JP2002198090A - Non-aqueous electrolyte secondary cell - Google Patents
Non-aqueous electrolyte secondary cellInfo
- Publication number
- JP2002198090A JP2002198090A JP2000392412A JP2000392412A JP2002198090A JP 2002198090 A JP2002198090 A JP 2002198090A JP 2000392412 A JP2000392412 A JP 2000392412A JP 2000392412 A JP2000392412 A JP 2000392412A JP 2002198090 A JP2002198090 A JP 2002198090A
- Authority
- JP
- Japan
- Prior art keywords
- secondary battery
- lithium
- aqueous electrolyte
- formula
- negative 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、非水系電解液二次
電池に関する。詳しくは、特定のホスフィン化合物が添
加された有機系溶媒を含む電解液を用いる非水系電解液
二次電池に関する。本発明によれば、電解液中の酸分が
低いため、長期安定性、サイクル特性に優れた高エネル
ギー密度の非水系電解液二次電池が得られる。[0001] The present invention relates to a non-aqueous electrolyte secondary battery. More specifically, the present invention relates to a non-aqueous electrolyte secondary battery using an electrolyte containing an organic solvent to which a specific phosphine compound is added. ADVANTAGE OF THE INVENTION According to this invention, since the acid content in electrolyte solution is low, the non-aqueous electrolyte secondary battery of high energy density excellent in long-term stability and cycle characteristics is obtained.
【０００２】[0002]
【従来の技術】近年、電気製品の軽量化、小型化に伴
い、高いエネルギー密度を持つリチウム二次電池が注目
されている。また、リチウム二次電池の適用分野の拡大
に伴い電池特性の改善も要望されている。このようなリ
チウム二次電池の電解液の溶媒としては、例えばエチレ
ンカーボネート、プロピレンカーボネート、ジエチルカ
ーボネート、γ−ブチロラクトン等のカーボネート類又
はエステル類の高誘電率非水系有機溶媒とジエチルカー
ボネート、ジメチルカーボネート、ジメトキシエタン等
の鎖状カーボネート類又はエーテル類を適宜混合したも
のが用いられている。2. Description of the Related Art In recent years, lithium secondary batteries having a high energy density have been attracting attention as electric appliances have become lighter and smaller. In addition, with the expansion of the application field of the lithium secondary battery, improvement in battery characteristics is also demanded. As a solvent for the electrolyte solution of such a lithium secondary battery, for example, ethylene carbonate, propylene carbonate, diethyl carbonate, a high dielectric constant non-aqueous organic solvent such as carbonates or esters such as γ-butyrolactone and diethyl carbonate, dimethyl carbonate, A mixture in which chain carbonates or ethers such as dimethoxyethane are appropriately mixed is used.
【０００３】また、溶質としてはＬｉＣｌＯ4、ＬｉＰ
Ｆ6、ＬｉＢＦ4等の無機リチウム塩又はＬｉＣＦ3Ｓ
Ｏ3、ＬｉＮ（ＣＦ3ＳＯ2）2、ＬｉＮ（ＣＦ3ＣＦ2ＳＯ
2）2、ＬｉＮ（ＣＦ3ＳＯ2）（Ｃ4Ｆ9ＳＯ2）、ＬｉＣ
（ＣＦ3ＳＯ2）3等の有機リチウム塩が用いられている
が、この中でも特性が好適なことからＬｉＰＦ6を最も
よく使われている。しかし一方、このＬｉＰＦ6或いは
ＬｉＢＦ4等の含フッ素無機リチウムは水分と反応し、
電解液中にＨＦが発生することも知られている。ＨＦ
は、電池缶の腐食を引き起こすだけでなく、電池容量を
低下させたり、サイクル特性に悪影響を及ぼす。上記の
ような問題点を改善するため、モレキュラーシーブで処
理して水分を除去した非水溶媒を用いた電解液（特開平
１０−２７００７４号公報）や、電解液中のＨＦを除去
するため、水素化リチウム、リチウムエトキサイド等の
ようなリチウム化合物を添加して処理した電解液（特開
平１０−２７００７７号公報）が提案されている。The solutes are LiClO 4 , LiP
Inorganic lithium salts such as F 6 and LiBF 4 or LiCF 3 S
O 3 , LiN (CF 3 SO 2 ) 2 , LiN (CF 3 CF 2 SO
2 ) 2 , LiN (CF 3 SO 2 ) (C 4 F 9 SO 2 ), LiC
Organic lithium salts such as (CF 3 SO 2 ) 3 are used, and among these, LiPF 6 is most often used because of its favorable characteristics. However, on the other hand, this fluorine-containing inorganic lithium such as LiPF 6 or LiBF 4 reacts with moisture,
It is also known that HF is generated in the electrolyte. HF
Not only causes corrosion of the battery can, but also lowers the battery capacity and adversely affects the cycle characteristics. In order to improve the above problems, an electrolytic solution using a non-aqueous solvent which has been treated with a molecular sieve to remove water (Japanese Patent Application Laid-Open No. 10-270074), and in order to remove HF in the electrolytic solution, An electrolyte (JP-A-10-270077) which has been treated by adding a lithium compound such as lithium hydride or lithium ethoxide has been proposed.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、これら
の方法により、電解液中に最初から含まれている水分は
除去できるが、電池として組み上げる際に他の部材から
持ち込まれる水分によってＨＦが発生するので、電池全
体の特性については十分ではないという問題がある。ま
た、これらの添加剤はいずれも溶解性が低いため、添加
剤を濾別した電解液を用いるので、注液後の工程におい
て発生するＨＦ分を除去することはできないという問題
もある。本発明はかかる問題点を踏まえて、電解液中の
ＨＦを低減し、なお且つ電池組立時に電極等から水分が
混入してもＨＦ分を低減させた状態を持続することので
きる非水系電解液二次電池を提供しようとするものであ
る。However, although these methods can remove the moisture contained in the electrolyte from the beginning, HF is generated by moisture brought in from other members when the battery is assembled. However, there is a problem that the characteristics of the entire battery are not sufficient. In addition, since all of these additives have low solubility, an electrolyte solution obtained by filtering the additives is used, so that there is a problem that HF generated in a step after the injection cannot be removed. The present invention has been made in view of the above-described problems, and is intended to reduce a HF in an electrolytic solution, and to maintain a state in which a HF component is reduced even when moisture is mixed in from an electrode or the like during battery assembly. It is intended to provide a secondary battery.
