JP2002216747A - Manufacturing method of electrode for lithium secondary battery - Google Patents
Manufacturing method of electrode for lithium secondary batteryInfo
- Publication number
- JP2002216747A JP2002216747A JP2001008692A JP2001008692A JP2002216747A JP 2002216747 A JP2002216747 A JP 2002216747A JP 2001008692 A JP2001008692 A JP 2001008692A JP 2001008692 A JP2001008692 A JP 2001008692A JP 2002216747 A JP2002216747 A JP 2002216747A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- active material
- electrode
- secondary battery
- lithium 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.)
- Withdrawn
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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Secondary Cells (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、新規なリチウム二
次電池用電極を製造する方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a novel electrode for a lithium secondary battery.
【０００２】[0002]
【従来の技術】近年、研究開発が盛んに行われているリ
チウム二次電池は、用いられる電極により充放電電圧、
充放電サイクル寿命特性、保存特性などの電池特性が大
きく左右される。このことから、電極に用いる活物質を
改善することにより、電池特性の向上が図られている。2. Description of the Related Art In recent years, a lithium secondary battery, which has been actively researched and developed, has a charge / discharge voltage,
Battery characteristics such as charge-discharge cycle life characteristics and storage characteristics are greatly affected. For this reason, the battery characteristics have been improved by improving the active material used for the electrode.
【０００３】負極活物質としてリチウム金属を用いる
と、重量当たり及び体積当たりともに高いエネルギー密
度の電池を構成することができるが、充電時にリチウム
がデンドライト状に析出し、内部短絡を引き起こすとい
う問題があった。[0003] When lithium metal is used as the negative electrode active material, a battery having a high energy density per weight and per volume can be formed. However, there is a problem that lithium precipitates in a dendrite shape during charging and causes an internal short circuit. Was.
【０００４】これに対し、充電の際に電気化学的にリチ
ウムと合金化するアルミニウム、シリコン、錫などを電
極として用いるリチウム二次電池が報告されている（So
lidState Ionics,113-115,p57(1998)) 。これらのう
ち、特にシリコンは理論容量が大きく、高い容量を示す
電池用負極として有望であり、これを負極とする種々の
二次電池が提案されている（特開平１０−２５５７６８
号公報）。しかしながら、この種の合金負極は、電極活
物質である合金自体が充放電により微粉化し集電特性が
悪化することから、十分なサイクル特性は得られていな
い。On the other hand, there has been reported a lithium secondary battery using, as an electrode, aluminum, silicon, tin or the like which electrochemically alloys with lithium during charging (So).
lidState Ionics, 113-115, p57 (1998)). Among these, silicon is particularly promising as a battery negative electrode having a large theoretical capacity and a high capacity, and various secondary batteries using this as a negative electrode have been proposed (Japanese Patent Application Laid-Open No. 10-255768).
No.). However, in this type of alloy negative electrode, sufficient cycle characteristics have not been obtained because the alloy itself, which is an electrode active material, is pulverized by charging and discharging and the current collecting characteristics are deteriorated.
【０００５】[0005]
【発明が解決しようとする課題】本出願人は、シリコン
を電極活物質とし、良好な充放電サイクル特性を示すリ
チウム二次電池用電極として、ＣＶＤ法またはスパッタ
リング法などの薄膜形成方法により、集電体上に微結晶
シリコン薄膜または非晶質シリコン薄膜を形成したリチ
ウム二次電池用電極を提案している（特願平１１−３０
１６４６号など）。SUMMARY OF THE INVENTION The present applicant has proposed a method of forming a thin film forming method such as a CVD method or a sputtering method as an electrode for a lithium secondary battery having silicon as an electrode active material and exhibiting good charge / discharge cycle characteristics. An electrode for a lithium secondary battery in which a microcrystalline silicon thin film or an amorphous silicon thin film is formed on an electric body has been proposed (Japanese Patent Application No. 11-30).
No. 1646).
