JP3133317B2 - Rechargeable battery - Google Patents
Rechargeable batteryInfo
- Publication number
- JP3133317B2 JP3133317B2 JP02249495A JP24949590A JP3133317B2 JP 3133317 B2 JP3133317 B2 JP 3133317B2 JP 02249495 A JP02249495 A JP 02249495A JP 24949590 A JP24949590 A JP 24949590A JP 3133317 B2 JP3133317 B2 JP 3133317B2
- Authority
- JP
- Japan
- Prior art keywords
- battery
- negative electrode
- carbon material
- lithium
- present
- 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.)
- Expired - Fee Related
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)
Description
【発明の詳細な説明】 （イ） 産業上の利用分野 本発明は、非水電解液を用いた二次電池に関する。The present invention relates to a secondary battery using a non-aqueous electrolyte.
（ロ） 従来の技術 リチウムを負極活物質とした二次電池は、そのエネル
ギー密度が大きく、特に研究が盛んである。この種、二
次電池は、そのリチウムの充放電効率が低いために、サ
イクル特性に問題がある。これを解決するために、リチ
ウムと合金化する金属、たとえばアルミニウムを用いて
リチウム−アルミニウム合金を形成して、これを負極と
する方法や、LiAsF6系の電解液を用いてリチウムの充放
電効率を向上させ、サイクル特性の向上を計る方法が提
案されている。(B) Conventional technology A secondary battery using lithium as a negative electrode active material has a large energy density, and research is particularly active. This kind of secondary battery has a problem in cycle characteristics due to low charge / discharge efficiency of lithium. To solve this problem, lithium and metal for alloying, for example lithium with aluminum - to form an aluminum alloy, which a method of the negative electrode, charge and discharge efficiency of the lithium with the electrolyte solution of LiAsF 6 system And a method for improving the cycle characteristics has been proposed.
しかし、前者の方法では作動電圧が低下するという欠
点があり、後者の方法では電解液が有毒であり安全性の
面で問題が生じる。However, the former method has a drawback that the operating voltage decreases, and the latter method has a problem in terms of safety because the electrolyte is toxic.
これらの問題点を改善するために、カーボン系の物質
を負極基材として用い、ここにリチウムを吸蔵、放出さ
せて負極を構成する方法が提案されている。この場合
は、前記せるような作動電圧の低下や毒性はなく、エネ
ルギー密度も大きい。In order to solve these problems, a method has been proposed in which a carbon-based material is used as a negative electrode base material, and lithium is absorbed and released therein to form a negative electrode. In this case, there is no reduction in operating voltage or toxicity as described above, and the energy density is large.
然し乍ら、不純物、特にコークス等の原料に含まれて
いる硫黄成分が、カオチンであるリチウムと反応し、保
存特性が低下するという問題がある。However, there is a problem in that impurities, particularly sulfur components contained in raw materials such as coke, react with lithium, which is chaotin, and the storage characteristics deteriorate.
（ハ） 発明が解決しようとする課題 本発明は前記問題点に鑑みて成されたものであって、
炭素材料中の硫黄成分と、カチオン例えばリチウムとの
反応を抑制することによって、サイクル特性が高く、且
つ保存特性に優れた二次電池を提供しようとするもので
ある。(C) Problems to be Solved by the Invention The present invention has been made in view of the above problems,
An object of the present invention is to provide a secondary battery having high cycle characteristics and excellent storage characteristics by suppressing a reaction between a sulfur component in a carbon material and a cation such as lithium.
（ニ） 課題を解決するための手段 本発明は、正極と、カチオンを吸蔵、放出する炭素材
料よりなる負極と、非水電解液とからなる二次電池にお
いて、前記炭素材料が脱硫化処理されたものであって、
この脱硫化処理により硫黄成分が５％以下に抑制された
ものであることを特徴とする。(D) Means for Solving the Problems The present invention provides a secondary battery comprising a positive electrode, a negative electrode made of a carbon material that occludes and releases cations, and a non-aqueous electrolyte, wherein the carbon material is subjected to a desulfurization treatment. That
The sulfur component is suppressed to 5% or less by the desulfurization treatment.
また、前記脱硫化処理としては、炭素材料を水素によ
り処理したものが好適する。Further, as the desulfurization treatment, one obtained by treating a carbon material with hydrogen is preferable.
