JPH08102319A - Nonaqueous secondary battery - Google Patents
Nonaqueous secondary batteryInfo
- Publication number
- JPH08102319A JPH08102319A JP6237878A JP23787894A JPH08102319A JP H08102319 A JPH08102319 A JP H08102319A JP 6237878 A JP6237878 A JP 6237878A JP 23787894 A JP23787894 A JP 23787894A JP H08102319 A JPH08102319 A JP H08102319A
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- secondary battery
- positive electrode
- battery
- electrolyte
- 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]
【産業上の利用分野】本発明は、非水系二次電池に関す
るものである。より詳しくは、特に小型、軽量の電子機
器用として好適な、リチウム二次電池を初めとする非水
系二次電池に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous secondary battery. More specifically, the present invention relates to a non-aqueous secondary battery such as a lithium secondary battery, which is suitable for small and lightweight electronic devices.
【０００２】[0002]
【従来の技術】近年、電子機器等の小型軽量化、省電力
化及び環境の保全の立場から、鉛蓄電池やニッカド電池
に替わるクリーンな非水系電池、特にリチウム二次電池
が注目され、実用段階にまで到達した。しかし、負極に
リチウム金属を用いると、リチウム金属が充電時にデン
ドライト状に成長し、内部短絡を引き起こすという問題
があった。その対策として、リチウム金属原子を吸収・
放出することのできる材料の開発が盛んに行われ、その
中でもコークスを用いたものは低コスト・高容量という
点で有望視されている（特開昭６２−９０８６３号、特
開平１−２２１８５９号、特開昭６３−１２１２５７号
公報）。2. Description of the Related Art In recent years, clean non-aqueous batteries, particularly lithium secondary batteries, which replace lead-acid batteries and nickel-cadmium batteries have been attracting attention from the standpoints of downsizing and weight saving of electronic devices, power saving, and environmental protection. Reached to. However, when lithium metal is used for the negative electrode, there is a problem that the lithium metal grows in a dendrite shape during charging and causes an internal short circuit. As a countermeasure, absorb lithium metal atoms
Materials that can be released are actively developed, and among them, those using coke are promising in terms of low cost and high capacity (JP-A-62-90863, JP-A-1-221859). , JP-A-63-1212257).
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、従来の
石炭系または石油系のコークスを用いて、電池を作成し
ても、充・放電容量が充分満足するものでなかった。ま
た、高特性の電池特性を有する提案は報告されている
が、実用的には石炭系または石油系のコークスが優れて
おり、今一なのが現状である。この理由は、炭素のどの
特性が電池特性に影響を及ぼすのか解っていないためで
ある。However, even if a battery is prepared by using conventional coal-based or petroleum-based coke, the charge / discharge capacity is not sufficiently satisfied. Further, although proposals having high battery characteristics have been reported, coal-based or petroleum-based coke is excellent in practical use, and it is the current situation. The reason for this is that it is not known which properties of carbon affect the battery properties.
【０００４】たとえば、種々の有機質を原料とする炭化
物が提案されており、特性的に見ても、特開平２−６６
８５６号公報の提案では真密度が１．７０未満、特公平
４−２４８３１号公報の提案では真密度が１．７０〜
２．１８、特公昭６２−２３４３３号公報の提案では材
料が黒鉛であり、真密度が２．１８以上のものになり、
真密度から見ると、炭素ならなんでもよいことになる。
その他に、Ｘ線回折よりのｄ002 、Ｌｃ、ラマンスペク
トル分析、元素分析による提案も報告されているが同様
の状況である。つまり、炭素のどの特性が電池特性に及
ぼすのか全く解っていないのが、現状である。For example, carbides made from various organic materials have been proposed, and even in terms of characteristics, they are disclosed in JP-A-2-66.
The true density is less than 1.70 in the proposal of Japanese Patent Publication No. 856,856, and the true density is 1.70 to in the proposal of Japanese Patent Publication No. 4-24831.
2.18, Japanese Patent Publication No. 62-23433 proposes that the material is graphite and the true density is 2.18 or more.
In terms of true density, any carbon will do.
In addition, proposals based on d 002 , Lc, Raman spectrum analysis and elemental analysis based on X-ray diffraction have been reported, but the situation is similar. In other words, it is the current situation that it is not known at all which characteristics of carbon affect the battery characteristics.
