JPH06124700A - Non-aqueous electrolyte secondary battery and manufacturing method thereof - Google Patents
Non-aqueous electrolyte secondary battery and manufacturing method thereofInfo
- Publication number
- JPH06124700A JPH06124700A JP4297656A JP29765692A JPH06124700A JP H06124700 A JPH06124700 A JP H06124700A JP 4297656 A JP4297656 A JP 4297656A JP 29765692 A JP29765692 A JP 29765692A JP H06124700 A JPH06124700 A JP H06124700A
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- aqueous electrolyte
- battery
- 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.)
- Granted
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)
Abstract
(57)【要約】
【目的】 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ことを目的とする。
【構成】 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
チウムを用いる。リチウム表面の炭酸リチウム被膜は、
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 以上にしたり、あるいはプラズマ処理
により形成する。
(57) [Abstract] [Purpose] A non-aqueous electrolyte secondary battery with excellent cycle characteristics that can be uniformly generated on the entire surface of lithium without locally causing lithium electrodeposition due to charging and prevents internal short circuit of the battery. The purpose is to provide a battery. In a non-aqueous electrolyte secondary battery including a non-aqueous electrolyte, a chargeable / dischargeable positive electrode, and a lithium negative electrode, lithium having a surface coated with lithium carbonate is used as the negative electrode. The lithium carbonate coating on the lithium surface is
The inside of the battery is made into a carbon dioxide gas atmosphere, the pressure inside the battery is set to 4 kg / cm 2 or more, or it is formed by plasma treatment.
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 non-aqueous electrolyte secondary battery having an improved negative electrode and a method for manufacturing 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 for consumer use,
Cordless is advancing rapidly. Along with this, there is an increasing demand for a small-sized, lightweight secondary battery having a high energy density, which serves as a driving power source. From this point of view, non-aqueous secondary batteries, especially lithium secondary batteries, have great expectations as batteries having high voltage and high energy density, and their development is urgently needed. Conventionally, manganese dioxide, vanadium pentoxide, titanium disulfide and the like have been used as the positive electrode active material of such lithium secondary batteries.
A battery was constituted by these positive electrodes, a lithium negative electrode and an organic electrolytic solution, and charging and discharging were repeated. However, in a secondary battery using lithium metal for the negative electrode, there is a problem that the cycle life is shortened due to an internal short circuit due to dendrite-like lithium generated during charging. Conventionally, the problem is to improve the charging method, or to propose a method of suppressing the generation of dendrite-like lithium by adding an additive to the electrolytic solution, or to improve the separator to prevent a battery internal short circuit due to dendrite-like 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 electrodeposited state on the lithium metal due to charging is non-uniform, and the electrodeposited lithium locally grows and penetrates the separator to cause an internal short circuit, resulting in a cycle. There was a problem of deteriorating the characteristics. MEANS TO SOLVE THE PROBLEM This invention solves such a subject, without causing lithium electrodeposition by charge locally, it is made to generate | occur | produce uniformly on the whole surface of lithium, and it is a nonaqueous water excellent in cycle characteristic by preventing a battery internal short circuit. It is an object of the present invention to provide an electrolytic solution secondary battery and also 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 of the present invention comprises a non-aqueous electrolyte, a chargeable / dischargeable positive electrode, and a lithium negative electrode. In the liquid secondary battery, lithium having a surface coated with lithium carbonate is used as the negative electrode. In such a non-aqueous electrolyte secondary battery, the inside of the battery is made into a carbon dioxide gas atmosphere and the pressure inside the battery is 4 kg / cm 2
It can be manufactured by the above, or by forming a coating 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 electrodeposited lithium due to charging is uniformly deposited on the lithium surface without segregation, and a non-aqueous electrolyte secondary battery having an excellent cycle life is realized. You can
【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。Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 shows a vertical cross-sectional view of the cylindrical battery used in this example. In FIG. 1, reference numeral 1 is a battery case formed by processing an organic electrolytic solution resistant stainless steel plate, 2 is a sealing plate provided with a safety valve, and 3 is an insulating packing. Reference numeral 4 denotes an electrode plate group, in which the positive electrode and the negative electrode are spirally wound a plurality of times with a separator interposed therebetween 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 portion 1 of the battery case. Insulating rings 7 are provided on the upper and lower portions of the electrode plate group, respectively. Hereinafter, the positive and negative electrode plates, the electrolytic solution 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 fluororesin-based 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 carboxymethylcellulose solution. To make paste. This paste has a thickness of 0.03
It was applied on both sides of an aluminum foil of mm, 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 lithium carbonate coating film formed on its surface was used.