また、前記カチオンとしては、リチウムイオンやナト
リウムイオン等のアルカリ金属イオン、カリウムイオン
やマグネシウムイオン等のアルカリ土類金属イオン、ア
ルミニウムイオン等が挙げられる。Examples of the cation include alkali metal ions such as lithium ions and sodium ions, alkaline earth metal ions such as potassium ions and magnesium ions, and aluminum ions.
（ホ） 作用 負極を構成する炭素材料は、カチオン、例えばリチウ
ムイオンを吸蔵、放出することができるが、従来の炭素
材料では硫黄成分が多く、これと吸蔵したカチオンが反
応して、電池の自己放電反応を生じていた。(E) Function The carbon material constituting the negative electrode can occlude and release cations, for example, lithium ions. However, conventional carbon materials have a large amount of sulfur components, and the occluded cations react with the carbon materials to cause self-reaction of the battery. A discharge reaction was occurring.
しかし、本発明では負極に使用する炭素材料が、脱硫
化処理されたものであって、この脱硫化処理により硫黄
成分が５％以下に抑制されたものを用いているため、自
己放電反応がほとんど生じない。このために自己特性が
向上する。However, in the present invention, since the carbon material used for the negative electrode is desulfurized, and the sulfur component is suppressed to 5% or less by the desulfurization, the self-discharge reaction hardly occurs. Does not occur. For this reason, self characteristics are improved.
ここで用いる炭素材料としては、ポリアクリロニトリ
ルなどの高分子を焼成した熱処理炭素、各種コークス、
黒鉛、更にはアセチレンブラック等の無定形炭素等があ
げられる。As the carbon material used here, heat-treated carbon obtained by firing a polymer such as polyacrylonitrile, various cokes,
Examples include graphite and amorphous carbon such as acetylene black.
（ヘ） 実施例 以下に、実施例を示し、本発明を具体的に説明する。(F) Examples Hereinafter, examples will be shown to specifically describe the present invention.
［実施例１］ 石油コークスを粉砕し、400メッシュパスした後、反
応温度300℃、反応圧力50kg/m2、水素循環量100m2/klに
て、石油コークスを水素化精製することで脱硫を行っ
た。この脱硫後の硫黄成分は0.5％であった。尚、ここ
で石油コークスを脱硫するために、水素を使用している
が、酸素を用いても同様の脱硫を行うことができる。そ
して、このように脱硫した炭素材料である石油コークス
を、金属リチウム粉末と混合、プレスして、負極を作製
した。[Example 1] After petroleum coke was pulverized and passed through a 400 mesh, desulfurization was performed by hydrorefining petroleum coke at a reaction temperature of 300 ° C, a reaction pressure of 50 kg / m 2 , and a hydrogen circulation rate of 100 m 2 / kl. went. The sulfur component after this desulfurization was 0.5%. Here, hydrogen is used for desulfurizing petroleum coke, but similar desulfurization can be performed using oxygen. Then, petroleum coke, which is a carbon material desulfurized in this way, was mixed with lithium metal powder and pressed to produce a negative electrode.
一方、正極としては二酸化マンガを用い、過塩素酸リ
チウム／プロピレンカーボネート溶液を電解液として、
第１図に示す本発明電池Ａを組み立てた。On the other hand, manganese dioxide was used as the positive electrode, and a lithium perchlorate / propylene carbonate solution was used as the electrolyte.
The battery A of the present invention shown in FIG. 1 was assembled.
第１図は、本発明電池の縦断面図である。第１図中、
１は正極外装体、２は負極外装体であり、絶縁性の樹脂
から成る絶縁パッキング３で、絶縁されている。また、
４は正極、５は負極であり、セパレータ６によって隔離
されている。また、前記正極外装体１の内底面には正極
集電体７が、前記負極外装体２の内底面には負極集電体
８が、それぞれ溶接固定されている。FIG. 1 is a longitudinal sectional view of the battery of the present invention. In FIG.
Reference numeral 1 denotes a positive electrode casing, and 2 denotes a negative electrode casing, which are insulated by an insulating packing 3 made of an insulating resin. Also,
Reference numeral 4 denotes a positive electrode, and 5 denotes a negative electrode, which are separated by a separator 6. Further, a positive electrode current collector 7 is fixed to the inner bottom surface of the positive electrode package 1 by welding, and a negative electrode current collector 8 is fixed to the inner bottom surface of the negative electrode package 2 by welding.
