JP3232710B2 - Manufacturing method of non-aqueous electrolyte secondary battery - Google Patents
Manufacturing method of non-aqueous electrolyte secondary batteryInfo
- Publication number
- JP3232710B2 JP3232710B2 JP29765692A JP29765692A JP3232710B2 JP 3232710 B2 JP3232710 B2 JP 3232710B2 JP 29765692 A JP29765692 A JP 29765692A JP 29765692 A JP29765692 A JP 29765692A JP 3232710 B2 JP3232710 B2 JP 3232710B2
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- battery
- aqueous electrolyte
- secondary battery
- electrolyte secondary
- 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
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
【産業上の利用分野】本発明は、非水電解液二次電池、
特に負極を改良した非水電解液二次電池とその製造方法
に関する。The present invention relates to a non-aqueous electrolyte secondary battery,
In particular, the present invention relates to a nonaqueous electrolyte secondary battery having an improved negative electrode and a method for producing the same.
【従来の技術】近年、民生用電子機器のポータブル化、
コードレス化が急速に進んでいる。これにつれて駆動用
電源を担う小形、軽量で、かつ高エネルギー密度を有す
る二次電池への要望も高まってきている。このような観
点から、非水系二次電池、特にリチウム二次電池は、と
りわけ高電圧、高エネルギー密度を有する電池としてそ
の期待は大きく、開発が急がれている。従来、かかるリ
チウム二次電池の正極活物質には、二酸化マンガン、五
酸化バナジウム、二硫化チタンなどが用いられていた。
これらの正極と、リチウム負極および有機電解液とで電
池を構成し、充放電を繰り返していた。ところが、一般
に負極にリチウム金属を用いた二次電池では、充電時に
生成するデンドライト状リチウムによる内部短絡によ
り、サイクル寿命が短くなる障害があった。従来、その
課題を充電法を改良したり、電解液に添加剤を入れてデ
ンドライト状リチウムの発生を抑制する方法が提案され
たり、セパレータを改善してデンドライト状リチウムに
よる電池内部短絡を防止することが試みられていた。2. Description of the Related Art In recent years, portable electronic devices have become more portable.
Cordless technology is rapidly advancing. Accordingly, there has been a growing demand for a small, lightweight, and high energy density secondary battery that serves as a driving power supply. From such a viewpoint, a non-aqueous secondary battery, particularly a lithium secondary battery, is expected to be a battery having a high voltage and a high energy density, and its development is urgently required. Conventionally, manganese dioxide, vanadium pentoxide, titanium disulfide, and the like have been used as the positive electrode active material of such a lithium secondary battery.
A battery was composed of these positive electrodes, a lithium negative electrode and an organic electrolyte, and charging and discharging were repeated. However, in general, in a secondary battery using lithium metal for the negative electrode, there is an obstacle that the cycle life is shortened due to an internal short circuit caused by dendritic lithium generated during charging. Conventionally, the problem has been solved by improving the charging method, or by adding an additive to the electrolytic solution to suppress the generation of dendritic lithium, or by improving the separator to prevent a short circuit inside the battery due to the dendritic lithium. Was being attempted.
【発明が解決しようとする課題】このような従来の構成
では、充電によるリチウム金属上の電析状態は不均一で
電析リチウムが局部的に成長し、セパレータを貫通し内
部短絡を起こしてサイクル特性を悪くするという課題を
有していた。本発明はこのような課題を解決するもの
で、充電によるリチウム電析を局部的に起こさせること
なく、リチウム全面に均一に発生させ、電池内部短絡を
防止することによりサイクル特性に優れた非水電解液二
次電池を提供すると共に併せてその製造方法を提供する
ことを目的とするものである。In such a conventional structure, the deposited state on the lithium metal due to charging is not uniform, and the deposited lithium locally grows, penetrates through the separator, causes an internal short circuit, and causes a cycle. There was a problem that the characteristics were deteriorated. The present invention solves such a problem. Non-aqueous liquids having excellent cycle characteristics by uniformly generating lithium on the entire surface of lithium without preventing local deposition of lithium by charging and preventing a short circuit inside the battery. It is an object of the present invention to provide an electrolyte secondary battery and to provide a manufacturing method thereof.