【０００５】[0005]
【課題を解決するための手段】そこで、本発明者等は、
上記の課題を解決すべく鋭意検討した結果、炭素中のト
チウム金属原子を取り込み、かつほぼ完全に放出する場
所が、結晶部分の他に水銀法による半径２〜０．０１μ
ｍの気孔部分であることを見いだし、本発明に到達し
た。Therefore, the present inventors have
As a result of diligent studies to solve the above-mentioned problems, the place where the totium metal atom in carbon is taken in and almost completely released is a radius of 2 to 0.01 μ by the mercury method in addition to the crystal part.
The present invention has been reached by finding that it is a pore portion of m.
【０００６】すなわち、本発明の目的は、高容量、かつ
サイクル使用による充・放電容量の低下が少ない等の電
池特性に優れた電池を提供することに存する。かかる本
発明の目的は、正極、負極および非水溶媒中に電解質を
溶解させた電解液を備えてなる非水系二次電池におい
て、負極材料として水銀法による半径２〜０．０１μｍ
の気孔量が１５〜１００ｍｍ3 ／ｇの炭素質材料を用い
ることによって達成される。That is, an object of the present invention is to provide a battery having excellent battery characteristics such as a high capacity and a small decrease in charge / discharge capacity due to cycle use. Such an object of the present invention is to provide a non-aqueous secondary battery comprising a positive electrode, a negative electrode and an electrolytic solution in which an electrolyte is dissolved in a non-aqueous solvent, and as a negative electrode material, a radius of 2 to 0.01 μm measured by the mercury method.
It is achieved by using a carbonaceous material having a porosity of 15 to 100 mm 3 / g.
【０００７】以下、本発明を詳細に説明する。まず、本
発明においては、負極材料として水銀法による半径２〜
０．０１μｍの気孔量が１５〜１００ｍｍ3 ／ｇの炭素
質材料を用いることが必要である。この気孔量が１５ｍ
ｍ3 ／ｇ未満であると充・放電容量の増加が小さく、一
方１００ｍ3 ／ｇを超えると多孔質化し、重量当りの充
・放電容量は大きいが、体積当りの充・放電容量が小さ
くなってしまうためである。Hereinafter, the present invention will be described in detail. First, in the present invention, as a negative electrode material, a radius of 2
It is necessary to use a carbonaceous material having a pore volume of 0.01 μm of 15 to 100 mm 3 / g. This porosity is 15m
If it is less than m 3 / g, the increase in charge / discharge capacity is small, while if it exceeds 100 m 3 / g, it becomes porous and the charge / discharge capacity per weight is large, but the charge / discharge capacity per volume becomes small. This is because it will end up.
【０００８】本発明において、上記の炭素質材料を得る
ための原料としては、石油系もしくは石炭系重質油等の
ように易黒鉛化性炭素を与えるもの、又はフェノール樹
脂等のように難黒鉛化性炭素を与えるもの、いずれも使
用しうる。そして、上記の気孔量が１５〜１００ｍｍ3
／ｇとするために、気孔量を増加させる方法としては種
々の方法を採用しうる。In the present invention, as a raw material for obtaining the above-mentioned carbonaceous material, those which give easily graphitizable carbon such as petroleum-based or coal-based heavy oil, or non-graphite such as phenol resin are used. Any of those which give a volatile carbon may be used. And the above-mentioned porosity is 15 to 100 mm 3.
Various methods can be adopted as a method of increasing the amount of pores in order to set the amount to / g.
【０００９】コールタールピッチを原料とした場合の例
を挙げると、芳香族指数（ｆａ）の低いコールタール
ピッチを原料とする、コールタールピッチ中の軽沸分
を還流させながらコーキングする、カーボンブラック
等を添加しコーキングする、水蒸気、炭酸ガス等と共
に加熱と同時に賦活しながら焼成する等の一種類以上を
用いることができる。An example of using coal tar pitch as a raw material is carbon black obtained from coal tar pitch having a low aromatic index (fa) as a raw material and caulking while refluxing light boiling components in the coal tar pitch. It is possible to use one or more types such as caulking with addition of the above, or baking with activating while simultaneously heating with steam and carbon dioxide gas.
【００１０】また、フェノール樹脂においても、エタノ
ール等の溶媒を残して硬化させる方法、焼成の昇温速度
を大きくする方法、水蒸気賦活法、等、種々の方法を採
用しうる。どの方法を採用しても、水銀法による半径２
〜０．０１μｍの気孔量が１５〜１００ｍｍ2 ／ｇの間
に入っていればよい。これらの炭素材料の最終的な加熱
処理温度は、目的に応じて６００〜１５００℃程度から
選択しうる。Also for the phenol resin, various methods such as a method of curing while leaving a solvent such as ethanol, a method of increasing the temperature rising rate of firing, a steam activation method, and the like can be adopted. No matter which method is used, the radius of the mercury method is 2
It is sufficient that the porosity of 0.01 μm falls within the range of 15 to 100 mm 2 / g. The final heat treatment temperature of these carbon materials can be selected from about 600 to 1500 ° C. depending on the purpose.
