JP2002170554A - Method for manufacturing electrode of lithium secondary battery - Google Patents
Method for manufacturing electrode of lithium secondary batteryInfo
- Publication number
- JP2002170554A JP2002170554A JP2000366876A JP2000366876A JP2002170554A JP 2002170554 A JP2002170554 A JP 2002170554A JP 2000366876 A JP2000366876 A JP 2000366876A JP 2000366876 A JP2000366876 A JP 2000366876A JP 2002170554 A JP2002170554 A JP 2002170554A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- electrode
- secondary battery
- lithium secondary
- active material
- 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.)
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Links
Classifications
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- 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
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Cell Electrode Carriers And Collectors (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用いたリチウム二次電池用電極であ
って、充放電容量が高く、かつ充放電サイクル特性に優
れた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 an electrode for a lithium secondary battery using such an active material thin film such as a silicon thin film, which has a high charge / discharge capacity and excellent charge / discharge cycle characteristics. It is to provide a method of manufacturing an electrode for use.
【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、金属箔の表面をウェットエッチング処理し
て粗面化し、粗面化した表面上に活物質薄膜を堆積する
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 surface of the metal foil is roughened by wet etching, 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、例えばニッケル
箔や銅箔などが挙げられる。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. Examples of such a metal foil include a nickel foil and a copper foil.
【００１２】本発明においては、金属箔の表面をウェッ
トエッチング処理して粗面化し、粗面化した表面上に活
物質薄膜を堆積する。ウェットエッチング処理すること
により、金属箔表面の表面粗さＲａを好ましくは１００
ｎｍ（０．１μｍ）以上、さらに好ましくは１５０ｎｍ
（０．１５μｍ）以上、さらに好ましくは２００ｎｍ
（０．２μｍ）以上にする。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。In the present invention, the surface of the metal foil is roughened by wet etching, and an active material thin film is deposited on the roughened surface. The surface roughness Ra of the metal foil surface is preferably set to 100
nm (0.1 μm) or more, more preferably 150 nm
(0.15 μm) or more, more preferably 200 nm
(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.
【００１３】ウェットエッチング処理に用いるエッチン
グ液としては、対象となる金属箔表面をエッチングでき
るものであれば特に限定されるものではないが、例え
ば、塩酸系エッチング液が用いられる。The etchant used for the wet etching process is not particularly limited as long as it can etch the surface of the target metal foil. For example, a hydrochloric acid-based etchant is used.
【００１４】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、充放電サイクル特性が向上することがわ
かっている。このような観点からは、金属箔が、活物質
薄膜中に拡散して固溶体を形成する成分を含有しない場
合、金属箔の上に、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。
ニッケル（Ｎｉ）は、シリコン（Ｓｉ）と固溶体を形成
しにくいので、金属箔としてニッケル箔を用い、活物質
薄膜としてシリコン薄膜を形成する場合、ニッケル箔の
上に銅層からなる中間層を形成し、この上にシリコン薄
膜を形成することが好ましい。銅（Ｃｕ）は、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。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 / discharge cycle characteristics are improved. From such a viewpoint, when the metal foil does not contain a component that diffuses into the active material thin film to form a solid solution, the metal foil contains a component that diffuses into the active material thin film to form a solid solution. It is preferable to provide an intermediate layer.
Since nickel (Ni) does not easily form a solid solution with silicon (Si), when a nickel foil is used as a metal foil and a silicon thin film is formed as an active material thin film, an intermediate layer made of a copper layer is formed on the nickel foil. Preferably, a silicon thin film is formed thereon. Copper (Cu) is a component that easily diffuses into a silicon thin film to form a solid solution.
【００１５】本発明によれば、ウェットエッチング処理
により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 metal foil roughened by wet etching. 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.
【００１６】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.
