JPH0552038B2 - - Google Patents
Info
- Publication number
- JPH0552038B2 JPH0552038B2 JP58104413A JP10441383A JPH0552038B2 JP H0552038 B2 JPH0552038 B2 JP H0552038B2 JP 58104413 A JP58104413 A JP 58104413A JP 10441383 A JP10441383 A JP 10441383A JP H0552038 B2 JPH0552038 B2 JP H0552038B2
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- alkali metal
- metal ions
- discharging
- charging
- 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.)
- Expired - Lifetime
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/40—Alloys based on alkali metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Description
【発明の詳細な説明】
産業上の利用分野
本発明は非水電解質２次電池の負極の製造方法
に関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for manufacturing a negative electrode for a non-aqueous electrolyte secondary battery.
従来例の構成とその問題点
現在まで、リチウム、ナトリウム等のアルカリ
金属を負極活物質材料として用い、γ−ブチロラ
クトン、テトラヒドロフラン、プロピレンカーボ
ネート、ジメトキシエタン等の溶媒中に、溶質と
して、過塩素酸リチウム、ホウ弗化リチウム、塩
化リチウム等を溶解したいわゆる非水電解質２電
池の開発が進められてきた。Structures of conventional examples and their problems Until now, alkali metals such as lithium and sodium have been used as negative electrode active materials, and lithium perchlorate has been used as a solute in a solvent such as γ-butyrolactone, tetrahydrofuran, propylene carbonate, dimethoxyethane, etc. The development of so-called non-aqueous electrolyte 2 batteries in which lithium fluoride, lithium borofluoride, lithium chloride, etc. are dissolved has been progressing.
しかし、この種の２次電池はまだ実用化されて
いない。その理由は、充放電回数の寿命が短く、
また、充放電に際しての充放電効率が低いためで
ある。 However, this type of secondary battery has not yet been put into practical use. The reason is that the lifespan of charging and discharging is short.
Another reason is that the charging and discharging efficiency during charging and discharging is low.
この性能劣化の原因は主に、正極及び負極活物
質の充放電に際しての、化学的又は物理的可逆性
が低下することである。特に、リチウム等の負極
活物質では、充放電に際して、負極表面上にデン
ドライトが発生し、このデンドライトが充放電効
率を落としている。また、しばしば、このデンド
ライトが充放電をくり返すうちに成長に、セパレ
ータを介して正極と内部短絡し、発熱、発火とい
う危険があつた。 The main cause of this performance deterioration is a decrease in chemical or physical reversibility during charging and discharging of the positive electrode and negative electrode active materials. In particular, in negative electrode active materials such as lithium, dendrites are generated on the surface of the negative electrode during charging and discharging, and these dendrites reduce the charging and discharging efficiency. In addition, as the dendrites are repeatedly charged and discharged, there is a risk of internal short-circuiting with the positive electrode through the separator, resulting in heat generation and fire.
このような負極の欠点を改良するために、リチ
ウム等のアルカリ金属との合金化をはかることが
従来から提案されてきた。たとえば、アルミニウ
ムとの合金化、銀（特開昭56−73860）、又は、水
銀（特開昭57−98978）、鉛（特開昭57−141869）
との合金化、及びウツド合金等の可融合性との合
金化が知られている。ところが、これらの金属又
は合金と、リチウム等のアルカリ金属を負極とし
て用いた場合、これらの負極は放電時にはアルカ
リ金属イオンを放出するために体積が著しく縮小
し、また、充電時にはアルカリ金属イオンを吸蔵
するために著しく膨張し、よつて充放電をくり返
すうちに、これらの負極が集電体より脱離し電極
としての形状を保持しなくなるという現象が発生
するため、充放電効率が急速に劣化するという問
題があつた。 In order to improve these drawbacks of negative electrodes, it has been proposed to alloy them with alkali metals such as lithium. For example, alloying with aluminum, silver (JP 56-73860), mercury (JP 57-98978), lead (JP 57-141869)
Alloying with fusible materials such as wood alloys, and fusible materials such as wood alloys are known. However, when these metals or alloys and alkali metals such as lithium are used as negative electrodes, these negative electrodes release alkali metal ions during discharge, resulting in a significant volume reduction, and during charging, they occlude alkali metal ions. During repeated charging and discharging, these negative electrodes detach from the current collector and no longer retain their shape as electrodes, resulting in rapid deterioration of charging and discharging efficiency. There was a problem.
