができ、Ａｌ−Ｆｅ系金属間化合物とＡｌ−Ｆｅ−Ｓｉ系金属間化合物、及び、アルミニウム合金にＭｎが含有される場合には、Ａｌ−Ｆｅ−Ｍｎ系金属間化合物とＡｌ−Ｆｅ−Ｓｉ−Ｍｎ系金属間化合物、ならびに、金属Ｓｉ等からなるＦｅやＳｉを含有する晶出物の粗大化が抑制される。すなわち、不可避的不純物として存在するＦｅ、Ｓｉの許容量を大幅に向上できるため、Ａｌ地金の低純化、スクラップの再利用が可能となり原料コストを低減できる。 Thus, by casting at a cooling rate of 200 ° C./second or more at the center of the plate thickness, crystallization of coarse Al—Sn intermetallic compounds is suppressed, and Al—Sn, Al—Sn—Ga based metals are suppressed. It becomes possible to crystallize the intermetallic compound finely. At the same time, an additive element having a low maximum solid solution amount, such as Sn, can be supersaturated, so that fine precipitation of the Al—Sn intermetallic compound is promoted in the rolling step described later. In addition, inevitable impurities represented by Fe with a low solid solubility limit can be dissolved in supersaturation in the casting process, and the amount of Fe dissolved as inevitable impurities can be greatly increased. -Fe-based intermetallic compound, Al-Fe-Si-based intermetallic compound, and Al-Fe-Mn-based intermetallic compound and Al-Fe-Si-Mn-based metal when aluminum alloy contains Mn The coarsening of the intercalation compound and the crystallized material containing Fe or Si made of metal Si or the like is suppressed. That is, since the allowable amounts of Fe and Si existing as inevitable impurities can be greatly improved, it is possible to reduce the purity of the Al metal and reuse the scrap, thereby reducing the raw material cost.
薄板連続鋳造法としては、双ロール式薄板連続鋳造法や双ベルト式薄板連続鋳造法等のように高い冷却速度で連続的に薄板を鋳造する方法であれば、特に限定されるものではない。双ロール式薄板連続鋳造法とは、耐火物製の給湯ノズルから一対の水冷ロール間にアルミニウム溶湯を供給し、薄板を連続的に鋳造圧延する方法であり、ハンター法や３Ｃ法等が知られている。また、双ベルト式薄板連続鋳造法は、上下に対峙し水冷されている回転ベルト間に溶湯を注湯して、ベルト面からの冷却で溶湯を凝固させて薄板を連続的に鋳造する方法であり、ハゼレー法やカイザー法等が知られている。いずれの方法も、鋳造機出側において薄板を連続して引き出して板状に切断するシャーまたは、コイル状に巻き取るコイラを有する。薄板連続鋳造法で作製された板材は、熱間圧延を実施する必要がなく、冷間圧延のみで最終板厚を得ることができる。したがって、製造コストを低減できる利点を有する。 The thin plate continuous casting method is not particularly limited as long as it is a method of continuously casting a thin plate at a high cooling rate such as a twin roll thin plate continuous casting method or a twin belt thin plate continuous casting method. The twin roll thin plate continuous casting method is a method in which molten aluminum is supplied between a pair of water-cooled rolls from a refractory hot water supply nozzle, and the thin plate is continuously cast and rolled. The Hunter method, 3C method, etc. are known. ing. In addition, the twin belt type thin plate continuous casting method is a method in which molten metal is poured between rotating belts facing each other up and down and solidified by cooling from the belt surface to continuously cast the thin plate. There are known the Hazelley method and the Kaiser method. Both methods have a shear that continuously draws out a thin plate on the delivery side of the casting machine and cuts it into a plate shape, or a coiler that winds it into a coil shape. The plate material produced by the thin plate continuous casting method does not need to be subjected to hot rolling, and the final thickness can be obtained only by cold rolling. Therefore, there is an advantage that the manufacturing cost can be reduced.
例えば、双ロール式薄板連続鋳造法で鋳造する際の溶湯温度は、６５０〜７５０℃の範囲が好ましい。溶湯温度とは、給湯ノズル直前にあるヘッドボックス内の溶湯温度である。溶湯温度が６５０℃未満の温度では、給湯ノズル内に粗大な金属間化合物の分散粒子が生成し、それらが鋳塊に混入することで圧延時の板切れの原因となる。溶湯温度が７５０℃を超えると、鋳造時にロール間でアルミニウム材が十分に凝固せず、正常な板状鋳塊が得られない。より好ましい溶湯温度は６８０〜７２０℃である。 For example, the molten metal temperature when casting by a twin roll thin plate continuous casting method is preferably in the range of 650 to 750 ° C. The molten metal temperature is the molten metal temperature in the head box immediately before the hot water supply nozzle. When the molten metal temperature is lower than 650 ° C., coarse intermetallic compound dispersed particles are generated in the hot water supply nozzle, and these are mixed into the ingot to cause sheet cutting during rolling. When the molten metal temperature exceeds 750 ° C., the aluminum material is not sufficiently solidified between the rolls during casting, and a normal plate-shaped ingot cannot be obtained. A more preferable molten metal temperature is 680 to 720 ° C.
