JP2001283844A - Nonaqueous electrolyte battery - Google Patents
Nonaqueous electrolyte batteryInfo
- Publication number
- JP2001283844A JP2001283844A JP2000090036A JP2000090036A JP2001283844A JP 2001283844 A JP2001283844 A JP 2001283844A JP 2000090036 A JP2000090036 A JP 2000090036A JP 2000090036 A JP2000090036 A JP 2000090036A JP 2001283844 A JP2001283844 A JP 2001283844A
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- active material
- graphite
- electrode active
- electrolyte battery
- 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
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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
- Carbon And Carbon Compounds (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- 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、銅箔から成る負極
芯体の表面に、黒鉛から成る負極活物質を主体とする負
極活物質層が形成された負極と、リチウムを吸蔵、放出
しうる正極活物質層を備えた正極と、非水電解質とを有
する非水電解質電池に関するものである。The present invention relates to a negative electrode in which a negative electrode active material layer mainly composed of a graphite negative electrode active material is formed on the surface of a negative electrode core made of a copper foil, and capable of inserting and extracting lithium. The present invention relates to a nonaqueous electrolyte battery including a positive electrode having a positive electrode active material layer and a nonaqueous electrolyte.
【０００２】[0002]
【従来の技術】近年、ＬｉＣｏＯ2 等のリチウム含有遷
移金属酸化物等を正極活物質とする一方、金属リチウム
又はリチウムイオンを吸蔵、放出し得る合金、酸化物又
は黒鉛、コークス等の炭素材料を負極活物質とする非水
電解質電池が、高容量化が可能な電池として注目されて
いる。 2. Description of the Related Art In recent years, while a lithium-containing transition metal oxide such as LiCoO 2 is used as a positive electrode active material, an alloy, an oxide or a carbon material such as graphite or coke capable of occluding and releasing metallic lithium or lithium ions is used. A non-aqueous electrolyte battery used as a negative electrode active material has attracted attention as a battery capable of increasing capacity.
【０００３】上記負極活物質のうちリチウム又はリチウ
ムを主体とする材料を用いた場合には、充放電により樹
枝状のリチウムが析出（デンドライトが発生）し、電池
内で短絡するおそれがあるのに対して、炭素材料を負極
材料として用いると、このような欠点を解消することが
できるという利点がある。その中でも、黒鉛を用いた場
合には、放電容量が増大し、且つ、初期の充放電効率が
向上すると共に、電位の平坦性が確保されるという利点
がある。[0003] When lithium or a material mainly composed of lithium is used among the above-mentioned negative electrode active materials, dendritic lithium is deposited (dendrites are generated) by charge and discharge, which may cause a short circuit in the battery. On the other hand, when a carbon material is used as a negative electrode material, there is an advantage that such a disadvantage can be solved. Among them, when graphite is used, there are advantages that the discharge capacity is increased, the initial charge / discharge efficiency is improved, and the flatness of the potential is ensured.
【０００４】ここで、上記黒鉛を用いて負極を作製する
場合には、先ず、黒鉛と結着剤等とを混合してスラリー
を調製した後、このスラリーを銅箔から成る負極芯体に
塗着し、更に、これを乾燥する。最後に、負極活物質の
充填密度を上げるべく、上記のようにして作製した極板
を、ローラープレスによって圧延するというものであ
る。[0004] When a negative electrode is produced using the above graphite, first, a slurry is prepared by mixing graphite and a binder and the like, and then this slurry is applied to a negative electrode core made of copper foil. And then dried. Finally, in order to increase the packing density of the negative electrode active material, the electrode plate manufactured as described above is rolled by a roller press.
【０００５】しかしながら、従来の黒鉛はリン片状〔Ｃ
ｕ−Ｋα線源を用いた粉末Ｘ線回折法による（００２）
面とこの（００２）面と垂直な（１１０）面とのピーク
強度比（Ｉ(002) ／Ｉ(110) ）が１０００より大きい黒
鉛〕で、配向度が高いため、極板の面方向と平行にベイ
サル面が配向される割合が高くなる。この結果、極板を
ローラープレスによって圧延する際、ベイサル面同士が
滑って、黒鉛同士或いは黒鉛と芯体との密着性が低下
し、電池の歩留りが低くなるという課題を有していた。However, conventional graphite has a flaky shape [C
By powder X-ray diffraction using a u-Kα source (002)
Graphite having a peak intensity ratio (I (002) / I (110) ) of more than 1000] between the surface and the (110) plane perpendicular to the (002) plane, and the degree of orientation is high. The proportion that the basal plane is oriented in parallel increases. As a result, when the electrode plate is rolled by the roller press, the basal surfaces slip, the adhesion between graphite or graphite and the core body is reduced, and the yield of the battery is reduced.