【０００５】[0005]
【課題を解決するための手段】即ち、本発明の要旨は、
リチウムを吸蔵・放出することが可能な負極及び正極
と、溶質及び有機系溶媒を含む非水系電解液とを少なく
とも備えた非水系電解液二次電池において、有機系溶媒
中に下記構造式（Ｉ）又は（II）で示されるホスフィン
化合物が添加されてなることを特徴とする非水系電解液
二次電池、にある。That is, the gist of the present invention is as follows.
In a non-aqueous electrolyte secondary battery including at least a negative electrode and a positive electrode capable of inserting and extracting lithium, and a non-aqueous electrolyte containing a solute and an organic solvent, the following structural formula (I) ) Or a non-aqueous electrolyte secondary battery comprising a phosphine compound represented by (II).
【０００６】[0006]
【化３】 （式中、Ｒ1、Ｒ2及びＲ3は、それぞれ独立して、芳香
環を有していてもよく、且つハロゲンで置換されていて
もよい炭化水素基を表す）Embedded image (Wherein, R 1 , R 2 and R 3 each independently represent a hydrocarbon group which may have an aromatic ring and may be substituted with halogen)
【０００７】[0007]
【化４】 （式中、Ｒ4、Ｒ5及びＲ6は、それぞれ独立して、芳香
環を有していてもよく、且つハロゲンで置換されていて
もよい炭化水素基を表す）Embedded image (In the formula, R 4 , R 5 and R 6 each independently represent a hydrocarbon group which may have an aromatic ring and may be substituted with halogen.)
【０００８】[0008]
【発明の実施の形態】以下、本発明を詳細に説明する。
本発明は、リチウムを吸蔵・放出することが可能な負極
及び正極と、溶質及び有機溶媒を含む非水系電解液とを
少なくとも備えた、好ましくはリチウムを吸蔵・放出す
ることが可能な負極及び正極と、負極集電体及び正極集
電体と、溶質及び有機系溶媒を含む非水系電解液と、セ
パレータ及び外缶とを備えた非水系二次電池において、
有機系溶媒中に式（Ｉ）又は（II）で示されるホスフィ
ン化合物が添加されてなるところの非水系電解液二次電
池である。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The present invention provides a negative electrode and a positive electrode, which preferably include at least a negative electrode and a positive electrode capable of inserting and extracting lithium, and a non-aqueous electrolytic solution containing a solute and an organic solvent, and preferably store and release lithium. And, a non-aqueous secondary battery including a negative electrode current collector and a positive electrode current collector, a non-aqueous electrolyte containing a solute and an organic solvent, and a separator and an outer can.
A non-aqueous electrolyte secondary battery in which a phosphine compound represented by the formula (I) or (II) is added to an organic solvent.
【０００９】（非水系電解液）非水系電解液は、溶質、
有機系溶媒及び添加剤の式（Ｉ）及び（II）のホスフィ
ン化合物を含有してなる。有機系溶媒としては、特に限
定されるものではないが、通常、非プロトン性の有機溶
媒が用いられる。(Non-Aqueous Electrolyte) The non-aqueous electrolyte is a solute,
It comprises an organic solvent and additives phosphine compounds of formulas (I) and (II). The organic solvent is not particularly limited, but usually an aprotic organic solvent is used.
【００１０】非プロトン性有機溶媒の具体例としては、
例えばエチレンカーボネート、プロピレンカーボネート
等の環状カーボネート類、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等の鎖状
カーボネート類、γ−ブチロラクトン、γ−バレロラク
トン等の環状エステル類、酢酸メチル、プロピオン酸メ
チル等の鎖状エステル類、テトラヒドロフラン、２−メ
チルテトラヒドロフラン、テトラヒドロピラン等の環状
エーテル類、ジメトキシエタン、ジメトキシメタン等の
鎖状エーテル類、スルフォラン、ジエチルスルホン等の
含硫黄有機溶媒等を挙げることができる。これらの中、
環状カーボネート類、鎖状カーボネート類、環状エステ
ル類、鎖状エステル類が好ましい。なお、これらの溶媒
は、単独で、或いは二種以上混合して用いてもよい。本
発明においては、有機系溶媒に式（Ｉ）又は（II）のホ
スフィン化合物が添加される。Specific examples of the aprotic organic solvent include:
For example, ethylene carbonate, cyclic carbonates such as propylene carbonate, dimethyl carbonate, diethyl carbonate, chain carbonates such as ethyl methyl carbonate, γ-butyrolactone, cyclic esters such as γ-valerolactone, methyl acetate, methyl propionate and the like Examples thereof include chain esters, cyclic ethers such as tetrahydrofuran, 2-methyltetrahydrofuran, and tetrahydropyran; chain ethers such as dimethoxyethane and dimethoxymethane; and sulfur-containing organic solvents such as sulfolane and diethyl sulfone. Of these,
Preferred are cyclic carbonates, chain carbonates, cyclic esters, and chain esters. These solvents may be used alone or as a mixture of two or more. In the present invention, a phosphine compound of the formula (I) or (II) is added to an organic solvent.