また、鋳造する板厚は２ｍｍ〜２０ｍｍが好ましい。この厚さ範囲においては、板厚中央の冷却速度も高く、板厚方向において均一な金属組織を得ることが可能である。鋳造板厚が２ｍｍ未満であると、単位時間当たりに鋳造機を通過するアルミニウム量が少なく、安定して溶湯を板幅方向に供給することが困難になる。一方、鋳造板厚が２０ｍｍを超えると、板厚方向において均一な組織を得ることが困難となり、均質化処理等の熱処理工程が必要となる。また、冷間圧延のみで板厚を低下させることが困難となり、熱間圧延を実施する必要が生じる。熱間圧延を実施すると、後述の理由により、鋳造時に微細に分散されたＡｌ−Ｓｎ系晶出物が粗大化し、上述のＳｎ系金属間化合物の粒子密度を得られない。さらに、熱処理工程や熱間圧延工程が必要になることで、製造コストの増加が回避できない。より好ましい鋳造板厚は、４ｍｍ〜１０ｍｍである。 Further, the plate thickness to be cast is preferably 2 mm to 20 mm. In this thickness range, the cooling rate at the center of the plate thickness is also high, and a uniform metal structure can be obtained in the plate thickness direction. When the cast plate thickness is less than 2 mm, the amount of aluminum passing through the casting machine per unit time is small, and it becomes difficult to stably supply the molten metal in the plate width direction. On the other hand, if the cast plate thickness exceeds 20 mm, it becomes difficult to obtain a uniform structure in the plate thickness direction, and a heat treatment step such as a homogenization treatment is required. Further, it is difficult to reduce the plate thickness only by cold rolling, and it is necessary to perform hot rolling. When hot rolling is carried out, for the reasons described later, the Al-Sn based crystallized finely dispersed during casting becomes coarse, and the particle density of the above Sn based intermetallic compound cannot be obtained. Furthermore, since a heat treatment process and a hot rolling process are required, an increase in manufacturing cost cannot be avoided. A more preferable cast plate thickness is 4 mm to 10 mm.
上述のように高い冷却速度で鋳造されたアルミニウム合金薄板材は鋳造工程後に、必要に応じて、後述の圧延工程により所望の最終板厚まで圧延される。その際、後述する理由によって、４５０℃を超えるような圧延工程は実施されない。 The aluminum alloy sheet material cast at a high cooling rate as described above is rolled to a desired final sheet thickness by a rolling process described later, if necessary, after the casting process. In that case, the rolling process exceeding 450 degreeC is not implemented for the reason mentioned later.
３−２．圧延工程
〔圧延温度〕
上記鋳造工程を経た鋳塊は、所定厚さまで圧延を施される。本発明では、圧延後の最終板厚さは、好ましくは０．１〜１５ｍｍ、より好ましくは１〜５ｍｍである。上述のように高い冷却速度で鋳造されたアルミニウム合金材には、Ｓｎが過飽和に固溶されているため、その後の圧延工程においてひずみが導入されると、そのひずみや結晶粒界を起点として、圧延中の局所的な微量の加工発熱によってＡｌ−Ｓｎ系金属間化合物の微細析出が促進される。ただし、Ａｌ−Ｓｎ−Ｍｇ−Ｇａ系晶出物の融点は４８０℃であるため、圧延は４８０℃未満で行なうのが好ましく、４５０℃以下で行うのがより好ましい。圧延中に材料温度が４８０℃を超えると、微細に分散されたＡｌ−Ｓｎ系金属間化合物とそれらを取り囲むα−Ａｌ母相が部分的に溶融してしまう。溶融して液相として繋がった領域は、再び凝固する際に最終凝固部にて粗大な晶出物が生成され、且つ微細な析出物が消失してしまう。また、Ａｌ−Ｓｎ系合金の共晶温度は２２８℃であるため、Ａｌ−Ｓｎ系金属間化合物の部分溶融を最小限に抑制するには、圧延時の温度は更に好ましくは２２８℃未満であり、最も好ましくは２００℃以下である。
3-2. Rolling process (rolling temperature)
The ingot that has undergone the casting process is rolled to a predetermined thickness. In the present invention, the final plate thickness after rolling is preferably 0.1 to 15 mm, more preferably 1 to 5 mm. In the aluminum alloy material cast at a high cooling rate as described above, Sn is supersaturated, so when strain is introduced in the subsequent rolling process, starting from the strain and grain boundaries, Fine precipitation of the Al—Sn intermetallic compound is promoted by a small amount of local heat generated during rolling. However, since the melting point of the Al—Sn—Mg—Ga-based crystallized product is 480 ° C., the rolling is preferably performed at less than 480 ° C., more preferably 450 ° C. or less. When the material temperature exceeds 480 ° C. during rolling, the finely dispersed Al—Sn intermetallic compounds and the α-Al matrix surrounding them are partially melted. In the melted region connected as a liquid phase, when the solidification is performed again, coarse crystallized products are generated in the final solidified portion, and fine precipitates disappear. Further, since the eutectic temperature of the Al—Sn alloy is 228 ° C., the temperature during rolling is more preferably less than 228 ° C. in order to minimize partial melting of the Al—Sn intermetallic compound. Most preferably, it is 200 ° C. or lower.
