JP3021517B2 - Organic electrolyte secondary battery - Google Patents
Organic electrolyte secondary batteryInfo
- Publication number
- JP3021517B2 JP3021517B2 JP2052339A JP5233990A JP3021517B2 JP 3021517 B2 JP3021517 B2 JP 3021517B2 JP 2052339 A JP2052339 A JP 2052339A JP 5233990 A JP5233990 A JP 5233990A JP 3021517 B2 JP3021517 B2 JP 3021517B2
- Authority
- JP
- Japan
- Prior art keywords
- battery
- negative electrode
- electrode plate
- lithium
- organic electrolyte
- 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 - Fee Related
Links
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
Description
【発明の詳細な説明】 産業条の利用分野 本発明は、有機電解液二次電池に関するものである。Description: FIELD OF THE INVENTION The present invention relates to an organic electrolyte secondary battery.
従来の技術 有機電解液二次電池は、充放電を繰り返したり、長期
間放置すると、内部抵抗が著しく増大して、充放電が困
難になることがある。このような内部抵抗の増大は、ア
ルミニウム、アルミニウム合金、グラファイト、フッ化
カーボンなどのリチウムインサーション電極、または、
金属リチウムからなる負極板の集電性能の低下に起因し
ている場合が多い。2. Description of the Related Art When an organic electrolyte secondary battery is repeatedly charged and discharged or left for a long period of time, the internal resistance is significantly increased, and charging and discharging may be difficult. Such an increase in internal resistance is caused by a lithium insertion electrode such as aluminum, aluminum alloy, graphite, and carbon fluoride, or
In many cases, this is caused by a decrease in current collecting performance of the negative electrode plate made of metallic lithium.
すなわち、負極を充電した場合に、負極電池ケースと
負極板との接触部に金属リチウムが析出して有機電解液
と直ちに反応して、不動態皮膜を形成することにより、
ケースと負極との接触抵抗が増大して電池の内部抵抗が
増大するものである。That is, when the negative electrode is charged, lithium metal is precipitated at the contact portion between the negative electrode battery case and the negative electrode plate and immediately reacts with the organic electrolyte to form a passive film,
The contact resistance between the case and the negative electrode increases, and the internal resistance of the battery increases.
また、金属リチウムを負極に用いた場合には、放置中
にも内部抵抗の増大が起こる場合がある。これは、リチ
ウム負極と電池ケースとの間に電解液が浸透して、リチ
ウムと反応して不動態皮膜を形成することに起因してい
る。In addition, when metal lithium is used for the negative electrode, the internal resistance may increase during standing. This is because the electrolytic solution permeates between the lithium negative electrode and the battery case and reacts with lithium to form a passive film.
このため、有機電解液二次電池では、負極と電池ケー
スとをスポット溶接したり、負極と電池ケースとの接触
部に、カーボンやニッケルネットなどの導電層を形成す
る方法によって負極板の集電性能の低下を抑制してい
る。For this reason, in the organic electrolyte secondary battery, the current collection of the negative electrode plate is performed by spot welding the negative electrode and the battery case, or by forming a conductive layer such as carbon or nickel net at a contact portion between the negative electrode and the battery case. It suppresses performance degradation.
発明が解決しようとする課題 しかし、スポット溶接は、作業がきわめて煩雑なこ
と、および、溶接状態の信頼性が乏しいことなどの欠点
がある。また、カーボンやニッケルネットなどを用いて
導電層を形成することは、コストが上昇すること、およ
び、電池内容積の一部を導電層が占めるので電池エネル
ギー密度が低下することなどの課題がある。従って、充
放電を繰り返しによっても、あるいは、長期間の放置に
よっても、内部抵抗の増大が少ない、安価でかつエネル
ギー密度の高い有機電解液電池が求められている。Problems to be Solved by the Invention However, spot welding has drawbacks such as extremely complicated work and poor reliability of a welding state. In addition, forming a conductive layer using carbon, nickel net, or the like has problems such as an increase in cost and a decrease in battery energy density because the conductive layer occupies a part of the internal volume of the battery. . Therefore, there is a need for an inexpensive and high-energy-density organic electrolyte battery that has a small increase in internal resistance even after repeated charging and discharging or leaving it for a long period of time.
