JP3550230B2 - Negative electrode active material for secondary battery, electrode using the same, and secondary battery - Google Patents
Negative electrode active material for secondary battery, electrode using the same, and secondary battery Download PDFInfo
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Description
【０００１】
【産業上の利用分野】
本発明は、Ｇａ−Ｓｎ−Ｚｎ三元系合金から成る二次電池用負極活物質およびそれを用いた二次電池用電極ならびに二次電池に関する。
【０００２】
【従来の技術】
従来から二次電池用の負極活物質として種々の物質を単独あるいは組み合わせて用いる研究がなされてきたが、今日実用化された二次電池用負極活物質としては、鉛蓄電池用のＰｂ、ニッケルーカドミウム電池用のＣｄ、水素電池用の水素吸蔵合金、その他Ｚｎ、Ｌｉ等を主成分とする物質に限られていた。
【０００３】
このため、電池の基本性能を左右する負極活物質の種類が限られていたので実用になる二次電池の種類が少なく、それらの電池だけでは互いの電池が持つ欠点を十分に補っているとは言えない状況であった。
【０００４】
こうした中で、本出願人は、先に特開平７−１９２７３１号公報「Ｇａを主成分とする負極活物質およびそれを用いる二次電池」で開示するように、上記従来の二次電池用活物質として、Ｃｄ、Ｐｂ、水素吸蔵合金、Ｌｉ等の欠点を補い得る新規物質として、Ｇａ主体とした負極活物質を使用できることを見いだしていた。
【０００５】
【発明が解決しようとする課題】
しかしながら、Ｇａ単独元素またはある合金組成からなる負極活物質は、高電位、高容量、高エネルギー容量等の、電池として非常に優れた特性を有する一方、高電流密度で放電を行うと、活物質であるＧａの表面に不働態皮膜が生成するために、放電電位が１．８Ｖから１．６Ｖに電位が急に低下し、放電曲線が２段となることが分かった。
【０００６】
このため高電流放電がしにくく、また放電のエネルギー容量も低くなるという欠点があることから、新規な活物質の開発により上記電池特性を生かしつつ、不導態皮膜が発生しない二次電池を得ることが望まれていた。
【０００７】
【課題を解決するための手段】
本発明者等は、前記の課題を解決するために鋭意研究したところ、Ｇａ−Ｓｎ−Ｚｎの三元系合金から成る負極活物質を用いることによって高電位、高容量、高エネルギー容量等の電池特性に優れた二次電池を開発することができた。
【０００８】
本発明は次のとおりである。
【０００９】
第１の発明は、(Ga=0.33 、 Sn=0.33 、 Zn=0.33 ）、 (Ga=0.6 、 Sn=0.2 、 Zn=0.2) 、 (Ga=0.2 、 Sn=0.6 、 Zn=0.2 ）、 (Ga=0.2 、 Sn=0.2 、 Zn=0.6 ）の組成で囲まれる範囲内のモル組成比を有するＧａ−Ｓｎ−Ｚｎ三元系合金から成ることを特徴とするアルカリ二次電池用負極活物質である。
【００１０】
第２の発明は、第１記載の活物質を含有するシート体を用いることを特徴とするアルカリ二次電池用負極である。
【００１１】
第３の発明は、銅板面を第１記載の活物質を含有するシート体で覆い、さらにこのシート体を微小孔を有する樹脂体で覆う構造であることを特徴とするアルカリ二次電池用負極である。
【００１２】
第４の発明は、第２または第３記載の負極を用いることを特徴とするアルカリ二次電池である。
【００１３】
【作用】
本発明の負極活物質に用いるＧａ、Ｓｎ、Ｚｎの各元素は、共に酸性およびアルカリ性の両領域にて溶解する両性金属であることから、何れの元素もアルカリ性溶液中では負極活物質として機能する。
【００１４】
特にＺｎについては、２次電池用負極活物質としての使用に向け、様々な研究が行われているが、ＧａとＳｎに関しては、Ｚｎに比べて電池用活物質としての使用や研究がほとんどなされていなかった。本発明者等は、特願平６−４４８８７号や平成７年９月５日付出願の「二次電池用負極活物質およびそれを用いた電極ならびに二次電池」において、ＧａおよびＳｎもＺｎと同様に電池用負極活物質として機能し、かつ充放電可能な電極材となり得ることを開示した。
