JPH05314975A - Secondary battery - Google Patents
Secondary batteryInfo
- Publication number
- JPH05314975A JPH05314975A JP4114881A JP11488192A JPH05314975A JP H05314975 A JPH05314975 A JP H05314975A JP 4114881 A JP4114881 A JP 4114881A JP 11488192 A JP11488192 A JP 11488192A JP H05314975 A JPH05314975 A JP H05314975A
- Authority
- JP
- Japan
- Prior art keywords
- secondary battery
- negative electrode
- aromatic hydrocarbon
- heat
- polycyclic aromatic
- 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
(57)【要約】
【目的】 放電容量の大きい二次電池を提供する。
【構成】 炭素質物質を活物質とする負極と、非水溶媒
にアルカリ金属塩を溶解した電解液を持つ二次電池にお
いて、該負極が、縮合多環芳香族炭化水素化合物を一種
類もしくは二種類以上組み合わせたものを架橋剤又はル
イス酸触媒を用いて重縮合させたのち５００℃以上の温
度で熱処理した物質からなることを特徴とする二次電
池。(57) [Abstract] [Purpose] To provide a secondary battery having a large discharge capacity. In a secondary battery having a negative electrode using a carbonaceous material as an active material and an electrolytic solution in which an alkali metal salt is dissolved in a non-aqueous solvent, the negative electrode contains one or two condensed polycyclic aromatic hydrocarbon compounds. A secondary battery comprising a material obtained by polycondensing a combination of two or more kinds using a cross-linking agent or a Lewis acid catalyst and then heat-treating at a temperature of 500 ° C. or higher.
Description
【０００１】[0001]
【従来の技術】近年、ビデオカメラや携帯電話などの普
及に併い、繰り返し使用できる二次電池に対する需要が
急速に高まっている。現在使用されている二次電池の大
部分はニッケル−カドミウム電池である。しかし、当電
池の電圧は約１．２Ｖと低いために、電池のエネルギー
密度を向上することは困難である。そこで、負極にリチ
ウム等のアルカリ金属を使用し、電解液に非水溶媒を使
用することによって、電圧が３Ｖ以上と高い二次電池が
検討された。しかし、このような二次電池では負極に使
用されているリチウム等が、充放電の繰返しによってデ
ンドライト状に成長し、この負極と正極が短絡してしま
うという不都合が起り易かった。そこで例えば、特開昭
６２−９０８６３号公報に示されているように、コーク
ス等の炭素質材料を負極として使用する二次電池が提案
された。この提案によって上述のような充放電の繰返し
による負極の劣化問題を回避できることが判った。ここ
で炭素質材料は、アルカリ金属イオンのドーピング、脱
ドーピングによって二次電池の負極として作用し、正極
はアルカリ金属イオンのカウンターアニオンがドーピン
グ、脱ドーピングして作用すると述べられている。しか
しながら炭素質材料を負極として使用した場合に、まだ
放電容量の絶対値レベルが低いのが現状である。2. Description of the Related Art In recent years, along with the widespread use of video cameras and mobile phones, demand for rechargeable secondary batteries has been rapidly increasing. Most of the secondary batteries currently used are nickel-cadmium batteries. However, since the voltage of this battery is as low as about 1.2 V, it is difficult to improve the energy density of the battery. Therefore, by using an alkali metal such as lithium for the negative electrode and using a non-aqueous solvent for the electrolytic solution, a secondary battery having a high voltage of 3 V or more has been studied. However, in such a secondary battery, lithium and the like used in the negative electrode easily grows in a dendrite state by repeated charging and discharging, and the negative electrode and the positive electrode are likely to be short-circuited. Therefore, for example, as disclosed in JP-A-62-90863, a secondary battery using a carbonaceous material such as coke as a negative electrode has been proposed. It has been found that this proposal can avoid the problem of deterioration of the negative electrode due to repeated charging and discharging as described above. Here, it is described that the carbonaceous material acts as a negative electrode of the secondary battery by doping and dedoping with alkali metal ions, and the positive electrode acts by doping and dedoping with counter anions of alkali metal ions. However, when a carbonaceous material is used as the negative electrode, the absolute value level of the discharge capacity is still low at present.