【００１７】[0017]
【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
【００１８】（実験１） 〔ウェットエッチング処理〕圧延ニッケル箔（厚み１５
μｍ）の表面をウェットエッチング処理した。エッチン
グ液としては、厚膜用Ｎｉエッチング液（塩酸系エッチ
ング液 メック株式会社製）を用いて、処理温度２５℃
で、２分間エッチング液中に浸漬しエッチング処理し
た。エッチング量としては片面約０．６μｍとした。そ
の後、水洗し水切りした後、７％塩酸水溶液中に２５℃
で３０秒間浸漬して酸洗い処理を行った。次に、水洗し
た後乾燥させて用いた。(Experiment 1) [Wet etching treatment] Rolled nickel foil (thickness: 15)
μm) was wet-etched. As the etching solution, a Ni etching solution for thick film (hydrochloric acid-based etching solution manufactured by Mec Co., Ltd.) was used at a processing temperature of 25 ° C.
Then, the substrate was immersed in an etching solution for 2 minutes to perform an etching process. The etching amount was about 0.6 μm on one side. Then, after washing with water and draining, 25 ° C. in a 7% hydrochloric acid aqueous solution.
For 30 seconds to perform pickling. Next, it was used after washing with water and drying.
【００１９】〔集電体の表面粗さＲａの測定〕集電体と
しては、ウェットエッチング処理した圧延ニッケル箔、
ウェットエッチング処理していない圧延ニッケル箔、及
び市販の電解ニッケル箔（厚み２０μｍ）を用いた。[Measurement of surface roughness Ra of current collector] Rolled nickel foil subjected to wet etching treatment,
A rolled nickel foil not subjected to wet etching treatment and a commercially available electrolytic nickel foil (thickness: 20 μm) were used.
【００２０】上記各金属箔の表面を、走査型プローブ顕
微鏡（ＳＰＭ）により観察した。図１は、ウェットエッ
チング処理した圧延ニッケル箔の表面状態を示すＳＰＭ
像である。図２は、ウェットエッチング処理していない
圧延ニッケル箔の表面状態を示すＳＰＭ像である。図３
は、電解ニッケル箔の表面状態を示すＳＰＭ像である。The surface of each of the above metal foils was observed with a scanning probe microscope (SPM). FIG. 1 is an SPM showing a surface state of a rolled nickel foil subjected to a wet etching process.
It is a statue. FIG. 2 is an SPM image showing a surface state of a rolled nickel foil that has not been subjected to wet etching. FIG.
Is an SPM image showing the surface state of the electrolytic nickel foil.
【００２１】図１と図２の比較から明らかなように、ウ
ェットエッチング処理することにより、圧延ニッケル箔
の表面に凹凸が形成され、粗面化されていることがわか
る。また、図３から明らかなように、電解ニッケル箔の
表面も、ウェットエッチング処理された圧延ニッケル箔
の表面と同様に凹凸が形成されていることがわかる。As is clear from the comparison between FIG. 1 and FIG. 2, it can be understood that the wet etching treatment forms irregularities on the surface of the rolled nickel foil and roughens the surface. In addition, as is apparent from FIG. 3, the surface of the electrolytic nickel foil is also formed with irregularities similarly to the surface of the wet-etched rolled nickel foil.
【００２２】ＳＰＭを用いて表面粗さＲａを測定したと
ころ、図１に示すウェットエッチング処理された圧延ニ
ッケル箔の表面粗さＲａは２００ｎｍ（０．２μｍ）で
あり、図２に示すウェットエッチング処理されていない
圧延ニッケル箔の表面粗さＲａは３０ｎｍ（０．０３μ
ｍ）であり、図３に示す電解ニッケル箔の表面粗さＲａ
は２００ｎｍ（０．２μｍ）であることがわかった。When the surface roughness Ra was measured using the SPM, the surface roughness Ra of the rolled nickel foil subjected to the wet etching treatment shown in FIG. 1 was 200 nm (0.2 μm), and the wet etching treatment shown in FIG. The surface roughness Ra of the unrolled rolled nickel foil is 30 nm (0.03 μm).
m) and the surface roughness Ra of the electrolytic nickel foil shown in FIG.
Was found to be 200 nm (0.2 μm).