【００１１】[0011]
【化５】 （式中、Ｒ1、Ｒ2及びＲ3は、それぞれ独立して、芳香
環を有していてもよく、且つハロゲンで置換されていて
もよい炭化水素基を表す）Embedded image (Wherein, R 1 , R 2 and R 3 each independently represent a hydrocarbon group which may have an aromatic ring and may be substituted with halogen)
【００１２】式（Ｉ）において、Ｒ1、Ｒ2及びＲ3が芳
香環を有していてもよい炭化水素基である場合、その具
体例としては、例えばメチル基、エチル基、プロピル
基、ブチル基等のようなアルキル基、及びフェニル基、
ナフチル基等のようなアリール基が挙げられる。そし
て、このような式（Ｉ）の化合物の具体例としては、例
えばジメトキシメチルホスフィン、ジエトキシエチルホ
スフィン、ジプロポキシプロピルホスフィン等のような
ジアルコキシアルキルホスフィン、ジメトキシフェニル
ホスフィン、ジエトキシフェニルホスフィン等のような
ジアルコキシアリールホスフィン、メトキシフェノキシ
メチルホスフィン、エトキシフェノキシエチルホスフィ
ン等のようなアルコキシアリールオキシアルキルホスフ
ィン、メチルジフェノキシホスフィン、エチルジフェノ
キシホスフィン等のようなアルキルジアリールオキシホ
スフィン、ジフェノキシフェニルホスフィン等のような
ジアリールオキシアリールホスフィン等が挙げられる。
これらの中、ジフェノキシフェニルホスフィン、ジメチ
ルジフェノキシホスフィン、エチルジフェノキシホスフ
ィン等のようなＲ1又はＲ2にフェニル基を有するものが
好ましい。In the formula (I), when R 1 , R 2 and R 3 are a hydrocarbon group which may have an aromatic ring, specific examples thereof include a methyl group, an ethyl group, a propyl group, An alkyl group such as a butyl group, and a phenyl group,
And an aryl group such as a naphthyl group. Specific examples of the compound of the formula (I) include dialkoxyalkylphosphines such as dimethoxymethylphosphine, diethoxyethylphosphine, and dipropoxypropylphosphine; dimethoxyphenylphosphine; and diethoxyphenylphosphine. Alkoxyaryloxyalkylphosphines such as dialkoxyarylphosphine, methoxyphenoxymethylphosphine, ethoxyphenoxyethylphosphine, etc., alkyldiaryloxyphosphines such as methyldiphenoxyphosphine, ethyldiphenoxyphosphine, etc., diphenoxyphenylphosphine, etc. Such diaryloxyaryl phosphines and the like.
Among these, those having a phenyl group at R 1 or R 2 such as diphenoxyphenylphosphine, dimethyldiphenoxyphosphine, ethyldiphenoxyphosphine and the like are preferable.
【００１３】[0013]
【化６】 （式中、Ｒ4、Ｒ5及びＲ6は、それぞれ独立して、芳香
環を有していてもよく、且つハロゲンで置換されていて
もよい炭化水素基を表す）Embedded image (In the formula, R 4 , R 5 and R 6 each independently represent a hydrocarbon group which may have an aromatic ring and may be substituted with halogen.)
【００１４】式（II)において、Ｒ4、Ｒ5及びＲ6が芳香
環を有していてもよい炭化水素基である場合、その具体
例としては、例えばメチル基、エチル基、プロピル基、
ブチル基等のようなアルキル基、及びフェニル基、ナフ
チル基等のようなアリール基が挙げられる。そして、こ
のような式（II）の化合物の具体例としては、例えばメ
トキシジメチルホスフィン、エトキシジエチルホスフィ
ン、プロポキシジプロピルホスフィン等のようなアルコ
キシジアルキル、ジメチルフェノキシホスフィン、ジエ
チルフェノキシホスフィン等のようなアリールオキシジ
アルキルホスフィン、フェノキシジフェニルホスフィン
等のようなアリールオキシジアリールホスフィン等が挙
げられる。これらの中、フェノキシジフェニルホスフィ
ン、ジメチルフェノキシホスフィン、ジエチルフェノキ
シホスフィン等のようなＲ4にフェニルを有するものが
好ましい。In the formula (II), when R 4 , R 5 and R 6 are a hydrocarbon group which may have an aromatic ring, specific examples thereof include a methyl group, an ethyl group, a propyl group,
Examples include an alkyl group such as a butyl group and the like, and an aryl group such as a phenyl group and a naphthyl group. Specific examples of such a compound of the formula (II) include, for example, alkoxydialkyl such as methoxydimethylphosphine, ethoxydiethylphosphine, and propoxydipropylphosphine, and aryloxy such as dimethylphenoxyphosphine and diethylphenoxyphosphine. And aryloxydiarylphosphines such as dialkylphosphine and phenoxydiphenylphosphine. Among these, those having phenyl at R 4 such as phenoxydiphenylphosphine, dimethylphenoxyphosphine, diethylphenoxyphosphine and the like are preferable.
【００１５】なお、式（Ｉ）の化合物又は式（II）の化
合物の添加量は、これらの化合物と有機系溶媒との合計
量に対して０．００１〜２０重量％、好ましくは０．０
１〜１０重量％、より好ましくは０．１〜５重量％であ
る。溶質としては、ＬｉＰＦ6、ＬｉＢＦ4から選ばれる
無機リチウム塩を用いる。電解液中の溶質のリチウム塩
のモル濃度は、０．５〜２．０モル／リットルであるこ
とが望ましい。０．５モル／リットルより少ないか２．
０モル／リットルを越えると、電解液の電気伝導率が低
く、電池の性能が低下するため好ましくない。The amount of the compound of the formula (I) or the compound of the formula (II) is 0.001 to 20% by weight, preferably 0.0 to 20% by weight, based on the total amount of the compound and the organic solvent.
It is 1 to 10% by weight, more preferably 0.1 to 5% by weight. As the solute, an inorganic lithium salt selected from LiPF 6 and LiBF 4 is used. The molar concentration of the solute lithium salt in the electrolyte is desirably 0.5 to 2.0 mol / liter. Less than 0.5 mol / l or 2.