【００１５】
これらの元素の電気化学当量は、Ｇａでは２２．３４、Ｓｎでは５９．３５（２価）または２９．６７（４価）、Ｚｎでは３２．７０であり、これらの値は従来からの二次電池用負極活物質であるＣｄの５６．２１やＰｂの１０３．６と比較してかなり小さいので、Ｇａ、ＳｎおよびＺｎが高容量の負極活物質となり得ることが分かる。
【００１６】
また、Ｇａ、ＳｎおよびＺｎが高ｐＨの電解液中へ溶解するときの酸化還元電位（ｖｓ ＮＨＥ）は、それぞれ約−１．５５Ｖ、約−１．１５Ｖ、および約−１．５０Ｖと、Ｃｄや水素吸蔵合金に比較してかなり卑な電位にあるため、Ｇａ、ＳｎおよびＺｎを電池用負極に使用した場合、高電圧の電池が得られる。すなわちこれらの物質は、高エネルギー容量の負極活物質である。
【００１７】
さらにこれらの３元素は、その酸化還元電位が水素発生電位より著しく卑であるにもかかわらず、水素過電圧が高いために自己放電も少ない上、これらの合金は共晶型の合金組成をとるために、開回路電極電位は最も卑なＧａの電位を示すという特徴を有している。
【００１８】
上述のように、Ｇａ、ＳｎおよびＺｎは電池用負極活物質として非常に良い特性を有する元素であるが、各元素単独で負極活物質を構成するには、それぞれの元素に特有の問題があった。
【００１９】
我々は、その中でも高電圧、高容量、高エネルギー容量を有するＧａに注目して試験を重ねてきたが、Ｇａにおいては、図２に示すように放電時に１．８Ｖと１．６Ｖの２段の電位が見られ、不安定な電位挙動が示されている。
【００２０】
その理由は、図３のＧａの分極測定結果に見られるように、電流密度がある値以上になると活物質であるＧａの表面に不働態皮膜が生成し、その後のＧａの溶解は不働態皮膜を通した溶解となるためであることが分かった。
【００２１】
そこで、本発明においては、活物質であるＧａをＳｎおよびＺｎと特定のモル比率で合金化することによって負極活物質を得、Ｇａの非不働態化および放電電位の安定化を図り、良好な結果を得ることができた。
【００２２】
【実施例１】
ＧａへのＳｎ添加の効果を調べるため、以下の方法により評価を行った。
【００２３】
Ｃｕ板（１×１ｃｍ２ ）上に所定量のＳｎとＧａをＳｎ、Ｇａの順に電析させた後、温度３０℃、電解液（３００ｇ／ｌ−ＫＯＨ）中で分極測定を行う。Ｓｎ／Ｇａのモル比を０．１〜１０まで変えてこの測定を行った。
【００２４】
本測定結果の例として、Ｓｎ／Ｇａ＝１の時の分極曲線を図４に、Ｓｎ／Ｇａ比と電流密度（ａｔ１．３５Ｖ）の関係を図５に示した。
【００２５】
図４より、図３のＧａのみの場合と比較して、本実施例ではＧａの不働態化する電流密度が１０倍以上に向上していることが分かる。すなわち、Ｓｎを添加したＧａを電池用負極活物質として使用した場合、安定した放電電位が得られると判断された。
【００２６】
【実施例２】
ＧａへのＺｎ添加の効果を調べるため、以下の方法により評価を行った。
【００２７】
Ｃｕ板（１×１ｃｍ２ ）上に所定量のＺｎとＧａをＺｎ、Ｇａの順に電析させた後、温度３０℃、電解液（３００ｇ／ｌ−ＫＯＨ）中で分極測定を行う。Ｚｎ／Ｇａのモル比を０．１〜１０まで変えてこの測定を行った。
【００２８】
本測定結果の例としてＺｎ／Ｇａ＝１の時の分極曲線を図６に、Ｚｎ／Ｇａ比と電流密度（ａｔ１．３５Ｖ）の関係を図７に示した。
【００２９】
図６より、Ｇａの不働態化が起こると、Ｚｎの溶出が速やかに進行し、電位の急激な変化は起こらなくなり、Ｚｎを添加したＧａを電池用負極活物質として使用した場合、安定した放電電位が得られると判断された。
【００３０】
【実施例３】
ＧａへのＳｎ、Ｚｎ２成分添加の効果を調べるため、以下の方法により評価を行った。
【００３１】
Ｃｕ板（１×１ｃｍ２ ）上に所定量のＳｎ、ＺｎおよびＧａをＳｎ、Ｚｎ、Ｇａの順に電析させた後、温度３０℃、電解液（３００ｇ／ｌ−ＫＯＨ）中で分極測定を行う。（Ｚｎ＋Ｓｎ）／Ｇａのモル比を０．１〜１０まで変えて（Ｚｎ＝１、Ｓｎ＝１に固定）この測定を行った。
【００３２】
本測定結果の例としてＺｎ＝１、Ｓｎ＝１、Ｇａ＝１の時の分極曲線を図８に、（Ｚｎ＋Ｓｎ）／Ｇａ比（Ｚｎ＝１、Ｓｎ＝１に固定）と電流密度（ａｔ１．３５Ｖ）の関係を図９に示した。
【００３３】