【０００６】本発明の目的は、このようなシリコン薄膜
などの活物質薄膜を集電体上に堆積して形成したリチウ
ム二次電池用電極において、集電体と活物質薄膜との密
着性が良好なリチウム二次電池用電極を製造する方法を
提供することにある。An object of the present invention is to provide a lithium secondary battery electrode formed by depositing an active material thin film such as a silicon thin film on a current collector, in which the adhesion between the current collector and the active material thin film is improved. An object of the present invention is to provide a method for producing a good electrode for a lithium secondary battery.
【０００７】[0007]
【課題を解決するための手段】本発明は、集電体として
用いる金属箔の上に、リチウムを吸蔵・放出する活物質
薄膜を堆積して形成するリチウム二次電池用電極の製造
方法であり、金属箔の表面に対して微粒子を噴射して衝
突させることにより、金属箔の表面を粗面化し、粗面化
した表面上に活物質薄膜を堆積させることを特徴として
いる。SUMMARY OF THE INVENTION The present invention is a method for manufacturing an electrode for a lithium secondary battery, comprising forming an active material thin film for absorbing and releasing lithium on a metal foil used as a current collector. The method is characterized in that the surface of the metal foil is roughened by spraying and colliding fine particles against the surface of the metal foil, and an active material thin film is deposited on the roughened surface.
【０００８】本発明における活物質薄膜は、金属箔の上
に堆積して形成される。活物質薄膜を堆積して形成する
方法としては、気相から原料を供給して形成する方法が
好ましく採用される。このような方法としては、スパッ
タリング法、ＣＶＤ法、蒸着法、及び溶射法などが挙げ
られる。また、液相から活物質薄膜を堆積して形成する
方法としては、電解めっき法や、無電解めっき法などが
挙げられる。In the present invention, the active material thin film is formed by depositing on a metal foil. As a method of depositing and forming the active material thin film, a method of supplying and forming a raw material from a gas phase is preferably adopted. Examples of such a method include a sputtering method, a CVD method, a vapor deposition method, and a thermal spraying method. Examples of a method of depositing and forming an active material thin film from a liquid phase include an electrolytic plating method and an electroless plating method.
【０００９】本発明における活物質薄膜は、リチウムを
吸蔵・放出する活物質からなる薄膜である。活物質薄膜
としては、リチウムと合金化することによりリチウムを
吸蔵する活物質薄膜が好ましく用いられる。このような
活物質薄膜を形成する材料としては、例えば、シリコ
ン、ゲルマニウム、錫、鉛、亜鉛、マグネシウム、ナト
リウム、アルミニウム、ガリウム、インジウムなどが挙
げられる。The active material thin film according to the present invention is a thin film made of an active material that absorbs and releases lithium. As the active material thin film, an active material thin film that occludes lithium by being alloyed with lithium is preferably used. Examples of a material for forming such an active material thin film include silicon, germanium, tin, lead, zinc, magnesium, sodium, aluminum, gallium, and indium.
【００１０】上記の気相からの薄膜形成方法により薄膜
として形成し易いという観点からは、シリコンまたはゲ
ルマニウムを主成分とする活物質が好ましい。また、高
い充放電容量の観点からは、シリコンを主成分とする活
物質が特に好ましい。また、活物質薄膜は、非晶質薄膜
または微結晶薄膜であることが好ましい。従って、活物
質薄膜としては、非晶質シリコン薄膜または微結晶シリ
コン薄膜が好ましく用いられる。非晶質シリコン薄膜
は、ラマン分光分析において結晶領域に対応する５２０
ｃｍ-1近傍のピークが実質的に検出されない薄膜であ
り、微結晶シリコン薄膜は、ラマン分光分析において、
結晶領域に対応する５２０ｃｍ-1近傍のピークと、非晶
質領域に対応する４８０ｃｍ-1近傍のピークの両方が実
質的に検出される薄膜である。また、非晶質ゲルマニウ
ム薄膜、微結晶ゲルマニウム薄膜、非晶質シリコンゲル
マニウム合金薄膜、及び微結晶シリコンゲルマニウム合
金薄膜も好ましく用いることができる。An active material containing silicon or germanium as a main component is preferable from the viewpoint that it is easy to form a thin film by the above-described method for forming a thin film from a gas phase. From the viewpoint of high charge / discharge capacity, an active material containing silicon as a main component is particularly preferable. Further, the active material thin film is preferably an amorphous thin film or a microcrystalline thin film. Therefore, an amorphous silicon thin film or a microcrystalline silicon thin film is preferably used as the active material thin film. The amorphous silicon thin film has a thickness of 520 corresponding to a crystalline region in Raman spectroscopy.
