JPH08162109A - Ga coated type or surface covered type negative electrode and secondary battery using the same - Google Patents
Ga coated type or surface covered type negative electrode and secondary battery using the sameInfo
- Publication number
- JPH08162109A JPH08162109A JP6329717A JP32971794A JPH08162109A JP H08162109 A JPH08162109 A JP H08162109A JP 6329717 A JP6329717 A JP 6329717A JP 32971794 A JP32971794 A JP 32971794A JP H08162109 A JPH08162109 A JP H08162109A
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- battery
- current collector
- electrode
- active material
- 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
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Classifications
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、金属ＧａまたはＧａを
主成分とするＧａ合金を負極活物質として電池用集電体
表面に吹きつけあるいは電析によって表面被覆した負極
として用いることを特徴とする新規な二次電池を提供す
ることを目的とする。BACKGROUND OF THE INVENTION The present invention is characterized in that metal Ga or a Ga alloy containing Ga as a main component is used as a negative electrode active material as a negative electrode having a surface coated by spraying or electrodeposition on the surface of a battery current collector. It is an object of the present invention to provide a novel secondary battery that
【０００２】[0002]
【従来の技術】従来から電池用の負極活物質として種々
の物質を単独で、またはいくつか組み合わせて使用する
ことが研究されてきたが、水溶液系電解質を用いた電池
用負極活物質は、亜鉛、鉛、カドミウム、水素吸蔵合金
などに限られていた。2. Description of the Related Art Conventionally, various materials have been studied to be used alone or in combination as a negative electrode active material for a battery. However, a negative electrode active material for a battery using an aqueous electrolyte is zinc. , Lead, cadmium, hydrogen storage alloy, etc.
【０００３】しかし、このような従来の技術において
は、電池の基本性能を左右する負極活物質の種類が上記
のように少なく、特に充放電可能な二次電池の種類とし
ては、鉛蓄電池、ニッケル−カドミウム電池、水素吸蔵
電池のほぼ３種類だけが実用化されているに過ぎない。
このように電池の種類が少ないので、互いに他の電池が
有する欠点を十分補うことができない状況となっていた
ため、従来の電池には次のような欠点があった。 充放電にともない、電極表面にデンドライトが生成
し、サイクル寿命が短くなる。 活物質そのものあるいは充放電時に析出する物質の電
気伝導性が低く、大きな電流を取り出しにくい。 電池としての容量が小さい（電気容量が小さい）。 電圧が低い（エネルギー容量が小さい）。 環境上問題となるような毒性がある。However, in such a conventional technique, the types of the negative electrode active material that influence the basic performance of the battery are small as described above, and particularly, as the types of the secondary battery which can be charged and discharged, a lead storage battery and a nickel battery are used. -Only about three types of cadmium batteries and hydrogen storage batteries have been put into practical use.
As described above, since the number of types of batteries is small, it is difficult to sufficiently compensate for the drawbacks of the other batteries. Therefore, the conventional batteries have the following drawbacks. With charge and discharge, dendrites are generated on the electrode surface and the cycle life is shortened. The electric conductivity of the active material itself or the material deposited during charging / discharging is low, and it is difficult to extract a large current. Battery capacity is small (electrical capacity is small). Low voltage (small energy capacity). Toxic to cause environmental problems.
【０００４】本出願人は上記欠点を解決する一手段とし
て、負極活物質として金属Ｇａ、Ｇａを主成分とする合
金またはガリウム化合物を使用した電池を提案した。そ
してその電池の負極およびその製法として、以下のもの
を開示した。 ＧａまたはＧａを主成分とした合金自体を負極とした
もの（特願平６−４４８８７号）。 ガリウム化合物に導電性を持たせる目的で、少量のケ
ッチェンブラックを混合、練り合わせたものを液体Ｇａ
が染み出ずかつ活電解液が染み込む程度の多孔体に詰め
込み構成した負極（同上）。 ガリウム化合物、金属Ｇａ混合物に結着剤を加え練り
合わせたものを引き延ばしてシート状に加工し、そのシ
ートを集電体に圧着させて作製した電極（特願平６−２
３４３８１号）。 導電性が高く、かつＧａと反応しにくい炭素系材料に
負極活物質であるＧａまたはＧａを主成分とする合金を
微細に分散、担持させその後圧延によりシート状に成形
した電極（同上）。As a means for solving the above drawbacks, the present applicant proposed a battery using metal Ga, an alloy containing Ga as a main component, or a gallium compound as a negative electrode active material. And the following was disclosed as the negative electrode of the battery and its manufacturing method. A negative electrode made of Ga or an alloy containing Ga as a main component (Japanese Patent Application No. 6-44887). Liquid Ga is prepared by mixing and kneading a small amount of Ketjen Black for the purpose of making the gallium compound conductive.
