JPH09139213A - Electrode material and secondary battery - Google Patents
Electrode material and secondary batteryInfo
- Publication number
- JPH09139213A JPH09139213A JP8038391A JP3839196A JPH09139213A JP H09139213 A JPH09139213 A JP H09139213A JP 8038391 A JP8038391 A JP 8038391A JP 3839196 A JP3839196 A JP 3839196A JP H09139213 A JPH09139213 A JP H09139213A
- Authority
- JP
- Japan
- Prior art keywords
- battery
- electrode material
- compound
- bonds
- organic
- 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.)
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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、電池用電極材料に関す
る。更に詳しくは、スルフィド系電極材料に関するもの
である。FIELD OF THE INVENTION The present invention relates to a battery electrode material. More specifically, it relates to a sulfide-based electrode material.
【０００２】[0002]
【従来の技術】近年、通信機器やＯＡ機器の可搬化がす
すみ、これら機器の軽量化及び小型化競争が繰り広げら
れている。このような各種機器や、或いは電気自動車等
の電源として利用される二次電池においてもその高効率
化が求められている。この要求に対し、新たな電極材を
用いた電池が開発されつつあるが、この中でエネルギー
密度が比較的高いことから、ジスルフィド化合物を用い
た電極材料（米国特許第４８３３０４８号等）が注目さ
れている。このものは、２つの有機物からなる基の間に
２つの硫黄からなるジスルフィド結合を有するもの（Ｒ
−Ｓ−Ｓ−Ｒ’）を電極材料に用いるものである。2. Description of the Related Art In recent years, communication equipment and office automation equipment have become portable, and competition for weight reduction and miniaturization of these equipment has been promoted. Higher efficiency is also required for such various devices and secondary batteries used as power sources for electric vehicles and the like. In response to this demand, batteries using new electrode materials are being developed, but among them, since the energy density is relatively high, electrode materials using disulfide compounds (US Pat. No. 4833048 and the like) have attracted attention. ing. This compound has a disulfide bond consisting of two sulfurs between two organic groups (R
-S-S-R ') is used as an electrode material.
【０００３】Ｓ−Ｓ結合は電解還元による２電子の供給
により開裂し、電解液中のカチオン或いはプロトン（Ｍ
+ ）と結合して２（Ｒ−Ｓ- ・Ｍ+ ）となり、電解酸化
時には元のＲ−Ｓ−Ｓ−Ｒに戻って、２電子を放出す
る。この二次電池においては、通常の他の二次電池並の
１５０Wh/kg 以上のエネルギー密度が期待できるとされ
ている。しかし、前述の米国特許の発明者らがJ.Electr
ochem.Soc.Vol.136.Ｎo.9,p.2570〜2575（1989）で報告
している内容から、このジスルフィド系二次電池の電極
反応の電子移動速度は極めて遅く、従って、室温付近で
は実用に見合う大電流を取り出すことが困難であり、６
０℃以上での使用に限られると云う問題が指摘された。The SS bond is cleaved by the supply of two electrons by electrolytic reduction, and the cation or proton (M
+) Combine with 2 (R-S - · M +) next, during electrolytic oxidation back to the original R-S-S-R, to release the 2 electrons. It is said that this secondary battery can be expected to have an energy density of 150 Wh / kg or more, which is equivalent to that of other secondary batteries. However, the inventors of the aforementioned U.S. Patent
From the content reported in ochem.Soc.Vol.136.No.9, p.2570-2575 (1989), the electron transfer rate of the electrode reaction of this disulfide secondary battery is extremely slow, and therefore, at room temperature, It is difficult to extract a large current suitable for practical use.
A problem was pointed out that the use was limited to 0 ° C or higher.
【０００４】その後、このジスルフィド系二次電池を改
良し、大電流に対応させる技術として、特開平５−７４
４５９号公報等に示されるように、このジスルフィド基
を有する有機化合物にポリアニリン等の導電性高分子を
組み合わせた電極材料が提案された。しかし、以上のよ
うな技術によるジスルフィド系二次電池のエネルギー密
度は、全て、重量あたりのジスルフィド基（Ｒ−Ｓ−Ｓ
−Ｒ）の数に依存するものであり、現状の理論的エネル
ギー密度を格段に向上させるような技術は存在しなかっ
た。Then, as a technique for improving this disulfide-based secondary battery to cope with a large current, Japanese Patent Application Laid-Open No. H5-74
As disclosed in Japanese Patent No. 459, etc., an electrode material has been proposed in which an organic compound having a disulfide group is combined with a conductive polymer such as polyaniline. However, the energy densities of the disulfide-based secondary batteries produced by the above techniques are all determined by the weight of the disulfide group (R-S-S).
It depends on the number of −R), and there has been no technology that significantly improves the current theoretical energy density.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、二次電池の
電極材料に応用した場合に、エネルギー密度を格段に向
上させることができるスルフィド系電極材料、及びエネ
ルギー密度が格段に高い二次電池を提供することを目的
とする。DISCLOSURE OF THE INVENTION The present invention, when applied to an electrode material of a secondary battery, can improve the energy density remarkably, and a sulfide-based electrode material having a remarkably high energy density. The purpose is to provide.
【０００６】[0006]
【課題を解決するための手段】本発明の有機電極材料
は、上記問題を解決するために、請求項１に記載の通
り、２以上６以下連続したＳ−Ｓ結合を有する構成を有
する。上記の課題を解決するための手段において、連続
したＳ−Ｓ結合が７の場合にはこれら硫黄は安定な単体
となって分離するため、現実には利用することができな
い。また、Ｓ−Ｓ結合が単独であって連続していない場
合には、エネルギー密度が低くなり、電極材料としての
利点を失う。In order to solve the above-mentioned problems, the organic electrode material of the present invention has a structure having two or more and six or less continuous SS bonds as described in claim 1. In the means for solving the above problems, when the number of continuous S—S bonds is 7, these sulfur is separated as a stable simple substance and cannot be used in practice. Further, when the S—S bond is single and not continuous, the energy density becomes low and the advantage as an electrode material is lost.
