JP3021837B2 - Non-aqueous secondary battery - Google Patents
Non-aqueous secondary batteryInfo
- Publication number
- JP3021837B2 JP3021837B2 JP3243592A JP24359291A JP3021837B2 JP 3021837 B2 JP3021837 B2 JP 3021837B2 JP 3243592 A JP3243592 A JP 3243592A JP 24359291 A JP24359291 A JP 24359291A JP 3021837 B2 JP3021837 B2 JP 3021837B2
- Authority
- JP
- Japan
- Prior art keywords
- anion
- negative electrode
- secondary battery
- temperature
- carbon material
- 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
Description
【０００１】[0001]
【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。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a secondary battery using a non-aqueous electrolyte.
【０００２】[0002]
【従来の技術】リチウムを負極としたリチウム二次電池
はそのエネルギー密度が大きいことから盛んに研究が行
われており、一部実用化の域に達している。2. Description of the Related Art Lithium secondary batteries using lithium as a negative electrode have been actively studied due to their high energy density, and some of them have reached practical use.
【０００３】然し乍ら、リチウム二次電池は金属リチウ
ムを用いており、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、サイクル特性向上をはかる方
法が考えられている。[0003] However, lithium secondary batteries use metallic lithium, and the charge / discharge efficiency of lithium is low, so that there is a problem in cycle characteristics. In order to solve this problem, a method of forming a lithium-aluminum alloy using a metal alloying with lithium, for example, aluminum, and using this as a negative electrode, or improving the charge / discharge efficiency of lithium using a LiAsF 6 -based electrolyte solution Thus, a method for improving the cycle characteristics has been considered.
【０００４】[0004]
【発明が解決しようとする課題】ところが前者の方法で
は作動電圧が低下するという欠点があり、また後者の方
法では電解液が有毒であり安全性の面で問題がある。However, the former method has a drawback that the operating voltage is reduced, and the latter method has a problem in terms of safety because the electrolyte is toxic.
【０００５】これらの欠点を改善するためにカーボン系
の物質を負極として用いる方法が考え出された。この場
合は作動電圧の低下や毒性はなく、安全性は高い反面、
エネルギー密度の点で問題があった。カーボン材料とし
てはいろいろ種類があるが、当然のこと乍らリチウムを
吸蔵・放出する性質を有するものに限られ、これにはコ
ークスと高分子炭化物が存在する。[0005] In order to improve these drawbacks, a method using a carbon-based material as a negative electrode has been devised. In this case, there is no reduction in operating voltage or toxicity, and although safety is high,
There was a problem in terms of energy density. There are various types of carbon materials, but naturally, they are limited to those having the property of inserting and extracting lithium, and there are coke and polymer carbide.
【０００６】このうちコークスは不純物が多いこととそ
の不純物の脱離が難しいことから実用化には不向きとさ
れている。一方、高分子炭化物は純度を上げることが簡
単でリチウム二次電池用負極に向いてはいるものの、エ
ネルギー密度はコークスとあまりかわらない。[0006] Among them, coke is not suitable for practical use because it has many impurities and it is difficult to remove the impurities. On the other hand, high-molecular carbides can easily increase the purity and are suitable for negative electrodes for lithium secondary batteries, but their energy density is not so different from that of coke.
【０００７】[0007]
【課題を解決するための手段】本発明はこのような種々
の問題点に鑑みて為されたものであって、アニオンを挿
入した後、該アニオンが分解、或いは気化する温度以上
で黒鉛化温度より低い温度で熱処理してそのアニオンを
除去することによって、層間距離が上記アニオンの大き
さに拡大された炭素材料を非水系二次電池の負極として
用いたものである。SUMMARY OF THE INVENTION The present invention has been made in view of such various problems, and has been made in view of the temperature at which an anion is decomposed or vaporized after insertion of the anion. A carbon material in which the interlayer distance is enlarged to the size of the anion by heat-treating at a temperature lower than the graphitization temperature to remove the anion as described above is used as a negative electrode of a non-aqueous secondary battery. It is.
【０００８】[0008]
【作用】本発明によれば、負極を構成する炭素材料の層
間距離が拡大するので、リチウムイオンのインターカレ
ートが容易になり、高容量の二次電池が得られる。According to the present invention, since the interlayer distance between the carbon materials constituting the negative electrode is increased, lithium ions can be easily intercalated, and a high capacity secondary battery can be obtained.