A negative electrode composed of a porous material that does not seep out and is soaked with an active electrolyte (same as above). An electrode prepared by adding a binder to a gallium compound / metal Ga mixture, kneading the mixture, processing the mixture into a sheet, and pressing the sheet onto a current collector (Japanese Patent Application No. 6-2
34381). An electrode formed by finely dispersing and supporting a negative electrode active material, Ga or an alloy containing Ga as a main component, on a carbon-based material having high conductivity and hardly reacting with Ga, and then forming the sheet by rolling (the same as above).
【０００５】しかしながらこれらの発明についてもその
後の研究において、 溶融状態になった負極活物質が正極と接触する。 電極表面が小さく大電流が取り出せない。 負極活物質以外の物質が存在するため電池の体積ある
いは重量当りの電池容量が小さい。 製造手順が繁雑で製造コストが高い。 という問題点があることが判明した。However, regarding these inventions as well, in the subsequent research, the negative electrode active material in a molten state comes into contact with the positive electrode. The electrode surface is small and a large current cannot be taken out. Since a substance other than the negative electrode active material is present, the battery capacity per volume or weight is small. The manufacturing procedure is complicated and the manufacturing cost is high. It turned out that there was a problem.
【０００６】[0006]
【発明が解決しようとする課題】上述のように負極活物
質としてＧａ、Ｇａを主成分とする合金またはＧａ化合
物を用いた負極やそれを用いた二次電池を開示している
が、本発明は上記負極の欠点を解消することを目的とす
るものである。DISCLOSURE OF THE INVENTION As described above, a negative electrode using Ga, an alloy containing Ga as a main component or a Ga compound as a negative electrode active material and a secondary battery using the same are disclosed. Is intended to eliminate the drawbacks of the negative electrode.
【０００７】[0007]
【課題を解決するための手段】本発明者等は斯かる課題
を解決するために鋭意研究したところ、溶融状態のＧａ
等を従来公知の集電体上に吹きつけたり、電析により適
当量析出させることによって負極体として使用できるこ
とを見いだし、本発明を提供することができた。Means for Solving the Problems The inventors of the present invention have conducted extensive studies in order to solve such problems and found that Ga
The inventors have found that they can be used as a negative electrode body by spraying the above onto a conventionally known current collector or by depositing an appropriate amount by electrodeposition, and thus the present invention can be provided.
【０００８】すなわち本発明は、第１に、電池用集電体
表面に金属ＧａまたはＧａ合金を吹きつけてあるいは電
析により表面被覆して負極と成したことを特徴とする負
極であり、第２に、負極として電池用集電体表面に金属
ＧａまたはＧａ合金を吹きつけてあるいは電析により表
面被覆して負極と成したものを用いることを特徴とする
二次電池に関するものである。That is, the present invention is, firstly, a negative electrode characterized by being formed by spraying metal Ga or Ga alloy on the surface of a current collector for a battery or coating the surface by electrodeposition to form a negative electrode. In the second aspect, the present invention relates to a secondary battery, wherein a negative electrode is obtained by spraying metal Ga or Ga alloy on the surface of a current collector for a battery or coating the surface by electrodeposition to form a negative electrode.
【０００９】[0009]
【作用】一般的に負極活物質としてはＺｎ、Ｃｄ、Ｐｂ
等の金属が用いられている。その他の金属も電池用電極
に用いられる可能性を有しているが、それらが実用的な
電池になり得るかは問題であった。Function Generally, the negative electrode active material is Zn, Cd, Pb.
And other metals are used. Other metals have the possibility of being used for battery electrodes, but it was a problem whether they could be practical batteries.
【００１０】Ｇａが電池用負極活物質として用いられる
ことについては、従来、Ｇａが約３０℃以上で液体とな
る他、他の金属と反応しやすく電池としての特性が不安
定であることがこれまで電池材料として用いられなかっ
た理由である。Regarding the fact that Ga is used as a negative electrode active material for batteries, conventionally, Ga becomes a liquid at about 30 ° C. or higher, and it easily reacts with other metals, resulting in unstable battery characteristics. This is the reason why it was not used as a battery material.