【０００７】[0007]
【発明の実施の形態】本発明において、これら２以上６
以下連続したＳ−Ｓ結合は、２，５−ジメルカプト−
１，３，４−チアジアゾール（以下「ＤＭｃＴ」と云
う。）、トリチオシアヌル酸（以下「ＴＴＣＡ」と云
う。）、及び、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメルカプト
エタン（（ＨＳ）2 ＮＣＨ2 ＣＨ2 Ｎ（ＳＨ）2 ）、２
−メチル−５−メルカプト−１，３，４−チアジアゾー
ル（以下「ＭＭＴ」と云う。）等の、質量の小さい分子
であって複数のＳ−Ｈ（チオール基）を有する化合物の
チオール基の水素と置換して結合しているものである
と、エネルギー密度が高くなるので望ましい。上記化合
物の他の例としては、化学式（Ｉ）〜（ＸＩＶ）で表せ
られるものがある。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, these two or more 6
Hereinafter, consecutive S-S bonds are 2,5-dimercapto-
1,3,4-thiadiazole (hereinafter referred to as “DMcT”), trithiocyanuric acid (hereinafter referred to as “TTCA”), and N, N, N ′, N′-tetramercaptoethane ((HS) 2 NCH). 2 CH 2 N (SH) 2 ), 2
-Methyl-5-mercapto-1,3,4-thiadiazole (hereinafter referred to as "MMT") and the like, hydrogen of a thiol group of a compound having a small mass and having a plurality of S-H (thiol groups). It is desirable that it is substituted by and is bonded to since it increases the energy density. Other examples of the above compounds include those represented by the chemical formulas (I) to (XIV).
【０００８】[0008]
【化１】 Embedded image
【化２】 Embedded image
【化３】 Embedded image
【化４】 Embedded image
【化５】 Embedded image
【化６】 [Chemical 6]
【化７】 Embedded image
【化８】 Embedded image
【化９】 Embedded image
【化１０】 Embedded image
【化１１】 Embedded image
【化１２】 Embedded image
【化１３】 Embedded image
【化１４】 Embedded image
【０００９】なお、これら化学式（Ｉ）〜（ＸＩＶ）に
おいて、ＸはＯ、Ｓ、Ｓｅ、ＮＨ、ＮＲ、ＣＨ2 、ＣＨ
Ｒ、ＣＲＲ’、Ｃ＝Ｏ、Ｃ＝ＮＨ、Ｃ＝ＮＲ、Ｃ＝Ｓな
どの基を示し、また、Ｙ1 、Ｙ2 、Ｙ3 及びＹ4 は、そ
れぞれ、−ＣＨ3 、−Ｃ2 Ｈ 5 で代表される脂肪族基及
びその誘導体、−Ｃ6 Ｈ5 で代表される芳香族基及びそ
の誘導体、−Ｆ、−Ｃｌ、−Ｂｒ、−Ｉ等のハロゲン
基、−ＣＯＯＲ、−ＮＲＲ’、−ＯＲ、−ＣＯＲ、−Ｓ
Ｏ3 Ｒ、−ＣＯＮＲＲ’、−Ｎ+ ＲＲ’Ｒ”、−ＳＲ、
−ＯＣＯＲ、−ＮＨＣＯＲ、−Ｎ＝ＣＲＲ’、−ＳＯ2
Ｒ、−ＳＯＲ、−ＳＳＲ、−Ｐ（＝Ｏ）ＲＲ’、−Ｐ
（＝Ｓ）ＲＲ’、−ＯＮＯ、−Ｎ＝Ｃ＝Ｏ、−Ｎ＝Ｃ＝
Ｓ、−ＯＣＮ、−ＳＣＮ、−ＣＮ、−ＮＯ2 、−Ｈ、−
ＰＲＲ’、−Ｐ+ Ｆ、−Ｐ+ Ｃｌ、−Ｐ+ Ｂｒ、−Ｐ+
Ｉであって、これらのＲ、Ｒ’及びＲ”は水素、脂肪族
或いは芳香族炭化水素基を示す。Incidentally, in these chemical formulas (I) to (XIV),
Where X is O, S, Se, NH, NR, CHTwo, CH
R, CRR ', C = O, C = NH, C = NR, C = S
Which group is shown, and also Y1, YTwo, YThreeAnd YFourIs
-CHThree, -CTwoH FiveAliphatic groups represented by
And its derivatives, -C6HFiveAnd aromatic groups represented by
Derivative, halogen such as -F, -Cl, -Br, -I
Group, -COOR, -NRR ', -OR, -COR, -S
OThreeR, -CONRR ', -N+RR'R ", -SR,
-OCOR, -NHCOR, -N = CRR ', -SOTwo
R, -SOR, -SSR, -P (= O) RR ', -P
(= S) RR ', -ONO, -N = C = O, -N = C =
S, -OCN, -SCN, -CN, -NOTwo, -H,-
PRR ', -P+F, -P+Cl, -P+Br, -P+
I, wherein R, R'and R "are hydrogen, aliphatic
Alternatively, it represents an aromatic hydrocarbon group.
【００１０】また、これら電極材料において、重合体で
あってもよいが、その重合度はエネルギー密度とは理論
上無関係である。The electrode material may be a polymer, but the degree of polymerization is theoretically independent of the energy density.
【００１１】本発明の電極材は、例えば、下に示すよう
にして得ることができる。分子中に１つ以上のチオール
基を有する物質を塩化メチレン等の有機溶媒に溶解し、
これに、そのチオール基の量に相当する量の二塩化二硫
黄或いは、二塩化硫黄を添加して２０時間程度反応させ
る。その後、この系をメタノールに注ぎ入れ、未反応の
二塩化二硫黄或いは二塩化硫黄をメタノールと反応さ
せ、分解したときに沈殿として得られる。The electrode material of the present invention can be obtained, for example, as shown below. Dissolving a substance having one or more thiol groups in the molecule in an organic solvent such as methylene chloride,
To this, an amount of disulfur dichloride or sulfur dichloride corresponding to the amount of the thiol group is added and reacted for about 20 hours. Then, this system is poured into methanol, and unreacted disulfur dichloride or sulfur dichloride is reacted with methanol to obtain a precipitate when decomposed.
