JP2007234338A - Secondary battery's positive electrode material, its manufacturing method and secondary battery - Google Patents
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Abstract
Description
本発明は、二次電池用正極材料、その製造方法、及びそれらを利用した二次電池に関し、さらに詳しくは、電極活物質としてジスルフィド結合の開裂−再結合によってレドックス反応を行う含イオウ化合物を利用した二次電池用正極材料、その製造方法、及びそれを利用した二次電池に関する。 The present invention relates to a positive electrode material for a secondary battery, a method for producing the same, and a secondary battery using them, and more specifically, a sulfur-containing compound that performs a redox reaction by cleavage-recombination of disulfide bonds as an electrode active material. The present invention relates to a positive electrode material for a secondary battery, a method for producing the same, and a secondary battery using the same.
近年、単体硫黄や有機ジスルフィド化合物などのジスルフィド結合を有する物質が、二次電池用の電極活物質として注目されている。これらの物質は、ジスルフィド結合の開裂−再結合によってレドックス反応を行うことができるため、充電及び放電を繰り返すことができる。また、こうしたジスルフィド結合を有する化合物は、理論容量密度が極めて高いため、大きな充電容量を有する二次電池を製造できるとして注目を集めている。 In recent years, substances having a disulfide bond such as elemental sulfur and organic disulfide compounds have attracted attention as electrode active materials for secondary batteries. Since these substances can perform a redox reaction by cleavage-recombination of disulfide bonds, charging and discharging can be repeated. Further, such a compound having a disulfide bond has attracted attention because it can produce a secondary battery having a large charge capacity because of its extremely high theoretical capacity density.
しかし、これらジスルフィド結合を有する物質は導電性に劣るため、レドックス反応を行うためには、いかに電子伝導パスを形成するかが問題となる。また、ジスルフィド結合の開裂反応によって低分子量の化学種が発生し、この化学種が電極の沖合いに拡散してしまうため、可逆的なレドックスサイクルが困難となる。このため、単にジスルフィド化合物とアセチレンブラックなどの炭素粉末とを混合しただけでは、円滑なレドックスサイクルを行わせることができず、現実の充電容量は理論容量密度から計算される値よりもはるかに低い値しか得られていない。 However, since these substances having a disulfide bond are inferior in conductivity, it is a problem how to form an electron conduction path in order to perform a redox reaction. Moreover, a low molecular weight chemical species is generated by the cleavage reaction of the disulfide bond, and this chemical species diffuses offshore of the electrode, so that a reversible redox cycle becomes difficult. For this reason, simply mixing a disulfide compound and carbon powder such as acetylene black cannot cause a smooth redox cycle, and the actual charge capacity is much lower than the value calculated from the theoretical capacity density. Only the value is obtained.
こうした問題を解決すべく、ジスルフィド化合物としての単体イオウを多層カーボンナノチューブと物理的に混合した二次電池用正極材料が提案されている（非特許文献１）。この二次電池用正極材料では、導電性に優れた多層カーボンナノチューブが絡み合って３次元ネットワークが構築され、そのネットワークの中に存在する単体イオウが多層カーボンナノチューブとの間で比較的円滑な電子のやり取りを行うことができる。このため、単に単体イオウをアセチレンブラックと物理的に混合しただけの二次電池用正極材料と比較して、導電性に優れ、容量の大きい二次電池とすることができる。 In order to solve such a problem, a positive electrode material for a secondary battery in which simple sulfur as a disulfide compound is physically mixed with multi-walled carbon nanotubes has been proposed (Non-Patent Document 1). In this positive electrode material for a secondary battery, multi-walled carbon nanotubes with excellent conductivity are intertwined to form a three-dimensional network, and single sulfur existing in the network allows relatively smooth electrons to flow between the multi-walled carbon nanotubes. Can communicate. For this reason, it can be set as the secondary battery which is excellent in electroconductivity and large capacity | capacitance compared with the positive electrode material for secondary batteries which only mixed simple sulfur with acetylene black.