If it exceeds 0 mol / liter, the electric conductivity of the electrolytic solution is low, and the performance of the battery is undesirably reduced.
【００１６】（負極）電池を構成する負極材料として
は、様々な熱分解条件での有機物の熱分解物や人造黒
鉛、天然黒鉛等のリチウムを吸蔵・放出可能な炭素質材
料、酸化錫、酸化珪素等のリチウムを吸蔵・放出可能な
金属酸化物材料、リチウム金属、種々のリチウム合金を
用いることができる。これらの負極材料は二種類以上混
合して用いてもよい。黒鉛系の炭素質材料を負極材料と
して用いる場合は、好適には種々の原料から得た易黒鉛
性ピッチの高温熱処理によって製造された人造黒鉛及び
天然黒鉛或いはこれらの黒鉛に種々の表面処理を施した
材料が主として使用されるが、これらの黒鉛材料はＸ線
回折で求めた格子面（００２面）のｄ値（層間距離）が
０．３３５〜０．３４ｎｍ、より好ましくは０．３３５
〜０．３３７ｎｍであるものが好ましい。(Negative Electrode) As negative electrode materials constituting a battery, pyrolytic products of organic substances under various thermal decomposition conditions, carbonaceous materials capable of occluding and releasing lithium such as artificial graphite and natural graphite, tin oxide, oxides Metal oxide materials capable of occluding and releasing lithium such as silicon, lithium metal, and various lithium alloys can be used. These negative electrode materials may be used as a mixture of two or more. When a graphite-based carbonaceous material is used as a negative electrode material, artificial graphite and natural graphite produced by high-temperature heat treatment of easily-graphitizable pitch obtained from various raw materials, or these graphites are subjected to various surface treatments. These materials are mainly used. These graphite materials have a d value (interlayer distance) of a lattice plane (002 plane) determined by X-ray diffraction of 0.335 to 0.34 nm, and more preferably 0.335 nm.
It is preferably about 0.337 nm.
【００１７】これらの負極材料を用いて負極を製造する
方法については、特に限定されない。例えば、負極材料
に、必要に応じて結着剤、増粘剤、導電材、溶媒等を加
えてスラリー状とし、集電体の基板に塗布し、乾燥する
ことにより負極を製造することができるし、また、該負
極材料をそのままロール成形してシート電極としたり、
圧縮成形によりペレット電極とすることもできる。The method for producing a negative electrode using these negative electrode materials is not particularly limited. For example, a negative electrode can be manufactured by adding a binder, a thickener, a conductive material, a solvent, and the like to a negative electrode material as needed to form a slurry, applying the slurry to a current collector substrate, and drying. Alternatively, the negative electrode material may be directly roll-formed into a sheet electrode,
A pellet electrode can be obtained by compression molding.
【００１８】電極の製造に用いられる結着剤について
は、電極製造時に使用する溶媒や電解液に対して安定な
材料であれば、特に限定されない。その具体例として
は、ポリフッ化ビニリデン、ポリテトラフルオロエチレ
ン、スチレン・ブタジエンゴム、イソプレンゴム、ブタ
ジエンゴム等を挙げることができる。増粘剤としては、
カルボキシメチルセルロース、メチルセルロース、ヒド
ロキシメチルセルロース、エチルセルロース、ポリビニ
ルアルコール、酸化スターチ、リン酸化スターチ、カゼ
イン等が挙げられる。導電材としては、銅やニッケル等
の金属材料、グラファイト、カーボンブラック等のよう
な炭素材料が挙げられる。The binder used in the production of the electrode is not particularly limited as long as it is a material that is stable with respect to the solvent and electrolyte used in the production of the electrode. Specific examples thereof include polyvinylidene fluoride, polytetrafluoroethylene, styrene / butadiene rubber, isoprene rubber, and butadiene rubber. As a thickener,
Examples include carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, casein and the like. Examples of the conductive material include metal materials such as copper and nickel, and carbon materials such as graphite and carbon black.
【００１９】（負極集電体）負極用集電体の材質は、
銅、ニッケル、ステンレス等の金属が使用され、これら
の中で薄膜に加工しやすいという点とコストの点から銅
箔が好ましい。(Negative electrode current collector) The material of the negative electrode current collector is as follows.
Metals such as copper, nickel, and stainless steel are used, and among these, copper foil is preferred from the viewpoint of easy processing into a thin film and cost.
【００２０】（正極）本発明の電池を構成する正極の材
料としては、リチウムコバルト酸化物、リチウムニッケ
ル酸化物、リチウムマンガン酸化物等のリチウム遷移金
属複合酸化物材料等のリチウムを吸蔵及び放出可能な材
料を使用することができる。正極の製造方法について
は、特に限定されず、上記の負極の製造方法に準じて製
造することができる。また、その形状については、正極
材料に必要に応じて結着剤、導電材、溶媒等を加えて混
合後、集電体の基板に塗布してシート電極としたり、プ
レス成形を施してペレット電極とすることができる。(Positive Electrode) As the material of the positive electrode constituting the battery of the present invention, lithium such as lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, and other lithium transition metal composite oxide materials can absorb and release lithium. Material can be used. The method for manufacturing the positive electrode is not particularly limited, and the positive electrode can be manufactured according to the above-described method for manufacturing the negative electrode. As for the shape, a binder, a conductive material, a solvent, and the like are added to the positive electrode material as necessary and mixed, and then applied to a current collector substrate to form a sheet electrode, or a pellet electrode formed by press molding. It can be.
【００２１】（正極集電体）正極用集電体の材質は、ア
ルミニウム、チタン、タンタル等の金属又はその合金が
用いられる。これらの中で、特にアルミニウム又はその
合金が軽量であるためエネルギー密度の点で望ましい。(Positive Electrode Current Collector) As the material of the positive electrode current collector, a metal such as aluminum, titanium, and tantalum or an alloy thereof is used. Among these, aluminum or its alloy is desirable in terms of energy density because it is lightweight.
