JPH10112315A - Secondary battery - Google Patents
Secondary batteryInfo
- Publication number
- JPH10112315A JPH10112315A JP8265792A JP26579296A JPH10112315A JP H10112315 A JPH10112315 A JP H10112315A JP 8265792 A JP8265792 A JP 8265792A JP 26579296 A JP26579296 A JP 26579296A JP H10112315 A JPH10112315 A JP H10112315A
- Authority
- JP
- Japan
- Prior art keywords
- secondary battery
- positive electrode
- active material
- electrode active
- 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.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は二次電池に関し、さ
らに詳しくは、正極合剤にリチウム遷移金属複合酸化物
を含有する二次電池に関する。The present invention relates to a secondary battery, and more particularly, to a secondary battery containing a lithium transition metal composite oxide in a positive electrode mixture.
【０００２】[0002]
【従来の技術】近年、電子手帳、電子計算機、携帯型電
話機等のコードレス電子機器の発達には目を見張るもの
があり、これらの電源用として電池電圧が高く、高エネ
ルギー密度を有し、自己放電が少なく、且つサイクル特
性に優れた非水電解質二次電池が期待されている。この
非水電解質二次電池の一例であるコイン型リチウム二次
電池の構造について図２を参照して説明する。2. Description of the Related Art In recent years, the development of cordless electronic devices such as electronic notebooks, computers, portable telephones and the like has been remarkable. A non-aqueous electrolyte secondary battery with low discharge and excellent cycle characteristics is expected. The structure of a coin-type lithium secondary battery as an example of the non-aqueous electrolyte secondary battery will be described with reference to FIG.
【０００３】図２は、コイン型リチウム電池の概略側面
断面図である。リチウムまたはリチウム合金等で構成さ
れた円盤状の負極活物質１が負極カップ５内に収納さ
れ、正極活物質であるＬｉＣｏＯ2 、ＬｉＮｉx Ｍ
(1-x) Ｏ2 （Ｍは金属元素を表し、０．５≦ｘ≦１）、
ＬｉＭｎ2 Ｏ4 等のリチウム遷移金属複合酸化物を導電
材や結着剤とともに混合し、ペレット状に成形された正
極合剤２が正極缶３に収納されている。そして、負極活
物質１と正極合剤２とはセパレータ４を介して対向配置
され、正極缶３と負極カップ５とは封口ガスケット６を
介する嵌合により密封されている。この封口ガスケット
６は、リチウム等の負極活物質１が水分と反応すると閉
路電圧特性や容量保存性等の電気特性が劣化する為、正
極缶３と負極カップ５とで構成されている電池缶内への
水分侵入を防止する役割も兼ねている。FIG. 2 is a schematic side sectional view of a coin-type lithium battery. A disc-shaped negative electrode active material 1 made of lithium or a lithium alloy or the like is housed in a negative electrode cup 5, and the positive electrode active materials LiCoO 2 and LiNi x M
(1-x) O 2 (M represents a metal element, 0.5 ≦ x ≦ 1),
A positive electrode mixture 2 formed by mixing a lithium transition metal composite oxide such as LiMn 2 O 4 with a conductive material and a binder and forming the mixture into a pellet is stored in a positive electrode can 3. The negative electrode active material 1 and the positive electrode mixture 2 are disposed to face each other with the separator 4 interposed therebetween, and the positive electrode can 3 and the negative electrode cup 5 are hermetically sealed by fitting through the sealing gasket 6. When the negative electrode active material 1 such as lithium reacts with moisture, the sealing gasket 6 deteriorates electrical characteristics such as closed-circuit voltage characteristics and capacity preservability. It also has the role of preventing moisture from entering the water.
【０００４】ところで、二次電池を電源とするコードレ
ス電子機器は、長期間にわたって使用可能であることが
益々求められており、充放電サイクル間隔を長くするサ
イクル特性の向上が求められている。[0004] By the way, cordless electronic devices using a secondary battery as a power source are increasingly required to be usable over a long period of time, and there is a demand for improvement in cycle characteristics for extending a charge / discharge cycle interval.