【００２３】〔銅層の形成〕各集電体の上に中間層とし
ての銅層を形成した後、その上にシリコン薄膜を形成し
た。[Formation of Copper Layer] After forming a copper layer as an intermediate layer on each current collector, a silicon thin film was formed thereon.
【００２４】銅層はスパッタリング法により形成した。
薄膜形成条件は、投入電力２００Ｗ、アルゴン（Ａｒ）
ガス流量６０ｓｃｃｍ、薄膜形成の際の圧力０．１Ｐａ
とした。ターゲットとしては直径２インチのものを用
い、電力密度が１５Ｗ／ｃｍ2となるようにした。チャ
ンバー内の初期の圧力は１×１０-4Ｐａ以下となるよう
に減圧し、２０ｎｍ／分の速度で薄膜を形成した。銅層
の厚みは約０．５μｍであった。The copper layer was formed by a sputtering method.
The conditions for forming the thin film are as follows: input power 200 W, argon (Ar)
Gas flow rate 60sccm, pressure 0.1Pa for thin film formation
And A target having a diameter of 2 inches was used, and the power density was set to 15 W / cm 2 . The initial pressure in the chamber was reduced to 1 × 10 −4 Pa or less, and a thin film was formed at a rate of 20 nm / min. The thickness of the copper layer was about 0.5 μm.
【００２５】〔シリコン薄膜の形成〕スパッタリング法
により、銅層の上にシリコン薄膜を形成した。薄膜形成
条件としては、投入電力３５０Ｗ、アルゴン（Ａｒ）ガ
ス流量１００ｓｃｃｍ、薄膜形成の際のチャンバー内圧
力０．１Ｐａとなるようにした。ターゲットとしては、
直径４インチのものを用い、電力密度が４．３Ｗ／ｃｍ
2 となるようにした。また、初期のチャンバー内圧力
は、１×１０-4Ｐａ以下となるように排気した。４５ｎ
ｍ／分の成膜速度で、厚み約５μｍの非晶質シリコン薄
膜を形成した。[Formation of Silicon Thin Film] A silicon thin film was formed on a copper layer by a sputtering method. The conditions for forming the thin film were such that the input power was 350 W, the flow rate of argon (Ar) gas was 100 sccm, and the pressure in the chamber at the time of forming the thin film was 0.1 Pa. As a target,
Power density of 4.3 W / cm using 4 inch diameter
It was set to 2 . The chamber was evacuated to an initial pressure of 1 × 10 −4 Pa or less. 45n
An amorphous silicon thin film having a thickness of about 5 μm was formed at a film forming rate of m / min.
【００２６】シリコン薄膜形成後の状態を観察したとこ
ろ、ウェットエッチング処理していない圧延ニッケル箔
を用いたものは、シリコン薄膜が金属箔から剥離した状
態であった。これに対し、ウェットエッチング処理した
圧延ニッケル箔を用いたもの及び電解ニッケル箔を用い
たものでは、シリコン薄膜が金属箔に対し良好に密着し
ていた。そこで、ウェットエッチング処理した圧延ニッ
ケル箔を用いた電極、及び電解ニッケル箔を用いた電極
について、それぞれ以下のようにして充放電特性を評価
した。Observation of the state after the formation of the silicon thin film showed that the silicon thin film peeled off from the metal foil in the case of using the rolled nickel foil which was not subjected to the wet etching treatment. In contrast, in the case of using the rolled nickel foil subjected to the wet etching treatment and the case of using the electrolytic nickel foil, the silicon thin film was in good contact with the metal foil. Then, the charge and discharge characteristics of the electrode using the rolled nickel foil and the electrode using the electrolytic nickel foil subjected to the wet etching were evaluated as follows.