【００２２】（セパレータ）本発明の電池に使用するセ
パレータの材質や形状については、特に限定されない。
但し、電解液に対して安定で、保液性の優れた材料の中
から選ぶのが好ましく、ポリエチレン、ポリプロピレン
等のポリオレフィンを原料とする多孔性シート又は不織
布等を用いるのが好ましい。(Separator) The material and shape of the separator used in the battery of the present invention are not particularly limited.
However, it is preferable to select from materials that are stable with respect to the electrolyte and have excellent liquid retention properties, and it is preferable to use a porous sheet or nonwoven fabric made of a polyolefin such as polyethylene or polypropylene as a raw material.
【００２３】（その他）負極、正極及び非水系電解液を
少なくとも有する本発明の電池を製造する方法について
は、特に限定されず、通常採用されている方法の中から
適宜選択することができる。また、電池の形状について
は特に限定されず、シート電極及びセパレータをスパイ
ラル状にしたシリンダータイプ、ペレット電極及びセパ
レータを組み合わせたインサイドアウト構造のシリンダ
ータイプ、ペレット電極及びセパレータを積層したコイ
ンタイプ等が使用可能である。図１にコインタイプの非
水系電解液電池の断面図を示す。図中、１は正極、２は
負極、３は正極缶、４は封口板、５はセパレータ、６は
ガスケット、７は正極集電体、８は負極集電体である。(Others) The method for producing the battery of the present invention having at least a negative electrode, a positive electrode, and a non-aqueous electrolyte is not particularly limited, and can be appropriately selected from commonly employed methods. The shape of the battery is not particularly limited, and a cylinder type in which a sheet electrode and a separator are formed into a spiral shape, a cylinder type having an inside-out structure in which a pellet electrode and a separator are combined, and a coin type in which a pellet electrode and a separator are stacked are used. It is possible. FIG. 1 shows a sectional view of a coin-type non-aqueous electrolyte battery. In the figure, 1 is a positive electrode, 2 is a negative electrode, 3 is a positive electrode can, 4 is a sealing plate, 5 is a separator, 6 is a gasket, 7 is a positive electrode current collector, and 8 is a negative electrode current collector.
【００２４】[0024]
【実施例】以下、実施例により、本発明を更に具体的に
説明するが、本発明はその要旨を越えない限りこれらに
限定されるものではない。 （実施例１、比較例１）電解液については、乾燥アルゴ
ン雰囲気下で、十分に乾燥を行った六フッ化リン酸リチ
ウム（ＬｉＰＦ6）を溶質として用い、エチレンカーボ
ネート（ＥＣ）、ジエチルカーボネート（ＤＥＣ）を表
−１に示す組成で混合した溶液にＬｉＰＦ6を１モル／
リットルの割合で溶解して調製した。その後、ジフェニ
ルホスフィン酸メチルを電解液に表−１で示す濃度にて
添加、各電解液の酸分を測定する。結果を表−１に示
す。EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these without departing from the gist thereof. (Example 1, Comparative Example 1) For an electrolyte solution, lithium carbonate hexafluoride (LiPF 6 ), which was sufficiently dried under a dry argon atmosphere, was used as a solute, and ethylene carbonate (EC), diethyl carbonate ( the LiPF 6 1 mol DEC) in a mixed solution of the compositions shown in Table 1 /
It was prepared by dissolving at a liter rate. Thereafter, methyl diphenylphosphinate is added to the electrolyte at the concentration shown in Table 1, and the acid content of each electrolyte is measured. The results are shown in Table 1.
【００２５】[0025]
【表１】 [Table 1]
【００２６】（実施例２、比較例２）実施例１、比較例
１において、調製した電解液に水を５００ｐｐｍ添加、
乾燥アルゴン雰囲気下で１２時間静置し各電解液の酸分
を測定する。結果を表−２に示す。Example 2, Comparative Example 2 In Example 1, Comparative Example 1, 500 ppm of water was added to the prepared electrolyte solution.
The mixture is allowed to stand for 12 hours in a dry argon atmosphere, and the acid content of each electrolytic solution is measured. Table 2 shows the results.