これらの欠点を解決するために、集電体を負極
材料に埋め込むことが提案されているが、製造工
程としては複雑で作業性に乏しいという問題があ
つた。 In order to solve these drawbacks, it has been proposed to embed the current collector in the negative electrode material, but the manufacturing process is complicated and has poor workability.
発明の目的
本発明はこのような従来の欠点を除去するもの
であり、高エネルギー密度で、充放電のくり返し
においても電極形状を保持し、また、製造工程に
おいて作業性の優れた負極を構成要素にもつ信頼
性の高い非水電解質２次電池の製造方法を提供す
るものである。Purpose of the Invention The present invention eliminates these conventional drawbacks, and uses a negative electrode as a component that has high energy density, maintains its electrode shape even after repeated charging and discharging, and has excellent workability in the manufacturing process. The present invention provides a method for manufacturing a highly reliable non-aqueous electrolyte secondary battery.
発明の構成
本発明の非水電解質２次電池の製造方法は、充
電時にアルカリ金属イオンを吸蔵し、放電時にア
ルカリ金属イオンを放出する負極材料を用いた負
極を構成要素とする電池において、前記負極材料
は、アルカリ金属イオンを含まない状態で集電体
上に圧着されるとともにスポツト溶接され、しか
る後にアルカリ金属イオンを前記負極材料中に吸
蔵させているものである。このため、充放電のく
り返しにおいても、該負極材料が集電体より脱離
することがなく電極形状を保持し、また、製造工
程においても作業性の優れたものである。Structure of the Invention The method for manufacturing a non-aqueous electrolyte secondary battery of the present invention provides a method for manufacturing a non-aqueous electrolyte secondary battery, in which a negative electrode is used as a component, which uses a negative electrode material that occludes alkali metal ions during charging and releases alkali metal ions during discharge. The material is crimped and spot welded onto the current collector without containing alkali metal ions, and then the alkali metal ions are occluded in the negative electrode material. Therefore, even during repeated charging and discharging, the negative electrode material does not separate from the current collector and maintains the electrode shape, and also has excellent workability in the manufacturing process.
実施例の説明 以下本発明の実施例について説明する。Description of examples Examples of the present invention will be described below.
充・放電時におけるアルカリ金属イオン吸蔵・
放出負極材料として、鉛（85wt％）・カドミウム
（15wt％）を用いた。 Alkali metal ion storage during charging and discharging
Lead (85wt%) and cadmium (15wt%) were used as emitting negative electrode materials.
上記組成の鉛・カドミウム合金をローラーにて
圧延し、厚さ0.2mmにしたあと、１cm×２cmの寸
法に切り出した。この圧延板を、これよりやや面
積の広いニツケルエキスパンドメタル集電体上に
乗せ、1.5tonにてプレスで加圧圧着し、しかるの
ち、ニツケルエキスパンドメタルとこの圧延板を
周辺部８ケ所と中央部１ケ所スポツト溶接にて固
定した。これに、ニツケルリボンをスポツト溶接
で、鉛・カドミウム圧延板のついていない集電体
部分に取り付けた。このようにして作成した電極
をＡとする。 A lead-cadmium alloy having the above composition was rolled with a roller to a thickness of 0.2 mm, and then cut into a size of 1 cm x 2 cm. This rolled plate is placed on a nickel expanded metal current collector, which has a slightly wider area, and is crimped with a press using a 1.5 ton press.Then, the nickel expanded metal and this rolled plate are placed in 8 peripheral areas and in the center. It was fixed by spot welding in one place. Next, a nickel ribbon was spot welded to the part of the current collector that did not have the rolled lead/cadmium plate attached. Let A be the electrode created in this way.
