JPH0317964A - Manufacture of lithium secondary battery - Google Patents
Manufacture of lithium secondary batteryInfo
- Publication number
- JPH0317964A JPH0317964A JP1151970A JP15197089A JPH0317964A JP H0317964 A JPH0317964 A JP H0317964A JP 1151970 A JP1151970 A JP 1151970A JP 15197089 A JP15197089 A JP 15197089A JP H0317964 A JPH0317964 A JP H0317964A
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- negative electrode
- battery
- aluminum
- secondary battery
- 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.)
- Pending
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 51
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 33
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 33
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 24
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 claims abstract description 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 5
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 15
- 229910003002 lithium salt Inorganic materials 0.000 abstract description 12
- 159000000002 lithium salts Chemical class 0.000 abstract description 12
- 239000003960 organic solvent Substances 0.000 abstract description 11
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 239000008188 pellet Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 241000219112 Cucumis Species 0.000 description 1
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical compound N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
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
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、負極にリチウムーアルくニウム合金を用いた
リチウム二次電池の製造方法に関するものである．
〔発明の概要〕
本発明は、リチウム二次電池の負極のリチウムアルもニ
ウム合金を、リチウムイオンを吸蔵した二酸化マンガン
正極とアルミニウム負極からなる電池組み立て後、充電
によりあらかしめ二酸化マンガンに吸蔵させたリチウム
を負極側のアルミニウム上に電着して、組み立てられた
電池内でリチウム−アルミニウム合金負極を１！造する
ことにより、サイクル寿命の優れたリチウム二次電池を
実現しようとするものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for manufacturing a lithium secondary battery using a lithium-aluminum alloy for the negative electrode. [Summary of the Invention] The present invention is a lithium secondary battery in which a lithium-aluminium alloy, which is a negative electrode, is warmed up by charging after assembling a battery consisting of a manganese dioxide positive electrode and an aluminum negative electrode that occludes lithium ions, and is occluded in manganese dioxide. Lithium is electrodeposited on the aluminum on the negative electrode side, and the lithium-aluminum alloy negative electrode is placed in the assembled battery. The aim is to create a lithium secondary battery with excellent cycle life.
近年、充放電可能な高工不ルギー密度電池として、リチ
ウム二次電池が注目されているが、このリチウム二次電
池の負極活物質に金属リチウムを使用した場合には、充
放電に伴い電池負極にデンドライトが発生するなどの問
題があり、これらの問題を解決するため、最近ではリチ
ウム合金、とりわけリチウム−アルミニウム合金が使用
されている。In recent years, lithium secondary batteries have attracted attention as highly engineered inert-density batteries that can be charged and discharged.When metallic lithium is used as the negative electrode active material of these lithium secondary batteries, the negative electrode of the battery deteriorates during charging and discharging. However, in order to solve these problems, lithium alloys, especially lithium-aluminum alloys, have recently been used.