【課題を解決するための手段】この課題を解決するため
に本発明の非水電解液二次電池は、非水電解液と、充放
電可能な正極と、リチウム負極とを備えた非水電解液二
次電池において、前記負極として表面に炭酸リチウムの
被膜が形成されているリチウムを用いたことを特徴とす
る。この様な非水電解液二次電池は、電池内部を炭酸ガ
ス雰囲気にすると共に電池内部の圧力を４ｋｇ／ｃｍ2
以上にすることにより、あるいはプラズマ処理によりリ
チウムの表面に炭酸リチウムの被膜を形成することによ
り製造することができる。To solve this problem, a non-aqueous electrolyte secondary battery according to the present invention comprises a non-aqueous electrolyte comprising a non-aqueous electrolyte, a chargeable and dischargeable positive electrode, and a lithium negative electrode. In the liquid secondary battery, lithium having a film of lithium carbonate formed on a surface is used as the negative electrode. In such a non-aqueous electrolyte secondary battery, the inside of the battery is set to a carbon dioxide atmosphere and the pressure inside the battery is set to 4 kg / cm 2.
It can be manufactured by the above or by forming a film of lithium carbonate on the surface of lithium by plasma treatment.
【作用】このような構成のリチウム金属を負極に用いる
と、充電による電析リチウムがリチウム表面に偏析する
ことなく均一に析出し、サイクル寿命が優れた非水電解
液二次電池を実現することができる。When the lithium metal having such a structure is used for the negative electrode, the deposited lithium by charging is uniformly deposited without segregation on the lithium surface, thereby realizing a non-aqueous electrolyte secondary battery having excellent cycle life. Can be.
【実施例】以下、本発明の実施例について、図を参照し
ながら説明する。図１に本実施例で用いた円筒形電池の
縦断面図を示す。この図１においては、１は耐有機電解
液性のステンレス鋼板を加工した電池ケース、２は安全
弁を設けた封口板、３は絶縁パッキングを示す。４は極
板群であり、正極および負極がセパレータを介して複数
回渦巻状に巻回されて収納されている。上記正極からは
正極リード５が引き出されて封口板２に接続され、一
方、負極からは負極リード６が引き出されて電池ケース
の底部１に接続されている。７は絶縁リングで、極板群
の上下部にそれぞれ設けられている。以下、正、負極
板、電解液等について説明する。正極を製造するため
に、まず、Ｌｉ2 ＣＯ3 と、ＣｏＣＯ3 とを混合し、９
００℃で１０時間焼成して合成したＬｉＣｏＯ2 の粉末
１００重量部に、アセチレンブラック３重量部、グラフ
ァイト４重量部およびフッ素樹脂系接着剤７重量部を混
合し、これをカルボキシメチルセルロース水溶液に懸濁
させてペースト状にした。このペーストを厚さ０．０３
ｍｍのアルミ箔の両面に塗着し、乾燥後圧延して厚さ
０．１９ｍｍ、幅４０ｍｍ、長さ２５０ｍｍの極板とし
た。合剤重量は５ｇであった。負極には、炭酸リチウム
の被膜が表面に形成されているリチウム金属を用いた。
炭酸リチウム膜は１００〜５０００オングストロームの
厚さが望ましいが、本実施例では全て５００オングスト
ロームの厚さとした。極板は厚さ０．１０ｍｍ、幅４０
ｍｍ、長さ２６０ｍｍとした。つぎに、負極板はそれぞ
れにリードを取り付け、厚さ０．０２５ｍｍ、幅４６ｍ
