JP2003017040A - Electrode for lithium secondary battery, and manufacturing method thereof - Google Patents
Electrode for lithium secondary battery, and manufacturing method thereofInfo
- Publication number
- JP2003017040A JP2003017040A JP2001196638A JP2001196638A JP2003017040A JP 2003017040 A JP2003017040 A JP 2003017040A JP 2001196638 A JP2001196638 A JP 2001196638A JP 2001196638 A JP2001196638 A JP 2001196638A JP 2003017040 A JP2003017040 A JP 2003017040A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- active material
- material thin
- current collector
- electrode
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、リチウム二次電池
用電極の製造方法及びリチウム二次電池用電極に関する
ものである。TECHNICAL FIELD The present invention relates to a method for manufacturing an electrode for a lithium secondary battery and an 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, lithium secondary batteries, which have been actively researched and developed, have a charging / discharging voltage depending on an electrode used.
Battery characteristics such as charge / discharge cycle life characteristics and storage characteristics are greatly affected. Therefore, the battery characteristics are 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。When lithium metal is used as the negative electrode active material, a battery having a high energy density per weight and volume can be constructed, but there is a problem that lithium is deposited in dendrite form during charging and causes an internal short circuit. It 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, a lithium secondary battery using aluminum, silicon, tin, or the like, which is electrochemically alloyed with lithium during charging, as an electrode has been reported (So.
lidState Ionics, 113-115, p57 (1998)). Of these, silicon is particularly promising as a negative electrode for a battery having a large theoretical capacity and a high capacity, and various secondary batteries using this as a negative electrode have been proposed (JP-A-10-255768).
Issue). 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, becomes fine powder due to charge and discharge and deteriorates current collecting characteristics.
【０００５】[0005]
【発明が解決しようとする課題】本出願人は、シリコン
等を電極活物質とし、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
晶薄膜または非晶質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１１−３０１６４６号な
ど）。The applicant of the present invention uses a thin film forming method such as a CVD method or a sputtering method as an electrode for a lithium secondary battery which uses silicon or the like as an electrode active material and exhibits good charge / discharge cycle characteristics. An electrode for a lithium secondary battery in which a microcrystalline thin film or an amorphous thin film is formed on a current collector has been proposed (Japanese Patent Application No. 11-301646, etc.).
【０００６】このようなリチウム二次電池用電極におい
ては、集電体の成分が活物質薄膜に拡散することによ
り、集電体と活物質薄膜との密着性が保たれ、充放電サ
イクル特性が向上することがわかっている。In such an electrode for a lithium secondary battery, the components of the current collector are diffused into the active material thin film, so that the adhesion between the current collector and the active material thin film is maintained and the charge / discharge cycle characteristics are improved. I know it will improve.
【０００７】しかしながら、このようなリチウム二次電
池用電極においては、活物質薄膜と集電体との密着性が
良好であるため、充放電によって活物質が膨張・収縮
し、これに伴い集電体が延びることによってしわなどの
変形が電極に発生する場合があった。特に銅箔などの延
性に富んだ金属箔を集電体として用いた場合、電極の変
形の度合いが大きくなる。電極が変形すると、これを収
納する電池内において体積が増加するため、電池の体積
当りのエネルギー密度が低下し、問題となる。However, in such an electrode for a lithium secondary battery, since the adhesion between the active material thin film and the current collector is good, the active material expands and contracts due to charge and discharge, and accordingly the current collection occurs. When the body extends, deformation such as wrinkles may occur in the electrodes. In particular, when a metal foil having a high ductility such as a copper foil is used as the current collector, the degree of deformation of the electrode increases. When the electrode is deformed, the volume in the battery accommodating the electrode is increased, and the energy density per volume of the battery is reduced, which is a problem.
【０００８】本発明の目的は、充放電容量が高く、充放
電サイクル特性に優れたリチウム二次電池用電極であっ
て、充放電に伴う活物質薄膜の膨張により集電体に変形
やしわが発生するのを抑制することができるリチウム二
次電池用電極の製造方法及びリチウム二次電池用電極並
びにこれを用いたリチウム二次電池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 having a high charge / discharge capacity and excellent charge / discharge cycle characteristics, wherein the active material thin film expands due to charge / discharge and the current collector is deformed or wrinkles. An object of the present invention is to provide a method for manufacturing an electrode for a lithium secondary battery that can suppress the generation, an electrode for a lithium secondary battery, and a lithium secondary battery using the same.
【０００９】[0009]
【課題を解決するための手段】本発明の第１の局面に従
うリチウム二次電池用電極の製造方法は、リチウムを吸
蔵・放出する活物質薄膜を集電体上に堆積して形成する
工程と、エッチングにより活物質薄膜の厚み方向に空隙
を形成し、活物質薄膜を微小領域に分割する工程とを備
えることを特徴としている。A method for manufacturing an electrode for a lithium secondary battery according to a first aspect of the present invention comprises a step of depositing and forming an active material thin film that absorbs and releases lithium on a current collector. A step of forming voids in the thickness direction of the active material thin film by etching and dividing the active material thin film into minute regions.
【００１０】第１の局面では、エッチングにより活物質
薄膜の厚み方向に空隙を形成し、活物質薄膜を微小領域
に分割している。このため、活物質薄膜の微小領域の周
囲には、充放電反応前において、すでに空隙が形成され
ている。従って、初回の充放電反応の際の活物質薄膜の
膨張を、その周囲の空隙により吸収することができ、初
回の充放電反応に伴う活物質薄膜の膨張による応力の発
生を緩和することができる。このため、充放電反応の際
に集電体に変形やしわが発生するのを抑制することがで
きる。In the first aspect, voids are formed in the thickness direction of the active material thin film by etching to divide the active material thin film into minute regions. Therefore, voids have already been formed around the minute region of the active material thin film before the charge / discharge reaction. Therefore, the expansion of the active material thin film during the initial charge / discharge reaction can be absorbed by the voids around the active material thin film, and the generation of stress due to the expansion of the active material thin film accompanying the initial charge / discharge reaction can be relieved. . Therefore, it is possible to prevent the current collector from being deformed or wrinkled during the charge / discharge reaction.
【００１１】本発明に従う第１の局面においては、厚み
方向に延びる低密度領域が活物質薄膜に形成されてお
り、該低密度領域におけるエッチング速度が他の領域に
おけるエッチング速度よりも速いことを利用して、上記
エッチングがなされることが好ましい。このような低密
度領域は、表面に凹凸が形成された集電体の上に活物質
薄膜をＣＶＤ法やスパッタリング法などにより堆積して
形成する場合に形成されることがわかっている。集電体
表面の凹凸の谷部においては、その両側の凸部の斜面上
に薄膜が堆積して成長し、その成長部分が集電体表面の
凹凸の谷部の上方で出会うため、このような低密度領域
が形成されるものと思われる。従って、このような低密
度領域は、集電体表面の凹凸の谷部の上方に延びるよう
に形成され、この結果、集電体表面の凹凸の谷部と活物
質薄膜表面の凹凸の谷部を結ぶ領域に形成される。In the first aspect of the present invention, it is utilized that the low density region extending in the thickness direction is formed in the active material thin film, and that the etching rate in the low density region is higher than the etching rate in other regions. Then, the above etching is preferably performed. It is known that such a low-density region is formed when an active material thin film is deposited by a CVD method, a sputtering method, or the like on a current collector having an uneven surface. In the valleys of the irregularities on the surface of the current collector, a thin film is deposited and grown on the slopes of the convexes on both sides of the valleys, and the grown portions meet above the valleys of the irregularities on the surface of the current collector. It seems that a very low density region is formed. Therefore, such a low-density region is formed so as to extend above the valleys of the unevenness on the surface of the current collector, and as a result, the valleys of the unevenness on the surface of the current collector and the valleys of the unevenness on the surface of the active material thin film are formed. It is formed in the area connecting the.
【００１２】このような低密度領域においては、薄膜の
密度が低いため、エッチング速度が、他の領域に比べ速
くなる。このため、低密度領域において選択的にエッチ
ングを進行させることができる。低密度領域は、厚み方
向に延びるように形成されているので、このような低密
度領域をエッチングすることにより、厚み方向に空隙を
形成し、活物質薄膜を微小領域に分割することができ
る。In such a low density region, since the thin film has a low density, the etching rate becomes faster than in other regions. Therefore, the etching can be selectively advanced in the low density region. Since the low density region is formed so as to extend in the thickness direction, by etching such a low density region, a void can be formed in the thickness direction and the active material thin film can be divided into minute regions.
【００１３】活物質薄膜に対するエッチングとしては、
化学的反応によるエッチングが好ましいが、物理的エッ
チングであってもよい。また、エッチャントを用いた湿
式エッチング（ウェットエッチング）であることが好ま
しいが、ＣＦ4によるエッチングや、プラズマエッチン
グ、反応性イオンエッチングなどのような乾式エッチン
グ（ドライエッチング）であってもよい。As the etching for the active material thin film,
Etching by a chemical reaction is preferable, but physical etching may be used. In addition, wet etching using an etchant is preferable, but dry etching such as etching with CF 4 , plasma etching, or reactive ion etching may be used.
【００１４】本発明において活物質薄膜に用いられる材
料は、リチウムを吸蔵・放出す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
化することによりリチウムを吸蔵する材料が好ましく用
いられる。このような材料としては、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、カリウム、インジウム及びこれらの合金な
どが挙げられる。これらの中でも、シリコン、ゲルマニ
ウム、シリコンゲルマニウムが特に好ましく用いられ
る。また、シリコン、ゲルマニウム、またはシリコンゲ
ルマニウムの非晶質もしくは微結晶薄膜が好ましく用い
られる。The material used for the active material thin film in the present invention is not particularly limited as long as it can absorb and release lithium, but a material that absorbs lithium by alloying with lithium. Is preferably used. Examples of such a material include silicon, germanium, tin, lead, zinc, magnesium, sodium, aluminum, potassium, indium and alloys thereof. Among these, silicon, germanium, and silicon germanium are particularly preferably used. Further, silicon, germanium, or an amorphous or microcrystalline thin film of silicon germanium is preferably used.
【００１５】本発明において活物質薄膜を堆積して形成
する方法としては、気相または液相から集電体の上に原
子またはイオンを移動し堆積するような方法が好ましく
用いられる。具体的には、ＣＶＤ法、スパッタリング
法、蒸着法、溶射法、またはめっき法などが挙げられ
る。As a method for depositing and forming an active material thin film in the present invention, a method of moving and depositing atoms or ions from a gas phase or a liquid phase onto a current collector is preferably used. Specifically, a CVD method, a sputtering method, a vapor deposition method, a thermal spraying method, a plating method, or the like can be given.
【００１６】本発明において用いられる集電体は、リチ
ウムと合金化しない金属から形成されていることが好ま
しく、このような材料としては、銅、銅を含む合金、ニ
ッケル、ステンレスなどが挙げられる。集電体の少なく
とも表面部分は、銅または銅を主体とする合金から形成
されていることが好ましい。集電体の表面部分を銅また
は銅を主体とする合金から形成することにより、活物質
薄膜が、シリコンまたはゲルマニウムを含む薄膜である
場合、活物質薄膜中に集電体成分である銅を拡散させる
ことができ、集電体と活物質薄膜との密着性を高めるこ
とができる。The current collector used in the present invention is preferably made of a metal that does not alloy with lithium. Examples of such a material include copper, alloys containing copper, nickel, stainless steel and the like. At least the surface portion of the current collector is preferably formed of copper or an alloy mainly containing copper. When the active material thin film is a thin film containing silicon or germanium, the current collector component copper is diffused in the active material thin film by forming the surface part of the current collector from copper or an alloy mainly composed of copper. It is possible to enhance the adhesion between the current collector and the active material thin film.
【００１７】活物質薄膜のエッチングは、上記のように
して集電体上に活物質薄膜を形成した後、行うことがで
きる。湿式エッチング（ウェットエッチング）によりエ
ッチングする場合、エッチャントを含むエッチング液中
に、集電体上に形成した活物質薄膜を浸漬することによ
り行うことができる。活物質薄膜が、例えば、シリコ
ン、ゲルマニウム、及びシリコンゲルマニウムなどであ
る場合、水酸化ナトリウム水溶液、水酸化カリウム水溶
液、及びアンモニア水溶液などをエッチング液として用
いることができる。必要に応じて、加熱したエッチング
液中に浸漬して、エッチングを行うことができる。エッ
チングの量は、エッチング液の種類や濃度、エッチング
液の温度、エッチングの時間などにより適宜制御するこ
とができる。The etching of the active material thin film can be performed after forming the active material thin film on the current collector as described above. When etching is performed by wet etching, it can be performed by immersing the active material thin film formed on the current collector in an etchant containing an etchant. When the active material thin film is, for example, silicon, germanium, silicon germanium, or the like, an aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide, an aqueous solution of ammonia, or the like can be used as the etching solution. If necessary, etching can be performed by immersing in a heated etching solution. The amount of etching can be appropriately controlled by the type and concentration of the etching solution, the temperature of the etching solution, the etching time, and the like.