【００１１】これらの炭素質材料は非水系二次電池の負
極として用いられるが、その粒径は最大粒径が５０μｍ
以下、最小粒径が３μｍ以上であるのが好ましい。正極
および非水溶媒中に電解質を溶解させてなる電解液につ
いては、従来、非水系二次電池に用いられているもので
よく、特に限定されない。具体的には、正極としては、
ＬｉＣｏＯ2 、ＭｎＯ2 、ＴｉＳ2 、ＦｅＳ2 、Ｎｂ3
Ｓ4 、Ｍｏ 3 Ｓ4 、ＣｏＳ2 、Ｖ2 Ｏ5 、 Ｐ2 Ｏ5 、Ｃ
ｒＯ3 、Ｖ3 Ｏ8 、ＴｅＯ2 、ＧｅＯ2 等が、電解質と
しては、ＬｉＣｌＯ4 、ＬｉＢＦ4 、ＬｉＰＦ6 等が、
電解液を溶解する非水溶媒としては、プロピレンカーボ
ネート、テトラヒドロフラン、１，２−ジメトキシエタ
ン、ジメチルスルホキシド、ジオキソラン、ジメチルホ
ルムアミド、ジメチルアセトアミド、およびこれらの２
種以上の混合溶媒等が用いられる。These carbonaceous materials are used in non-aqueous secondary batteries.
Used as a pole, the maximum particle size is 50 μm
Hereinafter, the minimum particle size is preferably 3 μm or more. Positive electrode
And an electrolyte solution prepared by dissolving an electrolyte in a non-aqueous solvent.
In other words, it has been used for non-aqueous secondary batteries in the past.
Well, it is not particularly limited. Specifically, as the positive electrode,
LiCoO2, MnO2, TiS2, FeS2, Nb3
SFour, Mo 3SFour, CoS2, V2OFive, P2OFive, C
rO3, V3O8, TeO2, GeO2Etc. with electrolyte
Then LiClOFour, LiBFFour, LiPF6Etc.
The non-aqueous solvent that dissolves the electrolyte is propylene carbonate.
Nate, tetrahydrofuran, 1,2-dimethoxyethane
Amine, dimethyl sulfoxide, dioxolane, dimethylphore
Lumamide, dimethylacetamide, and these two
A mixed solvent of at least one species is used.
【００１２】中でも、最も好ましい組合せは、ＬｉＣｏ
Ｏ2 −ＬｉＰＦ6 −プロピレンカーボネートと１，２−
ジメトキシエタンである。セパレータは、電池の内部抵
抗を小さくするために多孔体が好適であり、ポリプロピ
レン等の不織布、ガラスフィルターなどの耐有機溶媒性
材料のものが用いられる。Among them, the most preferable combination is LiCo.
O 2 -LiPF 6 - propylene carbonate and 1,2
It is dimethoxyethane. The separator is preferably a porous body in order to reduce the internal resistance of the battery, and a non-woven fabric such as polypropylene or an organic solvent resistant material such as a glass filter is used.
【００１３】これらの負極、正極、電解液及びセパレー
タは、たとえばステンレススチールまたはこれにニッケ
ルメッキした電池ケースに組み込むのが一般的である。
電池構造としては、帯状の正極、負極をセパレータを介
してうず巻き状にしたスパイラル構造またはボタン型ケ
ースにペレット状の正極、円盤状の負極をセパレータを
介して挿入する方法などが採用される。以下、本発明を
実施例により、更に詳細に説明するが、本発明は、その
要旨を超えない限り、以下実施例によって限定されるも
のでない。The negative electrode, the positive electrode, the electrolytic solution and the separator are generally incorporated in, for example, a stainless steel or a nickel plated battery case.
As the battery structure, a spiral structure in which a band-shaped positive electrode and a negative electrode are spirally wound with a separator interposed therebetween, or a method in which a pellet-shaped positive electrode and a disk-shaped negative electrode are inserted into a button-shaped case through a separator is adopted. Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.