【００２７】〔単極セルによる充放電特性の評価〕上記
各電極を作用極として用い、図４に示すようなビーカー
セルを作製した。図４に示すように、ビーカーセルは、
容器１内に入れられた電解液中に、対極３、作用極４、
及び参照極５を浸漬することにより構成されている。電
解液は、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
ットル溶解させて作製した。対極３及び参照極５として
はリチウム金属を用いた。[Evaluation of Charging / Discharging Characteristics Using Single Electrode Cell] A beaker cell as shown in FIG. 4 was prepared using each of the above electrodes as a working electrode. As shown in FIG. 4, the beaker cell is:
A counter electrode 3, a working electrode 4,
And the reference electrode 5 is immersed. The electrolyte was prepared by dissolving LiPF 6 at a mole ratio of 1: 1 in a mixed solvent of ethylene carbonate and diethyl carbonate at a volume ratio of 1: 1. As the counter electrode 3 and the reference electrode 5, lithium metal was used.
【００２８】作製したビーカーセルを、それぞれ２５℃
にて１ｍＡで０Ｖ（ｖｓ．Ｌｉ／Ｌｉ+ ）まで定電流充
電を行い、その後２Ｖ（ｖｓ．Ｌｉ／Ｌｉ+ ）まで定電
流放電を行い、これを１サイクルとして、１０サイクル
まで充放電を行って、以下の式に定義される容量残存率
を求めた。結果を表１に示す。なお、ここでは、作用極
の還元を充電とし、作用極の酸化を放電としている。Each of the prepared beaker cells was heated at 25 ° C.
At a constant current of 0 mA (vs. Li / Li + ) at 1 mA and then discharge at a constant current of 2 V (vs. Li / Li + ). Thus, the remaining capacity ratio defined by the following equation was determined. Table 1 shows the results. Here, the reduction of the working electrode is defined as charging, and the oxidation of the working electrode is defined as discharging.
【００２９】容量残存率（％）＝（１０サイクル目の放
電容量／１サイクル目の放電容量）×１００Residual capacity (%) = (discharge capacity at 10th cycle / discharge capacity at 1st cycle) × 100
【００３０】[0030]
【表１】 [Table 1]
【００３１】表１に示す結果から明らかなように、本発
明に従いウェットエッチング処理した圧延ニッケル箔を
集電体として用いた電極は、電解ニッケル箔と同程度あ
るいはそれ以上に良好な充放電サイクル特性を示してい
る。As is evident from the results shown in Table 1, the electrode using the rolled nickel foil wet-etched according to the present invention as a current collector had good charge / discharge cycle characteristics comparable to or better than the electrolytic nickel foil. Is shown.
【００３２】〔リチウム二次電池による充放電特性の評
価〕ウェットエッチング処理圧延ニッケル箔を用いた上
記電極を負極として用い、リチウム二次電池を作製し
た。[Evaluation of Charge / Discharge Characteristics by Lithium Secondary Battery] A lithium secondary battery was manufactured using the above-mentioned electrode using a wet-etched rolled nickel foil as a negative electrode.
【００３３】正極は以下のようにして作製した。ＬｉＣ
ｏＯ2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テトラフルオロエチ
レンを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１８μｍ）の上に塗布した後乾燥し、正
極活物質を形成した。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、正極を完
成した。The positive electrode was manufactured as follows. LiC
90 parts by weight of oO 2 powder and 5 parts by weight of artificial graphite powder as a conductive agent were mixed with a 5% by weight aqueous solution of N-methylpyrrolidone containing 5 parts by weight of polytetrafluoroethylene as a binder, and a positive electrode mixture was prepared. A slurry was obtained. The slurry was applied on an aluminum foil (thickness: 18 μm) as a positive electrode current collector by a doctor blade method and then dried to form a positive electrode active material. A positive electrode tab was attached on the area of the aluminum foil where the positive electrode active material was not applied, to complete the positive electrode.
【００３４】負極については、シリコン薄膜が形成され
ていない領域の上に負極タブを取り付け負極を完成し
た。以上のようにして得られた正極及び負極を用いて、
図５に示すようなリチウム二次電池を作製した。With respect to the negative electrode, a negative electrode tab was attached on a region where the silicon thin film was not formed to complete the negative electrode. Using the positive electrode and the negative electrode obtained as described above,
A lithium secondary battery as shown in FIG. 5 was manufactured.