【００１８】本発明の第２の局面に従うリチウム二次電
池用電極の製造方法は、リチウムを吸蔵・放出する活物
質薄膜であって、厚み方向に形成された空隙によって微
小領域に分割された活物質薄膜を集電体上に設ける工程
と、空隙が形成された上記活物質薄膜をマスクとして集
電体表面をエッチングすることにより、活物質薄膜の空
隙に対応した溝を集電体に形成する工程とを備えること
を特徴としている。A method for manufacturing an electrode for a lithium secondary battery according to a second aspect of the present invention is an active material thin film that absorbs and releases lithium, and is divided into minute regions by voids formed in the thickness direction. Forming a groove corresponding to the void of the active material thin film on the current collector by providing a thin film of the substance on the current collector and etching the surface of the current collector with the active material thin film in which the void is formed as a mask And a process.
【００１９】第２の局面においては、厚み方向に形成さ
れた空隙によって微小領域に分割された活物質薄膜をマ
スクとして、集電体の表面をエッチングすることによ
り、活物質薄膜の空隙に対応した溝を集電体表面に形成
する。活物質薄膜の微小領域の周りには、空隙が形成さ
れており、該空隙の下方の集電体表面には溝が形成れて
いる。このため、充放電に伴う活物質薄膜の膨張・収縮
を微小領域の周りに形成されている空隙により吸収する
ことができ、活物質薄膜の膨張・収縮による応力を低減
することができる。さらには、活物質薄膜の微小領域の
周囲の集電体の表面に溝が形成されているため、活物質
薄膜の膨張により集電体にかかる応力を、この集電体の
溝の部分で緩和することができる。従って、充放電に伴
う活物質薄膜の膨張により集電体に変形やしわが発生す
るのを抑制することができる。In the second aspect, the surface of the current collector is etched by using the thin film of the active material divided into minute regions by the voids formed in the thickness direction as a mask so as to correspond to the voids of the active material thin film. Grooves are formed on the surface of the current collector. A void is formed around a minute region of the active material thin film, and a groove is formed on the surface of the current collector below the void. Therefore, the expansion / contraction of the active material thin film due to charge / discharge can be absorbed by the voids formed around the minute region, and the stress due to the expansion / contraction of the active material thin film can be reduced. Furthermore, since the groove is formed on the surface of the current collector around the minute region of the active material thin film, the stress applied to the current collector due to the expansion of the active material thin film is relieved at the groove of the current collector. can do. Therefore, it is possible to prevent the current collector from being deformed or wrinkled due to the expansion of the active material thin film due to charge and discharge.
【００２０】第２の局面においては、活物質薄膜の微小
領域の周りに空隙が形成されており、さらに、活物質薄
膜の微小領域の周りの集電体の表面にも溝が形成されて
いる。このため、第１の局面よりもさらに集電体の変形
やしわの発生をより有効に抑制することができる。In the second aspect, voids are formed around the minute regions of the active material thin film, and further, grooves are formed on the surface of the current collector around the minute regions of the active material thin film. . Therefore, the deformation and wrinkling of the current collector can be suppressed more effectively than in the first aspect.
【００２１】第２の局面において、集電体に対するエッ
チングは、化学的反応によるエッチングであることが好
ましいが、物理的エッチングであってもよい。また、湿
式エッチング（ウェットエッチング）であることが好ま
しいが、乾式エッチング（ドライエッチング）であって
もよい。In the second aspect, the etching of the current collector is preferably etching by a chemical reaction, but may be physical etching. Further, although wet etching is preferable, dry etching may be used.
【００２２】ウェットエッチングに用いるエッチャント
としては、活物質薄膜よりも速い速度で集電体をエッチ
ングするものが好ましく用いられる。活物質薄膜とし
て、シリコン、ゲルマニウム、またはシリコンゲルマニ
ウムを用い、集電体として銅等を用いる場合には、エッ
チャントとしては、塩化第２鉄、塩化第２銅、過硫酸ア
ンモニウムなどが好ましく用いられる。As the etchant used in the wet etching, one that etches the current collector at a faster rate than the active material thin film is preferably used. When silicon, germanium, or silicon germanium is used as the active material thin film and copper or the like is used as the current collector, ferric chloride, cupric chloride, ammonium persulfate, or the like is preferably used as the etchant.
【００２３】第２の局面において、空隙を形成された活
物質薄膜を集電体上に設ける工程は、活物質薄膜を集電
体上に堆積して形成する工程と、エッチングにより活物
質薄膜に空隙を形成する工程とからなるものでもよい。
すなわち、厚み方向に空隙を形成することにより活物質
薄膜を微小領域に分割する第１の局面の工程であっても
よい。この場合、第１の局面と同様に、活物質薄膜の厚
み方向に形成された低密度領域に沿ってエッチングがな
され、厚み方向に空隙が形成されてもよい。In the second aspect, the step of providing the active material thin film on which the voids are formed on the current collector includes the step of depositing the active material thin film on the current collector and forming the active material thin film by etching. And a step of forming voids.
That is, it may be the step of the first aspect in which the active material thin film is divided into minute regions by forming voids in the thickness direction. In this case, similar to the first aspect, etching may be performed along the low-density region formed in the thickness direction of the active material thin film to form voids in the thickness direction.
【００２４】また、この場合、第１の局面と同様の方法
により活物質薄膜をエッチングすることができる。活物
質薄膜及び集電体は、第１の局面と同様の材質のものを
用いることができる。In this case, the active material thin film can be etched by the same method as in the first aspect. The active material thin film and the current collector can be made of the same material as in the first aspect.
【００２５】本発明の第３の局面に従うリチウム二次電
池用電極は、リチウムを吸蔵・放出する活物質薄膜を集
電体上に堆積して形成したリチウム二次電池用電極であ
り、活物質薄膜が厚み方向に形成された空隙によって微
小領域に分割されており、かつ集電体表面に活物質薄膜
の空隙に対応した溝が形成されていることを特徴として
いる。An electrode for a lithium secondary battery according to the third aspect of the present invention is an electrode for a lithium secondary battery, which is formed by depositing an active material thin film that absorbs and releases lithium on a current collector. The thin film is divided into minute regions by voids formed in the thickness direction, and a groove corresponding to the voids of the active material thin film is formed on the surface of the current collector.
【００２６】第３の局面に従うリチウム二次電池用電極
は、上記第２の局面に従う製造方法により製造すること
ができる電極であるが、上記第２の局面の方法により製
造された電極に限定されるものではない。The lithium secondary battery electrode according to the third aspect is an electrode that can be produced by the production method according to the second aspect, but is not limited to the electrode produced by the method according to the second aspect. Not something.
【００２７】第３の局面のリチウム二次電池用電極にお
いては、第２の局面の方法により製造されたリチウム二
次電池用電極と同様に、活物質薄膜が厚み方向に形成さ
れた空隙によって微小領域に分割されている。従って、
活物質薄膜の微小領域の周囲には空隙が存在しており、
充放電に伴う活物質薄膜の膨張を吸収することができる
ので、応力の発生を抑制することができる。また、活物
質薄膜の微小領域の周囲の集電体の表面には溝が形成さ
れているので、充放電に伴う活物質薄膜の膨張により集
電体に応力がかかっても、この応力を活物質薄膜の微小
領域の周囲の集電体の溝部分で吸収することができる。
従って、集電体に変形やしわが発生するのを抑制するこ
とができる。In the lithium secondary battery electrode of the third aspect, as in the lithium secondary battery electrode manufactured by the method of the second aspect, the active material thin film is minute by the voids formed in the thickness direction. It is divided into areas. Therefore,
There are voids around the minute area of the active material thin film,
Since the expansion of the active material thin film due to charge / discharge can be absorbed, it is possible to suppress the generation of stress. Further, since a groove is formed on the surface of the current collector around the minute region of the active material thin film, even if stress is applied to the current collector due to expansion of the active material thin film due to charge / discharge, this stress is not activated. It can be absorbed in the groove portion of the current collector around the minute region of the material thin film.
Therefore, it is possible to prevent the current collector from being deformed or wrinkled.
【００２８】第３の局面において用いられる活物質薄膜
及び集電体の材質としては、上記第１の局面及び第２の
局面と同様の材質のものを用いることができる。集電体
の表面粗さＲａは、０．０１μｍ以上であることが好ま
しく、さらに好ましくは０．１μｍ以上である。好まし
くは０．０１〜２μｍの範囲内であり、さらに好ましく
は０．１〜２μｍの範囲内である。As the material of the active material thin film and the current collector used in the third aspect, the same materials as those in the first aspect and the second aspect can be used. The surface roughness Ra of the current collector is preferably 0.01 μm or more, more preferably 0.1 μm or more. It is preferably in the range of 0.01 to 2 μm, and more preferably in the range of 0.1 to 2 μm.
【００２９】本発明における薄膜には、予めリチウムが
吸蔵または添加されていてもよい。リチウムは、薄膜を
形成する際に添加してもよい。すなわち、リチウムを含
有する薄膜を形成することにより、薄膜にリチウムを添
加してもよい。また、薄膜を形成した後に、薄膜にリチ
ウムを吸蔵または添加させてもよい。薄膜にリチウムを
吸蔵または添加させる方法としては、電気化学的にリチ
ウムを吸蔵または添加させる方法が挙げられる。Lithium may be occluded or added to the thin film of the present invention in advance. Lithium may be added when forming a thin film. That is, lithium may be added to the thin film by forming a thin film containing lithium. Further, after forming the thin film, lithium may be occluded or added to the thin film. Examples of a method of occluding or adding lithium to the thin film include a method of electrochemically occluding or adding lithium.
【００３０】本発明のリチウム二次電池は、上記本発明
の第１の局面または第２の局面の方法により製造された
電極または上記本発明の第３の局面に従う電極からなる
負極と、正極と、非水電解質とを備えることを特徴とし
ている。The lithium secondary battery of the present invention comprises a negative electrode composed of the electrode manufactured by the method of the first aspect or the second aspect of the present invention or the electrode according to the third aspect of the present invention, and a positive electrode. , A non-aqueous electrolyte.
【００３１】本発明のリチウム二次電池に用いる電解質
の溶媒は、特に限定されるものではないが、エチレンカ
ーボネート、プロピレンカーボネート、ブチレンカーボ
ネート、ビニレンカーボネートなどの環状カーボネート
と、ジメチルカーボネート、メチルエチルカーボネー
ト、ジエチルカーボネートなどの鎖状カーボネートとの
混合溶媒が例示される。また、前記環状カーボネートと
１，２−ジメトキシエタン、１，２−ジエトキシエタン
などのエーテル系溶媒や、γ−ブチロラクトン、スルホ
ラン、酢酸メチル等の鎖状エステル等との混合溶媒も例
示される。また、電解質の溶質としては、ＬｉＰＦ6、
ＬｉＢＦ4、ＬｉＣＦ3ＳＯ3、ＬｉＮ（ＣＦ 3ＳＯ2）2、
ＬｉＮ（Ｃ2Ｆ5ＳＯ2）2、ＬｉＮ（ＣＦ3ＳＯ2）（Ｃ4
Ｆ9ＳＯ2）、ＬｉＣ（ＣＦ3ＳＯ2）3、ＬｉＣ（Ｃ2Ｆ5
ＳＯ2）3、ＬｉＡｓＦ6、ＬｉＣｌＯ4、Ｌｉ2Ｂ10Ｃｌ
10、Ｌｉ2Ｂ12Ｃｌ12など及びそれらの混合物が例示さ
れる。さらに電解質として、ポリエチレンオキシド、ポ
リアクリロニトリル、ポリフッ化ビニリデンなどのポリ
マー電解質に電解液を含浸したゲル状ポリマー電解質
や、ＬｉＩ、Ｌｉ3Ｎなどの無機固体電解質が例示され
る。本発明のリチウム二次電池の電解質は、イオン導電
性を発現させる溶質としてのＬｉ化合物とこれを溶解・
保持する溶媒が電池の充電時や放電時あるいは保存時の
電圧で分解しない限り、制約なく用いることができる。Electrolyte used in the lithium secondary battery of the present invention
The solvent is not particularly limited, but is not limited to ethylene
Carbonate, propylene carbonate, butylene carbo
Cyclic carbonates such as nate and vinylene carbonate
And dimethyl carbonate, methyl ethyl carbonate
And chain carbonates such as diethyl carbonate
A mixed solvent is exemplified. Further, with the cyclic carbonate
1,2-dimethoxyethane, 1,2-diethoxyethane
Ether solvents such as γ-butyrolactone, sulfo
Examples of mixed solvents with chain esters such as orchid and methyl acetate
Shown. The solute of the electrolyte is LiPF6,
LiBFFour, LiCF3SO3, LiN (CF 3SO2)2,
LiN (C2FFiveSO2)2, LiN (CF3SO2) (CFour
F9SO2), LiC (CF3SO2)3, LiC (C2FFive
SO2)3, LiAsF6, LiClOFour, Li2BTenCl
Ten, Li2B12Cl12And mixtures thereof are exemplified.
Be done. Furthermore, as an electrolyte, polyethylene oxide,
Polyacrylonitrile, poly (vinylidene fluoride), etc.
Gel-like polymer electrolytes obtained by impregnating a mer electrolyte with an electrolytic solution
, LiI, Li3An inorganic solid electrolyte such as N is exemplified.
It The electrolyte of the lithium secondary battery of the present invention has an ionic conductivity.
Li compound as a solute that develops properties and dissolves it
The solvent that holds the battery is used when the battery is charged, discharged, or stored.
As long as it is not decomposed by voltage, it can be used without restriction.