図８の分極曲線の形および図９の（Ｚｎ＋Ｓｎ）／Ｇａ比−電流密度図の形は、何れも実施例１と実施例２の結果を合成した形となった。
【００３４】
すなわち、電池用負極活物質として使用した場合、安定した放電電位が得られると判断された。
【００３５】
【実施例４】
実施例１、２および３より、ＧａとＳｎ、Ｚｎの合金化は電池特性に良い影響を与えると判断されたので、いくつかのＧａ−Ｓｎ−Ｚｎ三元系の合金を合成し、さらに活物質として保持し易く電極として充分に作用する構造を考案した。この電極の作成は、例えば以下のような方法で行う。
【００３６】
Ｇａｘ Ｓｎｙ Ｚｎｚ （ｘ＋ｙ＋ｚ＝１、ｘ＝１．００〜０．０５、ｙ＝０．００〜０．９５、ｚ＝０．００〜０．９５）の範囲内の組成比（モル比）に各金属を混合した後、不活性な窒素雰囲気下で６００℃にて合金化させ、水中にてクエンチングする。さらにこれら合金が融解しない温度まで冷却し、粉砕する。
【００３７】
この粉砕粉１０ｇに対し、ＰＴＦＥディスパージョン液（固形分濃度６０％）０．３〜２ｃｃと、適当量のエタノールを加えて混練し、適当な大きさの塊にして乾燥した後、０．４ｍｍ厚になるまで圧延し、シート化する。このシートを１×１ｃｍ２ に切り出し、集電体であるエキスパンド銅上に圧着し、これを電極とする。上記電極を負極板１とし、正極板２には水酸化ニッケル極を、電解液３には３００ｇ／ｌ−ＫＯＨを用いて図１０の様な電池を構成し、０．２５Ｃ相当の充放電サイクル試験を行った。
【００３８】
図１に（Ｇａ＝０．３３、Ｓｎ＝０．３３、Ｚｎ＝０．３３）、（Ｇａ＝０．６、Ｓｎ＝０．２、Ｚｎ＝０．２）、（Ｇａ＝０．２、Ｓｎ＝０．６、Ｚｎ＝０．２）、（Ｇａ＝０．２、Ｓｎ＝０．２、Ｚｎ＝０．６）の組成について、第５０サイクル目の充放電曲線を示す。
【００３９】
何れの場合も、Ｇａのみの活物質に見られた電位の急激な落ち込みは見られなくなった。また、Ｓｎ添加量が増加するほど、放電電位および放電容量が向上することが分かった。
【００４０】
【発明の効果】
ＧａにＳｎおよびＺｎを添加して合金化した３成分系負極活物質を電池に使用すると、Ｇａ活物質特有の不働態皮膜生成に伴う電池電圧の落ち込みが消失する。これにより電池電圧が高電位で安定し、最大放電電流値も増加する。よって高容量、高電圧、高エネルギー容量および高電流放電の可能な電池が得られる。また、本活物質に使用される、Ｇａ、Ｓｎ、Ｚｎには環境上問題となる毒性がない。
【図面の簡単な説明】
【図１】４種の異なる組成のＧａ−Ｓｎ−Ｚｎ合金からなる活物質を用いた本発明の二次電池における充放電曲線図である。
【図２】Ｇａ単独で負極活物質を構成した場合の充放電曲線図である。
【図３】Ｇａ単独の場合の分極曲線図である。
【図４】実施例１におけるＳｎ／Ｇａ＝１の場合の分極曲線図である。
【図５】実施例１におけるＳｎ／Ｇａ比−電流密度図である。
【図６】実施例２におけるＺｎ／Ｇａ＝１の場合の分極曲線図である。
【図７】実施例２におけるＺｎ／Ｇａ比−電流密度図である。
【図８】実施例３における（Ｚｎ＋Ｓｎ）／Ｇａ＝１の場合の分極曲線図である。
【図９】実施例３における（Ｚｎ＋Ｓｎ）／Ｇａ比−電流密度図である。
【図１０】実施例４におけるセル構造図である。
【符号の説明】
１ 負極板
２ 正極板
３ 電解液[0001]
[Industrial applications]
The present invention relates to a negative electrode active material for a secondary battery made of a Ga—Sn—Zn ternary alloy, an electrode for a secondary battery using the same, and a secondary battery using the same.
[0002]
[Prior art]