【００３５】図５に示すように、正極１１と負極１２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
内に上記の単極セルと同様の電解液を注入し、注入後外
装体１０の開口部１０ａを封口して、リチウム二次電池
を完成した。As shown in FIG. 5, a separator 13 is disposed between the positive electrode 11 and the negative electrode 12, and the separator 13 is disposed on the positive electrode 11. The separator 13 is wound and flattened. Inserted in. Next, the exterior body 10
The same electrolytic solution as in the above-mentioned monopolar cell was injected into the inside, and after the injection, the opening 10a of the exterior body 10 was sealed to complete a lithium secondary battery.
【００３６】比較として、天然黒鉛を活物質として用い
た負極を作製した。具体的には、天然黒鉛粉末９５重量
部と結着剤としてのポリテトラフルオロエチレン５重量
部を含む５重量％のＮ−メチルピロリドン水溶液を作製
し、負極合剤スラリーとし、これをウェットエッチング
処理していない圧延ニッケル箔の上に銅層を形成した集
電体の上に塗布した後乾燥し、負極とした。この負極を
用いた以外は、上記と同様にして図５に示すリチウム二
次電池を作製した。For comparison, a negative electrode using natural graphite as an active material was prepared. Specifically, a 5% by weight aqueous solution of N-methylpyrrolidone containing 95 parts by weight of natural graphite powder and 5 parts by weight of polytetrafluoroethylene as a binder was prepared, and a negative electrode mixture slurry was prepared, and this was subjected to wet etching treatment. It was applied on a current collector in which a copper layer was formed on an unrolled rolled nickel foil and then dried to obtain a negative electrode. A lithium secondary battery shown in FIG. 5 was produced in the same manner as above except for using this negative electrode.
【００３７】上記のようにして作製した各リチウム二次
電池について、充放電サイクル試験を行った。充放電の
条件は、充放電ともに１ｍＡ／ｃｍ2 で、４．２Ｖとな
るまで充電した後、２．７５Ｖとなるまで放電し、これ
を１サイクルの充放電として、１０サイクルまで充放電
を行った。１０サイクル目の放電容量及び１０サイクル
目までの平均放電電圧、並びに二次電池の体積エネルギ
ー密度及び重量エネルギー密度を表２に示す。Each of the lithium secondary batteries produced as described above was subjected to a charge / discharge cycle test. The charging and discharging conditions are as follows: charging and discharging are performed at 1 mA / cm 2 until the voltage reaches 4.2 V, and then discharging is performed until the voltage reaches 2.75 V; Was. Table 2 shows the discharge capacity at the 10th cycle, the average discharge voltage up to the 10th cycle, and the volume energy density and weight energy density of the secondary battery.
【００３８】[0038]
【表２】 [Table 2]
【００３９】表２に示すように、本発明に従い製造され
るリチウム二次電池用電極は、従来のカーボンを活物質
とした電極に比べ高い放電容量を有しており、また体積
エネルギー密度及び重量エネルギー密度が高いリチウム
二次電池とすることができるものである。As shown in Table 2, the electrode for a lithium secondary battery manufactured according to the present invention has a higher discharge capacity than a conventional electrode using carbon as an active material, and has a higher volume energy density and weight. A lithium secondary battery having a high energy density can be obtained.
【００４０】[0040]
【発明の効果】本発明によれば、放電容量が高く、かつ
充放電サイクル特性に優れたリチウム二次電池用電極を
製造することができる。According to the present invention, an electrode for a lithium secondary battery having a high discharge capacity and excellent charge / discharge cycle characteristics can be manufactured.
【図１】ウェットエッチング処理した圧延ニッケル箔表
面のＳＰＭ像を示す図。FIG. 1 is a view showing an SPM image of a rolled nickel foil surface subjected to a wet etching process.
【図２】ウェットエッチング処理していない圧延ニッケ
ル箔表面のＳＰＭ像を示す図。FIG. 2 is a diagram showing an SPM image of a rolled nickel foil surface that has not been subjected to wet etching.