【００２７】[0027]
【表２】 [Table 2]
【００２８】（実施例３、比較例３）正極活物質として
ＬｉＣｏＯ2（８５重量部）にカーボンブラック（６重
量部）、ポリフッ化ビニリデン（９重量部）を加え混合
し、Ｎ−メチル−２−ピロリドンで分散し、スラリー状
としたものを正極集電体である厚さ２０μｍのアルミニ
ウム箔上に均一に塗布し、乾燥後、所定の形状に打ち抜
いて正極とした。負極活物質として、Ｘ線回折における
格子面（００２面）のｄ値が０．３３６ｎｍである人造
黒鉛粉末ＫＳ−４４（ティムカル社製、商品名）（９４
重量部）にポリフッ化ビニリデン（６重量部）を混合
し、Ｎ−メチル−２−ピロリドンで分散させスラリー状
としたものを負極集電体である厚さ１８μｍの銅箔上に
均一に塗布し、乾燥後、所定の形状に打ち抜いて負極と
した。電解液については実施例１、比較例１で調製した
ものを用いた。これらの正極、負極、電解液を用いて、
図１に示すようなコイン型非水系電解液電池を、乾燥ア
ルゴン雰囲気下で作製した。以下、図１に基づき説明す
ると、正極１と負極２とを、それぞれステンレス製の正
極缶３と封口板４に収容し、各電解液を含浸させたポリ
プロピレンの微孔性フィルムからなるセパレータ５を介
して積層して使用した。続いて、正極缶３と封口板４と
をガスケット７を介してかしめ密封して、コイン型電池
を作製した。これらの電池を２５℃において、０．５ｍ
Ａの定電流で充電終止電圧４．２Ｖ、放電終止電圧２．
５Ｖで充放電試験を行った。これらの電池の１００サイ
クル後の放電容量維持率を表−３に示す。放電容量維持
率とは下記の式に示す通りである。(Example 3, Comparative Example 3) Carbon black (6 parts by weight) and polyvinylidene fluoride (9 parts by weight) were added to LiCoO 2 (85 parts by weight) as a positive electrode active material and mixed, and N-methyl-2 was added. -A slurry obtained by dispersing with pyrrolidone and forming a slurry was uniformly applied on a 20 μm-thick aluminum foil serving as a positive electrode current collector, dried, and punched into a predetermined shape to obtain a positive electrode. As the negative electrode active material, artificial graphite powder KS-44 (trade name, manufactured by Timcal Co.) having a lattice plane (002 plane) d value of 0.336 nm in X-ray diffraction (94)
Parts by weight) of polyvinylidene fluoride (6 parts by weight), dispersed in N-methyl-2-pyrrolidone to form a slurry, and uniformly coated on a 18 μm-thick copper foil as a negative electrode current collector. After drying, the resultant was punched into a predetermined shape to obtain a negative electrode. As the electrolytic solution, those prepared in Example 1 and Comparative Example 1 were used. Using these positive electrode, negative electrode, and electrolyte,
A coin-type non-aqueous electrolyte battery as shown in FIG. 1 was produced under a dry argon atmosphere. In the following, referring to FIG. 1, the positive electrode 1 and the negative electrode 2 are accommodated in a stainless steel positive electrode can 3 and a sealing plate 4, respectively, and a separator 5 made of a polypropylene microporous film impregnated with each electrolytic solution is formed. Used for lamination. Subsequently, the positive electrode can 3 and the sealing plate 4 were caulked and sealed via the gasket 7 to produce a coin-type battery. At 25 ° C., these batteries
At a constant current of A, the charge end voltage is 4.2 V and the discharge end voltage is 2.
A charge / discharge test was performed at 5V. Table 3 shows the discharge capacity retention ratio of these batteries after 100 cycles. The discharge capacity retention ratio is as shown in the following equation.
【００２９】[0029]
【数１】放電容量維持率＝（１００サイクル目の放電容
量／１サイクル目の放電容量）×１００## EQU1 ## Discharge capacity retention ratio = (discharge capacity at 100th cycle / discharge capacity at 1st cycle) × 100
【００３０】[0030]
【表３】 [Table 3]
【００３１】表−１から表−３の結果よりメトキシジフ
ェニルホスフィンを含有する電解液は酸分を除去するこ
とにより、特にサイクル特性に優れた非水系電解液二次
電池が作製できる。From the results shown in Tables 1 to 3, it is possible to manufacture a nonaqueous electrolyte secondary battery having particularly excellent cycle characteristics by removing the acid component from the methoxydiphenylphosphine-containing electrolyte.
【００３２】[0032]
【発明の効果】非水系電解液二次電池の電解液の添加剤
として式（Ｉ）又は（II）のホスフィン化合物を選択す
ることによって、電解液中の酸分、更には、電池部材由
来の水分により発生する酸分も抑えることにより長期安
定性、サイクル特性が優れた電池を作成することがで
き、非水系電解液二次電池の小型化、高性能化に寄与す
ることができる。By selecting the phosphine compound of the formula (I) or (II) as an additive of the electrolytic solution of the non-aqueous electrolytic solution secondary battery, the acid content in the electrolytic solution and furthermore the origin of the battery component By suppressing the acid content generated by moisture, a battery having excellent long-term stability and cycle characteristics can be produced, which can contribute to miniaturization and high performance of the non-aqueous electrolyte secondary battery.
【図１】コイン型電池の構造を示した断面図である。FIG. 1 is a sectional view showing a structure of a coin-type battery.
１ 正極 ２ 負極 ３ 正極缶 ４ 封口板 ５ セパレータ ６ ガスケット ７ 正極集電体 ８ 負極集電体 Reference Signs List 1 positive electrode 2 negative electrode 3 positive electrode can 4 sealing plate 5 separator 6 gasket 7 positive electrode current collector 8 negative electrode current collector
───────────────────────────────────────────────────── フロントページの続き (72)発明者 島 邦久 茨城県稲敷郡阿見町中央八丁目３番１号 三菱化学株式会社筑波研究所内 (72)発明者 鈴木 仁 茨城県稲敷郡阿見町中央八丁目３番１号 三菱化学株式会社筑波研究所内 Ｆターム(参考） 5H029 AJ03 AJ04 AJ05 AK03 AL01 AL06 AL12 AM02 AM03 AM04 AM05 AM07 BJ03 DJ09 HJ01 HJ02 HJ10 5H050 AA07 AA08 AA09 BA16 BA17 CA07 CA08 CB01 CB07 CB08 CB12 DA02 DA03 EA10 EA24 FA19 HA13 ──────────────────────────────────────────────────続 き Continued on the front page (72) Kunihisa Shima 8-3-1 Chuo, Ami-cho, Inashiki-gun, Ibaraki Prefecture Inside the Tsukuba Research Laboratory, Mitsubishi Chemical Corporation (72) Inventor Hitoshi Suzuki 8-Chome, Ami-cho, Inashiki-gun, Ibaraki Prefecture No.3-1 F-term in the Tsukuba Research Laboratory, Mitsubishi Chemical Corporation (reference) FA19 HA13
Claims (7)
負極及び正極と、溶質及び有機系溶媒を含む非水系電解
液とを少なくとも備えた非水系電解液二次電池におい
て、有機系溶媒中に下記構造式（Ｉ）又は（II）で示さ
れるホスフィン化合物が添加されてなることを特徴とす
る非水系電解液二次電池。 【化１】 （式中、Ｒ1、Ｒ2及びＲ3は、それぞれ独立して、芳香
環を有していてもよく、且つハロゲンで置換されていて
もよい炭化水素基を表す） 【化２】 （式中、Ｒ4、Ｒ5及びＲ6は、それぞれ独立して、芳香
環を有していてもよく、且つハロゲンで置換されていて
もよい炭化水素基を表す）1. A non-aqueous electrolyte secondary battery comprising at least a negative electrode and a positive electrode capable of inserting and extracting lithium, and a non-aqueous electrolyte containing a solute and an organic solvent, wherein the organic solvent contains A non-aqueous electrolyte secondary battery comprising a phosphine compound represented by the following structural formula (I) or (II). Embedded image (Wherein, R 1 , R 2 and R 3 each independently represent a hydrocarbon group which may have an aromatic ring and may be substituted with halogen). (In the formula, R 4 , R 5 and R 6 each independently represent a hydrocarbon group which may have an aromatic ring and may be substituted with halogen.)