【００１２】また、同様に１つ以上のチオール基を有す
る物質を原料として、これをジエチルエーテルに溶解
し、そのチオール基の量に相当する量の二塩化二硫黄或
いは二塩化硫黄、及びピリジンを添加し、−８０℃付近
で反応させ、その後、この系を水酸化ナトリウム水溶液
で中和して得られる。なお、上記において二塩化二硫黄
を用いたときには、偶数個のＳが連結した結合が形成さ
れ、二塩化一硫黄を用いたときには、奇数個のＳが連結
した結合が形成される。Similarly, a substance having one or more thiol groups is used as a raw material, and this is dissolved in diethyl ether, and an amount of disulfur dichloride or sulfur dichloride corresponding to the amount of the thiol groups and pyridine are obtained. It is obtained by adding and reacting at around -80 ° C, and then neutralizing the system with an aqueous sodium hydroxide solution. When disulfur dichloride is used in the above, an even number of S-bonds is formed, and when monosulfur dichloride is used, an odd-numbered S-bond is formed.
【００１３】[0013]
〔実施例１及び比較例１〕本発明に係る電極材料である
ＤＭｃＴのテトラスルフィド化合物は次のように合成さ
れた。即ち、１ｍｏｌ／ lのＤＭｃＴと塩化メチレン溶
液と、同じく１ｍｏｌ／ lの二塩化二硫黄−塩化メチレ
ン溶液を２０時間室温で良く撹拌して、ＤＭｃＴと二塩
化二硫黄を反応させ重合させる。その後、この系をメタ
ノールに注ぎ入れ、未反応の二塩化二硫黄を分解・除去
する。これらをＧ４グレードのガラス濾過器で濾過した
のち、濾過残物をメタノールで洗浄後、６０℃で真空乾
燥して、重合体Ａを得た。[Example 1 and Comparative Example 1] The tetrasulfide compound of DMcT, which is the electrode material according to the present invention, was synthesized as follows. That is, 1 mol / l DMcT and methylene chloride solution and 1 mol / l disulfur dichloride-methylene chloride solution are well stirred at room temperature for 20 hours to react DMcT with disulfur dichloride to polymerize. Then, this system is poured into methanol to decompose and remove unreacted disulfur dichloride. After filtering these with a G4 grade glass filter, the filtration residue was washed with methanol and then vacuum dried at 60 ° C. to obtain a polymer A.
【００１４】この重合体ＡについてＣＨＮＳ元素分析を
行ったところ、それぞれの存在比は、２：０：２：５で
あった。また酸素その他の元素は存在しないと算定され
た。また、赤外線分光分析によりＣ−Ｓ結合及びＣ＝Ｎ
結合が存在し、Ｃ−Ｎ結合、Ｎ＝Ｎ結合及びＣ＝Ｓ結合
のないことが確認された。一方、この重合体Ａの質量分
析を行ったが、ＮとＳとの間の結合は検出されず、Ｃ2
Ｓ5 Ｎ2 、ＣＳ5 及びＮＮの各フラグメントが確認され
た。これらのことより、重合体Ａには、Ｃ−Ｓ−（Ｓ）
n −Ｓ結合（ｎ＞１）があることが確認され、反応は化
学式１５のように進行し、重合体Ａはテトラスルフィド
化合物重合体であると推測される。When CHNS elemental analysis was carried out on the polymer A, the abundance ratio of each was 2: 0: 2: 5. It was also calculated that oxygen and other elements do not exist. In addition, by infrared spectroscopy, C—S bond and C = N
It was confirmed that there was a bond and no C-N bond, N = N bond and C = S bond. On the other hand, when the mass analysis of this polymer A was carried out, the bond between N and S was not detected, and C 2
Fragments of S 5 N 2 , CS 5 and NN were confirmed. From these facts, the polymer A contains C-S- (S)
It was confirmed that an n- S bond (n> 1) was present, the reaction proceeded as in Chemical Formula 15, and it is speculated that the polymer A is a tetrasulfide compound polymer.
【００１５】[0015]
【化１５】 Embedded image
【００１６】以下に本発明に係る電極材料を用いて二次
電池を作製した際の結果について示す。なお、以下の作
業は特に記載がない限り、グローブボックスを用いてア
ルゴン気流中で行った。０．２１ｍｍ厚、２ｃｍ×２ｃ
ｍの大きさのリチウム金属板に直径が１ｍｍの白金線を
接続し、同じ大きさの黒鉛繊維補強黒鉛板に同様の白金
線を接続して他方の電極とし、これらを対向させて、か
つ、間に３０μｍ厚の多孔性ポリプロピレン製セパレー
ターとを挟んで密着させたものを電極部とし、これを２
つ用意した。The results of producing a secondary battery using the electrode material according to the present invention will be shown below. The following work was performed in an argon stream using a glove box unless otherwise specified. 0.21mm thick, 2cm x 2c
A platinum wire having a diameter of 1 mm is connected to a lithium metal plate having a size of m, a similar platinum wire is connected to a graphite fiber-reinforced graphite plate having the same size as the other electrode, and these electrodes are opposed to each other, and A porous polypropylene separator having a thickness of 30 μm was sandwiched between and adhered to each other to form an electrode portion.
I prepared one.