上述したような電池電極用リチウム−アルミニウム合金
は大別して、
（１）適当比率のリチウムとアルミニウムとを不活性雰
囲気中で溶融して合金化する冶金学的製造方法。The above-mentioned lithium-aluminum alloy for battery electrodes can be roughly divided into (1) a metallurgical production method in which lithium and aluminum in an appropriate ratio are melted and alloyed in an inert atmosphere;
（２）リチウム塩を含む有機溶媒中にアルミニウム威形
物を浸漬し、このアルミニウム戊形物上にリチウムを電
着して合金化する電気化学的製造方法の２つの方法によ
り製造することができるが、ｆｉｌの冶金学的製造方法
により電池電極用リチウムーアル旦ニウム合金を製造す
る場合には、高瓜加熱が必要であり、このため装置的に
大掛かりなものとなり、また作業取り扱い上にも難点が
あると言った問題がある．他方、（２）の電気化学的製
造方法に関しては、アルミニウム板上にリチウムを圧着
して圧着物を形成し、次いでこの圧着物をリチウム塩を
含む有ａ溶媒に浸漬することにより電池電極用リチウム
−アルミニウム合金を製造する方法が知られており、こ
の方法は比較的簡易であり、上述した冶金学的製造方法
のような問題点はないが、この方法で製造したリチウム
−アルミニウム合金を二次電池の電極として使用すると
、二次電池のサイクル寿命が短いという問題があった．
また、｛２｝の電気化学的方法でリチウム塩を含む有機
溶媒中にアルミニウム板を浸漬し、対極としてリチウム
を浸漬し、アルミニウム板上にリチウムを電着して製造
したリチウム−アルミニウム合金を二次電池用の電極と
して使用すると、二次電池のサイクル寿命は長くなるこ
とが知られている．〔発明が解決しようとする課題〕
上述のようなリチウム塩を含む有機溶媒中にアルミニウ
ム板を浸漬し、対極としてリチウムを浸漬し、アルミニ
ウム板上にリチウムを電着してリチウム−アルミニウム
合金を製造する方法では、製造したリチウム−アルミニ
ウム合金を電池内に組み込むための工程、例えばリチウ
ム−アルミニウム負極と外装缶とを固着するなどの工程
が必要となり、作業取り扱い上難点があった。(2) It can be produced by two methods: an electrochemical production method in which an aluminum shape is immersed in an organic solvent containing lithium salt, and lithium is electrodeposited onto the aluminum shape to form an alloy. However, when producing a lithium-aluminum alloy for battery electrodes using the fil metallurgical production method, it is necessary to heat the melon, which requires a large-scale equipment and is also difficult to handle. There is a problem that I mentioned. On the other hand, regarding the electrochemical production method (2), lithium for battery electrodes is produced by pressing lithium onto an aluminum plate to form a crimped object, and then immersing this crimped object in an aqueous solvent containing a lithium salt. - A method for producing an aluminum alloy is known, and although this method is relatively simple and does not have the problems of the metallurgical production method described above, it is possible to use the lithium-aluminum alloy produced by this method as a secondary When used as a battery electrode, there was a problem that the cycle life of the secondary battery was short.
In addition, a lithium-aluminum alloy produced by immersing an aluminum plate in an organic solvent containing a lithium salt using the electrochemical method of {2}, immersing lithium as a counter electrode, and electrodepositing lithium on the aluminum plate was used. It is known that when used as an electrode for secondary batteries, the cycle life of the secondary battery will be extended. [Problem to be solved by the invention] A lithium-aluminum alloy is produced by immersing an aluminum plate in an organic solvent containing a lithium salt as described above, immersing lithium as a counter electrode, and electrodepositing lithium onto the aluminum plate. This method requires a process for incorporating the manufactured lithium-aluminum alloy into the battery, such as fixing the lithium-aluminum negative electrode and the outer can, which is difficult to handle.
本発明は負極としてリチウム−アルミニウム合金を用い
た。サイクル寿命の優れたリチウム二次電池を簡単に製
造する方法を提供することを目的とする。In the present invention, a lithium-aluminum alloy was used as the negative electrode. The purpose of the present invention is to provide a method for easily manufacturing a lithium secondary battery with excellent cycle life.