【０００６】[0006]
【発明が解決しようとする課題】本発明は上記従来の課
題を考慮したものであって、負極活物質の充填密度を上
げるべく極板をローラープレスによって圧延した場合で
あっても、ベイサル面同士が滑るのを抑制することによ
り、黒鉛同士或いは黒鉛と芯体との密着性が低下するの
を抑えて、電池の歩留りを向上させることができる非水
電解質電池を提供することを目的としている。SUMMARY OF THE INVENTION The present invention has been made in consideration of the above-mentioned conventional problems. Even when the electrode plate is rolled by a roller press in order to increase the packing density of the negative electrode active material, the basal surfaces are not separated from each other. It is an object of the present invention to provide a non-aqueous electrolyte battery capable of suppressing a decrease in adhesion between graphite or between a graphite and a core body by suppressing slippage and improving a battery yield.
【０００７】[0007]
【課題を解決するための手段】上記目的を達成するため
に、本発明のうちで請求項１記載の発明は、銅箔から成
る負極芯体の表面に、黒鉛（Ｌｃ値は１５０Å以上、ｄ
(002) 値は３．３８Å以下）から成る負極活物質を主体
とする負極活物質層が形成された負極と、リチウムを吸
蔵、放出しうる正極活物質層を備えた正極と、非水電解
質とを有する非水電解質電池であって、上記黒鉛が、Ｃ
ｕ−Ｋα線源を用いた粉末Ｘ線回折法による（００２）
面と（１１０）面とのピーク強度比（Ｉ(002) ／Ｉ
(110) ）が１０００以下に規制されることを特徴とす
る。Means for Solving the Problems In order to achieve the above-mentioned object, the invention according to claim 1 of the present invention provides a method for producing a graphite (Lc value of 150 ° or more, d
(002 value is 3.38 ° or less), a negative electrode having a negative electrode active material layer mainly composed of a negative electrode active material, a positive electrode having a positive electrode active material layer capable of absorbing and releasing lithium, and a non-aqueous electrolyte. A non-aqueous electrolyte battery comprising:
By powder X-ray diffraction using a u-Kα source (002)
Intensity ratio between the (110) plane and the (110) plane (I (002) / I
(110) ) is regulated to 1000 or less.
【０００８】上記の如く、黒鉛が、Ｃｕ−Ｋα線源を用
いた粉末Ｘ線回折法による（００２）面とこの（００
２）面と垂直な（１１０）面とのピーク強度比（Ｉ
(002) ／Ｉ (110) ）が１０００以下に規制されていれ
ば、球状の黒鉛となる。したがって、負極活物質の充填
密度を上げるべく極板をローラープレスによって圧延し
た場合であっても、ベイサル面同士が滑るのを抑制する
ことができるので、負極活物質の密着性が低下するのを
抑えることができる。この結果、電池の歩留りを飛躍的
に向上させることが可能となる。As described above, graphite uses a Cu-Kα radiation source.
(002) plane by powder X-ray diffraction method
2) The peak intensity ratio (I) between the (110) plane and the perpendicular (110) plane
(002)/ I (110)) Is regulated to 1000 or less
If so, it becomes spherical graphite. Therefore, the filling of the negative electrode active material
Roll the plates with a roller press to increase the density
Control the slip between the basal surfaces even if
Can reduce the adhesion of the negative electrode active material.
Can be suppressed. As a result, the battery yield is dramatically improved
Can be improved.
【０００９】また、請求項２記載の発明は、請求項１記
載の発明において、前記銅箔から成る負極芯体の厚み
が、５μｍ以上１０μｍ以下に規制されることを特徴と
する。A second aspect of the present invention is characterized in that, in the first aspect of the present invention, the thickness of the negative electrode core made of the copper foil is regulated to 5 μm or more and 10 μm or less.
【００１０】このように、銅箔から成る負極芯体の厚み
を規制するのは、負極芯体の厚みが５μｍ未満であれば
負極芯体が破断する場合がある一方、負極芯体の厚みが
１０μｍを超えると、負極活物質の充填密度を著しく上
げる必要があるため、負荷特性が低下し、しかも負極に
おける密着強度も低下するからである。[0010] As described above, the thickness of the negative electrode core made of copper foil is regulated because if the thickness of the negative electrode core is less than 5 µm, the negative electrode core may be broken, while the thickness of the negative electrode core may be reduced. If the thickness exceeds 10 μm, the packing density of the negative electrode active material must be significantly increased, so that the load characteristics decrease and the adhesion strength at the negative electrode also decreases.