この圧延温度は、鋳造板厚、圧延ロール径、圧延率等の製造条件に依存するため、特に下限は規定するものではないが、０℃未満では水溶性のロール潤滑剤を使用した場合、ロール潤滑のための流動性が確保できなくなるため圧延が困難となる。なお、上記圧延温度とは圧延後の材料表面における温度を示している。 Since this rolling temperature depends on the production conditions such as the cast plate thickness, rolling roll diameter, rolling rate, etc., the lower limit is not particularly specified, but when using a water-soluble roll lubricant below 0 ° C, the roll Since fluidity for lubrication cannot be secured, rolling becomes difficult. In addition, the said rolling temperature has shown the temperature in the material surface after rolling.
ここで、双ロール式薄板連続鋳造や一部の双ベルト式薄板連続鋳造のように、凝固後の鋳造板に圧延工程が付随する鋳造工程を経た場合については、上述の圧延が不要となる場合もある。したがって、上記圧延工程における最終圧延率についても、前述のＳｎ系金属間化合物粒子密度が得られていれば、特に限定されるものではないが、本発明では、７５〜９５％とするのが好ましい。 Here, when the rolling process is accompanied by a rolling process on the cast plate after solidification, such as twin roll thin sheet continuous casting and some twin belt thin sheet continuous casting, the above-mentioned rolling is not necessary There is also. Accordingly, the final rolling rate in the rolling step is not particularly limited as long as the above Sn-based intermetallic compound particle density is obtained, but in the present invention, it is preferably set to 75 to 95%. .
４．塩水アルミニウム空気電池
本発明に係る塩水アルミニウム空気電池は、正極と、負極と、前記正極と負極との間に介在し、１．０〜４．０ｍｏｌ／リットルのＮａＣｌを含有する電解水溶液とを備える。正極は酸素を正極活物質とし、酸素の酸化還元触媒と、これを担持する導電性の触媒担体とから構成される。酸化還元触媒としては、二酸化マンガンなどの金属酸化物、白金（Ｐｔ）等の金属及びこれらの合金が用いられる。また、触媒担体としては、カーボンブラックなどのカーボン粒子が用いられる。負極には、上述の負極材用アルミニウム合金材が用いられる。圧延後のアルミニウム合金材は、表面の酸化皮膜を除去するためにアルカリ溶液で処理し、次いで中和のために酸溶液で処理し、最後に水洗したものが負極に用いられる。電解溶液としては、１．０〜４．０ｍｏｌ／リットルのＮａＣｌ（塩化ナトリウム）を含有する水溶液が好適に用いられる。そして、この電解水溶液を含浸したセパレータを介して、上記正極と負極を対向配置して塩水アルミニウム空気電池が作製される。
4). Salt water aluminum air battery The salt water aluminum air battery according to the present invention comprises a positive electrode, a negative electrode, and an electrolytic aqueous solution interposed between the positive electrode and the negative electrode and containing 1.0 to 4.0 mol / liter NaCl. . The positive electrode includes oxygen as a positive electrode active material, and includes an oxygen redox catalyst and a conductive catalyst carrier that supports the oxygen redox catalyst. As the redox catalyst, metal oxides such as manganese dioxide, metals such as platinum (Pt), and alloys thereof are used. Further, carbon particles such as carbon black are used as the catalyst carrier. The above-described aluminum alloy material for negative electrode material is used for the negative electrode. The aluminum alloy material after rolling is treated with an alkaline solution to remove the oxide film on the surface, then treated with an acid solution for neutralization, and finally washed with water is used for the negative electrode. As the electrolytic solution, an aqueous solution containing 1.0 to 4.0 mol / liter NaCl (sodium chloride) is preferably used. Then, the positive electrode and the negative electrode are arranged to face each other through the separator impregnated with the electrolytic aqueous solution, so that a salt water aluminum-air battery is manufactured.