課題を解決するための手段 本発明は、上記課題を解決するために、リチウムイン
サーション電極または金属リチウムを含む負極板を用
い、負極板表面もしくは電池ケースの表面またはこの両
者の表面に突起部、溝部または凹部を設け、負極板と電
池ケースとが液膜を介さずに密着していることを特徴と
する有機電解液二次電池を提供するものである。Means for Solving the Problems The present invention, in order to solve the above problems, using a lithium insertion electrode or a negative electrode plate containing metallic lithium, a projection on the surface of the negative electrode plate or the surface of the battery case or both surfaces, It is an object of the present invention to provide an organic electrolyte secondary battery in which a groove or a recess is provided, and the negative electrode plate and the battery case are in close contact with each other without a liquid film interposed therebetween.
作 用 前記のように、電池の内部抵抗の増大は、充放電によ
って、電池ケース上に電気伝導度の低い層が生成するこ
とに起因している。しかし、熱力学的には、充放電にと
もなう電気化学反応は、電池ケースよりも、当然、負極
板上でより容易に起こるはずである。Operation As described above, the increase in the internal resistance of the battery is caused by the formation of a layer having low electric conductivity on the battery case due to charge and discharge. However, thermodynamically, the electrochemical reaction associated with charging and discharging should naturally occur more easily on the negative electrode plate than on the battery case.
発明者は、このように負極よりも電池ケースで優先的
に電気化学反応が生起する逆転現象について検討した結
果、下記の原因を見いだした。すなわち、負極板と電池
ケースとの接触部が、面で接触している場合には、毛管
現象によって、接触部に電解液が浸透して、電極と電池
ケースとの間に液膜を生じる。そして、電池に通電する
と、本来、負電極上で優先的に起こるべき電気化学反応
が、液膜の大きな電気抵抗のために、電池ケース上で優
先的に起こり、前記のような伝導度の低い層が形成され
る。一旦、このような層が形成されると、負極板と電池
ケースとの間隙は、ますます大きくなり、電解液がさら
に浸透して、不動態皮膜の成長、すなわち、内部抵抗の
増大が助長されるものである。As a result of studying the reversal phenomenon in which an electrochemical reaction occurs preferentially in the battery case over the negative electrode as described above, the inventors have found the following causes. That is, when the contact portion between the negative electrode plate and the battery case is in surface contact, the electrolytic solution permeates the contact portion due to capillary action, and a liquid film is generated between the electrode and the battery case. When the battery is energized, the electrochemical reaction that should occur preferentially on the negative electrode occurs preferentially on the battery case due to the large electrical resistance of the liquid film, and the layer having low conductivity as described above. Is formed. Once such a layer is formed, the gap between the negative electrode plate and the battery case becomes larger and larger, and the electrolyte further penetrates, and the growth of the passive film, that is, the increase of the internal resistance is promoted. Things.
発明者は、上記の検討の結果、電池ケースと負極板と
の接触部に電解液が浸透しないようにすれば、不動態皮
膜の生成を防止できるものと考えた。そこで、本発明の
有機電解液二次電池では、負極板と電池ケースとの接触
部における、負極板の表面もしくは電池ケースの表面、
またはこの両者の表面に突起部，溝部または凹部を設け
て、電池を封口して負極板に圧迫が加わった時に、電極
と電池ケースとが液膜を介さずに密着するようにした。As a result of the above study, the inventors have considered that the formation of a passivation film can be prevented by preventing the electrolyte from penetrating into the contact portion between the battery case and the negative electrode plate. Therefore, in the organic electrolyte secondary battery of the present invention, at the contact portion between the negative electrode plate and the battery case, the surface of the negative electrode plate or the surface of the battery case,
Alternatively, a projection, a groove, or a recess is provided on the surface of each of the electrodes so that when the battery is sealed and pressure is applied to the negative electrode plate, the electrode and the battery case are in close contact with each other without a liquid film.
この結果、本発明の有機電解液二次電池は、後の実施
例に示すように、充放電によっても、また、長期間の放
置によっても、電池の内部抵抗の増大が著しく抑制され
る。As a result, in the organic electrolyte secondary battery of the present invention, the increase in the internal resistance of the battery is significantly suppressed by charging and discharging, and by leaving it for a long period of time, as will be described in Examples below.
実施例 以下本発明を好適な実施例を用いて説明する。Examples Hereinafter, the present invention will be described using preferred examples.
［実施例１］ 93重量部のリチウム・コバルト複合酸化物（LiCoO2）
に、５重量部のアセチレンブラックと２重量部のテフロ
ンディスパージョンを混合して、精製水を加えて乳鉢で
よく混合したのち、80℃で12時間以上乾燥して正極原料
を得た。この正極原料を100メッシュのニッケル金網に
0.165gだけ包み込んで1.5t/cm2の圧力でプレスして、直
径が15mmで厚さが0.8mmのポケット式電極を試作した。
この電極を実施例の１の正極板とする。Example 1 93 parts by weight of lithium-cobalt composite oxide (LiCoO 2 )
Then, 5 parts by weight of acetylene black and 2 parts by weight of Teflon dispersion were mixed, purified water was added and mixed well in a mortar, and then dried at 80 ° C. for 12 hours or more to obtain a positive electrode material. This positive electrode material is converted into a 100 mesh nickel wire mesh.