【００１１】しかしながら本発明者等は先にこのＧａま
たはＧａ合金が電池用の負極活物質として作用すること
を見いだし、これを用いた二次電池を提供した。すなわ
ち、Ｇａは周期律表第３１番元素で、電気化学反応に伴
う価数変化が３であり、アルカリ水溶液中では Ｇａ＋３Ｈ2 Ｏ＝ＧａＯ3 3-＋６Ｈ+ ＋３ｅ- （１） の反応で溶解すると考えられている。However, the present inventors have previously found that this Ga or Ga alloy acts as a negative electrode active material for a battery, and provided a secondary battery using the same. That is, Ga is the 31st element of the periodic table, has a valence change of 3 due to an electrochemical reaction, and dissolves in a reaction of Ga + 3H 2 O = GaO 3 3- + 6H + + 3e − (1) in an alkaline aqueous solution. It is considered.
【００１２】本発明において使用される集電体として
は、銅、ニッケル、鉄、ビスマス、亜鉛または炭素等の
公知の素材で形成した板、網および不織布から成る形状
であるが、シート状のものが好ましい。The current collector used in the present invention is in the form of a plate, a net and a non-woven fabric formed of a known material such as copper, nickel, iron, bismuth, zinc or carbon, but in the form of a sheet. Is preferred.
【００１３】また負極活物質として用いることができる
のは、金属Ｇａの他、該金属ＧａとＩｎ、Ｚｎ、Ｓｎ、
Ａｇ、Ｃｄ、Ｐｂ、Ｂｉ等の合金であるが、Ｇａとの合
金の好ましい組成範囲としてはＩｎが１〜４０wt% 、Ｓ
ｎが１〜３０wt% 、Ｚｎが１〜１０wt% 、Ａｇが１〜１
０wt% 、Ｃｄが１〜１０wt% 、Ｐｂが１〜１５wt% 、Ｂ
ｉが１〜１０wt% の範囲である。Further, as the negative electrode active material, in addition to the metal Ga, the metal Ga and In, Zn, Sn,
Although alloys of Ag, Cd, Pb, Bi, etc., the preferable composition range of the alloy with Ga is 1 to 40 wt% of In and S.
n is 1 to 30 wt%, Zn is 1 to 10 wt%, Ag is 1 to 1
0wt%, Cd 1-10wt%, Pb 1-15wt%, B
i is in the range of 1 to 10 wt%.
【００１４】これらのＧａを加熱溶解し液状にしたもの
を、スプレーガンで上記の集電体に吹きつけるか、ある
いはＧａを溶解させた電解液中に水酸化ニッケルの正極
を用いて集電体表面にＧａを析出させることによって、
これらの集電体を負極そのものとして用いる。A liquid obtained by heating and melting these Ga is sprayed on the above current collector with a spray gun, or a current collector using a nickel hydroxide positive electrode in the Ga dissolved electrolyte. By depositing Ga on the surface,
These current collectors are used as the negative electrode itself.
【００１５】以下実施例をもって詳細に説明するが、本
発明の範囲はこれらに限定されるものではない。The present invention will be described in detail below with reference to examples, but the scope of the present invention is not limited to these.
【００１６】[0016]
【実施例１】金属Ｇａを加熱溶解して液状にし、これを
スプレーガンを用いて予め形成した銅製の板、網および
不織布を使用した集電体（市販品）表面に均一に吹きつ
けたところ、Ｇａが該集電体表面上に均一に結着した。
この電極を３５℃の湯浴につけた状態で、軽い振動を与
えたがＧａは集電体から欠落しなく、結着が十分である
ことが確認できた。[Example 1] Metal Ga was melted into a liquid by heating and sprayed uniformly on the surface of a current collector (commercially available) using a copper plate, net and non-woven fabric formed in advance by using a spray gun. , Ga was uniformly bound on the surface of the current collector.
While this electrode was immersed in a hot water bath at 35 ° C., a slight vibration was applied, but Ga did not drop from the current collector, and it was confirmed that the binding was sufficient.
【００１７】同様に、集電体の材質を上記銅材に代え
て、鉄、ニッケル、ビスマス、亜鉛または炭素系材料と
して実験したところ、銅材と同じ効果を得ることができ
た。Similarly, when an experiment was conducted using iron, nickel, bismuth, zinc or a carbon-based material instead of the copper material as the material of the current collector, the same effect as the copper material could be obtained.
【００１８】[0018]
【実施例２】実施例１に示す金属Ｇａに代えて、Ｇａと
Ｉｎからなる合金（Ｇａ／Ｉｎ重量比７５：２５）を用
いた他は、実施例１と同様な実験をしたところ、同様に
集電体表面に均一に結着させることができた。Example 2 The same experiment was carried out as in Example 1 except that an alloy of Ga and In (Ga / In weight ratio 75:25) was used in place of the metal Ga shown in Example 1. In addition, it was possible to bind uniformly on the surface of the current collector.