次に、本発明を実施例に基づいてさらに詳細に説明する。なお、これらの実施例は、本発明を説明するための例示に過ぎず、本発明の技術的範囲を限定するものでない。 Next, the present invention will be described in more detail based on examples. In addition, these Examples are only the illustrations for demonstrating this invention, and do not limit the technical scope of this invention.
本発明例１〜１８及び比較例１〜１３
塩水アルミニウム空気電池の負極材用アルミニウム合金には、表１に示す組成の合金を用いた。これらの合金に対し、表２に示す鋳造工程及び圧延工程を実施した。鋳造工程と圧延工程の条件を表２に示す。表２に示す鋳造工程において実施した鋳造方法は、ＴＲＣ（Ｔｗｉｎ Ｒｏｌｌ Ｃａｓｔｉｎｇ）が双ロール式薄板連続鋳造、ＴＢＣ（Ｔｗｉｎ Ｂｅｌｔ Ｃａｓｔｉｎｇ）が双ベルト式連続鋳造、ＤＣがＤＣ鋳造である。
Invention Examples 1 to 18 and Comparative Examples 1 to 13
An alloy having the composition shown in Table 1 was used as the aluminum alloy for the negative electrode material of the brine aluminum air battery. The casting process and rolling process shown in Table 2 were performed on these alloys. Table 2 shows the conditions of the casting process and the rolling process. The casting method carried out in the casting process shown in Table 2 is TRC (Twin Roll Casting) twin roll thin plate continuous casting, TBC (Twin Belt Casting) twin belt continuous casting, and DC DC casting.
上記鋳造板又は鋳塊に、表２に示す条件で圧延を施して最終板厚１ｍｍ（幅：１５０ｃｍ、長さ：２ｍ）とする圧延板、又は、圧延を実施せず表面を両板表面から同厚さ面削して１ｍｍの板を作製した。更に、このようにして作製した圧延板と面削板を６０℃の５％水酸化ナトリウム水溶液に３０秒間浸漬した後に水洗した。次いで、これらを室温の３０％硝酸水溶液に６０秒間浸漬した後に、水洗、乾燥を行なって負極材用のアルミニウム合金を得た。このようにして作製した負極材用のアルミニウム合金を、幅１５ｍｍ×長さ５０ｍｍに切断して試料片とした。また、この試料片において、試験面として幅１０ｍｍ×長さ１０ｍｍを露出させ、試験面以外をシリコン系の樹脂で被覆して樹脂被覆試験片を得た。 The above-mentioned cast plate or ingot is rolled under the conditions shown in Table 2 to give a final plate thickness of 1 mm (width: 150 cm, length: 2 m), or the surface from both plate surfaces without rolling. A 1 mm plate was prepared by chamfering the same thickness. Further, the rolled plate and the faced plate thus prepared were immersed in a 5% aqueous sodium hydroxide solution at 60 ° C. for 30 seconds and then washed with water. Next, these were immersed in a 30% aqueous nitric acid solution at room temperature for 60 seconds, then washed with water and dried to obtain an aluminum alloy for a negative electrode material. The aluminum alloy for the negative electrode material thus produced was cut into a sample piece by cutting it into a width of 15 mm and a length of 50 mm. Moreover, in this sample piece, 10 mm in width x 10 mm in length was exposed as a test surface, and other than the test surface was coated with a silicon-based resin to obtain a resin-coated test piece.
上記のようにして得た試料片と樹脂被覆試験片を用いて、以下の測定及び評価試験を行った。 The following measurements and evaluation tests were performed using the sample pieces and resin-coated test pieces obtained as described above.
〔Ｓｎ系金属間化合物粒子密度〕
Ｓｎ系金属間化合物粒子密度は、ＳＥＭを用いて以下のように測定した。上記試料片の厚さ方向及び鋳造方向に沿った試料断面のＳＥＭ像（倍率：１５０００倍）を、一つの試料について、板表面近傍、両表面からそれぞれ板厚１／４部、ならびに、板厚中央部より任意に８箇所撮影し、Ｓｎ系金属間化合物粒子の断面積及び数を画像処理により測定した。次いで、測定したＳｎ金属間化合物粒子数を測定面積で割ることで各測定箇所の密度を求めた。更に、８個所の算術平均値をもって密度分布とした。
[Sn based intermetallic compound particle density]
The Sn-based intermetallic compound particle density was measured using SEM as follows. The SEM image (magnification: 15000 times) of the sample cross section along the thickness direction and the casting direction of the above sample piece is, for one sample, near the plate surface, 1/4 part of the plate thickness from both surfaces, and the plate thickness. Photographing was arbitrarily performed at eight locations from the center, and the cross-sectional area and number of Sn-based intermetallic compound particles were measured by image processing. Next, the density of each measurement location was determined by dividing the measured number of Sn intermetallic compound particles by the measurement area. Further, a density distribution was obtained with arithmetic average values at eight locations.