比較のため、従来の電極として、上記組成の
鉛・カドミウム合金圧延板とニツケルエキスパン
ドメタル集電体をスポツト溶接しない以外は同様
の方法で作成した電極をＢとする。 For comparison, an electrode B was prepared as a conventional electrode by the same method except that a rolled lead-cadmium alloy plate having the above composition and a nickel expanded metal current collector were not spot welded.
次にこれらの電極Ａ，Ｂをそれぞれ、ニツケル
エキスパンドメタルに圧着した金属リチウム対
極、及び対極と同じ構成の金属リチウム照合電極
と共にガラスセルに組み入れた。 Next, these electrodes A and B were each assembled into a glass cell together with a metal lithium counter electrode crimped onto nickel expanded metal and a metal lithium reference electrode having the same structure as the counter electrode.
電解液には、プロピレンカーボネートに１モ
ル／の割合で過塩素酸リチウムを溶解したもの
を用い、また、金属リチウム対極に発生するデン
ドライトによる内部短絡を防ぐため、セパレータ
にポリプロピレン不織布を用い、鉛・カドミウム
合金極と金属リチウム対極との間隔を充分にあけ
た。 The electrolyte was prepared by dissolving lithium perchlorate in propylene carbonate at a ratio of 1 mol/mole, and in order to prevent internal short circuits due to dendrites that occur at the metal lithium counter electrode, a polypropylene nonwoven fabric was used as the separator, and lead and A sufficient distance was left between the cadmium alloy electrode and the metal lithium counter electrode.
このように構成した電池を用いて、鉛・カドミ
ウム合金極に対してリチウムイオンの吸蔵・放出
のくり返しを２ｍＡを定電流、金属リチウム照合
電極に対し、0.05〜0.8Vの電位の範囲で行つた。 Using the battery constructed in this way, lithium ions were repeatedly inserted and released into the lead-cadmium alloy electrode at a constant current of 2 mA and at a potential range of 0.05 to 0.8 V relative to the metal lithium reference electrode. .
上記電極Ａ，Ｂを用いた各電池の各サイクルに
おける充放電電流効率の変化の様子を図に示す。 The figure shows how the charging/discharging current efficiency changes in each cycle of each battery using the electrodes A and B described above.
図より明らかなごとく、従来の電極Ｂを用いた
電池では、鉛・カドミウム合金負極材料が充放電
に際して、膨張、縮小をくり返したために、集電
体から脱離したり再び集電体と接触したりし、そ
のために充放電電流効率の乱れが生じ、７サイク
ル目では充分な充放電特性を示さないのが多かつ
た。これに対し、負極材料と集電体をスポツト溶
接にて固定した電極Ａを用いた電池では、充放電
電流効率の乱れがなく、ほとんど性能の低下が見
られないことがわかる。 As is clear from the figure, in a battery using conventional electrode B, the lead-cadmium alloy negative electrode material repeatedly expands and contracts during charging and discharging, causing it to detach from the current collector or come into contact with the current collector again. However, this caused disturbances in charge/discharge current efficiency, and in many cases, sufficient charge/discharge characteristics were not exhibited at the 7th cycle. On the other hand, it can be seen that in the battery using electrode A in which the negative electrode material and the current collector were fixed by spot welding, there was no disturbance in the charging/discharging current efficiency and almost no deterioration in performance was observed.
なお、本実施例では鉛・カドミウム合金を用い
たが、上記組成の鉛・カドミウム合金に限らず、
Sn、Bi、Pb、Cd、In、Hg、Sb、Zn、Agの中か
ら選ばれた１つの金属、あるいは２つ以上の合金
を用いてもよい。 Although a lead-cadmium alloy was used in this example, it is not limited to lead-cadmium alloys having the above composition.
One metal selected from Sn, Bi, Pb, Cd, In, Hg, Sb, Zn, and Ag, or an alloy of two or more may be used.