Conventionally, studies have been made on using various materials alone or in combination as a negative electrode active material for a secondary battery. However, as the negative electrode active material for a secondary battery that has been put into practical use today, Pb, nickel-based It has been limited to Cd for cadmium batteries, hydrogen storage alloys for hydrogen batteries, and other substances containing Zn, Li, and the like as main components.
[0003]
For this reason, the types of negative electrode active materials that affect the basic performance of batteries were limited, so there were few types of secondary batteries that could be used practically, and these batteries alone could sufficiently compensate for the disadvantages of each other's batteries. I could not say it.
[0004]
Under these circumstances, as disclosed in Japanese Patent Application Laid-Open No. 7-192731 entitled "Negative Electrode Active Material Containing Ga as a Main Component and Secondary Battery Using the Same", the applicant of the present invention discloses a conventional active material for a secondary battery. As a material, they have found that a Ga-based negative electrode active material can be used as a novel material that can compensate for defects such as Cd, Pb, a hydrogen storage alloy, and Li.
[0005]
[Problems to be solved by the invention]
However, a negative electrode active material composed of a single element of Ga or an alloy composition has very high characteristics as a battery, such as a high potential, a high capacity, and a high energy capacity. It was found that a passivation film was formed on the surface of Ga, which caused the discharge potential to drop suddenly from 1.8 V to 1.6 V, resulting in a two-step discharge curve.
[0006]
For this reason, high current discharge is difficult to perform, and there is a drawback that the energy capacity of discharge is low. Therefore, a secondary battery that does not generate a passivation film while obtaining the above battery characteristics by developing a new active material is obtained. It was desired.