【００３２】本発明のリチウム二次電池の正極活物質と
しては、ＬｉＣｏＯ2、ＬｉＮｉＯ2、ＬｉＭｎ2Ｏ4、Ｌ
ｉＭｎＯ2、ＬｉＣｏ0.5Ｎｉ0.5Ｏ2、ＬｉＮｉ0.7Ｃｏ
0.2Ｍｎ0.1Ｏ2などのリチウム含有遷移金属酸化物や、
ＭｎＯ2などのリチウムを含有していない金属酸化物が
例示される。また、この他にも、リチウムを電気化学的
に挿入・脱離する物質であれば、制限なく用いることが
できる。Examples of the positive electrode active material of the lithium secondary battery of the present invention include LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , and L.
iMnO 2 , LiCo 0.5 Ni 0.5 O 2 , LiNi 0.7 Co
Lithium-containing transition metal oxides such as 0.2 Mn 0.1 O 2 ,
Examples include metal oxides that do not contain lithium, such as MnO 2 . In addition to this, any substance that electrochemically inserts / desorbs lithium can be used without limitation.
【００３３】[0033]
【発明の実施の形態】図１は、本発明の第１の局面に従
う製造工程の一例を説明するための断面図である。1 is a sectional view for explaining an example of a manufacturing process according to the first aspect of the present invention.
【００３４】図１（ａ）に示すように、集電体１０の上
に、活物質薄膜１１が堆積して形成されている。集電体
１０の表面１０ａには凹凸が形成されており、この凹凸
に対応して、活物質薄膜１１の表面１１ａにも凹凸が形
成されている。As shown in FIG. 1 (a), an active material thin film 11 is deposited and formed on the current collector 10. Irregularities are formed on the surface 10a of the current collector 10, and irregularities are also formed on the surface 11a of the active material thin film 11 corresponding to the irregularities.
【００３５】集電体表面１０ａの凹凸の谷部１０ｃと、
活物質薄膜表面１１ａの凹凸の谷部１１ｃとを結ぶ領域
に、低密度領域１１ｂが形成されている。低密度領域１
１ｂは、集電体表面１０ａの上に薄膜が堆積される際、
両側の斜面からの成長表面がぶつかり合うことにより形
成される領域である。従って、低密度領域１１ｂは、集
電体表面１０ａの凹凸の谷部１０ｃから上方に厚み方向
に延びるように形成されている。Uneven valleys 10c on the surface 10a of the current collector,
A low-density region 11b is formed in a region connecting to the concave and convex valleys 11c on the active material thin film surface 11a. Low density area 1
1b is, when a thin film is deposited on the current collector surface 10a,
It is a region formed by the growth surfaces from the slopes on both sides colliding with each other. Therefore, the low-density region 11b is formed so as to extend upward in the thickness direction from the concave and convex valleys 10c of the current collector surface 10a.
【００３６】低密度領域１１ｂでは、密度が低いため、
他の領域に比べ、エッチング速度が速くなる。このた
め、低密度領域１１ｂにおいて、選択的にエッチングが
速く進行する。従って、低密度領域１１ｂを選択的にエ
ッチングすることができる。例えば、活物質薄膜１１を
集電体１０とともに、エッチング液中に浸漬させること
により、活物質薄膜１１の低密度領域１１ｂをエッチン
グすることができる。Since the density is low in the low density region 11b,
The etching rate is higher than in other regions. Therefore, in the low density region 11b, the etching selectively and rapidly progresses. Therefore, the low density region 11b can be selectively etched. For example, the low-density region 11b of the active material thin film 11 can be etched by immersing the active material thin film 11 together with the current collector 10 in an etching solution.
【００３７】図１（ｂ）は、このようにして低密度領域
１１ｂをエッチングした後の状態を示す断面図である。
図１（ｂ）に示すように、低密度領域１１ｂを選択的に
エッチングすることにより、厚み方向に空隙１２が形成
され、この空隙１２によって、活物質薄膜１１を微小領
域に分割することができる。活物質薄膜１１の微小領域
の周囲には、空隙１２が存在しているため、充放電によ
り活物質薄膜の微小領域１１が膨張しても、これをその
周囲の空隙１２で吸収することができ、活物質薄膜の膨
張による応力の発生を抑制することができる。従って、
集電体の変形やしわの発生を抑制することができる。FIG. 1B is a sectional view showing a state after the low density region 11b is etched in this way.
As shown in FIG. 1B, by selectively etching the low density region 11b, a void 12 is formed in the thickness direction, and the void 12 can divide the active material thin film 11 into minute regions. . Since the voids 12 exist around the minute regions of the active material thin film 11, even if the minute regions 11 of the active material thin film expand due to charge and discharge, they can be absorbed by the voids 12 around them. The generation of stress due to expansion of the active material thin film can be suppressed. Therefore,
It is possible to suppress deformation of the current collector and generation of wrinkles.
【００３８】特に、本発明によれば、空隙１２を、初回
の充放電の前に、予め形成させておくことができるの
で、初回の充放電の際の活物質薄膜の膨張による集電体
の変形やしわの発生を防止することができる。従来の活
物質薄膜においても、初回の充放電反応以降において、
活物質薄膜の膨張収縮により厚み方向に切れ目が形成さ
れ、微小領域に分割される。しかしながら、集電体の変
形やしわの発生が初回の充放電反応で発生するため、集
電体に変形やしわの発生が認められるものと思われる。
本発明では、初回の充放電前に、すでに空隙が形成され
ているので、初回の充放電の際にも、活物質薄膜の膨張
による応力を緩和することができ、集電体に変形やしわ
が発生するのを抑制することができるものと思われる。In particular, according to the present invention, the void 12 can be formed in advance before the first charge / discharge, so that the current collector is expanded by the expansion of the active material thin film at the first charge / discharge. It is possible to prevent deformation and wrinkles. Even in the conventional active material thin film, after the first charge / discharge reaction,
Due to the expansion and contraction of the active material thin film, a cut is formed in the thickness direction, and the active material thin film is divided into minute regions. However, since the current collector is deformed and wrinkles are generated in the first charge / discharge reaction, it is considered that the current collector is deformed and wrinkled.
In the present invention, since the voids are already formed before the first charge / discharge, the stress due to the expansion of the active material thin film can be relaxed even during the first charge / discharge, and the current collector is deformed. It seems that it is possible to suppress the occurrence of wadding.
【００３９】図２は、本発明の第２の局面に従う製造工
程の一例を説明するための断面図である。図２（ａ）及
び（ｂ）は、図１（ａ）及び（ｂ）と同様であり、活物
質薄膜１１の厚み方向に延びる低密度領域１１ｂをエッ
チングすることにより、空隙１２が形成され、この空隙
１２によって、活物質薄膜１１が微小領域に分割されて
いる。FIG. 2 is a sectional view for explaining an example of a manufacturing process according to the second aspect of the present invention. 2A and 2B are the same as FIGS. 1A and 1B, and the void 12 is formed by etching the low density region 11b extending in the thickness direction of the active material thin film 11, The voids 12 divide the active material thin film 11 into minute regions.
【００４０】第２の局面では、このように空隙１２が形
成された活物質薄膜１１をマスクとして、集電体１０の
表面１０ａをエッチングすることにより、図２（ｃ）に
示すように、集電体１０の表面１０ａに、溝１３を形成
する。溝１３は、空隙１２に対応して形成されている。
すなわち、空隙１２の下方に連通するように形成されて
いる。In the second aspect, the surface 10a of the current collector 10 is etched by using the active material thin film 11 in which the voids 12 are formed as a mask, as shown in FIG. 2 (c). The groove 13 is formed on the surface 10 a of the electric body 10. The groove 13 is formed corresponding to the void 12.
That is, it is formed so as to communicate below the void 12.
【００４１】第２の局面によれば、活物質薄膜１１の微
小領域の周囲に空隙１２が存在しているので、充放電に
伴う活物質薄膜の膨張を吸収することができ、活物質薄
膜の膨張による応力を低減することができる。さらに、
空隙１２の下方の集電体１０の表面１０ａには、溝１３
が形成されている。活物質薄膜１１は、集電体１０の表
面１０ａと密着しているので、活物質薄膜１１が膨張す
ると、集電体１０の表面付近においても、図２（ｃ）に
おいて矢印で示すような応力が働く、本発明の第２の局
面及び第３の局面においては、このような応力を、溝１
３によって吸収することができるので、集電体１０に働
く応力を低減することができ、集電体に変形やしわが発
生するのをさらに抑制することができる。According to the second aspect, since the voids 12 are present around the minute region of the active material thin film 11, the expansion of the active material thin film due to charge / discharge can be absorbed, and the active material thin film The stress due to expansion can be reduced. further,
A groove 13 is formed on the surface 10a of the current collector 10 below the void 12.
Are formed. Since the active material thin film 11 is in close contact with the surface 10a of the current collector 10, when the active material thin film 11 expands, the stress near the surface of the current collector 10 as shown by the arrow in FIG. In the second and third aspects of the present invention in which
Since it can be absorbed by 3, the stress acting on the current collector 10 can be reduced, and it is possible to further prevent the current collector from being deformed or wrinkled.
【００４２】本発明の第１の局面〜第３の局面における
活物質薄膜の微小領域の幅は、０．５〜２００μｍであ
ることが好ましく、さらに好ましくは１〜１００μｍで
ある。この微小領域の幅は、微小領域の水平方向（膜面
方向）の幅である。The width of the minute region of the active material thin film according to the first to third aspects of the present invention is preferably 0.5 to 200 μm, more preferably 1 to 100 μm. The width of this minute region is the width of the minute region in the horizontal direction (film surface direction).
【００４３】また、本発明の第２の局面及び第３の局面
における集電体表面の溝の深さは、２〜５μｍ程度であ
ることが好ましい。また、集電体表面の溝の幅は、０．
１〜５μｍであることが好ましい。The depth of the groove on the surface of the current collector in the second aspect and the third aspect of the present invention is preferably about 2 to 5 μm. The width of the groove on the surface of the current collector was 0.
It is preferably 1 to 5 μm.
【００４４】[0044]
【実施例】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。The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to the following examples, and various modifications may be made without departing from the scope of the invention. Is possible.
【００４５】まず、本発明の第１の局面に従う実施例に
ついて説明する。
（実施例１及び比較例１）
〔負極の作製〕単結晶シリコン（Ｐ型、導電率１Ωｃｍ
以下）をターゲットとして、ＤＣマグネトロンスパッタ
装置により、集電体の上に非晶質シリコン薄膜を堆積し
て形成した。集電体としては、厚み１８μｍの電解銅箔
（表面粗さＲａ＝０．１８８μｍ）を用いた。集電体を
冷却可能な支持基体上に貼り付け、スパッタ装置内部を
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、パワー密度：３Ｗ／ｃｍ2、ターゲット−基板間距
離：１５ｃｍのスパッタリング条件で、厚み１１μｍの
非晶質シリコン薄膜を形成した。First, an embodiment according to the first aspect of the present invention will be described. (Example 1 and Comparative Example 1) [Production of Negative Electrode] Single crystal silicon (P type, conductivity 1 Ωcm)
The following) was used as a target and an amorphous silicon thin film was deposited on the current collector by a DC magnetron sputtering device. As the current collector, an electrolytic copper foil having a thickness of 18 μm (surface roughness Ra = 0.188 μm) was used. The current collector was attached on a coolable support substrate, the interior of the sputtering apparatus was evacuated to 1 × 10 −3 Pa or less, and then argon gas was introduced from the inlet until the pressure reached 0.5 Pa. An amorphous silicon thin film having a thickness of 11 μm was formed under the sputtering conditions of power density: 3 W / cm 2 and target-substrate distance: 15 cm.
【００４６】次に、上記のようにして作製したシリコン
薄膜を水酸化リチウム水溶液によりエッチングした。水
酸化リチウム水溶液は、純水１リットルに対して水酸化
リチウム・１水和物を２０ｇの割合で添加し撹拌するこ
とにより調製した。水酸化リチウム水溶液の温度を７０
℃とし、この中に集電体上に形成したシリコン薄膜を１
分間浸漬することにより、シリコン薄膜をエッチングし
た。エッチング後、流水で洗浄し乾燥した。Next, the silicon thin film produced as described above was etched with an aqueous lithium hydroxide solution. The aqueous lithium hydroxide solution was prepared by adding 20 g of lithium hydroxide monohydrate to 1 liter of pure water and stirring the mixture. The temperature of the aqueous lithium hydroxide solution is 70
℃ and the silicon thin film formed on the current collector in 1
The silicon thin film was etched by dipping for a minute. After etching, it was washed with running water and dried.
【００４７】エッチング後のシリコン薄膜の表面を走査
型電子顕微鏡で観察した。図３は、エッチング後のシリ
コン薄膜の表面を斜め方向から見たときの走査型電子顕
微鏡写真（倍率７０００倍）である。図３から明らかな
ように、シリコン薄膜表面の凹凸の谷部に沿って厚み方
向に空隙が形成されており、この空隙によりシリコン薄
膜が柱状の微小領域に分割されている。柱状の微小領域
の水平方向（膜面方向）における幅は１〜４μｍ程度で
ある。The surface of the silicon thin film after etching was observed with a scanning electron microscope. FIG. 3 is a scanning electron microscope photograph (magnification: 7,000 times) when the surface of the silicon thin film after etching is viewed from an oblique direction. As is clear from FIG. 3, voids are formed in the thickness direction along the valleys of the irregularities on the surface of the silicon thin film, and the voids divide the silicon thin film into columnar minute regions. The width of the columnar minute region in the horizontal direction (the film surface direction) is about 1 to 4 μm.