ｍ、長さ７００ｍｍのポリプロピレン製のセパレータを
介して渦巻状に巻回し、これを直径１３．８ｍｍ、高さ
５０ｍｍの電池ケース内に収納した。電解液には炭酸プ
ロピレンと炭酸エチレンの等容積混合溶媒に、過塩素酸
リチウムを１モル／リットルの割合で溶解したものを用
いた。比較例として負極に炭酸リチウムが形成されてい
ないリチウム金属を用いた。リチウム金属以外はまった
く実施例の電池と同一条件で構成を行った。上述の実施
例の電池並びに比較例の電池について、ぞれぞれ充放電
電流１００ｍＡ、充電終止電圧４．１Ｖ、放電終止電圧
３．０Ｖの条件下で定電流充放電試験を行った。これら
のサイクル特性の比較を図２に示す。図２において本発
明実施例の曲線１、２、３はプラズマ処理により炭酸リ
チウム被膜が表面に設けられたリチウム金属である。こ
の製造法は後述する。図２より明らかなように、実施例
の炭酸リチウムが表面に形成されたリチウム金属を用い
た電池ではサイクル平坦性が良好であり、３００サイク
ル以上の充放電が可能である。一方、比較例の電池は、
サイクルに伴う劣化が著しく、２００サイクルで初期容
量の半分以下であった。炭酸リチウムがリチウム金属表
面に均一に被膜形成されていると、何故局部的なリチウ
ムの電析が発生しないのか不明である。しかしながら我
々は炭酸リチウム被膜が形成されたリチウムを充電電流
で印加すると電析リチウムが均一化することを実験的に
見出した。炭酸リチウムがリチウム金属表面に存在する
ことはすでに知られている。たとえば文献としてＪ．Ｅ
ｌｅｃｔｒｏｃｈｅｍ．Ｓｏｃ．ｖｏｌ．１３４，Ｎｏ
７，１６１１（８７）のなかに炭酸プロピレンの電解液
を用いるとリチウム金属の表面に炭酸リチウムができる
ことが書かれている。しかしながら、その膜は電解液と
リチウムが反応したリチウムアルキルカーボネートと炭
酸リチウムが混在した膜であり、本発明の炭酸リチウム
の被膜とは異なる。本発明は炭酸リチウムを主成分とし
た無機質の被膜である。図４に炭酸リチウムの被膜を設
けたリチウムと、未処理リチウムの充電における電析状
態を示す。充電電流は１ｍＡ／ｃｍ2 、電解液は上記の
電池に用いた液と同一である。写真Ａは炭酸リチウム被
膜を設けたリチウム、写真Ｂは未処理リチウムである。
写真から明らかなように炭酸リチウム被膜を設けたリチ
ウムの電析状態は均一であることがわかる。次に、炭酸
リチウム被膜を形成したリチウム金属の二つの製造方法
について説明する。第１の製造方法は、上記の電池構成
を有する電池において、電池を密閉する際、炭酸ガスを
注入すると共に、その電池内部圧力を４ｋｇ／ｃｍ2 以
上にする製造方法である。この場合、負極のリチウム金
属は未処理でよい。図３は電池内部圧力とサイクル特性
の関係を示す。それぞれ充放電電流１００ｍＡ、充電終
止電圧４．１Ｖ、放電終止電圧３．０Ｖの条件下で定電
流充放電試験を行った。炭酸ガスの電池内部圧力が３ｋ
ｇ／ｃｍ2 以下ではサイクル特性は悪いが、４ｋｇ／ｃ
ｍ2 以上では優れたサイクル特性が得られる。炭酸ガス
の注入によってサイクル特性が改善される理由はリチウ
ム金属表面に炭酸リチウムの被膜が形成されるからであ
る。さらに電池内部の圧力が高くなるにつれてサイクル
特性が良化しているのは炭酸リチウム膜の形成がより完
全になっているからと考えられる。炭酸ガスを非水電解
液電池内部に充填することは、以前から知られている
が、充填内圧を従来より高めることにより更にサイクル
寿命が向上することは知られていない。第２の製造方法
は、リチウム表面に炭酸リチウム被膜をプラズマ処理に
より設ける製造方法である。プラズマ処理により製造す
る方法は３方法ある。なお、プラズマ処理の前にはベル
ジャー内を真空度１×１０-7Ｔｏｒｒまで減圧し、酸素
の影響を除外した。第１の方法では、リチウムの表面を
真空度２×１０-2〜４×１０-2Ｔｏｒｒのアルゴン雰囲
気下で出力５０Ｗの高周波プラズマエッチング後、炭酸
ガス雰囲気にして常圧に戻し、リチウム表面に炭酸リチ
ウムの被膜を形成した。なお、エッチング処理時間は１
０分とした。図２の実施例１にそのサイクル特性を示
す。プラズマ処理による第２の方法では、炭酸リチウム
ををソースターゲットとして、出力５０Ｗ、真空度２×
１０-2Ｔｏｒｒの条件で、５分間高周波マグネトロンス
パッタを行ってリチウム表面に炭酸リチウム被膜を形成
した。なお、被膜形成の前に上記と同様のプラズマエッ
チングを３０秒間行った。図２の実施例２にそのサイク
ル特性を示す。プラズマ処理による第３の方法は、反応
性スパッタを用いる方法である。雰囲気として、アルゴ