【００１９】[0019]
【実施例３】３００g/l のＫＯＨ液に２５０g/l のＧａ
を溶解させた電解液中に、水酸化ニッケルの正極と銅製
の板、網および不織布から集電体を浸漬して電流を通
し、該集電体表面にＧａを電析させた。この電極を３５
℃の湯浴につけた状態で、軽い振動を与えたがＧａは集
電体から欠落しなく、結着が十分であることが確認でき
た。Example 3 250 g / l Ga in 300 g / l KOH liquid
A current collector was immersed in a positive electrode made of nickel hydroxide, a copper plate, a net, and a non-woven fabric in an electrolyte solution in which was passed a current to deposit Ga on the surface of the current collector. 35 this electrode
It was confirmed that Ga was not lost from the current collector, and that the binding was sufficient, although light vibration was applied in a state of being immersed in a hot water bath at ℃.
【００２０】[0020]
【実施例４】実施例１において作製した銅製集電体表面
にＧａを均一に吹きつけた負極２を用い、図１に示すセ
ルに組み入れて充放電試験を行った。この場合、正極１
には１５mm角の水酸化ニッケル極、上記負極は１５mm角
であり、電解液３は３００g/l ＫＯＨ液にＧａを２５０
g/l 溶解させた水溶液を１０ml使用した。Example 4 Using the negative electrode 2 prepared in Example 1 in which Ga was uniformly sprayed on the surface of the current collector made of copper, the negative electrode 2 was incorporated into the cell shown in FIG. 1 and a charge / discharge test was conducted. In this case, the positive electrode 1
Is a 15 mm square nickel hydroxide electrode, the above negative electrode is a 15 mm square, and the electrolyte 3 is 300 g / l KOH solution with 250 Ga.
10 ml of a g / l dissolved aqueous solution was used.
【００２１】充放電条件は、充電が２０mAで２時間、放
電が４０mAで放電終了電圧は１Ｖとし、その結果を図３
に示した。また、本発明と従来の技術を比較するために
負極に、φ５．５mm−Ｌ１５０mmのＧａ棒を使用して同
様の実験をし、その結果を図３に併せて示した。The charging and discharging conditions were as follows: charging was 20 mA for 2 hours, discharging was 40 mA, and the discharge end voltage was 1 V. The results are shown in FIG.
It was shown to. Further, in order to compare the present invention with the conventional technique, a similar experiment was performed using a Ga rod of φ5.5 mm-L150 mm as a negative electrode, and the results are also shown in FIG.
【００２２】図３から明らかのように、本発明の負極を
使用した場合の方が、従来技術であるＧａ棒を使用した
場合と比較して、同じ電流を放電した時の電圧が高いこ
とが確認できた。このことから、本発明の負極が、従来
の負極に比べ大きい電流を放電できることが認められ
た。As is apparent from FIG. 3, when the negative electrode of the present invention is used, the voltage when the same current is discharged is higher than when the Ga rod of the prior art is used. It could be confirmed. From this, it was confirmed that the negative electrode of the present invention can discharge a larger current than the conventional negative electrode.
【００２３】[0023]
【実施例５】実施例３に示すように銅製集電体表面にＧ
ａを電析させた負極を用いた他は、実施例４と同一の手
段で充放電試験を行った。この結果、実施例４に示す結
果とほとんど同一の結果が得られ、本発明の負極も従来
の負極と比べ、大きい電流が放電できることが認められ
た。[Embodiment 5] As shown in Embodiment 3, G is formed on the surface of the copper current collector.
A charge / discharge test was conducted in the same manner as in Example 4 except that the negative electrode obtained by electrodepositing a was used. As a result, almost the same result as the result shown in Example 4 was obtained, and it was confirmed that the negative electrode of the present invention can discharge a larger current than the conventional negative electrode.
【００２４】[0024]
【実施例６】従来の技術であるＧａ微粉末、炭素系材料
の微粉体および有機系ポリマーを重量比で１１：１：１
で混合したものをシート状に圧延して成形した負極と、
実施例１に示す銅製集電体にスプレーガンでＧａを吹き
つけた負極と、実施例３に示す集電体表面にＧａを電析
してなる負極とを用いて、それぞれに存在するＧａ含有
率を分析したところ、重量比率においてシート状負極
が、平均８５％であったが、本発明の２負極は共に平均
９８％であった。Example 6 The weight ratio of the conventional fine Ga powder, the fine carbon material powder and the organic polymer is 11: 1: 1.
A negative electrode formed by rolling a mixture of the above into a sheet shape,
Using the negative electrode obtained by spraying Ga on the copper current collector shown in Example 1 with a spray gun, and the negative electrode obtained by electrodepositing Ga on the current collector surface shown in Example 3, each containing Ga When the ratio was analyzed, the average weight of the sheet-shaped negative electrodes was 85%, but the average of the two negative electrodes of the present invention was 98%.