cm- 1 is a thin film in which a peak is not substantially detected, and the microcrystalline silicon thin film is analyzed by Raman spectroscopy.
This is a thin film in which both a peak near 520 cm -1 corresponding to a crystalline region and a peak near 480 cm -1 corresponding to an amorphous region are substantially detected. Further, an amorphous germanium thin film, a microcrystalline germanium thin film, an amorphous silicon germanium alloy thin film, and a microcrystalline silicon germanium alloy thin film can also be preferably used.
【００１１】本発明において集電体として用いる金属箔
は、リチウム二次電池用電極の集電体として用いること
ができるものであれば特に限定されるものではないが、
リチウムと合金化しない金属からなるものであることが
好ましい。このような金属箔としては、例えば、銅、
鉄、ニッケル、タンタル、モリブデン、タングステンま
たはこれらの金属を含む合金からなる金属箔が挙げられ
る。The metal foil used as a current collector in the present invention is not particularly limited as long as it can be used as a current collector of a lithium secondary battery electrode.
It is preferably made of a metal that does not alloy with lithium. As such a metal foil, for example, copper,
A metal foil made of iron, nickel, tantalum, molybdenum, tungsten, or an alloy containing these metals is used.
【００１２】本発明においては、金属箔の表面に対して
微粒子を噴射して衝突させることにより、金属箔の表面
を粗面化する。金属箔の表面に噴射する微粒子は、金属
箔よりも固い材質からなる微粒子が一般に用いられる。
このような微粒子としては、アルミナ、炭化珪素、ガラ
ス、スチール、ステンレス、亜鉛、銅などからなる微粒
子が用いられる。In the present invention, the surface of the metal foil is roughened by spraying and colliding fine particles against the surface of the metal foil. As the fine particles sprayed on the surface of the metal foil, fine particles made of a material harder than the metal foil are generally used.
As such fine particles, fine particles made of alumina, silicon carbide, glass, steel, stainless steel, zinc, copper, or the like are used.
【００１３】金属箔表面の粗面化の度合いは、表面に対
して噴射する微粒子の種類、大きさ、噴射量、噴射圧力
などによって制御することができる。また、一般には、
微粒子が噴射されている領域に金属箔を供給し通過させ
ることにより金属箔表面に微粒子を衝突させるが、この
時の金属箔の送り速度によっても粗面化の度合いを制御
することができる。The degree of surface roughening of the metal foil surface can be controlled by the type, size, spray amount, spray pressure, etc. of the fine particles sprayed on the surface. Also, in general,
The fine particles collide with the surface of the metal foil by supplying and passing the metal foil through the region where the fine particles are sprayed. The degree of surface roughening can also be controlled by the feeding speed of the metal foil at this time.
【００１４】微粒子の大きさとしては、例えば、♯２０
０〜♯２０００のグレードのもの、すなわち最大粒径が
１０μｍ〜１５０μｍのものを用いることができる。本
発明において金属箔の表面は、例えばその表面粗さＲａ
が０．１μｍ以上となるように粗面化されることが好ま
しい。さらに好ましくは０．１５μｍ以上、さらに好ま
しくは０．２μｍ以上の表面粗さＲａとなるように粗面
化されることが好ましい。表面粗さＲａは日本工業規格
（ＪＩＳ Ｂ ０６０１−１９９４）に定められてお
り、表面粗さ計や走査型プローブ顕微鏡（ＳＰＭ）など
により測定することができる。The size of the fine particles is, for example, $ 20
Grades of 0 to $ 2000, that is, those having a maximum particle size of 10 m to 150 m can be used. In the present invention, the surface of the metal foil has, for example, its surface roughness Ra.