【００１４】[0014]
（実施例１）コールタールピッチをオートクレーブで４
８０℃・３０時間熱処理して、生コークスを得た。該生
コークスをハンマーミルにて４４μｍ以下に粉砕し、不
活性雰囲気下、１０００℃にて３時間焼成し、水銀法に
よる半径２〜０．０１μｍの気孔量が２２ｍｍ3 ／ｇの
本発明のコークスを得た。(Example 1) 4 coal tar pitch was autoclaved
Heat treatment was performed at 80 ° C. for 30 hours to obtain raw coke. The raw coke was crushed to 44 μm or less by a hammer mill, and calcined at 1000 ° C. for 3 hours in an inert atmosphere, and the coke of the present invention having a radius of 2 to 0.01 μm and a porosity of 22 mm 3 / g by a mercury method. Got
【００１５】図１に本発明の実施例としてのボタン型非
水系二次電池の半断面図を示す。ここで、負極１は本発
明のコークスから構成される。この負極は、負極集電体
２の内面に接合されており、この集電体２はフェライト
系ステンレス鋼（ＳＵＳ４３０）からなる負極缶３の内
部に固着されている。前記負極缶３の周端は、ポリプロ
ピレン製の絶縁パッキング４の内部に固定されており、
絶縁パッキング４の外周には、ステンレスからなる前記
負極缶３とは反対方向に正極缶５が固定されている。こ
の正極缶５の内底面には正極集電体６が固定されてお
り、この正極集電体６の内面には正極７が固定されてい
る。この正極７と前記負極１との間には、セパレータが
介在されており、ここには電解質が溶解された電解液が
含浸されている。FIG. 1 is a half sectional view of a button type non-aqueous secondary battery as an embodiment of the present invention. Here, the negative electrode 1 is composed of the coke of the present invention. The negative electrode is joined to the inner surface of the negative electrode current collector 2, and the current collector 2 is fixed inside the negative electrode can 3 made of ferritic stainless steel (SUS430). The peripheral edge of the negative electrode can 3 is fixed inside a polypropylene insulating packing 4,
A positive electrode can 5 is fixed to the outer periphery of the insulating packing 4 in a direction opposite to the negative electrode can 3 made of stainless steel. A positive electrode current collector 6 is fixed to the inner bottom surface of the positive electrode can 5, and a positive electrode 7 is fixed to the inner surface of the positive electrode current collector 6. A separator is interposed between the positive electrode 7 and the negative electrode 1 and is impregnated with an electrolytic solution in which an electrolyte is dissolved.
【００１６】そして、前記負極は本発明コークスとポリ
プロピレン粉末と９０：１０の重量比で混合したものを
加圧成形して作成した。また、正極はＬｉＣｏＯ2 と導
電剤としてのアセチレンブラックと結着剤としてのフッ
素樹脂とを、８５：１０：５の重量比で混合したものを
加圧成形して作成した。The negative electrode was prepared by pressure molding a mixture of the coke of the present invention and polypropylene powder in a weight ratio of 90:10. The positive electrode was prepared by pressure molding a mixture of LiCoO 2 , acetylene black as a conductive agent, and fluororesin as a binder in a weight ratio of 85: 10: 5.
【００１７】また、電解液にはプロピレンカーボネート
（ＰＣ）と１，２−ジメトキシエタンの混合溶媒（溶媒
比で１：１）に、電解質としてＬｉＰＦ6 を１モル／リ
ットルの割合で溶解したものを用いた。尚、この電池の
容量に関しては、正極に比べて、負極を十分小さくし、
負極支配になるように設定している。この電池を充電電
流及び放電電流１ｍＡ／ｃｍ2 とし、充電は３．６Ｖま
で、放電は２．５Ｖまで行った。結果を表１に示す。The electrolytic solution is prepared by dissolving LiPF 6 as an electrolyte in a mixed solvent of propylene carbonate (PC) and 1,2-dimethoxyethane (a solvent ratio of 1: 1) at a ratio of 1 mol / liter. Using. Regarding the capacity of this battery, the negative electrode was made sufficiently smaller than the positive electrode,
It is set so that the negative electrode is dominant. The battery was charged at a charging current and a discharging current of 1 mA / cm 2 , charged up to 3.6 V and discharged up to 2.5 V. The results are shown in Table 1.
【００１８】（実施例２）実施例１の生コークスを不活
性雰囲気下で８００℃加熱処理を実施した以外は実施例
１と同様にした。結果を表１に示す。(Example 2) The same procedure as in Example 1 was carried out except that the raw coke of Example 1 was heat-treated at 800 ° C in an inert atmosphere. The results are shown in Table 1.
【００１９】（実施例３）実施例１の生コークスを粉砕
しないで９００℃にて２時間、一旦冷却後１１００℃に
て３時間焼成後粉砕し、平均粒径４４μｍに調製した以
外は実施例１と同様にした。結果を表１に示す。(Example 3) The raw coke of Example 1 was crushed for 2 hours at 900 ° C without crushing, once cooled and then calcined for 3 hours at 1100 ° C and then crushed to prepare an average particle size of 44 µm. Same as 1. The results are shown in Table 1.