【０００９】[0009]
【実施例】以下に本発明の実施例について具体的に説明
する。炭素材料としてのピッチコークスを粉砕し、ＮＯ
ＢＦ4・アセトニトリル溶液に１昼夜浸漬することでア
ニオンのＢＦ4ーをピッチコークス内に化学的に挿入し
た。このアニオンの挿入により、炭素の層間距離が拡大
する。続いてこのアニオンが挿入された炭素材料を７５
０℃で５時間の真空熱処理を施す。その結果、炭素材料
の層間に挿入されたアニオンは分解されて層間から除去
されるが、その時アニオンを挿入することによって広が
った層間距離は縮まることなくそのままの状態が保持さ
れる。このようにして層間距離が広がった炭素材料を４
００メッシュパスした後、プレスすることにより負極１
を作製した。DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be specifically described below. Pulverize pitch coke as carbon material, NO
Chemically inserted into pitch coke inside the BF 4 over the anion by one day immersion in BF 4 · acetonitrile solution. The insertion of the anion increases the carbon interlayer distance. Subsequently, the carbon material having the anion inserted therein is replaced by 75
A vacuum heat treatment is performed at 0 ° C. for 5 hours. As a result, the anions inserted between the layers of the carbon material are decomposed and removed from the layers. At that time, the distance between the layers expanded by inserting the anions is maintained without being shortened. The carbon material whose interlayer distance is widened in this way is
After passing through a 00 mesh pass, the anode 1 was pressed by pressing.
Was prepared.
【００１０】一方、正極２としてコバルト酸化物を用
い、セパレータ３に電解液としての過塩素酸リチウム／
プロピレンカーボネート溶液を含浸させて図１に示す本
発明に係る電池Ａを組み立てた。図１において４は負極
集電体、５は正極集電体、６は負極缶、７は正極缶、８
は絶縁パッキングである。On the other hand, cobalt oxide is used as the positive electrode 2, and lithium perchlorate /
The battery A according to the present invention shown in FIG. 1 was assembled by impregnating with a propylene carbonate solution. In FIG. 1, 4 is a negative electrode current collector, 5 is a positive electrode current collector, 6 is a negative electrode can, 7 is a positive electrode can, 8
Is an insulating packing.
【００１１】また、負極１に７５０℃でそれぞれ熱処理
した以外は同様にして比較例としての電池Ｂを組み立て
た。A battery B as a comparative example was assembled in the same manner except that the negative electrode 1 was heat-treated at 750 ° C., respectively.
【００１２】これらの電池を１ｍＡで３Ｖまで充電した
後、２．０Ｖまで放電し、充放電特性を測定した。図２
にその結果を示す。本発明に係る電池Ａは２０ｍＡｈの
放電容量を示したが、比較例電池Ｂは１０ｍＡｈの放電
容量しか示さなかった。These batteries were charged to 3 V at 1 mA and then discharged to 2.0 V, and charge / discharge characteristics were measured. FIG.
Shows the results. Battery A according to the present invention exhibited a discharge capacity of 20 mAh, whereas Comparative Battery B exhibited only a discharge capacity of 10 mAh.
【００１３】このように本発明によって充放電容量の向
上が実現できた。As described above, the improvement of the charge / discharge capacity can be realized by the present invention.
【００１４】従来負極に用いられている種々の炭素材料
はリチウムイオンをインターカレートすることができる
が、その層間距離が容量に影響することが発明者らの研
究で明らかになっている。Various carbon materials conventionally used for the negative electrode can intercalate lithium ions, but it has been found by the inventors that the interlayer distance affects the capacity.
【００１５】然し乍ら、従来の方法では層間距離は主に
炭素材料の処理温度によって制御されるため、均一な層
間をもつ炭素材料を得るのは非常に困難である。また、
炭素材料により制御できる層間距離の範囲が異なる上、
熱をかけることで黒鉛化が進み、リチウムイオンのイン
ターカレートがしにくくなる欠点があった。However, in the conventional method, since the interlayer distance is mainly controlled by the processing temperature of the carbon material, it is very difficult to obtain a carbon material having a uniform interlayer. Also,
The range of interlayer distances that can be controlled differs depending on the carbon material.
There was a drawback that the application of heat promoted graphitization and made it difficult to intercalate lithium ions.