【００１７】一方、重合体Ａを４０℃での真空乾燥後、
２ｇ／ l、及びＬｉＣＦ3 ＳＯ3 を１ｍｏｌ／ lの濃度
になるよう溶解させたγ−ブチロラクトン（溶液１）
と、常法（米国特許４８３３０４８号）に従って合成
し、ヘキサン溶媒中１９４ｎｍと２５０ｎｍでの紫外吸
収ピークによって、Ｃ−Ｓ−Ｓ−Ｃ結合の存在を確認し
たジスルフィド化合物１を４０℃での真空乾燥後、これ
を２ｇ／ l、及びＬｉＣＦ3 ＳＯ3 を１ｍｏｌ／ lの濃
度になるよう溶解させたγ−ブチロラクトン（溶液２）
を作成した。On the other hand, after the polymer A was vacuum dried at 40 ° C.,
Γ-butyrolactone (solution 1) in which 2 g / l and LiCF 3 SO 3 were dissolved to a concentration of 1 mol / l
And a disulfide compound 1 synthesized according to a conventional method (US Pat. No. 4,83,048) and confirmed by existence of a C--S--S--C bond in a hexane solvent by ultraviolet absorption peaks at 194 nm and 250 nm at 40.degree. Then, this was dissolved in 2 g / l and LiCF 3 SO 3 to a concentration of 1 mol / l, and γ-butyrolactone (solution 2) was dissolved.
It was created.
【００１８】これら溶液１及び溶液２をそれぞれ５０ml
づつ、１００mlのトールビーカーに取り、それぞれに前
述の電極部を、電極全体が溶液内に浸漬するように入
れ、電池１（実施例１）及び電池２（比較例１）とし
た。電池１、電池２をそれぞれの初期電圧の７０％にな
るまで１００μＡの電流で放電させ、その後放電前の初
期電圧と等しくなるまで１００μＡの電流で充電させ、
再度、前記放電と同条件で再放電させた。このときのそ
れぞれの電池についての電気量（Ａｈ）を比較したとこ
ろ、電池１での再放電電気量（α）は電池２での再放電
電気量（β）の２．２倍であった。50 ml of each of Solution 1 and Solution 2
Then, each was placed in a 100 ml tall beaker, and the above-mentioned electrode portions were placed in each so that the whole electrode was immersed in the solution, to obtain a battery 1 (Example 1) and a battery 2 (Comparative Example 1). Batteries 1 and 2 were discharged with a current of 100 μA until they reached 70% of their respective initial voltages, and then charged with a current of 100 μA until they became equal to the initial voltage before discharge,
It was again discharged again under the same conditions as the above discharge. When the electricity amounts (Ah) of the respective batteries at this time were compared, the re-discharge electricity amount (α) in the battery 1 was 2.2 times the re-discharge electricity amount (β) in the battery 2.
【００１９】この後、電池１の電極を短絡させ１０時間
放置し、その後、電池１の炭素板表面（サンプル１Ａ）
及び電池溶液（サンプル１Ｂ）を微少量採取した後、更
に前記条件で充電させ、このときの電池１の炭素板表面
（サンプル２Ａ）及び電池溶液（サンプル２Ｂ）を微少
量採取した。これらサンプル１Ａ及びサンプル２Ａは、
ジエチルエーテルで洗浄後、測定室がアルゴン置換され
たＦＴ−ＩＲで分光分析を行ったところ、サンプル１
Ａ、サンプル２ＡにはＣ−Ｓ結合が確認された。また、
レーザーラマン分析を行ったところ、サンプル１Ａには
Ｓ−Ｓ基は検出されず、一方、サンプル２ＡにはＳ−Ｓ
基の存在が確認された。After that, the electrodes of the battery 1 were short-circuited and left for 10 hours, and then the carbon plate surface of the battery 1 (Sample 1A).
After collecting a small amount of the battery solution (Sample 1B), the battery was further charged under the above conditions, and a minute amount of the carbon plate surface (Sample 2A) and the battery solution (Sample 2B) of the battery 1 at this time were collected. These sample 1A and sample 2A are
After washing with diethyl ether, spectroscopic analysis was performed with FT-IR in which the measurement chamber was replaced with argon, and sample 1 was obtained.
C—S bond was confirmed in A and sample 2A. Also,
When laser Raman analysis was carried out, no S-S group was detected in sample 1A, while S-S group was detected in sample 2A.
The presence of the group was confirmed.
【００２０】〔実施例２、実施例３及び比較例２〕次い
で、２−メチル−５−メルカプト−１，３，４−チアジ
アゾール（ＭＭＴ）のジスルフィド、トリスルフィド、
及びテトラスルフィド化合物について、二次電池を形成
した。[Examples 2, 3 and Comparative Example 2] Next, 2-methyl-5-mercapto-1,3,4-thiadiazole (MMT) disulfide, trisulfide,
A secondary battery was formed with the tetrasulfide compound.
【００２１】ＭＭＴのジスルフィド化合物は下記のよう
に合成した。すなわち、アルゴン雰囲気下で、ヨウ素５
ｍｍｏｌを溶解した３０ｍｌのメタノールに、１０ｍｍ
ｏｌのＭＭＴ及び５ｍｍｏｌのナトリウムメトキシドを
３０ｍｌのメタノールに溶解した溶液をゆっくり滴下
し、その後４時間攪拌を行った。次いで、これら系を−
６０℃に冷却して析出した沈殿を濾過によって取り出
し、減圧乾燥後、エタノールで３回再結晶を行ってＭＭ
Ｔのジスルフィドを得た。The disulfide compound of MMT was synthesized as follows. That is, under an argon atmosphere, iodine 5
10 mm in 30 ml of methanol in which mmol was dissolved
A solution of ol MMT and 5 mmol of sodium methoxide dissolved in 30 ml of methanol was slowly added dropwise, followed by stirring for 4 hours. Then these systems
After cooling to 60 ° C, the deposited precipitate was taken out by filtration, dried under reduced pressure, and recrystallized three times with ethanol to give MM.
A disulfide of T was obtained.
【００２２】また、ＭＭＴのトリスルフィド化合物は次
のようにして得た。すなわち、アルゴン雰囲気下−２０
℃で１５ｍｍｏｌのＭＭＴを３５０ｍｌのアセトニトリ
ルに溶解し、これに７．５ｍｍｏｌの二塩化一硫黄を１
５ｍｌのアセトニトリルに溶解して作製した溶液をゆっ
くり滴下し、滴下終了後室温まで昇温する。生成した沈
殿を再度これを溶解するためにアセトニトリル２００ｍ
ｌを追加する。その後２４時間攪拌を継続した後、クロ
ロフォルムを２００ｍｌ添加し、エバポレーターで溶媒
を蒸発除去する。残留した固形物を塩化メチレンで溶解
し、その溶液から濾過によって夾雑物を除去し、この濾
液にヘキサンを加え、生じた沈殿物がＭＭＴのトリスル
フィド化合物である。これをエタノールから再結晶させ
て精製する。The MMT trisulfide compound was obtained as follows. That is, in an argon atmosphere-20
Dissolve 15 mmol of MMT in 350 ml of acetonitrile at ℃ and add 7.5 mmol of monosulfur dichloride to the solution.