【００２０】（実施例４）実施例１の生コークスを不活
性雰囲気下で６００℃・１０時間加熱処理を実施した以
外は実施例１と同様にした。結果を表１に示す。(Example 4) The procedure of Example 1 was repeated, except that the raw coke of Example 1 was heat-treated at 600 ° C for 10 hours in an inert atmosphere. The results are shown in Table 1.
【００２１】（比較例１）実施例１の生コークスを不活
性雰囲気下で１３００℃加熱処理を実施した以外は実施
例１と同様にした。結果を表１に示す。Comparative Example 1 The same procedure as in Example 1 was carried out except that the raw coke of Example 1 was heat-treated at 1300 ° C. in an inert atmosphere. The results are shown in Table 1.
【００２２】[0022]
【表１】 ５００サイクル後の容量は全例でその値はほとんど低下
しなかった。 水銀気孔量；カルロエルバ社製水銀気孔量計による測定
値である。[Table 1] The capacity after 500 cycles did not decrease in all cases. Mercury porosity: The value measured by a mercury porosimeter manufactured by Carlo Erba.
【００２３】[0023]
【発明の効果】本発明の非水系二次電池は高容量、かつ
サイクル使用による充・放電容量の低下の少ない等の電
池特性に優れた電池を提供しうる。INDUSTRIAL APPLICABILITY The non-aqueous secondary battery of the present invention can provide a battery having a high capacity and excellent battery characteristics such as less decrease in charge / discharge capacity due to cycle use.
【図１】本発明非水二次電池の一例であるボタン型非水
電解液二次電池の断面説明図である。FIG. 1 is a cross-sectional explanatory view of a button type non-aqueous electrolyte secondary battery which is an example of the non-aqueous secondary battery of the present invention.
【符号の説明】 １ 負極 ２ 負極集電体 ３ 負極缶 ４ 絶縁パッキング ５ 正極缶 ６ 正極集電体 ７ 正極[Explanation of symbols] 1 negative electrode 2 negative electrode current collector 3 negative electrode can 4 insulating packing 5 positive electrode can 6 positive electrode current collector 7 positive electrode
Claims (1)
溶解させた電解液を備えてなる非水系二次電池におい
て、負極として水銀法による半径２〜０．０１μｍの気
孔量が１５〜１００ｍｍ3 ／ｇの炭素質材料を用いてな
る非水系二次電池。1. A non-aqueous secondary battery comprising a positive electrode, a negative electrode and an electrolytic solution in which an electrolyte is dissolved in a non-aqueous solvent, wherein the negative electrode has a porosity of 2 to 0.01 μm and a radius of 2 to 0.01 μm of 15 to 100 mm. A non-aqueous secondary battery using 3 / g of carbonaceous material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6237878A JPH08102319A (en) | 1994-09-30 | 1994-09-30 | Nonaqueous secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6237878A JPH08102319A (en) | 1994-09-30 | 1994-09-30 | Nonaqueous secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08102319A true JPH08102319A (en) | 1996-04-16 |
Family
ID=17021766
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6237878A Pending JPH08102319A (en) | 1994-09-30 | 1994-09-30 | Nonaqueous secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08102319A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08287911A (en) * | 1995-04-18 | 1996-11-01 | Mitsubishi Chem Corp | Nonaqueous secondary battery |
| US6994763B2 (en) | 2002-10-24 | 2006-02-07 | Advanced Design Concept Gmbh | Elastomeric multicomponent fibers, nonwoven webs and nonwoven fabrics |
| JP2007115749A (en) * | 2005-10-18 | 2007-05-10 | Nippon Oil Corp | Method of manufacturing carbon material for electric double layer capacitor electrode |
-
1994
- 1994-09-30 JP JP6237878A patent/JPH08102319A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08287911A (en) * | 1995-04-18 | 1996-11-01 | Mitsubishi Chem Corp | Nonaqueous secondary battery |
| US6994763B2 (en) | 2002-10-24 | 2006-02-07 | Advanced Design Concept Gmbh | Elastomeric multicomponent fibers, nonwoven webs and nonwoven fabrics |
| JP2007115749A (en) * | 2005-10-18 | 2007-05-10 | Nippon Oil Corp | Method of manufacturing carbon material for electric double layer capacitor electrode |
| JP4708152B2 (en) * | 2005-10-18 | 2011-06-22 | Ｊｘ日鉱日石エネルギー株式会社 | Method for producing carbon material for electric double layer capacitor electrode |
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