[0007]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to solve the above-mentioned problems, and found that a battery having a high potential, a high capacity, a high energy capacity, and the like was obtained by using a negative electrode active material composed of a ternary alloy of Ga-Sn-Zn. A secondary battery with excellent characteristics was developed.
[0008]
The present invention is as follows.
[0009]
In the first invention, (Ga = 0.33 , Sn = 0.33 , Zn = 0.33 ), (Ga = 0.6 , Sn = 0.2 , Zn = 0.2) , (Ga = 0.2 , Sn = 0.6 , Zn = 0.2 ), (Ga = 0.2 , Sn = 0.2 , Zn = 0.6 ) is a Ga—Sn—Zn ternary alloy having a molar composition ratio within a range surrounded by a composition of the negative electrode active material for an alkaline secondary battery. .
[0010]
A second invention is a negative electrode for an alkaline secondary battery, characterized by using a sheet body containing the active material according to the first invention.
[0011]
A third invention is a negative electrode for an alkaline secondary battery, which has a structure in which a surface of a copper plate is covered with a sheet body containing the active material described in the first aspect, and the sheet body is further covered with a resin body having micropores. It is.
[0012]
A fourth invention is an alkaline secondary battery using the negative electrode according to the second or third invention.
[0013]
[Action]
Since each element of Ga, Sn, and Zn used in the negative electrode active material of the present invention is an amphoteric metal that dissolves in both acidic and alkaline regions, any element functions as a negative electrode active material in an alkaline solution. .
[0014]
In particular, various researches have been conducted on Zn for use as a negative electrode active material for secondary batteries, but Ga and Sn have been mostly used and researched as active materials for batteries compared to Zn. I didn't. The present inventors have disclosed in Japanese Patent Application No. 6-44887 and “Anode Active Material for Secondary Battery and Electrode and Secondary Battery Using It,” filed on Sep. 5, 1995, that Ga and Sn are also Zn and Similarly, it has been disclosed that the electrode material functions as a negative electrode active material for a battery and can be a chargeable / dischargeable electrode material.
[0015]
The electrochemical equivalents of these elements are 22.34 for Ga, 59.35 (divalent) or 29.67 (tetravalent) for Sn, and 32.70 for Zn. Since it is considerably smaller than 56.21 of Cd and 103.6 of Pb, which are negative electrode active materials for a battery, it is understood that Ga, Sn and Zn can be high-capacity negative electrode active materials.
[0016]
The oxidation-reduction potential (vs NHE) when Ga, Sn and Zn are dissolved in a high pH electrolytic solution are about −1.55 V, about −1.15 V and about −1.50 V, respectively, and Cd Since it has a considerably lower potential than that of a hydrogen storage alloy, a high-voltage battery can be obtained when Ga, Sn, and Zn are used for the battery negative electrode. That is, these materials are high energy capacity negative electrode active materials.
[0017]
Further, these three elements have low self-discharge due to high hydrogen overpotential despite their oxidation-reduction potential being significantly lower than the hydrogen generation potential, and these alloys have a eutectic alloy composition. In addition, the open-circuit electrode potential has the characteristic of showing the lowest potential of Ga.
[0018]
As described above, Ga, Sn, and Zn are elements having very good characteristics as a negative electrode active material for a battery. However, when each of these elements alone constitutes a negative electrode active material, there is a problem unique to each element. Was.
[0019]
We have repeatedly conducted tests focusing on Ga, which has high voltage, high capacity, and high energy capacity. Among Ga, as shown in FIG. 2, two stages of 1.8 V and 1.6 V during discharging are shown. And the unstable potential behavior is shown.
[0020]
The reason is that as shown in the polarization measurement result of Ga in FIG. 3, when the current density exceeds a certain value, a passive film is formed on the surface of Ga which is an active material, and the subsequent dissolution of Ga is performed by the passive film. It was found that this was due to dissolution through
[0021]
Therefore, in the present invention, a negative electrode active material is obtained by alloying Ga, which is an active material, with Sn and Zn at a specific molar ratio, thereby achieving passivation of Ga and stabilization of a discharge potential. The result was able to be obtained.