I）のホスフィン化合物の含有量がこれらの化合物と有
機系溶媒との合計量に対して０．００１〜２０重量％で
ある請求項１に記載の二次電池。2. A phosphine compound of the formula (I) or a compound of the formula (I
The secondary battery according to claim 1, wherein the content of the phosphine compound of I) is 0.001 to 20% by weight based on the total amount of these compounds and the organic solvent.
求項１又は２に記載の二次電池。3. The secondary battery according to claim 1, wherein the solute is LiPF 6 or LiBF 4 .
２．０モル／リットルである請求項１ないし３のいずれ
かに記載の二次電池。4. A solute concentration in a non-aqueous electrolytic solution of 0.5 to 0.5.
4. The secondary battery according to claim 1, wherein the amount is 2.0 mol / liter.
正極がリチウムを吸蔵・放出することが可能なリチウム
遷移金属複合酸化物を含有する請求項１ないし４のいず
れかに記載の二次電池。5. The secondary battery according to claim 1, wherein the positive electrode capable of inserting and extracting lithium contains a lithium transition metal composite oxide capable of inserting and extracting lithium. .
負極がリチウムを吸蔵・放出することが可能に炭素質
物、金属化合物及びリチウム合金から選ばれる少なくと
も一種である請求項１ないし５のいずれかに記載の二次
電池。6. The negative electrode capable of occluding and releasing lithium is at least one selected from a carbonaceous substance, a metal compound, and a lithium alloy capable of occluding and releasing lithium. 2. The secondary battery according to 1.
負極が、Ｘ線回折における格子面（００２面）のｄ値が
０．３３５〜０．３４ｎｍの炭素材料からなる請求項１
ないし６のいずれかに記載の二次電池。7. The negative electrode capable of inserting and extracting lithium is made of a carbon material having a lattice plane (002 plane) having a d value of 0.335 to 0.34 nm in X-ray diffraction.
7. The secondary battery according to any one of claims 6 to 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000392412A JP4876313B2 (en) | 2000-12-25 | 2000-12-25 | Non-aqueous electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000392412A JP4876313B2 (en) | 2000-12-25 | 2000-12-25 | Non-aqueous electrolyte secondary battery |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2002198090A true JP2002198090A (en) | 2002-07-12 |
| JP2002198090A5 JP2002198090A5 (en) | 2008-03-06 |
| JP4876313B2 JP4876313B2 (en) | 2012-02-15 |
Family
ID=18858408
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000392412A Expired - Fee Related JP4876313B2 (en) | 2000-12-25 | 2000-12-25 | Non-aqueous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4876313B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004038846A1 (en) * | 2002-10-22 | 2004-05-06 | Mitsubishi Chemical Corporation | Nonaqueous electrolytic solution and nonaqueous electrolyte secondary battery containing the same |
| WO2005099023A1 (en) * | 2004-04-07 | 2005-10-20 | Matsushita Electric Industrial Co., Ltd. | Nonaqueous electrolyte secondary battery |
| WO2005104289A1 (en) * | 2004-04-19 | 2005-11-03 | Bridgestone Corporation | Nonaqueous electrolyte solution for battery and nonaqueous electrolyte battery using same |
| WO2005106906A1 (en) * | 2004-04-27 | 2005-11-10 | Bridgestone Corporation | Additive for non-aqueous electrolyte solution of electric double layer capacitor, non-aqueous electrolyte solution for electric double layer capacitor and non-aqueous electrolyte solution electric double layer capacitor |
| JP2006004746A (en) * | 2004-06-17 | 2006-01-05 | Mitsubishi Chemicals Corp | Nonaqueous electrolytic solution for secondary battery and nonaqueous electrolytic solution secondary battery using it |
| US8277973B2 (en) | 2006-06-16 | 2012-10-02 | Sony Corporation | Nonaqueous electrolyte composition and nonaqueous electrolyte secondary battery |
| CN111342134A (en) * | 2020-03-13 | 2020-06-26 | 河南电池研究院有限公司 | Wide-temperature-range lithium ion battery non-aqueous electrolyte and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6280976A (en) * | 1985-10-01 | 1987-04-14 | Hitachi Maxell Ltd | Organic electrolyte battery |
| JPH08321313A (en) * | 1995-05-24 | 1996-12-03 | Sanyo Electric Co Ltd | Nonaqueous electrolyte battery |
| JPH10154528A (en) * | 1996-11-22 | 1998-06-09 | Mitsui Chem Inc | Nonaqueous electrolyte and nonaqueous electrolyte secondary battery |
| JPH11238513A (en) * | 1998-02-23 | 1999-08-31 | Yuasa Corp | Nonaqueous electrolyte battery |
| JP2000228216A (en) * | 1999-02-08 | 2000-08-15 | Denso Corp | Non-aqueous electrolyte and non-aqueous electrolyte secondary battery |
-
2000
- 2000-12-25 JP JP2000392412A patent/JP4876313B2/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6280976A (en) * | 1985-10-01 | 1987-04-14 | Hitachi Maxell Ltd | Organic electrolyte battery |
| JPH08321313A (en) * | 1995-05-24 | 1996-12-03 | Sanyo Electric Co Ltd | Nonaqueous electrolyte battery |
| JPH10154528A (en) * | 1996-11-22 | 1998-06-09 | Mitsui Chem Inc | Nonaqueous electrolyte and nonaqueous electrolyte secondary battery |
| JPH11238513A (en) * | 1998-02-23 | 1999-08-31 | Yuasa Corp | Nonaqueous electrolyte battery |
| JP2000228216A (en) * | 1999-02-08 | 2000-08-15 | Denso Corp | Non-aqueous electrolyte and non-aqueous electrolyte secondary battery |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7169511B2 (en) | 2002-10-22 | 2007-01-30 | Mitsubishi Chemical Corporation | Nonaqueous electrolyte solution and nonaqueous electrolyte solution secondary battery employing the same |
| WO2004038846A1 (en) * | 2002-10-22 | 2004-05-06 | Mitsubishi Chemical Corporation | Nonaqueous electrolytic solution and nonaqueous electrolyte secondary battery containing the same |
| WO2005099023A1 (en) * | 2004-04-07 | 2005-10-20 | Matsushita Electric Industrial Co., Ltd. | Nonaqueous electrolyte secondary battery |
| CN100463284C (en) * | 2004-04-07 | 2009-02-18 | 松下电器产业株式会社 | Nonaqueous electrolyte secondary battery |
| US7468225B2 (en) | 2004-04-07 | 2008-12-23 | Panasonic Corporation | Non-aqueous electrolyte secondary battery |
| US7947399B2 (en) | 2004-04-19 | 2011-05-24 | Bridgestone Corporation | Non-aqueous electrolyte for battery and non-aqueous electrolyte battery comprising the same |
| WO2005104289A1 (en) * | 2004-04-19 | 2005-11-03 | Bridgestone Corporation | Nonaqueous electrolyte solution for battery and nonaqueous electrolyte battery using same |
| WO2005106906A1 (en) * | 2004-04-27 | 2005-11-10 | Bridgestone Corporation | Additive for non-aqueous electrolyte solution of electric double layer capacitor, non-aqueous electrolyte solution for electric double layer capacitor and non-aqueous electrolyte solution electric double layer capacitor |
| JP2006004746A (en) * | 2004-06-17 | 2006-01-05 | Mitsubishi Chemicals Corp | Nonaqueous electrolytic solution for secondary battery and nonaqueous electrolytic solution secondary battery using it |
| JP4599901B2 (en) * | 2004-06-17 | 2010-12-15 | 三菱化学株式会社 | Non-aqueous electrolyte for secondary battery and non-aqueous electrolyte secondary battery using the same |
| US8277973B2 (en) | 2006-06-16 | 2012-10-02 | Sony Corporation | Nonaqueous electrolyte composition and nonaqueous electrolyte secondary battery |
| CN111342134A (en) * | 2020-03-13 | 2020-06-26 | 河南电池研究院有限公司 | Wide-temperature-range lithium ion battery non-aqueous electrolyte and preparation method thereof |
| CN111342134B (en) * | 2020-03-13 | 2022-09-13 | 河南电池研究院有限公司 | Wide-temperature-range lithium ion battery non-aqueous electrolyte and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4876313B2 (en) | 2012-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5348090B2 (en) | Non-aqueous electrolyte and lithium secondary battery | |
| JP2001006729A (en) | Nonaqueous electrolyte secondary battery | |
| JP2000133304A (en) | Non-aqueous electrolyte and lithium secondary battery using it | |
| JP2004031079A (en) | Nonaqueous electrolyte secondary battery | |
| JP2001313071A (en) | Nonaqueous electrolyte and lithium secondary cell using it | |
| JP2007173014A (en) | Nonaqueous electrolyte secondary battery | |
| JP2003297423A (en) | Nonaqueous system electrolyte solution and nonaqueous system electrolyte solution secondary battery using the same | |
| JP4934917B2 (en) | Non-aqueous electrolyte secondary battery and non-aqueous electrolyte used therefor | |
| JP2000235866A (en) | Nonaqueous electrolyte secondary battery | |
| JP4910239B2 (en) | Non-aqueous electrolyte secondary battery | |
| JP2001023688A (en) | Nonaqueous electrolyte and lithium secondary battery using it | |
| JP4197079B2 (en) | Non-aqueous electrolyte secondary battery | |
| JP4211159B2 (en) | Non-aqueous electrolyte secondary battery | |
| JPH11121032A (en) | Nonaqueous electrolyte secondary battery | |
| JP3978960B2 (en) | Non-aqueous electrolyte secondary battery | |
| JP4876313B2 (en) | Non-aqueous electrolyte secondary battery | |
| JP3893627B2 (en) | Method for manufacturing lithium ion battery | |
| JP2003203675A (en) | Nonaqueous electrolyte and nonaqueous electrolyte secondary cell | |
| JP4075180B2 (en) | Nonaqueous electrolyte and lithium secondary battery using the same | |
| JP2002352851A (en) | Nonaqueous electrolyte secondary cell | |
| JP3959927B2 (en) | Non-aqueous electrolyte secondary battery and electrolyte used therefor | |
| JP4706088B2 (en) | Non-aqueous electrolyte secondary battery | |
| JP4406947B2 (en) | Non-aqueous electrolyte battery | |
| JP4237531B2 (en) | Lithium secondary battery and method for producing lithium secondary battery | |
| JP2000331709A (en) | Nonaqueous electrolyte secondary battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20071221 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20071221 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20071221 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20071221 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20101124 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20110308 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110428 |
|
| 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: 20111101 |
|
| 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: 20111114 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20141209 Year of fee payment: 3 |
|
| LAPS | Cancellation because of no payment of annual fees |