〔冷却速度〕
板厚中央における鋳造時の冷却速度は、デンドライト２次アーム間隔（Ｄｅｎｄｒｉｔｅ Ａｒｍ Ｓｐａｃｉｎｇ：以下、単にＤＡＳと記す）を測定して算出する。アルミニウム合金の冷却速度Ｃα（℃／秒）と、公線法で測定したＤＡＳ、ｄｒ（μｍ）には下記式（３）に示す関係がある。
（３）冷却速度とＤＡＳの関係：ｄｒ＝６６．７Ｃα −０．３６
(Cooling rate)
The cooling rate during casting at the center of the plate thickness is calculated by measuring the dendrite secondary arm spacing (hereinafter simply referred to as DAS). The cooling rate C α (° C./second) of the aluminum alloy and DAS and dr (μm) measured by the public line method have the relationship shown in the following formula (3).
(3) The relationship of the cooling rate and the DAS: d r = 66.7C α -0.36
同一条件で鋳造した鋳造板を、厚さ方向及び鋳造方向に沿って板巾中央で切断し、断面研磨した後に、板厚中央断面の金属組織を光学顕微鏡により倍率５００倍で観察して交線法によりＤＡＳを求めた。なお、ＤＡＳの関係式及び測定法自体については「アルミニウムのデンドライトアームスペーシングと冷却速度の測定法」、軽金属学会研究部会報告書Ｎｏ２０（１９８８年）、４６〜５２頁の記載に従った。 A cast plate cast under the same conditions is cut at the center of the plate width along the thickness direction and the casting direction, and after cross-sectional polishing, the metal structure of the central cross-section of the plate thickness is observed with an optical microscope at a magnification of 500 times to intersect. DAS was determined by the method. The DAS relational expression and the measurement method itself were as described in “Dendrite arm spacing of aluminum and measurement method of cooling rate”, Light Metal Society Research Group Report No. 20 (1988), pages 46-52.
〔電池特性〕
２５℃に保たれた２．０ｍｏｌ／リットルのＮａＣｌ水溶液中において、Ｐｔ板を正極に用い、上記で得た樹脂被覆試験片を負極に用いて、アルミニウム空気電池を作製した。この電池を用いて、１００ｍＡ／ｃｍ２のアノード電流を６０分間流した。このときの電位を、Ａｇ／ＡｇＣｌ電極を基準として測定した。電流付与から、負極材の電位が−１０００ｍＶ以下となるまでの時間を応答時間（分）とし、−１０００ｍＶ以下の電位に保持された時間を有効時間（分）とし、１００ｍＡ／ｃｍ２のアノード電流を６０分間流したことから算出されるＡｌの溶解量を試験前後における負極の質量変化量（試験前−試験後）で除した値を電流効率とした。
[Battery characteristics]
In a 2.0 mol / liter NaCl aqueous solution kept at 25 ° C., an aluminum-air battery was produced using a Pt plate as the positive electrode and the resin-coated test piece obtained above as the negative electrode. Using this battery, an anode current of 100 mA / cm 2 was passed for 60 minutes. The potential at this time was measured with reference to an Ag / AgCl electrode. The time from application of current until the potential of the negative electrode material becomes −1000 mV or less is defined as the response time (minutes), and the time maintained at the potential of −1000 mV or less is defined as the effective time (minutes), and the anode current is 100 mA / cm 2 . Was obtained by dividing the dissolution amount of Al calculated from flowing for 60 minutes by the mass change amount of the negative electrode before and after the test (before the test and after the test).
ここで、応答時間は、電池として作動させたときに所定電圧に到達するまでの時間を応答性として評価する項目であり、短時間である程好ましい。また、有効時間は、電池として作用できる時間を評価するための項目であり、得られる電流密度が高く、通電を続けても負極の電位が卑のままの状態が維持され、塩水環境においても均一にアノード反応が進行するほど、長い有効時間が得られる。電流効率は、自己腐食の程度の評価項目である。 Here, the response time is an item that evaluates the time required to reach a predetermined voltage when operated as a battery as responsiveness, and a shorter time is preferable. In addition, the effective time is an item for evaluating the time during which the battery can function. The obtained current density is high, and the negative electrode potential is maintained even when energization is continued, and even in a salt water environment. The longer the anodic reaction, the longer the effective time is obtained. Current efficiency is an evaluation item of the degree of self-corrosion.