ン中に１０体積％の炭酸ガスを出力５０Ｗ、真空度２×
１０-2Ｔｏｒｒの条件で、高周波マグネトロンスパッタ
を行い、リチウム表面に炭酸リチウムの被膜を形成し
た。この場合、ソースターゲットを炭酸リチウムとして
も、あるいはプラズマエッチングであってもほぼ同様の
被膜が得られる。図２の実施例３にそのサイクル特性を
示す。図２から明らかなように、プラズマ処理により得
られる炭酸リチウム被膜を表面に有するリチウム金属は
サイクル特性が優れていることがわかる。以上のように
本実施例によれば、リチウム金属表面に炭酸リチウムの
被膜を設けることにより、サイクル特性の優れた非水電
解液電池が実現できる。DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 shows a longitudinal sectional view of the cylindrical battery used in this example. In FIG. 1, reference numeral 1 denotes a battery case formed by processing a stainless steel plate having resistance to organic electrolyte, 2 denotes a sealing plate provided with a safety valve, and 3 denotes an insulating packing. Reference numeral 4 denotes an electrode group, in which a positive electrode and a negative electrode are spirally wound a plurality of times via a separator and housed. A positive electrode lead 5 is drawn out from the positive electrode and connected to the sealing plate 2, while a negative electrode lead 6 is drawn out from the negative electrode and connected to the bottom 1 of the battery case. Reference numeral 7 denotes an insulating ring provided at the upper and lower portions of the electrode plate group. Hereinafter, the positive and negative electrode plates, the electrolyte and the like will be described. In order to manufacture a positive electrode, first, Li 2 CO 3 and CoCO 3 are mixed, and 9
3 parts by weight of acetylene black, 4 parts by weight of graphite and 7 parts by weight of a fluororesin adhesive were mixed with 100 parts by weight of LiCoO 2 powder synthesized by firing at 00 ° C. for 10 hours, and suspended in an aqueous solution of carboxymethyl cellulose. To form a paste. This paste has a thickness of 0.03
mm was coated on both sides of an aluminum foil, dried and rolled to obtain an electrode plate having a thickness of 0.19 mm, a width of 40 mm and a length of 250 mm. The mixture weight was 5 g. For the negative electrode, lithium metal having a film of lithium carbonate formed on the surface was used.