【００１６】それに対して、本発明においては適当な大
きさのアニオンあるいはカチオンを炭素材料にインター
カレートすることで層間距離をこれらの挿入物の大きさ
により制御することが可能であり、均一で高容量の炭素
材料が生成できる。On the other hand, in the present invention, by intercalating an anion or cation of an appropriate size to the carbon material, the interlayer distance can be controlled by the size of these inserts, and the uniformity can be obtained. High capacity carbon materials can be produced.
【００１７】本発明において用られる炭素材料として
は、コークス（石油コークス、石炭コークス、ピッチコ
ークス、ニードルコークスなど）、無定形炭素（アセチ
レンブラック、ケッチンブラック）、黒鉛、膨張黒鉛、
発泡黒鉛、高分子熱処理炭化物などどのような炭素材料
が適している。The carbon material used in the present invention includes coke (petroleum coke, coal coke, pitch coke, needle coke, etc.), amorphous carbon (acetylene black, ketchin black), graphite, expanded graphite,
Any carbon material is suitable, such as expanded graphite and carbide-treated polymer.
【００１８】また、本発明において用いるアニオンとし
ては、希望の層間距離に相当するものならなんでも良
く、ＢＦ4-、ＣｌＯ4-、ＰＦ6-、ＣＦ3ＳＯ3-、Ｂ10Ｃ
ｌ10-、Ｂ12Ｃｌ12-、Ｃｌ-、Ｆ-などのハロゲンが挙げ
られる。The anion used in the present invention may be any anion corresponding to a desired interlayer distance, such as BF4-, ClO4-, PF6-, CF3SO3-, B10C
halogens such as 110-, B12Cl12-, Cl- and F-.
【００１９】[0019]
【００２０】処理温度はこれらの挿入物が分解、或いは
気化する温度であれば良く、また黒鉛化される程の高温
にする必要はない。The treatment temperature may be any temperature at which these inserts decompose or vaporize, and need not be so high as to be graphitized.
【００２１】[0021]
【発明の効果】本発明は以上の説明から明らかなよう
に、アニオンを挿入した後、該アニオンが分解、或いは
気化する温度以上で黒鉛化温度より低い温度で熱処理し
てそのアニオンを除去することによって、層間距離が上
記アニオンの大きさに拡大された炭素材料を負極として
用いているので、その負極がリチウムイオンをインター
カレートし易くなり、非水系二次電池の充放電容量の向
上が実現し、その工業的価値は非常に大きい。According to the present invention As apparent from the above description, after inserting the anion, the anion is decomposed, or more vaporization temperature and heat-treated at a temperature lower than the graphitization temperature to remove the anion As a result, the carbon material whose interlayer distance is enlarged to the size of the anion is used as the negative electrode, so that the negative electrode can easily intercalate lithium ions, thereby improving the charge / discharge capacity of the nonaqueous secondary battery. And its industrial value is very large.
【図１】本発明電池の構造を示す断面図である。FIG. 1 is a sectional view showing the structure of the battery of the present invention.
【図２】本発明電池の充放電特性を従来電池と比較して
示した特性図である。FIG. 2 is a characteristic diagram showing the charge / discharge characteristics of the battery of the present invention in comparison with a conventional battery.