The thickness of the lithium carbonate film is preferably 100 to 5000 angstroms, but in this embodiment, it is 500 angstroms. The electrode plate has a thickness of 0.10 mm and a width of 40
mm and length 260 mm. Next, a lead is attached to each of the negative electrode plates, and the thickness is 0.025 mm and the width is 46 m.
It was wound in a spiral shape through a polypropylene separator having a length of m and a length of 700 mm and was housed 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 in a mixed solvent of equal volume of propylene carbonate and ethylene carbonate at a rate of 1 mol / liter was used. As a comparative example, lithium metal in which lithium carbonate was not formed was used for the negative electrode. The battery was constructed under exactly the same conditions as those of the batteries of the examples except for lithium metal. A constant current charge / discharge test was performed on the batteries of the above-mentioned examples and the batteries of the comparative examples under 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. A comparison of these cycle characteristics is shown in FIG. In FIG. 2, curves 1, 2, and 3 of the example of the present invention are lithium metal having a lithium carbonate coating film provided 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 be charged and discharged for 300 cycles or more. On the other hand, the battery of the comparative example
Deterioration due to cycling was remarkable, and was less than half of the initial capacity at 200 cycles. When lithium carbonate is uniformly formed on the surface of lithium metal, it is unclear why local lithium electrodeposition does not occur. However, we have experimentally found that when lithium having a lithium carbonate film formed thereon is applied at a charging current, the deposited lithium becomes uniform. It is already known that lithium carbonate is present on the lithium metal surface. For example, as a reference, J. E
retrochem. Soc. vol. 134, No
It is described that lithium carbonate is formed on the surface of lithium metal by using an electrolyte solution of propylene carbonate in 7,1611 (87). However, the film is a film in which lithium carbonate and lithium carbonate in which the electrolytic solution reacts with lithium are mixed, and is different from the film of lithium carbonate of the present invention. The present invention is an inorganic coating containing lithium carbonate as a main component. FIG. 4 shows the state of electrodeposition of lithium with a coating of lithium carbonate and untreated lithium during charging. The charging current was 1 mA / cm 2 , and the electrolytic solution was the same as that used in the above battery. Photo A is lithium with a lithium carbonate coating, and photo B is untreated lithium.
As is clear from the photograph, it is understood that the lithium electrodeposited with the lithium carbonate coating has a uniform electrodeposition state. Next, two methods for producing lithium metal having a lithium carbonate film formed thereon will be described. The first manufacturing method is a manufacturing method in which a carbon dioxide gas is injected and the internal pressure of the battery is set to 4 kg / cm 2 or more when the battery is sealed in the battery having the above-described battery configuration. In this case, the lithium metal of the negative electrode may be untreated. FIG. 3 shows the relationship between the internal pressure of the battery and the 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 4.1V, and a discharge end voltage of 3.0V. Carbon dioxide pressure inside the battery is 3k
If g / cm 2 or less, cycle characteristics are poor, but 4 kg / c
When m 2 or more, excellent cycle characteristics are obtained. The reason why the cycle characteristics are improved by injecting carbon dioxide is that a lithium carbonate film is formed on the lithium metal surface. Furthermore, it is considered that the cycle characteristics are improved as the pressure inside the battery is increased because the formation of the lithium carbonate film is more complete. It has been known for a long time to fill the inside of the non-aqueous electrolyte battery with carbon dioxide gas, but it is not known that the cycle life is further improved by increasing the filling internal pressure as compared with the conventional case. The second manufacturing method is a manufacturing method in which a lithium carbonate coating film is provided on the surface of lithium by plasma treatment. There are three methods of manufacturing by plasma treatment. Before the plasma treatment, the inside of the bell jar was depressurized to a vacuum degree of 1 × 10 −7 Torr to eliminate 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 in an argon atmosphere having a degree of vacuum of 2 × 10 −2 to 4 × 10 −2 Torr, and then the atmosphere of carbon dioxide is returned to normal pressure to form a lithium surface. A coating of lithium carbonate was formed. The etching process time is 1
It was set to 0 minutes. The cycle characteristics are shown in Example 1 of FIG. In the second method by plasma treatment, lithium carbonate is used as a source target, output is 50 W, and vacuum degree is 2 ×.