The thickness of the lithium carbonate film is desirably 100 to 5000 angstroms, but in this embodiment, the thickness is 500 angstroms. The electrode plate is 0.10mm thick and 40 width
mm and length 260 mm. Next, a lead was attached to each negative electrode plate, and the thickness was 0.025 mm and the width was 46 m.
m, spirally wound through a 700 mm long polypropylene separator, and stored in a battery case having a diameter of 13.8 mm and a height of 50 mm. As the electrolytic solution, a solution prepared by dissolving lithium perchlorate at a ratio of 1 mol / liter in a mixed solvent of equal volumes of propylene carbonate and ethylene carbonate was used. As a comparative example, lithium metal without lithium carbonate was used for the negative electrode. Except for lithium metal, the battery was constructed under the same conditions as the battery of the example. A constant current charge / discharge test was performed on the battery of the above-described example and the battery of the comparative example under the conditions of a charge / discharge current of 100 mA, a charge end voltage of 4.1 V, and a discharge end voltage of 3.0 V, respectively. FIG. 2 shows a comparison of these cycle characteristics. In FIG. 2, curves 1, 2, and 3 of the embodiment of the present invention represent lithium metal provided with a lithium carbonate coating on the surface by plasma treatment. This manufacturing method will be described later. As is clear from FIG. 2, the battery using lithium metal having lithium carbonate formed on the surface of the example has good cycle flatness, and can perform charge and discharge for 300 cycles or more. On the other hand, the battery of the comparative example
The deterioration due to the cycle was remarkable, and was less than half of the initial capacity in 200 cycles. It is not clear why local deposition of lithium does not occur when lithium carbonate is uniformly formed on the lithium metal surface. However, we have experimentally found that when lithium with a lithium carbonate coating is applied at a charging current, the deposited lithium is made uniform. It is already known that lithium carbonate is present on lithium metal surfaces. For example, J. J. E
electrochem. Soc. vol. 134, No
7, 1611 (87) describes that when an electrolyte of propylene carbonate is used, lithium carbonate can be formed on the surface of lithium metal. However, the film is a film in which a lithium alkyl carbonate in which an electrolytic solution and lithium have reacted and lithium carbonate are mixed, and is different from the lithium carbonate film of the present invention. The present invention is an inorganic coating containing lithium carbonate as a main component. FIG. 4 shows the electrodeposited state of lithium provided with a lithium carbonate coating and of untreated lithium. The charging current was 1 mA / cm 2 , and the electrolytic solution was the same as the solution used for the battery. Photo A is lithium provided with a lithium carbonate coating, and Photo B is untreated lithium.
As is clear from the photograph, the electrodeposited state of lithium provided with the lithium carbonate coating is uniform. Next, two methods for producing lithium metal on which a lithium carbonate film is formed will be described. The first manufacturing method is a manufacturing method in which a battery having the above-described battery configuration is filled with carbon dioxide gas and the internal pressure of the battery is set to 4 kg / cm 2 or more when the battery is sealed. In this case, the lithium metal of the negative electrode may be untreated. FIG. 3 shows the relationship between battery internal pressure and cycle characteristics. A constant current charge / discharge test was performed under the conditions of a charge / discharge current of 100 mA, a charge end voltage of 4.1 V, and a discharge end voltage of 3.0 V, respectively. Internal pressure of carbon dioxide gas is 3k
Although the cycle characteristics are poor at g / cm 2 or less, 4 kg / c
At m 2 or more, excellent cycle characteristics can be obtained. The reason why the cycle characteristics are improved by injecting carbon dioxide gas is that a film of lithium carbonate is formed on the surface of the lithium metal. Furthermore, the reason why the cycle characteristics are improved as the internal pressure of the battery increases is considered that the formation of the lithium carbonate film is more complete. Filling carbon dioxide gas into a nonaqueous electrolyte battery has been known for a long time, but it is not known that increasing the internal pressure of the filling further improves the cycle life. The second manufacturing method is a manufacturing method in which a lithium carbonate film is provided on a lithium surface by plasma treatment. There are three methods for manufacturing by plasma processing. Before the plasma treatment, the inside of the bell jar was depressurized to a degree of vacuum of 1 × 10 −7 Torr to exclude the influence of oxygen. In the first method, the surface of lithium is subjected to high-frequency plasma etching with an output of 50 W under an argon atmosphere with a vacuum degree of 2 × 10 −2 to 4 × 10 −2 Torr, and then a carbon dioxide gas atmosphere is returned to normal pressure, and the surface of the lithium A film of lithium carbonate was formed. The etching time is 1
0 minutes. Example 1 of FIG. 2 shows the cycle characteristics. In a second method using plasma processing, lithium carbonate is used as a source target, an output of 50 W, a degree of vacuum of 2 ×.