[0022]
In order to examine the effect of adding Sn to Ga, evaluation was performed by the following method.
[0023]
After depositing predetermined amounts of Sn and Ga on a Cu plate (1 × 1 cm 2 ) in the order of Sn and Ga, polarization measurement is performed at a temperature of 30 ° C. in an electrolytic solution (300 g / l-KOH). This measurement was performed by changing the Sn / Ga molar ratio from 0.1 to 10.
[0024]
As an example of the measurement result, FIG. 4 shows a polarization curve when Sn / Ga = 1, and FIG. 5 shows a relationship between the Sn / Ga ratio and the current density (at 1.35 V).
[0025]
From FIG. 4, it can be seen that the current density for passivating Ga is increased by a factor of 10 or more in this embodiment as compared with the case of only Ga in FIG. That is, it was determined that a stable discharge potential was obtained when Ga to which Sn was added was used as the negative electrode active material for a battery.
[0026]
In order to examine the effect of adding Zn to Ga, evaluation was performed by the following method.
[0027]
After a predetermined amount of Zn and Ga are deposited on a Cu plate (1 × 1 cm 2 ) in the order of Zn and Ga, polarization measurement is performed at a temperature of 30 ° C. in an electrolytic solution (300 g / l-KOH). This measurement was performed by changing the molar ratio of Zn / Ga from 0.1 to 10.
[0028]
As an example of the measurement results, a polarization curve when Zn / Ga = 1 is shown in FIG. 6, and a relationship between the Zn / Ga ratio and the current density (at 1.35 V) is shown in FIG.
[0029]
As shown in FIG. 6, when the passivation of Ga occurs, the elution of Zn progresses rapidly, and a rapid change in potential does not occur. When Ga to which Zn is added is used as a negative electrode active material for a battery, stable discharge occurs. It was determined that a potential was obtained.
[0030]
The following method was used to evaluate the effect of adding two components of Sn and Zn to Ga.
[0031]
After a predetermined amount of Sn, Zn, and Ga were deposited on a Cu plate (1 × 1 cm 2 ) in the order of Sn, Zn, and Ga, the polarization was measured in an electrolyte (300 g / l-KOH) at a temperature of 30 ° C. Do. This measurement was performed by changing the molar ratio of (Zn + Sn) / Ga from 0.1 to 10 (fixed at Zn = 1 and Sn = 1).
[0032]
As an example of the measurement result, FIG. 8 shows a polarization curve when Zn = 1, Sn = 1, and Ga = 1, and shows a (Zn + Sn) / Ga ratio (fixed to Zn = 1 and Sn = 1) and a current density (at1. 35V) is shown in FIG.
[0033]
The shape of the polarization curve in FIG. 8 and the shape of the (Zn + Sn) / Ga ratio-current density diagram in FIG. 9 are both shapes obtained by combining the results of Example 1 and Example 2.
[0034]
That is, it was determined that a stable discharge potential was obtained when used as a negative electrode active material for a battery.
[0035]
From Examples 1, 2 and 3, it was determined that alloying Ga with Sn and Zn had a good effect on battery characteristics. Therefore, several Ga-Sn-Zn ternary alloys were synthesized and further activated. A structure has been devised which can be easily held as a substance and sufficiently functions as an electrode. This electrode is formed, for example, by the following method.
[0036]
Ga x Sn y Zn z (x + y + z = 1, x = 1.00-0.05, y = 0.00-0.95, z = 0.00-0.95) composition ratio (molar ratio) ), Alloyed at 600 ° C. under an inert nitrogen atmosphere, and quenched in water. Further, the alloy is cooled to a temperature at which it does not melt and pulverized.