【０００５】[0005]
【発明が解決しようとする課題】本発明の課題は、充放
電サイクル間隔を長くするサイクル特性の向上を図り、
長期間にわたってコードレス電子機器の電源として使用
可能である二次電池を提供することである。SUMMARY OF THE INVENTION An object of the present invention is to improve the cycle characteristics for increasing the charge / discharge cycle interval,
An object of the present invention is to provide a secondary battery that can be used as a power source of a cordless electronic device for a long time.
【０００６】[0006]
【課題を解決するための手段】上記課題を解決するため
に請求項１の発明の二次電池では、負極活物質とリチウ
ム遷移金属複合酸化物を含有する正極合剤とがセパレー
タを介して対向配置され、電池缶内に封口ガスケットを
介して密封される二次電池において、正極合剤に含有す
るＮａ量が２０００ｐｐｍ以上５０００ｐｐｍ以下であ
ることを特徴とする。In order to solve the above-mentioned problems, in the secondary battery according to the first aspect of the present invention, a negative electrode active material and a positive electrode mixture containing a lithium transition metal composite oxide are opposed to each other via a separator. In a secondary battery arranged and sealed in a battery can via a sealing gasket, the amount of Na contained in the positive electrode mixture is 2,000 ppm or more and 5000 ppm or less.
【０００７】請求項２の発明の二次電池では、負極活物
質とリチウム遷移金属複合酸化物を含有する正極合剤と
がセパレータを介して対向配置され、電池缶内に封口ガ
スケットを介して密封される二次電池において、正極合
剤に含有するＫ量が５０ｐｐｍ以上２００ｐｐｍ以下で
あることを特徴とする。In the secondary battery according to the second aspect of the present invention, the negative electrode active material and the positive electrode mixture containing the lithium transition metal composite oxide are opposed to each other with the separator interposed therebetween, and are sealed in the battery can with the sealing gasket interposed therebetween. In the secondary battery, the amount of K contained in the positive electrode mixture is not less than 50 ppm and not more than 200 ppm.
【０００８】上述した手段のように、正極活物質に混入
する不純物であるＮａまたはＫの量を規制すれば、充放
電サイクルを繰り返した時の電気容量の劣化率を小とす
る作用があり、二次電池の充放電サイクル間隔を長くす
るサイクル特性の向上を図ることができる。If the amount of Na or K, which is an impurity mixed into the positive electrode active material, is regulated as in the above-described means, there is an effect that the rate of deterioration of electric capacity when charge / discharge cycles are repeated is reduced. It is possible to improve the cycle characteristics of extending the charge / discharge cycle interval of the secondary battery.
【０００９】[0009]
【実施例】本発明は正極合剤を構成する正極活物質であ
るＬｉＣｏＯ2 、ＬｉＮｉx Ｍ(1-x) Ｏ2 （Ｍは金属元
素を表し、０．５≦ｘ≦１）、ＬｉＭｎ2 Ｏ4 等のリチ
ウム遷移金属複合酸化物に混入する不純物としてＮａ、
Ｋに注目し、これ等の物質の含有量を規定することによ
り二次電池のサイクル特性の向上を図るものである。以
下、本発明の具体的な実施例とこれと比較する比較例に
ついて、従来の技術と同様の図２を参照して説明する。
なお、正極活物質のリチウム遷移金属複合酸化物として
はＬｉＣｏＯ2 を用いた。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention relates to a positive electrode active material constituting a positive electrode mixture, LiCoO 2 , LiNi x M (1-x) O 2 (M is a metal element, 0.5 ≦ x ≦ 1), LiMn 2 Na as an impurity mixed into a lithium transition metal composite oxide such as O 4 ,
Attention is paid to K, and the content of these substances is specified to improve the cycle characteristics of the secondary battery. Hereinafter, specific examples of the present invention and comparative examples to be compared with the examples will be described with reference to FIG.
Note that LiCoO 2 was used as the lithium transition metal composite oxide of the positive electrode active material.