【００２５】また体積比率をそれぞれ測定したところ、
シート状負極は平均４５％であったが、本発明の２負極
が共に平均８５％であった。このことから、本発明の負
極中の活物質の量を増加させることができることが認め
られ、この結果、本発明に係る負極を用いた電池は、従
来の電池と比較し重量および体積当りの容量が向上する
ことを示していた。When the volume ratios were measured, respectively,
The sheet-shaped negative electrode had an average of 45%, while the two negative electrodes of the present invention had an average of 85%. From this, it was confirmed that the amount of the active material in the negative electrode of the present invention can be increased, and as a result, the battery using the negative electrode of the present invention has a capacity per weight and volume as compared with the conventional battery. Was shown to improve.
【００２６】[0026]
【発明の効果】上述のように本発明の負極は、従来のＧ
ａ担持負極やシート状負極に比較すると、 負極活物質の溶融状態における集電体からの欠落およ
びそれによる短絡を防止した。 放電電流量の向上 電池の容量の向上 を計ることができる上、簡単に負極を製造できることか
らコスト上の効果も大きい。As described above, the negative electrode of the present invention is
As compared with the a-supported negative electrode and the sheet-shaped negative electrode, the lack of the negative electrode active material from the current collector in the molten state and the resulting short circuit were prevented. Improvement of discharge current amount The capacity of the battery can be improved, and the negative electrode can be easily manufactured, so that the cost effect is large.
【図１】実施例４における本発明負極を使用した電池セ
ルの概略図である。FIG. 1 is a schematic view of a battery cell using the negative electrode of the present invention in Example 4.
【図２】実施例４における従来の負極を使用した電池セ
ルの概略図である。FIG. 2 is a schematic view of a battery cell using a conventional negative electrode in Example 4.
【図３】実施例４における充放電特性図であるFIG. 3 is a charge / discharge characteristic diagram in Example 4.
１ 正極 ２ 負極 ３ 電解液 ４ ＰＰ蓋 ５ ＰＰセル ６ Ｇａ棒 1 Positive electrode 2 Negative electrode 3 Electrolyte 4 PP lid 5 PP cell 6 Ga rod
───────────────────────────────────────────────────── フロントページの続き (72)発明者 坂本 陵 東京都千代田区丸の内１丁目８番２号 同 和鉱業株式会社内 (72)発明者 柳沢 真樹子 東京都千代田区丸の内１丁目８番２号 同 和鉱業株式会社内 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Ryo Sakamoto 1-8-2 Marunouchi, Chiyoda-ku, Tokyo Dowa Mining Co., Ltd. (72) Inventor Makiko Yanagisawa 1-2-8 Marunouchi, Chiyoda-ku, Tokyo Within Wa Mining Co., Ltd.
Claims (2)
合金を吹きつけあるいは電析により表面被覆した負極と
成すことを特徴とするＧａ塗布または表面被覆型負極。1. Metal Ga or Ga on the surface of a battery current collector.
A Ga-coated or surface-coated negative electrode comprising a negative electrode whose surface is coated by spraying or electrodeposition of an alloy.
またはＧａ合金を吹きつけあるいは電析により表面被覆
して負極と成したものを用いることを特徴とする二次電
池。2. A metal Ga as a negative electrode on the surface of a battery current collector.
Alternatively, a secondary battery is used which is formed by spraying a Ga alloy or coating the surface by electrodeposition to form a negative electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32971794A JP3550200B2 (en) | 1994-12-02 | 1994-12-02 | Ga-coated or surface-coated negative electrode and secondary battery using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32971794A JP3550200B2 (en) | 1994-12-02 | 1994-12-02 | Ga-coated or surface-coated negative electrode and secondary battery using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08162109A true JPH08162109A (en) | 1996-06-21 |
| JP3550200B2 JP3550200B2 (en) | 2004-08-04 |
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ID=18224483
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32971794A Expired - Fee Related JP3550200B2 (en) | 1994-12-02 | 1994-12-02 | Ga-coated or surface-coated negative electrode and secondary battery using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3550200B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113471446A (en) * | 2021-07-06 | 2021-10-01 | 山东大学 | Iron-based current collector and preparation method and application thereof |
-
1994
- 1994-12-02 JP JP32971794A patent/JP3550200B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113471446A (en) * | 2021-07-06 | 2021-10-01 | 山东大学 | Iron-based current collector and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3550200B2 (en) | 2004-08-04 |
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