本発明者らは、上記目的を達成するため鋭意検討を重ね
た結果、負極側にアルミニウム板を用い、正極側にリチ
ウムを吸蔵させた二酸化マンガンを用い、電解液として
リチウム塩を含む有機溶媒を用いて組み立てた電池を、
通常の電池を充電するのと同しことをすると正極側に用
いた二酸化マンガンに吸蔵させたリチウムが、負極側の
アルミニウム板上に電着されることにより、前述した電
気化学的方法で、リチウム塩を含む有機溶媒中にアルミ
ニウム板を浸漬し、対極としてリチウムを浸清し、アル
ミニウム板上にリチウムを電着することにより製造した
リチウム−アルミニウム合金を二次電池用の電極として
使用したリチウム二次電池と同程度のサイクル寿命の優
れたリチウム二次電池が製造できることを知見し、本発
明を完威させるに至ったものである．
なお、正極側にリチウムを吸蔵させた二酸化マンガンを
用い、負極側にアルミニウム板を用い、電解液としてリ
チウム塩を含む有機溶媒を用いて組み立たて電池の充電
方法は用いるリチウム塩や有機溶媒によっても異なるが
、充電の際の電池の電圧を上限電圧を設定して充電を行
う方法が好適である．
〔作用〕
電池電極用のリチウム−アルミニウム合金の製造方法で
、サイクル寿命の優れたリチウム−アルミニウム合金の
製造方法としては、リチウム塩を含む有機溶媒中にアル
ミニウム板と、リチウムを浸漬し、アルξニウム板上に
リチウムを電着する方法が好適であるが、製造工程上難
点があった。As a result of intensive studies to achieve the above object, the present inventors used an aluminum plate on the negative electrode side, used manganese dioxide with lithium occluded on the positive electrode side, and used an organic solvent containing lithium salt as the electrolyte. The battery assembled using
When charging a normal battery, the lithium occluded in the manganese dioxide used on the positive electrode side is electrodeposited on the aluminum plate on the negative electrode side, and lithium is charged by the electrochemical method described above. A lithium secondary battery using a lithium-aluminum alloy produced by immersing an aluminum plate in an organic solvent containing salt, immersing lithium as a counter electrode, and electrodepositing lithium on the aluminum plate as an electrode for a secondary battery. It was discovered that it was possible to manufacture a lithium secondary battery with a cycle life comparable to that of secondary batteries, and this led to the completion of the present invention. In addition, the battery is assembled using manganese dioxide with lithium occluded for the positive electrode side, an aluminum plate for the negative electrode side, and an organic solvent containing lithium salt as the electrolyte.The charging method for the battery depends on the lithium salt and organic solvent used. However, the preferred method is to set an upper limit voltage for the battery voltage during charging. [Function] A method for producing a lithium-aluminum alloy with excellent cycle life for use in battery electrodes is to immerse an aluminum plate and lithium in an organic solvent containing a lithium salt, A method of electrodepositing lithium on a metal plate is suitable, but there are some difficulties in the manufacturing process.
このように、従来のリチウム−アルミニウム合金負極は
、電池組み立て前に予め作製するものである。In this way, conventional lithium-aluminum alloy negative electrodes are prepared in advance before battery assembly.
一方、本発明のリチウム二次電池の製造方法は、電池内
で負極側のアルミニウム板にリチウムを電着させ、リチ
ウム−アルミニウム合金を製造する方法であり、電池組
み立てのときは、正極側にリチウムを吸蔵させた二酸化
マンガン、負極側にアルミニウム板、電解液としてリチ
ウム塩を含む有機溶媒を用いて電池を組み立てることが
できるので、組み立ての時にリチウム−アルミニウム合
金を用いる方法に較べて、製造工程が簡略化でき、コス
トメリットが大きい。On the other hand, the method for manufacturing a lithium secondary battery of the present invention is a method of electrodepositing lithium on an aluminum plate on the negative electrode side in the battery to manufacture a lithium-aluminum alloy, and when assembling the battery, lithium is placed on the positive electrode side. Since a battery can be assembled using manganese dioxide occluded with carbon dioxide, an aluminum plate on the negative electrode side, and an organic solvent containing lithium salt as the electrolyte, the manufacturing process is faster than when using a lithium-aluminum alloy. It can be simplified and has great cost benefits.
以下、本発明を具体的な実験例に基づいて説明するが、
本発明がこれら実験例に限定されるものではない．
（実施例）
以下に示す手順に従って第ｌ図に示すコイン型電池を作
威した。The present invention will be explained below based on specific experimental examples.
The present invention is not limited to these experimental examples. (Example) A coin type battery shown in FIG. 1 was produced according to the procedure shown below.