【００１０】実施例１ 先ず本実施例では、以下のようにして正極活物質のＬｉ
ＣｏＯ2 を作製した。酸化コバルト（ＩＩＩ）１モルと
炭酸リチウム０．５モルとを混合し、９００℃の空気中
で５時間焼成してＬｉＣｏＯ2 を作製した。Embodiment 1 First, in this embodiment, as the cathode active material Li
CoO 2 was produced. 1 mol of cobalt (III) oxide and 0.5 mol of lithium carbonate were mixed and calcined in air at 900 ° C. for 5 hours to produce LiCoO 2 .
【００１１】次に、以下のようにして正極合剤２を作製
した。得られたＬｉＣｏＯ2 ９１重量部、導電材として
グラファイトパウダー６重量部および結着剤としてポリ
テトラフルオロエチレンパウダー３重量部とを均一に混
合して正極活物質を得た。この正極活物質の質量５００
ｍｇを予備成型した後、集電体としてのアルミニウム製
ネットを載せて加圧成型し、外径１５．５ｍｍ、厚さ
０．７ｍｍの正極合剤２を作製した。Next, a positive electrode mixture 2 was prepared as follows. The positive electrode active material was obtained by uniformly mixing 91 parts by weight of the obtained LiCoO 2 , 6 parts by weight of graphite powder as a conductive material, and 3 parts by weight of polytetrafluoroethylene powder as a binder. Mass of this positive electrode active material 500
After pre-molding, a positive electrode mixture 2 having an outer diameter of 15.5 mm and a thickness of 0.7 mm was prepared by placing an aluminum net as a current collector thereon and performing pressure molding.
【００１２】次に、以下のようにして負極活物質を作製
した。難黒鉛化炭素材料９０重量部に結着剤としてポリ
フッ化ビニリデン１０重量部を加えて均一に混合し、こ
れに分散剤であるＮ−メチルニピロリドンを適量添加し
て乾燥させ、圧縮成型して外径１５．６ｍｍ、厚さ０．
８ｍｍ、質量１８０ｍｇの負極活物質１を作製した。Next, a negative electrode active material was prepared as follows. To 90 parts by weight of the non-graphitizable carbon material, 10 parts by weight of polyvinylidene fluoride as a binder is added and uniformly mixed, and an appropriate amount of N-methylnipyrrolidone as a dispersant is added thereto, followed by drying and compression molding. Outer diameter 15.6mm, thickness 0.
A negative electrode active material 1 having a mass of 8 mm and a mass of 180 mg was produced.
【００１３】次に、以下のようにして非水電解質二次電
池を完成させた。ステンレス鋼板等で構成された負極カ
ップ５に外径１５．８ｍｍ、内径１５．６ｍｍ、厚さ
０．７５ｍｍのステンレス鋼板等で構成された負極集電
体７をスポット溶接し、この負極集電体７に負極活物質
１を収納した。そして、負極活物質１を覆うように厚さ
５０μｍの多数の微細孔を有するポリプロピレンフィル
ムで構成されたセパレータ４を載置し、このセパレータ
４の外周縁をポリプロピレンで構成された封口ガスケッ
ト６を負極カップ５の外周縁に挿着するとともに挟着し
た後、プロピレンカーボネートと炭酸メチルエチルを体
積比５０対５０の割合で混合した溶媒にＬｉＰＦ6 を１
モル／ｌの割合で溶解した電解液を滴下した。さらに、
正極合剤２をセパレータ４の上に載置した後に再びプロ
ピレンカーボネートと炭酸メチルエチルを体積比５０対
５０の割合で混合した溶媒にＬｉＰＦ6 を１モル／ｌの
割合で溶解した電解液を滴下し、アルミニウム板、ステ
ンレス鋼板およびニッケル板の三層構造である正極缶３
を被せて負極カップ５と正極缶３とを封口ガスケット６
によりシールし、外径２０ｍｍ、厚さ２．５ｍｍのコイ
ン型非水電解質二次電池を完成した。Next, a non-aqueous electrolyte secondary battery was completed as follows. A negative electrode current collector 7 composed of a stainless steel plate or the like having an outer diameter of 15.8 mm, an inner diameter of 15.6 mm, and a thickness of 0.75 mm is spot-welded to a negative electrode cup 5 composed of a stainless steel plate or the like. 7, the negative electrode active material 1 was stored. Then, a separator 4 made of a polypropylene film having a large number of fine pores having a thickness of 50 μm is placed so as to cover the negative electrode active material 1, and an outer peripheral edge of the separator 4 is sealed with a sealing gasket 6 made of polypropylene. After being inserted and pinched on the outer periphery of the cup 5, LiPF 6 was added to a solvent in which propylene carbonate and methyl ethyl carbonate were mixed at a volume ratio of 50:50.