［比較例１］ 負極に脱硫処理を行わない石油コークスを炭素材料と
して用いた以外は、前記実施例１と同様の炭素材料を使
用して、比較電池Ｘを組み立てた。尚、この脱硫処理を
施していない石油コークスの硫黄成分は10％であった。Comparative Example 1 A comparative battery X was assembled using the same carbon material as in Example 1 except that petroleum coke not subjected to desulfurization treatment was used as the carbon material for the negative electrode. The sulfur component of the petroleum coke not subjected to the desulfurization treatment was 10%.
これらの電池Ａ、Ｘを用い、電池の保存特性を比較し
た。この時の実験条件は、10mAhで10回充放電した後、1
0mAh充電し、60℃で保存し、電池の放電容量を測定する
というものである。Using these batteries A and X, the storage characteristics of the batteries were compared. The experimental conditions at this time were: after charging and discharging 10 times at 10 mAh,
It charges 0 mAh, stores it at 60 ° C, and measures the discharge capacity of the battery.
第２図に、この結果を示す。第２図は、電池の保存特
性図である。これより、本発明電池Ａは30日経過しても
容量残存率が95％あるのに対し、比較電池Ｘは70％しか
容量残存率がない。このように本発明電池Ａは、保存特
性において優れたものであることが分かる。FIG. 2 shows this result. FIG. 2 is a storage characteristic diagram of the battery. Thus, the battery A of the present invention has a remaining capacity of 95% even after 30 days, while the comparative battery X has only a remaining capacity of 70%. Thus, it can be seen that the battery A of the present invention is excellent in storage characteristics.
［実施例２］ 石炭コークスを粉砕し、400メッシュパスした後、反
応温度は300℃、反応圧力50kg/m2、水素循環量100m2/kl
にて、石炭コークスを水素化精製することで脱硫した。
この脱硫後の硫黄成分は0.9％であった。このように脱
硫した炭素材料である石炭コークスを、金属リチウム粉
末と混合、プレスすることにより、負極を作製した。Example 2 After pulverizing coal coke and passing it through a 400 mesh, the reaction temperature was 300 ° C., the reaction pressure was 50 kg / m 2 , and the hydrogen circulation amount was 100 m 2 / kl.
In the above, coal coke was desulfurized by hydrorefining.
The sulfur component after desulfurization was 0.9%. The thus-desulfurized carbon material, coal coke, was mixed with metallic lithium powder and pressed to produce a negative electrode.
一方、正極として二酸化マンガンを用いて、過塩素酸
リチウム／プロピレンカーボネート溶液を電解液とし
て、前記第１図に示す構造と同一構造を有する、本発明
電池Ｂを組み立てた。On the other hand, a battery B of the present invention having the same structure as that shown in FIG. 1 was assembled using manganese dioxide as a positive electrode and a lithium perchlorate / propylene carbonate solution as an electrolyte.
［比較例２］ 負極に脱硫処理を行わない石炭コークスを炭素材料と
して用いた以外は、前記実施例２と同様の炭素材料を使
用して、比較電池Ｙを組み立てた。尚、この脱硫処理を
施していない石炭コークスの硫黄成分は10％であった。[Comparative Example 2] A comparative battery Y was assembled using the same carbon material as in Example 2 except that coal coke not subjected to desulfurization treatment was used as the carbon material for the negative electrode. The sulfur component of the coal coke not subjected to the desulfurization treatment was 10%.
これらの電池Ｂ、Ｙを用い、電池の保存特性を比較し
た。この時の実験条件は、10mAhで10回充放電した後、1
0mAh充電し、60℃で保存し、電池の放電容量を測定する
というものである。Using these batteries B and Y, the storage characteristics of the batteries were compared. The experimental conditions at this time were: after charging and discharging 10 times at 10 mAh,
It charges 0 mAh, stores it at 60 ° C, and measures the discharge capacity of the battery.
第３図に、この結果を示す。第３図は、電池の保存特
性図である。これにより、本発明電池Ｂは30日経過して
も容量残存率が95％あるのに対し、比較電池Ｙは50％し
か容量残存率がない。このように本発明電池Ｂは、保存
特性において優れたものであることが理解される。FIG. 3 shows the results. FIG. 3 is a storage characteristic diagram of the battery. Thus, the battery B of the present invention has a remaining capacity of 95% even after 30 days, while the comparative battery Y has only a remaining capacity of 50%. Thus, it is understood that the battery B of the present invention is excellent in storage characteristics.