市販の電解二酸化マンガンと市販のｎ−ブチルリチウム
を所定量反応させて、マンガンに対するモル比が０．８
の量だけリチウムイオンを吸蔵した二酸化マンガンを得
た．
上述のようにして得られたリチウムを吸藏した二酸化マ
ンガンを正極活物質として用い、これに導電剤としてグ
ラファイト，バインダーとしてポリテトラフルオ口エチ
レンを重量比で８５：１０：５の割合で混合し正極合剤
とした．これを直径１５．５關、厚さ０．６１ｍ、重量
０．３００ｇに加圧戒型して正極ベレソト５を作戒した
。A predetermined amount of commercially available electrolytic manganese dioxide and commercially available n-butyllithium are reacted to produce a molar ratio of 0.8 to manganese.
We obtained manganese dioxide that occluded lithium ions in an amount equal to . The lithium-adsorbed manganese dioxide obtained as described above was used as a positive electrode active material, and graphite as a conductive agent and polytetrafluoroethylene as a binder were mixed in a weight ratio of 85:10:5. It was used as a positive electrode mixture. This was pressurized into a mold with a diameter of 15.5 mm, a thickness of 0.61 m, and a weight of 0.300 g to form a positive electrode Veresoto 5.
次に、厚さ０．２ １−のアルミニウム板を直径１５．
５關に打ち抜き、負極ベレ７｝１とし負極缶２にスポッ
ト溶接し、負極を作威した．
この負極上にセパレータ３を置き、プラスチック製のガ
スケフト４をはめこみ、電解液７として１モル１ｌの割
合でＬｉ Ｂ Ｆ ａを溶解したプロピレンカーボネー
トを注入し、先に作威した正極ペレット５を入れ、正極
缶６を被せた後、開口部を密封するようにカシメてシー
ルし外径２０，Ｏｘ、厚み１．５ｗｍのリチウム二次電
池を作威した。この電池を電流１ｍＡで充電し、充電終
止電圧を３．７ｖとしたところ、５５ｍＡＨの容量だけ
充電できた。Next, we cut an aluminum plate with a thickness of 0.2 mm and a diameter of 15 mm.
5 pieces were punched out, the negative electrode bevel 7}1 was spot welded to the negative electrode can 2, and the negative electrode was made. A separator 3 is placed on this negative electrode, a plastic gasket 4 is fitted, propylene carbonate in which LiBFa is dissolved at a ratio of 1 mol 1 liter is injected as an electrolytic solution 7, and the positive electrode pellets 5 prepared earlier are placed. After covering the positive electrode can 6, the opening was caulked and sealed to produce a lithium secondary battery with an outer diameter of 20 mm and a thickness of 1.5 wm. When this battery was charged with a current of 1 mA and the charging end voltage was set to 3.7 V, it was possible to charge the battery to a capacity of 55 mAH.
上記のように組み立てた後充電した電池をサンプル電池
Ａとした．
（比較例１）
市販の二酸化マンガンを正極活物質として用い、これに
導電剤としてグラファイト，バインダーとしてポリテト
ラフルオロエチレンを重量比で８２＝１２：６の割合で
混合し正極合剤とした。これを直径１５．５ｎ、厚さ０
．４ｆｌ、重量０．２８５ｇに加圧成型して正極ベレッ
ト５を作或した．
次に、厚さ０．２ｆｌのアルミニウム板を直径ｌ５．５
ｎに打ち抜き、負極缶２にスポット溶接し、その上に直
径１５．０ｙ、厚さ０．２ ｍｍのリチウム板を打ち抜
いたものを圧着し負極ペレソト１として負極を作威した
。上記の直径１５．０ｍ，厚さ０．２Ｈのリチウムの容
量を測定したところ５５ｍＡＨの容量であった．
この負極上にセパレータ３を置き、プラスチック製のガ
スケット４をはめ込み、電解液７としてｌモル／ｌの割
合でＬｉＢＦ４を溶解したプロビレンカーボネートを注
入し、先に作威した正極ベレット５を入れ、正極缶６を
被せた後、開口部を密封するようにカシメてシールし外
径２０．０ｍｍ、厚み１．６ ０のリチウム二次電池を
作戒した。この電池をサンプル電池Ｂとした。The battery assembled and charged as described above was designated as sample battery A. (Comparative Example 1) Commercially available manganese dioxide was used as a positive electrode active material, and a positive electrode mixture was prepared by mixing graphite as a conductive agent and polytetrafluoroethylene as a binder in a weight ratio of 82=12:6. This has a diameter of 15.5n and a thickness of 0.