一方、正極材料として2,5−ジメルカプト-1,3,4−チアジアゾール（以下「ＤＭｃＴ」と略す）を用いたリチウム二次電池についても報告がなされている（非特許文献２〜４）。この化合物は、下式（１）に示すように、ＤＭｃＴの多量体ポリマーであるＤＭｃＴｎが電解還元されて開裂してＤＭｃＴ２−となり、さらにＤＭｃＴ２−が電解酸化されて元の多量体ポリマーに戻ることができる。
しかし、上記非特許文献１に記載された、単体イオウをカーボンナノチューブと混合した二次電池用正極材料では、多層のカーボンナノチューブを用いているため、単層カーボンナノチューブに比べてチューブを形成している壁が厚く、そのため管状の細孔部分の体積が小さい。このため、単体イオウは細孔外部に存在するものが多くなり、細孔内部に閉じ込められた単体イオウ分は少なくなる。このため、単体イオウの還元体が沖合いに溶出しやすくなり、可逆的なレドックス反応が困難となり、ひいては二次電池として用いた場合に、充放電の繰り返しによる容量の低下が著しくなる。 However, the positive electrode material for a secondary battery in which simple sulfur is mixed with carbon nanotubes described in Non-Patent Document 1 uses multi-walled carbon nanotubes, so that a tube is formed as compared with single-walled carbon nanotubes. The wall is thick, so the volume of the tubular pore portion is small. For this reason, the amount of simple sulfur that exists outside the pores increases, and the content of simple sulfur trapped inside the pores decreases. For this reason, the reductant of simple sulfur is likely to elute offshore, making reversible redox reaction difficult, and as a result, when used as a secondary battery, the capacity is significantly reduced due to repeated charge and discharge.
また、上記非特許文献２〜５に記載されたＤＭｃＴ用いたリチウム二次電池では、多量体ポリマーのＤＭｃＴｎが還元されて生じたＤＭｃＴ２−は溶解しやすいため、電極であるカーボン粒子の表面近傍から沖合いに溶出してしまい、可逆的なレドックス反応が困難となる。このため、二次電池として用いた場合に、充放電の繰り返しによる容量の低下が顕著となる。 Further, in the lithium secondary battery using DMcT described in Non-Patent Documents 2 to 5, DMcT 2- produced by reducing DMcT n of the multimeric polymer is easily dissolved, so that the surface of the carbon particle as the electrode It elutes offshore from the vicinity, making reversible redox reaction difficult. For this reason, when it uses as a secondary battery, the fall of the capacity | capacitance by repetition of charging / discharging becomes remarkable.
本発明は、上記従来の実情に鑑みなされたものであり、ジスルフィド結合の開裂−再結合によってレドックス反応を行う含イオウ化合物を電極活物質として用いており、充電可能な電気量が大きく、充放電の繰り返しによる容量低下の少ない二次電池用正極材料、その製造方法、及びそれらを利用した二次電池を提供することを解決すべき課題としている。 The present invention has been made in view of the above-described conventional situation, and uses a sulfur-containing compound that performs a redox reaction by cleavage-recombination of disulfide bonds as an electrode active material, and has a large amount of chargeable charge and charge / discharge. It is an object to be solved to provide a positive electrode material for a secondary battery with a small capacity drop due to repetition of the above, a manufacturing method thereof, and a secondary battery using them.
第１発明の二次電池用正極材料は、ジスルフィド結合の開裂−再結合によってレドックス反応を行う含イオウ化合物と、カーボンとを含んだ二次電池用正極材料であって、前記カーボンは単層カーボンナノチューブであることを特徴とする。 The positive electrode material for a secondary battery of the first invention is a positive electrode material for a secondary battery containing a sulfur-containing compound that performs a redox reaction by cleavage-recombination of disulfide bonds and carbon, and the carbon is a single-layer carbon It is a nanotube.
第１発明の二次電池用正極材料は、電極活物質としてジスルフィド結合の開裂−再結合によってレドックス反応を行う含イオウ化合物を用いているため、理論容量密度が極めて高くなる。
また、電極材料として伝導性に優れたカーボンナノチューブを用いており、その細長い分子が互いに絡み合って３次元ネットワークを構築するため、緻密な電子伝導パスが形成され、含イオウ化合物の電極反応を円滑に行うことができる。
さらに、カーボンナノチューブは細長い管状の細孔を有しており、含イオウ化合物がカーボンナノチューブの細長い管状の細孔に封じ込められ、沖合いへの溶出が阻止される。また、狭い管状の細孔というナノサイズの領域に含イオウ化合物を存在させることができるため、可逆的なレドックス反応が迅速に進行することとなる。
さらに、カーボンナノチューブの中でも特に単層カーボンナノチューブを用いているため、その管状の分子構造における壁が薄く、相対的に管状の細孔の占める体積割合が大きくなることから、多層カーボンナノチューブを用いた場合よりも、多くの含イオウ化合物を細孔内部に入れることができ、電気容量が大きくなる。
したがって、第１発明の二次電池用正極材料は、充電可能な電気量が大きく、充放電の繰り返しによる容量低下の少ない二次電池を構築することができる。
Since the positive electrode material for a secondary battery according to the first invention uses a sulfur-containing compound that performs a redox reaction by cleavage-recombination of disulfide bonds as an electrode active material, the theoretical capacity density becomes extremely high.