【００４８】なお、エッチング溶液として、本実施例で
は水酸化リチウム水溶液を用いているが、例えば、水酸
化ナトリウム水溶液、水酸化カリウム水溶液、アンモニ
ア水溶液などを用いても同様にエッチングすることがで
きる。Although the lithium hydroxide aqueous solution is used as the etching solution in this embodiment, the same etching can be performed by using, for example, a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, an ammonia aqueous solution or the like.
【００４９】エッチングされたシリコン薄膜について、
蛍光Ｘ線分析により単位面積当りのシリコン重量を測定
したところ、１１１７μｇ／ｃｍ2であることが確認さ
れた。Regarding the etched silicon thin film,
When the silicon weight per unit area was measured by fluorescent X-ray analysis, it was confirmed to be 1117 μg / cm 2 .
【００５０】エッチングしたシリコン薄膜を集電体とと
もに２．５ｃｍ×２．５ｃｍの大きさに切り出し、これ
を１５０℃で２時間真空加熱処理して、実施例１の負極
とした。The etched silicon thin film was cut into a size of 2.5 cm × 2.5 cm together with a current collector, and this was vacuum-heated at 150 ° C. for 2 hours to obtain a negative electrode of Example 1.
【００５１】なお、比較の電極として、シリコン薄膜の
厚みを６μｍとする以外は、上記と同様にして電解銅箔
の集電体上に非晶質シリコン薄膜を形成した。得られた
シリコン薄膜について、走査型電子顕微鏡で観察した。
図４は、得られたシリコン薄膜の表面を斜め方向から見
たときの走査型電子顕微鏡写真（倍率７０００倍）であ
る。図４から明らかなように、集電体表面の凹凸に対応
した凹凸がシリコン薄膜の表面に形成されており、図３
における実施例１のシリコン薄膜では、このようなシリ
コン薄膜表面の凹凸の谷部に沿って厚み方向にエッチン
グがなされ空隙が形成されていることがわかる。As a comparative electrode, an amorphous silicon thin film was formed on the current collector of the electrolytic copper foil in the same manner as above except that the thickness of the silicon thin film was 6 μm. The obtained silicon thin film was observed with a scanning electron microscope.
FIG. 4 is a scanning electron microscope photograph (magnification: 7,000 times) when the surface of the obtained silicon thin film is viewed from an oblique direction. As is apparent from FIG. 4, irregularities corresponding to the irregularities on the surface of the current collector are formed on the surface of the silicon thin film.
It can be seen that in the silicon thin film of Example 1 in Example 1, a void is formed by etching in the thickness direction along the valleys of the irregularities on the surface of the silicon thin film.
【００５２】単位面積当りのシリコン重量を、蛍光Ｘ線
分析で測定したところ、１１３２μｇ／ｃｍ2であっ
た。この電極を、上記実施例１の電極と同様に、２．５
ｃｍ×２．５ｃｍの大きさに切り出し、これを１５０℃
で２時間真空加熱処理して、比較例１の負極とした。The silicon weight per unit area was measured by fluorescent X-ray analysis and found to be 1132 μg / cm 2 . This electrode was used in the same manner as the electrode of Example 1 above, but the
Cut out into a size of cm x 2.5 cm and cut it at 150 ° C
Was vacuum-heated for 2 hours to obtain the negative electrode of Comparative Example 1.
【００５３】〔正極の作製〕平均粒径１０μｍのＬｉＣ
ｏＯ2粉末９０重量％と、導電剤としての炭素粉末５重
量％と、結着剤としてポリフッ化ビニリデン粉末５重量
％とを混合し、得られた混合物にＮ−メチルピロリドン
を加えて混練してスラリーを作製し、このスラリーを厚
さ２０μｍのアルミニウム製集電体の片面にドクターブ
レード法により塗布した。これを２．０ｃｍ×２．０ｃ
ｍの大きさに切り出し、１５０℃で２時間真空加熱処理
して、正極を得た。[Preparation of Positive Electrode] LiC having an average particle size of 10 μm
90% by weight of oO 2 powder, 5% by weight of carbon powder as a conductive agent, and 5% by weight of polyvinylidene fluoride powder as a binder were mixed, and N-methylpyrrolidone was added to the obtained mixture and kneaded. A slurry was prepared, and this slurry was applied to one surface of an aluminum current collector having a thickness of 20 μm by the doctor blade method. 2.0 cm x 2.0 c
It was cut into a size of m and subjected to vacuum heat treatment at 150 ° C. for 2 hours to obtain a positive electrode.
【００５４】〔電解液の作製〕アルゴンの不活性ガス雰
囲気中で、エチレンカーボネート（ＥＣ）とジエチルカ
ーボネート（ＤＥＣ）を体積比３：７となるように混合
した溶媒に、ＬｉＰＦ 6を１モル／リットルとなるよう
に溶解して電解液を作製した。[Preparation of Electrolyte Solution] Argon inert gas atmosphere
In an ambient atmosphere, ethylene carbonate (EC) and diethyl carbonate
Carbonate (DEC) is mixed in a volume ratio of 3: 7.
LiPF 6To be 1 mol / liter
To prepare an electrolytic solution.
【００５５】〔電池の作製〕上記実施例１及び比較例１
の負極と、上記正極とを用いて、以下のようにしてリチ
ウム二次電池を作製した。[Fabrication of Battery] Example 1 and Comparative Example 1
A lithium secondary battery was produced in the following manner using the negative electrode of and the positive electrode.
【００５６】アルゴンガス雰囲気下のグローブボックス
中にて、正極と負極とをポリエチレン製微多孔膜を介し
て貼り合わせ、アルミニウム製ラミネート材からなる外
装体に挿入した。これに、上記電解液を５００μｌ注入
し、リチウム二次電池を作製した。電池の設計容量は１
４ｍＡｈである。The positive electrode and the negative electrode were attached to each other through a polyethylene microporous film in a glove box under an argon gas atmosphere and inserted into an exterior body made of an aluminum laminate material. 500 μl of the above-mentioned electrolytic solution was injected into this to manufacture a lithium secondary battery. Battery design capacity is 1
It is 4 mAh.
【００５７】図５は、作製したリチウム二次電池を示す
平面図である。図５に示すように、ポリエチレン製微多
孔膜からなるセパレータ２を介して、正極１と負極３と
が組合わされて外装体４内に挿入されている。外装体４
に挿入した後に、電解液を注入し、外装体４の封止部４
ａを封止することにより、リチウム二次電池が作製され
ている。FIG. 5 is a plan view showing the manufactured lithium secondary battery. As shown in FIG. 5, the positive electrode 1 and the negative electrode 3 are combined and inserted into the exterior body 4 via a separator 2 made of a polyethylene microporous film. Exterior body 4
After being inserted into the casing, the electrolytic solution is injected to seal the sealing portion 4 of the exterior body 4.
A lithium secondary battery is produced by sealing a.
【００５８】図６は、電池内部における電池の組合せ状
態を示すための断面図である。図６に示すように、セパ
レータ２を介して正極１と負極３が対向するように組み
合わされている。正極１においてはアルミニウムからな
る正極集電体１ｂの上に、正極活物質層１ａが設けられ
ており、この正極活物質層１ａがセパレータ２と接して
いる。また、負極３においては、銅からなる負極集電体
３ｂの上に、負極活物質層３ａが設けられおり、この負
極活物質層３ａがセパレータ２に接している。FIG. 6 is a sectional view showing a combined state of the batteries inside the battery. As shown in FIG. 6, the positive electrode 1 and the negative electrode 3 are combined so as to face each other via the separator 2. In the positive electrode 1, the positive electrode active material layer 1 a is provided on the positive electrode current collector 1 b made of aluminum, and the positive electrode active material layer 1 a is in contact with the separator 2. Further, in the negative electrode 3, the negative electrode active material layer 3 a is provided on the negative electrode current collector 3 b made of copper, and the negative electrode active material layer 3 a is in contact with the separator 2.
【００５９】図６に示すように、正極集電体１ｂには、
外部取り出しのためのアルミニウムからなる正極タブ１
ｃが取り付けられている。また、負極集電体３ｂにも、
外部取り出しのためのニッケルからなる負極タブ３ｃが
取り付けられている。As shown in FIG. 6, the positive electrode current collector 1b includes:
Aluminum positive electrode tab 1 for external extraction
c is attached. Also, for the negative electrode current collector 3b,
A negative electrode tab 3c made of nickel for external extraction is attached.
【００６０】〔充放電サイクル特性の測定〕上記実施例
１及び比較例１の負極を用いた各電池について、充放電
サイクル特性を評価した。充電は１４ｍＡの定電流で
４．２０Ｖまで行い、サイクル４．２０Ｖの定電圧充電
を０．７ｍＡまで行った。放電は１４ｍＡの定電流で
２．７５Ｖまでとし、これを１サイクルとした。３０サ
イクル後の容量維持率を以下の計算式より求めた。結果
を表１に示す。なお、測定は２５℃で行った。[Measurement of Charge / Discharge Cycle Characteristics] The charge / discharge cycle characteristics of each battery using the negative electrode of Example 1 and Comparative Example 1 were evaluated. Charging was performed up to 4.20 V at a constant current of 14 mA, and constant voltage charging at a cycle of 4.20 V was performed up to 0.7 mA. The discharge was performed at a constant current of 14 mA up to 2.75 V, and this was one cycle. The capacity retention rate after 30 cycles was calculated by the following formula. The results are shown in Table 1. The measurement was performed at 25 ° C.
【００６１】容量維持率（％）＝（３０サイクル目の放
電容量／１サイクル目の放電容量）×１００
また、充放電サイクル試験前及び試験後の負極の厚みを
測定し、（試験後の負極の厚み）−（試験前の負極の厚
み）を負極の厚み変化として、表１に示した。なお、実
施例１の負極の試験前の厚みは３６μｍであり、比較例
１の負極の試験前の厚みは３２μｍであった。Capacity retention rate (%) = (Discharge capacity at 30th cycle / Discharge capacity at 1st cycle) × 100 Further, the thickness of the negative electrode before and after the charge / discharge cycle test was measured, and (the negative electrode after the test was measured. Thickness)-(thickness of negative electrode before test) is shown in Table 1 as a change in negative electrode thickness. The thickness of the negative electrode of Example 1 before the test was 36 μm, and the thickness of the negative electrode of Comparative Example 1 before the test was 32 μm.
【００６２】[0062]
【表１】 [Table 1]
【００６３】表１に示す結果から明らかなように、本発
明の第１の局面に従う実施例１の負極は、比較例１の負
極と同様に、高い充放電容量を示し、かつ優れた充放電
サイクル特性を示している。一方、負極の厚み変化は、
比較例１の負極よりもかなり小さくなっており、集電体
の変形及びしわの発生が抑制されていることがわかる。As is clear from the results shown in Table 1, the negative electrode of Example 1 according to the first aspect of the present invention exhibits a high charge / discharge capacity and excellent charge / discharge as in the negative electrode of Comparative Example 1. Shows cycle characteristics. On the other hand, the thickness change of the negative electrode is
It is much smaller than the negative electrode of Comparative Example 1, and it can be seen that the deformation and wrinkle of the current collector are suppressed.
【００６４】次に、本発明の第２の局面及び第３の局面
に従う実施例について説明する。
（実施例２）実施例１と同様にして集電体上に非晶質シ
リコン薄膜を形成し、形成したシリコン薄膜を水酸化リ
チウム水溶液を用いてエッチングした後、集電体表面を
エッチングして集電体表面に溝を形成した。集電体をエ
ッチングするのに用いたエッチング液としては、塩化第
２鉄水溶液を用いた。具体的には塩化第２鉄を純水で５
重量％に希釈したものをエッチング液として用いた。エ
ッチング液の温度は室温とし、エッチング時間は３０秒
とした。エッチング後流水で１０分間洗浄した後、１５
０℃で２時間真空加熱処理した。Next, examples according to the second and third aspects of the present invention will be described. (Example 2) An amorphous silicon thin film was formed on a current collector in the same manner as in Example 1, the formed silicon thin film was etched using an aqueous solution of lithium hydroxide, and then the current collector surface was etched. Grooves were formed on the surface of the current collector. An aqueous ferric chloride solution was used as an etching solution used for etching the current collector. Specifically, ferric chloride is diluted with pure water to 5
What was diluted to weight% was used as an etching liquid. The temperature of the etching solution was room temperature, and the etching time was 30 seconds. After etching, rinse with running water for 10 minutes, and then
A vacuum heat treatment was performed at 0 ° C. for 2 hours.
【００６５】集電体をエッチングした後の負極における
単位面積当りのシリコン重量を、蛍光Ｘ線分析により測
定したところ、１０９５μｇ／ｃｍ2であった。走査型
電子顕微鏡により、集電体に形成した溝を観察したとこ
ろ、集電体の溝の深さは２〜５μｍの範囲であり、溝の
幅は０．１〜０．３μｍの範囲であった。また、エッチ
ングしたシリコン薄膜の柱状の微小領域の幅は、実施例
１と同様に１〜４μｍであった。The weight of silicon per unit area of the negative electrode after etching the current collector was measured by fluorescent X-ray analysis and found to be 1095 μg / cm 2 . Observation of the grooves formed on the current collector with a scanning electron microscope revealed that the depth of the grooves of the current collector was in the range of 2 to 5 μm and the width of the grooves was in the range of 0.1 to 0.3 μm. It was The width of the pillar-shaped minute region of the etched silicon thin film was 1 to 4 μm as in Example 1.