0.165 g was wrapped and pressed at a pressure of 1.5 t / cm 2 to prototype a pocket electrode having a diameter of 15 mm and a thickness of 0.8 mm.
This electrode is used as the positive electrode plate of Example 1.
リチウムを３重量部だけ含有する厚さが0.5mmのリチ
ウム・アルミニウム合金板を直径16mmの円板状に打ち抜
いた後、第一図のごとく円板の片面に複数の突起部１を
プレス成形によって設けてリチウム・アルミニウム合金
負極板２を試作した。After punching a 0.5mm thick lithium-aluminum alloy plate containing only 3 parts by weight of lithium into a disk shape having a diameter of 16mm, a plurality of protrusions 1 are formed by pressing on one surface of the disk as shown in Fig. 1. The lithium-aluminum alloy negative electrode plate 2 was manufactured as a trial.
葉脈状の無孔部と、孔が３次元的に配列した有孔部と
を有する、厚さが約20ミクロンのポリエチレン製微孔膜
セパレーターを直径19mmに打ち抜いてバリアーセパレー
ターとした。A polyethylene microporous membrane separator having a leaf vein-like nonporous portion and a perforated portion in which pores are three-dimensionally arranged and having a thickness of about 20 μm was punched out to a diameter of 19 mm to obtain a barrier separator.
厚さが約0.2mmのポリエチレン製の不織布を直径16mm
に打ち抜いて補液セパレーターとした。Polyethylene non-woven fabric with a thickness of about 0.2 mm and a diameter of 16 mm
Into a replacement fluid separator.
これらの部品と2020形ボタン電池の電池ケースとPP樹
脂製のパッキングとを45℃で12時間真空乾燥した後、ア
ルゴンドライボックス内に持ち込んだ。そして、バリヤ
ーセパレータ、補液セパレーター、および、正極板に1M
LiClO4/γ−ブチロラクトン電解液を真空含浸した。つ
ぎに、パッキングを装着した負極電池ケースに、突起の
ある方の面を負極電池ケース側にして負極板を積層し、
さらに、バリヤーセパレーター、補液セパレーター、正
極板、および、正極電池ケースをこの記述の順に積層し
て、封口金型を用いて電池を封口した。こうして試作し
た2020形ボタン電池を本発明による電池Ａとする。These parts, the battery case of the 2020 type button battery and the packing made of PP resin were vacuum-dried at 45 ° C. for 12 hours, and then brought into an argon dry box. Then, 1M is applied to the barrier separator, replacement fluid separator, and positive electrode plate.
LiClO 4 / γ-butyrolactone electrolyte was vacuum impregnated. Next, on the negative electrode battery case with the packing, the negative electrode plate was laminated with the surface with the protrusion on the negative electrode battery case side,
Further, a barrier separator, a replacement fluid separator, a positive electrode plate, and a positive electrode battery case were laminated in the order described above, and the battery was sealed using a sealing mold. The prototype 2020 button battery thus manufactured is referred to as Battery A according to the present invention.
［実施例２］ 負極ケースが、第二図のような内面に複数の溝部３を
有する負極電池ケース４であって、負極板に厚さが0.5m
mで直径が16mmの金属リチウム板を用いており、電解液
に1M LiAsF6/プロピレンカーボネイトを用いており、他
の構成は、電池Ａと同様な2020形ボタン電池を本発明に
よる電池Ｂとする。金属リチウムは、柔らかい金属なの
で、突起を設けることが難しい。この場合には、本実施
例のごとく負極ケース側に溝部や凹部、または、突起部
を設けて、電池封口時の圧迫によって、ケースの溝部や
凹部に金属リチウムが埋め込まれるようにしたり、ケー
スの突起が金属リチウムに突き刺さるようにしたりする
方法が有効である。Example 2 A negative electrode case was a negative electrode battery case 4 having a plurality of grooves 3 on the inner surface as shown in FIG.