．． A positive electrode pellet 5 was prepared by pressure molding to a size of 4 fl and a weight of 0.285 g. Next, a 0.2fl thick aluminum plate with a diameter l5.5
A lithium plate having a diameter of 15.0 mm and a thickness of 0.2 mm was press-bonded thereon to produce a negative electrode as the negative electrode 1. The capacity of the above 15.0m diameter, 0.2H thick lithium was measured and found to be 55mAH. A separator 3 is placed on this negative electrode, a plastic gasket 4 is fitted, propylene carbonate in which LiBF4 is dissolved at a ratio of 1 mol/l is injected as an electrolytic solution 7, and the previously prepared positive electrode pellet 5 is placed. After covering the positive electrode can 6, the opening was caulked and sealed, and a lithium secondary battery having an outer diameter of 20.0 mm and a thickness of 1.6 mm was prepared. This battery was designated as sample battery B.
（比較例２） 比較例Ｉと同様にして正極ペレソト５を作威した。(Comparative example 2) A positive electrode Peresoto 5 was produced in the same manner as in Comparative Example I.
次に、厚さＱ，２１ｍのアルミニウム板を直径ｌ５，５
ｎに打ち抜いて、その打ち抜いたアルミニウム板をリチ
ウム塩を含む有機溶媒中に浸漬する．そして対極として
リチウムを浸漬し、打ち抜いたアルミニウム板上に５５
ｍＡＨの容量の分だけのリチウムを電着させてリチウム
−アルミニウム合金を製造した。Next, an aluminum plate with a thickness of Q and 21 m was placed with a diameter of l5.
The aluminum plate was punched out into an aluminum plate and immersed in an organic solvent containing a lithium salt. Then, as a counter electrode, lithium was immersed and placed on a punched aluminum plate.
A lithium-aluminum alloy was manufactured by electrodepositing lithium in an amount corresponding to the capacity of mAH.
次に、上記のリチウム−アルミニウム合金を負極缶２に
スポット溶接して負極を作威した。Next, the above lithium-aluminum alloy was spot welded to the negative electrode can 2 to produce a negative electrode.
この負極上にセバレーター３を置き、プラスチック製の
ガスケット４をはめ込み、電解液７として１モル／Ｉｌ
の割合でＬ ｉ Ｂ Ｆ ａを溶解したプロピレンカー
ボネートを注入し、先に作成した正極ペレット５を入れ
、正極缶６を被せた後、開口部を密封するようにカシメ
てシールし外径２０．０關、厚み１．６ ｔｍのリチウ
ム二次電池を作威した．この電池をサンフ゜ノレ電冫也
Ｃとした．
第２図はサンプル電池Ａ，サンプル電池Ｂ，サンプル電
池Ｃの充放電サイクル特性図を示す。なお、充放電条件
はｔ流１ｍＡで１０時間放電し、電ｉ！ｔ １ ｍ Ａ
で充電し、充電終止電圧３．７ｖとした。A separator 3 is placed on this negative electrode, a plastic gasket 4 is fitted, and an electrolytic solution 7 of 1 mol/Il is placed on top of the negative electrode.
After injecting propylene carbonate in which LiBFa is dissolved at a ratio of 20.0, the positive electrode pellet 5 prepared earlier is placed, and the positive electrode can 6 is placed on top.The opening is caulked to seal the opening, and the outer diameter is 20. We have created a lithium secondary battery with a thickness of 1.6 tm. This battery was designated as Sanfunore Denya C. FIG. 2 shows charge/discharge cycle characteristics of sample battery A, sample battery B, and sample battery C. The charging and discharging conditions were to discharge at a current of 1 mA for 10 hours, and to obtain an electric i! t 1 m A
The battery was charged at a charge end voltage of 3.7V.