次に、負極を構成する炭素材料中の硫黄の濃度と、電
池の自己放電率との関係を調べた。Next, the relationship between the concentration of sulfur in the carbon material constituting the negative electrode and the self-discharge rate of the battery was examined.
この結果を、第４図に示す。第４図は、硫黄の濃度
と、電池の自己放電率との関係を示す図である。これよ
り、電池の保存特性の観点から、炭素材料中における硫
黄の濃度を５％以下とする必要がある。The result is shown in FIG. FIG. 4 is a diagram showing the relationship between the sulfur concentration and the self-discharge rate of the battery. Therefore, from the viewpoint of the storage characteristics of the battery, the concentration of sulfur in the carbon material needs to be 5% or less.
（ト）発明の効果 以上述べた如く、本発明によれば、電池の保存特性を
向上させることが可能となり、その工業的価値は極めて
大きい。(G) Effects of the Invention As described above, according to the present invention, it is possible to improve the storage characteristics of a battery, and its industrial value is extremely large.
【図面の簡単な説明】 第１図は本発明電池の縦断面図、第２図及び第３図は電
池の保存特性図、第４図は硫黄の濃度と電池の自己放電
率の関係を示す図である。 １……正極外装体、２……負極外装体、３……絶縁パッ
キング、４……正極、５……負極、６……セパレータ、
７……正極集電体、８……負極集電体、 Ａ、Ｂ……本発明電池、 Ｘ、Ｙ……比較電池。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a longitudinal sectional view of the battery of the present invention, FIGS. 2 and 3 are storage characteristic diagrams of the battery, and FIG. 4 shows the relationship between the concentration of sulfur and the self-discharge rate of the battery. FIG. DESCRIPTION OF SYMBOLS 1 ... positive electrode exterior body, 2 ... negative electrode exterior body, 3 ... insulating packing, 4 ... positive electrode, 5 ... negative electrode, 6 ... separator,
7 Positive electrode current collector, 8 Negative electrode current collector, A, B ... Battery of the present invention, X, Y ... Comparative battery.
フロントページの続き (56)参考文献 特開 昭62−90863（ＪＰ，Ａ) 特開 昭59−91667（ＪＰ，Ａ) 特開 昭60−59659（ＪＰ，Ａ) 特開 昭62−136766（ＪＰ，Ａ) 特開 昭62−154461（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 10/40 H01M 4/02 H01M 4/58 Continuation of front page (56) References JP-A-62-90863 (JP, A) JP-A-59-91667 (JP, A) JP-A-60-59659 (JP, A) JP-A-62-136766 (JP) (A) JP-A-62-154461 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) H01M 10/40 H01M 4/02 H01M 4/58
Claims (2)
料よりなる負極と、非水電解液とを有する二次電池にお
いて、 前記炭素材料が脱硫化処理されたものであって、この脱
硫化処理により硫黄成分が５％以下に抑制されたもので
あることを特徴とする二次電池。1. A secondary battery comprising a positive electrode, a negative electrode made of a carbon material that occludes and releases cations, and a non-aqueous electrolyte, wherein the carbon material is subjected to a desulfurization treatment. A secondary battery, wherein the sulfur component is suppressed to 5% or less by the treatment.
処理したものであることを特徴とする請求項記載の二
次電池。2. The secondary battery according to claim 1, wherein the desulfurization treatment is obtained by treating a carbon material with hydrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02249495A JP3133317B2 (en) | 1990-09-18 | 1990-09-18 | Rechargeable battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02249495A JP3133317B2 (en) | 1990-09-18 | 1990-09-18 | Rechargeable battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04126373A JPH04126373A (en) | 1992-04-27 |
| JP3133317B2 true JP3133317B2 (en) | 2001-02-05 |
Family
ID=17193821
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02249495A Expired - Fee Related JP3133317B2 (en) | 1990-09-18 | 1990-09-18 | Rechargeable battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3133317B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69733293T2 (en) * | 1996-05-27 | 2006-02-02 | Sanyo Electric Co., Ltd., Moriguchi | Carbon electrode and battery with non-aqueous electrolyte |
| CN102399339B (en) * | 2010-09-08 | 2013-08-28 | 清华大学 | Preparation method of sulfurized polyacrylonitrile |
-
1990
- 1990-09-18 JP JP02249495A patent/JP3133317B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04126373A (en) | 1992-04-27 |
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