High frequency magnetron sputtering was performed for 5 minutes under the condition of 10 -2 Torr to form a lithium carbonate coating film on the lithium surface. The same plasma etching as above was carried out for 30 seconds before the film formation. The cycle characteristics are shown in Example 2 of FIG. The third method using plasma treatment is a method using reactive sputtering. As an atmosphere, 10 vol% carbon dioxide gas in argon with an output of 50 W and a degree of vacuum of 2 ×
High-frequency magnetron sputtering was performed under the condition of 10 -2 Torr to form a lithium carbonate coating film on the lithium surface. In this case, almost the same coating can be obtained even if the source target is lithium carbonate or plasma etching. The cycle characteristics are shown in Example 3 of FIG. As is clear from FIG. 2, lithium metal having a lithium carbonate coating film obtained by plasma treatment on its surface has excellent cycle characteristics. As described above, according to the present embodiment, by providing the lithium carbonate coating film on the surface of lithium metal, it is possible to realize a non-aqueous electrolyte battery having excellent cycle characteristics.
【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 film formed on the negative electrode, a non-aqueous electrolyte battery having excellent cycle characteristics can be obtained. Further, according to the method for producing a non-aqueous electrolyte secondary battery of the present invention, the non-aqueous electrolyte secondary battery having a uniform lithium carbonate coating film can be easily produced.
【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 vertical 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 of 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 the 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
す図面代用写真 Ａ 本発明のリチウム金属表面の電析状態を示す倍率
２００倍の顕微鏡写真 Ｂ 従来例のリチウム金属表面の電析状態を示す倍率
２００倍の顕微鏡写真FIG. 4 is a drawing-substituting photograph showing a comparison between the electrodeposited states of the present invention and the conventional example. A Micrograph showing the electrodeposited state of the lithium metal surface of the present invention at a magnification of 200. B. Electrodeposition of the lithium metal surface of the conventional example. Micrograph with 200x magnification showing condition
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 1 Battery Case 2 Sealing Plate 3 Insulation Packing 4 Electrode Plate Group 5 Positive Electrode Lead 6 Negative Electrode Lead 7 Insulation Ring
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成５年８月２日[Submission date] August 2, 1993
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】図面の簡単な説明[Name of item to be corrected] Brief description of the drawing
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【図面の簡単な説明】[Brief description of drawings]
【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 vertical 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 of 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 the 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 electrodeposited states of the present invention and a conventional example. A A metallographic diagram with a magnification of 200 showing the electrodeposited state of the lithium metal surface of the present invention. Metallographic chart with a magnification of 200 times showing the deposited state
【符号の説明】 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[Explanation of symbols] 1 battery case 2 sealing plate 3 insulating packing 4 electrode plate group 5 positive electrode lead 6 negative electrode lead 7 insulating ring
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】図面[Document name to be corrected] Drawing
【補正対象項目名】図４[Name of item to be corrected] Fig. 4
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【図４】 [Figure 4]
───────────────────────────────────────────────────── 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 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazunori Haraguchi 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (72) Yoshiaki Nitta 1006 Kadoma, Kadoma City, Osaka Matsushita Electric Industrial Co., Ltd. (72) Inventor Kazuhiro Okamura 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd.
