JP2003045434A - Lithium secondary battery - Google Patents
Lithium secondary batteryInfo
- Publication number
- JP2003045434A JP2003045434A JP2001230837A JP2001230837A JP2003045434A JP 2003045434 A JP2003045434 A JP 2003045434A JP 2001230837 A JP2001230837 A JP 2001230837A JP 2001230837 A JP2001230837 A JP 2001230837A JP 2003045434 A JP2003045434 A JP 2003045434A
- Authority
- JP
- Japan
- Prior art keywords
- boron
- graphite
- carbon
- secondary battery
- positive 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.)
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、リチウム二次電池
に係り、特に、リチウム遷移金属複合酸化物及び炭素材
を含む正極と、リチウムイオンを脱挿入可能な炭素材及
び選択的に炭素質導電材を含む負極とを備えたリチウム
二次電池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithium secondary battery, and more particularly to a positive electrode containing a lithium transition metal composite oxide and a carbon material, a carbon material capable of deintercalating lithium ions, and a selectively carbonaceous conductive material. And a negative electrode including a material.
【０００２】[0002]
【従来の技術】従来の民生用携帯機器で使用されるリチ
ウム二次電池の大電流放電は、２〜３Ｃ程度の高率放電
特性を満足すれば良かった。しかし、電気自動車（Ｅ
Ｖ）用、特にエンジンとモータとの両方を持つハイブリ
ット車（ＨＥＶ）などのモータ駆動に利用される電池
は、数秒から数十秒の短時間に１０〜３０Ｃの大電流を
供給することが要求され、従来にはない短時間での高出
力特性を必要とされている。2. Description of the Related Art A large current discharge of a lithium secondary battery used in a conventional portable device for consumer use has only to satisfy a high rate discharge characteristic of about 2 to 3C. However, electric vehicles (E
V), in particular, a battery used for driving a motor of a hybrid vehicle (HEV) having both an engine and a motor is required to supply a large current of 10 to 30 C in a short time of several seconds to several tens of seconds. Therefore, it is required to have a high output characteristic in a short time, which has never been seen before.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、大電流
で放電する際、リチウムイオンが正極の表面に集中し
て、電子を受け取り内部拡散していく過程において抵抗
成分が発生する。抵抗成分の影響で電圧の低下を生じ、
電池の出力が低下するため、正極の表面での抵抗を減少
させることが、高出力の電池を得るために有効かつ重要
である。また、抵抗成分を小さくすることで、局部的な
正極材の構造破壊や電解液の劣化も抑制できると考えら
れる。However, when a large current is discharged, lithium ions are concentrated on the surface of the positive electrode and a resistance component is generated in the process of receiving electrons and internally diffusing. The voltage drop occurs due to the effect of the resistance component,
Since the output of the battery decreases, it is effective and important to reduce the resistance on the surface of the positive electrode in order to obtain a high output battery. Further, it is considered that by reducing the resistance component, local structural destruction of the positive electrode material and deterioration of the electrolytic solution can be suppressed.
【０００４】本発明は、上記事案に鑑み、高出力かつ寿
命特性に優れたリチウム二次電池を提供することを課題
とする。In view of the above problems, it is an object of the present invention to provide a lithium secondary battery having high output and excellent life characteristics.
【０００５】[0005]
【課題を解決するための手段】上記課題を解決するため
に、本発明は、リチウム遷移金属複合酸化物及び炭素材
を含む正極と、リチウムイオンを脱挿入可能な炭素材及
び選択的に炭素質導電材を含む負極とを備えたリチウム
二次電池において、前記正負極の炭素材及び前記炭素質
導電材の少なくともいずれかにホウ素を所定量含有する
ことを特徴とする。In order to solve the above problems, the present invention provides a positive electrode containing a lithium transition metal composite oxide and a carbon material, a carbon material capable of deintercalating lithium ions, and a carbonaceous material selectively. In a lithium secondary battery including a negative electrode containing a conductive material, a predetermined amount of boron is contained in at least one of the carbon material of the positive and negative electrodes and the carbonaceous conductive material.
【０００６】本発明では、正極に炭素材、負極にリチウ
ムイオンを脱挿入可能な炭素材及び選択的に炭素質導電
材を含んでおり、正負極の炭素材及び炭素質導電材の少
なくともいずれかにホウ素を含有させたため、瞬間的な
大電流放電時に必要な電子を供給できるので、正極の表
面の電子とリチウムイオンとの反応を円滑にし抵抗を低
減でき高出力を得ることができると共に、局部的な抵抗
を小さくできるので、正極のストレスも緩和され寿命を
向上させることができる。In the present invention, the positive electrode contains a carbon material, the negative electrode contains a carbon material capable of deintercalating lithium ions, and optionally a carbonaceous conductive material, and at least one of the positive and negative electrode carbon materials and the carbonaceous conductive material. Since boron is contained in the cathode, necessary electrons can be supplied during momentary high-current discharge, so that the reaction between the electrons on the surface of the positive electrode and lithium ions can be made smooth and the resistance can be reduced to obtain a high output. Since the effective resistance can be reduced, the stress of the positive electrode can be relieved and the life can be improved.