【００１１】また、請求項３記載の発明は、請求項１又
は２記載の発明において、前記負極板における負極活物
質の充填密度が、１．５ｇ／ｃｃ以上１．８ｇ／ｃｃ以
下に規制されることを特徴とする。According to a third aspect of the present invention, in the first or second aspect, the packing density of the negative electrode active material in the negative electrode plate is regulated to 1.5 g / cc or more and 1.8 g / cc or less. It is characterized by that.
【００１２】このように、負極活物質の充填密度を規制
するのは、負極活物質の充填密度が１．５ｇ／ｃｃ未満
になると、単位体積当たりの負極容量が低下する一方、
負極活物質の充填密度が１．８ｇ／ｃｃを超えると、負
荷特性が低下すると共に負極における密着強度が低下す
るからである。As described above, the packing density of the negative electrode active material is regulated when the packing density of the negative electrode active material is less than 1.5 g / cc, while the capacity of the negative electrode per unit volume decreases,
If the packing density of the negative electrode active material exceeds 1.8 g / cc, the load characteristics decrease and the adhesion strength at the negative electrode decreases.
【００１３】また、請求項４記載の発明は、請求項１、
２又は３記載の発明において、前記負極活物質は、ジェ
ットミルにて高圧ガスを噴出させることにより球状化す
ることを特徴とする。[0013] The invention described in claim 4 is based on claim 1,
In the invention described in 2 or 3, the negative electrode active material is formed into a sphere by ejecting a high-pressure gas by a jet mill.
【００１４】このような製造方法により、球状黒鉛を得
ることができるが、本発明はこのような方法に限定する
ものではない。Although spherical graphite can be obtained by such a production method, the present invention is not limited to such a method.
【００１５】[0015]
【発明の実施の形態】（正極の作製）先ず、正極活物質
としてのＬｉＣｏＯ2 粉末（平均粒径：５μｍ）と、導
電剤としての人造黒鉛粉末とを、重量比で９：１の割合
で混合して正極合剤を作製した。次に、この正極合剤
と、結着剤としてのポリフッ化ビニリデンが５重量％溶
解されたＮ−メチル−２−ピロリドン（ＮＭＰ）溶液と
を、固形分重量比が９５：５となるように混合してスラ
リーを調製した後、このスラリーを正極芯体としてのア
ルミニウム箔の両面にドクターブレード法により塗布し
た（厚みは各面１００μｍである）。その後、溶剤を乾
燥し、ローラーで所定の厚みにまで圧縮した後、１５０
℃で２時間真空乾燥させて、正極（活物質の充填密度：
３．０ｇ／ｃｃ）を作製した。 （負極の作製）先ず、リン片状の天然黒鉛〔Ｃｕ−Ｋα
線源を用いた粉末Ｘ線回折法による（００２）面と（１
１０）面とのピーク強度比（Ｉ(002) ／Ｉ(110) ）（以
下、ピーク強度比と略する）が５００、Ｌｃ値：７８０
Å、ｄ(002) 値：３．３５８Å、平均粒径：４０μｍ〕
をカウンタージェットミルに５００ｇ装填し、空気圧４
ｋｇ／ｃｍ2 、噴出ノズル径５ｍｍφに設定して、カウ
ンタージェットミルを２０分間運転することにより、ピ
ーク強度比が５００の球状黒鉛〔Ｌｃ値：７８０Å、ｄ
(002) 値：３．３５８Å、平均粒径：２０μｍ〕を作製
した。DESCRIPTION OF THE PREFERRED EMBODIMENTS (Preparation of Positive Electrode) First, LiCoO 2 powder (average particle size: 5 μm) as a positive electrode active material and artificial graphite powder as a conductive agent were mixed at a weight ratio of 9: 1. The mixture was mixed to produce a positive electrode mixture. Next, this positive electrode mixture and an N-methyl-2-pyrrolidone (NMP) solution in which 5% by weight of polyvinylidene fluoride as a binder were dissolved, so that the solid content weight ratio was 95: 5. After mixing to prepare a slurry, the slurry was applied to both sides of an aluminum foil as a positive electrode core by a doctor blade method (the thickness was 100 μm on each side). Thereafter, the solvent was dried and compressed to a predetermined thickness with a roller.