Claims (3)
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非水電解液二次電
池。1. A non-aqueous electrolyte secondary battery comprising a non-aqueous electrolyte, a chargeable / dischargeable positive electrode, and a lithium negative electrode, wherein lithium having a lithium carbonate film formed on its surface is used as the negative electrode. The non-aqueous electrolyte secondary battery characterized in that
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。2. A non-aqueous electrolyte secondary battery using lithium, which comprises a non-aqueous electrolyte, a chargeable / dischargeable positive electrode, and a lithium negative electrode, and has a lithium carbonate coating film formed on the surface of the negative electrode. A method of manufacturing a non-aqueous electrolyte secondary battery, characterized in that the inside of the battery is made into 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被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。3. A non-aqueous electrolyte secondary battery comprising a non-aqueous electrolyte, a chargeable / dischargeable positive electrode, and a lithium negative electrode, wherein lithium is used as the negative electrode and a lithium carbonate coating film is formed on the surface of the non-aqueous electrolyte secondary battery. A method of manufacturing a non-aqueous electrolyte secondary battery, which comprises forming a coating film of lithium carbonate on the 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 true JPH06124700A (en) | 1994-05-06 |
| JP3232710B2 JP3232710B2 (en) | 2001-11-26 |
Family
ID=17849423
Family Applications (1)
| 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 |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3232710B2 (en) |
Cited By (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07176323A (en) * | 1993-12-21 | 1995-07-14 | Mitsubishi Cable Ind Ltd | Electrolytic solution and negative electrode for li secondary battery |
| JPH07302617A (en) * | 1994-04-28 | 1995-11-14 | Nippondenso Co Ltd | Nonaqueous electrolyte battery and its manufacture |
| JP2001266893A (en) * | 2000-03-23 | 2001-09-28 | Matsushita Battery Industrial Co Ltd | Non-aqueous electrolyte secondary battery |
| WO2002091514A1 (en) * | 2001-05-09 | 2002-11-14 | Japan Storage Battery Co., Ltd. | Nonaqueous electrolyte cell and its manufacturing method |
| WO2004109839A1 (en) | 2003-06-09 | 2004-12-16 | Sanyo Electric Co., Ltd. | Lithium secondary battery and method for producing same |
| WO2004114453A1 (en) * | 2003-06-19 | 2004-12-29 | Sanyo Electric Co., Ltd. | Lithium secondary battery and method for producing same |
| CN100359748C (en) * | 2003-06-19 | 2008-01-02 | 三洋电机株式会社 | Lithium secondary battery and manufacturing method thereof |
| KR100950038B1 (en) * | 2006-02-20 | 2010-03-29 | 주식회사 엘지화학 | Lithium secondary battery with improved safety against overcharging |
| JP2011530784A (en) * | 2008-08-05 | 2011-12-22 | シオン・パワー・コーポレーション | Force application in electrochemical cells |
| US9040197B2 (en) | 2011-10-13 | 2015-05-26 | Sion Power Corporation | Electrode structure and method for making the same |
| US9425441B2 (en) | 2004-01-28 | 2016-08-23 | Sony Corporation | Anode and battery |
| CN106099073A (en) * | 2016-08-19 | 2016-11-09 | 中航锂电（洛阳）有限公司 | The preparation method of composite cathode material for lithium ion cell, composite cathode material for lithium ion cell and lithium ion battery |
| US9548492B2 (en) | 2011-06-17 | 2017-01-17 | Sion Power Corporation | Plating technique for electrode |
| US9577267B2 (en) | 2012-12-19 | 2017-02-21 | Sion Power Corporation | Electrode structure and method for making same |