An electrolytic solution dissolved at a rate of mol / l was dropped. further,
After placing the positive electrode mixture 2 on the separator 4, an electrolytic solution in which LiPF 6 is dissolved at a ratio of 1 mol / l in a solvent in which propylene carbonate and methyl ethyl carbonate are mixed at a volume ratio of 50 to 50 is dropped again. And a positive electrode can 3 having a three-layer structure of an aluminum plate, a stainless steel plate, and a nickel plate.
And cover the negative electrode cup 5 and the positive electrode can 3 with a sealing gasket 6.
To complete a coin-type nonaqueous electrolyte secondary battery having an outer diameter of 20 mm and a thickness of 2.5 mm.
【００１４】実施例２ 本実施例は、実施例１で用いた酸化コバルト（ＩＩＩ）
と異なるベンダーの酸化コバルト（ＩＩＩ）１モルと炭
酸リチウム０．５モルとを混合し、９００℃の空気中で
５時間焼成してＬｉＣｏＯ2 を作製したものであり、以
下は実施例１と同様にして非水電解質二次電池を完成し
た。Example 2 This example uses the cobalt (III) oxide used in Example 1.
1 mol of cobalt (III) oxide and 0.5 mol of lithium carbonate were mixed and calcined in air at 900 ° C. for 5 hours to produce LiCoO 2. Thus, a non-aqueous electrolyte secondary battery was completed.
【００１５】なお、実施例１および２において、Ｎａや
Ｋの添加量を管理する為、正極活物質を焼成する工程に
おいて炭酸ナトリウムや炭酸カリウム、あるいはこれ等
の化合物を添加しても良い。In Examples 1 and 2, in order to control the addition amount of Na or K, sodium carbonate, potassium carbonate, or a compound thereof may be added in the step of firing the positive electrode active material.
【００１６】比較例 本比較例では、以下のようにして正極活物質のＬｉＣｏ
Ｏ2 を作製した。試薬特級グレードの酸化コバルト（Ｉ
ＩＩ）１モルと試薬特級グレードの炭酸リチウム０．５
モルとを混合し、９００℃の空気中で５時間焼成してＬ
ｉＣｏＯ2 を作製し、以下は実施例１と同様にして非水
電解質二次電池を完成した。Comparative Example In this comparative example, LiCo as a positive electrode active material was
O 2 was produced. Special grade reagent grade cobalt oxide (I
II) 1 mol and 0.5 grade of special grade lithium carbonate
And baked for 5 hours in air at 900 ° C.
iCoO 2 was prepared, and a non-aqueous electrolyte secondary battery was completed in the same manner as in Example 1 below.
【００１７】上記した実施例１〜２および比較例で得ら
れたＬｉＣｏＯ2 の蛍光Ｘ線による定性分析結果を表１
に示す。Table 1 shows the results of qualitative analysis of the LiCoO 2 obtained in Examples 1 and 2 and Comparative Example by fluorescent X-ray.
Shown in
【００１８】[0018]
【表１】 [Table 1]
【００１９】表１から明らかなように、実施例１〜２は
比較例と比較して不純物としてのＮａ、Ｋの含有量が何
れも大であり、Ｎａ量が２０００ｐｐｍ以上５０００ｐ
ｐｍ以下、Ｋ量が５０ｐｐｍ以上２００ｐｐｍ以下に管
理されていることが確認された。As is clear from Table 1, Examples 1 and 2 have larger contents of Na and K as impurities as compared with Comparative Examples, and the amount of Na is 2,000 ppm or more and 5000 p.
It was confirmed that the amount of K was controlled to 50 ppm or less and 200 ppm or less.
【００２０】図１は、実施例１〜２および比較例の各々
のサンプルに対して充電（４．２Ｖ、１ｍＡ、２４時
間）と放電（２．５Ｖ、１ｍＡ、２４時間）を１サイク
ルとしてこれを繰り返し、１サイクル目の放電容量を１
００％とした時の容量劣化率をグラフに示したものであ
る。FIG. 1 shows the charging (4.2 V, 1 mA, 24 hours) and discharging (2.5 V, 1 mA, 24 hours) of each sample as one cycle for each of the samples of Examples 1 and 2 and Comparative Example. And discharge capacity at the first cycle is set to 1
The graph shows the capacity deterioration rate when the value is set to 00%.
【００２１】図１に示したように、２００サイクル後の
容量劣化率では比較例が８４％であったのに対して、本
発明の実施例１では９３％、実施例１では９２％と何れ
も良好なサイクル特性を示した。As shown in FIG. 1, the capacity deterioration rate after 200 cycles was 84% in the comparative example, 93% in the first embodiment of the present invention, and 92% in the first embodiment. Also showed good cycle characteristics.
【００２２】[0022]
【発明の効果】本発明の二次電池によれば、充放電サイ
クル間隔を長くするサイクル特性の向上が図られ、長期
間にわたってコードレス電子機器の電源として使用可能
な二次電池を提供することができる。According to the secondary battery of the present invention, it is possible to provide a secondary battery which can be used as a power source of a cordless electronic device for a long period of time by improving the cycle characteristics for extending the charge / discharge cycle interval. it can.
【図１】 本発明の実施例と比較例とのサイクル特性
（容量劣化率）を比較したグラフである。FIG. 1 is a graph comparing cycle characteristics (capacity deterioration rate) of an example of the present invention and a comparative example.
【図２】 非水電解質二次電池の一例であるコイン型リ
チウム二次電池の概略側面断面図である。FIG. 2 is a schematic side sectional view of a coin-type lithium secondary battery which is an example of a non-aqueous electrolyte secondary battery.
１…負極活物質、２…正極合剤、３…正極缶、４…セパ
レータ、５…負極カップ、６…封口ガスケット、７…負
極集電体DESCRIPTION OF SYMBOLS 1 ... Negative electrode active material, 2 ... Positive electrode mixture, 3 ... Positive electrode can, 4 ... Separator, 5 ... Negative cup, 6 ... Seal gasket, 7 ... Negative electrode current collector
Claims (2)
パレータを介して対向配置され、 電池缶内に封口ガスケットを介して密封される二次電池
において、 前記正極合剤に含有するＮａ量が２０００ｐｐｍ以上５
０００ｐｐｍ以下であることを特徴とする二次電池。1. A secondary battery in which a negative electrode active material and a positive electrode mixture containing a lithium transition metal composite oxide are arranged to face each other with a separator interposed therebetween, and sealed in a battery can with a sealing gasket, The amount of Na contained in the positive electrode mixture is 2,000 ppm or more 5
2,000 ppm or less, a secondary battery.
パレータを介して対向配置され、 電池缶内に封口ガスケットを介して密封される二次電池
において、 前記正極合剤に含有するＫ量が５０ｐｐｍ以上２００ｐ
ｐｍ以下であることを特徴とする二次電池。2. A secondary battery in which a negative electrode active material and a positive electrode mixture containing a lithium transition metal composite oxide are disposed to face each other with a separator interposed therebetween, and sealed in a battery can with a sealing gasket, The amount of K contained in the positive electrode mixture is 50 ppm or more and 200 p
pm or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8265792A JPH10112315A (en) | 1996-10-07 | 1996-10-07 | Secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8265792A JPH10112315A (en) | 1996-10-07 | 1996-10-07 | Secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10112315A true JPH10112315A (en) | 1998-04-28 |
Family
ID=17422115
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8265792A Pending JPH10112315A (en) | 1996-10-07 | 1996-10-07 | Secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10112315A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2019167875A1 (en) * | 2018-03-01 | 2021-02-25 | 株式会社Adeka | Organic sulfur-based electrode active material |
-
1996
- 1996-10-07 JP JP8265792A patent/JPH10112315A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2019167875A1 (en) * | 2018-03-01 | 2021-02-25 | 株式会社Adeka | Organic sulfur-based electrode active material |
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