第２図より本発明の製造方法によるサンプル電池Ａは、
アルミニウム板上にリチウムを圧着して作威したりチウ
ムーアルミニウム合金負極を用いたサンプル電池Ｂより
もサイクル寿命が優れている。又、本発明の製造方法に
よるサンプル電他Ａは、リチウム塩を含む有ｍ？８媒中
にアルミニウム板を浸漬し、対極としてリチウムを浸冫
１し、アルミニウム板上にリチウムを電着して製造した
リチウム−アルミニウム合金負極を用いたサンプル電池
Ｃと同程度のサイクル寿命を示しており、製造工程が簡
略化できるという本発明の製造方法が優れている．
〔発明の効果〕
上述の説明からも明らかなように、リチウムを吸蔵させ
た二酸化マンガンからなる正極と、アルミニウムからな
る負極と、非水電解液からなる電池を充電する本発明の
リチウム二次電池の製造方法は、充放電のサイクル寿命
の優れたリチウム二次電池を、簡略な製造方法で提供す
ることができFrom FIG. 2, sample battery A manufactured by the manufacturing method of the present invention is as follows:
The cycle life is better than that of sample battery B, which is made by press-bonding lithium onto an aluminum plate or uses a lithium-aluminum alloy negative electrode. In addition, Sample A produced by the production method of the present invention contains lithium salt. The battery exhibited a cycle life comparable to that of sample battery C, which used a lithium-aluminum alloy negative electrode produced by immersing an aluminum plate in 8 medium, immersing it in lithium as a counter electrode, and electrodepositing lithium on the aluminum plate. The manufacturing method of the present invention is superior in that it can simplify the manufacturing process. [Effects of the Invention] As is clear from the above description, the lithium secondary battery of the present invention charges a battery comprising a positive electrode made of manganese dioxide occluded with lithium, a negative electrode made of aluminum, and a non-aqueous electrolyte. This manufacturing method can provide a lithium secondary battery with an excellent charge/discharge cycle life using a simple manufacturing method.
第１図は本発明方法により製造したリチウム二次電池の
構或例を示す概略断面図である．第２図は電池の充放電
サイクル特性図である．・負極ペレフト
・負極缶
・セパレーター
・ガスケフト
・正極ベレフト
・正極缶
以上FIG. 1 is a schematic cross-sectional view showing an example of the structure of a lithium secondary battery manufactured by the method of the present invention. Figure 2 shows the charge/discharge cycle characteristics of the battery.・Negative pole left, negative pole can, separator, gaskeft, positive pole left, positive pole can or above
Claims (1)
極と、アルミニウムからなる負極と、非水電解液とから
なる電池を組み立てた後、充電により、正極である二酸
化マンガンに吸蔵しているリチウムイオンを放出せしめ
、負極のアルミニウム上にリチウムを電着せしめ、リチ
ウム−アルミニウム合金負極とすることを特徴とするリ
チウム二次電池の製造方法。After assembling a battery consisting of a positive electrode made of manganese dioxide that occludes lithium ions, a negative electrode made of aluminum, and a non-aqueous electrolyte, charging releases the lithium ions occluded in the manganese dioxide that is the cathode. A method for producing a lithium secondary battery, which comprises electrodepositing lithium on aluminum as a negative electrode to obtain a lithium-aluminum alloy negative electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1151970A JPH0317964A (en) | 1989-06-14 | 1989-06-14 | Manufacture of lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1151970A JPH0317964A (en) | 1989-06-14 | 1989-06-14 | Manufacture of lithium secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0317964A true JPH0317964A (en) | 1991-01-25 |
Family
ID=15530202
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1151970A Pending JPH0317964A (en) | 1989-06-14 | 1989-06-14 | Manufacture of lithium secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0317964A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6538385B2 (en) | 2000-06-22 | 2003-03-25 | Hitachi, Ltd. | Cathode-ray tube and flat electrode of electronic gun and production method |
-
1989
- 1989-06-14 JP JP1151970A patent/JPH0317964A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6538385B2 (en) | 2000-06-22 | 2003-03-25 | Hitachi, Ltd. | Cathode-ray tube and flat electrode of electronic gun and production method |
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