【００６６】〔電池の作製〕実施例１と同様にして、正
極及び電解液を作製し、実施例１と同様にしてリチウム
二次電池を作製した。[Production of Battery] A positive electrode and an electrolytic solution were produced in the same manner as in Example 1, and a lithium secondary battery was produced in the same manner as in Example 1.
【００６７】〔充放電サイクル特性の測定〕上記実施例
２の負極を用いた電池について、上記実施例１と同様に
して充放電サイクル特性を評価し、初期放電容量及び容
量維持率を測定した。この結果を表２に示す。また、負
極の厚み変化についても測定し、結果を表２に示した。
実施例２の負極の試験前の厚みは３６μｍであった。[Measurement of Charge / Discharge Cycle Characteristics] With respect to the battery using the negative electrode of Example 2 above, charge / discharge cycle characteristics were evaluated in the same manner as in Example 1 above, and the initial discharge capacity and capacity retention rate were measured. The results are shown in Table 2. The change in the thickness of the negative electrode was also measured, and the results are shown in Table 2.
The thickness of the negative electrode of Example 2 before the test was 36 μm.
【００６８】なお、表２には、表１に示した比較例１の
結果も併せて示す。Table 2 also shows the results of Comparative Example 1 shown in Table 1.
【００６９】[0069]
【表２】 [Table 2]
【００７０】表２に示す結果から明らかなように、本発
明の第２の局面及び第３の局面に従う実施例２の負極を
用いた電池は、充放電容量が高く、かつ充放電サイクル
特性に優れており、しかも、充放電試験における負極の
厚み変化が著しく低減している。従って、集電体の変形
やしわの発生がより効果的に抑制されていることがわか
る。As is clear from the results shown in Table 2, the battery using the negative electrode of Example 2 according to the second and third aspects of the present invention has a high charge / discharge capacity and charge / discharge cycle characteristics. It is excellent, and the thickness change of the negative electrode in the charge / discharge test is significantly reduced. Therefore, it is understood that the deformation of the current collector and the generation of wrinkles are more effectively suppressed.
【００７１】[0071]
【発明の効果】本発明によれば、充放電容量が高く、充
放電サイクル特性に優れたリチウム二次電池用電極であ
って、充放電に伴う活物質薄膜の膨張により集電体に変
形やしわが発生するのを抑制することができる。従っ
て、本発明のリチウム二次電池用電極を用いることによ
り、電池の体積当りのエネルギー密度を高めることがで
きる。According to the present invention, an electrode for a lithium secondary battery having a high charge / discharge capacity and excellent charge / discharge cycle characteristics, which is transformed into a current collector due to expansion of the active material thin film due to charge / discharge. It is possible to suppress the generation of wrinkles. Therefore, by using the lithium secondary battery electrode of the present invention, the energy density per volume of the battery can be increased.
【図１】本発明の第１の局面に従う製造工程の一例を説
明するための断面図。FIG. 1 is a cross-sectional view for explaining an example of a manufacturing process according to a first aspect of the present invention.
【図２】本発明の第２の局面に従う製造工程の一例を説
明するための断面図。FIG. 2 is a cross-sectional view for explaining an example of a manufacturing process according to the second aspect of the present invention.
【図３】活物質薄膜であるシリコン薄膜をエッチングし
た後の状態を示す走査型電子顕微鏡写真（倍率７０００
倍）。FIG. 3 is a scanning electron microscope photograph (magnification: 7000) showing a state after etching a silicon thin film which is an active material thin film.
Times).
【図４】活物質薄膜であるシリコン薄膜をエッチングす
る前の状態を示す走査型電子顕微鏡写真（倍率７０００
倍）。FIG. 4 is a scanning electron microscope photograph (magnification: 7000) showing a state before etching a silicon thin film which is an active material thin film.
Times).
【図５】本発明の実施例において作製したリチウム二次
電池を示す平面図。FIG. 5 is a plan view showing a lithium secondary battery manufactured in an example of the present invention.
【図６】図５に示すリチウム二次電池における電極の組
み合わせ構造を示す断面図。6 is a sectional view showing a combined structure of electrodes in the lithium secondary battery shown in FIG.
１０…集電体 １０ａ…集電体表面 １０ｃ…集電体表面の凹凸の谷部 １１…活物質薄膜 １１ａ…活物質薄膜の表面 １１ｂ…活物質薄膜の低密度領域 １１ｃ…活物質薄膜表面の凹凸の谷部 １２…活物質薄膜に形成された空隙 １３…集電体表面に形成された溝 10 ... Current collector 10a ... Current collector surface 10c ... Valley of irregularities on current collector surface 11 ... Active material thin film 11a ... Surface of active material thin film 11b ... Low density region of active material thin film 11c ... Valley of irregularities on thin film of active material 12 ... Void formed in active material thin film 13 ... Grooves formed on the surface of the current collector
───────────────────────────────────────────────────── フロントページの続き (72)発明者 佐山 勝信 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 AS00 BB16 CC01 DD01 EE01 5H029 AJ03 AJ05 AJ14 AK11 AL11 AM03 AM04 AM05 AM07 BJ04 CJ11 CJ24 DJ07 DJ12 DJ14 DJ17 DJ18 EJ01 HJ12 5H050 AA07 AA08 AA19 BA17 CA17 CB11 DA07 FA01 FA08 FA10 FA19 FA20 GA25 HA12 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Katsunobu Sayama 2-5-3 Keihan Hondori, Moriguchi City, Osaka Prefecture Within Yo Denki Co., Ltd. F-term (reference) 5H017 AA03 AS00 BB16 CC01 DD01 EE01 5H029 AJ03 AJ05 AJ14 AK11 AL11 AM03 AM04 AM05 AM07 BJ04 CJ11 CJ24 DJ07 DJ12 DJ14 DJ17 DJ18 EJ01 HJ12 5H050 AA07 AA08 AA19 BA17 CA17 CB11 DA07 FA01 FA08 FA10 FA19 FA20 GA25 HA12
Claims (16)
集電体上に堆積して形成する工程と、 エッチングにより前記活物質薄膜の厚み方向に空隙を形
成し、前記活物質薄膜を微小領域に分割する工程とを備
え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 step of depositing and forming an active material thin film that absorbs and releases lithium on a current collector, and forming a void in the thickness direction of the active material thin film by etching to form the active material thin film in a minute region. The method for producing an electrode for a lithium secondary battery, comprising:
度領域が形成されており、該低密度領域におけるエッチ
ング速度が他の領域におけるエッチング速度よりも速い
ことを利用して、前記エッチングがなされることを特徴
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 etching is performed by utilizing the fact that a low density region extending in the thickness direction is formed in the active material thin film, and the etching rate in the low density region is higher than the etching rates in other regions. The method for producing an electrode for a lithium secondary battery according to claim 1, wherein:
の凹凸に対応した凹凸が形成されており、前記集電体表
面の凹凸の谷部と前記活物質薄膜表面の凹凸の谷部とを
結ぶ領域に前記低密度領域が形成されていることを特徴
とする請求項２に記載のリチウム二次電池用電極の製造
方法。3. The surface of the active material thin film is formed with irregularities corresponding to the irregularities of the surface of the current collector, and the valleys of the irregularities on the surface of the current collector and the valleys of the irregularities on the surface of the active material thin film. The method for manufacturing an electrode for a lithium secondary battery according to claim 2, wherein the low-density region is formed in a region connecting with.
化学的反応によるエッチング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 etching of the active material thin film comprises:
It is etching by a chemical reaction, The manufacturing method of the electrode for lithium secondary batteries of any one of Claims 1-3 characterized by the above-mentioned.
あって、厚み方向に形成された空隙によって微小領域に
分割された活物質薄膜を集電体上に設ける工程と、 前記空隙が形成された前記活物質薄膜をマスクとして前
記集電体表面をエッチングすることにより、前記活物質
薄膜の前記空隙に対応した溝を前記集電体に形成する工
程とを備え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。5. A step of providing, on a current collector, an active material thin film that absorbs and desorbs lithium and is divided into minute regions by voids formed in the thickness direction, and the voids are formed. And a step of forming a groove in the current collector corresponding to the void of the active material thin film by etching the surface of the current collector using the active material thin film as a mask. Manufacturing method of battery electrode.
的な反応によるエッチングであることを特徴とする請求
項５に記載のリチウム二次電池用電極の製造方法。6. The method for manufacturing an electrode for a lithium secondary battery according to claim 5, wherein the etching of the current collector is etching by a chemical reaction.
集電体上に設ける工程が、前記活物質薄膜を集電体上に
堆積して形成する工程と、エッチングにより前記活物質
薄膜に前記空隙を形成する工程とを含むことを特徴とす
る請求項５または６に記載のリチウム二次電池用電極の
製造方法。7. The step of providing the active material thin film in which the voids are formed on a current collector, the step of depositing the active material thin film on the current collector and forming the active material thin film on the current collector by etching. 7. The method for manufacturing an electrode for a lithium secondary battery according to claim 5, further comprising the step of forming the void.
度領域が形成されており、該低密度領域におけるエッチ
ング速度が他の領域におけるエッチング速度よりも速い
ことを利用して、前記エッチングがなされることを特徴
とする請求項７に記載のリチウム二次電池用電極の製造
方法。8. The etching is performed by utilizing the fact that a low density region extending in the thickness direction is formed in the active material thin film and the etching rate in the low density region is higher than the etching rates in other regions. The method for manufacturing an electrode for a lithium secondary battery according to claim 7, wherein:
の凹凸に対応した凹凸が形成されており、前記集電体表
面の凹凸の谷部と前記活物質薄膜表面の凹凸の谷部とを
結ぶ領域に前記低密度領域が形成されていることを特徴
とする請求項８に記載のリチウム二次電池用電極の製造
方法。9. The surface of the active material thin film is formed with irregularities corresponding to the irregularities of the surface of the current collector, and the valleys of the irregularities on the surface of the current collector and the valleys of the irregularities on the surface of the active material thin film. The method for manufacturing an electrode for a lithium secondary battery according to claim 8, wherein the low-density region is formed in a region connecting with.
が、化学的反応によるエッチングであることを特徴とす
る請求項７〜９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。10. The method for manufacturing an electrode for a lithium secondary battery according to claim 7, wherein the etching of the active material thin film is etching by a chemical reaction.
ニウム、またはシリコンゲルマニウムの非晶質もしくは
微結晶薄膜であることを特徴とする請求項１〜１０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。11. The lithium secondary battery according to claim 1, wherein the active material thin film is an amorphous or microcrystalline thin film of silicon, germanium, or silicon germanium. For manufacturing electrodes for use.
銅または銅を主体とする合金から形成されることを特徴
とする請求項１〜１１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。12. At least a surface portion of the current collector,
The method for manufacturing an electrode for a lithium secondary battery according to any one of claims 1 to 11, which is formed of copper or an alloy mainly containing copper.
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
であって、 前記活物質薄膜が厚み方向に形成された空隙によって微
小領域に分割されており、かつ前記集電体の表面に前記
活物質薄膜の空隙に対応した溝が形成されていることを
特徴とするリチウム二次電池用電極。13. A lithium secondary battery electrode formed by depositing an active material thin film that absorbs and desorbs lithium on a current collector, wherein the active material thin film is a minute region formed by a void formed in the thickness direction. And a groove corresponding to the void of the active material thin film is formed on the surface of the current collector, the electrode for a lithium secondary battery.
ニウム、またはシリコンゲルマニウムの非晶質もしくは
微結晶薄膜であることを特徴とする請求項１３に記載の
リチウム二次電池用電極。14. The electrode for a lithium secondary battery according to claim 13, wherein the active material thin film is an amorphous or microcrystalline thin film of silicon, germanium, or silicon germanium.
銅または銅を主体とする合金から形成されていることを
特徴とする請求項１３または１４に記載のリチウム二次
電池用電極。15. At least a surface portion of the current collector is
The electrode for a lithium secondary battery according to claim 13 or 14, wherein the electrode is made of copper or an alloy mainly containing copper.
の方法により製造された電極または請求項１３〜１５の
いずれか１項に記載の電極からなる負極と、正極と、非
水電解質とを備えることを特徴とするリチウム二次電
池。16. An electrode manufactured by the method according to any one of claims 1 to 12 or a negative electrode comprising the electrode according to any one of claims 13 to 15, a positive electrode, and a non-aqueous electrolyte. And a lithium secondary battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001196638A JP4183401B2 (en) | 2001-06-28 | 2001-06-28 | Method for manufacturing electrode for lithium secondary battery and lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001196638A JP4183401B2 (en) | 2001-06-28 | 2001-06-28 | Method for manufacturing electrode for lithium secondary battery and lithium secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2003017040A true JP2003017040A (en) | 2003-01-17 |
| JP4183401B2 JP4183401B2 (en) | 2008-11-19 |
Family
ID=19034408
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001196638A Expired - Fee Related JP4183401B2 (en) | 2001-06-28 | 2001-06-28 | Method for manufacturing electrode for lithium secondary battery and lithium secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4183401B2 (en) |
Cited By (77)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004036670A1 (en) * | 2002-10-15 | 2004-04-29 | Kabushiki Kaisha Toshiba | Nonacqueous electrolyte secondary cell |
| WO2004109839A1 (en) * | 2003-06-09 | 2004-12-16 | Sanyo Electric Co., Ltd. | Lithium secondary battery and method for producing same |
| JP2005116519A (en) * | 2003-09-17 | 2005-04-28 | Hitachi Maxell Ltd | Electrode for nonaqueous secondary battery and nonaqueous secondary battery |
| WO2005064714A1 (en) * | 2003-12-26 | 2005-07-14 | Nec Corporation | Negative electrode material for secondary battery, negative electrode for secondary battery and secondary battery using same |
| JP2005267955A (en) * | 2004-03-17 | 2005-09-29 | Toshiba Corp | Nonaqueous electrolyte secondary battery |
| WO2006028316A1 (en) * | 2004-09-11 | 2006-03-16 | Lg Chem, Ltd. | Method for improvement of performance of si thin film anode for lithium rechargeable battery |
| WO2006043382A1 (en) * | 2004-10-21 | 2006-04-27 | Matsushita Electric Industrial Co., Ltd. | Negative electrode for nonaqueous electrolyte secondary battery and method for producing same |
| JP2006134891A (en) * | 2004-09-09 | 2006-05-25 | Mitsui Mining & Smelting Co Ltd | Negative electrode for nonaqueous electrolyte secondary battery |
| JP2006228512A (en) * | 2005-02-16 | 2006-08-31 | Mitsui Mining & Smelting Co Ltd | Anode for nonaqueous electrolyte secondary battery |
| JP2007165226A (en) * | 2005-12-16 | 2007-06-28 | Sumitomo Electric Ind Ltd | Manufacturing method of electrode for lithium secondary battery |
| WO2007074654A1 (en) * | 2005-12-28 | 2007-07-05 | Matsushita Electric Industrial Co., Ltd. | Nonaqueous electrolyte secondary battery |
| CN100347904C (en) * | 2003-06-09 | 2007-11-07 | 三洋电机株式会社 | Lithium secondary battery and method for producing same |
| WO2008029890A1 (en) * | 2006-09-07 | 2008-03-13 | Toyota Jidosha Kabushiki Kaisha | Method for producing nonaqueous secondary battery |
| WO2008044683A1 (en) * | 2006-10-10 | 2008-04-17 | Panasonic Corporation | Negative electrode for nonaqueous electrolyte secondary battery |
| WO2008044449A1 (en) | 2006-10-13 | 2008-04-17 | Panasonic Corporation | Negative electrode for nonaqueous electrolyte secondary battery, process for producing the same and nonaqueous electrolyte secondary battery utilizing the electrode |
| WO2008047668A1 (en) * | 2006-10-19 | 2008-04-24 | Panasonic Corporation | Nonaqueous electrolyte secondary battery and method for producing negative electrode for nonaqueous electrolyte secondary battery |
| WO2008050586A1 (en) * | 2006-10-19 | 2008-05-02 | Panasonic Corporation | Negative electrode for lithium secondary battery and lithium secondary battery containing the same |
| JP2008124003A (en) * | 2006-10-19 | 2008-05-29 | Matsushita Electric Ind Co Ltd | Negative electrode for lithium secondary battery, and lithium secondary battery including it |
| WO2008072430A1 (en) | 2006-12-13 | 2008-06-19 | Panasonic Corporation | Negative electrode for nonaqueous electrolyte secondary battery and method for producing the same and nonaqueous electrolyte secondary battery employing it |
| WO2008072460A1 (en) | 2006-12-13 | 2008-06-19 | Panasonic Corporation | Negative electrode for rechargeable battery with nonaqueous electrolyte, process for producing the negative electrode, and rechargeable battery with nonaqueous electrolyte using the negative electrode |
| JP2008146840A (en) * | 2006-12-06 | 2008-06-26 | Matsushita Electric Ind Co Ltd | Negative electrode for lithium secondary battery |
| WO2008124227A1 (en) * | 2007-04-05 | 2008-10-16 | 3M Innovative Properties Company | Electrodes with raised patterns |
| WO2008136166A1 (en) | 2007-04-26 | 2008-11-13 | Panasonic Corporation | Electrode for electrochemical elment, process for producing the electrode, and electrochemical element using the electrode |
| CN101310400A (en) * | 2005-11-17 | 2008-11-19 | 无穷动力解决方案股份有限公司 | Hybrid thin-film battery |
| WO2008139157A1 (en) * | 2007-05-11 | 2008-11-20 | Nexeon Ltd | A silicon anode for a rechargeable battery |
| WO2009010757A1 (en) * | 2007-07-17 | 2009-01-22 | Nexeon Limited | Production |
| WO2009010759A1 (en) * | 2007-07-17 | 2009-01-22 | Nexeon Limited | Method |
| WO2009010758A3 (en) * | 2007-07-17 | 2009-03-12 | Nexeon Ltd | A method of fabricating structured particles composed of silicon or a silicon-based material and their use in lithium rechargeable batteries |
| JP2009135084A (en) * | 2007-11-02 | 2009-06-18 | Panasonic Corp | Lithium ion secondary battery |
| JP2010008266A (en) * | 2008-06-27 | 2010-01-14 | Panasonic Corp | Metal sheet inspecting method and battery manufacturing method |
| US7683359B2 (en) | 2002-11-05 | 2010-03-23 | Nexeon Ltd. | Structured silicon anode |
| US7794878B2 (en) | 2006-01-19 | 2010-09-14 | Panasonic Corporation | Negative electrode for lithium secondary battery and lithium secondary battery using the negative electrode |
| GB2470056A (en) * | 2009-05-07 | 2010-11-10 | Nexeon Ltd | A method of forming a silicon anode material for rechargeable cells |
| JP2011023710A (en) * | 2009-06-19 | 2011-02-03 | Semiconductor Energy Lab Co Ltd | Method for manufacturing electric storage device |
| JP2011096646A (en) * | 2009-09-30 | 2011-05-12 | Semiconductor Energy Lab Co Ltd | Manufacturing method for electrode for power storage device, and manufacturing method for power storage device |
| JP2011129344A (en) * | 2009-12-17 | 2011-06-30 | Toyota Motor Corp | Lithium ion secondary battery |
| US8080334B2 (en) | 2005-08-02 | 2011-12-20 | Panasonic Corporation | Lithium secondary battery |
| US8101298B2 (en) | 2006-01-23 | 2012-01-24 | Nexeon Ltd. | Method of fabricating fibres composed of silicon or a silicon-based material and their use in lithium rechargeable batteries |
| US8148012B2 (en) | 2007-02-01 | 2012-04-03 | Panasonic Corporation | Method for forming active material on a current collector of negative electrode using feedback process with measuring collector |
| US8192864B2 (en) | 2007-02-01 | 2012-06-05 | Panasonic Corporation | Battery, examination method and manufacturing method for negative electrode thereof, and examination apparatus and manufacturing apparatus for negative electrode thereof |
| US8257869B2 (en) | 2007-06-01 | 2012-09-04 | Panasonic Corporation | Electrode for electrochemical element and electrochemical element using the electrode |
| US8273136B2 (en) | 2007-03-16 | 2012-09-25 | Panasonic Corporation | Electrochemical element, and method and apparatus for manufacturing electrode thereof |
| US8303672B2 (en) | 2005-11-07 | 2012-11-06 | Panasonic Corporation | Electrode for lithium secondary battery, lithium secondary battery and method for producing the same |
| US8334073B2 (en) | 2006-10-12 | 2012-12-18 | Panasonic Corporation | Non-aqueous electrolyte secondary battery and method of manufacturing negative electrode thereof |
| US8389156B2 (en) | 2006-08-25 | 2013-03-05 | Panasonic Corporation | Negative electrode for non-aqueous electrolyte secondary battery, method for producing the same, and non-aqueous electrolyte secondary battery |
| JP2013510405A (en) * | 2009-11-03 | 2013-03-21 | エンビア・システムズ・インコーポレイテッド | High capacity anode materials for lithium ion batteries |
| JP2013131506A (en) * | 2013-04-03 | 2013-07-04 | Toyota Motor Corp | Positive electrode current collector foil for battery, method of manufacturing the same, and battery |
| US20130177804A1 (en) * | 2012-01-05 | 2013-07-11 | GM Global Technology Operations LLC | Methods for making battery electrode systems |
| US8585918B2 (en) | 2006-01-23 | 2013-11-19 | Nexeon Ltd. | Method of etching a silicon-based material |
| US8658313B2 (en) | 2009-09-30 | 2014-02-25 | Semiconductor Energy Laboratory Co., Ltd. | Method for manufacturing electrode, and method for manufacturing power storage device and power generation and storage device having the electrode |
| US8728285B2 (en) | 2003-05-23 | 2014-05-20 | Demaray, Llc | Transparent conductive oxides |
| KR101410803B1 (en) | 2014-03-10 | 2014-06-24 | 경상대학교산학협력단 | A discontinuous electrode, battery using the same, a method for producing thereof |
| US8772174B2 (en) | 2010-04-09 | 2014-07-08 | Nexeon Ltd. | Method of fabricating structured particles composed of silicon or silicon-based material and their use in lithium rechargeable batteries |
| WO2014192637A1 (en) * | 2013-05-31 | 2014-12-04 | 株式会社安永 | Electrode for non-aqueous electrolyte secondary battery, and manufacturing method of electrode for non-aqueous electrolyte secondary battery |
| US8906523B2 (en) | 2008-08-11 | 2014-12-09 | Infinite Power Solutions, Inc. | Energy device with integral collector surface for electromagnetic energy harvesting and method thereof |
| US8932759B2 (en) | 2008-10-10 | 2015-01-13 | Nexeon Ltd. | Method of fabricating structured particles composed of silicon or a silicon-based material |
| US8940441B2 (en) | 2006-04-04 | 2015-01-27 | Sony Corporatin | Anode and battery |
| US8945774B2 (en) | 2010-06-07 | 2015-02-03 | Nexeon Ltd. | Additive for lithium ion rechageable battery cells |
| US9184438B2 (en) | 2008-10-10 | 2015-11-10 | Nexeon Ltd. | Method of fabricating structured particles composed of silicon or a silicon-based material and their use in lithium rechargeable batteries |
| KR20160048668A (en) * | 2014-10-24 | 2016-05-04 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | Secondary battery and manufacturing method of the same |
| US9334557B2 (en) | 2007-12-21 | 2016-05-10 | Sapurast Research Llc | Method for sputter targets for electrolyte films |
| US9532453B2 (en) | 2009-09-01 | 2016-12-27 | Sapurast Research Llc | Printed circuit board with integrated thin film battery |
| US9608272B2 (en) | 2009-05-11 | 2017-03-28 | Nexeon Limited | Composition for a secondary battery cell |
| US9614214B2 (en) | 2004-12-16 | 2017-04-04 | Lg Chem, Ltd. | Method for improvement of performance of si thin film anode for lithium rechargeable battery |
| US9634296B2 (en) | 2002-08-09 | 2017-04-25 | Sapurast Research Llc | Thin film battery on an integrated circuit or circuit board and method thereof |
| US9647263B2 (en) | 2010-09-03 | 2017-05-09 | Nexeon Limited | Electroactive material |
| US9735419B2 (en) | 2010-03-26 | 2017-08-15 | Semiconductor Energy Laboratory Co., Ltd. | Secondary battery and method for forming electrode of secondary battery |
| US9786873B2 (en) | 2008-01-11 | 2017-10-10 | Sapurast Research Llc | Thin film encapsulation for thin film batteries and other devices |
| US9793523B2 (en) | 2002-08-09 | 2017-10-17 | Sapurast Research Llc | Electrochemical apparatus with barrier layer protected substrate |
| US9853292B2 (en) | 2009-05-11 | 2017-12-26 | Nexeon Limited | Electrode composition for a secondary battery cell |
| US9871248B2 (en) | 2010-09-03 | 2018-01-16 | Nexeon Limited | Porous electroactive material |
| US20180019466A1 (en) * | 2012-10-05 | 2018-01-18 | Semiconductor Energy Laboratory Co., Ltd. | Negative electrode for lithium-ion secondary battery, manufacturing method thereof, and lithium-ion secondary battery |
| WO2018038479A1 (en) * | 2016-08-25 | 2018-03-01 | 주식회사 엘지화학 | Electrode for secondary battery comprising fine holes |
| KR20180042712A (en) * | 2016-10-18 | 2018-04-26 | 서울대학교산학협력단 | Lithium battery and method for manufacturing electrode of the lithium battery |
| CN108292737A (en) * | 2016-08-25 | 2018-07-17 | 株式会社Lg化学 | Has punctulate electrode for secondary battery |
| US10680277B2 (en) | 2010-06-07 | 2020-06-09 | Sapurast Research Llc | Rechargeable, high-density electrochemical device |
| JP2022126945A (en) * | 2021-02-19 | 2022-08-31 | プライムアースＥｖエナジー株式会社 | Nonaqueous electrolyte secondary battery and manufacturing method thereof |
-
2001
- 2001-06-28 JP JP2001196638A patent/JP4183401B2/en not_active Expired - Fee Related
Cited By (148)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9793523B2 (en) | 2002-08-09 | 2017-10-17 | Sapurast Research Llc | Electrochemical apparatus with barrier layer protected substrate |
| US9634296B2 (en) | 2002-08-09 | 2017-04-25 | Sapurast Research Llc | Thin film battery on an integrated circuit or circuit board and method thereof |
| WO2004036670A1 (en) * | 2002-10-15 | 2004-04-29 | Kabushiki Kaisha Toshiba | Nonacqueous electrolyte secondary cell |
| US8017430B2 (en) | 2002-11-05 | 2011-09-13 | Nexeon Ltd. | Structured silicon anode |
| US7842535B2 (en) | 2002-11-05 | 2010-11-30 | Nexeon Ltd. | Structured silicon anode |
| JP2010135332A (en) * | 2002-11-05 | 2010-06-17 | Nexeon Ltd | Structured silicon anode |
| US7683359B2 (en) | 2002-11-05 | 2010-03-23 | Nexeon Ltd. | Structured silicon anode |
| US8384058B2 (en) | 2002-11-05 | 2013-02-26 | Nexeon Ltd. | Structured silicon anode |
| US8728285B2 (en) | 2003-05-23 | 2014-05-20 | Demaray, Llc | Transparent conductive oxides |
| WO2004109839A1 (en) * | 2003-06-09 | 2004-12-16 | Sanyo Electric Co., Ltd. | Lithium secondary battery and method for producing same |
| CN100347904C (en) * | 2003-06-09 | 2007-11-07 | 三洋电机株式会社 | 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 |
| JP2005116519A (en) * | 2003-09-17 | 2005-04-28 | Hitachi Maxell Ltd | Electrode for nonaqueous secondary battery and nonaqueous secondary battery |
| JPWO2005064714A1 (en) * | 2003-12-26 | 2007-12-20 | 日本電気株式会社 | Secondary battery negative electrode material, secondary battery negative electrode and secondary battery using the same |
| JP4752508B2 (en) * | 2003-12-26 | 2011-08-17 | 日本電気株式会社 | Secondary battery negative electrode material, secondary battery negative electrode and secondary battery using the same |
| WO2005064714A1 (en) * | 2003-12-26 | 2005-07-14 | Nec Corporation | Negative electrode material for secondary battery, negative electrode for secondary battery and secondary battery using same |
| US8377591B2 (en) | 2003-12-26 | 2013-02-19 | Nec Corporation | Anode material for secondary battery, anode for secondary battery and secondary battery therewith |
| JP4599070B2 (en) * | 2004-03-17 | 2010-12-15 | 株式会社東芝 | Nonaqueous electrolyte secondary battery |
| JP2005267955A (en) * | 2004-03-17 | 2005-09-29 | Toshiba Corp | Nonaqueous electrolyte secondary battery |
| JP2006134891A (en) * | 2004-09-09 | 2006-05-25 | Mitsui Mining & Smelting Co Ltd | Negative electrode for nonaqueous electrolyte secondary battery |
| WO2006028316A1 (en) * | 2004-09-11 | 2006-03-16 | Lg Chem, Ltd. | Method for improvement of performance of si thin film anode for lithium rechargeable battery |
| US7807294B2 (en) | 2004-10-21 | 2010-10-05 | Panasonic Corporation | Negative electrode for non-aqueous electrolyte secondary battery and method for producing the same |
| WO2006043382A1 (en) * | 2004-10-21 | 2006-04-27 | Matsushita Electric Industrial Co., Ltd. | Negative electrode for nonaqueous electrolyte secondary battery and method for producing same |
| JP2006120445A (en) * | 2004-10-21 | 2006-05-11 | Matsushita Electric Ind Co Ltd | Anode for nonaqueous electrolyte secondary battery and its manufacturing method |
| US9614214B2 (en) | 2004-12-16 | 2017-04-04 | Lg Chem, Ltd. | Method for improvement of performance of si thin film anode for lithium rechargeable battery |
| JP2006228512A (en) * | 2005-02-16 | 2006-08-31 | Mitsui Mining & Smelting Co Ltd | Anode for nonaqueous electrolyte secondary battery |
| US8080334B2 (en) | 2005-08-02 | 2011-12-20 | Panasonic Corporation | Lithium secondary battery |
| US8888870B2 (en) | 2005-08-02 | 2014-11-18 | Panasonic Corporation | Lithium secondary battery |
| US8303672B2 (en) | 2005-11-07 | 2012-11-06 | Panasonic Corporation | Electrode for lithium secondary battery, lithium secondary battery and method for producing the same |
| US8318359B2 (en) | 2005-11-07 | 2012-11-27 | Panasonic Corporation | Electrode for lithium secondary battery, lithium secondary battery and method for producing the same |
| CN101310400A (en) * | 2005-11-17 | 2008-11-19 | 无穷动力解决方案股份有限公司 | Hybrid thin-film battery |
| JP2007165226A (en) * | 2005-12-16 | 2007-06-28 | Sumitomo Electric Ind Ltd | Manufacturing method of electrode for lithium secondary battery |
| JPWO2007074654A1 (en) * | 2005-12-28 | 2009-06-04 | パナソニック株式会社 | Nonaqueous electrolyte secondary battery |
| KR100901048B1 (en) | 2005-12-28 | 2009-06-04 | 파나소닉 주식회사 | Nonaqueous electrolyte secondary battery |
| JP4613953B2 (en) * | 2005-12-28 | 2011-01-19 | パナソニック株式会社 | Nonaqueous electrolyte secondary battery |
| WO2007074654A1 (en) * | 2005-12-28 | 2007-07-05 | Matsushita Electric Industrial Co., Ltd. | Nonaqueous electrolyte secondary battery |
| US7794878B2 (en) | 2006-01-19 | 2010-09-14 | Panasonic Corporation | Negative electrode for lithium secondary battery and lithium secondary battery using the negative electrode |
| US8585918B2 (en) | 2006-01-23 | 2013-11-19 | Nexeon Ltd. | Method of etching a silicon-based material |
| US8101298B2 (en) | 2006-01-23 | 2012-01-24 | Nexeon Ltd. | Method of fabricating fibres composed of silicon or a silicon-based material and their use in lithium rechargeable batteries |
| US8597831B2 (en) | 2006-01-23 | 2013-12-03 | Nexeon Ltd. | Method of fabricating fibres composed of silicon or a silicon-based material and their use in lithium rechargeable batteries |
| US9583762B2 (en) | 2006-01-23 | 2017-02-28 | Nexeon Limited | Method of fabricating fibres composed of silicon or a silicon-based material and their use in lithium rechargeable batteries |
| US8940441B2 (en) | 2006-04-04 | 2015-01-27 | Sony Corporatin | Anode and battery |
| US8389156B2 (en) | 2006-08-25 | 2013-03-05 | Panasonic Corporation | Negative electrode for non-aqueous electrolyte secondary battery, method for producing the same, and non-aqueous electrolyte secondary battery |
| WO2008029890A1 (en) * | 2006-09-07 | 2008-03-13 | Toyota Jidosha Kabushiki Kaisha | Method for producing nonaqueous secondary battery |
| WO2008044683A1 (en) * | 2006-10-10 | 2008-04-17 | Panasonic Corporation | Negative electrode for nonaqueous electrolyte secondary battery |
| US8734997B2 (en) | 2006-10-10 | 2014-05-27 | Panasonic Corporation | Negative electrode for nonaqueous electrolyte secondary battery |
| US8334073B2 (en) | 2006-10-12 | 2012-12-18 | Panasonic Corporation | Non-aqueous electrolyte secondary battery and method of manufacturing negative electrode thereof |
| WO2008044449A1 (en) | 2006-10-13 | 2008-04-17 | Panasonic Corporation | Negative electrode for nonaqueous electrolyte secondary battery, process for producing the same and nonaqueous electrolyte secondary battery utilizing the electrode |
| US8029933B2 (en) | 2006-10-13 | 2011-10-04 | Panasonic Corporation | Negative electrode for non-aqueous electrolyte secondary battery, method for manufacturing the same, and non-aqueous electrolyte secondary battery using the same |
| US8399129B2 (en) | 2006-10-19 | 2013-03-19 | Panasonic Corporation | Negative electrode for lithium secondary battery, and lithium secondary battery including the same |
| EP2077596A1 (en) * | 2006-10-19 | 2009-07-08 | Panasonic Corporation | Negative electrode for lithium secondary battery and lithium secondary battery containing the same |
| CN101449408B (en) * | 2006-10-19 | 2011-04-13 | 松下电器产业株式会社 | Negative electrode for lithium secondary battery and lithium secondary battery containing the same |
| WO2008047668A1 (en) * | 2006-10-19 | 2008-04-24 | Panasonic Corporation | Nonaqueous electrolyte secondary battery and method for producing negative electrode for nonaqueous electrolyte secondary battery |
| JP2008124003A (en) * | 2006-10-19 | 2008-05-29 | Matsushita Electric Ind Co Ltd | Negative electrode for lithium secondary battery, and lithium secondary battery including it |
| WO2008050586A1 (en) * | 2006-10-19 | 2008-05-02 | Panasonic Corporation | Negative electrode for lithium secondary battery and lithium secondary battery containing the same |
| KR101109285B1 (en) * | 2006-10-19 | 2012-01-31 | 파나소닉 주식회사 | Nonaqueous electrolyte secondary battery and method of manufacturing negative electrode thereof |
| EP2077596A4 (en) * | 2006-10-19 | 2012-02-01 | Panasonic Corp | Negative electrode for lithium secondary battery and lithium secondary battery containing the same |
| US8142931B2 (en) | 2006-10-19 | 2012-03-27 | Panasonic Corporation | Nonaqueous electrolyte secondary battery and method of manufacturing negative electrode thereof |
| JP2008146840A (en) * | 2006-12-06 | 2008-06-26 | Matsushita Electric Ind Co Ltd | Negative electrode for lithium secondary battery |
| US7947396B2 (en) | 2006-12-13 | 2011-05-24 | Panasonic Corporation | Negative electrode for non-aqueous electrolyte secondary battery, method of manufacturing the same, and non-aqueous electrolyte secondary battery using the same |
| WO2008072430A1 (en) | 2006-12-13 | 2008-06-19 | Panasonic Corporation | Negative electrode for nonaqueous electrolyte secondary battery and method for producing the same and nonaqueous electrolyte secondary battery employing it |
| WO2008072460A1 (en) | 2006-12-13 | 2008-06-19 | Panasonic Corporation | Negative electrode for rechargeable battery with nonaqueous electrolyte, process for producing the negative electrode, and rechargeable battery with nonaqueous electrolyte using the negative electrode |
| US8148012B2 (en) | 2007-02-01 | 2012-04-03 | Panasonic Corporation | Method for forming active material on a current collector of negative electrode using feedback process with measuring collector |
| US8192864B2 (en) | 2007-02-01 | 2012-06-05 | Panasonic Corporation | Battery, examination method and manufacturing method for negative electrode thereof, and examination apparatus and manufacturing apparatus for negative electrode thereof |
| US8273136B2 (en) | 2007-03-16 | 2012-09-25 | Panasonic Corporation | Electrochemical element, and method and apparatus for manufacturing electrode thereof |
| WO2008124227A1 (en) * | 2007-04-05 | 2008-10-16 | 3M Innovative Properties Company | Electrodes with raised patterns |
| WO2008136166A1 (en) | 2007-04-26 | 2008-11-13 | Panasonic Corporation | Electrode for electrochemical elment, process for producing the electrode, and electrochemical element using the electrode |
| US8187755B2 (en) | 2007-04-26 | 2012-05-29 | Panasonic Corporation | Electrode for electrochemical element, its manufacturing method, and electrochemical element using the same |
| US9871249B2 (en) | 2007-05-11 | 2018-01-16 | Nexeon Limited | Silicon anode for a rechargeable battery |
| US9252426B2 (en) | 2007-05-11 | 2016-02-02 | Nexeon Limited | Silicon anode for a rechargeable battery |
| WO2008139157A1 (en) * | 2007-05-11 | 2008-11-20 | Nexeon Ltd | A silicon anode for a rechargeable battery |
| US8257869B2 (en) | 2007-06-01 | 2012-09-04 | Panasonic Corporation | Electrode for electrochemical element and electrochemical element using the electrode |
| KR101217452B1 (en) * | 2007-07-17 | 2013-01-02 | 넥세온 엘티디 | Composite electrode |
| WO2009010757A1 (en) * | 2007-07-17 | 2009-01-22 | Nexeon Limited | Production |
| KR101243604B1 (en) | 2007-07-17 | 2013-03-14 | 넥세온 엘티디 | Bonded silicon fibres |
| WO2009010758A3 (en) * | 2007-07-17 | 2009-03-12 | Nexeon Ltd | A method of fabricating structured particles composed of silicon or a silicon-based material and their use in lithium rechargeable batteries |
| US8870975B2 (en) | 2007-07-17 | 2014-10-28 | Nexeon Ltd. | Method of fabricating structured particles composed of silicon or a silicon-based material and their use in lithium rechargeable batteries |
| EP2194596A3 (en) * | 2007-07-17 | 2010-11-17 | Nexeon Limited | A method of fabricating structured particles composed of silicon or a silicon-based material and their use in lithium rechargeable batteries |
| RU2451368C2 (en) * | 2007-07-17 | 2012-05-20 | Нексеон Лимитед | Method to manufacture structured particles containing silicon or silicon-based material and their application in rechargeable lithium batteries |
| CN101790804B (en) * | 2007-07-17 | 2014-09-17 | 奈克松有限公司 | Method for manufacturing electrode and method for manufacturing lithium rechargeable battery and lithium ion battery electrode |
| WO2009010759A1 (en) * | 2007-07-17 | 2009-01-22 | Nexeon Limited | Method |
| US9012079B2 (en) | 2007-07-17 | 2015-04-21 | Nexeon Ltd | Electrode comprising structured silicon-based material |
| US9871244B2 (en) | 2007-07-17 | 2018-01-16 | Nexeon Limited | Method of fabricating structured particles composed of silicon or a silicon-based material and their use in lithium rechargeable batteries |
| US8642211B2 (en) | 2007-07-17 | 2014-02-04 | Nexeon Limited | Electrode including silicon-comprising fibres and electrochemical cells including the same |
| US8940437B2 (en) | 2007-07-17 | 2015-01-27 | Nexeon Limited | Method of fabricating structured particles composed of silicon or a silicon-based material and their use in lithium rechargeable batteries |
| JP2010533945A (en) * | 2007-07-17 | 2010-10-28 | ネグゼオン・リミテッド | Product |
| JP2010533946A (en) * | 2007-07-17 | 2010-10-28 | ネグゼオン・リミテッド | Method |
| JP4563478B2 (en) * | 2007-11-02 | 2010-10-13 | パナソニック株式会社 | Lithium ion secondary battery |
| JP2009135084A (en) * | 2007-11-02 | 2009-06-18 | Panasonic Corp | Lithium ion secondary battery |
| US9334557B2 (en) | 2007-12-21 | 2016-05-10 | Sapurast Research Llc | Method for sputter targets for electrolyte films |
| US9786873B2 (en) | 2008-01-11 | 2017-10-10 | Sapurast Research Llc | Thin film encapsulation for thin film batteries and other devices |
| JP2010008266A (en) * | 2008-06-27 | 2010-01-14 | Panasonic Corp | Metal sheet inspecting method and battery manufacturing method |
| US8906523B2 (en) | 2008-08-11 | 2014-12-09 | Infinite Power Solutions, Inc. | Energy device with integral collector surface for electromagnetic energy harvesting and method thereof |
| US9184438B2 (en) | 2008-10-10 | 2015-11-10 | Nexeon Ltd. | Method of fabricating structured particles composed of silicon or a silicon-based material and their use in lithium rechargeable batteries |
| US8932759B2 (en) | 2008-10-10 | 2015-01-13 | Nexeon Ltd. | Method of fabricating structured particles composed of silicon or a silicon-based material |
| US8962183B2 (en) | 2009-05-07 | 2015-02-24 | Nexeon Limited | Method of making silicon anode material for rechargeable cells |
| GB2470056B (en) * | 2009-05-07 | 2013-09-11 | Nexeon Ltd | A method of making silicon anode material for rechargeable cells |
| EP2321441A1 (en) * | 2009-05-07 | 2011-05-18 | Nexeon Limited | A method of making silicon anode material for rechargeable cells |
| GB2470056A (en) * | 2009-05-07 | 2010-11-10 | Nexeon Ltd | A method of forming a silicon anode material for rechargeable cells |
| US9553304B2 (en) | 2009-05-07 | 2017-01-24 | Nexeon Limited | Method of making silicon anode material for rechargeable cells |
| EP2321441B1 (en) * | 2009-05-07 | 2016-10-12 | Nexeon Limited | A method of making silicon anode material for rechargeable cells |
| US9608272B2 (en) | 2009-05-11 | 2017-03-28 | Nexeon Limited | Composition for a secondary battery cell |
| US10050275B2 (en) | 2009-05-11 | 2018-08-14 | Nexeon Limited | Binder for lithium ion rechargeable battery cells |
| US9853292B2 (en) | 2009-05-11 | 2017-12-26 | Nexeon Limited | Electrode composition for a secondary battery cell |
| JP2011023710A (en) * | 2009-06-19 | 2011-02-03 | Semiconductor Energy Lab Co Ltd | Method for manufacturing electric storage device |
| US9532453B2 (en) | 2009-09-01 | 2016-12-27 | Sapurast Research Llc | Printed circuit board with integrated thin film battery |
| JP2011096646A (en) * | 2009-09-30 | 2011-05-12 | Semiconductor Energy Lab Co Ltd | Manufacturing method for electrode for power storage device, and manufacturing method for power storage device |
| US8658313B2 (en) | 2009-09-30 | 2014-02-25 | Semiconductor Energy Laboratory Co., Ltd. | Method for manufacturing electrode, and method for manufacturing power storage device and power generation and storage device having the electrode |
| US9011702B2 (en) | 2009-09-30 | 2015-04-21 | Semiconductor Energy Laboratory Co., Ltd. | Method for manufacturing electrode for power storage device and method for manufacturing power storage device |
| KR101740692B1 (en) * | 2009-09-30 | 2017-05-26 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | Method for manufacturing electrode for power storage device and method for manufacturing power storage device |
| US10003068B2 (en) | 2009-11-03 | 2018-06-19 | Zenlabs Energy, Inc. | High capacity anode materials for lithium ion batteries |
| US9190694B2 (en) | 2009-11-03 | 2015-11-17 | Envia Systems, Inc. | High capacity anode materials for lithium ion batteries |
| JP2013510405A (en) * | 2009-11-03 | 2013-03-21 | エンビア・システムズ・インコーポレイテッド | High capacity anode materials for lithium ion batteries |
| US11309534B2 (en) | 2009-11-03 | 2022-04-19 | Zenlabs Energy, Inc. | Electrodes and lithium ion cells with high capacity anode materials |
| JP2011129344A (en) * | 2009-12-17 | 2011-06-30 | Toyota Motor Corp | Lithium ion secondary battery |
| US9735419B2 (en) | 2010-03-26 | 2017-08-15 | Semiconductor Energy Laboratory Co., Ltd. | Secondary battery and method for forming electrode of secondary battery |
| US8772174B2 (en) | 2010-04-09 | 2014-07-08 | Nexeon Ltd. | Method of fabricating structured particles composed of silicon or silicon-based material and their use in lithium rechargeable batteries |
| US9368836B2 (en) | 2010-06-07 | 2016-06-14 | Nexeon Ltd. | Additive for lithium ion rechargeable battery cells |
| US10680277B2 (en) | 2010-06-07 | 2020-06-09 | Sapurast Research Llc | Rechargeable, high-density electrochemical device |
| US8945774B2 (en) | 2010-06-07 | 2015-02-03 | Nexeon Ltd. | Additive for lithium ion rechageable battery cells |
| US9871248B2 (en) | 2010-09-03 | 2018-01-16 | Nexeon Limited | Porous electroactive material |
| US9647263B2 (en) | 2010-09-03 | 2017-05-09 | Nexeon Limited | Electroactive material |
| US9947920B2 (en) | 2010-09-03 | 2018-04-17 | Nexeon Limited | Electroactive material |
| US9583767B2 (en) * | 2012-01-05 | 2017-02-28 | GM Global Technology Operations LLC | Methods for making battery electrode systems |
| US20130177804A1 (en) * | 2012-01-05 | 2013-07-11 | GM Global Technology Operations LLC | Methods for making battery electrode systems |
| US20180019466A1 (en) * | 2012-10-05 | 2018-01-18 | Semiconductor Energy Laboratory Co., Ltd. | Negative electrode for lithium-ion secondary battery, manufacturing method thereof, and lithium-ion secondary battery |
| JP2013131506A (en) * | 2013-04-03 | 2013-07-04 | Toyota Motor Corp | Positive electrode current collector foil for battery, method of manufacturing the same, and battery |
| CN105190955B (en) * | 2013-05-31 | 2017-09-26 | 株式会社安永 | The manufacture method of electrode for nonaqueous electrolyte secondary battery and electrode for nonaqueous electrolyte secondary battery |
| KR20160014621A (en) * | 2013-05-31 | 2016-02-11 | 가부시기가이샤야스나가 | Electrode for non-aqueous electrolyte secondary battery, and manufacturing method of electrode for non-aqueous electrolyte secondary battery |
| WO2014192637A1 (en) * | 2013-05-31 | 2014-12-04 | 株式会社安永 | Electrode for non-aqueous electrolyte secondary battery, and manufacturing method of electrode for non-aqueous electrolyte secondary battery |
| KR102212144B1 (en) * | 2013-05-31 | 2021-02-04 | 가부시기가이샤야스나가 | Electrode for non-aqueous electrolyte secondary battery, and manufacturing method of electrode for non-aqueous electrolyte secondary battery |
| JPWO2014192637A1 (en) * | 2013-05-31 | 2017-02-23 | 株式会社安永 | Non-aqueous electrolyte secondary battery electrode and method for producing non-aqueous electrolyte secondary battery electrode |
| TWI622209B (en) * | 2013-05-31 | 2018-04-21 | Yasunaga Kk | Electrode for nonaqueous electrolyte secondary battery and method for producing nonaqueous electrolyte secondary battery |
| CN105190955A (en) * | 2013-05-31 | 2015-12-23 | 株式会社安永 | Electrode for non-aqueous electrolyte secondary battery, and manufacturing method of electrode for non-aqueous electrolyte secondary battery |
| KR101410803B1 (en) | 2014-03-10 | 2014-06-24 | 경상대학교산학협력단 | A discontinuous electrode, battery using the same, a method for producing thereof |
| JP2016085978A (en) * | 2014-10-24 | 2016-05-19 | 株式会社半導体エネルギー研究所 | Secondary battery and manufacturing method of the same |
| JP2020145203A (en) * | 2014-10-24 | 2020-09-10 | 株式会社半導体エネルギー研究所 | Secondary battery |
| US10978696B2 (en) | 2014-10-24 | 2021-04-13 | Semiconductor Energy Laboratory Co., Ltd. | Secondary battery and manufacturing method of the same |
| KR20160048668A (en) * | 2014-10-24 | 2016-05-04 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | Secondary battery and manufacturing method of the same |
| JP2022095800A (en) * | 2014-10-24 | 2022-06-28 | 株式会社半導体エネルギー研究所 | Secondary battery |
| KR102471728B1 (en) * | 2014-10-24 | 2022-11-29 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | Secondary battery and manufacturing method of the same |
| CN108292737A (en) * | 2016-08-25 | 2018-07-17 | 株式会社Lg化学 | Has punctulate electrode for secondary battery |
| US10818929B2 (en) | 2016-08-25 | 2020-10-27 | Lg Chem, Ltd. | Electrode for secondary battery having fine holes |
| WO2018038479A1 (en) * | 2016-08-25 | 2018-03-01 | 주식회사 엘지화학 | Electrode for secondary battery comprising fine holes |
| KR101882396B1 (en) * | 2016-10-18 | 2018-07-26 | 서울대학교산학협력단 | Lithium battery and method for manufacturing electrode of the lithium battery |
| KR20180042712A (en) * | 2016-10-18 | 2018-04-26 | 서울대학교산학협력단 | Lithium battery and method for manufacturing electrode of the lithium battery |
| JP2022126945A (en) * | 2021-02-19 | 2022-08-31 | プライムアースＥｖエナジー株式会社 | Nonaqueous electrolyte secondary battery and manufacturing method thereof |
| JP7342050B2 (en) | 2021-02-19 | 2023-09-11 | プライムアースＥｖエナジー株式会社 | Non-aqueous electrolyte secondary battery and method for manufacturing non-aqueous electrolyte secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4183401B2 (en) | 2008-11-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4183401B2 (en) | Method for manufacturing electrode for lithium secondary battery and lithium secondary battery | |
| JP3733071B2 (en) | Lithium battery electrode and lithium secondary battery | |
| JP4248240B2 (en) | Lithium secondary battery | |
| JP4027255B2 (en) | Negative electrode for lithium secondary battery and method for producing the same | |
| JP4610213B2 (en) | Lithium secondary battery and manufacturing method thereof | |
| JP3913490B2 (en) | Method for producing electrode for lithium secondary battery | |
| KR101195672B1 (en) | Lithium Secondary Battery | |
| JP2003007305A (en) | Electrode for secondary lithium battery and secondary lithium battery | |
| JP2002319408A (en) | Lithium secondary battery electrode and lithium secondary battery | |
| WO2010110205A1 (en) | Lithium ion secondary battery, electrode for the battery, and electrodeposited copper foil for the electrode for the battery | |
| JP4212458B2 (en) | Lithium secondary battery | |
| JP2004296103A (en) | Non-aqueous electrolyte for secondary battery and non-aqueous electrolyte secondary battery | |
| WO2004109839A1 (en) | Lithium secondary battery and method for producing same | |
| JP4497899B2 (en) | Lithium secondary battery | |
| JP2004296104A (en) | Non-aqueous electrolyte for secondary battery and non-aqueous electrolyte secondary battery | |
| JP4148665B2 (en) | Electrode for lithium secondary battery and lithium secondary battery | |
| JP2002042783A (en) | Lithium secondary battery | |
| JP2002231224A (en) | Lithium secondary battery electrode, its manufacturing method, and lithium secondary battery | |
| JP5084140B2 (en) | Method for producing negative electrode for lithium secondary battery | |
| JP4318405B2 (en) | Lithium secondary battery | |
| WO2006103829A1 (en) | Nonaqueous electrolyte secondary battery | |
| JP2003017069A (en) | Electrode for lithium secondary battery and lithium secondary battery | |
| JP4436624B2 (en) | Lithium secondary battery | |
| JP5127888B2 (en) | Lithium secondary battery and manufacturing method thereof | |
| JP4471603B2 (en) | Lithium secondary battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20050712 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20070620 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080325 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20080522 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20080805 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20080902 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110912 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110912 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110912 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120912 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120912 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130912 Year of fee payment: 5 |
|
| LAPS | Cancellation because of no payment of annual fees |