| WO2018193993A1 (en) * | 2017-04-19 | 2018-10-25 | 株式会社アルバック | Film forming apparatus and film forming method |
| US10319988B2 (en) | 2014-05-01 | 2019-06-11 | Sion Power Corporation | Electrode fabrication methods and associated systems and articles |
| JP6547089B1 (en) * | 2018-02-07 | 2019-07-17 | 株式会社アルバック | Thin film forming method, thin film forming apparatus and lithium battery |
| WO2019156005A1 (en) * | 2018-02-07 | 2019-08-15 | 株式会社アルバック | Thin film formation method, thin film formation device, and lithium battery |
| US10629947B2 (en) | 2008-08-05 | 2020-04-21 | Sion Power Corporation | Electrochemical cell |
| WO2020111094A1 (en) * | 2018-11-30 | 2020-06-04 | パナソニックＩｐマネジメント株式会社 | Electrochemical device negative electrode and electrochemical device, and method for manufacturing electrochemical device negative electrode and method for manufacturing electrochemical device |
| JP2020523751A (en) * | 2017-06-20 | 2020-08-06 | エルジー・ケム・リミテッド | Lithium electrode and lithium secondary battery including the same |
| CN114975886A (en) * | 2022-06-16 | 2022-08-30 | 上海交通大学 | A kind of lithium foil surface passivation method and its application in lithium metal battery |
| KR102540475B1 (en) * | 2022-08-09 | 2023-06-07 | 주식회사 비츠로셀 | Battery including plasma-treated lithium electrode |
| US11791511B2 (en) | 2019-11-19 | 2023-10-17 | Sion Power Corporation | Thermally insulating compressible components for battery packs |
| US11824228B2 (en) | 2019-11-19 | 2023-11-21 | Sion Power Corporation | Compression systems for batteries |
| US11923495B2 (en) | 2020-03-13 | 2024-03-05 | Sion Power Corporation | Application of pressure to electrochemical devices including deformable solids, and related systems |
| US11978917B2 (en) | 2019-11-19 | 2024-05-07 | Sion Power Corporation | Batteries with components including carbon fiber, and associated systems and methods |
| US11984575B2 (en) | 2019-11-19 | 2024-05-14 | Sion Power Corporation | Battery alignment, and associated systems and methods |
| US12394817B2 (en) | 2019-06-21 | 2025-08-19 | Sion Power Corporation | Methods, systems, and devices for applying forces to electrochemical devices |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3487556B2 (en) | 1992-11-30 | 2004-01-19 | キヤノン株式会社 | Lithium secondary battery |
| RU2182556C1 (en) * | 2001-09-28 | 2002-05-20 | Зао "Астор-Электроникс" | Method of obtaining nitrogen trifluoride |
-
1992
- 1992-10-08 JP JP29765692A patent/JP3232710B2/en not_active Expired - Fee Related
Cited By (44)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07176323A (en) * | 1993-12-21 | 1995-07-14 | Mitsubishi Cable Ind Ltd | Electrolytic solution and negative electrode for li secondary battery |
| JPH07302617A (en) * | 1994-04-28 | 1995-11-14 | Nippondenso Co Ltd | Nonaqueous electrolyte battery and its manufacture |
| JP2001266893A (en) * | 2000-03-23 | 2001-09-28 | Matsushita Battery Industrial Co Ltd | Non-aqueous electrolyte secondary battery |
| WO2002091514A1 (en) * | 2001-05-09 | 2002-11-14 | Japan Storage Battery Co., Ltd. | Nonaqueous electrolyte cell and its manufacturing method |
| WO2004109839A1 (en) | 2003-06-09 | 2004-12-16 | Sanyo Electric Co., Ltd. | Lithium secondary battery and method for producing same |
| US8609279B2 (en) | 2003-06-09 | 2013-12-17 | Sanyo Electric Co., Ltd. | Lithium secondary battery and method for producing same |
| WO2004114453A1 (en) * | 2003-06-19 | 2004-12-29 | Sanyo Electric Co., Ltd. | Lithium secondary battery and method for producing same |
| CN100359748C (en) * | 2003-06-19 | 2008-01-02 | 三洋电机株式会社 | Lithium secondary battery and manufacturing method thereof |