１ 負極 ２ 正極 ３ セパレーター 1 negative electrode 2 positive electrode 3 separator
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平３−134970（ＪＰ，Ａ) 特開 昭58−157064（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 4/58 H01M 4/02 - 4/04 H01M 10/40 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-3-134970 (JP, A) JP-A-58-157064 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) H01M 4/58 H01M 4/02-4/04 H01M 10/40
Claims (1)
る非水系二次電池において、該負極としてアニオンを挿
入した後、該アニオンが分解、或いは気化する温度以上
で黒鉛化温度より低い温度で熱処理してそのアニオンを
除去して層間距離が上記アニオンの大きさに拡大された
炭素材料を用いたことを特徴とする非水系二次電池。1. A non-aqueous secondary battery comprising a positive electrode, a negative electrode, and a non-aqueous electrolyte as main components. After inserting an anion as the negative electrode, the temperature is higher than a temperature at which the anion is decomposed or vaporized. A non-aqueous secondary battery using a carbon material whose heat treatment is performed at a temperature lower than the graphitization temperature to remove its anions and to increase the interlayer distance to the size of the anions .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3243592A JP3021837B2 (en) | 1991-09-24 | 1991-09-24 | Non-aqueous secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3243592A JP3021837B2 (en) | 1991-09-24 | 1991-09-24 | Non-aqueous secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0582130A JPH0582130A (en) | 1993-04-02 |
| JP3021837B2 true JP3021837B2 (en) | 2000-03-15 |
Family
ID=17106111
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3243592A Expired - Fee Related JP3021837B2 (en) | 1991-09-24 | 1991-09-24 | Non-aqueous secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3021837B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2127621C (en) * | 1994-07-08 | 1999-12-07 | Alfred Macdonald Wilson | Carbonaceous insertion compounds and use as anodes in rechargeable batteries |
| JP4617702B2 (en) * | 2004-04-15 | 2011-01-26 | トヨタ自動車株式会社 | Lithium secondary battery and manufacturing method thereof |
| JP5057294B2 (en) * | 2008-09-30 | 2012-10-24 | 株式会社日立プラントテクノロジー | Animal breeding room |
| JP6285643B2 (en) * | 2013-03-04 | 2018-02-28 | 積水化学工業株式会社 | Negative electrode material for lithium ion secondary battery, method for producing the same, and lithium ion secondary battery |
| JP2017112080A (en) * | 2015-12-15 | 2017-06-22 | 株式会社パワージャパンプリュス | Positive electrode active material for nonaqueous electrolyte secondary battery, nonaqueous electrolyte secondary battery, and its manufacturing method and system |
| CN110707323B (en) * | 2019-09-27 | 2022-12-27 | 太原理工大学 | Anion layer-expanding carbon material and preparation method and application thereof |
-
1991
- 1991-09-24 JP JP3243592A patent/JP3021837B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0582130A (en) | 1993-04-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6835215B2 (en) | Non-aqueous secondary battery and a method of manufacturing graphite powder | |
| CN100511784C (en) | Electrode active material with molti-element based oxide layers and preparation method thereof | |
| JP2940172B2 (en) | Non-aqueous electrolyte secondary battery | |
| US6759168B2 (en) | Nonaqueous secondary battery with lithium titanium cathode | |
| JPH05190209A (en) | Liquid electrolyte and rechargeable chemical cell with lithium/carbon anode | |
| KR20080029479A (en) | Cathode active material, lithium secondary battery comprising same, and hybrid capacitor comprising same | |
| JP3133318B2 (en) | Rechargeable battery | |
| JP3021837B2 (en) | Non-aqueous secondary battery | |
| JPH1097870A (en) | Lithium secondary battery | |
| JP3239302B2 (en) | Organic electrolyte secondary battery | |
| JPH08213014A (en) | Nonaqueous electrolyte secondary battery | |
| JP3054473B2 (en) | Rechargeable battery | |
| US10777805B2 (en) | Negative electrode active material containing graphite material and battery including negative electrode containing negative electrode active material | |
| JPH0737618A (en) | Nonaqueous electrolyte secondary battery | |
| KR100269918B1 (en) | A negative active material for a lithium-based secondary cell and a method of preparing the same | |
| US20060228630A1 (en) | Non-aqueous secondary battery having negative electrode including graphite powder | |
| KR102244226B1 (en) | Silicon Composite Anode Active Material including Network of Conductive Fibers, Manufacturing method thereof and Lithium Secondary Battery Comprising the Same | |
| JP2008257888A (en) | Carbon material for electrode of electrochemical element, manufacturing method therefor, and electrode for electrochemical element | |
| JP6396040B2 (en) | Negative electrode material for lithium secondary battery, method for producing the same, negative electrode for lithium secondary battery and lithium secondary battery using the negative electrode material | |
| JPH1050312A (en) | Nonaqueous electrolyte secondary battery | |
| JP3041738B2 (en) | Method for producing carbonaceous material and secondary battery | |
| JP3104264B2 (en) | Coin type non-aqueous electrolyte secondary battery | |
| JP2647015B2 (en) | Non-aqueous electrolyte secondary battery | |
| JP3518543B2 (en) | Manufacturing method of secondary battery | |
| JPH09259891A (en) | Nonaqueous electrolyte secondary battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090114 Year of fee payment: 9 |
|
| LAPS | Cancellation because of no payment of annual fees |