発明の効果
以上のように本発明の非水電解質２次電池の製
造方法は、充・放電時にアルカリ金属イオンを吸
蔵・放出する負極材料を使用した負極を構成要素
にもつ電池において、前記負極材料はアルカリ金
属イオンを含まない状態で集電体上に圧着される
とともにスポツト溶接され、しかる後にアルカリ
金属イオンを前記負極材料に吸蔵させるものであ
り、したがつて充放電をくり返した場合でも負極
材料が集電体より脱離することなく電極形状を保
持し、充放電中に内部抵抗が変動することなく、
平坦でかつ良好な充放電特性を得られ、しかも、
製造工程において作業性の優れた非水電解質２次
電池を得られる。Effects of the Invention As described above, the method for manufacturing a non-aqueous electrolyte secondary battery of the present invention provides a method for producing a non-aqueous electrolyte secondary battery in a battery having a negative electrode as a component that uses a negative electrode material that occludes and releases alkali metal ions during charging and discharging. is crimped and spot-welded onto the current collector in a state that does not contain alkali metal ions, and then the alkali metal ions are occluded in the negative electrode material. Therefore, even after repeated charging and discharging, the negative electrode material remains The electrode maintains its shape without detaching from the current collector, and the internal resistance does not change during charging and discharging.
Flat and good charge/discharge characteristics can be obtained, and
A nonaqueous electrolyte secondary battery with excellent workability can be obtained in the manufacturing process.
図は、本発明の実施例及び比較例の非水電解質
２次電池における負極の充放電電流効率を示す図
である。
The figure is a diagram showing the charging/discharging current efficiency of the negative electrode in non-aqueous electrolyte secondary batteries of Examples and Comparative Examples of the present invention.
Claims (1)
と、充電時にアルカリ金属イオンを吸蔵し放電時
にアルカリ金属イオンを放出する負極材料を用い
た負極を構成要素とする電池の製造方法であつ
て、前記負極材料はアルカリ金属イオンを含まな
い状態で集電体上に圧着するとともにスポツト溶
接され、しかる後にアルカリ金属イオンを吸蔵さ
せていることを特徴とする非水電解質２次電池の
製造方法。1. A method for producing a battery comprising a positive electrode, an electrolyte conductive to alkali metal ions, and a negative electrode using a negative electrode material that occludes alkali metal ions during charging and releases alkali metal ions during discharge, the negative electrode comprising: A method for manufacturing a nonaqueous electrolyte secondary battery, characterized in that the material is crimped onto a current collector and spot welded in a state that does not contain alkali metal ions, and then the material is occluded with alkali metal ions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58104413A JPS59228370A (en) | 1983-06-10 | 1983-06-10 | Manufacturing method of non-aqueous electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58104413A JPS59228370A (en) | 1983-06-10 | 1983-06-10 | Manufacturing method of non-aqueous electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59228370A JPS59228370A (en) | 1984-12-21 |
| JPH0552038B2 true JPH0552038B2 (en) | 1993-08-04 |
Family
ID=14380005
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58104413A Granted JPS59228370A (en) | 1983-06-10 | 1983-06-10 | Manufacturing method of non-aqueous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59228370A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0347952A3 (en) * | 1985-04-19 | 1990-02-07 | AlliedSignal Inc. | Negative electrodes for non-aqueous secondary batteries composed of sodium alloy |
| JPH08153541A (en) * | 1994-11-28 | 1996-06-11 | Mitsubishi Cable Ind Ltd | Lithium secondary battery |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5753423Y2 (en) * | 1977-07-09 | 1982-11-19 | ||
| JPS5798978A (en) * | 1980-12-11 | 1982-06-19 | Sanyo Electric Co Ltd | Chargeable organic electrolytic battery |
| JPS633091Y2 (en) * | 1981-02-20 | 1988-01-26 |
-
1983
- 1983-06-10 JP JP58104413A patent/JPS59228370A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59228370A (en) | 1984-12-21 |
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