【０００２】[0002]
【課題を解決するための手段】そこで本発明者らは、か
かる課題を解決すべく鋭意検討の結果、負極に特定の熱
処理をされた特定の材料を用いることにより、かかる課
題が解決することを見出し本発明に到達した。すなわち
本発明の目的は、従来に比べて放電容量の大きい二次電
池を提供することにあり、かかる目的は、炭素質物質を
活物質とする負極と、非水溶媒にアルカリ金属塩を溶解
した電解液を持つ二次電池において、該負極が、縮合多
環芳香族炭化水素化合物を一種類もしくは二種類以上組
み合わせたものを架橋剤又はルイス酸触媒を用いて重縮
合させたのち５００℃以上の温度で熱処理した物質から
なることを特徴とする二次電池により容易に達成され
る。Therefore, as a result of intensive studies to solve the above problems, the present inventors have found that the problems can be solved by using a specific material that has been subjected to a specific heat treatment for the negative electrode. Heading The invention has been reached. That is, an object of the present invention is to provide a secondary battery having a larger discharge capacity than before, and such an object is to dissolve a negative electrode using a carbonaceous material as an active material and an alkali metal salt in a non-aqueous solvent. In a secondary battery having an electrolytic solution, the negative electrode is subjected to polycondensation of one kind or a combination of two or more kinds of condensed polycyclic aromatic hydrocarbon compounds using a cross-linking agent or a Lewis acid catalyst, and then at 500 ° C. or higher. It is easily achieved by a secondary battery characterized by comprising a material heat-treated at a temperature.
【０００３】以下本発明をより詳細に説明する。本発明
は、炭素質材料を活物質とする負極と、アルカリ金属塩
を非水溶媒に溶解した非水電解液と、正極とを有する二
次電池であって、前記炭素質材料が、縮合多環芳香族炭
化水素化合物を単体もしくは２種類以上組合せたものを
架橋剤またはルイス酸触媒を用いて重縮合させたものを
さらに高温で熱処理して炭素化したものを使用する。重
縮合反応は、反応の種類によって異なるが、縮合多環芳
香族炭化水素と架橋剤またはルイス酸触媒を混合し、通
常４００℃以下の温度にて所定時間行う。この反応はあ
まり高温で行うと副反応を誘発してしまい炭素の前駆体
としての分子構造を制御できなくなる可能性がある。こ
の理由から重縮合反応と炭素化反応を分けて行うことが
望ましい。炭素化反応は特に上限温度は制約はなく、３
０００℃程度まで行ってもよいが、放電容量および工業
的利点等を配慮すると５００℃以上１５００℃以下が好
ましい。また炭素化反応は、重縮合反応物が熱で溶融す
るものである場合には通常５００℃程度までゆるやかに
熱処理して熱重縮合、固化を行ってから、さらに高温ま
で熱処理するのが望ましい。しかしながら重縮合反応物
を直接高温まで熱処理しても何ら問題はない。The present invention will be described in more detail below. The present invention is a secondary battery comprising a negative electrode using a carbonaceous material as an active material, a non-aqueous electrolytic solution in which an alkali metal salt is dissolved in a non-aqueous solvent, and a positive electrode, wherein the carbonaceous material is a polycondensed polymer. A polyaromatic hydrocarbon compound alone or in a combination of two or more kinds is polycondensed with a crosslinking agent or a Lewis acid catalyst and further heat-treated at a high temperature to be carbonized. The polycondensation reaction, which differs depending on the type of reaction, is carried out by mixing a condensed polycyclic aromatic hydrocarbon with a crosslinking agent or a Lewis acid catalyst and usually at a temperature of 400 ° C. or lower for a predetermined time. If this reaction is carried out at an excessively high temperature, side reactions may be induced and the molecular structure of the carbon precursor may not be controlled. For this reason, it is desirable to carry out the polycondensation reaction and the carbonization reaction separately. The carbonization reaction has no particular restriction on the upper limit temperature, and 3
The temperature may be up to about 000 ° C., but 500 ° C. or more and 1500 ° C. or less is preferable in consideration of the discharge capacity and industrial advantages. When the polycondensation reaction product melts by heat, it is preferable that the carbonization reaction is usually performed by gently heat-treating to about 500 ° C. for thermal polycondensation and solidification, and then further heat-treating to a higher temperature. However, there is no problem if the polycondensation reaction product is directly heat-treated to a high temperature.