評価基準は、次の通りである。応答時間については、１５分以下を合格とし、それを超えるものを不合格とした。有効時間については、４０分以上を合格とし、それ未満のものを不合格とした。電流効率については、３０％以上を合格とし、それ未満のものを不合格とした。 The evaluation criteria are as follows. About response time, 15 minutes or less was set as the pass, and the thing exceeding it was made unsuccessful. About valid time, 40 minutes or more was set as the pass, and less than that was set as the failure. About current efficiency, 30% or more was set as the pass, and less than it was set as the failure.
本発明例１〜１８では、０．２μｍ以下の円相当直径を有するＳｎ系金属間化合物の粒子密度が適切であり、電池特性としての応答時間、有効時間及び電流効率も合格であった。 In Invention Examples 1 to 18, the particle density of the Sn-based intermetallic compound having an equivalent circle diameter of 0.2 μm or less was appropriate, and the response time, effective time, and current efficiency as battery characteristics were also acceptable.
これに対して、比較例１では、鋳造時の冷却速度が低かったため、０．２μｍ以下の円相当直径を有するＳｎ系金属間化合物粒子の密度が少な過ぎて、有効時間が不合格となった。 On the other hand, in Comparative Example 1, since the cooling rate at the time of casting was low, the density of the Sn-based intermetallic compound particles having a circle-equivalent diameter of 0.2 μm or less was too small, and the effective time was not acceptable. .
比較例２では、圧延工程の温度が高かったため、０．２μｍ以下の円相当直径を有するＳｎ系金属間化合物の粒子密度が少な過ぎて、有効時間と電流効率が不合格となった。 In Comparative Example 2, since the temperature of the rolling process was high, the particle density of the Sn-based intermetallic compound having a circle-equivalent diameter of 0.2 μm or less was too small, and the effective time and current efficiency were rejected.
比較例３では、鋳造時の冷却速度が低かったため、０．２μｍ以下の円相当直径を有するＳｎ系金属間化合物の粒子密度が少な過ぎて、有効時間と電流効率が不合格となった。 In Comparative Example 3, since the cooling rate at the time of casting was low, the particle density of the Sn-based intermetallic compound having a circle-equivalent diameter of 0.2 μm or less was too small, and the effective time and current efficiency were rejected.
比較例４では、鋳造時の冷却速度が低かったため、０．２μｍ以下の円相当直径を有するＳｎ系金属間化合物の粒子密度が少な過ぎて、有効時間と電流効率が不合格となった。 In Comparative Example 4, since the cooling rate during casting was low, the particle density of the Sn-based intermetallic compound having a circle-equivalent diameter of 0.2 μm or less was too small, and the effective time and current efficiency were rejected.
比較例５では、アルミニウム合金のＳｉ含有量が多過ぎたため、−８００ｍＶ以下の電位に保持されなかったため、応答時間は「−」となり、有効時間が不合格となり、電流効率は測定しなかった。 In Comparative Example 5, since the Si content of the aluminum alloy was too high, the potential was not maintained at a potential of −800 mV or less, so the response time was “−”, the effective time was rejected, and the current efficiency was not measured.
比較例６では、アルミニウム合金のＦｅ含有量が多過ぎたため、−１０００ｍＶ以下の電位に保持されなかったため応答時間は「−」となり、有効時間が不合格となり、電流効率は測定しなかった。 In Comparative Example 6, since the Fe content of the aluminum alloy was excessive, the response time was “−” because it was not held at a potential of −1000 mV or less, the effective time was rejected, and the current efficiency was not measured.
比較例７では、アルミニウム合金のＭｇ含有量が少な過ぎたため、有効時間と電流効率が不合格となった。 In Comparative Example 7, the effective time and current efficiency were rejected because the Mg content of the aluminum alloy was too small.
比較例８では、アルミニウム合金のＭｇ含有量が多過ぎたため酸化皮膜が厚過ぎ、応答時間と有効時間が不合格となった。 In Comparative Example 8, since the Mg content of the aluminum alloy was too large, the oxide film was too thick, and the response time and the effective time were unacceptable.