C. for 2 hours under vacuum to form a positive electrode (filling density of active material:
3.0 g / cc). (Preparation of negative electrode) First, flaky natural graphite [Cu-Kα
(002) plane and (1) by powder X-ray diffraction using a radiation source.
10) The peak intensity ratio to the plane (I (002) / I (110) ) (hereinafter abbreviated as peak intensity ratio) is 500, and the Lc value is 780.
{, D (002) value: 3.358}, average particle size: 40 μm]
Into a counter jet mill and air pressure 4
kg / cm 2, by setting the ejection nozzle diameter 5 mm.phi, by operating the counter jet mill 20 min, the peak intensity ratio 500 of spheroidal graphite [Lc value: 780 Å, d
(002) value: 3.358 °, average particle size: 20 μm].
【００１６】次に、上記球状黒鉛と、結着剤としてのス
チレン−ブタジエンゴム（ＳＢＲ）のディスパージョン
（固形分：４８％）とを水に分散させ、更に、増粘剤で
あるカルボキシメチルセルロース（ＣＭＣ）を添加し
て、スラリーを調製した。尚、上記球状黒鉛と、ＳＢＲ
と、ＣＭＣとの混合割合は、負極乾燥後の重量比が、球
状黒鉛：ＳＢＲ：ＣＭＣ＝１００：３：２となるように
混合した。この後、上記スラリーを負極芯体としての銅
箔（厚み：８μｍ）の両面にドクターブレード法により
塗布した（厚みは各面１００μｍである）。しかる後、
溶剤を乾燥し、ローラーで所定の厚みにまで圧縮した
後、１１０℃で２時間真空乾燥させて、負極（活物質の
充填密度：１．５ｇ／ｃｃ）を作製した。 （電解液の調製）電解液としては、ＥＣ（エチレンカー
ボネート）とＤＥＣ（ジエチルカーボネート）とが体積
比で５０：５０の割合で混合された混合溶媒に、ＬｉＰ
Ｆ6 が１Ｍ（モル／リットル）の割合で溶解された非水
電解液を用いた。 （電池の作製）上記正極と負極とをポリプロピレン製の
微多孔膜から成るセパレータを介して巻回して発電要素
を作製した後、この発電要素を有底筒状の外装缶内に挿
入した。最後に、上記電解液を外装缶内に注入した後、
封口板を外装缶の開口部に取り付けることにより、円筒
形の電池（ＡＡサイズ、理論容量：６００ｍＡ）を作製
した。Next, the above spherical graphite and a dispersion (solid content: 48%) of styrene-butadiene rubber (SBR) as a binder are dispersed in water, and carboxymethyl cellulose (a thickener) is dispersed. CMC) was added to prepare a slurry. In addition, the above-mentioned spherical graphite, SBR
And CMC were mixed such that the weight ratio after drying of the negative electrode became spherical graphite: SBR: CMC = 100: 3: 2. Thereafter, the slurry was applied to both surfaces of a copper foil (thickness: 8 μm) as a negative electrode core by a doctor blade method (the thickness was 100 μm on each surface). After a while
After drying the solvent and compressing it to a predetermined thickness with a roller, it was vacuum-dried at 110 ° C. for 2 hours to prepare a negative electrode (filling density of active material: 1.5 g / cc). (Preparation of Electrolyte Solution) As an electrolyte solution, a mixed solvent of EC (ethylene carbonate) and DEC (diethyl carbonate) mixed at a volume ratio of 50:50 was mixed with LiP.
A non-aqueous electrolyte in which F 6 was dissolved at a rate of 1 M (mol / liter) was used. (Preparation of Battery) After the positive electrode and the negative electrode were wound through a separator made of a microporous polypropylene film to produce a power generating element, the power generating element was inserted into a bottomed cylindrical outer can. Finally, after injecting the above electrolyte into the outer can,
A cylindrical battery (AA size, theoretical capacity: 600 mA) was produced by attaching the sealing plate to the opening of the outer can.
【００１７】尚、上記発明の実施の形態では出発材料と
しての黒鉛として天然黒鉛を用いたが、これに限定され
るものではなく、人造黒鉛を用いることも可能である。In the embodiment of the present invention, natural graphite is used as a starting material. However, the present invention is not limited to this, and artificial graphite may be used.
【００１８】また、正極材料としては上記ＬｉＣｏＯ2
に限定されるものではなく、その他のリチウム含有金属
複合酸化物（金属として、Ｃｏ、Ｍｎ、Ｎｉ、Ｖ、Ｎｂ
から選択される少なくとも１種を用いる）等を用いるこ
とが可能である。The above-mentioned LiCoO 2 is used as a cathode material.