[0037]
To 10 g of the pulverized powder, 0.3 to 2 cc of a PTFE dispersion liquid (solid content: 60%) and an appropriate amount of ethanol are added, kneaded, dried into a lump of an appropriate size, and dried. Rolled to a thicker sheet. This sheet is cut into 1 × 1 cm 2 and pressed on expanded copper as a current collector to form an electrode. A battery as shown in FIG. 10 was constructed using the above-mentioned electrode as the
[0038]
FIG. 1 shows (Ga = 0.33, Sn = 0.33, Zn = 0.33), (Ga = 0.6, Sn = 0.2, Zn = 0.2), (Ga = 0.2, For the compositions of Sn = 0.6, Zn = 0.2) and (Ga = 0.2, Sn = 0.2, Zn = 0.6), the charge / discharge curves of the 50th cycle are shown.
[0039]
In each case, the sharp drop in the potential observed in the Ga-only active material was not observed. In addition, it was found that the discharge potential and the discharge capacity were improved as the Sn addition amount was increased.
[0040]
【The invention's effect】
When a three-component negative electrode active material obtained by adding Sn and Zn to Ga and alloying is used for a battery, the drop in battery voltage accompanying the formation of a passive film unique to the Ga active material disappears. As a result, the battery voltage is stabilized at a high potential, and the maximum discharge current value also increases. Therefore, a battery capable of high capacity, high voltage, high energy capacity and high current discharge can be obtained. In addition, Ga, Sn, and Zn used in the present active material do not have environmentally toxic toxicity.
[Brief description of the drawings]
FIG. 1 is a charge / discharge curve diagram of a secondary battery of the present invention using an active material composed of four different types of Ga—Sn—Zn alloys.
FIG. 2 is a charge / discharge curve diagram when a negative electrode active material is composed of Ga alone.
FIG. 3 is a polarization curve diagram when Ga is used alone.
FIG. 4 is a polarization curve diagram in the case of Sn / Ga = 1 in Example 1.
5 is an Sn / Ga ratio-current density diagram in Example 1. FIG.
FIG. 6 is a polarization curve diagram when Zn / Ga = 1 in Example 2.
FIG. 7 is a diagram showing a Zn / Ga ratio-current density in Example 2.
FIG. 8 is a polarization curve diagram when (Zn + Sn) / Ga = 1 in Example 3.
FIG. 9 is a (Zn + Sn) / Ga ratio-current density diagram in Example 3.
FIG. 10 is a diagram illustrating a cell structure according to a fourth embodiment.
[Explanation of symbols]
1
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26780395A JP3550230B2 (en) | 1995-09-21 | 1995-09-21 | Negative electrode active material for secondary battery, electrode using the same, and secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26780395A JP3550230B2 (en) | 1995-09-21 | 1995-09-21 | Negative electrode active material for secondary battery, electrode using the same, and secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0992277A JPH0992277A (en) | 1997-04-04 |
| JP3550230B2 true JP3550230B2 (en) | 2004-08-04 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP3726958B2 (en) | 2002-04-11 | 2005-12-14 | ソニー株式会社 | battery |
| KR100786864B1 (en) * | 2006-02-10 | 2007-12-20 | 삼성에스디아이 주식회사 | Negative active material for rechargeable lithium battery, method of preparing same and rechargeable lithium battery comprising same |
| JP5342165B2 (en) * | 2008-04-25 | 2013-11-13 | 株式会社コベルコ科研 | Air secondary battery |
| WO2009048146A1 (en) * | 2007-10-10 | 2009-04-16 | Kobelco Research Institute, Inc. | Negative electrode active material for rechargeable battery, rechargeble battery using the negative electrode active material, and air rechargeable battery |
| JP5329066B2 (en) * | 2007-10-10 | 2013-10-30 | 株式会社コベルコ科研 | Negative electrode active material for secondary battery and secondary battery using the same |
| CN108060328A (en) * | 2017-12-14 | 2018-05-22 | 蔡郅林 | One kind has writing function alloy and preparation method |
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