【０００４】ここで縮合多環芳香族炭化水素とは、ナフ
タレン、アントラセン、アセナフテン、アセナフチレ
ン、ピレン乃至それらに脂肪族側鎖例えばメチル基、エ
チル基などが１つもしくはそれ以上付加された誘導体が
好ましく、架橋剤としてはホルマリン、ホルマリン誘導
体、ベンズアルデヒド、テレフタルアルデヒド、パラキ
シリレングリコール、ジメチルパラキシリレングリコー
ル、キノン類などが使用できる。またルイス酸としては
三フッ化ホウ素塩化アルミニウム、臭化アルミニウム、
塩化スズ、塩化鉄、塩化亜鉛、ＨＦ・ＢＦ3 などが使用
できる。The fused polycyclic aromatic hydrocarbon is preferably naphthalene, anthracene, acenaphthene, acenaphthylene, pyrene or a derivative thereof to which one or more aliphatic side chains such as methyl group and ethyl group are added. As the cross-linking agent, formalin, formalin derivative, benzaldehyde, terephthalaldehyde, paraxylylene glycol, dimethylparaxylylene glycol, quinones and the like can be used. As the Lewis acid, boron trifluoride aluminum chloride, aluminum bromide,
Tin chloride, iron chloride, zinc chloride, HF / BF 3, etc. can be used.
【０００５】本発明に用いられる正極材料としては一般
にリチウム二次電池に用いられる例えば二酸化マンガ
ン、五酸化バナジウムのような遷移金属化合物、リチウ
ム合金、硫化鉄等の遷移金属カルコゲン化合物等が好適
に使用できる。電解液としては、アルカリ金属塩を非水
溶媒に溶解したものが使用できるが、中でもリチウム塩
が好ましい。リチウム塩としては従来より公知のものが
いづれも使用可能であり、ＬｉＣｌＯ4 ，ＬｉＢＦ4 ，
ＬｉＢｒ，ＬｉＣｌ，ＬｉＰＦ6 ，ＬｉＡｓＦ6，Ｌｉ
Ｂ（Ｃ6 Ｈ5 ）4 ，ＣＨ2 ＳＯ3 Ｌｉ，ＣＦ3 ＳＯ3 Ｌ
ｉ等が好ましい。また非水溶媒としては例えば、プロピ
レンカーボネート、エチレンカーボネート、１，２−ジ
メトキシエタン、１，２−ジエトキシエタン、γ−ブチ
ロラクトン、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、プロピオニトリル等があるが特に限定されるもので
はなく、単独もしくは２種以上混合して使用できる。As the positive electrode material used in the present invention, transition metal compounds such as manganese dioxide and vanadium pentoxide, which are generally used for lithium secondary batteries, lithium alloys, transition metal chalcogen compounds such as iron sulfide are preferably used. it can. As the electrolytic solution, a solution prepared by dissolving an alkali metal salt in a non-aqueous solvent can be used, and among them, a lithium salt is preferable. As the lithium salt, any conventionally known one can be used, such as LiClO 4 , LiBF 4 ,
LiBr, LiCl, LiPF 6 , LiAsF 6 , Li
B (C 6 H 5 ) 4 , CH 2 SO 3 Li, CF 3 SO 3 L
i and the like are preferable. Examples of the non-aqueous solvent include propylene carbonate, ethylene carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane, γ-butyrolactone, tetrahydrofuran, 1,3-dioxolane, 4-methyl-1,3-dioxolane. , Diethyl ether, sulfolane, methyl sulfolane, acetonitrile, propionitrile and the like, but are not particularly limited, and they can be used alone or in combination of two or more.
【０００６】以上本発明を実施例を用いてより詳細に説
明するが、本発明はその要旨を超えない限り、実施例に
限定されるものではない。The present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples as long as the gist thereof is not exceeded.