A solution prepared by dissolving in 5 ml of acetonitrile is slowly added dropwise, and after the addition is completed, the temperature is raised to room temperature. 200m of acetonitrile was added to dissolve the formed precipitate again.
Add l. After continuing stirring for 24 hours thereafter, 200 ml of chloroform is added, and the solvent is removed by evaporation with an evaporator. The residual solid matter was dissolved with methylene chloride, impurities were removed from the solution by filtration, hexane was added to the filtrate, and the resulting precipitate was a trisulfide compound of MMT. This is recrystallized from ethanol for purification.
【００２３】一方、ＭＭＴのテトラスルフィド化合物
は、次のようにして得た。すなわち、アルゴン雰囲気下
で１０ｍｍｏｌのＭＭＴを３０ｍｌの塩化メチレンに溶
解し、これに５ｍｍｏｌの二塩化二硫黄を２０ｍｌの塩
化メチレンに溶解した溶液をゆっくり滴下し、その後３
時間攪拌した。この系を−６０℃に冷却し、生じた沈殿
を濾過によって取り出し、その溶媒を減圧下で蒸発除去
し、エタノールで３回再結晶を行い、ＭＭＴのトリスル
フィド化合物を得た。On the other hand, the tetrasulfide compound of MMT was obtained as follows. That is, under an argon atmosphere, 10 mmol of MMT was dissolved in 30 ml of methylene chloride, and a solution of 5 mmol of disulfur dichloride in 20 ml of methylene chloride was slowly added dropwise to the solution.
Stirred for hours. The system was cooled to −60 ° C., the resulting precipitate was taken out by filtration, the solvent was removed by evaporation under reduced pressure, and recrystallized three times with ethanol to obtain a trisulfide compound of MMT.
【００２４】なお、上記各合成の濾過工程において濾過
物以外に濾液中に目的物が含有されているため、その回
収及び精製を別途行ったが、それについての記載は省略
してある。また、これら得られた生成物については、Ｆ
ＡＢ質量分析器、赤外分光分析装置によって目的物であ
ることが確認されている。In addition, since the target substance is contained in the filtrate in addition to the filtered substance in the filtration step of each synthesis described above, the target substance was collected and purified separately, but the description thereof is omitted. Further, regarding these obtained products, F
It has been confirmed to be a target substance by an AB mass spectrometer and an infrared spectroscopic analyzer.
【００２５】上述のように得たＭＭＴのジスルフィド、
トリスルフィド、テトラスルフィドの各化合物を用いて
電池を形成した。なお、以下の作業はすべてグローブボ
ックス内アルゴン気流下で行った。電解質としてトリフ
ルオロメタンスルホン酸リチウムを２ｍｍｏｌ／ lの濃
度になるよう３０ｍｌのγ−ブチロラクトンに溶解した
電解液を３つ調製し、これらに上記で合成した３種のＭ
ＭＴのスルフィド化合物をそれぞれ５ｍｍｏｌ／ lの濃
度になるよう溶解した。MMT disulfide obtained as described above,
A battery was formed using each compound of trisulfide and tetrasulfide. Note that all the following work was performed under an argon gas flow in the glove box. Three electrolytes were prepared by dissolving lithium trifluoromethanesulfonate as an electrolyte in 30 ml of γ-butyrolactone so as to have a concentration of 2 mmol / l.
The MT sulfide compound was dissolved to a concentration of 5 mmol / l.
【００２６】これらの溶液を用いて試料極としてグラッ
シーカーボン、対極として金属リチウム板、参照極とし
て銀−銀イオン電極を用いて電池を形成した。このとき
ＭＭＴのジスルフィドを有する電池を電池３（比較例
２）、ＭＭＴのトリスルフィドを有する電池を電池４
（実施例２）、そしてＭＭＴのテトラスルフィドを有す
る電池を電池５（実施例３）とした。これら電池３、４
及び５についてサイクリックボルタモグラムを測定し
た。それぞれの結果を図１（ａ）、（ｂ）及び（ｃ）に
示す。Using these solutions, a battery was formed using glassy carbon as a sample electrode, a metallic lithium plate as a counter electrode, and a silver-silver ion electrode as a reference electrode. At this time, the battery having MMT disulfide is battery 3 (Comparative Example 2), and the battery having MMT trisulfide is battery 4.
(Example 2) and a battery having MMT tetrasulfide was used as a battery 5 (Example 3). These batteries 3, 4
Cyclic voltammograms were measured for samples Nos. 5 and 5. The respective results are shown in FIGS. 1 (a), (b) and (c).
【００２７】図１により、放電電気量に相当する還元電
気量は、電池３は電池２の１．６倍、電池４は電池の
１．７倍となることが判った。このことによりＭＭＴの
スルフィド化合物においても、トリスルフィド化合物及
びテトラスルフィド化合物は、ジスルフィド化合物に比
較して、より電気化学的活性が高いことが判る。From FIG. 1, it was found that the reducing electricity quantity corresponding to the discharging electricity quantity was 1.6 times that of the battery 2 in the battery 3 and 1.7 times that of the battery 4 in the battery 4. This shows that even in the sulfide compound of MMT, the trisulfide compound and the tetrasulfide compound have higher electrochemical activity than the disulfide compound.