比較例９では、アルミニウム合金のＳｎ含有量が少な過ぎたため、０．２μｍ以下の円相当直径を有するＳｎ系金属間化合物密度が少な過ぎ、−１０００ｍＶ以下の電位に保持されなかったため応答時間は「−」となり、有効時間が不合格となり、電流効率は測定しなかった。 In Comparative Example 9, since the Sn content of the aluminum alloy was too small, the density of the Sn-based intermetallic compound having a circle-equivalent diameter of 0.2 μm or less was too small, and the response time was “−1000 mV or less. The effective time was rejected and the current efficiency was not measured.
比較例１０では、アルミニウム合金のＳｎ含有量が多過ぎたため、自己腐食速度が増大し、有効時間と電流効率が不合格となった。 In Comparative Example 10, since the Sn content of the aluminum alloy was too large, the self-corrosion rate increased and the effective time and current efficiency were rejected.
比較例１１では、アルミニウム合金のＧａ含有量が少な過ぎたため、−１０００ｍＶ以下の電位に保持されなかったため応答時間は「−」となり、有効時間が不合格となり、電流効率は測定しなかった。 In Comparative Example 11, since the Ga content of the aluminum alloy was too small, the response time was “−” because it was not held at a potential of −1000 mV or less, the effective time was rejected, and the current efficiency was not measured.
比較例１２では、アルミニウム合金のＧａ含有量が多過ぎたため、有効時間と電流効率が不合格となった。 In Comparative Example 12, since the Ga content of the aluminum alloy was excessive, the effective time and current efficiency were rejected.
請求項２を対象とした比較例１３では、アルミニウム合金のＭｎ含有量が多過ぎたため自己腐食速度が増大し、−１０００ｍＶ以下の電位に保持されなかったため応答時間は「−」となり、有効時間が不合格となり、電流効率は測定しなかった。 In Comparative Example 13 for claim 2, since the Mn content of the aluminum alloy was too high, the self-corrosion rate increased, and the response time was “−” because it was not held at a potential of −1000 mV or less, and the effective time was Fail and current efficiency was not measured.
本発明に係る塩水アルミニウム空気電池の負極材用アルミニウム合金は、常温でも電流密度が高く、通電を続けても負極の電位が卑のままの状態が維持され、塩水環境においても均一にアノード反応が進行し、自己腐食が少なく、ならびに、原料コスト及び製造コストが安価であるという産業上の利点を有する。 The aluminum alloy for the negative electrode material of the salt water aluminum-air battery according to the present invention has a high current density even at room temperature, and the negative electrode potential is maintained even when energization is continued, and the anode reaction is uniformly performed even in a salt water environment. It has the industrial advantage of progressing, low self-corrosion, and low raw material costs and manufacturing costs.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015088841A JP6512922B2 (en) | 2015-04-24 | 2015-04-24 | Aluminum alloy for negative electrode material, method for producing the same, and brine aluminum battery provided with negative electrode containing the aluminum alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015088841A JP6512922B2 (en) | 2015-04-24 | 2015-04-24 | Aluminum alloy for negative electrode material, method for producing the same, and brine aluminum battery provided with negative electrode containing the aluminum alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2016204713A true JP2016204713A (en) | 2016-12-08 |
| JP6512922B2 JP6512922B2 (en) | 2019-05-15 |
Family
ID=57486796
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2015088841A Active JP6512922B2 (en) | 2015-04-24 | 2015-04-24 | Aluminum alloy for negative electrode material, method for producing the same, and brine aluminum battery provided with negative electrode containing the aluminum alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6512922B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108808007A (en) * | 2018-06-01 | 2018-11-13 | 安徽工业大学 | A kind of preparation method of the aluminium-air cell anode material of high Fe content |
| CN109963956A (en) * | 2016-12-15 | 2019-07-02 | 奥科宁克公司 | Anticorrosion aluminium |
| WO2020105330A1 (en) * | 2018-11-22 | 2020-05-28 | 住友化学株式会社 | Negative-electrode active material for non-aqueous electrolyte secondary cell, negative electrode, cell, and laminate |
| EP3676032A4 (en) * | 2017-08-31 | 2021-02-17 | Arconic Technologies LLC | Aluminum alloys for use in electrochemical cells and methods of making and using the same |
| CN115874119A (en) * | 2021-09-29 | 2023-03-31 | 中国石油天然气股份有限公司 | Soluble aluminum alloy for underground restrictor part and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5112441B1 (en) * | 1964-04-21 | 1976-04-20 | ||
| US4150204A (en) * | 1977-06-24 | 1979-04-17 | The United States Of America As Represented By The Secretary Of The Navy | Aluminum anode alloy for primary high power density alkaline fuel cells and batteries |
| JPH02168558A (en) * | 1988-08-09 | 1990-06-28 | Alcan Internatl Ltd | Aluminum cell |
| JP2015076224A (en) * | 2013-10-08 | 2015-04-20 | 株式会社Uacj | Aluminum air battery |
-
2015
- 2015-04-24 JP JP2015088841A patent/JP6512922B2/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5112441B1 (en) * | 1964-04-21 | 1976-04-20 | ||