Is preferably roughened so as to be 0.1 μm or more. The surface is preferably roughened to have a surface roughness Ra of preferably 0.15 μm or more, more preferably 0.2 μm or more. The surface roughness Ra is defined in Japanese Industrial Standards (JIS B 0601-1994) and can be measured by a surface roughness meter, a scanning probe microscope (SPM), or the like.
【００１５】金属箔の表面には、表面酸化膜が形成され
ている場合があり、活物質薄膜を堆積する前に、表面酸
化膜を除去しておくことが好ましい場合がある。本発明
では、金属箔の表面に対して微粒子を衝突させて粗面化
しているので、このような粗面化処理の際に、金属箔表
面の表面酸化膜を除去することができる。また、金属箔
の表面に防錆処理が施されて防錆処理層が存在する場合
にも、このような防錆処理層を粗面化処理の際に除去す
ることができる。In some cases, a surface oxide film is formed on the surface of the metal foil. In some cases, it is preferable to remove the surface oxide film before depositing the active material thin film. In the present invention, the surface of the metal foil is roughened by colliding the fine particles against the surface of the metal foil, so that the surface oxide film on the surface of the metal foil can be removed during such a roughening treatment. Further, even when the surface of the metal foil is subjected to a rust prevention treatment and a rust prevention treatment layer is present, such a rust prevention treatment layer can be removed during the surface roughening treatment.
【００１６】本発明においては、金属箔の粗面化した表
面上に中間層を形成し、該中間層の上に活物質薄膜を形
成してもよい。活物質薄膜中に集電体成分が拡散して固
溶体を形成することにより、集電体と活物質薄膜との密
着性が向上し、充放電サイクルが向上することがわかっ
ている。このような観点からは、活物質薄膜中に拡散し
て固溶体を形成する成分を含有する中間層を設けること
が好ましい。活物質薄膜としてシリコン薄膜を形成する
場合、シリコン薄膜中に拡散して固溶体を形成しやすい
成分である銅（Ｃｕ）を含む中間層を形成することが好
ましい。In the present invention, an intermediate layer may be formed on the roughened surface of the metal foil, and an active material thin film may be formed on the intermediate layer. It has been found that when the current collector component is diffused into the active material thin film to form a solid solution, the adhesion between the current collector and the active material thin film is improved, and the charge and discharge cycle is improved. From such a viewpoint, it is preferable to provide an intermediate layer containing a component that diffuses into the active material thin film to form a solid solution. When a silicon thin film is formed as the active material thin film, it is preferable to form an intermediate layer containing copper (Cu), which is a component that easily diffuses into the silicon thin film to form a solid solution.
【００１７】本発明によれば、粗面化した金属箔の表面
上に活物質薄膜を堆積して形成する。金属箔表面が粗面
化されているので、活物質薄膜と金属箔表面との接触面
積が大きくなり、活物質薄膜の金属箔に対する密着性を
向上させることができる。このため、充放電反応によ
り、活物質薄膜が膨張収縮しても、その応力によって活
物質薄膜が集電体から剥離するのを防止することができ
る。According to the present invention, an active material thin film is deposited and formed on the surface of a roughened metal foil. Since the metal foil surface is roughened, the contact area between the active material thin film and the metal foil surface is increased, and the adhesion of the active material thin film to the metal foil can be improved. For this reason, even if the active material thin film expands and contracts due to the charge / discharge reaction, the active material thin film can be prevented from peeling off from the current collector due to the stress.
【００１８】また、粗面化した金属箔の表面上に活物質
薄膜を堆積して形成すると、金属箔表面の凹凸に対応し
た凹凸が活物質薄膜の表面に形成されることがわかって
いる。また、表面に凹凸が形成された活物質薄膜は、充
放電反応により膨張収縮する際、凹凸の谷部を起点とす
る切れ目が厚み方向に形成されることがわかっており、
この切れ目によって、活物質薄膜が膨張収縮する際の応
力が緩和され、この結果として良好な充放電サイクル特
性を示すことがわかっている。It is also known that when an active material thin film is deposited and formed on the surface of a roughened metal foil, irregularities corresponding to the irregularities on the surface of the metal foil are formed on the surface of the active material thin film. Further, it is known that when the active material thin film having irregularities formed on the surface expands and contracts due to a charge-discharge reaction, a cut starting from a valley of the irregularities is formed in the thickness direction,
It has been found that the cuts reduce the stress when the active material thin film expands and contracts, and as a result, show good charge / discharge cycle characteristics.
【００１９】また、本発明によれば、微粒子を噴射して
衝突させることにより金属箔の表面を粗面化しているの
で、微粒子の種類や大きさ、噴射量や噴射圧力などを調
整することにより、金属箔表面の粗面化の度合いを自由
に制御することができる。また、種々の材質の金属箔に
対して適用することができる。さらには、粗面化の工程
がドライ工程であるので、製造工程が複雑化することな
く、金属箔の表面を粗面化することができる。Further, according to the present invention, the surface of the metal foil is roughened by injecting and colliding the fine particles, so that the type and size of the fine particles, the injection amount and the injection pressure are adjusted. The degree of surface roughening of the metal foil surface can be freely controlled. Further, the present invention can be applied to metal foils of various materials. Furthermore, since the roughening step is a dry step, the surface of the metal foil can be roughened without complicating the manufacturing process.
【００２０】[0020]
【発明の実施の形態】以下、本発明を実施例に基づいて
さらに詳細に説明するが、本発明は以下の実施例に何ら
限定されるものではなく、その要旨を変更しない範囲に
おいて適宜変更して実施することが可能なものである。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described below in more detail with reference to examples. However, the present invention is not limited to the following examples, and may be appropriately modified within the scope of the invention. It can be implemented by
【００２１】（実施例１） ［ブラスト加工による粗面化処理］圧延ステンレス箔
（表面粗さＲａ＝０．０２５μｍ）をステンレス板に貼
りつけて固定し、このステンレス箔の表面に微粒子を噴
射して衝突させブラスト加工を施した。衝突させる微粒
子としては、♯３２０（最大粒径８０μｍ）のアルミナ
材を用いた。噴射量は３２０ｇ／分、噴射圧力は０．２
５ＭＰａとした。微粒子を噴射するノズルを左右方向に
往復運動させながら微粒子を噴射し、これに対して垂直
方向からステンレス箔を送り出しノズル噴射領域を通過
させることによりブラスト加工を施した。ノズルの送り
速度は５０ｍｍ／秒とし、ステンレス箔の送り速度は
０．６ｍｍ／秒とした。上記のブラスト加工により表面
を粗面化した圧延ステンレス箔の表面粗さＲａは０．３
２μｍであった。(Example 1) [Roughening treatment by blasting] A rolled stainless steel foil (surface roughness Ra = 0.025 µm) is attached and fixed to a stainless steel plate, and fine particles are sprayed on the surface of the stainless steel foil. And blasted. As the fine particles to be collided, an alumina material having a size of # 320 (maximum particle size: 80 μm) was used. The injection amount is 320 g / min and the injection pressure is 0.2
It was 5 MPa. Blasting was performed by injecting the fine particles while reciprocating the nozzle for injecting the fine particles in the left-right direction, sending out the stainless steel foil from the perpendicular direction, and passing the stainless steel foil through the nozzle injection area. The feed speed of the nozzle was 50 mm / sec, and the feed speed of the stainless steel foil was 0.6 mm / sec. The surface roughness Ra of the rolled stainless steel foil whose surface has been roughened by the blast processing is 0.3
It was 2 μm.
【００２２】［シリコン薄膜の形成］上記のようにして
粗面化した圧延ステンレス箔の表面上に、ＲＦスパッタ
リング法により非晶質シリコン薄膜を形成した。単結晶
シリコン（Ｐ型、１Ωｃｍ以下）をターゲットとして用
い、ステンレス箔をステンレス板に貼りつけて固定した
状態で、真空チャンバー内部に入れ、真空チャンバー内
部を１×１０-3Ｐａ以下になるまで真空引きした後、ア
ルゴンガスを導入口から圧力が０．５Ｐａになるまで導
入し、ＲＦパワー密度：３Ｗ／ｃｍ2、ターゲット−基
板間距離：１０ｃｍの条件でスパッタリングして、厚み
６μｍの非晶質シリコン薄膜を形成した。[Formation of Silicon Thin Film] An amorphous silicon thin film was formed on the surface of the rolled stainless steel foil roughened as described above by RF sputtering. Using single-crystal silicon (P type, 1 Ωcm or less) as a target, a stainless steel foil is stuck on a stainless steel plate and fixed, and then placed in a vacuum chamber, and the inside of the vacuum chamber is evacuated until the pressure becomes 1 × 10 −3 Pa or less. After pulling, argon gas was introduced from the inlet until the pressure became 0.5 Pa, and sputtered under the conditions of RF power density: 3 W / cm 2 , target-substrate distance: 10 cm, and a 6 μm-thick amorphous A silicon thin film was formed.
【００２３】［負極の作製］以上のようにしてシリコン
薄膜を形成したステンレス箔を用い、シリコン薄膜が形
成されていないステンレス箔の上に負極タブを取り付け
て負極とした。[Preparation of Negative Electrode] A stainless steel foil on which a silicon thin film was formed as described above was used, and a negative electrode tab was attached on a stainless steel foil on which no silicon thin film was formed to form a negative electrode.
【００２４】［正極の作製］ＬｉＣｏＯ2粉末９０重量
部、及び導電剤としての人造黒鉛粉末５重量部を、結着
剤としてのポリフッ化ビニリデンを５重量部含む５重量
％のＮ−メチルピロリドン水溶液に混合し、正極合剤ス
ラリーとした。このスラリーをドクターブレード法によ
り、正極集電体であるアルミニウム箔（厚み２０μｍ）
の上に塗布した後乾燥し、正極活物質層を形成した。正
極活物質を塗布しなかったアルミニウム箔の領域の上に
正極タブを取り付け、正極とした。[Preparation of Positive Electrode] A 5% by weight aqueous solution of N-methylpyrrolidone containing 90 parts by weight of LiCoO 2 powder, 5 parts by weight of artificial graphite powder as a conductive agent, and 5 parts by weight of polyvinylidene fluoride as a binder To obtain a positive electrode mixture slurry. This slurry was subjected to a doctor blade method to form an aluminum foil (thickness: 20 μm) as a positive electrode current collector.
And then dried to form a positive electrode active material layer. A positive electrode tab was attached on the area of the aluminum foil where the positive electrode active material was not applied, to obtain a positive electrode.
【００２５】［電池の作製］以上のようにして作製した
正極及び負極を用いて、図１に示すようなリチウム二次
電池を作製した。図１に示すように、正極１１と負極１
２の間にセパレータ１３を配置し、さらに正極１１の上
にセパレータ１３を配置した状態で、これを巻き付け扁
平状態にした後、外装体１０内に挿入した。次に外装体
１０内に電解液を注入し、注入後外装体１０の開口部１
０ａを封口して、リチウム二次電池を完成した。電解液
としては、エチレンカーボネートとジエチルカーボネー
トとの体積比１：１の混合溶媒にＬｉＰＦ6を１モル／
リットル溶解させたものを用いた。[Preparation of Battery] Using the positive electrode and negative electrode prepared as described above, a lithium secondary battery as shown in FIG. 1 was prepared. As shown in FIG. 1, the positive electrode 11 and the negative electrode 1
The separator 13 was disposed between the two, and the separator 13 was disposed on the positive electrode 11. The separator 13 was wound into a flat state, and then inserted into the exterior body 10. Next, an electrolytic solution is injected into the outer package 10, and after the injection, the opening 1 of the outer package 10 is formed.
0a was sealed to complete a lithium secondary battery. As an electrolytic solution, LiPF 6 was added to a mixed solvent of ethylene carbonate and diethyl carbonate at a volume ratio of 1: 1 by 1 mol / mol.
One liter dissolved was used.
【００２６】（比較例）集電体として、ブラスト加工し
ていない、すなわち粗面化処理していない圧延ステンレ
ス箔をそのまま使用する以外は、上記実施例と同様にし
て、その上にシリコン薄膜を形成し負極を作製した。こ
の負極を用いて上記と同様にしてリチウム二次電池を作
製した。なお、圧延ステンレス箔の表面粗さＲａは０．
０２５μｍであった。Comparative Example A silicon thin film was formed thereon in the same manner as in the above example, except that a rolled stainless steel foil that had not been blasted, ie, had not been subjected to surface roughening, was used as a current collector. The negative electrode was formed. Using this negative electrode, a lithium secondary battery was produced in the same manner as described above. In addition, the surface roughness Ra of the rolled stainless steel foil was 0.1.
It was 025 μm.
【００２７】（電池の初期放電容量の評価）上記のよう
に作製した各リチウム二次電池について、初期の放電容
量を測定した。充放電の条件は、充放電ともに１４０ｍ
Ａの定電流で、４．２Ｖとなるまで充電した後、２．７
５Ｖとなるまで放電し、これを初期の充放電とした。各
リチウム二次電池の初期の放電容量を表１に示す。(Evaluation of Initial Discharge Capacity of Battery) The initial discharge capacity of each lithium secondary battery prepared as described above was measured. The charging and discharging conditions are 140 m for both charging and discharging.
After charging at 4.2 A with the constant current of A, 2.7
Discharge was performed until the voltage reached 5 V, which was used as initial charge and discharge. Table 1 shows the initial discharge capacity of each lithium secondary battery.
【００２８】[0028]
【表１】 [Table 1]
【００２９】表１に示すように、比較例の電池において
は、集電体から薄膜が剥離したため放電容量を測定する
ことができなかった。これに対し、実施例の電池におい
ては、高い放電容量が得られている。As shown in Table 1, in the battery of the comparative example, the discharge capacity could not be measured because the thin film was separated from the current collector. On the other hand, in the batteries of the examples, a high discharge capacity was obtained.
【００３０】以上のことから、本発明に従い、ブラスト
加工を施し金属箔の表面を粗面化した後、粗面化した表
面上に活物質薄膜を堆積させることにより、集電体であ
る金属箔と活物質薄膜との密着性を向上させ得ることが
わかる。From the above, according to the present invention, after the surface of the metal foil is roughened by blasting, an active material thin film is deposited on the roughened surface to obtain a metal foil as a current collector. It can be seen that the adhesion between the film and the active material thin film can be improved.
【００３１】[0031]
【発明の効果】本発明によれば、集電体と活物質薄膜と
の密着性が良好なリチウム二次電池用電極とすることが
できる。According to the present invention, an electrode for a lithium secondary battery having good adhesion between the current collector and the active material thin film can be obtained.
【図１】本発明の実施例で作製したリチウム二次電池を
示す分解斜視図。FIG. 1 is an exploded perspective view showing a lithium secondary battery manufactured in an example of the present invention.
１０…外装体 １１…正極 １２…負極 １３…セパレータ DESCRIPTION OF SYMBOLS 10 ... Outer body 11 ... Positive electrode 12 ... Negative electrode 13 ... Separator
───────────────────────────────────────────────────── フロントページの続き (72)発明者 中野 真吾 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内 Ｆターム(参考） 5H017 AA03 BB00 CC01 DD01 EE01 EE04 HH03 5H029 AJ05 AK03 AL11 AM03 AM05 AM07 BJ02 BJ14 CJ24 CJ25 DJ07 DJ14 DJ18 EJ01 HJ05 5H050 AA07 BA17 CA08 CB11 DA03 DA04 DA06 FA05 FA15 FA20 GA24 GA25 HA05 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Shingo Nakano 2-5-5 Keihanhondori, Moriguchi-shi, Osaka F-term in Sanyo Electric Co., Ltd. 5H017 AA03 BB00 CC01 DD01 EE01 EE04 HH03 5H029 AJ05 AK03 AL11 AM03 AM05 AM07 BJ02 BJ14 CJ24 CJ25 DJ07 DJ14 DJ18 EJ01 HJ05 5H050 AA07 BA17 CA08 CB11 DA03 DA04 DA06 FA05 FA15 FA20 GA24 GA25 HA05
Claims (4)
ウムを吸蔵・放出する活物質薄膜を堆積して形成するリ
チウム二次電池用電極の製造方法において、前記金属箔
の表面に対して微粒子を噴射して衝突させることによ
り、前記金属箔の表面を粗面化し、粗面化した表面上に
前記活物質薄膜を堆積させることを特徴とするリチウム
二次電池用電極の製造方法。1. A method for manufacturing an electrode for a lithium secondary battery, comprising forming an active material thin film for absorbing and releasing lithium on a metal foil used as a current collector. A method for manufacturing an electrode for a lithium secondary battery, characterized in that the surface of the metal foil is roughened by injecting and colliding fine particles, and the active material thin film is deposited on the roughened surface.
ル、モリブデン、タングステンまたはこれらの金属を含
む合金から形成されていることを特徴とする請求項１に
記載のリチウム二次電池用電極の製造方法。2. The electrode for a lithium secondary battery according to claim 1, wherein the metal foil is formed of copper, iron, nickel, tantalum, molybdenum, tungsten, or an alloy containing these metals. Production method.
０μｍであることを特徴とする請求項１または２に記載
のリチウム二次電池用電極の製造方法。3. The maximum particle size of the fine particles is 10 μm to 15 μm.
The method for producing an electrode for a lithium secondary battery according to claim 1, wherein the thickness is 0 μm.
膜、微結晶シリコン薄膜、非晶質ゲルマニウム薄膜、微
結晶ゲルマニウム薄膜、非晶質シリコンゲルマニウム合
金薄膜、または微結晶シリコンゲルマニウム合金薄膜で
あることを特徴とする請求項１〜３のいずれか１項に記
載のリチウム二次電池用電極の製造方法。4. The active material thin film is an amorphous silicon thin film, a microcrystalline silicon thin film, an amorphous germanium thin film, a microcrystalline germanium thin film, an amorphous silicon germanium alloy thin film, or a microcrystalline silicon germanium alloy thin film. The method for producing an electrode for a lithium secondary battery according to any one of claims 1 to 3, wherein:
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001008692A JP2002216747A (en) | 2001-01-17 | 2001-01-17 | Manufacturing method of electrode for lithium secondary battery |
| US09/995,863 US6815003B2 (en) | 2000-12-01 | 2001-11-29 | Method for fabricating electrode for lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001008692A JP2002216747A (en) | 2001-01-17 | 2001-01-17 | Manufacturing method of electrode for lithium secondary battery |
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|---|---|
| JP2002216747A true JP2002216747A (en) | 2002-08-02 |
Family
ID=18876273
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001008692A Withdrawn JP2002216747A (en) | 2000-12-01 | 2001-01-17 | Manufacturing method of electrode for lithium secondary battery |
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| Country | Link |
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| JP (1) | JP2002216747A (en) |
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| JP2006156330A (en) * | 2004-11-02 | 2006-06-15 | Sanyo Electric Co Ltd | Lithium secondary battery and method of manufacturing the same |
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