【０００７】この場合において、正負極の炭素材及び炭
素質導電材の少なくともいずれかに対しホウ素が０．０
８重量％以上３重量％以下含有されていることが好まし
い。また、この場合において、正極の炭素材及び炭素質
導電材はカーボンブラック又は黒鉛であることが好まし
い。更に、正極にカーボンブラック及び黒鉛を含有し、
カーボンブラック及び黒鉛の少なくともカーボンブラッ
クにホウ素を含有し、該ホウ素がカーボンブラック及び
黒鉛中に３重量％以下の割合で含有されていることがよ
り好ましい。[0007] In this case, boron is 0.0
It is preferable that the content is 8% by weight or more and 3% by weight or less. Further, in this case, the carbon material and the carbonaceous conductive material of the positive electrode are preferably carbon black or graphite. Furthermore, the positive electrode contains carbon black and graphite,
It is more preferable that at least carbon black of carbon black and graphite contains boron, and the boron is contained in carbon black and graphite at a ratio of 3% by weight or less.
【０００８】[0008]
【発明の実施の形態】以下、本発明をＨＥＶ用の非水電
解液リチウム二次電池に適用した実施の形態について説
明する。BEST MODE FOR CARRYING OUT THE INVENTION Embodiments in which the present invention is applied to a non-aqueous electrolyte lithium secondary battery for HEV will be described below.
【０００９】（正極）平均粒径２０μｍのリチウム遷移
金属複合酸化物（正極活物質）としてのマンガン酸リチ
ウムと、炭素材としてのカーボンブラック、黒鉛と、結
着剤としてポリフッ化ビニリデン（ＰＶＤＦ）とを、後
述する所定割合（以下、配合割合Ｒｐという。）で配合
し、正極合剤とした。正極合剤に分散溶媒としてＮ−メ
チルピロリドンを添加し、混練したスラリを、厚さ２０
μｍのアルミニウム箔の両面に均一に塗布し、乾燥させ
た後、プレスすることで正極を得た。(Cathode) Lithium manganate as a lithium-transition metal composite oxide (cathode active material) having an average particle size of 20 μm, carbon black and graphite as a carbon material, and polyvinylidene fluoride (PVDF) as a binder. Was mixed at a predetermined ratio described below (hereinafter, referred to as a mixing ratio R p ) to obtain a positive electrode mixture. N-methylpyrrolidone was added as a dispersion solvent to the positive electrode mixture, and the kneaded slurry was adjusted to a thickness of 20.
A positive electrode was obtained by uniformly coating both sides of a μm aluminum foil, drying and pressing.
【００１０】（負極）平均粒径１０μｍの炭素材として
の非晶質炭素と、選択的に配合する炭素質導電材として
のアセチレンブラック、黒鉛と、結着剤としてポリフッ
化ビニリデンとを、後述する所定割合（以下、配合割合
Ｒｎという。）で配合し負極合剤とした。負極合剤に分
散溶媒としてＮ−メチルピロリドンを添加し、混練した
スラリを、厚さ１０μｍの圧延銅箔の両面に塗布し、乾
燥させた後、プレスすることで負極を得た。(Negative electrode) Amorphous carbon as a carbon material having an average particle size of 10 μm, acetylene black and graphite as a carbonaceous conductive material to be selectively mixed, and polyvinylidene fluoride as a binder will be described later. predetermined ratio was compounded negative electrode mixture (hereinafter, referred to. compounding ratio R n). N-methylpyrrolidone was added as a dispersion solvent to the negative electrode mixture, and the kneaded slurry was applied to both surfaces of a rolled copper foil having a thickness of 10 μm, dried and then pressed to obtain a negative electrode.
【００１１】（ホウ素含有材）正極のカーボンブラック
（以下、ＣＢと略称する。）又は黒鉛（以下、ＧＰと略
称する。）、負極の非晶質炭素（以下、負極活物質と略
称する。）、アセチレンブラック（以下、ＡＢと略称す
る。）又は黒鉛（以下、Ｇｎと略称する。）の少なくと
もいずれかにホウ素を含有させた。ＧＰ又はＧｎにホウ
素を含有させたホウ素含有黒鉛は、天然黒鉛とボロン化
合物とを所定量で混合し、２０００゜Ｃで焼成したり、
ＧＰ又はＧｎを繊維状に合成する過程でホウ酸トリメチ
ルを加熱し、気相中に流し込むことで得た。また、負極
活物質にホウ素を含有させたホウ素含有負極活物質は、
前駆体に所定量のホウ酸を混合してから焼成して得た。
更に、ＣＢにホウ素を含有させたホウ素含有カーボンブ
ラックは、アセチレンガスとホウ酸トリメチルを予め所
定量で混合し、約２０００゜Ｃの反応層に噴霧すること
で得た。また、ＡＢにホウ素を含有させたホウ素含有ア
セチレンブラックもホウ素含有カーボンブラックと同様
に得た。ＣＢ、ＡＢ、ＧＰ、Ｇｎに対するホウ素の割合
（以下、ホウ素含有割合Ｂｒという。）を０．０８重量
％〜３重量％とした。(Boron-containing material) Carbon black (hereinafter abbreviated as CB) or graphite (hereinafter abbreviated as GP ) of the positive electrode, amorphous carbon of the negative electrode (hereinafter abbreviated as negative electrode active material). ), Acetylene black (hereinafter abbreviated as AB) or graphite (hereinafter abbreviated as Gn ) at least one of which contains boron. The boron-containing graphite containing boron in G P or G n is a mixture of natural graphite and a boron compound in a predetermined amount, followed by firing at 2000 ° C.
It was obtained by heating trimethyl borate in the process of synthesizing G P or G n into a fibrous state and pouring it into the gas phase. Further, the boron-containing negative electrode active material obtained by containing boron in the negative electrode active material,
It was obtained by mixing a predetermined amount of boric acid with the precursor and then firing it.
Further, the boron-containing carbon black in which CB contains boron was obtained by previously mixing a predetermined amount of acetylene gas and trimethyl borate and spraying the mixture onto a reaction layer at about 2000 ° C. Further, boron-containing acetylene black obtained by containing AB in boron was also obtained in the same manner as the boron-containing carbon black. CB, AB, G P, the proportion of boron for G n (hereinafter, referred to as boron-containing fraction B r.) Was 0.08 wt% to 3 wt%.
【００１２】（電池の作製）以上のように作製した正極
及び負極を、厚さ４０μｍのポリオレフィン系セパレー
タを介して捲回し電極群とし、この電極群を直径４０ｍ
ｍ、高さ８０ｍｍの円筒状のステンレス製有底電池缶内
に挿入し、エチレンカーボネートとジメチルカーボネー
トの混合有機溶媒に、６フッ化リン酸リチウム（ＬｉＰ
Ｆ６）を１モル／リットル溶解した非水電解液を注液し
て上蓋をカシメ封口して非水電解液リチウム二次電池を
作製した。(Production of Battery) The positive electrode and the negative electrode produced as described above are wound with a 40 μm-thick polyolefin separator as an electrode group to form an electrode group having a diameter of 40 m.
m, a height of 80 mm, and inserted into a cylindrical stainless steel bottomed battery can, and mixed with a mixed organic solvent of ethylene carbonate and dimethyl carbonate, lithium hexafluorophosphate (LiP
A non-aqueous electrolyte solution in which F 6 ) was dissolved at 1 mol / liter was injected, and the upper lid was caulked to form a non-aqueous electrolyte lithium secondary battery.
【００１３】[0013]
【実施例】次に、上述した本実施形態に従って作製した
実施例の非水電解液リチウム二次電池について説明す
る。比較のために作製した比較例の電池についても併記
する。なお、これら実施例及び比較例の電池の容量は
５．０Ａｈとした。EXAMPLE Next, a non-aqueous electrolyte lithium secondary battery of an example produced according to the above-described embodiment will be described. The batteries of Comparative Examples prepared for comparison are also shown. The capacities of the batteries of these examples and comparative examples were 5.0 Ah.
【００１４】（実施例１）下表１に示すように、実施例
１では、正極活物質：ＣＢ：ＧＰ：ＰＶＤＦの配合割合
ＲＰを、９０：５：０：５（重量％）とし、ＣＢ中のホ
ウ素含有割合Ｂｒを０．０８重量％とした。また、下表
２に示すように、負極活物質：ＡＢ：Ｇｎ：ＰＶＤＦの
配合割合Ｒｎを、９０：０：０：１０（重量％）とし、
ＡＢ及びＧ ｎにはホウ素を含有しないものを用いた。(Example 1) As shown in Table 1 below, examples
1, the positive electrode active material: CB: GP: PVDF blending ratio
RPTo 90: 5: 0: 5 (% by weight),
Arsenic content ratio BrWas 0.08% by weight. Also, the table below
2, the negative electrode active material: AB: Gn: PVDF
Mixing ratio RnTo 90: 0: 0: 10 (wt%),
AB and G nThe material used did not contain boron.
【００１５】[0015]
【表１】 [Table 1]
【００１６】（実施例２〜４）表１に示すように、実施
例２〜４では、ＣＢ中のホウ素含有割合Ｂｒをそれぞれ
０．１、１．０、３．０重量％とした以外は実施例１と
同様に電池を作製した。[0016] As shown in (Example 2-4) Table 1, in Examples 2-4, except that the boron content B r in CB respectively 0.1,1.0,3.0 wt% A battery was manufactured in the same manner as in Example 1.
【００１７】（実施例５〜８）表１に示すように、実施
例５〜８では、配合割合ＲＰを、８５：０：１０：５と
し、Ｇｐ中のホウ素含有割合Ｂｒをそれぞれ０．０８、
０．１、１．０、３．０重量％とした以外は実施例１と
同様に電池を作製した。As shown in (Example 5-8) Table 1, in Examples 5-8, the proportion R P, 85: 0: 10 : and 5, respectively boron content B r in G p 0.08,
A battery was produced in the same manner as in Example 1 except that the amounts were 0.1, 1.0 and 3.0% by weight.
【００１８】（実施例９）表１に示すように、実施例９
では、配合割合ＲＰを、８５：２：８：５とし、ＣＢ中
のホウ素含有割合Ｂｒを１．０重量％とした以外は実施
例１と同様に電池を作製した。(Example 9) As shown in Table 1, Example 9
In the mixing ratio R P, 85: 2: 8 : and 5, was prepared in the same manner as the battery of Example 1 except that the 1.0 wt% boron content B r in CB.
【００１９】（実施例１０）表１に示すように、実施例
１０では、配合割合ＲＰを、８５：２：８：５とし、Ｃ
Ｂ及びＧｐ中のホウ素含有割合Ｂｒをそれぞれ１．０重
量％とした以外は実施例１と同様に電池を作製した。(Example 10) As shown in Table 1, in Example 10, the compounding ratio R P was 85: 2: 8: 5, and C
A battery was produced in the same manner as in Example 1 except that the boron content ratios B r in B and G p were each 1.0 wt%.
【００２０】（比較例１〜３）表１に示すように、比較
例１〜３では、正極のＣＢ及びＧｐにはホウ素を含有せ
ず、配合割合ＲＰを、それぞれ９０：５：０：５、８
５：０：１０：５、８５：２：８：５とした以外は実施
例１と同様に電池を作製した。(Comparative Examples 1 to 3) As shown in Table 1, in Comparative Examples 1 to 3, CB and G p of the positive electrode did not contain boron and the compounding ratio R P was 90: 5: 0, respectively. : 5, 8
A battery was made in the same manner as in Example 1 except that the time was 5: 0: 10: 5 and 85: 2: 8: 5.
【００２１】（実施例１１）表２に示すように、実施例
１１では、配合割合Ｒｎを、９０：０：０：１０とし、
負極活物質中のホウ素含有割合Ｂｒを０．０８重量％と
した。配合割合Ｒｐを、９０：５：０：５とし、ＣＢ及
びＧｎにはホウ素を含有しないものを用いた。(Example 11) As shown in Table 2, in Example 11, the compounding ratio R n was set to 90: 0: 0: 10,
Boron content B r of the negative electrode active material was 0.08 wt%. The compounding ratio R p was 90: 5: 0: 5, and CB and G n did not contain boron.
【００２２】[0022]
【表２】 [Table 2]
【００２３】（実施例１２〜１４）表２に示すように、
実施例１２〜１４では、負極活物質中のホウ素含有割合
Ｂ ｒをそれぞれ０．１、１．０、３．０重量％とした以
外は実施例１１と同様に電池を作製した。(Examples 12 to 14) As shown in Table 2,
In Examples 12 to 14, the boron content in the negative electrode active material
B rBelow 0.1, 1.0 and 3.0% by weight respectively.
A battery was produced in the same manner as in Example 11 except for the above.
【００２４】（実施例１５〜１８）表２に示すように、
実施例１５〜１８では、配合割合Ｒｎを、８８：２：
０：１０とし、ＡＢ中のホウ素含有割合Ｂｒをそれぞれ
０．０８、０．１、１．０、３．０重量％とした以外は
実施例１１と同様に電池を作製した。(Examples 15 to 18) As shown in Table 2,
In Examples 15 to 18, the compounding ratio R n was 88: 2 :.
And 0:10, except that the boron content B r in AB respectively 0.08,0.1,1.0,3.0 wt% was prepared in the same manner as the battery of Example 11.
【００２５】（実施例１９〜２２）表２に示すように、
実施例１９〜２２では、配合割合Ｒｎを、８５：０：
５：１０とし、Ｇｎ中のホウ素含有割合Ｂｒをそれぞれ
０．０８、０．１、１．０、３．０重量％とした以外は
実施例１１と同様に電池を作製した。(Examples 19 to 22) As shown in Table 2,
In Examples 19 to 22, the blending ratio R n was set to 85: 0:
A battery was produced in the same manner as in Example 11 except that the boron content ratio B r in G n was set to 5:10 and 0.08, 0.1, 1.0, and 3.0% by weight, respectively.
【００２６】（実施例２３〜２７）表２に示すように、
実施例２３〜２７では、負極活物質とＡＢとの割合をそ
れぞれ８９．２：０．８、８９：１、８５：５、８０：
１０、７９：１１とし、ＡＢ中のホウ素含有割合Ｂｒを
１．０重量％とした以外は実施例１１と同様に電池を作
製した。(Examples 23 to 27) As shown in Table 2,
In Examples 23 to 27, the ratios of the negative electrode active material and AB were 89.2: 0.8, 89: 1, 85: 5 and 80 :, respectively.
10,79: 11 and then, except that the 1.0 wt% boron content B r in AB was prepared in the same manner as the battery of Example 11.
【００２７】（比較例４〜６）表２に示すように、比較
例４〜６では、ＡＢ及びＧｎにはホウ素を含有せず、配
合割合Ｒｎを、それぞれ９０：０：０：１０、８８：
２：０：１０、８５：０：５：１０とした以外は実施例
１１と同様に電池を作製した。[0027] (Comparative Examples 4-6) Table As shown in 2, in Comparative Example 4-6 contained no boron in the AB and G n, the mixing ratio R n, respectively 90: 0: 0:10 , 88:
A battery was produced in the same manner as in Example 11 except that the time was 2: 0: 10 and 85: 0: 5: 10.
【００２８】＜試験・評価＞以上のように作製した実施
例及び比較例の電池について出力を測定するための出力
試験及び寿命を測定するためのパルスサイクル試験を行
った。<Test / Evaluation> The batteries of Examples and Comparative Examples manufactured as described above were subjected to an output test for measuring the output and a pulse cycle test for measuring the life.
【００２９】（出力試験）出力試験では、まず、電池を
定電圧で４Ｖに保持した後、２５Ａ、５０Ａ、１００Ａ
で放電させた時の５秒目電圧を測定した。次に、その電
圧を電流値に対してプロットした直線が、３Ｖと交差す
る点の電流値（Ｉａ）を読み取り、出力（Ｗ）＝Ｉａ×
３．０として出力を求めた。(Output test) In the output test, first, the battery was kept at 4V at a constant voltage, and then 25A, 50A, 100A.
The voltage was measured at 5 seconds when the battery was discharged at. Next, the current value (Ia) at the point where the straight line obtained by plotting the voltage with respect to the current value intersects 3V is read, and the output (W) = Ia ×
The output was determined as 3.0.
【００３０】（パルスサイクル試験）パルスサイクル試
験では、電池の状態が徐々に放電状態になるパターン１
は、充電を５０Ａで１０秒間、放電を１００Ａで５秒間
と５０Ａで５秒間との２回、休止時間をそれぞれ５秒間
とした。電池の状態が徐々に充電方向となるパターン２
は、充電を５０Ａで１０秒間と５秒間との２回、放電を
１００Ａで５秒、休止時間をそれぞれ５秒間とした。こ
のパターン１と２の切り替えは、電圧が上限電圧４．２
Ｖ、下限電圧３．０Ｖに達したときに行った。また、こ
の試験を加速するために周囲温度を５０゜Ｃとした。電
池の寿命は、出力試験で求めた出力が初期の出力の７０
％に低下したときとする。下表３及び表４にそれぞれの
試験結果を示す。(Pulse cycle test) In the pulse cycle test, pattern 1 in which the state of the battery gradually becomes the discharge state
Was charged at 50 A for 10 seconds, discharged twice at 100 A for 5 seconds and 50 A for 5 seconds, and the rest time was 5 seconds each. Pattern 2 in which the battery state gradually changes to the charging direction
Was charged twice at 50 A for 10 seconds and 5 seconds, discharged at 100 A for 5 seconds, and rested for 5 seconds. When switching between patterns 1 and 2, the upper limit voltage is 4.2.
V, when the lower limit voltage of 3.0V was reached. Also, the ambient temperature was 50 ° C. to accelerate this test. As for the battery life, the output obtained in the output test is 70% of the initial output.
When it drops to%. The test results are shown in Tables 3 and 4 below.
【００３１】[0031]
【表３】 [Table 3]
【００３２】[0032]
【表４】 [Table 4]
【００３３】表３に示すように、正極にカーボンブラッ
クを配合した場合、比較例１と実施例１〜４の試験結果
を見ると、ホウ素を含有したカーボンブラックの方が、
出力、寿命が向上することが分かる。また、ホウ素含有
割合Ｂｒを０．１重量％以上にすると特に寿命特性の向
上が大きく見られる。As shown in Table 3, when carbon black was mixed in the positive electrode, the test results of Comparative Example 1 and Examples 1 to 4 showed that the carbon black containing boron was
It can be seen that the output and life are improved. Further, when the boron content ratio Br is set to 0.1% by weight or more, the life characteristics are particularly greatly improved.
【００３４】正極に黒鉛を配合した場合、比較例２と実
施例５〜８の試験結果を表３から見ると、ホウ素を含有
した黒鉛の方が、出力、寿命が向上することが分かる。
また、ホウ素含有量を０．１重量％以上にすると特に寿
命特性の向上が大きく見られる。When graphite is blended in the positive electrode, the test results of Comparative Example 2 and Examples 5 to 8 are seen from Table 3, and it can be seen that the graphite containing boron improves the output and life.
Further, when the boron content is 0.1% by weight or more, the life characteristics are particularly improved.
【００３５】正極に力ーボンブラックと黒鉛とを共に配
合した場合、実施例３と実施例９、１０の試験結果を表
３から見ると、ホウ素を含有したカーボンブランクの使
用により、寿命が２００以上になる。また、カーボンブ
ラックだけでなく、黒鉛もホウ素を含有すると、更に寿
命を向上させることができる。When the carbon black and graphite were mixed together in the positive electrode, the test results of Examples 3 and 9 and 10 are seen in Table 3, and the life of the carbon blank containing boron was 200 or more. Become. If not only carbon black but also graphite contains boron, the life can be further improved.
【００３６】また、表４に示すように、負極の非晶質炭
素にホウ素を含有した場合は、比較例４と実施例１１〜
１４の試験結果を見ると、ホウ素を含有した非晶質炭素
の方が、出力、寿命が向上することが分かる。また、ホ
ウ素含有割合Ｂｒを０．１重量％以上にすると効果が大
きくなる。Further, as shown in Table 4, when boron was contained in the amorphous carbon of the negative electrode, Comparative Example 4 and Examples 11 to 11 were used.
From the test results of No. 14, it is understood that the amorphous carbon containing boron has improved output and life. Further, when the boron content ratio Br is 0.1% by weight or more, the effect becomes large.
【００３７】負極にアセチレンブラックを配合した場
合、比較例５と実施例１５〜１８の試験結果を表４から
見ると、ホウ素を含有したアセチレンブラックの方が、
出力、寿命が向上することが分かる。また、ホウ素含有
割合Ｂｒを０．１重量％以上にすると効果が大きくな
る。When acetylene black is blended in the negative electrode, the test results of Comparative Example 5 and Examples 15 to 18 are seen from Table 4, and the acetylene black containing boron is
It can be seen that the output and life are improved. Further, when the boron content ratio Br is 0.1% by weight or more, the effect becomes large.
【００３８】負極に黒鉛を配合した場合、比較例６と実
施例１９〜２２の試験結果を表４から見ると、ホウ素を
含有した黒鉛の方が、出力、寿命が向上することが分か
る。また、ホウ素含有割合Ｂｒを０．１重量％以上にす
ると効果が大きくなる。When graphite is blended in the negative electrode, the test results of Comparative Example 6 and Examples 19 to 22 are seen from Table 4, and it is understood that the graphite containing boron has improved output and life. Further, when the boron content ratio Br is 0.1% by weight or more, the effect becomes large.
【００３９】負極にアセチレンブラックを配合した場合
のアセチレンブラックの量は、実施例２３〜２７の試験
結果を表４から見ると、１〜１０重量％で効果が大き
い、１１重量％含有させると、負極の銅箔との密着性が
悪くなり、配合したアセチレンブラックの効果が薄れて
しまう。The amount of acetylene black in the case of incorporating acetylene black in the negative electrode is 1 to 10% by weight when the results of the tests of Examples 23 to 27 are seen from Table 4, and 11% by weight is large. The adhesion of the negative electrode to the copper foil is deteriorated, and the effect of the compounded acetylene black is diminished.
【００４０】ホウ素の原子半径は炭素の原子半径より小
さいため、ホウ素は容易に炭素の結晶構造の炭素原子の
位置に入り込むことができる。ホウ素が炭素原子の位置
に入り込むと、炭素材の中で、電子の移動に寄与してい
る不対電子の数が増加する。電子伝導性が向上し、瞬間
的な大電流放電時に必要な電子を供給できると考えられ
ている。また、局部的な抵抗が小さくなることで、正負
極の活物質のストレスも緩和され、長期的な寿命特性も
向上されると考えられる。Since the atomic radius of boron is smaller than that of carbon, boron can easily enter the positions of carbon atoms in the crystal structure of carbon. When boron enters the position of a carbon atom, the number of unpaired electrons contributing to the movement of electrons in the carbon material increases. It is considered that the electron conductivity is improved and the necessary electrons can be supplied at the momentary high-current discharge. Further, it is considered that the local resistance becomes small, so that the stress of the positive and negative electrode active materials is relieved and the long-term life characteristics are improved.
【００４１】なお、本実施形態では、ホウ素を含有させ
る炭素材にカーボンブラック及び黒鉛を、炭素質導電材
にアセチレンブラック及び黒鉛を用いた例を示したが、
これに限定されるものではなく、ケッチンブラックやフ
ァーネスカーボン等のカーボンブラックや人工黒鉛を用
いてもよいし、ホウ素含有割合が３重量％以下であれ
ば、例えば、負極のアセチレンブラック及び黒鉛に同時
にホウ素を含有させてもよい。In this embodiment, carbon black and graphite are used as the carbon material containing boron, and acetylene black and graphite are used as the carbonaceous conductive material.
The present invention is not limited to this, and carbon black such as Ketchin black or furnace carbon or artificial graphite may be used, and if the boron content is 3% by weight or less, for example, acetylene black and graphite of the negative electrode may be used at the same time. Boron may be contained.
【００４２】また、本実施形態では、正極の活物質にマ
ンガン酸リチウムを用いた例を示したが、マンガン（Ｍ
ｎ）ではなくＣｏやＮｉの複合酸化物や、Ｍｎ、Ｃｏ、
Ｎｉの一部を例えば、Ｌｉ、Ｃｏ、Ｎｉ、Ｍｎ、Ｆｅ、
Ｃｕ、Ａｌ、Ｃｒ、Ｍｇ、Ｚｎ、Ｖ、Ｇａ、Ｂ、Ｆの少
なくとも１種類以上の元素で置換又はドープした遷移金
属複合酸化物を用いてもよい。In this embodiment, lithium manganese oxide is used as the active material of the positive electrode.
n), not Co or Ni composite oxide, Mn, Co,
For example, Li, Co, Ni, Mn, Fe,
A transition metal composite oxide substituted or doped with at least one element of Cu, Al, Cr, Mg, Zn, V, Ga, B, and F may be used.
【００４３】更に、本実施形態では、負極の活物質に非
晶質炭素を用いた例を示したが、リチウムイオンを挿
入、脱離可能な黒鉛であればその他の炭素材料を用いて
もよい。Furthermore, in the present embodiment, an example in which amorphous carbon is used as the negative electrode active material has been shown, but other carbon materials may be used as long as graphite is capable of inserting and releasing lithium ions. .
【００４４】更にまた、本実施形態では、電解質として
ＬｉＰＦ６を使用したが、これに限定されるものではな
く、例えば、ＬｉＣｌＯ４、ＬｉＡｓＦ６、ＬｉＢ
Ｆ４、ＬｉＢ（Ｃ６Ｈ５）４、ＣＨ３ＳＯ３Ｌｉ、ＣＦ
３ＳＯＬｉなどやこれらの混合物を用いてもよい。ま
た、非水電解液の溶媒として、プロピレンカーボネー
ト、ジエチルカーボネート、１，２−ジメトキシエタ
ン、１，２−ジエトキシエタン、γ−ブチルラクトン、
テトラヒドロフラン、１，３−ジオキソラン、４−メチ
ル−１，３−ジオキソラン、ジエチルエーテル、スルホ
ラン、メチルスルホラン、アセトニトリル、プロピオニ
トリルなどを混合した混合溶媒を用いてもよい。Furthermore, in the present embodiment, LiPF 6 was used as the electrolyte, but the electrolyte is not limited to this, and for example, LiClO 4 , LiAsF 6 , LiB.
F 4 , LiB (C 6 H 5 ) 4 , CH 3 SO 3 Li, CF
3 SOLi or the like or a mixture thereof may be used. Further, as a solvent for the non-aqueous electrolyte, propylene carbonate, diethyl carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane, γ-butyl lactone,
A mixed solvent obtained by mixing tetrahydrofuran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, diethyl ether, sulfolane, methylsulfolane, acetonitrile, propionitrile and the like may be used.
【００４５】また、本実施形態では、結着材としてＰＶ
ＤＦを用いた例を示したが、テフロン（登録商標）、ポ
リエチレン、ポリスチレン、ポリブタジエン、ブチルゴ
ム、ニトリルゴム、スチレン／ブタジエンゴム、多硫化
ゴム、ニトロセルロース、シアノエチルセルロース、各
種ラテックス、アクリロニトリル、フッ化ビニル、フッ
化ビニリデン、フッ化プロピレン、フッ化クロロプレ
ン、アクリル系樹脂などの重合体及びこれらの混合体な
どを使用してもよい。In this embodiment, PV is used as the binder.
Examples using DF have been shown, but Teflon (registered trademark), polyethylene, polystyrene, polybutadiene, butyl rubber, nitrile rubber, styrene / butadiene rubber, polysulfide rubber, nitrocellulose, cyanoethyl cellulose, various latexes, acrylonitrile, vinyl fluoride. Polymers such as vinylidene fluoride, propylene fluoride, chloroprene fluoride and acrylic resins, and mixtures thereof may be used.
【００４６】更に、本実施形態では、円筒状の有底電池
缶を使用した例を示したが、形には関係なく、角型や扁
平型などの形の電池缶を用いてもよい。Further, in this embodiment, an example of using a cylindrical bottomed battery can is shown, but a rectangular or flat battery can may be used regardless of the shape.
【００４７】また、本実施形態では、高出力タイプの電
池の例を示したが、高容量タイプの電池でも本発明を利
用することができる。In this embodiment, an example of a high output type battery is shown, but the present invention can be applied to a high capacity type battery.
【００４８】[0048]
【発明の効果】以上説明したように、本発明によれば、
正極に炭素材、負極にリチウムイオンを脱挿入可能な炭
素材及び選択的に炭素質導電材を含んでおり、正負極の
炭素材及び炭素質導電材の少なくともいずれかにホウ素
を含有させたため、瞬間的な大電流放電時に必要な電子
を供給できるので、正極の表面の電子とリチウムイオン
との反応を円滑にし抵抗を低減でき高出力を得ることが
できると共に、局部的な抵抗を小さくできるので、正極
のストレスも緩和され寿命を向上させることができる、
という効果を得ることができる。As described above, according to the present invention,
The positive electrode is a carbon material, and the negative electrode contains a carbon material capable of deintercalating lithium ions and selectively contains a carbonaceous conductive material, and at least one of the carbon material and the carbonaceous conductive material of the positive and negative electrodes contains boron, Since necessary electrons can be supplied at the time of momentary high-current discharge, the reaction between the electrons on the surface of the positive electrode and lithium ions can be smoothed, the resistance can be reduced, high output can be obtained, and the local resistance can be reduced. , Stress of the positive electrode can be relieved and life can be improved.
The effect can be obtained.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 原 賢二 東京都中央区日本橋本町二丁目８番７号 新神戸電機株式会社内 Ｆターム(参考） 5H029 AJ02 AK03 AL06 AM05 AM07 BJ02 BJ14 EJ01 EJ04 EJ12 HJ01 5H050 AA02 BA17 CA07 CB07 DA10 EA01 EA09 EA10 EA24 HA01 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Kenji Hara 2-8-7 Nihonbashihonmachi, Chuo-ku, Tokyo Inside Shin-Kobe Electric Machinery Co., Ltd. F-term (reference) 5H029 AJ02 AK03 AL06 AM05 AM07 BJ02 BJ14 EJ01 EJ04 EJ12 HJ01 5H050 AA02 BA17 CA07 CB07 DA10 EA01 EA09 EA10 EA24 HA01
Claims (4)
を含む正極と、リチウムイオンを脱挿入可能な炭素材及
び選択的に炭素質導電材を含む負極とを備えたリチウム
二次電池において、前記正負極の炭素材及び前記炭素質
導電材の少なくともいずれかにホウ素を所定量含有する
ことを特徴とするリチウム二次電池。1. A lithium secondary battery comprising a positive electrode containing a lithium-transition metal composite oxide and a carbon material, and a negative electrode containing a carbon material capable of deintercalating lithium ions and optionally a carbonaceous conductive material, A lithium secondary battery comprising a predetermined amount of boron in at least one of the positive and negative electrode carbon materials and the carbonaceous conductive material.
前記炭素質導電材の少なくともいずれかに対し０．０８
重量％以上３重量％以下の割合で含有されていることを
特徴とする請求項１に記載のリチウム二次電池。2. The boron content is 0.08 with respect to at least one of the carbon material of the positive and negative electrodes and the carbonaceous conductive material.
The lithium secondary battery according to claim 1, wherein the lithium secondary battery is contained in a ratio of not less than 3% by weight and not more than 3% by weight.
カーボンブラック又は黒鉛であることを特徴とする請求
項２に記載のリチウム二次電池。3. The carbonaceous material and carbonaceous conductive material of the positive electrode,
The lithium secondary battery according to claim 2, which is carbon black or graphite.
記黒鉛を含有し、該カーボンブラック及び黒鉛のうち少
なくともカーボンブラックにホウ素を含有し、該ホウ素
が前記カーボンブラック及び黒鉛中に３重量％以下の割
合で含有されていることを特徴とする請求項３に記載の
リチウム二次電池。4. The positive electrode contains the carbon black and the graphite, at least carbon black of the carbon black and graphite contains boron, and the boron is contained in the carbon black and the graphite in an amount of 3% by weight or less. The lithium secondary battery according to claim 3, wherein the lithium secondary battery is contained in.
Priority Applications (1)
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|---|---|---|---|
| JP2001230837A JP2003045434A (en) | 2001-07-31 | 2001-07-31 | Lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001230837A JP2003045434A (en) | 2001-07-31 | 2001-07-31 | Lithium secondary battery |
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| Publication Number | Publication Date |
|---|---|
| JP2003045434A true JP2003045434A (en) | 2003-02-14 |
Family
ID=19062979
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006324194A (en) * | 2005-05-20 | 2006-11-30 | Nec Corp | Secondary battery |
| JP2009295675A (en) * | 2008-06-03 | 2009-12-17 | Nippon Zeon Co Ltd | Electrode for electrochemical element and electrochemical element |
| JP2012028211A (en) * | 2010-07-26 | 2012-02-09 | Hitachi Chem Co Ltd | Lithium secondary battery negative electrode material, lithium secondary battery negative electrode using the same and lithium secondary battery using the electrode |
| WO2015129186A1 (en) * | 2014-02-28 | 2015-09-03 | 三洋電機株式会社 | Positive electrode for non-aqueous electrolyte secondary cell and non-aqueous electrolyte secondary cell using same |
-
2001
- 2001-07-31 JP JP2001230837A patent/JP2003045434A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006324194A (en) * | 2005-05-20 | 2006-11-30 | Nec Corp | Secondary battery |
| JP2009295675A (en) * | 2008-06-03 | 2009-12-17 | Nippon Zeon Co Ltd | Electrode for electrochemical element and electrochemical element |
| JP2012028211A (en) * | 2010-07-26 | 2012-02-09 | Hitachi Chem Co Ltd | Lithium secondary battery negative electrode material, lithium secondary battery negative electrode using the same and lithium secondary battery using the electrode |
| WO2015129186A1 (en) * | 2014-02-28 | 2015-09-03 | 三洋電機株式会社 | Positive electrode for non-aqueous electrolyte secondary cell and non-aqueous electrolyte secondary cell using same |
| CN106063000A (en) * | 2014-02-28 | 2016-10-26 | 三洋电机株式会社 | Positive electrode for non-aqueous electrolyte secondary cell and non-aqueous electrolyte secondary cell using same |
| JPWO2015129186A1 (en) * | 2014-02-28 | 2017-03-30 | 三洋電機株式会社 | Positive electrode for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery using the same |
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