【００２８】〔実施例４、実施例５及び比較例３〕上記
比較例２、実施例３及び実施例４で用いたＭＭＴのジス
ルフィド化合物、トリスルフィド化合物、テトラスルフ
ィド化合物を用いてアルゴン雰囲気下で扁平型電池を作
製して、実使用時に近い状態での検討を行った。Example 4, Example 5 and Comparative Example 3 The disulfide compound, trisulfide compound and tetrasulfide compound of MMT used in Comparative Example 2, Example 3 and Example 4 were used under an argon atmosphere. A flat-type battery was manufactured and examined in a state close to actual use.
【００２９】（正極の作製）ＭＭＴのジスルフィド化合
物３００ｍｇと分散剤３０ｍｇ（アルドリッチ社製Ｂｒ
ｉｊ３５）、電解質である過塩素酸リチウム１８５ｍ
ｇ、及び導電剤であるケッチェンブラック７０ｍｇ、ポ
リエチレンオキサイド４１５ｍｇをアセトニトリルと混
合し、これらの分散液を得た。この液体をシャーレ上に
展開してアセトニトリルを揮発させて、厚さ５００μｍ
のシートとした。これを直径１４ｍｍに打ち抜いて、以
下、正極として用いた。(Preparation of Positive Electrode) MMT disulfide compound 300 mg and dispersant 30 mg (Br manufactured by Aldrich)
ij35), an electrolyte, lithium perchlorate 185 m
g, and Ketjenblack 70 mg as a conductive agent and polyethylene oxide 415 mg were mixed with acetonitrile to obtain a dispersion liquid of these. This liquid is spread on a petri dish to evaporate acetonitrile to a thickness of 500 μm.
And the sheet. This was punched to a diameter of 14 mm and used as a positive electrode hereinafter.
【００３０】（固体電解質の作製）アクリロニトリルと
メチルアクリレートとの共重合体１．５ｇを、１ｍｏｌ
／lの濃度の過塩素酸リチウムγ−ブチロラクトン溶液
に混合し均一分散させ、その後１２０℃に加熱シャーレ
上に展開して放冷し、厚さ１５００μｍの固体電解質を
得た。これを直径１６ｍｍに打ち抜いて以下セパレータ
として用いた。 （負極の作製）厚さ４００μｍのリチウム金属箔を直径
１５ｍｍに打ち抜いて負極とした。(Preparation of Solid Electrolyte) 1 mol of 1.5 g of a copolymer of acrylonitrile and methyl acrylate
The mixture was uniformly dispersed in a lithium perchlorate γ-butyrolactone solution having a concentration of 1 / l, then spread on a petri dish heated to 120 ° C. and allowed to cool to obtain a solid electrolyte having a thickness of 1500 μm. This was punched into a diameter of 16 mm and used as a separator below. (Production of Negative Electrode) A lithium metal foil having a thickness of 400 μm was punched out to a diameter of 15 mm to obtain a negative electrode.
【００３１】（電池の作製）上記正極、セパレータ、負
極を用いて扁平型電池（電池６：比較例３）を作製し
た。その電池のモデル断面図を図２に示す。図中符号１
は正極で正極缶２に圧着されている。正極１は固体電解
質からなるセパレータ６を挟んでリチウム箔からなる負
極３に面しており、負極３の他面は負極缶５に接してい
る。なお、正極缶２及び負極缶５の内部は絶縁パッキン
グによって気密となっている。(Production of Battery) A flat battery (Battery 6: Comparative Example 3) was produced using the above positive electrode, separator and negative electrode. A model cross-sectional view of the battery is shown in FIG. Reference numeral 1 in the figure
Is a positive electrode and is pressure-bonded to the positive electrode can 2. The positive electrode 1 faces the negative electrode 3 made of lithium foil with a separator 6 made of a solid electrolyte interposed therebetween, and the other surface of the negative electrode 3 is in contact with the negative electrode can 5. The insides of the positive electrode can 2 and the negative electrode can 5 are hermetically sealed by insulating packing.
【００３２】上記電池６と同様に、ただし正極活物質と
してＭＭＴのジスルフィド化合物の代わりに、ＭＭＴの
トリスルフィド化合物、或いはＭＭＴのテトラスルフィ
ド化合物を用いて、電池７（実施例４）及び電池８（実
施例５）を作製した。Similar to the above battery 6, except that the trisulfide compound of MMT or the tetrasulfide compound of MMT was used as the positive electrode active material instead of the disulfide compound of MMT, and batteries 7 (Example 4) and 8 ( Example 5) was made.
【００３３】（電池の評価）これら電池６、電池７及び
電池８について、その放電容量を調べた。これら電池に
０．１ＣｍＡの電流規制で１０時間の充電を行い、その
後０．１ＣｍＡの電流規制で電圧が２．０Ｖとなるまで
放電を行った。なお、上記において「ＣｍＡ」とは満充
電の電池を１時間で完全放電させる電流量の設定値を表
す単位である。このときの放電状況を図３に示した。な
お、図３において横軸は電池６の放電容量を１００％と
したときの放電容量率である。図３より、本発明に係る
電池である電池７及び電池８の放電容量は、比較例であ
る電池６の放電容量の１．５倍及び１．８であり、本発
明の効果は明らかである。(Evaluation of Battery) The discharge capacities of these batteries 6, 7 and 8 were examined. These batteries were charged for 10 hours under the current regulation of 0.1 CmA, and then discharged until the voltage reached 2.0 V under the current regulation of 0.1 CmA. In the above description, “CmA” is a unit representing a set value of the amount of current for completely discharging a fully charged battery in 1 hour. The discharge situation at this time is shown in FIG. In FIG. 3, the horizontal axis represents the discharge capacity ratio when the discharge capacity of the battery 6 is 100%. From FIG. 3, the discharge capacities of the batteries 7 and 8 which are batteries according to the present invention are 1.5 times and 1.8 times the discharge capacities of the battery 6 as a comparative example, and the effect of the present invention is clear. .