A lithium metal plate having a diameter of 16 mm and a diameter of 16 mm is used, and 1M LiAsF 6 / propylene carbonate is used as an electrolyte. In the other configuration, a 2020 type button battery similar to the battery A is used as the battery B according to the present invention. . Since metallic lithium is a soft metal, it is difficult to provide protrusions. In this case, as in the present embodiment, a groove or a concave portion or a protruding portion is provided on the negative electrode case side so that metallic lithium is buried in the groove or the concave portion of the case by pressing when closing the battery, or It is effective to use a method in which the projection pierces the metallic lithium.
［実施例３］ 負極ケースが、第二図のような内面に溝部を有する負
極電池ケースであって、他の構成は、電池Ａと同様な20
20形ボタン電池を本発明による電池Ｃとする。本実施例
では、負極ケースにも、リチウム・アルミニウム合金負
極板にも、それぞれ溝部、および、突起部を設けてい
る。このようにすることによって接触信頼性は、さらに
高まる。Example 3 The negative electrode case was a negative electrode battery case having a groove on the inner surface as shown in FIG.
The 20-type button battery is referred to as a battery C according to the present invention. In this embodiment, both the negative electrode case and the lithium-aluminum alloy negative electrode plate are provided with a groove and a projection, respectively. By doing so, the contact reliability is further increased.
［実施例４］ 電解二酸化マンガンを250℃で20時間焼成したのち、
二酸化マンガン80重量部に対して、10重量部のアセチレ
ンブラック、10重量部のテフロンディスパージョン、お
よび、精製水を加えて混合したのち、120℃で12時間熱
風乾燥して正極合剤を得た。この正極合剤を用いた以外
は、電池Ｂと同じ構成を有するボタン型電池を本発明に
よる電池Ｄとする。Example 4 After calcining electrolytic manganese dioxide at 250 ° C. for 20 hours,
80 parts by weight of manganese dioxide, 10 parts by weight of acetylene black, 10 parts by weight of Teflon dispersion, and purified water were added and mixed, followed by hot air drying at 120 ° C. for 12 hours to obtain a positive electrode mixture. . A button-type battery having the same configuration as the battery B except that this positive electrode mixture was used is referred to as a battery D according to the present invention.
［実施例５］ 実施例の４の正極合剤を厚さが0.03mmのステンレス穿
孔板に塗布したのち加圧成形して、幅25mmで長さが230m
mで厚さが0.6mmの二酸化マンガン正極板を得た。この二
酸化マンガン正極板と、幅22mmで長さが250mmで厚さが
0.10mmの金属リチウム負極板とをバリヤーセパレーター
および補液セパレーターを介して、最外側にリチウム極
が露出するように巻回して、電池ケース５に挿入した。
この電池ケースは、第三図に示すような山形の突起部６
を電池の高さ方向に複数条設けている。巻回した電極群
７を電池ケースに挿入する際に、この山形突起がリチウ
ム負極板に食い込むことによって、負極板と電池ケース
との電気的接触が確実に得られる。この後、電解液を注
液して正極板と正極端子をスポット溶接したのち封口し
た。こうして得られたCR−2/3AA形リチウム電池を本発
明による電池Ｅとする。[Example 5] The positive electrode mixture of Example 4 was applied to a perforated stainless steel plate having a thickness of 0.03 mm, and then press-molded to obtain a width of 25 mm and a length of 230 m.
A manganese dioxide positive electrode plate having a thickness of 0.6 mm and a thickness of 0.6 mm was obtained. This manganese dioxide cathode plate is 22 mm wide, 250 mm long and thick
A 0.10 mm metal lithium negative electrode plate was wound through a barrier separator and a replacement fluid separator so that the lithium electrode was exposed to the outermost side, and inserted into the battery case 5.
This battery case has an angled projection 6 as shown in FIG.
Are provided in the height direction of the battery. When the wound electrode group 7 is inserted into the battery case, the chevron-shaped protrusions bite into the lithium negative electrode plate, so that electrical contact between the negative electrode plate and the battery case is reliably obtained. Thereafter, the positive electrode plate and the positive electrode terminal were spot-welded by pouring an electrolytic solution, and then sealed. The CR-2 / 3AA lithium battery thus obtained is referred to as Battery E according to the present invention.
本発明の効果を検討するために、次のような比較のた
めの電池を試作した。すなわち、負極板に突起部を有さ
ないこと以外は、電池Ａと同様の構成を有するボタン形
リチウム電池を比較のための電池Ｆとする。また、電池
ケースに溝部を有さない以外は、電池Ｂと同様の構成を
有するボタン形リチウム電池を比較のための電池Ｇとす
る。また、円筒ケースの内面に山形の突起部を有さない
こと以外は、電池Ｄと同様の構成を有する円筒形リチウ
ム電池を比較のための電池Ｈとする。In order to study the effects of the present invention, the following comparative battery was experimentally manufactured. That is, a button-type lithium battery having the same configuration as that of the battery A except that the negative electrode plate does not have a protrusion is used as the battery F for comparison. A button-type lithium battery having the same configuration as the battery B except that the battery case has no groove is used as the battery G for comparison. A battery H for comparison is a cylindrical lithium battery having the same configuration as the battery D except that the inner surface of the cylindrical case does not have a mountain-shaped protrusion.