However, other lithium-containing metal composite oxides (metals such as Co, Mn, Ni, V, and Nb
Or at least one selected from the following) can be used.
【００１９】更に、電解液の溶媒としては上記のものに
限らず、エチレンカーボネート、プロピレンカーボネー
ト、ブチレンカーボネート、ビニレンカーボネート、シ
クロペンタノン、スルホラン、３−メチルスルホラン、
２，４−ジメチルスルホラン、３−メチル１，３−オキ
サゾリジン−２−オン、γ−ブチロラクトン、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、メチルプロピルカーボネート、ブチルメチ
ルカーボネート、エチルプロピルカーボネート、ブチル
エチルカーボネート、ジプロピルカーボネート、１，２
−ジメトキシエタン、テトラヒドロフラン、２−メチル
テトラヒドロフラン、１，３−ジオキソラン、酢酸メチ
ル、酢酸エチル等の単体、或いは２成分及び３成分混合
物であっても良い。Further, the solvent of the electrolytic solution is not limited to those described above, but may be ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, cyclopentanone, sulfolane, 3-methylsulfolane,
2,4-dimethylsulfolane, 3-methyl-1,3-oxazolidin-2-one, γ-butyrolactone, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, butyl methyl carbonate, ethyl propyl carbonate, butyl ethyl carbonate, Dipropyl carbonate, 1,2
It may be a simple substance such as dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolan, methyl acetate, ethyl acetate, or a mixture of two and three components.
【００２０】加えて、電解液の溶質としては上記のもの
に限らず、ＬｉＢＦ4 、ＬｉＣＦ3ＳＯ3 、ＬｉＡｓＦ
6 、ＬｉＮ（ＣＦ3 ＳＯ2 ）2 、ＬｉＣｌＯ4 等であっ
ても良い。In addition, the solutes of the electrolytic solution are not limited to those described above, but may be LiBF 4 , LiCF 3 SO 3 , LiAsF
6 , LiN (CF 3 SO 2 ) 2 , LiClO 4, etc.
【００２１】また、結着剤としては、上記のものに限定
するものではなく、メチル（メタ）アクリレート、エチ
ル（メタ）アクリレート、ブチル（メタ）アクリレー
ト、（メタ）アクリロニトリル、ヒドロキシエチル（メ
タ）アクリレート等のエチレン性不飽和カルボン酸エス
テル、或いは、アクリル酸、メタクリル酸、イタコン
酸、フマル酸、マレイン酸等のエチレン性不飽和カルボ
ン酸を使用することもできる。The binder is not limited to those described above, but may be methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylonitrile, or hydroxyethyl (meth) acrylate. And the like, or ethylenically unsaturated carboxylic acid esters such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, and maleic acid.
【００２２】[0022]
【実施例】（第１実施例） 〔実施例１〕実施例１としては、上記発明の実施の形態
に示す方法と同様の方法にて作製した電池を用いた。EXAMPLES (First Example) [Example 1] In Example 1, a battery manufactured by a method similar to the method described in the above embodiment of the present invention was used.
【００２３】このようにして作製した電池を、以下、本
発明電池Ａ１と称する。 〔実施例２〜４〕負極活物質の充填密度を、各々１．４
ｇ／ｃｃ、１．８ｇ／ｃｃ、１．９ｇ／ｃｃとする他
は、上記実施例１と同様にして電池を作製した。The battery fabricated in this manner is hereinafter referred to as Battery A1 of the present invention. Examples 2 to 4 Each of the packing densities of the negative electrode active materials was 1.4.
A battery was fabricated in the same manner as in Example 1 except that the g / cc was 1.8 g / cc and 1.9 g / cc.
【００２４】このようにして作製した電池を、以下、そ
れぞれ本発明電池Ａ２〜Ａ４と称する。 〔実施例５〜８〕ピーク強度比を３００とする他は、各
々上記実施例１〜実施例４と同様にして電池を作製し
た。The batteries fabricated in this manner are hereinafter referred to as Batteries A2 to A4 of the present invention, respectively. [Examples 5 to 8] Batteries were produced in the same manner as in Examples 1 to 4 except that the peak intensity ratio was set to 300.
【００２５】このようにして作製した電池を、以下、そ
れぞれ本発明電池Ａ１１〜Ａ１４と称する。 〔実施例５〜８〕ピーク強度比を１０００とする他は、
各々上記実施例１〜実施例４と同様にして電池を作製し
た。The batteries fabricated in this manner are hereinafter referred to as Batteries A11 to A14 of the present invention, respectively. [Examples 5 to 8] Except that the peak intensity ratio was 1000,
Batteries were produced in the same manner as in Examples 1 to 4, respectively.