【００３４】[0034]
【発明の効果】従来のスルフィド系電極材料は、そのジ
スルフィド基（Ｒ−Ｓ−Ｓ−Ｒ、Ｒ：有機化合物からな
る基。以下同じ。）での電解還元・電解酸化反応を利用
するものであり、下式のように、この電解還元・電解酸
化反応には基当たり２つの電子しか関与しない。なお、
以下式中Ｍは金属（ここでは金属の例として１価のもの
について記載するが、多価の金属であっても差し支えは
ない。）、または水素を表す。EFFECTS OF THE INVENTION Conventional sulfide-based electrode materials utilize electrolytic reduction / electrolytic oxidation reactions at their disulfide groups (R—S—S—R, R: a group consisting of an organic compound; the same applies hereinafter). Therefore, as shown in the following formula, only two electrons are involved in this electrolytic reduction / electrolytic oxidation reaction per group. In addition,
In the following formula, M represents a metal (here, a monovalent one is described as an example of the metal, but a polyvalent metal may be used) or hydrogen.
【００３５】[0035]
【化１６】 Embedded image
【００３６】一方、本発明に係る電極材料は、例えば、
Ｒ−Ｓ−（Ｓ）n −Ｓ−Ｒ’（１≦ｎ≦５、Ｒ及びＲ’
は有機物からなる基）でｎ＝２のとき、即ちテトラスル
フィド化合物のとき、化学式１７で表すことができる。On the other hand, the electrode material according to the present invention is, for example,
R-S- (S) n- S-R '(1≤n≤5, R and R'
Is a group consisting of an organic substance) and n = 2, that is, a tetrasulfide compound, can be represented by the chemical formula 17.
【００３７】[0037]
【化１７】 Embedded image
【００３８】化学式１７より、テトラスルフィド化合物
を用いた場合、６電子反応となることが判る。ここで、
重量当たりの電子の数がジスルフィド化合物の場合に比
べ増加し、エネルギー密度が増加する。From the chemical formula 17, it can be seen that a 6-electron reaction occurs when a tetrasulfide compound is used. here,
The number of electrons per weight is increased as compared with the case of the disulfide compound, and the energy density is increased.
【００３９】ここで、例えば、ＤＭｃＴ分子中の２つの
チオール基の水素が、それぞれ別のＤＭｃＴの２つの硫
黄の１つと置換し硫黄同士が結合して重合しているジス
ルフィド化合物重合体、このＤＭｃＴによるジスルフィ
ド結合の間に１〜５個の硫黄が入り込んだトリスルフィ
ド、テトラスルフィド、ペンタスルフィド、ヘキサスル
フィド、ヘプタスルフィドの各化合物重合体を想定した
場合、これらの電解還元及び電解酸化反応はそれぞれ、
２電子反応、４電子反応、６電子反応、８電子反応、１
０電子反応、１２電子反応である。これらＤＭｃＴのス
ルフィド化合物重合体を電池の電極材料として用い、他
方電極にリチウムを用いた場合、起電力が３．５Ｖであ
るので、それぞれの理論エネルギー密度は図４に示すよ
うになる。Here, for example, the hydrogen of the two thiol groups in the DMcT molecule is replaced with one of the two sulfurs of different DMcT, and the sulfur is bonded to each other to polymerize the disulfide compound polymer. Assuming each compound polymer of trisulfide, tetrasulfide, pentasulfide, hexasulfide, and heptasulfide in which 1 to 5 sulfurs are introduced between the disulfide bonds by, the electrolytic reduction and electrolytic oxidation reactions are
2-electron reaction, 4-electron reaction, 6-electron reaction, 8-electron reaction, 1
It is a 0-electron reaction and a 12-electron reaction. When these DMcT sulfide compound polymers are used as the electrode material of the battery and lithium is used for the other electrode, the electromotive force is 3.5 V, so the theoretical energy densities are as shown in FIG.
【００４０】また、トリチオシアヌル酸（以下「ＴＴＣ
Ａ」と云う。）、及び、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメ
ルカプトエタン（（ＨＳ）2 ＮＣＨ2 ＣＨ2 Ｎ（ＳＨ）
2 ）についても、そのジスルフィド、トリスルフィド、
テトラスルフィド、ペンタスルフィド、ヘキサスルフィ
ド、ヘプタスルフィド化合物の重合体での同様の理論エ
ネルギー密度を併せて図１に示す。なお、参考として化
学式１８にＴＴＣＡのテトラスルフィド化合物重合体の
酸化還元反応式を示す。Further, trithiocyanuric acid (hereinafter referred to as "TTC
"A". ) And N, N, N ′, N′-tetramercaptoethane ((HS) 2 NCH 2 CH 2 N (SH)
For 2 ), the disulfide, trisulfide,
Similar theoretical energy densities for polymers of tetrasulfide, pentasulfide, hexasulfide, and heptasulfide compounds are also shown in FIG. For reference, chemical formula 18 shows a redox reaction formula of a tetrasulfide compound polymer of TTCA.
【００４１】[0041]
【化１８】 Embedded image
【００４２】図４より、本発明に係る電極材料を用いた
電池の理論エネルギー値が従来のジスルフィド化合物重
合体を用いた電池の理論エネルギー値より格段に高いこ
と、即ち、本発明に係る電極材料が優れた特性を持つこ
とが理解される。上記実施例により明らかにされるよう
に、本発明に係る電極材料を用い二次電池を作製する
と、そのエネルギー密度は従来のジスルフィド系電極材
料を用いた場合に比べ、格段に大きくなる。From FIG. 4, the theoretical energy value of the battery using the electrode material according to the present invention is significantly higher than the theoretical energy value of the battery using the conventional disulfide compound polymer, that is, the electrode material according to the present invention. Is understood to have excellent properties. As is clear from the above-described examples, when a secondary battery is manufactured using the electrode material according to the present invention, its energy density is significantly higher than that when a conventional disulfide-based electrode material is used.
【図１】本発明の比較例である電池３、実施例である電
池４及び電池５のサイクリックボルタモグラフである。 （ａ）電池３のサイクリックボルタモグラフ （ｂ）電池４のサイクリックボルタモグラフ （ｃ）電池５のサイクリックボルタモグラフFIG. 1 is a cyclic voltammogram of a battery 3 as a comparative example of the present invention, and batteries 4 and 5 as examples. (A) Cyclic voltamograph of battery 3 (b) Cyclic voltamograph of battery 4 (c) Cyclic voltamograph of battery 5
【図２】扁平型電池モデルの断面図である。FIG. 2 is a cross-sectional view of a flat battery model.