本発明による電池A,B,C,D,Eおよび比較のための電池
F,G,Hをそれぞれ10セルずつ試作して、10日間放置した
のち、それぞれ10時間率で10サイクル充放電した。そし
て、充放電が不可能であった不良電池の数を調べた。そ
の結果を第一表に示す。これらの不良電池は、1KHz交流
法によって内部抵抗を測定すると、内部抵抗がいずれも
数百キロオームにまで増大していた。Batteries A, B, C, D, E and batteries for comparison according to the invention
Ten cells of F, G, and H were each manufactured and allowed to stand for 10 days, and then charged and discharged for 10 cycles at a rate of 10 hours. Then, the number of defective batteries that could not be charged and discharged was examined. The results are shown in Table 1. When the internal resistance of each of these defective batteries was measured by the 1 KHz AC method, the internal resistance was found to have increased to several hundred kilohms.
同表から明らかなように本発明の実施例の電池は、い
ずれも不良電池の発生が無い。これは、本発明によって
内部抵抗の増大が抑制されたことによるものである。As is clear from the table, none of the batteries of the examples of the present invention have any defective batteries. This is because an increase in internal resistance was suppressed by the present invention.
発明の効果 以上述べたように、本発明によって、有機電解液二次
電池の保存性能およびサイクル寿命性能が著しく向上し
た。これは、本発明によって、有機電解液二次電池の負
極板の集電性能の低下が効果的に抑制された結果であ
る。 Effect of the Invention As described above, according to the present invention, the storage performance and the cycle life performance of the organic electrolyte secondary battery are significantly improved. This is a result of the present invention that a reduction in the current collection performance of the negative electrode plate of the organic electrolyte secondary battery was effectively suppressed.
【図面の簡単な説明】 第一図は、本発明の有機電解液二次電池に用いるリチウ
ムアルミニウム合金負極板を示した図。第二図は、本発
明の有機電解液二次電池に用いる負極ケースを示した
図。第三図は、本発明の有機電解液二次電池に用いる負
極ケースおよび巻回した極板群を示した図である。 １……突起部,2……負極板 ３……溝部,4……電池ケースBRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a view showing a lithium aluminum alloy negative electrode plate used for an organic electrolyte secondary battery of the present invention. FIG. 2 is a diagram showing a negative electrode case used for the organic electrolyte secondary battery of the present invention. FIG. 3 is a diagram showing a negative electrode case and a wound electrode plate group used in the organic electrolyte secondary battery of the present invention. DESCRIPTION OF SYMBOLS 1 ... Projection part, 2 ... Negative electrode plate 3 ... Groove part, 4 ... Battery case
Claims (1)
チウムからなる負極板を用い、負極板表面もしくは電池
ケースの表面またはこの両者の表面に突起部、溝部また
は凹部を設け、負極板と電池ケースとが液膜を介さずに
密着するようにしたことを特徴とする有機電解液二次電
池。1. A negative electrode plate made of a lithium insertion electrode or metallic lithium, and a projection, a groove, or a concave portion is provided on the surface of the negative electrode plate, the surface of the battery case, or both surfaces. An organic electrolyte secondary battery characterized in that it comes into close contact without interposing a membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2052339A JP3021517B2 (en) | 1990-03-02 | 1990-03-02 | Organic electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2052339A JP3021517B2 (en) | 1990-03-02 | 1990-03-02 | Organic electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03254074A JPH03254074A (en) | 1991-11-13 |
| JP3021517B2 true JP3021517B2 (en) | 2000-03-15 |
Family
ID=12912042
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2052339A Expired - Fee Related JP3021517B2 (en) | 1990-03-02 | 1990-03-02 | Organic electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3021517B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3402047B2 (en) * | 1996-02-08 | 2003-04-28 | 松下電器産業株式会社 | Battery |
| KR100670441B1 (en) * | 2005-11-29 | 2007-01-16 | 삼성에스디아이 주식회사 | Secondary battery |
-
1990
- 1990-03-02 JP JP2052339A patent/JP3021517B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03254074A (en) | 1991-11-13 |
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| LAPS | Cancellation because of no payment of annual fees |