【００２６】このようにして作製した電池を、以下、そ
れぞれ本発明電池Ａ２１〜Ａ２４と称する。 〔比較例１〜４〕ピーク強度比を１５００とする他は、
各々上記実施例１〜実施例４と同様にして電池を作製し
た。The batteries fabricated in this manner are hereinafter referred to as Batteries A21 to A24 of the present invention, respectively. [Comparative Examples 1-4] Except that the peak intensity ratio was 1500,
Batteries were produced in the same manner as in Examples 1 to 4, respectively.
【００２７】このようにして作製した電池を、以下、そ
れぞれ比較電池Ｘ１〜Ｘ４と称する。 〔比較例５〜８〕ピーク強度比を２０００とする他は、
各々上記実施例１〜実施例４と同様にして電池を作製し
た。The batteries fabricated in this manner are hereinafter referred to as comparative batteries X1 to X4, respectively. [Comparative Examples 5 to 8] Except that the peak intensity ratio was 2000,
Batteries were produced in the same manner as in Examples 1 to 4, respectively.
【００２８】このようにして作製した電池を、以下、そ
れぞれ比較電池Ｘ１１〜Ｘ１４と称する。 〔実験〕本発明電池Ａ１〜Ａ４、Ａ１１〜Ａ１４、Ａ２
１〜Ａ２４及び比較電池Ｘ１〜Ｘ４、Ｘ１１〜Ｘ１４に
おける負極を用いて、負極の密着強度を調べたので、そ
の結果を表１に示す。尚、負極の密着強度の測定方法
は、１ｃｍ2 の両面テープを各負極に貼り付け、負極平
面に対して垂直方向に引き上げるときの荷重を調べるこ
とにより行い、また、表１においては、負極活物質の充
填密度が１．４ｇ／ｃｃでピーク強度比が３００のとき
の荷重を１００％として示している。The batteries fabricated in this manner are hereinafter referred to as comparative batteries X11 to X14, respectively. [Experiment] Batteries A1 to A4, A11 to A14 and A2 of the present invention
The adhesion strength of the negative electrodes was examined using the negative electrodes of Nos. 1 to A24 and Comparative Batteries X1 to X4 and X11 to X14, and the results are shown in Table 1. The adhesion strength of the negative electrode was measured by attaching a 1 cm 2 double-sided tape to each negative electrode and examining the load when pulling up in the direction perpendicular to the negative electrode plane. The load when the packing density of the substance is 1.4 g / cc and the peak intensity ratio is 300 is shown as 100%.
【００２９】[0029]
【表１】 [Table 1]
【００３０】上記表１から明らかなように、本発明電池
Ａ１〜Ａ４、Ａ１１〜Ａ１４、Ａ２１〜Ａ２４は比較電
池Ｘ１〜Ｘ４、Ｘ１１〜Ｘ１４に比べて、負極の密着強
度が大きくなっていることが認められる。したがって、
負極の密着強度という面からは、ピーク強度比が１００
０以下の球状黒鉛を負極活物質として用いることが望ま
しいことがわかる。As is clear from Table 1, the batteries A1 to A4, A11 to A14, and A21 to A24 of the present invention have a greater negative electrode adhesion strength than the comparative batteries X1 to X4 and X11 to X14. Is recognized. Therefore,
From the viewpoint of the adhesion strength of the negative electrode, the peak intensity ratio is 100%.
It is understood that it is desirable to use spherical graphite of 0 or less as the negative electrode active material.
【００３１】また、本発明電池Ａ１〜Ａ３、Ａ１１〜Ａ
１３、Ａ２１〜Ａ２３は、本発明電池Ａ４、Ａ１４、Ａ
２４にに比べて、負極の密着強度が更に大きくなってい
ることが認められる。その一方、上記表１には示してい
ないが、負極活物質の充填密度が１．５ｇ／ｃｃ未満に
なると、単位体積当たりの負極容量が低下することが認
められた。したがって、負極の密着強度を更に向上させ
つつ、負極容量の低下を防止するには、ピーク強度比が
１０００以下の球状黒鉛を負極活物質として用い、しか
も負極活物質の充填密度を１．５ｇ／ｃｃ〜１．８ｇ／
ｃｃに規制することが望ましいことがわかる。The batteries A1 to A3, A11 to A3 of the present invention
13, A21 to A23 correspond to the batteries A4, A14, A of the present invention.