【図３】電解ニッケル箔表面のＳＰＭ像を示す図。FIG. 3 is a view showing an SPM image of the surface of an electrolytic nickel foil.
【図４】本発明の実施例で作製した単極セルを示す模式
図。FIG. 4 is a schematic view showing a monopolar cell manufactured in an example of the present invention.
【図５】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. 5 is an exploded perspective view showing a lithium secondary battery manufactured in an example of the present invention.
１…容器 ２…電解液 ３…対極 ４…作用極 ５…参照極 １０…外装体 １１…正極 １２…負極 １３…セパレータ DESCRIPTION OF SYMBOLS 1 ... Container 2 ... Electrolyte 3 ... Counter electrode 4 ... Working electrode 5 ... Reference electrode 10 ... Outer body 11 ... Positive electrode 12 ... Negative electrode 13 ... Separator
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 5H017 AA03 AS01 AS02 BB06 BB16 CC01 DD01 EE04 HH03 HH05 5H029 AJ03 AJ05 AK03 AL12 AM03 AM05 AM07 BJ04 BJ14 CJ03 CJ14 CJ25 DJ07 DJ17 DJ18 EJ01 HJ04 HJ12 5H050 AA07 AA08 BA16 CA08 CB12 DA03 DA04 DA06 DA09 EA04 FA05 FA19 FA20 GA03 GA15 GA25 HA04 HA12 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 5H017 AA03 AS01 AS02 BB06 BB16 CC01 DD01 EE04 HH03 HH05 5H029 AJ03 AJ05 AK03 AL12 AM03 AM05 AM07 BJ04 BJ14 CJ03 CJ14 CJ25 DJ07 DJ17 DJ18 EJ01 HJ04 HJ12 A08BAB DAA DA06 DA09 EA04 FA05 FA19 FA20 GA03 GA15 GA25 HA04 HA12
Claims (9)
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、 前記金属箔の表面をウェットエッチング処理して粗面化
し、粗面化した表面上に前記活物質薄膜を堆積すること
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, wherein the surface of the metal foil is wet-etched. A method for producing an electrode for a lithium secondary battery, comprising: treating and roughening a surface; and depositing the active material thin film on the roughened surface.
金属箔表面の表面粗さＲａを１００ｎｍ以上にすること
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 method for producing an electrode for a lithium secondary battery according to claim 1, wherein the surface roughness Ra of the surface of the metal foil is adjusted to 100 nm or more by the wet etching treatment.
エッチング液を用いたエッチング処理であることを特徴
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 method for manufacturing an electrode for a lithium secondary battery according to claim 1, wherein the wet etching process is an etching process using a hydrochloric acid-based etchant.
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 method for producing an electrode for a lithium secondary battery according to claim 1, wherein the metal foil is a nickel foil.
ことを特徴とする請求項４に記載のリチウム二次電池用
電極の製造方法。5. The method for producing an electrode for a lithium secondary battery according to claim 4, wherein the nickel foil is a rolled nickel foil.
を形成し、該中間層の上に前記活物質薄膜を形成するこ
とを特徴とする請求項１〜５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。6. The metal foil according to claim 1, wherein an intermediate layer is formed on the roughened surface of the metal foil, and the active material thin film is formed on the intermediate layer. 3. The method for producing an electrode for a lithium secondary battery according to item 1.
る成分を含有することを特徴とする請求項６に記載のリ
チウム二次電池用電極の製造方法。7. The method for producing an electrode for a lithium secondary battery according to claim 6, wherein the intermediate layer contains a component that diffuses into the active material thin film.
る請求項６または７に記載のリチウム二次電池用電極の
製造方法。8. The method for producing an electrode for a lithium secondary battery according to claim 6, wherein the intermediate layer is a copper layer.
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１〜８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。9. 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 8, wherein:
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| CN117276476A (en) * | 2022-06-14 | 2023-12-22 | 广东小天才科技有限公司 | Intermediate structure and preparation method thereof, lithium secondary battery electrode and preparation method thereof |
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