In addition, carbon nanotubes with excellent conductivity are used as the electrode material, and the elongated molecules are intertwined with each other to form a three-dimensional network, so that a dense electron conduction path is formed, and the electrode reaction of sulfur-containing compounds is facilitated. It can be carried out.
Further, the carbon nanotube has elongated tubular pores, and the sulfur-containing compound is confined in the elongated tubular pores of the carbon nanotube, and elution to the offshore is prevented. Further, since the sulfur-containing compound can be present in a nano-sized region called a narrow tubular pore, a reversible redox reaction proceeds rapidly.
Furthermore, since single-walled carbon nanotubes are used among carbon nanotubes, the wall in the tubular molecular structure is thin, and the volume ratio occupied by tubular pores is relatively large. More sulfur-containing compounds can be put inside the pores than in the case, and the electric capacity is increased.
Therefore, the positive electrode material for the secondary battery according to the first aspect of the present invention can construct a secondary battery that has a large chargeable amount of electricity and a small capacity decrease due to repeated charge and discharge.
含イオウ化合物は単層カーボンナノチューブの管状の細孔内に存在させることが好ましい。こうであれば、含イオウ化合物がカーボンナノチューブ内に留められるため、含イオウ化合物の溶出を防ぐことができ、円滑に可逆的なレドックス反応を行うことができる。このため、充放電の繰り返しによる容量低下が少なくなる。 The sulfur-containing compound is preferably present in the tubular pores of the single-walled carbon nanotube. In this case, since the sulfur-containing compound is retained in the carbon nanotube, elution of the sulfur-containing compound can be prevented and a reversible redox reaction can be performed smoothly. For this reason, the capacity | capacitance reduction by repetition of charging / discharging decreases.
含イオウ化合物は有機ジスルフィド、カーボンスルフィド、ポリスルフィド及びそれらの還元体の少なくとも一種とすることができる。これらの化合物は、ジスルフィド結合の開裂−再結合によってレドックス反応を行うことができる。有機ジスルフィドとしては、
例えば下記化学式（ａ）〜（ｈ）に示すものが挙げられる。
その中でも、五員環の複素環式化合物は特に良い効率でレドックスサイクルが実現される。発明者らの試験結果によれば、最も好ましい含イオウ化合物はジメルカプトチアジアゾール若しくはそのリチウム塩又はそれらの多量体である。
The sulfur-containing compound can be at least one of organic disulfides, carbon sulfides, polysulfides, and their reduced forms. These compounds can undergo a redox reaction by cleavage-recombination of disulfide bonds. As organic disulfide,
Examples thereof include those represented by the following chemical formulas (a) to (h).
Among them, a 5-membered heterocyclic compound can realize a redox cycle with particularly good efficiency. According to the test results of the inventors, the most preferred sulfur-containing compound is dimercaptothiadiazole or a lithium salt thereof or a multimer thereof.
第２発明の二次電池用正極材料は、ジスルフィド結合の開裂−再結合によってレドックス反応を行う含イオウ化合物と、カーボンと、を含んだ二次電池用正極材料であって、含イオウ化合物は２以上のチオール基若しくはその塩を有する複素環式化合物又はそれらの多量体であり、前記カーボンはカーボンナノチューブであることを特徴とする。 A positive electrode material for a secondary battery according to a second invention is a positive electrode material for a secondary battery containing a sulfur-containing compound that performs a redox reaction by cleavage-recombination of disulfide bonds and carbon, and the sulfur-containing compound is 2 A heterocyclic compound having a thiol group or a salt thereof or a multimer thereof, wherein the carbon is a carbon nanotube.