【図３】本発明の比較例である電池６、実施例である電
池７及び電池８の放電容量率を示す図である。FIG. 3 is a diagram showing discharge capacity ratios of a battery 6 which is a comparative example of the present invention, a battery 7 and a battery 8 which are examples.
【図４】本発明に係る電極材料を用いたリチウム二次電
池の理論エネルギー密度を示した図である。FIG. 4 is a diagram showing a theoretical energy density of a lithium secondary battery using the electrode material according to the present invention.
１ 正極 ２ 正極缶 ３ 負極 ４ 絶縁パッキング ５ 負極缶 ６ セパレータ 1 positive electrode 2 positive electrode can 3 negative electrode 4 insulating packing 5 negative electrode can 6 separator
Claims (7)
ることを特徴とする有機電極材料。1. An organic electrode material having continuous S—S bonds of 2 or more and 6 or less.
れることを特徴とする請求項１記載の有機電極材料。2. The following formula: R—S— (S) n —S—R ′ (1 ≦ n ≦ 5, R and R ′ are organic groups) Organic electrode material.
水素）で示されることを特徴とする電極材料。3. An electrode material represented by the following formula: R—S— (S) n —M (1 ≦ n ≦ 6, R is a group consisting of an organic material, and M is a metal or hydrogen).
る有機電極材料を含有することを特徴とする二次電池。4. A secondary battery containing an organic electrode material having continuous S—S bonds of 2 or more and 6 or less.
れる有機電極材料を含有することを特徴とする請求項４
記載の二次電池。5. An organic electrode material represented by the following formula: R—S— (S) n —S—R ′ (1 ≦ n ≦ 5, R and R ′ are groups consisting of an organic substance) is contained. Claim 4
The secondary battery according to any one of the preceding claims.
水素）で示される有機電極材料を含有することを特徴と
する二次電池。6. An organic electrode material represented by the following formula: R—S— (S) n —M (1 ≦ n ≦ 6, R is a group composed of an organic material, and M is a metal or hydrogen). Rechargeable battery.
水素） で示される有機電極材料を含有し、かつ、硫化金属を含
有する電解液を有することを特徴とする二次電池。7. An electrolytic solution containing an organic electrode material represented by the following formula: R—S—M (R is a group consisting of an organic substance, M is a metal or hydrogen) and containing a metal sulfide. And a secondary battery.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03839196A JP3497318B2 (en) | 1995-02-27 | 1996-02-26 | Electrode materials and secondary batteries |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7-38285 | 1995-02-27 | ||
| JP3828595 | 1995-02-27 | ||
| JP23277095 | 1995-09-11 | ||
| JP7-232770 | 1995-09-11 | ||
| JP03839196A JP3497318B2 (en) | 1995-02-27 | 1996-02-26 | Electrode materials and secondary batteries |
Publications (2)
| Publication Number | Publication Date |
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| JPH09139213A true JPH09139213A (en) | 1997-05-27 |
| JP3497318B2 JP3497318B2 (en) | 2004-02-16 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP03839196A Expired - Fee Related JP3497318B2 (en) | 1995-02-27 | 1996-02-26 | Electrode materials and secondary batteries |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999033130A1 (en) * | 1997-12-19 | 1999-07-01 | Moltech Corporation | Electroactive, energy-storing, highly crosslinked, polysulfide-containing, organic polymers for use in electrochemical cells |
| US6117590A (en) * | 1995-06-07 | 2000-09-12 | Moltech Corporation | Electroactive high storage capacity polyacetylene-co-polysulfur materials and electrolytic cells containing same |
| US6309778B1 (en) | 1996-02-16 | 2001-10-30 | Moltech Corporation | Electroactive high storage capacity polyacetylene-co-polysulfur materials and electrolytic cells containing same |
| JP2001332306A (en) * | 1999-11-22 | 2001-11-30 | Hitachi Maxell Ltd | Polymer electrolyte and secondary cell |
| JP2015054834A (en) * | 2013-09-11 | 2015-03-23 | 独立行政法人国立高等専門学校機構 | Method for producing organic polysulfide compound and organic polysulfide compound |
-
1996
- 1996-02-26 JP JP03839196A patent/JP3497318B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6117590A (en) * | 1995-06-07 | 2000-09-12 | Moltech Corporation | Electroactive high storage capacity polyacetylene-co-polysulfur materials and electrolytic cells containing same |
| US6174621B1 (en) | 1995-06-07 | 2001-01-16 | Moltech Corporation | Electroactive high storage capacity polyacetylene-co-polysulfur materials and electrolytic cells containing same |
| US6309778B1 (en) | 1996-02-16 | 2001-10-30 | Moltech Corporation | Electroactive high storage capacity polyacetylene-co-polysulfur materials and electrolytic cells containing same |
| WO1999033130A1 (en) * | 1997-12-19 | 1999-07-01 | Moltech Corporation | Electroactive, energy-storing, highly crosslinked, polysulfide-containing, organic polymers for use in electrochemical cells |
| US6201100B1 (en) | 1997-12-19 | 2001-03-13 | Moltech Corporation | Electroactive, energy-storing, highly crosslinked, polysulfide-containing organic polymers and methods for making same |
| JP2001332306A (en) * | 1999-11-22 | 2001-11-30 | Hitachi Maxell Ltd | Polymer electrolyte and secondary cell |
| JP4562896B2 (en) * | 1999-11-22 | 2010-10-13 | 日立マクセル株式会社 | Gel polymer electrolyte and secondary battery |
| JP2015054834A (en) * | 2013-09-11 | 2015-03-23 | 独立行政法人国立高等専門学校機構 | Method for producing organic polysulfide compound and organic polysulfide compound |
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| Publication number | Publication date |
|---|---|
| JP3497318B2 (en) | 2004-02-16 |
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