Under a condition of 10 -2 Torr, high-frequency magnetron sputtering was performed for 5 minutes to form a lithium carbonate film on the lithium surface. In addition, the same plasma etching as described above was performed for 30 seconds before the film formation. Example 2 of FIG. 2 shows the cycle characteristics. A third method using plasma processing is a method using reactive sputtering. As an atmosphere, a 10% by volume carbon dioxide gas in argon was output at a power of 50 W and a degree of vacuum of 2 ×.
Under a condition of 10 -2 Torr, high-frequency magnetron sputtering was performed to form a lithium carbonate film on the lithium surface. In this case, substantially the same coating can be obtained even if the source target is lithium carbonate or plasma etching. Example 3 of FIG. 2 shows the cycle characteristics. As is clear from FIG. 2, it is found that lithium metal having a lithium carbonate film obtained by plasma treatment on its surface has excellent cycle characteristics. As described above, according to the present embodiment, a nonaqueous electrolyte battery having excellent cycle characteristics can be realized by providing a lithium carbonate film on the surface of lithium metal.
【発明の効果】本発明の非水電解液二次電池によれば、
炭酸リチウム被膜を形成したリチウム金属を負極に用い
ることにより、サイクル特性の優れた非水電解液電池が
得られる。また、本発明の非水電解液二次電池の製造方
法によれば、均一な炭酸リチウム被膜を備えた前記非水
電解液二次電池を簡易に製造することができる。According to the non-aqueous electrolyte secondary battery of the present invention,
By using lithium metal having a lithium carbonate coating formed on the negative electrode, a non-aqueous electrolyte battery having excellent cycle characteristics can be obtained. Further, according to the method for manufacturing a non-aqueous electrolyte secondary battery of the present invention, the non-aqueous electrolyte secondary battery having a uniform lithium carbonate coating can be easily manufactured.
【図１】本発明と従来例の円筒形非水電解液二次電池の
縦断面図FIG. 1 is a longitudinal sectional view of a cylindrical non-aqueous electrolyte secondary battery of the present invention and a conventional example.
【図２】本発明と従来例のサイクル特性の比較を示す図FIG. 2 is a diagram showing a comparison of cycle characteristics between the present invention and a conventional example.
【図３】炭酸ガスで満たされた電池の内圧とサイクル特
性の関係を示す図FIG. 3 is a diagram showing a relationship between internal pressure and cycle characteristics of a battery filled with carbon dioxide gas.
【図４】本発明と従来例のリチウム電析状態の比較を示
す金属組織図 Ａ 本発明のリチウム金属表面の電析状態を示す倍率
２００倍の金属組織図 Ｂ 従来例のリチウム金属表面の電析状態を示す倍率
２００倍の金属組織図FIG. 4 is a metallographic diagram showing a comparison between the lithium deposition state of the present invention and the conventional example. A metallographic diagram at a magnification of 200 times showing the electrodeposition state of the lithium metal surface of the present invention. Metallographic diagram at 200x magnification showing the precipitation state
１ 電池ケース ２ 封口板 ３ 絶縁パッキング ４ 極板群 ５ 正極リード ６ 負極リード ７ 絶縁リング DESCRIPTION OF SYMBOLS 1 Battery case 2 Sealing plate 3 Insulation packing 4 Electrode group 5 Positive electrode lead 6 Negative electrode lead 7 Insulation ring
フロントページの続き (72)発明者 原口 和典 大阪府門真市大字門真1006番地 松下電 器産業株式会社内 (72)発明者 新田 芳明 大阪府門真市大字門真1006番地 松下電 器産業株式会社内 (72)発明者 岡村 一広 大阪府門真市大字門真1006番地 松下電 器産業株式会社内 (56)参考文献 特開 平２−168562（ＪＰ，Ａ) 特開 平１−225063（ＪＰ，Ａ) 特開 平４−248276（ＪＰ，Ａ) 特開 昭59−31573（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 10/36 - 10/40 H01M 4/02 - 4/04 H01M 6/16 Continued on the front page (72) Inventor Kazunori Haraguchi 1006 Kazuma Kadoma, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. 72) Inventor Kazuhiro Okamura 1006 Kazuma Kadoma, Kadoma City, Osaka Prefecture Inside Matsushita Electric Industrial Co., Ltd. (56) References JP-A-2-168562 (JP, A) JP-A 1-225063 (JP, A) Kaihei 4-248276 (JP, A) JP-A-59-31573 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) H01M 10/36-10/40 H01M 4/02- 4/04 H01M 6/16
Claims (2)
チウム負極とを備え、前記負極として表面に炭酸リチウ
ムの被膜が形成されているリチウムを用いた非水電解液
二次電池の製造方法であって、電池内部を炭酸ガス雰囲
気にすると共に電池内部の圧力を４ｋｇ／ｃｍ2以上に
することを特徴とする非水電解液二次電池の製造方法。1. A non-aqueous electrolyte secondary battery comprising a non-aqueous electrolyte, a chargeable / dischargeable positive electrode, and a lithium negative electrode, wherein the negative electrode is made of lithium having a surface coated with lithium carbonate. A method for producing a non-aqueous electrolyte secondary battery, characterized in that the inside of the battery is set to a carbon dioxide gas atmosphere and the pressure inside the battery is set to 4 kg / cm 2 or more.
チウム負極とを備え、前記負極として表面に炭酸リチウ
ムの被膜が形成されているリチウムを用いた非水電解液
二次電池の製造方法であって、プラズマ処理によりリチ
ウムの表面に炭酸リチウムの皮膜を形成することを特徴
とする非水電解液二次電池の製造方法。2. A non-aqueous electrolyte secondary battery comprising a non-aqueous electrolyte, a chargeable / dischargeable positive electrode, and a lithium negative electrode, wherein the negative electrode is made of lithium having a lithium carbonate film formed on its surface. A method for manufacturing a non-aqueous electrolyte secondary battery, comprising forming a film of lithium carbonate on a surface of lithium by plasma treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29765692A JP3232710B2 (en) | 1992-10-08 | 1992-10-08 | Manufacturing method of non-aqueous electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29765692A JP3232710B2 (en) | 1992-10-08 | 1992-10-08 | Manufacturing method of non-aqueous electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06124700A JPH06124700A (en) | 1994-05-06 |
| JP3232710B2 true JP3232710B2 (en) | 2001-11-26 |
Family
ID=17849423
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29765692A Expired - Fee Related JP3232710B2 (en) | 1992-10-08 | 1992-10-08 | Manufacturing method of non-aqueous electrolyte secondary battery |
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| Country | Link |
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| JP (1) | JP3232710B2 (en) |
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| RU2182556C1 (en) * | 2001-09-28 | 2002-05-20 | Зао "Астор-Электроникс" | Method of obtaining nitrogen trifluoride |
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| Publication number | Publication date |
|---|---|
| JPH06124700A (en) | 1994-05-06 |
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