【０００７】[0007]
【実施例−１】ピレン１モルにベンズアルデヒドを１．
２４６倍重量及びパラトルエンスルホン酸をピレン＋ベ
ンズアルデヒドの５重量％量加えて、還流下１６０℃で
重縮合反応を行い、Ｂステージの樹脂状物を得た。この
樹脂をガラスチューブに入れてＮ2 ガスを吹込みながら
５００℃で熱処理し、さらにＮ2 流通下８００℃で熱処
理した。Example 1 1 mol of pyrene was mixed with 1.
246 times weight and p-toluenesulfonic acid were added in an amount of 5% by weight of pyrene + benzaldehyde, and polycondensation reaction was carried out at 160 ° C. under reflux to obtain a B-stage resinous material. This resin was put in a glass tube, heat-treated at 500 ° C. while blowing N 2 gas, and further heat-treated at 800 ° C. under N 2 flow.
【０００８】この熱処理物を粉砕したもの９０重量部に
ポリフッ化ビニリデン１０重量部及びジメチルホルムア
ミドを加えて、ＳＵＳ網にはさんで５．２ ton／cm2 の
圧力で圧縮成形した。その後１００℃で減圧乾燥して負
極を作製した。正極はＬｉ合金を活物質とし、導電剤と
して黒鉛粉末、結着剤としてポリテトラフルオロエチレ
ンを混合したものをＳＵＳ網にはさんで５．２ ton／cm
2 の圧力で圧縮成形した。その後１００℃で減圧乾燥し
て正極を作製した。To 90 parts by weight of the pulverized product of this heat treatment, 10 parts by weight of polyvinylidene fluoride and dimethylformamide were added, and the mixture was sandwiched between SUS nets and compression molded at a pressure of 5.2 ton / cm 2 . Then, it was dried under reduced pressure at 100 ° C. to prepare a negative electrode. The positive electrode was made of Li alloy as an active material, graphite powder as a conductive agent, and polytetrafluoroethylene as a binder, and a mixture of 5.2 ton / cm was inserted in the SUS net.
It was compression molded at a pressure of 2 . Then, it was dried under reduced pressure at 100 ° C. to prepare a positive electrode.
【０００９】また電解液は、過塩素酸リチウム（和光純
薬製 無水）をプロピレンカーボネートと１，２−ジメ
トキシエタンの混合溶媒に１モル／dm-3で溶解したもの
を用いた。アルゴン雰囲気中でガラスセルの中に正極、
負極電解液をセットし密閉した。なお、電池の活物質使
用量は電気化学当量として正極≫負極となるようにし、
電池容量が負極規制になるようにした。電池評価は、充
電、放電ともに０．６４mA／cm2 の電流密度で、充電は
４Ｖ Cut、放電は２．５Ｖ Cutで３サイクル充放電を繰
返してそれぞれの充放電容量を求めた。結果を表−１に
示した。The electrolyte used was lithium perchlorate (manufactured by Wako Pure Chemical Industries, anhydrous) dissolved in a mixed solvent of propylene carbonate and 1,2-dimethoxyethane at 1 mol / dm -3 . Positive electrode in a glass cell in an argon atmosphere,
The negative electrode electrolyte was set and sealed. The amount of active material used in the battery should be such that the electrochemical equivalent is positive electrode >> negative electrode,
The battery capacity is regulated to the negative electrode. The battery was evaluated by repeating charge and discharge at a current density of 0.64 mA / cm 2 for both charging and discharging, 4 V Cut for discharging and 2.5 V Cut for discharging for 3 cycles to obtain the charge and discharge capacities thereof. The results are shown in Table-1.
【００１０】[0010]
【実施例−２】ナフタレンと塩化アルミニウムを２６０
℃で２５Kg／cm2 Ｇの圧力で重縮合反応後、取出してガ
ラスチューブに入れてＮ2 ガスを吹込みながら５００℃
で熱処理し、さらにＮ2 流通下８００℃で熱処理した。
この熱処理物を粉砕したものを用いて実施例−１と同様
にして負極を作製した。また正極、電解液の調製及び電
池評価は実施例−１と同様に行った。結果を表−１に示
した。[Example-2] 260 with naphthalene and aluminum chloride
After polycondensation reaction at a pressure of 25 Kg / cm 2 G at ℃, put it into a glass tube and blow it with N 2 gas at 500 ℃
And heat treatment at 800 ° C. under N 2 flow.