| US4150204A (en) * | 1977-06-24 | 1979-04-17 | The United States Of America As Represented By The Secretary Of The Navy | Aluminum anode alloy for primary high power density alkaline fuel cells and batteries |
| JPH02168558A (en) * | 1988-08-09 | 1990-06-28 | Alcan Internatl Ltd | Aluminum cell |
| JP2015076224A (en) * | 2013-10-08 | 2015-04-20 | 株式会社Uacj | Aluminum air battery |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109963956A (en) * | 2016-12-15 | 2019-07-02 | 奥科宁克公司 | Anticorrosion aluminium |
| CN109963956B (en) * | 2016-12-15 | 2021-09-21 | 奥科宁克技术有限责任公司 | Corrosion-resistant aluminum alloy |
| EP3676032A4 (en) * | 2017-08-31 | 2021-02-17 | Arconic Technologies LLC | Aluminum alloys for use in electrochemical cells and methods of making and using the same |
| CN108808007A (en) * | 2018-06-01 | 2018-11-13 | 安徽工业大学 | A kind of preparation method of the aluminium-air cell anode material of high Fe content |
| WO2020105330A1 (en) * | 2018-11-22 | 2020-05-28 | 住友化学株式会社 | Negative-electrode active material for non-aqueous electrolyte secondary cell, negative electrode, cell, and laminate |
| JP6731130B1 (en) * | 2018-11-22 | 2020-07-29 | 住友化学株式会社 | Negative electrode active material for non-aqueous electrolyte secondary battery, negative electrode, battery and laminate |
| CN115874119A (en) * | 2021-09-29 | 2023-03-31 | 中国石油天然气股份有限公司 | Soluble aluminum alloy for underground restrictor part and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6512922B2 (en) | 2019-05-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6512922B2 (en) | Aluminum alloy for negative electrode material, method for producing the same, and brine aluminum battery provided with negative electrode containing the aluminum alloy | |
| JP5160849B2 (en) | Aluminum alloy foil for current collector | |
| JP5160839B2 (en) | Aluminum alloy foil for current collector | |
| JP5791719B2 (en) | Aluminum alloy foil for electrode current collector and method for producing the same | |
| JP5158675B2 (en) | Magnesium alloy sheet material excellent in corrosion resistance and surface treatment and method for producing the same | |
| CN105925862B (en) | A kind of magnesium-alloy anode material and preparation method thereof | |
| JP5791720B2 (en) | Aluminum alloy foil for electrode current collector and method for producing the same | |
| US20220002892A1 (en) | Method and apparatus for producing aluminum material | |
| TW201321527A (en) | Rolled copper foil for secondary battery collector and production method therefor | |
| JP2013122838A (en) | Positive electrode grid for lead acid battery | |
| CN103898354A (en) | Lead alloy anode material for zinc electrodeposition and rolling method thereof | |
| JP2012122112A (en) | Cast magnesium alloy plate with excellent surface texture, method for producing the same, and magnesium alloy plate with excellent surface texture | |
| JP5460102B2 (en) | Aluminum alloy foil for lithium ion secondary battery and method for producing the same | |
| CN101792875B (en) | Aluminum foil and production method thereof | |
| JP2015076224A (en) | Aluminum air battery | |
| JP6512921B2 (en) | Aluminum negative electrode material for brine air battery, brine aluminum air battery, and method of manufacturing aluminum negative electrode material for brine air battery | |
| CN106191930B (en) | A kind of metallurgical alloy lead anode plate and preparation method thereof of electrification | |
| JPH06179936A (en) | Negative electrode material for aluminum battery | |
| CN104321452A (en) | Aluminum alloy plate for battery cases, which has excellent moldability and weldability | |
| US20020148539A1 (en) | Aluminum anodes and method of manufacture thereof | |
| JP2015076223A (en) | Aluminum alloy for negative electrode material of aluminum air battery, and aluminum air battery | |
| RU2262159C1 (en) | Anode for chemical current supply, method for its manufacture, and chemical current supply | |
| JP4395751B2 (en) | Method for producing Pb-Sn-Ca-Al-based lead alloy sheet for storage battery | |
| RU2813495C1 (en) | Aluminium-based alloy and article made from it | |
| JP3809558B2 (en) | Aluminum alloy for cathode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20180327 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20190220 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20190301 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20190312 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20190322 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20190409 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6512922 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |