JPH11354104A - Nonaqueous electrolyte secondary battery and manufacture for electrode - Google Patents
Nonaqueous electrolyte secondary battery and manufacture for electrodeInfo
- Publication number
- JPH11354104A JPH11354104A JP11074117A JP7411799A JPH11354104A JP H11354104 A JPH11354104 A JP H11354104A JP 11074117 A JP11074117 A JP 11074117A JP 7411799 A JP7411799 A JP 7411799A JP H11354104 A JPH11354104 A JP H11354104A
- Authority
- JP
- Japan
- Prior art keywords
- secondary battery
- silane compound
- electrolyte secondary
- negative electrode
- aqueous electrolyte
- 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.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、非水電解液を備え
る非水電解液二次電池に関する。The present invention relates to a non-aqueous electrolyte secondary battery having a non-aqueous electrolyte.
【０００２】[0002]
【従来の技術】従来より、リチウムイオンを放出及び吸
蔵する正極と、該正極から放出されたリチウムイオンを
吸蔵及び放出する負極と、該正極及び該負極の間に介在
して該リチウムイオンを移動させる非水電解液とから構
成される非水電解液二次電池がある。その非水電解液に
は、ＬｉＰＦ6などのリチウム塩をエチレンカーボネー
トなどの有機溶媒に溶解したものが多用されている。2. Description of the Related Art Conventionally, a positive electrode for releasing and occluding lithium ions, a negative electrode for occluding and releasing lithium ions released from the positive electrode, and moving the lithium ions between the positive electrode and the negative electrode. And a non-aqueous electrolyte secondary battery. As the non-aqueous electrolyte, a solution in which a lithium salt such as LiPF 6 is dissolved in an organic solvent such as ethylene carbonate is frequently used.
【０００３】このように電解液に有機溶媒が用いられて
いる電池では、リチウムイオンが電極に吸蔵される時に
電極界面で副反応が発生すると、吸蔵されたリチウムイ
オンの一部で放出不能になるものが生じることがある。
このように放出不能となったリチウムイオン量はリテン
ション容量と呼ばれる。従来の電池では、このリテンシ
ョン容量が大きく、十分満足される充放電効率及び充放
電サイクル特性が得られていなかった。In a battery in which an organic solvent is used as an electrolyte as described above, if a side reaction occurs at the electrode interface when lithium ions are occluded by the electrode, some of the occluded lithium ions cannot be released. Things can happen.
The amount of lithium ions that cannot be released in this way is called a retention capacity. In a conventional battery, the retention capacity is large, and satisfactory charge / discharge efficiency and charge / discharge cycle characteristics have not been obtained.
【０００４】[0004]
【発明が解決しようとする課題】本発明は上記実情に鑑
みてなされたものであり、従来の非水電解液二次電池よ
りもリテンション容量が小さく、より高い充放電効率
と、より優れた充放電サイクル特性とを有する非水電解
液二次電池を提供することを課題とする。また、非水電
解液二次電池に、より高い充放電効率と、より優れた充
放電サイクル特性とを確実に付与することのできる電極
の製造方法を提供することを課題とする。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has a smaller retention capacity, higher charge / discharge efficiency, and superior charge / discharge efficiency than conventional non-aqueous electrolyte secondary batteries. It is an object to provide a non-aqueous electrolyte secondary battery having discharge cycle characteristics. It is another object of the present invention to provide a method for manufacturing an electrode that can reliably impart higher charge / discharge efficiency and better charge / discharge cycle characteristics to a nonaqueous electrolyte secondary battery.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、リチウム
イオンを放出及び吸蔵する正極と、該正極から放出され
たリチウムイオンを吸蔵及び放出する負極と、該正極及
び該負極の間に介在して該リチウムイオンを移動させる
非水電解液とから構成される非水電解液二次電池におい
ては、正極及び負極の少なくとも一方の電極活物質の表
面に、水酸基やカルボキシル基など、非水電解液と反応
性の高い官能基が存在し、こうした官能基が、リチウム
イオンが電極に吸蔵される時に電極界面で発生する副反
応に関与していると考えた。Means for Solving the Problems The present inventors have developed a positive electrode for releasing and storing lithium ions, a negative electrode for storing and releasing lithium ions released from the positive electrode, and an intervening member between the positive electrode and the negative electrode. In the non-aqueous electrolyte secondary battery composed of a non-aqueous electrolyte solution for transferring lithium ions, a non-aqueous electrolyte such as a hydroxyl group or a carboxyl group is formed on the surface of at least one of the positive electrode and the negative electrode. There was a functional group having high reactivity with the liquid, and it was considered that such a functional group was involved in a side reaction occurring at the electrode interface when lithium ions were inserted into the electrode.
【０００６】そこで、本発明者らは、こうした官能基に
よる副反応を抑制することを目的として、正極及び負極
の少なくとも一方をアルコキシ基を有するシラン化合
物、及びフッ素系界面活性剤の少なくとも一方で処理す
ることを試みた。そして、その電極を非水電解液二次電
池に用いたところ、電池のリテンション容量が低下し、
充放電効率及び充放電サイクル特性がともに向上してい
ることを発見した。本発明は、このような知見に基づい
てなされたものである。In order to suppress such side reactions due to the functional groups, the present inventors treated at least one of a positive electrode and a negative electrode with at least one of a silane compound having an alkoxy group and at least one of a fluorine-based surfactant. Tried to do. And when the electrode was used for a non-aqueous electrolyte secondary battery, the retention capacity of the battery was reduced,
It was found that both the charge and discharge efficiency and the charge and discharge cycle characteristics were improved. The present invention has been made based on such findings.
【０００７】すなわち、本発明の非水電解液二次電池
は、リチウムイオンを放出及び吸蔵する正極と、該正極
から放出されたリチウムイオンを吸蔵及び放出する負極
と、該正極及び該負極の間に介在して該リチウムイオン
を移動させる非水電解液とから構成される非水電解液二
次電池において、前記正極及び前記負極の少なくとも一
方は、アルコキシ基を有するシラン化合物、及びフッ素
系界面活性剤の少なくとも一方で処理されていることを
特徴とする。That is, the nonaqueous electrolyte secondary battery of the present invention comprises a positive electrode for releasing and occluding lithium ions, a negative electrode for occluding and releasing lithium ions released from the positive electrode, and a negative electrode between the positive electrode and the negative electrode. And a non-aqueous electrolyte secondary battery comprising: a non-aqueous electrolyte that moves the lithium ions through the intermediary of at least one of the positive electrode and the negative electrode, wherein at least one of the positive electrode and the negative electrode is a silane compound having an alkoxy group; Characterized in that at least one of the agents has been treated.
【０００８】この非水電解液二次電池では、従来の非水
電解液二次電池よりもリテンション容量が小さいため、
より高い充放電効率と、より優れた充放電サイクル特性
とが得られる。リテンション容量が小さくなったのは、
前記シラン化合物及び前記フッ素系界面活性剤の少なく
とも一方が、電極表面に化学的に安定な皮膜を形成する
ことで、電極と電解液との副反応を抑制しているからと
考えられる。[0008] This non-aqueous electrolyte secondary battery has a smaller retention capacity than a conventional non-aqueous electrolyte secondary battery.
Higher charge / discharge efficiency and better charge / discharge cycle characteristics can be obtained. The reason that the retention capacity has decreased is that
It is considered that at least one of the silane compound and the fluorine-based surfactant suppresses a side reaction between the electrode and the electrolytic solution by forming a chemically stable film on the electrode surface.
【０００９】このようにシラン化合物より形成された皮
膜が電極の表面で安定に存在するためには、電池の充放
電反応時に電極の表面で起こる酸化還元反応に対しても
安定でなければならない。特に、リチウム二次電池にお
いては、正極が３．５Ｖ〜４．５Ｖ（ｖ．ｓ．Ｌｉ）の
強い酸化雰囲気に曝され、負極は０Ｖ〜１．０Ｖの強い
還元雰囲気にさらされる。それゆえ、正極に用いるシラ
ン化合物には耐酸化性をもたせるとともに、負極に用い
るシラン化合物には耐還元性を持たせることにより、従
来よりも化学的安定性を一層高めることができ、サイク
ル特性の向上を図ることができる。In order for the film formed of the silane compound to exist stably on the surface of the electrode, it must be stable against the oxidation-reduction reaction occurring on the surface of the electrode during the charge / discharge reaction of the battery. In particular, in a lithium secondary battery, the positive electrode is exposed to a strong oxidizing atmosphere of 3.5 V to 4.5 V (vs. Li), and the negative electrode is exposed to a strong reducing atmosphere of 0 V to 1.0 V. Therefore, by providing the silane compound used for the positive electrode with oxidation resistance and the silane compound used for the negative electrode with reduction resistance, the chemical stability can be further improved than before, and the cycle characteristics can be improved. Improvement can be achieved.
【００１０】さらに、本発明者らは、前記処理におい
て、予めアルコキシ基を有するシラン化合物と水とを含
む処理液で処理した電極活物質を用いて電極を成形し
た。その電極を非水電解液二次電池に用いたところ、そ
の電池でより高い充放電効率と、より優れた充放電サイ
クル特性とを確実に得ることができることを見出した。
このことから、前記処理では、電極活物質をあらかじめ
アルコキシ基を有するシラン化合物と水とを含む処理液
で処理することが好ましい。ここで用いる処理液中には
水が含まれており、この水とシラン化合物のアルコキシ
基との反応でシラノールができ、このシラノールと電極
活物質表面の官能基との脱水縮合反応により、電極活物
質の表面にシラン化合物層が形成される。Further, the present inventors formed an electrode using an electrode active material previously treated with a treatment solution containing a silane compound having an alkoxy group and water in the above treatment. When the electrode was used in a non-aqueous electrolyte secondary battery, it was found that higher charge / discharge efficiency and better charge / discharge cycle characteristics could be reliably obtained in the battery.
For this reason, in the treatment, it is preferable to treat the electrode active material in advance with a treatment liquid containing a silane compound having an alkoxy group and water. The processing liquid used here contains water, and silanol is formed by the reaction of the water with the alkoxy group of the silane compound. The dehydration condensation reaction between the silanol and the functional group on the surface of the electrode active material causes the electrode active. A silane compound layer is formed on the surface of the substance.
【００１１】このように処理液中の水の存在で、シラン
化合物層と電極活物質の表面との結合が強固になる。従
って、こうして処理された電極活物質より成形された電
極を非水電解液二次電池に用いれば、より高い充放電効
率と、より優れた充放電サイクル特性とを得ることがで
きる。一方、本発明者らは、サイクル劣化が、正極活物
質の界面での副反応に伴ってリチウムの消耗が起こる機
構によって起こることに着目し、正極活物質の表面をあ
らかじめ、アルコキシ基を有するシラン化合物を含む処
理液で処理して、正極活物質の表面にシラン化合物より
なるシラン化合物層を形成することにより、正極活物質
表面の反応性を低減して、電解液の分解反応を抑制する
ことができることを見出した。As described above, the presence of water in the treatment liquid strengthens the bond between the silane compound layer and the surface of the electrode active material. Therefore, if the electrode formed from the electrode active material thus treated is used for a nonaqueous electrolyte secondary battery, higher charge / discharge efficiency and better charge / discharge cycle characteristics can be obtained. On the other hand, the present inventors have focused on the fact that cycle deterioration occurs due to a mechanism in which lithium is consumed by a side reaction at the interface of the positive electrode active material, and the surface of the positive electrode active material is previously treated with a silane having an alkoxy group. Forming a silane compound layer composed of a silane compound on the surface of the positive electrode active material by treating with a treatment solution containing a compound, thereby reducing the reactivity of the positive electrode active material surface and suppressing the decomposition reaction of the electrolytic solution I found that I can do it.
【００１２】また、サイクル劣化が、リチウムが負極に
吸蔵されるときに、図５に示されるように負極表面上の
反応性の高い官能基（水酸基やカルボキシル基）と、リ
チウムとが反応して、リチウムが失活する機構によって
起こることに着目して、負極活物質の表面に存在する電
解液と反応性の高い官能基を、あらかじめアルコキシ基
を有するシラン化合物を含む処理液で処理して、負極活
物質の表面にシラン化合物よりなるシラン化合物層を形
成することにより、電解液の分解反応を抑制することが
できることを見出した。Further, when the lithium is occluded in the negative electrode, the highly reactive functional group (hydroxyl group or carboxyl group) on the negative electrode surface reacts with the lithium as shown in FIG. Focusing on what happens by the mechanism by which lithium is deactivated, a functional group having high reactivity with the electrolytic solution present on the surface of the negative electrode active material is treated with a treating solution containing a silane compound having an alkoxy group in advance, By forming a silane compound layer made of a silane compound on the surface of the negative electrode active material, it has been found that the decomposition reaction of the electrolytic solution can be suppressed.
【００１３】上記課題を解決する本発明の電極の製造方
法は、これらの知見に基づいてなされたものである。す
なわち、本発明の電極の製造方法は、電極活物質をあら
かじめアルコキシ基を有するシラン化合物を含む処理液
に曝して、該電極活物質の表面部にシラン化合物よりな
るシラン化合物層を形成した後、該シラン化合物層が形
成された該電極活物質と、結着剤と、溶剤とを混合して
スラリー状の合剤を調製し、該合剤を集電体に塗布して
乾燥させることにより電極を製造することを特徴とす
る。The method of manufacturing an electrode according to the present invention which solves the above problems has been made based on these findings. That is, in the method for producing an electrode of the present invention, after exposing the electrode active material to a treatment solution containing a silane compound having an alkoxy group in advance, forming a silane compound layer made of a silane compound on the surface of the electrode active material, The electrode active material on which the silane compound layer is formed, a binder, and a solvent are mixed to prepare a slurry mixture, and the mixture is applied to a current collector and dried to form an electrode. Is manufactured.
【００１４】この非水電解液二次電池では、電極活物質
をあらかじめ処理液で処理するため、確実にシラン化合
物層が電極活物質の表面に形成されることになる。こう
して得られた電極は、従来の電極よりも、非水電解液二
次電池に対して、より高い充放電効率と、より優れた充
放電サイクル特性とを確実に付与することができる。こ
のとき、前記処理液には水を含むもの、すなわちアルコ
キシ基を有するシラン化合物と水とを含むものを用いる
ことが好ましい。前述したように、処理液中の水の存在
で、シラン化合物層と電極活物質の表面との結合が強固
になる。従って、こうして製造された電極は、処理液に
は水を含まないものを用いて製造した電極よりも、非水
電解液二次電池に対して、より一層高い充放電効率と、
より一層優れた充放電サイクル特性とを確実に付与する
ことができる。In this non-aqueous electrolyte secondary battery, since the electrode active material is preliminarily treated with the treatment liquid, a silane compound layer is surely formed on the surface of the electrode active material. The electrode thus obtained can surely impart higher charge / discharge efficiency and more excellent charge / discharge cycle characteristics to the nonaqueous electrolyte secondary battery than conventional electrodes. At this time, it is preferable to use a treatment liquid containing water, that is, a treatment liquid containing a silane compound having an alkoxy group and water. As described above, the bond between the silane compound layer and the surface of the electrode active material becomes stronger due to the presence of water in the treatment liquid. Therefore, the electrode manufactured in this manner is higher than the electrode manufactured using a treatment liquid that does not contain water, with respect to the non-aqueous electrolyte secondary battery, with higher charging and discharging efficiency,
Even better charge / discharge cycle characteristics can be reliably provided.
【００１５】[0015]
【発明の実施の形態】本発明の非水電解液二次電池で
は、コイン型電池やボタン型電池、円筒型電池、角型電
池等の公知の電池構造をとることができる。正極には公
知の正極活物質を用いることができるが、正極活物質は
ＬｉＣｏＯ 2、ＬｉＮｉＯ2及びＬｉＭｎ2Ｏ4の少なくと
も一種からなることが好ましい。これらのリチウムと遷
移金属との複合酸化物は、電子とリチウムイオンの拡散
性能に優れ、高い充放電効率と良好な充放電サイクル特
性とが得られる。中でも、ＬｉＭｎ2Ｏ4は、マンガンの
資源が豊富であることから低コスト化を図ることができ
る。BEST MODE FOR CARRYING OUT THE INVENTION The non-aqueous electrolyte secondary battery of the present invention
Are coin-type batteries, button-type batteries, cylindrical batteries,
A known battery structure such as a pond can be used. The positive electrode
A known positive electrode active material can be used.
LiCoO Two, LiNiOTwoAnd LiMnTwoOFourAt least
Is also preferably composed of one kind. These lithium and transition
Complex oxide with metal transfer, diffusion of electrons and lithium ions
Excellent performance, high charge / discharge efficiency and good charge / discharge cycle characteristics
Sex is obtained. Among them, LiMnTwoOFourOf manganese
Abundant resources enable cost reduction
You.
【００１６】また、負極には公知の負極活物質を用いる
ことができるが、負極活物質は主として炭素からなるこ
とが好ましい。中でも結晶性の高い天然黒鉛や人造黒鉛
などからなるものを用いることが好ましい。このような
結晶性の高い炭素材を用いることにより、負極のリチウ
ムイオンの受け渡し効率を向上させることができる。正
極および負極のいずれも、電極活物質を集電体上に塗設
した電極を用いることが好ましい。Although a known negative electrode active material can be used for the negative electrode, it is preferable that the negative electrode active material is mainly composed of carbon. Above all, it is preferable to use one made of natural graphite or artificial graphite having high crystallinity. By using such a highly crystalline carbon material, the lithium ion transfer efficiency of the negative electrode can be improved. It is preferable to use an electrode in which an electrode active material is provided on a current collector for both the positive electrode and the negative electrode.
【００１７】非水電解液にも公知のものを用いることが
できるが、特に、エチレンカーボネート、プロピレンカ
ーボネートなどの高誘電率の主溶媒と、ジメチルカーボ
ネート、ジエチルカーボネート、エチルメチルカーボネ
ートなどの低粘性の副溶媒との混合有機溶媒に、支持電
解質としてＬｉＰＦ6 やＬｉＢＦ4、ＬｉＡｓＦ6、Ｌｉ
Ｎ（ＳＯ2ＣＦ3）3、ＬｉＣ（ＳＯ2ＣＦ3）2などのリチ
ウム塩を溶解させたものを用いることが好ましい。ま
た、副溶媒として、ジメトキシエタン、テトラヒドロフ
ラン及びブチルラクトンなどを用いてもよい。Known nonaqueous electrolytes can be used. In particular, a high dielectric constant main solvent such as ethylene carbonate and propylene carbonate and a low viscosity main solvent such as dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate are used. LiPF 6 , LiBF 4 , LiAsF 6 , or LiPF 6 as a supporting electrolyte in a mixed organic solvent with a sub-solvent
It is preferable to use a material in which a lithium salt such as N (SO 2 CF 3 ) 3 or LiC (SO 2 CF 3 ) 2 is dissolved. Further, dimethoxyethane, tetrahydrofuran, butyl lactone, or the like may be used as a secondary solvent.
【００１８】本発明の非水電解液二次電池では、アルコ
キシ基を有するシラン化合物、及びフッ素系界面活性剤
の少なくとも一方で処理された電極が用いられる。以
下、断らない限り、「処理する」とは、アルコキシ基を
有するシラン化合物、及びフッ素系界面活性剤の少なく
とも一方で処理することを意味するものとする。本発明
では、成形された電極を処理してもよいが、電極活物質
をあらかじめアルコキシ基を有するシラン化合物、及び
フッ素系界面活性剤の少なくとも一方で処理してもよ
い。後者の処理の方が電極活物質を確実に処理すること
ができる。In the non-aqueous electrolyte secondary battery of the present invention, an electrode treated with at least one of a silane compound having an alkoxy group and a fluorinated surfactant is used. Hereinafter, unless otherwise specified, “treat” means to treat at least one of a silane compound having an alkoxy group and a fluorinated surfactant. In the present invention, the formed electrode may be treated, but the electrode active material may be treated in advance with at least one of a silane compound having an alkoxy group and a fluorine-based surfactant. The latter treatment can more reliably treat the electrode active material.
【００１９】処理する方法としては特に限定されない
が、例えば、前記シラン化合物及び前記フッ素系界面活
性剤が所定量含まれる処理液を調整した後、この処理液
を電極又は電極活物質に塗布する方法、あるいはこの処
理液中に電極又は電極活物質を浸漬する方法などが挙げ
られる。電極活物質を処理する場合には、後者の方が容
易に処理することができる。また、ここに挙げた２つの
方法において、処理溶液中のシラン化合物及びフッ素系
界面活性剤の含有量は、電極の面積又は電極活物質の比
表面積、並びに処理時間等によって決定される。The method of treatment is not particularly limited. For example, a method of preparing a treatment solution containing a predetermined amount of the silane compound and the fluorine-based surfactant, and applying the treatment solution to an electrode or an electrode active material. Alternatively, a method of immersing the electrode or the electrode active material in the treatment liquid may be used. When the electrode active material is processed, the latter can be easily processed. In the two methods described above, the contents of the silane compound and the fluorine-based surfactant in the treatment solution are determined by the area of the electrode or the specific surface area of the electrode active material, the treatment time, and the like.
【００２０】ところで、前記シラン化合物のアルコキシ
基として、例えば表１に示される各種のアルコキシ基が
挙げられる。By the way, examples of the alkoxy group of the silane compound include various alkoxy groups shown in Table 1.
【００２１】[0021]
【表１】 [Table 1]
【００２２】前記シラン化合物はシランカップリング剤
であることが好ましい。電極に存在する、非水電解液と
反応性の高い官能基を、シランカップリング剤により置
換することにより、官能基の反応性を低減させることが
できる。このシランカップリング剤は、アルキル基系、
フッ素系、イソシアネート系及びアミノ系の少なくとも
一種の系の有機官能基を有することが好ましい。The silane compound is preferably a silane coupling agent. By replacing the functional group having high reactivity with the non-aqueous electrolyte present in the electrode with the silane coupling agent, the reactivity of the functional group can be reduced. This silane coupling agent is based on an alkyl group,
It preferably has at least one organic functional group of fluorine, isocyanate and amino.
【００２３】また、シランカップリング剤は、化学式１
で示されるものであることが好ましい。The silane coupling agent is represented by the following chemical formula 1.
It is preferable that it is shown by these.
【００２４】（化１）Ｙ−Ｓｉ−Ｘ3 ｛Ｙ：ＣＨ3 （ＣＨ2 ）n （ｎ＝０〜１０）、ＣＦ
3 （ＣＦ2 ）n （ＣＨ2 ）2（ｎ＝０〜１０）、Ｏ＝Ｃ
＝Ｎ（ＣＨ2 ）n （ｎ＝０〜１０）、ＣＨ2ＯＣＨＣＨ2
Ｏ（ＣＨ2）n（ｎ＝０〜１０）、ＮＨ2（ＣＨ2）2ＮＨ
（ＣＨ2）n（ｎ＝０〜１０）、あるいはＮＨ2 （Ｃ
Ｈ2 ）n（ｎ＝０〜１０）｝ ｛Ｘ：Ｏ−Ｒ （Ｒ：（ＣＨ2 ）n ＣＨ3 （ｎ＝０〜１
０）、ＣＯＣＨ3 、ＮＣＣＨ3 ＣＨ3 、ＮＣ2 Ｈ5 ＣＯ
ＣＨ3 又はＣＣＨ3 ＣＨ2 ）の加水分解性基｝ 上記に挙げたＹ基の好適な例（Ｎｏ．１〜Ｎｏ．４、Ｎ
ｏ．７及びＮｏ．１０）を表２に示す。また、Ｎｏ．
５、Ｎｏ．６、Ｎｏ．８、Ｎｏ．９及びＮｏ．１１の官
能基をもつシランカップリング剤を用いてもよい。(Chemical Formula 1) Y—Si—X 3 ｛Y: CH 3 (CH 2 ) n (n = 0 to 10), CF
3 (CF 2 ) n (CH 2 ) 2 (n = 0 to 10), O = C
= N (CH 2) n ( n = 0~10), CH 2 OCHCH 2
O (CH 2 ) n (n = 0 to 10), NH 2 (CH 2 ) 2 NH
(CH 2 ) n (n = 0 to 10) or NH 2 (C
H 2 ) n (n = 0 to 10)｝ {X: OR (R: (CH 2 ) n CH 3 (n = 0 to 1)
0), COCH 3 , NCCH 3 CH 3 , NC 2 H 5 CO
CH 3 or CCH 3 CH 2 ) Hydrolyzable group｝ Suitable examples of the above-mentioned Y group (No. 1 to No. 4, N
o. 7 and No. 7 10) is shown in Table 2. In addition, No.
5, no. 6, no. 8, No. 9 and No. 9 A silane coupling agent having 11 functional groups may be used.
【００２５】[0025]
【表２】 [Table 2]
【００２６】ところで、前記正極の処理で用いる前記シ
ラン化合物は、耐酸化性に優れた分子構造を有すること
が好ましい。また、前記負極の処理で用いる前記シラン
化合物は、耐還元性に優れた分子構造を有することが好
ましい。ここで、前記シランカップリング剤の耐酸化性
及び耐還元性は、Ｙ基の構造によって異なることが、電
子計算機を用いた分子軌道計算シミュレーションによっ
て明らかとなった。この分子軌道計算に用いたソフトウ
ェアは、一般に広く知られているＭＯＰＡＣ（ｖｅｒ．
７）を用い、Ａｕｓｔｉｎ Ｍｏｄｅｌ１（ＡＭ１法）
に基づく半経験的な分子軌道計算を行った。例えば、表
２に示した官能基をＹ基として有するシランカップリン
グ剤について分子軌道計算を行ったところ、表２に示さ
れる計算結果を得た。Incidentally, the silane compound used in the treatment of the positive electrode preferably has a molecular structure excellent in oxidation resistance. Further, the silane compound used in the treatment of the negative electrode preferably has a molecular structure with excellent reduction resistance. Here, it has been clarified by a molecular orbital calculation simulation using an electronic computer that the oxidation resistance and the reduction resistance of the silane coupling agent differ depending on the structure of the Y group. The software used for this molecular orbital calculation is generally known as MOPAC (ver.
7) Using Austin Model 1 (AM1 method)
Semi-empirical molecular orbital calculations based on For example, when the molecular orbital calculation was performed on the silane coupling agent having the functional group shown in Table 2 as the Y group, the calculation results shown in Table 2 were obtained.
【００２７】なお、耐酸化性の指標は、最高被占軌道
（ＨＯＭＯ：Ｈｉｇｈｅｓｔ ｏｃｃｕｐｉｅｄ Ｍｏ
ｌｅｃｕｌａｒ Ｏｒｂｉｔａｌ）のエネルギー準位で
あり、その準位の大きさ（ＨＯＭＯ値）が小さいものほ
ど耐酸化性に優れる。また、耐還元性の指標は、最低空
軌道（ＬＵＭＯ：Ｌｏｗｅｓｔ Ｕｎｏｃｃｕｐｉｅｄ
Ｍｏｌｅｃｕｌａｒ Ｏｒｂｉｔａｌ）のエネルギー準
位であり、その準位の大きさ（ＬＵＭＯ値）が大きいも
のほど耐還元性に優れる。The index of oxidation resistance is determined by the highest occupied orbit (HOMO: Highest occupied Mo).
It is an energy level of a molecular orbital, and the smaller the level (HOMO value) of the level, the better the oxidation resistance. The index of the reduction resistance is the lowest unoccupied orbit (LUMO: Lowest Unoccupied).
It is an energy level of a molecular orbital, and the higher the level (LUMO value), the better the reduction resistance.
【００２８】すなわち、電極表面にシラン化合物によっ
て形成される皮膜の耐熱化、耐還元性は、シランカップ
リング剤のＹ基の構造に依存し、耐酸化性の優れたＹ基
を有するシラン化合物皮膜を正極に形成し、耐還元性の
優れたＹ基を有するシラン化合物皮膜を負極に形成する
ことで、電極表面の皮膜は、より一層安定化する。その
結果、非水電解液二次電池において、より一層のサイク
ル特性の向上を図ることができる。That is, the heat resistance and the reduction resistance of the film formed by the silane compound on the electrode surface depend on the structure of the Y group of the silane coupling agent, and the silane compound film having the excellent oxidation resistance has a Y group. Is formed on the positive electrode and a silane compound film having a Y group having excellent reduction resistance is formed on the negative electrode, whereby the film on the electrode surface is further stabilized. As a result, in the non-aqueous electrolyte secondary battery, the cycle characteristics can be further improved.
【００２９】こうした耐酸化性に優れるシランカップリ
ング剤として、−９．７ｅＶ以下のＨＯＭＯ値を有する
ものが好ましく、例えば、メチルトリメトキシシラン
や、３−イソシアネートプロピルトリエトキシシラン、
３，３，３−トリフロロプロピルトリメトキシシラン、
γ−アミノプロピルトリエトキシシランを挙げることが
できる。As such a silane coupling agent having excellent oxidation resistance, those having a HOMO value of -9.7 eV or less are preferable. For example, methyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane,
3,3,3-trifluoropropyltrimethoxysilane,
γ-aminopropyltriethoxysilane can be mentioned.
【００３０】また、耐還元性に優れるシランカップリン
グ剤として、１ｅＶ以上のＬＵＭＯ値を有するものが好
ましく、例えば、γーアミノプロピルトリエトキシシラ
ンや、Ｎ−β（アミノエチル）γ−アミノプロピルトリ
エトキシシラン、メチルトリメトキシシラン、γ−グリ
シドキシドキシプロピルトリエトキシシランを挙げるこ
とができる。As the silane coupling agent having excellent reduction resistance, those having a LUMO value of 1 eV or more are preferable. For example, γ-aminopropyltriethoxysilane and N-β (aminoethyl) γ-aminopropyltrisilane Examples include ethoxysilane, methyltrimethoxysilane, and γ-glycidoxydoxypropyltriethoxysilane.
【００３１】一方、前記シランカップリング剤は、フッ
素系の官能基を有することが好ましいことは先にも述べ
た。このとき、シランカップリング剤が化学式１の分子
構造を有する場合には、Ｙ基がフッ素系の官能基とな
る。このフッ素系の官能基としては、化学式１で示した
パーフルオロアルキル基｛−（ＣＨ2）2（ＣＦ2）nＣＦ
3（ｎ＝０〜１０）｝などを挙げることができる。On the other hand, the silane coupling agent is
As mentioned earlier, it is preferable to have basic functional groups.
Was. At this time, the silane coupling agent is a molecule represented by Chemical Formula 1.
When it has a structure, the Y group becomes a fluorine-based functional group.
You. The fluorine-based functional group is represented by the following chemical formula 1.
Perfluoroalkyl group ｛-(CHTwo)Two(CFTwo)nCF
Three(N = 0 to 10)}.
【００３２】ところで、Ｙ基が化学式１及び表２で示さ
れる官能基である場合、電極活物質を前記シランカップ
リング剤で処理する際に、それらのＹ基が、非水電解液
と反応性の高い官能基（電極活物質に存在する）と反応
し、電極活物質どうしを凝集させてしまうことがある。
このことは、電極活物質を含む合剤が金属箔などの集電
体に塗布されて電極が成形されるような場合、合剤を集
電体に塗布するときに、電極活物質どうしの凝集によっ
て合剤がだま状となり、その合剤を集電体に均一に薄く
塗布することが困難となるという問題を引き起こす。そ
こで、電極活物質どうしの凝集を解くために、乾式にお
いては、ボールミルやスタンプミルなどを用いた分砕工
程を必要とし、湿式においては、ホモジナイザなどを用
いた分散工程が必要となる。When the Y group is a functional group represented by Formula 1 and Table 2, when the electrode active material is treated with the silane coupling agent, the Y group reacts with the non-aqueous electrolyte. Reacts with a high-functional group (existing in the electrode active material) to aggregate the electrode active materials.
This means that when the mixture containing the electrode active material is applied to a current collector such as a metal foil to form an electrode, when the mixture is applied to the current collector, aggregation of the electrode active materials occurs. As a result, the mixture becomes a lumpy state, which causes a problem that it is difficult to apply the mixture uniformly and thinly to the current collector. Therefore, in order to dissolve the aggregation of the electrode active materials, a dry process requires a crushing process using a ball mill or a stamp mill, and a wet process requires a dispersion process using a homogenizer or the like.
【００３３】ところが、Ｙ基が先に挙げたパーフルオロ
アルキル基などようなフッ素系の官能基であると、Ｙ基
は電極活物質と反応せず、活物質同士が凝集することが
防止される。その結果、活物質どうしの凝集を解くため
の工程が省かれることから、塗布工程の簡略化を図るこ
とができる。また、アルコキシ基を有するシラン化合物
として、変性シリコーンオイルを用いることが好まし
い。このような変性シリコーンオイルとして、化学式２
に示される側鎖変性のものや、化学式３に示される末端
変性のものなどが挙げられる。なお、化学式２及び化学
式３の式中のｌ、ｍはそれぞれ任意の整数である。However, when the Y group is a fluorine-based functional group such as the above-mentioned perfluoroalkyl group, the Y group does not react with the electrode active material, and the active materials are prevented from aggregating. . As a result, the step of dissolving the aggregation of the active materials is omitted, so that the application step can be simplified. Further, it is preferable to use a modified silicone oil as the silane compound having an alkoxy group. As such a modified silicone oil, chemical formula 2
And the terminal-modified one represented by Chemical Formula 3. Here, l and m in the formulas 2 and 3 are arbitrary integers.
【００３４】（化２） (Formula 2)
【００３５】（化３） (Formula 3)
【００３６】一方、フッ素系界面活性剤は化学式４に示
される構造を有する。On the other hand, the fluorine-based surfactant has a structure represented by the following chemical formula 4.
【００３７】（化４） ＲF−Ｚ ＲF はフッ素化水素疎水基であり、Ｚは親水あるいは親
有機基である。このようなフッ素系界面活性剤の特徴と
して、１．耐酸化、還元性に対し安定である、２．表面
張力を著しく低下させる。３．熱的に安定である、とい
うことがあげられる．これらの特徴を持ったフッ素系界
面活性剤により、電子吸引基であるフッ素末端が活性点
に吸着し、電解液の副反応を抑制する。さらに、活物質
表面の表面張力も低下させるため、活物質表面への電解
液の濡れ性も向上し、充放電効率及び充放電サイクル特
性が向上する。(Formula 4) R F -Z R F is a hydrogen fluorinated hydrophobic group, and Z is a hydrophilic or organophilic group. Characteristics of such a fluorine-based surfactant include: 1. stable against oxidation and reduction. Significantly reduces surface tension. 3. It is thermally stable. By the fluorine-based surfactant having these characteristics, the fluorine terminal, which is an electron-withdrawing group, is adsorbed to the active site, thereby suppressing a side reaction of the electrolytic solution. Furthermore, since the surface tension of the surface of the active material is also reduced, the wettability of the electrolyte on the surface of the active material is improved, and the charge / discharge efficiency and the charge / discharge cycle characteristics are improved.
【００３８】このフッ素系界面活性剤は、フッ素化アル
キルエステル、パーフルオロアルキルアルコキシレート
及びパーフルオロアルキルスルホン酸のいずれかのアン
モニウム塩あるいはアルカリ塩、並びにパーフルオロア
ルキル第４級アンモニウムヨウ化物及びパーフルオロア
ルキルポリオキシエチレンエタノール、並びに該アンモ
ニウム塩、該アルカリ塩、パーフルオロアルキル第４級
アンモニウムヨウ化物及びパーフルオロアルキルポリオ
キシエチレンエタノールの誘導体の少なくとも一種であ
ることが好ましい。This fluorine-based surfactant includes ammonium salts or alkali salts of any of fluorinated alkyl esters, perfluoroalkyl alkoxylates and perfluoroalkyl sulfonic acids, and perfluoroalkyl quaternary ammonium iodides and perfluoroalkyl sulfonic acids. Alkyl polyoxyethylene ethanol, and preferably at least one of the ammonium salt, the alkali salt, a perfluoroalkyl quaternary ammonium iodide and a derivative of perfluoroalkyl polyoxyethylene ethanol.
【００３９】[0039]
【実施例】以下、実施例により本発明を具体的に説明す
る。 （実施例１−１）本実施例の非水電解液二次電池は、図
１に示されるコイン型リチウム二次電池（ＣＲ２０３２
０）である。The present invention will be described below in detail with reference to examples. (Example 1-1) The non-aqueous electrolyte secondary battery of this example is a coin-type lithium secondary battery (CR2032) shown in FIG.
0).
【００４０】このリチウム二次電池は、リチウムイオン
を放出及び吸蔵できる正極１０と、正極１０から放出さ
れたリチウムイオンを吸蔵及び放出できる炭素材料より
なる負極２０と、電解液３０とを備えるコイン型のリチ
ウムイオン二次電池である。正極１０、負極２０及び非
水電解液３０は、それぞれステンレスによりなる正極ケ
ース４０及び負極ケース５０内に収納されている。正極
１０と負極２０との間には、ポリエチレン製の微多孔絶
縁膜（東燃タピルス製）によりなるセパレータ６０が介
在している。正極ケース４０及び負極ケース５０の開口
端は、ポリプロピレンによりなるガスケット７０によっ
て封止されている。This lithium secondary battery includes a positive electrode 10 capable of releasing and storing lithium ions, a negative electrode 20 made of a carbon material capable of storing and releasing lithium ions released from the positive electrode 10, and an electrolyte solution 30. Lithium ion secondary battery. The positive electrode 10, the negative electrode 20, and the nonaqueous electrolyte 30 are accommodated in a positive electrode case 40 and a negative electrode case 50 made of stainless steel, respectively. A separator 60 made of a polyethylene microporous insulating film (manufactured by Tonen Tapils) is interposed between the positive electrode 10 and the negative electrode 20. Open ends of the positive electrode case 40 and the negative electrode case 50 are sealed with a gasket 70 made of polypropylene.
【００４１】正極１０は、アルミニウムよりなる正極集
電体１０ａ（厚さ１５μｍ）と、リチウムマンガン酸化
物（ＬｉＭｎ2Ｏ4）が含まれる正極活物質層１０ｂとか
ら構成される。この正極１０は、次のようにして成形し
たものである。正極活物質としてＬｉＭｎ2Ｏ4粉末を用
意するとともに、導電材として炭素粉末（ＫＳ−１５）
を用意した。また、結着剤としてポリビニリデンフロラ
イド（ＰＶＤＦ）を用意し、分散溶媒としてＮ−メチル
−２ピロリドン（ＮＭＰ）を用意した。これらＬｉＭｎ
2Ｏ4粉末及び炭素粉末をＰＶＤＦとともにＮＭＰに加
え、よく混ぜ合わせてスラリー様の正極用合剤を得た。
ここでは、ＬｉＭｎ2Ｏ4粉末、炭素粉末及びＰＶＤＦを
８７：１０：３の重量比で配合した。この正極用合剤を
正極集電体１０ａに塗布した後、高温槽で十分に乾燥さ
せ、正極活物質層１０ｂを形成した。この正極活物質層
１０ｂをプレス処理して所定の密度にし、正極２０を得
た。The positive electrode 10 includes a positive electrode current collector 10a (15 μm thick) made of aluminum and a positive electrode active material layer 10b containing lithium manganese oxide (LiMn 2 O 4 ). This positive electrode 10 is formed as follows. LiMn 2 O 4 powder is prepared as a positive electrode active material, and carbon powder (KS-15) is used as a conductive material.
Was prepared. Further, polyvinylidene fluoride (PVDF) was prepared as a binder, and N-methyl-2-pyrrolidone (NMP) was prepared as a dispersion solvent. These LiMn
2 O 4 powder and carbon powder were added to NMP together with PVDF and mixed well to obtain a slurry-like mixture for positive electrode.
Here, LiMn 2 O 4 powder, carbon powder and PVDF were blended in a weight ratio of 87: 10: 3. After applying this positive electrode mixture to the positive electrode current collector 10a, it was sufficiently dried in a high-temperature bath to form the positive electrode active material layer 10b. The positive electrode active material layer 10b was pressed to a predetermined density to obtain a positive electrode 20.
【００４２】負極２０は、銅箔よりなる負極集電体２０
ａ（厚さ１０μｍ）と、負極活物質が含まれる負極活物
質層２０ｂとから構成され、アルコキシ基を有するシラ
ン化合物で処理されている。この負極２０は次のように
して成形したものである。負極活物質としてメソフェー
ズマイクロビーズ（ＭＣＭＢ）粉末を用意した。このＭ
ＣＭＢをＰＶＤＦとともにＮＭＰに加え、よく混ぜ合わ
せてスラリー様の負極用合剤を得た。ここでは、ＭＣＭ
ＢとＰＶＤＦとを９５：５の重量比で配合した。この負
極用合剤を銅箔２０ａに塗布した後、高温槽で十分に乾
燥させて負極活物質層２０ｂを形成し、負極２０の中間
成形体を成形した。The negative electrode 20 is a negative electrode current collector 20 made of copper foil.
a (thickness: 10 μm) and a negative electrode active material layer 20 b containing a negative electrode active material, and are treated with a silane compound having an alkoxy group. This negative electrode 20 is formed as follows. Mesophase microbead (MCMB) powder was prepared as a negative electrode active material. This M
CMB was added to NMP together with PVDF and mixed well to obtain a slurry-like negative electrode mixture. Here, MCM
B and PVDF were blended in a weight ratio of 95: 5. After applying this negative electrode mixture to the copper foil 20a, it was sufficiently dried in a high-temperature bath to form the negative electrode active material layer 20b, and an intermediate molded body of the negative electrode 20 was formed.
【００４３】アルコキシ基を有するシラン化合物とし
て、3,3,3−トリフロロプロピルトリメトキシシラン
（信越化学工業社製ＫＢＭ−７１０３）を用意し、これ
をエタノール及び水の混合溶媒に溶解させて処理液を調
整した。3,3,3−トリフロロプロピルトリメトキシシラ
ンは、フッ素系の官能基（パーフルオロアルキル基）を
有するシランカップリング剤である。処理液中に含まれ
る3,3,3−トリフロロプロピルトリメトキシシランの濃
度は、処理液全体の重量を１００重量％とすると、０．
１〜１０重量％の範囲にあることが好ましいが、ここで
は、エタノールが９４重量％含まれ、かつ水が５重量％
含まれる混合溶媒に対し、3,3,3−トリフロロプロピル
トリメトキシシランを１重量％溶解させた。As a silane compound having an alkoxy group, 3,3,3-trifluoropropyltrimethoxysilane (KBM-7103 manufactured by Shin-Etsu Chemical Co., Ltd.) was prepared and dissolved in a mixed solvent of ethanol and water for treatment. The liquid was adjusted. 3,3,3-Trifluoropropyltrimethoxysilane is a silane coupling agent having a fluorine-based functional group (perfluoroalkyl group). The concentration of 3,3,3-trifluoropropyltrimethoxysilane contained in the treatment liquid is 0.1% when the total weight of the treatment liquid is 100% by weight.
It is preferably in the range of 1 to 10% by weight, but here contains 94% by weight of ethanol and 5% by weight of water.
1% by weight of 3,3,3-trifluoropropyltrimethoxysilane was dissolved in the mixed solvent contained.
【００４４】先の負極２０の中間成形体をこの処理液に
１分間浸漬して、アルコキシ基を有するシラン化合物に
よる処理を行った。その後、高温槽で十分に乾燥させ、
処理液の溶媒を除去した。最後に、負極活物質層２０ｂ
が所定の密度となるように負極２０の中間成形体をプレ
ス処理して、負極２０を完成した。また、非水電解液３
０には、エチレンカーボネート及びジエチルカーボネー
トを体積比３０：７０で混合した溶媒に、支持塩として
ＬｉＰＦ6 を１ｍｏｌ／ｌ溶解させたものを用いた。 （実施例１−２）アルコキシ基を有するシラン化合物と
して、3,3,3−トリフロロプロピルトリメトキシシラン
の代わりに、10,10,10,9,9,8,8,7,7,6,6,5,5,4,4,3,3−
ヘプタデカフロロデシルトリメトキシシラン（信越化学
工業社製ＫＢＭ−７８０３）を用いて負極を処理した他
は、実施例１−１と同様にして非水電解液二次電池を作
製した。10,10,10,9,9,8,8,7,7,6,6,5,5,4,4,3,3−ヘプ
タデカフロロデシルトリメトキシシランは、フッ素系の
官能基（パーフルオロアルキル基）を有するシランカッ
プリング剤である。 （実施例１−３）下記のように、アルコキシ基を有する
シラン化合物であらかじめ処理した負極活物質を用いて
負極２０を成形した他は、実施例１−１と同様にして非
水電解液二次電池を作製した。The intermediate molded body of the negative electrode 20 was immersed in the treatment liquid for one minute, and treated with a silane compound having an alkoxy group. After that, dry thoroughly in a high-temperature bath,
The solvent of the treatment liquid was removed. Finally, the negative electrode active material layer 20b
The intermediate molded body of the negative electrode 20 was subjected to a press treatment so as to have a predetermined density, thereby completing the negative electrode 20. In addition, the non-aqueous electrolyte 3
For 0, a solution obtained by dissolving 1 mol / l of LiPF 6 as a supporting salt in a solvent obtained by mixing ethylene carbonate and diethyl carbonate at a volume ratio of 30:70 was used. (Example 1-2) As a silane compound having an alkoxy group, instead of 3,3,3-trifluoropropyltrimethoxysilane, 10,10,10,9,9,8,8,7,7,6 , 6,5,5,4,4,3,3-
A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1-1, except that the negative electrode was treated with heptadecafluorodecyltrimethoxysilane (KBM-7803 manufactured by Shin-Etsu Chemical Co., Ltd.). 10,10,10,9,9,8,8,7,7,6,6,5,5,4,4,3,3-heptadecafluorodecyltrimethoxysilane is a fluorine-based functional group (Fluoroalkyl group). (Example 1-3) A nonaqueous electrolyte solution 2 was formed in the same manner as in Example 1-1, except that the negative electrode 20 was formed using a negative electrode active material previously treated with a silane compound having an alkoxy group as described below. A secondary battery was manufactured.
【００４５】負極活物質としてＭＣＭＢ粉末を用意し
た。また、アルコキシ基を有するシラン化合物として、
3,3,3−トリフロロプロピルトリメトキシシラン（信越
化学工業社製ＫＢＭ−７１０３）を用意し、これをエタ
ノール及び水の混合溶媒に溶解させて処理液を調整し
た。処理液中に含まれる3,3,3−トリフロロプロピルト
リメトキシシランの濃度は、処理液全体の重量を１００
重量％とすると、０．１〜１０重量％の範囲にあること
が好ましいが、ここでは、エタノールが９４重量％含ま
れ、かつ水が５重量％含まれる混合溶媒に対し、3,3,3
−トリフロロプロピルトリメトキシシランを１重量％溶
解させた。An MCMB powder was prepared as a negative electrode active material. Further, as a silane compound having an alkoxy group,
3,3,3-Trifluoropropyltrimethoxysilane (KBM-7103 manufactured by Shin-Etsu Chemical Co., Ltd.) was prepared and dissolved in a mixed solvent of ethanol and water to prepare a treatment solution. The concentration of 3,3,3-trifluoropropyltrimethoxysilane contained in the treatment liquid is determined by setting the weight of the entire treatment liquid to 100.
%, It is preferably in the range of 0.1 to 10% by weight. In this case, the mixed solvent containing 94% by weight of ethanol and 5% by weight of water is 3,3,3.
1% by weight of trifluoropropyltrimethoxysilane was dissolved.
【００４６】ＭＣＭＢ粉末をこの処理液に６０分間浸漬
攪拌して、アルコキシ基を有するシラン化合物による処
理を行った。その後、８０℃の恒温槽中で十分に乾燥さ
せ、処理液の溶媒を除去した。こうしてアルコキシ基を
有するシラン化合物によって処理されたＭＣＭＢ粉末
を、ＰＶＤＦとともにＮＭＰに加え、よく混ぜ合わせて
ペースト状の負極用合剤を得た。ここでは、処理された
ＭＣＭＢ粉末とＰＶＤＦとを９５：５の重量比で配合し
た。この負極用合剤を銅箔２０ａに塗布した後、高温槽
で乾燥させて負極活物質層２０ｂを形成し、負極２０の
中間成形体を成形した。最後に、負極活物質層２０ｂが
所定の密度となるように負極２０の中間成形体をプレス
処理して、負極２０を完成した。 （実施例２−１）アルコキシ基を有するシラン化合物と
して、3,3,3−トリフロロプロピルトリメトキシシラン
の代わりに、側鎖アルコキシ変性シリコーンオイル（日
本ユニカー製ＦＺ−３７７８）を用いて負極２０を処理
した他は、実施例１−１と同様にして非水電解液二次電
池を作製した。The MCMB powder was immersed in this treatment solution for 60 minutes and stirred to carry out treatment with a silane compound having an alkoxy group. Then, it was sufficiently dried in a constant temperature bath at 80 ° C. to remove the solvent of the treatment liquid. The MCMB powder thus treated with the silane compound having an alkoxy group was added to NMP together with PVDF, and mixed well to obtain a paste-like negative electrode mixture. Here, the treated MCMB powder and PVDF were blended in a weight ratio of 95: 5. After this negative electrode mixture was applied to the copper foil 20a, it was dried in a high-temperature bath to form the negative electrode active material layer 20b, and an intermediate molded body of the negative electrode 20 was formed. Finally, the intermediate molded body of the negative electrode 20 was pressed so that the negative electrode active material layer 20b had a predetermined density, thereby completing the negative electrode 20. (Example 2-1) As a silane compound having an alkoxy group, instead of 3,3,3-trifluoropropyltrimethoxysilane, a side chain alkoxy-modified silicone oil (FZ-3778 manufactured by Nippon Unicar) was used to prepare a negative electrode 20. A non-aqueous electrolyte secondary battery was fabricated in the same manner as in Example 1-1, except that was treated.
【００４７】なお、処理液中に含まれる側鎖アルコキシ
変性シリコーンオイルの濃度は、処理液全体の重量を１
００重量％とすると、０．１〜１０重量％の範囲にある
ことが好ましいが、ここでは実施例１と同様に、エタノ
ールが９４重量％含まれ、かつ水が５重量％含まれる混
合溶媒に対し、側鎖アルコキシ変性シリコーンオイルを
１重量％溶解させた。 （実施例２−２）アルコキシ基を有するシラン化合物と
して、側鎖アルコキシ変性シリコーンオイルの代わりに
末端アルコキシ変性シリコーンオイル（日本ユニカー製
ＦＺ−３７０４）を用いた他は、実施例２−１と同様に
して非水電解液二次電池を作製した。 （実施例２−３）アルコキシ基を有するシラン化合物と
して、3,3,3−トリフロロプロピルトリメトキシシラン
の代わりに側鎖アルコキシ変性シリコーンオイル（日本
ユニカー製ＦＺ−３７７８）を用いた他は、実施例１−
３と同様にして非水電解液二次電池を作製した。 （実施例３−１）負極２０として、次のようにして成形
した負極を用いた他は、実施例１−１と同様にして非水
電解液二次電池を作製した。The concentration of the side chain alkoxy-modified silicone oil contained in the treatment liquid is determined by the weight of the entire treatment liquid being 1%.
If it is 00% by weight, it is preferably in the range of 0.1 to 10% by weight. Here, as in Example 1, a mixed solvent containing 94% by weight of ethanol and 5% by weight of water is used. On the other hand, 1% by weight of a side chain alkoxy-modified silicone oil was dissolved. (Example 2-2) The same as Example 2-1 except that a terminal alkoxy-modified silicone oil (FZ-3704 manufactured by Nippon Unicar) was used as the silane compound having an alkoxy group instead of the side-chain alkoxy-modified silicone oil. Thus, a non-aqueous electrolyte secondary battery was manufactured. (Example 2-3) As a silane compound having an alkoxy group, a side chain alkoxy-modified silicone oil (Nippon Unicar FZ-3778) was used instead of 3,3,3-trifluoropropyltrimethoxysilane. Example 1
In the same manner as in No. 3, a non-aqueous electrolyte secondary battery was produced. (Example 3-1) A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1-1, except that a negative electrode formed as follows was used as the negative electrode 20.
【００４８】負極活物質としてＭＣＭＢ粉末（大阪ガス
ケミカル製グラファイト；ＭＣＭＢ６−２８）を用意し
た。また、フッ素系界面活性剤として、パーフルオロア
ルキルアルコキシレート（住友３Ｍ製ＦＣ−１７１）を
用意した。ＭＣＭＢ粉末、パーフルオロアルキルアルコ
キシレート及びＰＶＤＦをＮＭＰに加え、よく混ぜ合わ
せてペースト状の負極用合剤を得た。ここでは、ＭＣＭ
Ｂ粉末、パーフルオロアルキルアルコキシレート及びＰ
ＶＤＦを９５：１：５の重量比で配合した。この負極用
合剤を銅箔２０ａに塗布した後、高温槽で乾燥させて負
極活物質層２０ｂを形成した。最後に、負極活物質層２
０ｂが所定の密度となるようにプレス処理して、負極２
０を完成した。 （実施例３−２）フッ素系界面活性剤として、パーフル
オロアルキルアルコキシレートの代わりにフッ素化アル
キルエステル（住友３Ｍ製ＦＣ−４３０）を用いた他
は、実施例３−１と同様にして非水電解液二次電池を作
製した。 （比較例１）負極２０として、下記のように、アルコキ
シ基を有するシラン化合物又はフッ素系界面活性剤で処
理せずに成形された負極を用いた他は、実施例１−１と
同様にして非水電解液二次電池を作製した。As the negative electrode active material, MCMB powder (graphite manufactured by Osaka Gas Chemical; MCMB6-28) was prepared. In addition, a perfluoroalkyl alkoxylate (FC-171 manufactured by Sumitomo 3M) was prepared as a fluorine-based surfactant. MCMB powder, perfluoroalkyl alkoxylate and PVDF were added to NMP and mixed well to obtain a paste-like negative electrode mixture. Here, MCM
B powder, perfluoroalkyl alkoxylate and P
VDF was blended at a weight ratio of 95: 1: 5. After applying this negative electrode mixture to the copper foil 20a, it was dried in a high-temperature bath to form a negative electrode active material layer 20b. Finally, the negative electrode active material layer 2
0b to have a predetermined density.
0 completed. (Example 3-2) A non-fluorinated surfactant was used in the same manner as in Example 3-1 except that a fluorinated alkyl ester (FC-430 manufactured by Sumitomo 3M) was used instead of the perfluoroalkyl alkoxylate. A water electrolyte secondary battery was produced. (Comparative Example 1) A negative electrode 20 was prepared in the same manner as in Example 1-1, except that a negative electrode formed without treatment with a silane compound having an alkoxy group or a fluorine-based surfactant was used as described below. A non-aqueous electrolyte secondary battery was manufactured.
【００４９】実施例１−１と同様にして負極用合剤を調
整し、これを負極集電体２０ａに塗布した後、高温槽で
十分に乾燥させて負極活物質層２０ｂを形成し、負極２
０の中間成形体を成形した。続いて、負極活物質層２０
ｂが所定の密度となるように負極２０の中間成形体をプ
レス処理して、負極２０を完成した。 ［リテンション容量の評価］以上、実施例及び比較例で
作製された各非水電解液二次電池について、リテンショ
ン容量を評価するために、次の充放電条件で充放電試験
を行った。A negative electrode mixture was prepared in the same manner as in Example 1-1, applied to the negative electrode current collector 20a, and then sufficiently dried in a high-temperature bath to form the negative electrode active material layer 20b. 2
0 was molded. Subsequently, the negative electrode active material layer 20
The intermediate molded body of the negative electrode 20 was subjected to a press treatment so that b had a predetermined density, thereby completing the negative electrode 20. [Evaluation of Retention Capacity] In order to evaluate the retention capacity of each of the non-aqueous electrolyte secondary batteries manufactured in Examples and Comparative Examples, a charge / discharge test was performed under the following charge / discharge conditions.
【００５０】先ず、１Ｃ充電（終止電圧４．２Ｖ、ＣＣ
−ＣＶ）及び１／３Ｃ放電（終止電圧３．０Ｖ、ＣＣ）
を各５サイクル行い、初期サイクルでの充電容量（Ｃ
１）と放電容量（Ｄ１）とを測定した。その測定結果よ
り、各非水電解液二次電池の充放電効率（Ｄ１／Ｃ１）
を求めた。その結果を表３に示す。First, 1C charging (final voltage 4.2V, CC
-CV) and 1 / 3C discharge (final voltage 3.0V, CC)
Is performed for each of 5 cycles, and the charge capacity (C
1) and the discharge capacity (D1) were measured. From the measurement results, the charge / discharge efficiency (D1 / C1) of each non-aqueous electrolyte secondary battery was obtained.
I asked. Table 3 shows the results.
【００５１】[0051]
【表３】 表３より、各実施例の非水電解液二次電池は、いずれも
比較例のものと比較して、充放電効率（Ｄ１／Ｃ１）が
高いことがわかる。この結果から、本発明の非水電解液
二次電池では、従来のものに比べてリテンション容量が
低くなっていることが明らかである。[Table 3] From Table 3, it can be seen that the non-aqueous electrolyte secondary batteries of the respective examples have higher charge / discharge efficiency (D1 / C1) than those of the comparative examples. From these results, it is apparent that the nonaqueous electrolyte secondary battery of the present invention has a lower retention capacity than the conventional one.
【００５２】また、実施例１−１の非水電解液二次電池
よりも、実施例１−２の電池の方が高い充放電効率を有
することもわかる。双方の電池とも、アルコキシ基及び
パーフルオロアルキル基を有するシラン化合物により負
極を処理したものであるにも関わらず、充放電効率に差
が生じた。その理由としては、そのパーフルオロアルキ
ル基の鎖長が長いほど電解液との反応性が低くなること
が考えられる。It can also be seen that the battery of Example 1-2 has higher charge / discharge efficiency than the non-aqueous electrolyte secondary battery of Example 1-1. In both batteries, although the negative electrode was treated with a silane compound having an alkoxy group and a perfluoroalkyl group, there was a difference in charge / discharge efficiency. The reason is considered that the longer the chain length of the perfluoroalkyl group, the lower the reactivity with the electrolytic solution.
【００５３】さらに、負極活物質を処理した実施例２−
３の非水電解液二次電池の方が、電極を成形した後に処
理した実施例２−２の電池よりも高い充放電効率を有す
ることがわかる。これは、実施例２−２の電池におい
て、負極２０の内部に、若干ではあるが未処理の負極活
物質が残っていたためと考えられる。このことから、負
極の中間成形体を処理するよりも、電極活物質を処理し
た方が確実に処理できることがわかる。Example 2 in which the negative electrode active material was further treated
It can be seen that the non-aqueous electrolyte secondary battery of No. 3 has higher charge / discharge efficiency than the battery of Example 2-2, which was treated after forming the electrodes. This is presumably because in the battery of Example 2-2, a small but untreated negative electrode active material remained inside the negative electrode 20. This indicates that the treatment with the electrode active material can be more reliably performed than the treatment with the intermediate molded body of the negative electrode.
【００５４】次に、実施例１−１及び比較例１の各非水
電解液二次電池について、正極１０の面積当たりの電流
密度を１．１ｍＡ／ｃｍ2とし、かつ４．２Ｖ（ＣＣ）
の終止電圧で充電を行った後、正極１０の面積当たりの
電流密度を１．１ｍＡ／ｃｍ 2 とし、かつ３．０Ｖ（Ｃ
Ｃ）の終止電圧で放電を行って、それぞれ充放電サイク
ル特性試験を行った。初期サイクルでの放電容量（Ｄ
１）とｎサイクル目（ｎ＝２〜５０）での放電容量（Ｄ
ｎ）とを測定し、それぞれの非水電解液二次電池の充放
電効率（Ｄｎ／Ｄ１）を求めた。図２に、その結果を示
す。Next, each non-aqueous solution of Example 1-1 and Comparative Example 1 was used.
Current per area of positive electrode 10 for electrolyte secondary battery
Density 1.1 mA / cmTwoAnd 4.2V (CC)
After charging at the final voltage of the positive electrode 10 per unit area
Current density of 1.1 mA / cm TwoAnd 3.0 V (C
Discharge at the final voltage of C) and charge / discharge cycle respectively.
Characteristics test. Discharge capacity in initial cycle (D
1) and the discharge capacity (D) at the nth cycle (n = 2 to 50)
n) and charge and discharge of each non-aqueous electrolyte secondary battery.
The electric efficiency (Dn / D1) was determined. Figure 2 shows the results.
You.
【００５５】図２より、実施例１−１の非水電解液二次
電池では、放電容量比（Ｄｎ／Ｄ１）の低下の程度が比
較例１のものより低いことがわかる。従って、本発明の
非水電解液二次電池は、従来のものに比べて優れた充放
電サイクル特性を有する。（実施例４−１）負極２０と
して、次のようにして成形した負極を用いた他は、実施
例１−１と同様にして非水電解液二次電池を作製した。FIG. 2 shows that in the nonaqueous electrolyte secondary battery of Example 1-1, the degree of decrease in the discharge capacity ratio (Dn / D1) was lower than that of Comparative Example 1. Therefore, the non-aqueous electrolyte secondary battery of the present invention has better charge / discharge cycle characteristics than the conventional one. (Example 4-1) A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1-1, except that a negative electrode formed as follows was used as the negative electrode 20.
【００５６】先ず、負極活物質としてメソフェーズマイ
クロビーズ（ＭＣＭＢ）粉末を用意した。また、アルコ
キシ基を有するシラン化合物として耐還元性の高いγー
アミノプロピルトリエトキシンシラン（日本ユニカー製
Ａ１１００）を用意し、これをイソプロピルアルコール
及び水の混合溶媒に溶解させて処理液を調整した。処理
液中に含まれるγーアミノプロピルトリエトキシンシラ
ンの濃度は、処理液全体の重量を１００重量％とする
と、０．１〜１０重量％の範囲であることが好ましい
が、ここでは、イソプロピルアルコールが９４重量％含
まれ、かつ水が１０重量％含まれる混合溶媒に対し、γ
ーアミノプロピルトリエトキシンシランを１重量％溶解
させた。First, mesophase microbead (MCMB) powder was prepared as a negative electrode active material. Further, as a silane compound having an alkoxy group, γ-aminopropyltrietoxin silane (A1100 manufactured by Nippon Unicar) having a high resistance to reduction was prepared, and was dissolved in a mixed solvent of isopropyl alcohol and water to prepare a treatment liquid. The concentration of γ-aminopropyltrietoxin silane contained in the treatment liquid is preferably in the range of 0.1 to 10% by weight, assuming that the total weight of the treatment liquid is 100% by weight. Is contained in a mixed solvent containing 94% by weight of water and 10% by weight of water,
1% by weight of -aminopropyltrietoxin silane was dissolved.
【００５７】ＭＣＭＢ粉末をこの処理液に６０分間浸漬
及び攪拌して、アルコキシ基を有するシラン化合物によ
る処理を行った。このとき、ＭＣＭＢ粒子の表面部にシ
ラン化合物よりなるシラン化合物層が形成される。しか
し、そのシラン化合物層が厚すぎると電極の抵抗が増
し、ひいては容量の低下を引き起こすため、シラン化合
物層の厚さを適切に制御することが好ましい。このシラ
ン化合物層の好適な厚さは、ＭＣＭＢ粉末の比表面積か
ら計算することができ、１分子層〜１０分子層の範囲が
好ましい。The MCMB powder was immersed in this treatment solution for 60 minutes and stirred to carry out treatment with a silane compound having an alkoxy group. At this time, a silane compound layer made of a silane compound is formed on the surface of the MCMB particles. However, if the thickness of the silane compound layer is too large, the resistance of the electrode increases, which causes a decrease in capacity. Therefore, it is preferable to appropriately control the thickness of the silane compound layer. The preferred thickness of the silane compound layer can be calculated from the specific surface area of the MCMB powder, and is preferably in the range of 1 to 10 molecular layers.
【００５８】こうしたシラン化合物層の厚さは、ＭＣＭ
Ｂ粉末と処理液の重量比を調整することにより制御する
ことができる。ここでは２分子層が形成されるようにＭ
ＣＭＢ粉末と処理後の重量比を決定した。なお、シラン
化合物層の厚さの制御は、ＭＣＭＢ粉末と処理液の重量
比の調整だけではなく、処理液の濃度を調整することに
よっても行うことができる。The thickness of such a silane compound layer is determined by MCM
It can be controlled by adjusting the weight ratio between the B powder and the processing liquid. Here, M is set so that a bimolecular layer is formed.
The weight ratio of the CMB powder to the post-treatment was determined. The thickness of the silane compound layer can be controlled not only by adjusting the weight ratio of the MCMB powder to the processing liquid but also by adjusting the concentration of the processing liquid.
【００５９】このようにＭＣＭＢ粉末のシラン化合物に
よる処理を行った後、そのＭＣＭＢ粉末を８０℃の恒温
槽中で十分に乾燥させて、処理液の溶媒を除去した。こ
うしてアルコキシ基を有するシラン化合物によって処理
されたＭＣＭＢをＰＶＤＦとともにＮＭＰに加え、よく
混ぜ合わせてスラリー様の負極用合剤を得た。ここで
は、ＭＣＭＢ粉末とＰＶＤＦとを９５：５の重量比で配
合した。この負極用合剤を銅箔２０ａに塗布した後、高
温槽で十分に乾燥させて負極活物質層２０ｂを形成し、
負極２０の中間成形体を成形した。最後に、負極活物質
層２０ｂが所定の密度となるように負極２０の中間成形
体をプレス処理して、負極２０を完成した。After the treatment of the MCMB powder with the silane compound as described above, the MCMB powder was sufficiently dried in a constant temperature bath at 80 ° C. to remove the solvent of the treatment liquid. The MCMB thus treated with the silane compound having an alkoxy group was added to NMP together with PVDF, and mixed well to obtain a slurry-like negative electrode mixture. Here, MCMB powder and PVDF were blended at a weight ratio of 95: 5. After applying this negative electrode mixture to the copper foil 20a, it is sufficiently dried in a high-temperature bath to form a negative electrode active material layer 20b,
An intermediate molded body of the negative electrode 20 was formed. Finally, the intermediate molded body of the negative electrode 20 was pressed so that the negative electrode active material layer 20b had a predetermined density, thereby completing the negative electrode 20.
【００６０】一方、非水電解液３０には、エチレンカー
ボネート及びジエチルカーボネートを体積比３０：７０
で混合した溶媒に、支持塩としてＬｉＰＦ6 を１ｍｏｌ
／ｌ溶解させたものを用いた。 （実施例４−２）アルコキシ基を有するシラン化合物と
して、γ−アミノプロピルトリエトキシンシランの代わ
りに、３−イソシアネートプロピルトリエトキシンシラ
ン（信越化学製、ＫＢＥ−９００７）を用いて負極２０
を処理した他は、実施例１−１と同様にして非水電解液
電池を作製した。 （実施例４−３）アルコキシ基を有するシラン化合物と
して、γ−アミノプロピルトリエトキシンシランの代わ
りに、ビニルトリメトキシシラン（信越化学製、ＫＢＭ
−１００３）を用いて負極２０を処理した他は、実施例
１−１と同様にして非水電解液電池を作製した。 （実施例４−４）アルコキシ基を有するシラン化合物と
して、γ−アミノプロピルトリエトキシンシランの代わ
りに、メチルトリメトキシシラン（信越化学製、ＫＢＭ
−１３）を用いて負極２０を処理した他は、実施例１−
１と同様にして非水電解液電池を作製した。 （実施例４−５）アルコキシ基を有するシラン化合物と
して、γ−アミノプロピルトリエトキシンシランの代わ
りに、β−（３，４エポキシシクロヘキシル）エチルト
リメトキシシラン（信越化学製、ＫＢＭ−３０３）を用
いて負極２０を処理した他は、実施例１−１と同様にし
て非水電解液電池を作製した。 （実施例４−６）アルコキシ基を有するシラン化合物と
して、γ−アミノプロピルトリエトキシンシランの代わ
りに、γ−グリシドキシプロピルトリメトキシシラン
（信越化学製、ＫＢＭ−４０３）を用いて負極２０を処
理した他は、実施例１−１と同様にして非水電解液電池
を作製した。 （実施例４−７）アルコキシ基を有するシラン化合物と
して、γ−アミノプロピルトリメトキシンシランの代わ
りに、Ｎ−フェニル−γ−アミノプロピルトリエトキシ
ンシラン（信越化学製、ＫＢＭ−５７３）を用いて負極
２０を処理した他は、実施例１−１と同様にして非水電
解液電池を作製した。 （実施例４−８）アルコキシ基を有するシラン化合物と
して、γーアミノプロピルトリメトキシンシランの代わ
りに、３−ユレイドプロピルトリエトキシンシラン（信
越化学製、ＫＢＭ−５８５）を用いて負極２０を処理し
た他は、実施例１−１と同様にして非水電解液電池を作
製した。 （実施例４−９）アルコキシ基を有するシラン化合物と
して、γ−アミノプロピルトリメトキシンシランの代わ
りに、Ｎ−β（アミノエチル）γ−アミノプロピルトリ
メトキシンシラン（信越化学製、ＫＢＭ−６０３）を用
いて負極２０を処理した他は、実施例１−１と同様にし
て非水電解液電池を作製した。 （実施例４−１０）アルコキシ基を有するシラン化合物
として、γ−アミノプロピルトリメトキシンシランの代
わりに、３，３，３−トリフロロプロピルトリメトキシ
ンシラン（信越化学製、ＫＢＭ−７１０３）を用いて負
極２０を処理した他は、実施例１−１と同様にして非水
電解液電池を作製した。 （実施例４−１１）アルコキシ基を有するシラン化合物
として、γ−アミノプロピルトリメトキシンシランの代
わりに、γ−メルカプトプロピルトリメトキシンシラン
（信越化学製、ＫＢＭ−８０３）を用いて負極２０を処
理した他は、実施例１−１と同様にして非水電解液電池
を作製した。 （実施例５−１）正極１０及び負極２０として、次のよ
うにそれぞれ成形したものを用いた他は、実施例１−１
と同様にして非水電解液二次電池を作製した。 ［正極の成形］先ず、正極活物質としてＬｉＭｎ2Ｏ4粉
末を用意した。また、アルコキシ基を有するシラン化合
物として耐酸化性の高いメチルトリメトキシンシラン
（信越化学製、ＫＢＭ−１３）を用意し、これをイソプ
ロピルアルコール及び水の混合溶媒に溶解させて処理液
を調整した。処理液中に含まれるメチルトリメトキシン
シランの濃度は、処理液全体の重量を１００重量％とす
ると、０．１〜１０重量％の範囲であることが好ましい
が、ここでは、イソプロピルアルコールが９４重量％含
まれ、かつ水が１０重量％含まれる混合溶媒に対し、メ
チルトリメトキシンシランを１重量％溶解させた。On the other hand, the nonaqueous electrolyte 30 contains ethylene carbonate and diethyl carbonate in a volume ratio of 30:70.
1 mol of LiPF 6 as a supporting salt in the solvent
/ L dissolved. (Example 4-2) As the silane compound having an alkoxy group, instead of γ-aminopropyltriethoxy silane, 3-isocyanatopropyltriethoxy silane (KBE-9007, manufactured by Shin-Etsu Chemical Co., Ltd.) was used, and the negative electrode 20 was used.
Was prepared in the same manner as in Example 1-1, except that was treated. (Example 4-3) As a silane compound having an alkoxy group, vinyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM) was used instead of γ-aminopropyltrietoxin silane.
A non-aqueous electrolyte battery was manufactured in the same manner as in Example 1-1, except that the negative electrode 20 was treated using -1003). (Example 4-4) As a silane compound having an alkoxy group, instead of γ-aminopropyltrietoxin silane, methyltrimethoxysilane (manufactured by Shin-Etsu Chemical, KBM)
-13), except that the negative electrode 20 was treated using
In the same manner as in Example 1, a non-aqueous electrolyte battery was manufactured. (Example 4-5) As a silane compound having an alkoxy group, β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane (KBM-303, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of γ-aminopropyltriethoxy silane. A non-aqueous electrolyte battery was produced in the same manner as in Example 1-1, except that the negative electrode 20 was treated. (Example 4-6) As the silane compound having an alkoxy group, instead of γ-aminopropyltriethoxy silane, γ-glycidoxypropyltrimethoxysilane (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.) was used to form the negative electrode 20. A non-aqueous electrolyte battery was fabricated in the same manner as in Example 1-1, except for the treatment. (Example 4-7) As a silane compound having an alkoxy group, instead of γ-aminopropyltrimethoxine silane, N-phenyl-γ-aminopropyltrietoxine silane (KBM-573, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as a negative electrode. A non-aqueous electrolyte battery was fabricated in the same manner as in Example 1-1, except that the sample No. 20 was treated. (Example 4-8) As the silane compound having an alkoxy group, the negative electrode 20 was treated using 3-ureidopropyltrietoxin silane (KBM-585, manufactured by Shin-Etsu Chemical Co., Ltd.) instead of γ-aminopropyltrimethoxine silane. A non-aqueous electrolyte battery was manufactured in the same manner as in Example 1-1, except for the above. (Example 4-9) As a silane compound having an alkoxy group, N-β (aminoethyl) γ-aminopropyltrimethoxine silane (manufactured by Shin-Etsu Chemical, KBM-603) was used instead of γ-aminopropyl trimethoxy silane. A non-aqueous electrolyte battery was manufactured in the same manner as in Example 1-1, except that the negative electrode 20 was treated using the same. (Example 4-10) As a silane compound having an alkoxy group, instead of γ-aminopropyltrimethoxinesilane, 3,3,3-trifluoropropyltrimethoxinesilane (KBM-7103 manufactured by Shin-Etsu Chemical Co., Ltd.) was used. A non-aqueous electrolyte battery was manufactured in the same manner as in Example 1-1, except that the negative electrode 20 was treated. (Example 4-11) As the silane compound having an alkoxy group, the negative electrode 20 was treated using γ-mercaptopropyltrimethoxysilane (KBM-803, manufactured by Shin-Etsu Chemical) instead of γ-aminopropyltrimethoxysilane. Otherwise, a non-aqueous electrolyte battery was manufactured in the same manner as in Example 1-1. (Example 5-1) Example 1-1 except that the positive electrode 10 and the negative electrode 20 were respectively formed as follows.
In the same manner as in the above, a non-aqueous electrolyte secondary battery was produced. [Molding of Positive Electrode] First, LiMn 2 O 4 powder was prepared as a positive electrode active material. Also, methyltrimethoxy silane (KBM-13, manufactured by Shin-Etsu Chemical Co., Ltd.) having high oxidation resistance was prepared as a silane compound having an alkoxy group, and this was dissolved in a mixed solvent of isopropyl alcohol and water to prepare a treatment solution. The concentration of methyltrimethoxine silane contained in the treatment liquid is preferably in the range of 0.1 to 10% by weight, assuming that the total weight of the treatment liquid is 100% by weight. 1% by weight of methyltrimethoxysilane was dissolved in a mixed solvent containing 10% by weight of water and 10% by weight of water.
【００６１】ＬｉＭｎ2Ｏ4粉末をこの処理液に６０分間
浸漬及び攪拌して、アルコキシ基を有するシラン化合物
による処理を行った。ここでも、ＭＣＭＢ粉末のときと
同様、ＬｉＭｎ2Ｏ4粒子の表面部にシラン化合物層が形
成される。しかし、シラン化合物層が厚すぎると電極の
抵抗が増し、ひいては容量の低下を引き起こすため、シ
ラン化合物層の厚さを適切に制御することが好ましい。
このシラン化合物層の好適な厚さは、ＬｉＭｎ2Ｏ4粉末
の比表面積から計算することができ、１分子層〜１０分
子層の範囲が好ましい。The LiMn 2 O 4 powder was immersed in this treatment solution for 60 minutes and stirred to carry out treatment with a silane compound having an alkoxy group. Here, as in the case of the MCMB powder, a silane compound layer is formed on the surface of the LiMn 2 O 4 particles. However, if the thickness of the silane compound layer is too large, the resistance of the electrode is increased, and the capacity is decreased. Therefore, it is preferable to appropriately control the thickness of the silane compound layer.
The preferred thickness of the silane compound layer can be calculated from the specific surface area of the LiMn 2 O 4 powder, and is preferably in the range of 1 to 10 molecular layers.
【００６２】こうしたシラン化合物層の厚さは、ＬｉＭ
ｎ2Ｏ4粉末と処理液の重量比を調整することにより制御
することができる。ここでは２分子層が形成されるよう
にＬｉＭｎ2Ｏ4粉末と処理後の重量比を決定した。な
お、ここでもシラン化合物層の厚さの制御は、ＬｉＭｎ
2Ｏ4粉末と処理液の重量比の調整だけではなく、処理液
の濃度を調整することによっても行うことができる。The thickness of such a silane compound layer is LiM
It can be controlled by adjusting the weight ratio between the n 2 O 4 powder and the processing liquid. Here, the weight ratio of the LiMn 2 O 4 powder to that after the treatment was determined so that a bimolecular layer was formed. Here, the thickness of the silane compound layer is controlled by LiMn.
The adjustment can be performed not only by adjusting the weight ratio between the 2 O 4 powder and the processing solution but also by adjusting the concentration of the processing solution.
【００６３】このようにＬｉＭｎ2Ｏ4粉末のシラン化合
物による処理を行った後、そのＬｉＭｎ2Ｏ4粉末を８０
℃の恒温槽中で十分に乾燥させて、処理液の溶媒を除去
した。こうしてアルコキシ基を有するシラン化合物によ
って処理されたＬｉＭｎ2Ｏ4 粉末を用意するとともに、
導電材として炭素粉末（ＫＳ−１５）を用意した。また
結着剤としてポリビニルデンフロライド（ＰＶＤＦ）を
用意し、分散溶媒としてＮ−メチル−２ピロリドン（Ｎ
ＭＰ）を用意した。これらこうしてアルコキシ基を有す
るシラン化合物によって処理されたＬｉＭｎ2Ｏ4 粉末
及び炭素粉末のＰＶＤＦとともにＮＭＰに加え、よく混
ぜ合わせてスラリー様の正極合剤を得た。ここでは、Ｌ
ｉＭｎ2Ｏ4粉末、炭素粉末及びＰＶＤＦを８７：１０：
３の重量比で配合した。 ［負極の成形］負極活物質としてＭＣＭＢ粉末を用意
し、このＭＣＭＢ粉末をＰＶＤＦとともにＮＭＰに加
え、よく混ぜ合わせてスラリー様の負極合剤を得た。こ
こでは、ＭＣＭＢ粉末とＰＶＤＦとを９５：５の重量比
で配合した。この負極合剤を銅箔２０ａに塗布した後、
高温槽で十分に乾燥させて負極活物質層２０ｂを形成
し、正極２０の中間体を成形した。最後に負極活物質層
２０ｂが所定の密度となるように負極２０の中間成形体
をプレス処理して、負極２０を完成した。 （実施例５−２）アルコキシ基を有するシラン化合物と
して、メチルトリメトキシシランの代わりに、３，３，
３−トリフロロプロピルトリメトキシシラン（信越化学
製、ＫＢＭ−７１０３）を用いて負極２０を処理した他
は、実施例５−１と同様にして非水電解液電池を作製し
た。 （実施例５−３）アルコキシ基を有するシラン化合物と
して、メチルトリメトキシシランの代わりに、３−イソ
シアネートプロピルトリメトキシシラン（信越化学製、
ＫＢＥ−９００７）を用いて負極２０を処理した他は、
実施例５−１と同様にして非水電解液電池を作製した。 （実施例５−４）アルコキシ基を有するシラン化合物と
して、メチルトリメトキシシランの代わりに、γ−アミ
ノプロピルトリメトキシシラン（信越化学製、ＫＢＥ−
９０３）を用いて負極２０を処理した他は、実施例５−
１と同様にして非水電解液電池を作製した。 （実施例５−５）アルコキシ基を有するシラン化合物と
して、メチルトリメトキシシランの代わりに、Ｎ−β
（アミノエチル）γ−アミノプロピルトリメトキシシラ
ン（信越化学製、ＫＢＭ−６０３）を用いて負極２０を
処理した他は、実施例５−１と同様にして非水電解液電
池を作製した。 （実施例５−６）アルコキシ基を有するシラン化合物と
して、メチルトリメトキシシランの代わりに、Ｎ−フェ
ニル−γ−アミノプロピルトリメトキシシラン（信越化
学製、ＫＢＭ−５７３）を用いて負極２０を処理した他
は、実施例５−１と同様にして非水電解液電池を作製し
た。 ［サイクル特性の評価］先ず、実施例４−１〜実施例４
−１１の非水電解液二次電池を用いて、１Ｃ充電（終止
電圧４．２Ｖ、ＣＣ−ＣＶ）及び１／３Ｃ放電（終止電
圧３．０Ｖ、ＣＣ）を行って充放電サイクル特性試験を
行った。初期サイクルでの放電容量Ｄ1とｎサイクル目
（ｎ＝２〜５０）での放電容量（Ｄn）とを測定し、１
サイクル目に対する５０サイクル目の放電容量比（Ｄ50
／Ｄ1）を求めた。その結果と、表２に示される耐還元
性の指標との関係を図３に示す。As described above, LiMnTwoOFourSilane compound of powder
After the treatment with the material, the LiMnTwoOFour80 powder
Thoroughly dry in a constant temperature bath at ℃ to remove the solvent of the processing solution
did. Thus, the silane compound having an alkoxy group
Treated LiMnTwoOFour Prepare the powder,
Carbon powder (KS-15) was prepared as a conductive material. Also
Polyvinyldenfluoride (PVDF) as a binder
Prepared, and N-methyl-2-pyrrolidone (N
MP) was prepared. These have an alkoxy group in this way
LiMn treated with a silane compoundTwoOFourPowder
And NDF together with PVDF of carbon powder and mix well
The resultant mixture was mixed to obtain a slurry-like positive electrode mixture. Here, L
iMnTwoOFour87:10 powder, carbon powder and PVDF
3 in a weight ratio. [Molding of negative electrode] Prepare MCMB powder as negative electrode active material
The MCMB powder was added to NMP together with PVDF.
Then, they were mixed well to obtain a slurry-like negative electrode mixture. This
Here, the MCMB powder and PVDF are mixed in a weight ratio of 95: 5.
Was blended. After applying this negative electrode mixture to the copper foil 20a,
Dry sufficiently in a high-temperature bath to form the negative electrode active material layer 20b
Then, an intermediate of the positive electrode 20 was formed. Finally, the negative electrode active material layer
An intermediate molded body of the negative electrode 20 so that 20b has a predetermined density.
Was pressed to complete the negative electrode 20. (Example 5-2) A silane compound having an alkoxy group and
And instead of methyltrimethoxysilane,
3-trifluoropropyltrimethoxysilane (Shin-Etsu Chemical
Of negative electrode 20 using KBM-7103)
Prepared a non-aqueous electrolyte battery in the same manner as in Example 5-1.
Was. (Example 5-3) A silane compound having an alkoxy group and
To replace 3-triisopropane with methyltrimethoxysilane.
Cyanate propyl trimethoxysilane (Shin-Etsu Chemical,
KBE-9007), except that the negative electrode 20 was treated.
A non-aqueous electrolyte battery was manufactured in the same manner as in Example 5-1. (Example 5-4) Silane compound having alkoxy group and
Γ-amido instead of methyltrimethoxysilane
Nopropyl trimethoxysilane (KBE-, Shin-Etsu Chemical Co., Ltd.)
903), except that the negative electrode 20 was treated using
In the same manner as in Example 1, a non-aqueous electrolyte battery was manufactured. (Example 5-5) Silane compound having alkoxy group
Then, instead of methyltrimethoxysilane, N-β
(Aminoethyl) γ-aminopropyltrimethoxysila
The negative electrode 20 is formed by using an electrode (Shin-Etsu Chemical, KBM-603).
Other than the treatment, the non-aqueous electrolyte was charged in the same manner as in Example 5-1.
A pond was made. (Example 5-6) Silane compound having alkoxy group and
Then, instead of methyltrimethoxysilane,
Nyl-γ-aminopropyltrimethoxysilane (Shin-Etsu Chemical
In addition to treating the negative electrode 20 using KBM-573)
Prepared a non-aqueous electrolyte battery in the same manner as in Example 5-1.
Was. [Evaluation of Cycle Characteristics] First, Examples 4-1 to 4
1C charging using non-aqueous electrolyte secondary battery
Voltage 4.2V, CC-CV) and 1 / 3C discharge (final power)
(3.0V, CC) to perform a charge / discharge cycle characteristic test.
went. Discharge capacity D in initial cycle1And the nth cycle
(N = 2 to 50) and the discharge capacity (Dn) And measure 1
The discharge capacity ratio of the 50th cycle to the 50th cycle (D50
/ D1). The results and reduction resistance shown in Table 2
FIG. 3 shows the relationship with the sex index.
【００６４】図３より、実施例４−１〜実施例４−１１
のいずれの非水電解液二次電池においても、放電容量比
（Ｄ50／Ｄ1）が０．７５以上にあり、サイクル特性に
優れることがわかる。これらの非水電解液二次電池のい
ずれの負極にも、耐還元性に優れるシランカップリング
剤によって処理された負極活物質が用いられている。こ
うした処理がなされた負極活物質では、図５に示したよ
うに表面に存在する電解液と反応性の高い官能基が、ア
ルコキシ基を有するシランカップリング剤で置換され、
図６に示すように表面にシラン化合物よりなるシラン化
合物層を形成されていると考えられる。特に、本処理で
は、処理液中には水が含まれており、この水と上記シラ
ン化合物のアルコキシ基との脱水縮合反応により、負極
活物質の表面にシラン化合物層が形成されたものと考え
られる。その結果、このシラン化合物層により電解液の
分解反応が抑制され、高いサイクル特性が得られたもの
と考えられる。FIG. 3 shows that the embodiments 4-1 to 4-11 are implemented.
In any of the non-aqueous electrolyte secondary batteries, the discharge capacity ratio (D 50 / D 1 ) is 0.75 or more, which indicates that the battery has excellent cycle characteristics. For each of the negative electrodes of these nonaqueous electrolyte secondary batteries, a negative electrode active material treated with a silane coupling agent having excellent reduction resistance is used. In the thus-treated negative electrode active material, as shown in FIG. 5, a functional group having high reactivity with an electrolyte present on the surface is replaced with a silane coupling agent having an alkoxy group,
It is considered that a silane compound layer made of a silane compound is formed on the surface as shown in FIG. In particular, in this treatment, the treatment liquid contains water, and it is considered that a silane compound layer was formed on the surface of the negative electrode active material by a dehydration condensation reaction between the water and the alkoxy group of the silane compound. Can be As a result, it is considered that the decomposition reaction of the electrolytic solution was suppressed by the silane compound layer, and high cycle characteristics were obtained.
【００６５】また、図３に示した各非水電解液二次電池
の放電容量比をそれぞれ比較してわかるように、ＬＵＭ
Ｏ値が１．０ｅＶ以上であるシランカップリング剤を用
いた非水電解液二次電池では、特に優れたサイクル特性
が得られる傾向にある。この結果からも、負極活物質の
処理に用いるシランカップリング剤には、１．０ｅＶ以
上のＬＵＭＯ値を有して優れた耐還元性をもつものが好
ましいことがわかる。As can be seen by comparing the discharge capacity ratios of the nonaqueous electrolyte secondary batteries shown in FIG.
In a non-aqueous electrolyte secondary battery using a silane coupling agent having an O value of 1.0 eV or more, particularly excellent cycle characteristics tend to be obtained. This result also indicates that a silane coupling agent having a LUMO value of 1.0 eV or more and having excellent reduction resistance is preferable as the silane coupling agent used for treating the negative electrode active material.
【００６６】その一方で、実施例５−１〜実施例５−６
の非水電解液二次電池を用いて、１Ｃ充電（終止電圧
４．２Ｖ、ＣＣ−ＣＶ）及び１／３Ｃ放電（終止電圧
３．０Ｖ、ＣＣ）を行って充放電サイクル特性試験を行
った。初期サイクルでの放電容量Ｄ１とｎサイクル目
（ｎ＝２〜３０）での放電容量（Ｄｎ）とを測定し、１
サイクル目に対する３０サイクル目の放電容量比（Ｄ３
０／Ｄ１）を求めた。その結果と、表２に示される耐酸
化性の指標との関係を図３に示す。On the other hand, Examples 5-1 to 5-6
1C charging (4.2 V, CC-CV) and 1 / 3C discharging (3.0 V, CC) to perform a charge / discharge cycle characteristic test using the nonaqueous electrolyte secondary battery. . The discharge capacity D1 in the initial cycle and the discharge capacity (Dn) in the nth cycle (n = 2 to 30) were measured.
The discharge capacity ratio at the 30th cycle to the cycle (D3
0 / D1). FIG. 3 shows the relationship between the result and the oxidation resistance index shown in Table 2.
【００６７】図４より、実施例５−１〜実施例５−６の
いずれの非水電解液二次電池においても放電容量比（Ｄ
３０／Ｄ１）が０．９を超え、サイクル特性に優れるこ
とがわかる。これらの非水電解液二次電池のいずれの正
極にも、耐酸化性に優れるシランカップリング剤によっ
て処理された負極活物質が用いられている。こうした処
理がなされた正極活物質では、その表面において、図７
に示すようにアルコキシ基を有するシランカップリング
剤よりなるシラン化合物層が形成され、正極活物質がシ
ラン化合物層により被覆されていると考えられる。特
に、本処理でも、処理液中には水が含まれており、この
水とシラン化合物のアルコキシ基との脱水縮合反応によ
り、正極活物質の表面にシラン化合物層が形成されたも
のと考えられる。その結果、このシラン化合物層により
電解液の分解反応が抑制され、高いサイクル特性が得ら
れたものと考えられる。FIG. 4 shows that the discharge capacity ratio (D) of any of the non-aqueous electrolyte secondary batteries of Examples 5-1 to 5-6.
30 / D1) exceeds 0.9, indicating that the cycle characteristics are excellent. For each of the positive electrodes of these nonaqueous electrolyte secondary batteries, a negative electrode active material treated with a silane coupling agent having excellent oxidation resistance is used. In the surface of the positive electrode active material thus treated,
It is considered that a silane compound layer composed of a silane coupling agent having an alkoxy group was formed as shown in (1), and the positive electrode active material was covered with the silane compound layer. In particular, even in the present treatment, it is considered that the treatment liquid contains water, and the silane compound layer was formed on the surface of the positive electrode active material by the dehydration condensation reaction between the water and the alkoxy group of the silane compound. . As a result, it is considered that the decomposition reaction of the electrolytic solution was suppressed by the silane compound layer, and high cycle characteristics were obtained.
【００６８】また、図４に示した各非水電解液二次電池
の放電容量比をそれぞれ比較してわかるように、ＨＯＭ
Ｏ値が−１０ｅＶ以下であるシランカップリング剤を用
いた非水電解液二次電池では、特に優れたサイクル特性
が得られる傾向にある。この結果からも、正極活物質の
処理に用いるシランカップリング剤には、−１０ｅＶ以
下のＨＯＭＯ値を有して優れた耐酸化性をもつものが好
ましいことがわかる。As can be seen by comparing the discharge capacity ratios of the nonaqueous electrolyte secondary batteries shown in FIG.
In a nonaqueous electrolyte secondary battery using a silane coupling agent having an O value of −10 eV or less, particularly excellent cycle characteristics tend to be obtained. This result also indicates that the silane coupling agent used for treating the positive electrode active material preferably has a HOMO value of −10 eV or less and has excellent oxidation resistance.
【図１】 本実施例及び本比較例の非水電解液二次電池
の構造を概略的に示す電池の縦断面図である。FIG. 1 is a longitudinal sectional view of a battery schematically showing the structure of a non-aqueous electrolyte secondary battery of the present example and a comparative example.
【図２】 実施例１−１及び比較例１の各非水電解液二
次電池について、充放電のサイクル数に対する放電容量
比の変化を示すグラフである。FIG. 2 is a graph showing a change in a discharge capacity ratio with respect to the number of charge / discharge cycles for each of the non-aqueous electrolyte secondary batteries of Example 1-1 and Comparative Example 1.
【図３】 実施例４−１〜実施例４−１１の非水電解液
二次電池について、各電池のＬＵＭＯ値と放電容量比
（Ｄ50／Ｄ1）との関係をそれぞれ示す図である。FIG. 3 is a diagram showing the relationship between the LUMO value of each battery and the discharge capacity ratio (D 50 / D 1 ) for the non-aqueous electrolyte secondary batteries of Examples 4-1 to 4-11. .
【図４】 実施例５−１〜実施例５−６の非水電解液二
次電池について、各電池のＬＵＭＯ値と放電容量比（Ｄ
50／Ｄ1）との関係をそれぞれ示す図である。FIG. 4 shows the LUMO value of each battery and the discharge capacity ratio (D) of the non-aqueous electrolyte secondary batteries of Examples 5-1 to 5-6.
50 / D 1 ).
【図５】 従来の非水電解液二次電池において、負極活
物質の表面の様子を模式的に示した模式図である。FIG. 5 is a schematic diagram schematically showing a state of a surface of a negative electrode active material in a conventional nonaqueous electrolyte secondary battery.
【図６】 本発明の非水電解液二次電池において、負極
活物質の表面の様子を模式的に示した模式図である。FIG. 6 is a schematic diagram schematically showing a state of a surface of a negative electrode active material in the nonaqueous electrolyte secondary battery of the present invention.
【図７】 本発明の非水電解液二次電池において、正極
活物質の表面の様子を模式的に示した模式図である。FIG. 7 is a schematic diagram schematically showing a state of a surface of a positive electrode active material in the nonaqueous electrolyte secondary battery of the present invention.
１０：正極 １０ａ：正極集電体 １０ｂ：正極活物質
層 ２０：負極 ２０ａ：負極集電体 ２０ｂ：負極活物質
層 ３０：電解液 ４０：正極ケース ５０：負極ケース ６０：セパレータ ７０：ガスケット10: Positive electrode 10a: Positive electrode current collector 10b: Positive electrode active material layer 20: Negative electrode 20a: Negative electrode current collector 20b: Negative electrode active material layer 30: Electrolyte 40: Positive electrode case 50: Negative electrode case 60: Separator 70: Gasket
───────────────────────────────────────────────────── フロントページの続き (72)発明者 上嶋 啓史 愛知県刈谷市昭和町１丁目１番地 株式会 社デンソー内 (72)発明者 加美 謙一郎 愛知県刈谷市昭和町１丁目１番地 株式会 社デンソー内 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Keishi Uejima 1-1-1, Showa-cho, Kariya, Aichi Prefecture Inside Denso Corporation (72) Inventor Kenichiro Kami 1-1-1, Showa-cho, Kariya City, Aichi Prefecture Denso Corporation Inside
Claims (16)
と、該正極から放出されたリチウムイオンを吸蔵及び放
出する負極と、該正極及び該負極の間に介在して該リチ
ウムイオンを移動させる非水電解液とから構成される非
水電解液二次電池において、前記正極及び前記負極の少
なくとも一方は、アルコキシ基を有するシラン化合物、
及びフッ素系界面活性剤の少なくとも一方で処理されて
いることを特徴とする非水電解液二次電池。1. A positive electrode for releasing and occluding lithium ions, a negative electrode for occluding and releasing lithium ions released from the positive electrode, and a non-aqueous solution interposed between the positive electrode and the negative electrode to move the lithium ions. In a non-aqueous electrolyte secondary battery composed of an electrolyte and at least one of the positive electrode and the negative electrode, a silane compound having an alkoxy group,
And a non-aqueous electrolyte secondary battery which is treated with at least one of a fluorine-based surfactant.
剤である請求項１に記載の非水電解液二次電池。2. The non-aqueous electrolyte secondary battery according to claim 1, wherein the silane compound is a silane coupling agent.
基系、フッ素系、イソシアネート系及びアミノ系の少な
くとも一種の系の有機官能基を有する請求項２に記載の
非水電解液二次電池。3. The non-aqueous electrolyte secondary battery according to claim 2, wherein the silane coupling agent has at least one of an alkyl group-based, fluorine-based, isocyanate-based, and amino-based organic functional group.
で示されるものである請求項２に記載の非水電解液二次
電池。 （化１）Ｙ−Ｓｉ−Ｘ3 ｛Ｙ：ＣＨ3 （ＣＨ2 ）n （ｎ＝０〜１０）、ＣＦ
3 （ＣＦ2 ）n （ＣＨ2 ）2（ｎ＝０〜１０）、Ｏ＝Ｃ
＝Ｎ（ＣＨ2 ）n （ｎ＝０〜１０）、ＣＨ2ＯＣＨＣＨ2
Ｏ（ＣＨ2）n（ｎ＝０〜１０）、ＮＨ2（ＣＨ2）2ＮＨ
（ＣＨ2）n（ｎ＝０〜１０）、あるいはＮＨ2 （Ｃ
Ｈ2 ）n（ｎ＝０〜１０）｝ ｛Ｘ：Ｏ−Ｒ （Ｒ：（ＣＨ2 ）n ＣＨ3 （ｎ＝０〜１
０）、ＣＯＣＨ3 、ＮＣＣＨ3 ＣＨ3 、ＮＣ2 Ｈ5 ＣＯ
ＣＨ3 あるいはＣＣＨ3 ＣＨ2 ）の加水分解性基｝4. The silane coupling agent according to claim 1,
The non-aqueous electrolyte secondary battery according to claim 2, wherein: (Formula 1) Y—Si—X 3 3Y: CH 3 (CH 2 ) n (n = 0 to 10), CF
3 (CF 2 ) n (CH 2 ) 2 (n = 0 to 10), O = C
= N (CH 2) n ( n = 0~10), CH 2 OCHCH 2
O (CH 2 ) n (n = 0 to 10), NH 2 (CH 2 ) 2 NH
(CH 2 ) n (n = 0 to 10) or NH 2 (C
H 2 ) n (n = 0 to 10)｝ {X: OR (R: (CH 2 ) n CH 3 (n = 0 to 1)
0), COCH 3 , NCCH 3 CH 3 , NC 2 H 5 CO
CH 3 or CCH 3 CH 2 ) hydrolyzable group
物は、耐酸化性に優れた分子構造を有する請求項１〜４
のいずれかに記載の非水電解液二次電池。5. The silane compound used in the treatment of the positive electrode has a molecular structure excellent in oxidation resistance.
The non-aqueous electrolyte secondary battery according to any one of the above.
の最高被占軌道（ＨＯＭＯ）の準位を有する請求項５に
記載の非水電解液二次電池。6. The non-aqueous electrolyte secondary battery according to claim 5, wherein the silane compound has a level of the highest occupied orbital (HOMO) of −9.7 eV or less.
物は、耐還元性に優れた分子構造を有する請求項１〜４
のいずれかに記載の非水電解液二次電池。7. The silane compound used in the treatment of the negative electrode has a molecular structure excellent in reduction resistance.
The non-aqueous electrolyte secondary battery according to any one of the above.
最低空軌道（ＬＵＭＯ）の準位を有する請求項７に記載
の非水電解液二次電池。8. The non-aqueous electrolyte secondary battery according to claim 7, wherein the silane compound has a lowest unoccupied orbital (LUMO) level of 1.0 eV or more.
ルである請求項１に記載の非水電解液二次電池。9. The non-aqueous electrolyte secondary battery according to claim 1, wherein the silane compound is a modified silicone oil.
アルキルエステル、パーフルオロアルキルアルコキシレ
ート及びパーフルオロアルキルスルホン酸のいずれかの
アンモニウム塩あるいはアルカリ塩、並びにパーフルオ
ロアルキル第４級アンモニウムヨウ化物及びパーフルオ
ロアルキルポリオキシエチレンエタノール、並びに該ア
ンモニウム塩、該アルカリ塩、パーフルオロアルキル第
４級アンモニウムヨウ化物及びパーフルオロアルキルポ
リオキシエチレンエタノールの誘導体の少なくとも一種
である請求項１に記載の非水電解液二次電池。10. The fluorosurfactant may be an ammonium salt or an alkali salt of any one of a fluorinated alkyl ester, a perfluoroalkyl alkoxylate and a perfluoroalkyl sulfonic acid, and a perfluoroalkyl quaternary ammonium iodide. The non-aqueous electrolysis according to claim 1, wherein the non-aqueous electrolysis is perfluoroalkylpolyoxyethylene ethanol, and at least one of the ammonium salt, the alkali salt, a perfluoroalkyl quaternary ammonium iodide, and a derivative of perfluoroalkyl polyoxyethylene ethanol. Liquid secondary battery.
処理するものである請求項１に記載の非水電解液二次電
池。11. The non-aqueous electrolyte secondary battery according to claim 1, wherein the treatment is to previously treat an electrode active material.
素からなる請求項１に記載の非水電解液二次電池。12. The non-aqueous electrolyte secondary battery according to claim 1, wherein the negative electrode active material of the negative electrode mainly comprises carbon.
2、ＬｉＮｉＯ2及びＬｉＭｎ2Ｏ4の少なくとも一種から
なる請求項１に記載の非水電解液二次電池。13. The positive electrode active material of the positive electrode is LiCoO.
2, the non-aqueous electrolyte secondary battery according to claim 1 comprising at least one LiNiO 2 and LiMn 2 O 4.
めアルコキシ基を有するシラン化合物と水とを含む処理
液で処理する請求項１に記載の非水電解液二次電池。14. The non-aqueous electrolyte secondary battery according to claim 1, wherein in the treatment, the electrode active material is treated with a treatment solution containing a silane compound having an alkoxy group and water in advance.
を有するシラン化合物を含む処理液に曝して、該電極活
物質の表面部にシラン化合物よりなるシラン化合物層を
形成した後、該シラン化合物層が形成された該電極活物
質と、結着剤と、溶剤とを混合してスラリー状の合剤を
調製し、該合剤を集電体に塗布して乾燥させることによ
り電極を製造することを特徴とする電極の製造方法。15. An electrode active material is exposed in advance to a treatment solution containing a silane compound having an alkoxy group to form a silane compound layer made of a silane compound on the surface of the electrode active material, and then the silane compound layer is formed. The electrode active material, a binder, and a solvent are mixed to prepare a slurry mixture, and the mixture is applied to a current collector and dried to produce an electrode. Method for manufacturing an electrode.
載の電極の製造方法。16. The method for manufacturing an electrode according to claim 15, wherein the treatment liquid contains water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11074117A JPH11354104A (en) | 1998-04-09 | 1999-03-18 | Nonaqueous electrolyte secondary battery and manufacture for electrode |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10-97346 | 1998-04-09 | ||
| JP9734698 | 1998-04-09 | ||
| JP11074117A JPH11354104A (en) | 1998-04-09 | 1999-03-18 | Nonaqueous electrolyte secondary battery and manufacture for electrode |
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| Publication Number | Publication Date |
|---|---|
| JPH11354104A true JPH11354104A (en) | 1999-12-24 |
Family
ID=26415254
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11074117A Pending JPH11354104A (en) | 1998-04-09 | 1999-03-18 | Nonaqueous electrolyte secondary battery and manufacture for electrode |
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