It can be seen that the adhesion strength of the negative electrode was further increased as compared with 24. On the other hand, although not shown in Table 1 above, it was recognized that when the packing density of the negative electrode active material was less than 1.5 g / cc, the negative electrode capacity per unit volume was reduced. Therefore, in order to further improve the adhesive strength of the negative electrode and prevent a decrease in the negative electrode capacity, spherical graphite having a peak intensity ratio of 1000 or less is used as the negative electrode active material, and the packing density of the negative electrode active material is 1.5 g / g. cc to 1.8 g /
It can be seen that it is desirable to regulate to cc.
【００３２】（第２実施例） 〔実施例１〜６〕下記表２に示すように、負極芯体であ
る銅箔の厚みと負極活物質の充填密度とを変化させる他
は、上記第１実施例の実施例１と同様にして電池を作製
した。尚、各負極の厚みは、上記第１実施例の実施例１
に示す負極と同じである。(Example 2) [Examples 1 to 6] As shown in Table 2 below, except that the thickness of the copper foil serving as the anode core and the packing density of the anode active material were changed, A battery was produced in the same manner as in Example 1 of the example. The thickness of each negative electrode is the same as that of Example 1 of the first embodiment.
This is the same as the negative electrode shown in FIG.
【００３３】このようにして作製した電池を、以下、そ
れぞれ本発明電池Ｂ１〜Ｂ６と称する。 〔実験〕前記第１実施例に示す本発明電池Ａ１及び上記
本発明電池Ｂ１〜Ｂ６の負荷特性を調べたので、その結
果を表２に示す。尚、負荷特性は、下記の条件で充放電
を行い、電流１Ｃ（６００ｍＡ）での放電容量（温度：
２５℃）に対する電流２Ｃ（１２００ｍＡ）での放電容
量（温度：２５℃）の割合〔電流１Ｃでの放電容量／電
流２Ｃでの放電容量×１００（％）〕で示される。The batteries fabricated in this manner are hereinafter referred to as Batteries B1 to B6 of the present invention, respectively. [Experiment] The load characteristics of the battery A1 of the present invention and the batteries B1 to B6 of the present invention shown in the first embodiment were examined. The results are shown in Table 2. The load characteristics are as follows: charge and discharge are performed under the following conditions, and the discharge capacity (temperature:
The ratio of the discharge capacity (temperature: 25 ° C.) at a current of 2 C (1200 mA) to the discharge capacity at 25 ° C. [discharge capacity at a current of 1 C / discharge capacity at a current of 2 C × 100 (%)].
【００３４】充電条件：電流１Ｃで電池電圧が４．１Ｖ
になるまで充電した後、４．１Ｖの定電圧充電で電流が
１０ｍＡ低下するまで充電。Charge condition: battery voltage is 4.1 V at current 1 C
After the battery was charged until it became, the battery was charged at a constant voltage of 4.1 V until the current dropped by 10 mA.
【００３５】放電条件：電流１Ｃ又は２Ｃで電池電圧が
２．７５Ｖになるまで放電。Discharge conditions: Discharge at a current of 1 C or 2 C until the battery voltage reaches 2.75 V.
【００３６】[0036]
【表２】 [Table 2]
【００３７】上記表２から明らかなように、負極芯体で
ある銅箔の厚みが１０μｍを超える本発明電池Ｂ４〜Ｂ
６では、負極活物質の充填密度を大きくする必要がある
ため、負荷特性が低下し、また銅箔の厚みが５μｍ未満
の本発明電池Ｂ１では、負極芯体が薄すぎて負極が破断
するという問題がある。これに対して、本発明電池Ａ
１、Ｂ２、Ｂ３では負極が破断するという問題はなく、
しかも負荷特性に優れる。As is clear from Table 2, the batteries B4 to B of the present invention in which the thickness of the copper foil as the negative electrode core exceeds 10 μm.
In No. 6, since the packing density of the negative electrode active material needs to be increased, the load characteristics are reduced, and in the battery B1 of the present invention in which the thickness of the copper foil is less than 5 μm, the negative electrode core is too thin and the negative electrode is broken. There's a problem. On the other hand, the battery A of the present invention
In 1, B2 and B3, there is no problem that the negative electrode is broken,
Moreover, it has excellent load characteristics.
【００３８】したがって、負極の破断を防止しつつ負荷
特性の向上を図るには、負極芯体である銅箔の厚みを５
〜１０μｍに規制するのが望ましい。Therefore, in order to improve the load characteristics while preventing the negative electrode from breaking, the thickness of the copper foil as the negative electrode core must be 5
It is desirable to regulate to 10 μm.