第２発明の二次電池用正極材料は、第１発明と同様、電極活物質としてジスルフィド結合の開裂−再結合によってレドックス反応を行う含イオウ化合物を用いているため、理論容量密度が極めて高くなる。
また、電極材料として伝導性に優れたカーボンナノチューブを用いており、その細長い分子が互いに絡み合って３次元ネットワークを構築するため、緻密な電子伝導パスが形成され、含イオウ化合物の電極反応を円滑に行うことができる。
さらに、カーボンナノチューブは細長い管状の細孔を有しており、含イオウ化合物がカーボンナノチューブの細長い管状の細孔に封じ込められ、沖合いへの溶出が阻止される。
また、狭い管状の細孔というナノサイズの領域に含イオウ化合物を存在させることができるため、可逆的なレドックス反応が迅速に進行することとなる。
したがって、第２発明の二次電池用正極材料は、充電可能な電気量が大きく、充放電の繰り返しによる容量低下の少ない二次電池を構築することができる。
As in the first invention, the positive electrode material for a secondary battery according to the second invention uses a sulfur-containing compound that performs a redox reaction by cleavage-recombination of disulfide bonds as an electrode active material, and therefore has a very high theoretical capacity density. .
In addition, carbon nanotubes with excellent conductivity are used as the electrode material, and the elongated molecules are intertwined with each other to form a three-dimensional network, so that a dense electron conduction path is formed, and the electrode reaction of sulfur-containing compounds is facilitated. It can be carried out.
Further, the carbon nanotube has elongated tubular pores, and the sulfur-containing compound is confined in the elongated tubular pores of the carbon nanotube, and elution to the offshore is prevented.
Further, since the sulfur-containing compound can be present in a nano-sized region called a narrow tubular pore, a reversible redox reaction proceeds rapidly.
Therefore, the positive electrode material for the secondary battery of the second invention can construct a secondary battery having a large chargeable amount of electricity and a small capacity decrease due to repeated charge and discharge.
カーボンナノチューブは、単層カーボンナノチューブであることが好ましい。単層カーボンナノチューブは、その管状の分子構造における壁が薄く、相対的に管状の細孔の占める体積割合が大きくなることから、多層カーボンナノチューブを用いた場合よりも、多くの含イオウ化合物を細孔内部に入れることができ、電気容量が大きくなる。 The carbon nanotube is preferably a single-walled carbon nanotube. Single-walled carbon nanotubes have a thin wall in the tubular molecular structure, and the volume ratio occupied by tubular pores is relatively large, so that more sulfur-containing compounds are finer than those using multi-walled carbon nanotubes. It can be put inside the hole, increasing the electric capacity.
含イオウ化合物は単層カーボンナノチューブの管状の細孔内に存在させることが好ましい。こうであれば、含イオウ化合物がカーボンナノチューブ内に留められるため、含イオウ化合物の溶出を防ぐことができ、円滑に可逆的なレドックス反応を行わせることができる。このため、充放電の繰り返しによる容量低下が少なくなる。 The sulfur-containing compound is preferably present in the tubular pores of the single-walled carbon nanotube. In this case, since the sulfur-containing compound is retained in the carbon nanotube, elution of the sulfur-containing compound can be prevented, and a reversible redox reaction can be performed smoothly. For this reason, the capacity | capacitance reduction by repetition of charging / discharging decreases.
２以上のチオール基若しくはその塩を有する複素環式化合物の中でも五員環の複素環式化合物は特に良い効率でレドックスサイクルが実現される。発明者らの試験結果によれば、もっとも好ましい含イオウ化合物はジメルカプトチアジアゾール又はそれらの多量体である。 Among the heterocyclic compounds having two or more thiol groups or salts thereof, a five-membered heterocyclic compound realizes a redox cycle with particularly good efficiency. According to the test results of the inventors, the most preferred sulfur-containing compound is dimercaptothiadiazole or a multimer thereof.
第１発明及び第２発明の二次電池用正極材料は、次のように製造することができる。
すなわち、本発明の二次電池用正極材料の製造方法は、ジスルフィド結合の開裂−再結合によってレドックス反応を行う含イオウ化合物の溶液とカーボンナノチューブとを混合する混合工程と、該混合工程によって得られた混合液を固液分離して含イオウ化合物を含むカーボンナノチューブを得る分離工程と、分離工程によって得られた含イオウ化合物を含むカーボンナノチューブを洗浄する洗浄工程と、を備えることを特徴とする。
The positive electrode material for a secondary battery according to the first and second inventions can be manufactured as follows.
That is, the method for producing a positive electrode material for a secondary battery according to the present invention is obtained by mixing a solution of a sulfur-containing compound that performs a redox reaction by cleavage-recombination of disulfide bonds and a carbon nanotube, and the mixing step. And a separation step of obtaining a carbon nanotube containing a sulfur-containing compound by solid-liquid separation of the mixed liquid, and a washing step of washing the carbon nanotube containing a sulfur-containing compound obtained by the separation step.
また、第１発明及び第２発明の二次電池用正極材料は、セパレータをはさんで負極材料と組み合わせることによって、二次電池とすることができる。こうして組み立てた二次電池は、充電可能な電気量が大きく、充放電の繰り返しによる容量低下も少ない。 Moreover, the positive electrode material for secondary batteries of 1st invention and 2nd invention can be made into a secondary battery by combining with a negative electrode material on both sides of a separator. The secondary battery assembled in this way has a large amount of electricity that can be charged, and has a small capacity drop due to repeated charge and discharge.
以下、本発明を具体化した実施例について図面を参照しつつ説明する。 DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments embodying the present invention will be described below with reference to the drawings.
（ 実施例 ）
二次電池用電池材料の調製
実施例では、含イオウ化合物として下記に示す2,5−ジメルカプト-1,3,4−チアジアゾール（ＤＭｃＴ）を用い、これを単層ナノチューブの細孔に吸着させて二次電池用正極材料とした。以下、その製造方法について詳述する。
アルゴン雰囲気下のグローブボックス内にてＤＭｃＴ2.0ｇをはかりとり、無水エタノール500mlに加えて分散溶解させた。そして、ＤＭｃＴのチオール基の当量と同当量の水酸化リチウム／無水エタノール溶液を加えてリチウム塩溶液とした。さらに、キャップを除去した単層カーボンナノチューブ500ｍｇを加えて撹拌した後、50℃で5時間静置させた。以上の操作は、すべてアルゴン雰囲気下で行った。
（分離工程）
そして、混合工程で得られた混合物をろ過した。
（洗浄工程）
さらに、無水エタノールで洗浄した。こうして単層カーボンナノチューブの細孔内にＤＭｃＴリチウム塩が内包されたＤＭｃＴリチウム塩含有カーボンナノチューブを得た。
( Example )
In the example of preparing the battery material for the secondary battery, the following 2,5-dimercapto-1,3,4-thiadiazole (DMcT) was used as the sulfur-containing compound, and this was adsorbed to the pores of the single-walled nanotube. A positive electrode material for a secondary battery was obtained. Hereinafter, the manufacturing method will be described in detail.
In a glove box under an argon atmosphere, 2.0 g of DMcT was weighed and added to 500 ml of absolute ethanol to be dispersed and dissolved. Then, a lithium hydroxide / anhydrous ethanol solution having the same equivalent as the equivalent of the thiol group of DMcT was added to obtain a lithium salt solution. Further, 500 mg of single-walled carbon nanotubes from which the cap was removed was added and stirred, and then allowed to stand at 50 ° C. for 5 hours. All the above operations were performed under an argon atmosphere.
(Separation process)
And the mixture obtained at the mixing process was filtered.
(Washing process)
Furthermore, it was washed with absolute ethanol. Thus, DMcT lithium salt-containing carbon nanotubes in which DMcT lithium salt was encapsulated in the pores of single-walled carbon nanotubes were obtained.
二次電池用正極の調製
上記のようにして得た実施例のＤＭｃＴリチウム塩含有カーボンナノチューブ500ｍｇ
をPVｄF（ポリビニリデンフルオライド）50mgのＮＭＰ（Ｎ-メチル-２-ピロリドン）分散液に加え、スラリーとする。このスラリーをアルミ箔に塗布した後、１６ｍｍの円盤型に打ち抜いて二次電池用正極を調製した。この電極にはＤＭｃＴが24mg、単層カーボンナノチューブが102ｍｇ、PVｄFが10ｍｇ含まれている。
Preparation of positive electrode for secondary battery 500 mg of DMcT lithium salt-containing carbon nanotubes of Examples obtained as described above
Is added to a dispersion of 50 mg of PVdF (polyvinylidene fluoride) in NMP (N-methyl-2-pyrrolidone) to form a slurry. This slurry was applied to an aluminum foil, and then punched into a 16 mm disk shape to prepare a positive electrode for a secondary battery. This electrode contains 24 mg of DMcT, 102 mg of single-walled carbon nanotubes, and 10 mg of PVdF.
二次電池用負極の調製
銅箔に人造黒鉛（10μm）を塗布し、１６ｍｍの円盤型に打ち抜き、電位走査を数サイクル行って二次電池用負極とした。面積あたりの活物質量は70mg/cm2であった。
Preparation of negative electrode for secondary battery Artificial graphite (10 μm) was applied to a copper foil, punched into a 16 mm disk, and subjected to several cycles of potential scanning to obtain a negative electrode for a secondary battery. The amount of active material per area was 70 mg / cm 2 .
二次電池の組み立て
上記のようにして得られた二次電池用正極及び二次電池用負極をセル組みする前に、脱水工程として１７０℃で8時間の加熱を行った。電解液は１ＭのＬｉＰＦ6／（エチレンカーボネート+ジエチルカーボネート）を用い、密閉式のコイン型ステンレス製容器に二次電池用正極、電解液で湿らせたポリプロピレン製セパレータ、二次電池用負極の順でセットし、ステンレス製の蓋を取り付けて二次電池とした。
Assembly of Secondary Battery Before assembling the positive electrode for secondary battery and the negative electrode for secondary battery obtained as described above, heating was performed at 170 ° C. for 8 hours as a dehydration step. The electrolyte used was 1M LiPF 6 / (ethylene carbonate + diethyl carbonate). The positive electrode for the secondary battery, the polypropylene separator moistened with the electrolyte, and the negative electrode for the secondary battery in a sealed coin-type stainless steel container. A secondary battery was made by attaching a stainless steel lid.
＜評 価＞
以上のように構成され実施例の二次電池について、放電容量−電圧曲線を測定した。測定は２極式により、10mA/cm2の定電流密度条件下で行った。結果を図１に示す。試験当初において、ＤＭｃＴ当たりの容量は185mAh/gで、利用率は５２％であり、充電可能な電気量が大きいことがわかった。また、1000サイクルの電位走査を行った後においても、容量の減少は僅か8％であり、充放電の繰り返しによる容量低下も少ないことがわかった。
これらの結果は、次のように説明される。すなわち、実施例の二次電池では、正極材料として理論容量密度の大きなＤＭｃＴを用いており、図２に示すように、ＤＭｃＴリチウム塩１が伝導性に優れた単層カーボンナノチューブ２の細孔内部に内包されている。このため、ＤＭｃＴリチウム塩１ａの溶出が阻止されることなく、狭い管状の細孔というナノサイズの領域において酸化（充電）されてＤＭｃＴリチウム塩二量体１ｂとなる。さらに、還元（放電）工程ではＤＭｃＴリチウム塩二量体１ｂが還元されてＤＭｃＴリチウム塩１ａとなる。こうして、単層カーボンナノチューブ２という、狭い管状の細孔というナノサイズの領域でDMcT化合物が、可逆的なレドックス反応を円滑に行うことができる。さらに、カーボンナノチューブの中でも特に単層カーボンナノチューブ２を用いているため、その管状の分子構造における壁が薄く、相対的に管状の細孔の占める体積割合が大きくなることから、多層カーボンナノチューブを用いた場合よりも、多くのDMcT化合物を細孔内部に入れることができ、電気容量が大きくなるのである。
<Evaluation>
About the secondary battery of the Example comprised as mentioned above, the discharge capacity-voltage curve was measured. The measurement was performed by a bipolar method under a constant current density condition of 10 mA / cm 2 . The results are shown in FIG. At the beginning of the test, the capacity per DMcT was 185 mAh / g, the utilization rate was 52%, and it was found that the amount of electricity that can be charged was large. Further, it was found that even after 1000 cycles of potential scanning, the capacity decrease was only 8%, and the capacity decrease due to repeated charge and discharge was small.
These results are explained as follows. That is, in the secondary battery of the example, DMcT having a large theoretical capacity density is used as the positive electrode material. As shown in FIG. 2, the DMcT lithium salt 1 has an excellent conductivity inside the pores of the single-walled carbon nanotube 2. Is included. For this reason, the elution of DMcT lithium salt 1a is not inhibited, and it is oxidized (charged) in a nano-sized region of narrow tubular pores to form DMcT lithium salt dimer 1b. Further, in the reduction (discharge) step, DMcT lithium salt dimer 1b is reduced to DMcT lithium salt 1a. Thus, the DMcT compound can smoothly perform a reversible redox reaction in the nano-sized region of single-walled carbon nanotubes 2 such as narrow tubular pores. Furthermore, since the single-walled carbon nanotube 2 is used among the carbon nanotubes, the wall in the tubular molecular structure is thin, and the volume ratio occupied by the tubular pores is relatively large. More DMcT compounds can be put inside the pores than in the case of increasing the electric capacity.
１ａ…ＤＭｃＴリチウム塩（含イオウ化合物）
１ｂ…ＤＭｃＴリチウム塩二量体（含イオウ化合物）
２…単層カーボンナノチューブ
1a ... DMcT lithium salt (sulfur-containing compound)
1b ... DMcT lithium salt dimer (sulfur-containing compound)
2 ... Single-walled carbon nanotube
Claims (13)
前記カーボンは単層カーボンナノチューブであることを特徴とする二次電池用正極材料。 A positive electrode material for a secondary battery containing a sulfur-containing compound that performs a redox reaction by cleavage-recombination of disulfide bonds and carbon,
The positive electrode material for a secondary battery, wherein the carbon is a single-walled carbon nanotube.
前記含イオウ化合物は２以上のチオール基若しくはその塩を有する複素環式化合物又はそれらの多量体であり、前記カーボンはカーボンナノチューブであることを特徴とする二次電池用正極材料。 A positive electrode material for a secondary battery containing a sulfur-containing compound that performs a redox reaction by cleavage-recombination of disulfide bonds and carbon,
The positive electrode material for a secondary battery, wherein the sulfur-containing compound is a heterocyclic compound having two or more thiol groups or a salt thereof or a multimer thereof, and the carbon is a carbon nanotube.
該混合工程によって得られた混合液を固液分離して含イオウ化合物を含むカーボンナノチューブを得る分離工程と、
該分離工程によって得られた含イオウ化合物を含むカーボンナノチューブを洗浄する洗浄工程と、を備えることを特徴とする二次電池用正極材料の製造方法。 A mixing step of mixing a carbon nanotube with a solution of a sulfur-containing compound that performs a redox reaction by cleavage-recombination of disulfide bonds;
A separation step of obtaining a carbon nanotube containing a sulfur-containing compound by solid-liquid separation of the mixed solution obtained by the mixing step;
And a washing step of washing the carbon nanotubes containing the sulfur-containing compound obtained by the separation step. A method for producing a positive electrode material for a secondary battery, comprising:
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009114314A3 (en) * | 2008-03-12 | 2009-11-26 | Toyota Motor Engineering & Manufacturing North America, Inc. | Sulfur-carbon material |
| WO2011031297A3 (en) * | 2009-08-28 | 2011-07-21 | Sion Power Corporation | Electrochemical cells comprising porous structures comprising sulfur |
| CN102263257A (en) * | 2011-06-28 | 2011-11-30 | 中国科学院金属研究所 | High energy flexible electrode material and preparation method thereof and application thereof in storage battery |
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| JP2018503945A (en) * | 2014-12-22 | 2018-02-08 | アルケマ フランス | Active electrode material for Li-S battery |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11329413A (en) * | 1998-03-31 | 1999-11-30 | Aventis Res & Technol Gmbh & Co Kg | Lithium battery and electrode |
| JPH11329414A (en) * | 1998-03-31 | 1999-11-30 | Aventis Res & Technol Gmbh & Co Kg | Lithium battery and electrode |
| JP2002510842A (en) * | 1998-03-31 | 2002-04-09 | セラニーズ・ヴェンチャーズ・ゲーエムベーハー | Lithium batteries and electrodes |
| JP2002334697A (en) * | 2001-05-08 | 2002-11-22 | Hitachi Maxell Ltd | Non-aqueous secondary battery |
| JP2005050669A (en) * | 2003-07-28 | 2005-02-24 | Tdk Corp | Electrode and electrochemical element using it |
| JP2005158305A (en) * | 2003-11-20 | 2005-06-16 | Fukuda Metal Foil & Powder Co Ltd | Negative electrode material for lithium secondary battery, and its manufacturing method |
| JP2007153682A (en) * | 2005-12-06 | 2007-06-21 | Nagoya Institute Of Technology | Lithium ion storage body and lithium ion storage method |
| JP2007525787A (en) * | 2003-05-20 | 2007-09-06 | フェニックス イノベーション，インク． | New carbon nanotube lithium battery |
-
2006
- 2006-02-28 JP JP2006053195A patent/JP5099299B2/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11329413A (en) * | 1998-03-31 | 1999-11-30 | Aventis Res & Technol Gmbh & Co Kg | Lithium battery and electrode |
| JPH11329414A (en) * | 1998-03-31 | 1999-11-30 | Aventis Res & Technol Gmbh & Co Kg | Lithium battery and electrode |
| JP2002510842A (en) * | 1998-03-31 | 2002-04-09 | セラニーズ・ヴェンチャーズ・ゲーエムベーハー | Lithium batteries and electrodes |
| JP2002334697A (en) * | 2001-05-08 | 2002-11-22 | Hitachi Maxell Ltd | Non-aqueous secondary battery |
| JP2007525787A (en) * | 2003-05-20 | 2007-09-06 | フェニックス イノベーション，インク． | New carbon nanotube lithium battery |
| JP2005050669A (en) * | 2003-07-28 | 2005-02-24 | Tdk Corp | Electrode and electrochemical element using it |
| JP2005158305A (en) * | 2003-11-20 | 2005-06-16 | Fukuda Metal Foil & Powder Co Ltd | Negative electrode material for lithium secondary battery, and its manufacturing method |
| JP2007153682A (en) * | 2005-12-06 | 2007-06-21 | Nagoya Institute Of Technology | Lithium ion storage body and lithium ion storage method |
Cited By (27)
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|---|---|---|---|---|
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| JP2013118191A (en) * | 2008-03-12 | 2013-06-13 | Toyota Motor Engineering & Manufacturing North America Inc | Sulfur-carbon material |
| WO2009114314A3 (en) * | 2008-03-12 | 2009-11-26 | Toyota Motor Engineering & Manufacturing North America, Inc. | Sulfur-carbon material |
| JP2011518743A (en) * | 2008-03-12 | 2011-06-30 | トヨタ モーター エンジニアリング アンド マニュファクチャリング ノース アメリカ，インコーポレイティド | Sulfur-carbon material |
| US8173302B2 (en) | 2008-06-11 | 2012-05-08 | Toyota Motor Engineering & Manufacturing North America, Inc. | Sulfur-carbon material |
| US10629947B2 (en) | 2008-08-05 | 2020-04-21 | Sion Power Corporation | Electrochemical cell |
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| US9005809B2 (en) | 2009-08-28 | 2015-04-14 | Sion Power Corporation | Electrochemical cells comprising porous structures comprising sulfur |
| CN102598364A (en) * | 2009-08-28 | 2012-07-18 | 赛昂能源有限公司 | Electrochemical cells comprising porous structures comprising sulfur |
| US9419274B2 (en) | 2009-08-28 | 2016-08-16 | Sion Power Corporation | Electrochemical cells comprising porous structures comprising sulfur |
| US9548492B2 (en) | 2011-06-17 | 2017-01-17 | Sion Power Corporation | Plating technique for electrode |
| US11456459B2 (en) | 2011-06-17 | 2022-09-27 | Sion Power Corporation | Plating technique for electrode |
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| JP2013197595A (en) * | 2012-03-22 | 2013-09-30 | Boeing Co:The | Redox polymer energy storage system |
| US9728346B2 (en) | 2012-03-22 | 2017-08-08 | The Boeing Company | Redox polymer energy storage system |
| JPWO2014080974A1 (en) * | 2012-11-21 | 2017-01-05 | 国立大学法人信州大学 | Carbon nanotube and method for producing the same |
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| JP2016535716A (en) * | 2013-10-18 | 2016-11-17 | エルジー・ケム・リミテッド | Carbon nanotube-sulfur composite containing carbon nanotube aggregate and method for producing the same |
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