| US8211569B2 (en) | 2003-06-19 | 2012-07-03 | Sanyo Electric Co., Ltd. | Lithium secondary battery including a negative electrode which is a sintered layer of silicon particles and/or silicon alloy particles and a nonaqueous electrolyte containing carbon dioxide dissolved therein and method for producing same |
| US9425441B2 (en) | 2004-01-28 | 2016-08-23 | Sony Corporation | Anode and battery |
| KR100950038B1 (en) * | 2006-02-20 | 2010-03-29 | 주식회사 엘지화학 | Lithium secondary battery with improved safety against overcharging |
| US9105938B2 (en) | 2008-08-05 | 2015-08-11 | Sion Power Corporation | Application of force in electrochemical cells |
| US10320027B2 (en) | 2008-08-05 | 2019-06-11 | Sion Power Corporation | Application of force in electrochemical cells |
| US11108077B2 (en) | 2008-08-05 | 2021-08-31 | Sion Power Corporation | Application of force in electrochemical cells |
| US10629947B2 (en) | 2008-08-05 | 2020-04-21 | Sion Power Corporation | Electrochemical cell |
| US11121397B2 (en) | 2008-08-05 | 2021-09-14 | Sion Power Corporation | Application of force in electrochemical cells |
| JP2011530784A (en) * | 2008-08-05 | 2011-12-22 | シオン・パワー・コーポレーション | Force application in electrochemical cells |
| US9780404B2 (en) | 2008-08-05 | 2017-10-03 | Sion Power Corporation | Application of force in electrochemical cells |
| US11735761B2 (en) | 2008-08-05 | 2023-08-22 | Sion Power Corporation | Application of force in electrochemical cells |
| US10312545B2 (en) | 2008-08-05 | 2019-06-04 | Sion Power Corporation | Application of force in electrochemical cells |
| US11108076B2 (en) | 2008-08-05 | 2021-08-31 | Sion Power Corporation | Application of force in electrochemical cells |
| US11456459B2 (en) | 2011-06-17 | 2022-09-27 | Sion Power Corporation | Plating technique for electrode |
| US9548492B2 (en) | 2011-06-17 | 2017-01-17 | Sion Power Corporation | Plating technique for electrode |
| US9040197B2 (en) | 2011-10-13 | 2015-05-26 | Sion Power Corporation | Electrode structure and method for making the same |
| US9577267B2 (en) | 2012-12-19 | 2017-02-21 | Sion Power Corporation | Electrode structure and method for making same |
| US10319988B2 (en) | 2014-05-01 | 2019-06-11 | Sion Power Corporation | Electrode fabrication methods and associated systems and articles |
| CN106099073A (en) * | 2016-08-19 | 2016-11-09 | 中航锂电（洛阳）有限公司 | The preparation method of composite cathode material for lithium ion cell, composite cathode material for lithium ion cell and lithium ion battery |
| JPWO2018193993A1 (en) * | 2017-04-19 | 2019-06-27 | 株式会社アルバック | Film forming apparatus and film forming method |
| WO2018193993A1 (en) * | 2017-04-19 | 2018-10-25 | 株式会社アルバック | Film forming apparatus and film forming method |
| US11594719B2 (en) | 2017-06-20 | 2023-02-28 | Lg Energy Solution, Ltd. | Lithium electrode and lithium secondary battery including same |
| JP2020523751A (en) * | 2017-06-20 | 2020-08-06 | エルジー・ケム・リミテッド | Lithium electrode and lithium secondary battery including the same |
| WO2019156005A1 (en) * | 2018-02-07 | 2019-08-15 | 株式会社アルバック | Thin film formation method, thin film formation device, and lithium battery |
| JP6547089B1 (en) * | 2018-02-07 | 2019-07-17 | 株式会社アルバック | Thin film forming method, thin film forming apparatus and lithium battery |
| WO2020111094A1 (en) * | 2018-11-30 | 2020-06-04 | パナソニックＩｐマネジメント株式会社 | Electrochemical device negative electrode and electrochemical device, and method for manufacturing electrochemical device negative electrode and method for manufacturing electrochemical device |
| US12394817B2 (en) | 2019-06-21 | 2025-08-19 | Sion Power Corporation | Methods, systems, and devices for applying forces to electrochemical devices |
| US11791511B2 (en) | 2019-11-19 | 2023-10-17 | Sion Power Corporation | Thermally insulating compressible components for battery packs |
| US11824228B2 (en) | 2019-11-19 | 2023-11-21 | Sion Power Corporation | Compression systems for batteries |
| US11929523B2 (en) | 2019-11-19 | 2024-03-12 | Sion Power Corporation | Batteries, and associated systems and methods |
| US11978917B2 (en) | 2019-11-19 | 2024-05-07 | Sion Power Corporation | Batteries with components including carbon fiber, and associated systems and methods |
| US11984575B2 (en) | 2019-11-19 | 2024-05-14 | Sion Power Corporation | Battery alignment, and associated systems and methods |
| US12051829B2 (en) | 2019-11-19 | 2024-07-30 | Sion Power Corporation | Systems and methods for applying and maintaining compression pressure on electrochemical cells |
| US11923495B2 (en) | 2020-03-13 | 2024-03-05 | Sion Power Corporation | Application of pressure to electrochemical devices including deformable solids, and related systems |
| CN114975886A (en) * | 2022-06-16 | 2022-08-30 | 上海交通大学 | A kind of lithium foil surface passivation method and its application in lithium metal battery |
| KR102540475B1 (en) * | 2022-08-09 | 2023-06-07 | 주식회사 비츠로셀 | Battery including plasma-treated lithium electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3232710B2 (en) | 2001-11-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3232710B2 (en) | Manufacturing method of non-aqueous electrolyte secondary battery | |
| US6649033B2 (en) | Method for producing electrode for lithium secondary battery | |
| JPH01200557A (en) | Nonaqueous electrolytic battery | |
| US20050003277A1 (en) | Negative electrode for lithium secondary battery, method of preparing same, and lithium secondary battery comprising same | |
| JPH07296853A (en) | Charging method | |
| WO2019230322A1 (en) | Negative electrode for lithium ion secondary battery | |
| JP3182786B2 (en) | Battery | |
| JPH06260168A (en) | Lithium secondary battery | |
| JP2964833B2 (en) | Lithium secondary battery | |
| JPH06181058A (en) | Looseness restraining means of wound electrode body for nonaqueous electrolyte type battery | |
| EP1191618B1 (en) | Rechargeable battery using nonaqueous electrolyte | |
| JPH11339856A (en) | Manufacture of sheet-type lithium-ion secondary battery | |
| JPH08329946A (en) | Manufacturing method of non-aqueous electrolyte secondary battery | |
| JP3234251B2 (en) | Rechargeable battery | |
| JP3456650B2 (en) | Organic electrolytes Organic electrolytes for secondary batteries | |
| JPH08138671A (en) | Electrode for non-aqueous electrolyte secondary battery | |
| JPH0750162A (en) | Negative electrode for lithium secondary battery | |
| JPH01128371A (en) | Nonaqueous electrolyte secondary cell | |
| JP2011210654A (en) | Method for manufacturing nonaqueous electrolyte secondary battery | |
| WO2021100272A1 (en) | Secondary battery and method for producing same | |
| JPH0521069A (en) | Nonaqueous electrolytic battery and electrode therefor | |
| JP2767853B2 (en) | Cylindrical lithium secondary battery | |
| JPH05234592A (en) | Nonaqueous electrolyte secondary battery and its negative electrode active material | |
| JPH02215043A (en) | Nonaqueous solvent secondary battery | |
| JP2707664B2 (en) | Lithium secondary battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080921 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080921 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090921 Year of fee payment: 8 |
|
| LAPS | Cancellation because of no payment of annual fees |