Using this crushed product of the heat treatment, a negative electrode was prepared in the same manner as in Example-1. Further, the preparation of the positive electrode and the electrolytic solution and the battery evaluation were performed in the same manner as in Example-1. The results are shown in Table-1.
【００１１】[0011]
【比較例】フルフリルアルコールをＮ2 流通下８０℃で
攪拌しながら重縮合反応を行い、さらにＮ2 流通下８０
０℃で熱処理した。この熱処理物を粉砕したものを用い
て実施例−１と同様にして負極を作製した。また正極、
電解液の調製及び電池評価は実施例−１と同様に行っ
た。結果を表−１に示した。[Comparative Example] furfuryl alcohol perform polycondensation reaction while stirring under N 2 flow under 80 ° C., under further N 2 flow 80
Heat treatment was performed at 0 ° C. Using this crushed product of the heat treatment, a negative electrode was prepared in the same manner as in Example-1. Also the positive electrode,
Preparation of the electrolytic solution and evaluation of the battery were performed in the same manner as in Example-1. The results are shown in Table-1.
【００１２】[0012]
【表１】 [Table 1]
【００１３】[0013]
【本発明の効果】本発明によれば、リチウムイオン二次
電池における負極の放電容量を顕著に増大させることが
でき、高容量化された二次電池を得ることができる。According to the present invention, the discharge capacity of the negative electrode in the lithium ion secondary battery can be remarkably increased, and a secondary battery having a high capacity can be obtained.
Claims (2)
溶媒にアルカリ金属塩を溶解した電解液を持つ二次電池
において、該負極が、縮合多環芳香族炭化水素化合物を
一種類もしくは二種類以上組み合わせたものを架橋剤又
はルイス酸触媒を用いて重縮合させたのち５００℃以上
の温度で熱処理した物質からなることを特徴とする二次
電池。1. A secondary battery having a negative electrode using a carbonaceous material as an active material and an electrolyte solution in which an alkali metal salt is dissolved in a non-aqueous solvent, wherein the negative electrode is one kind of condensed polycyclic aromatic hydrocarbon compound. Alternatively, a secondary battery comprising a substance obtained by polycondensing a combination of two or more kinds using a cross-linking agent or a Lewis acid catalyst and then heat-treating at a temperature of 500 ° C. or higher.
タレン、アントラセン、アセナフテン、アセナフチレ
ン、ピレン乃至それらに脂肪族側鎖が置換した誘導体で
ある請求項１記載の二次電池。2. The secondary battery according to claim 1, wherein the condensed polycyclic aromatic hydrocarbon compound is naphthalene, anthracene, acenaphthene, acenaphthylene, pyrene or a derivative thereof in which an aliphatic side chain is substituted.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4114881A JPH05314975A (en) | 1992-05-07 | 1992-05-07 | Secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4114881A JPH05314975A (en) | 1992-05-07 | 1992-05-07 | Secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05314975A true JPH05314975A (en) | 1993-11-26 |
Family
ID=14649018
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4114881A Pending JPH05314975A (en) | 1992-05-07 | 1992-05-07 | Secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05314975A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0766328A1 (en) * | 1995-09-26 | 1997-04-02 | Kureha Kagaku Kogyo Kabushiki Kaisha | Graphitic electrode material for secondary battery and process for production thereof |
-
1992
- 1992-05-07 JP JP4114881A patent/JPH05314975A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0766328A1 (en) * | 1995-09-26 | 1997-04-02 | Kureha Kagaku Kogyo Kabushiki Kaisha | Graphitic electrode material for secondary battery and process for production thereof |
| US5721071A (en) * | 1995-09-26 | 1998-02-24 | Kureha Kagaku Kogyo Kabushiki Kaisha | Graphitic electrode material for secondary battery and process for production thereof |
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