【００３９】[0039]
【発明の効果】以上説明したように、本発明によれば、
負極活物質の充填密度を上げるべく極板をローラープレ
スによって圧延した場合であっても、ベイサル面同士が
滑るのを抑制することにより、黒鉛同士或いは黒鉛と芯
体との密着性が低下するのを抑えて、電池の歩留りを向
上させることができるといった優れた効果を奏する。As described above, according to the present invention,
Even when the electrode plate is rolled by a roller press in order to increase the packing density of the negative electrode active material, by suppressing the sliding between the basal surfaces, the adhesion between graphite or between graphite and the core decreases. And an excellent effect that battery yield can be improved.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 高橋 昌利 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内 Ｆターム(参考） 5H017 AA03 AS02 CC01 EE01 HH03 5H029 AJ14 AK03 AL07 AM03 AM05 AM07 CJ01 CJ23 DJ07 DJ11 EJ01 HJ04 HJ08 HJ13 5H050 AA19 BA17 CA07 CA08 CA09 CB08 DA03 DA07 FA17 GA05 HA04 HA13 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Masatoshi Takahashi 2-5-5 Keihanhondori, Moriguchi-shi, Osaka Sanyo Electric Co., Ltd. F-term (reference) 5H017 AA03 AS02 CC01 EE01 HH03 5H029 AJ14 AK03 AL07 AM03 AM05 AM07 CJ01 CJ23 DJ07 DJ11 EJ01 HJ04 HJ08 HJ13 5H050 AA19 BA17 CA07 CA08 CA09 CB08 DA03 DA07 FA17 GA05 HA04 HA13
Claims (4)
（Ｌｃ値は１５０Å以上、ｄ(002) 値は３．３８Å以
下）から成る負極活物質を主体とする負極活物質層が形
成された負極と、リチウムを吸蔵、放出しうる正極活物
質層を備えた正極と、非水電解質とを有する非水電解質
電池において、 上記黒鉛は、Ｃｕ−Ｋα線源を用いた粉末Ｘ線回折法に
よる（００２）面と（１１０）面とのピーク強度比（Ｉ
(002) ／Ｉ(110) ）が１０００以下に規制されることを
特徴とする非水電解質電池。1. A negative electrode active material layer mainly composed of a negative electrode active material made of graphite (Lc value is 150 ° or more and d (002) value is 3.38 ° or less) is formed on the surface of a negative electrode core made of copper foil. A non-aqueous electrolyte battery having a negative electrode, a positive electrode having a positive electrode active material layer capable of inserting and extracting lithium, and a non-aqueous electrolyte, wherein the graphite is powder X-ray diffraction using a Cu-Kα ray source. Peak intensity ratio (I) between the (002) plane and the (110) plane
(002) / I (110) ) is regulated to 1000 or less.
μｍ以上１０μｍ以下に規制される、請求項１記載の非
水電解質電池。2. The negative electrode core comprising a copper foil having a thickness of 5
The non-aqueous electrolyte battery according to claim 1, wherein the non-aqueous electrolyte battery is regulated to not less than μm and not more than 10 μm.
度が、１．５ｇ／ｃｃ以上１．８ｇ／ｃｃ以下に規制さ
れる、請求項１又は２記載の非水電解質電池。3. The non-aqueous electrolyte battery according to claim 1, wherein a packing density of the negative electrode active material in the negative electrode plate is regulated to 1.5 g / cc or more and 1.8 g / cc or less.
圧ガスを噴出させることにより球状化する、請求項１、
２又は３記載の非水電解質電池。4. The negative electrode active material is spheroidized by jetting a high-pressure gas with a jet mill.
4. The non-aqueous electrolyte battery according to 2 or 3.
Priority Applications (1)
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|---|---|---|---|
| JP2000090036A JP2001283844A (en) | 2000-03-29 | 2000-03-29 | Nonaqueous electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000090036A JP2001283844A (en) | 2000-03-29 | 2000-03-29 | Nonaqueous electrolyte battery |
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| Publication Number | Publication Date |
|---|---|
| JP2001283844A true JP2001283844A (en) | 2001-10-12 |
Family
ID=18605699
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000090036A Pending JP2001283844A (en) | 2000-03-29 | 2000-03-29 | Nonaqueous electrolyte battery |
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| Country | Link |
|---|---|
| JP (1) | JP2001283844A (en) |
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