JP2004111374A - Electrochemical device - Google Patents
Electrochemical device Download PDFInfo
- Publication number
- JP2004111374A JP2004111374A JP2003290160A JP2003290160A JP2004111374A JP 2004111374 A JP2004111374 A JP 2004111374A JP 2003290160 A JP2003290160 A JP 2003290160A JP 2003290160 A JP2003290160 A JP 2003290160A JP 2004111374 A JP2004111374 A JP 2004111374A
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- Prior art keywords
- atom
- group
- compound
- active material
- electrochemical device
- Prior art date
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- 238000006479 redox reaction Methods 0.000 claims abstract description 18
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- 239000011149 active material Substances 0.000 claims description 32
- 125000001931 aliphatic group Chemical group 0.000 claims description 31
- 125000004434 sulfur atom Chemical group 0.000 claims description 27
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- 229910052744 lithium Inorganic materials 0.000 claims description 25
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 25
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
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- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 2
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 229910011939 Li2.6 Co0.4 N Inorganic materials 0.000 description 2
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- 125000003545 alkoxy group Chemical group 0.000 description 2
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- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
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- MPCRDALPQLDDFX-UHFFFAOYSA-L Magnesium perchlorate Chemical compound [Mg+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O MPCRDALPQLDDFX-UHFFFAOYSA-L 0.000 description 1
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- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
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- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000004001 thioalkyl group Chemical group 0.000 description 1
- 125000004055 thiomethyl group Chemical group [H]SC([H])([H])* 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000002827 triflate group Chemical class FC(S(=O)(=O)O*)(F)F 0.000 description 1
Images
Classifications
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- 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
本発明は、軽量かつ高エネルギー密度でサイクル特性に優れた電気化学素子およびそれに用いる電極活物質に関する。 (4) The present invention relates to an electrochemical device which is lightweight, has a high energy density and is excellent in cycle characteristics, and an electrode active material used therefor.
近年、移動体通信機器、携帯電子機器の開発にともない、その電源の需要は非常に大きくなっている。電池、なかでも繰り返し充放電が可能なリチウム二次電池は、起電力が高く、高いエネルギー密度が得られ、繰り返し使用が可能なことから、携帯電子機器等の電源として広範囲に用いられている。 2. Description of the Related Art In recent years, with the development of mobile communication devices and portable electronic devices, the demand for power supplies has become extremely large. Batteries, especially lithium secondary batteries that can be repeatedly charged and discharged, are widely used as power sources for portable electronic devices and the like because of their high electromotive force, high energy density, and reusability.
しかし、携帯電子機器の小型軽量化に伴い、電池の高エネルギー密度化に対する要望もますます高まってきており、さらに高いエネルギー密度を有する新規な電極材料の出現が望まれている。このような背景のもと、電池の高エネルギー密度化に直接的に結びつく電極材料の高エネルギー密度化を目指して、材料開発の取り組みが積極的に行われている。 However, as portable electronic devices have become smaller and lighter, the demand for higher energy density of batteries has been increasing, and the appearance of new electrode materials having higher energy density has been desired. Against this background, material development is being actively pursued with the aim of increasing the energy density of electrode materials that is directly linked to higher energy density of batteries.
近年、エネルギー密度が高く、より軽量な電池を作製するために、有機化合物を電極材料に用いる検討が行われている。有機化合物は、比重が１ｇ／ｃｍ3程度と軽く、現在リチウム二次電池の材料として用いられているコバルト酸リチウムなどの酸化物と比較して軽量である。このため、より軽量で高容量な電池を作製することが可能となる。 In recent years, studies have been made to use an organic compound as an electrode material in order to produce a lighter battery with a high energy density. The organic compound has a light specific gravity of about 1 g / cm 3, and is lighter than oxides such as lithium cobalt oxide which is currently used as a material for lithium secondary batteries. Therefore, a lighter and higher capacity battery can be manufactured.
例えば、ジスルフィド結合を持つ有機化合物を電極材料に用いた二次電池が提案されている（特許文献１、２参照）。この有機硫黄化合物は、最も簡単には、Ｍ+−-Ｓ−Ｒ−Ｓ-−Ｍ+と表される。ここで、Ｒは脂肪族あるいは芳香族の有機基、Ｓは硫黄、Ｍ+はプロトンあるいは金属カチオンを示す。この化合物は、電気化学的酸化反応によりＳ−Ｓ結合を介して互いに結合し、
Ｍ+−-Ｓ−Ｒ−Ｓ−Ｓ−Ｒ−Ｓ−Ｓ−Ｒ−Ｓ-−Ｍ+
のような形で高分子化する。こうして生成した高分子は、電気化学的還元反応により、元のモノマーに戻る。二次電池では、この反応を充放電反応に用いる。
For example, secondary batteries using an organic compound having a disulfide bond as an electrode material have been proposed (see Patent Documents 1 and 2). This organic sulfur compound is most simply represented as M + -- S-R-S -- M + . Here, R represents an aliphatic or aromatic organic group, S represents sulfur, and M + represents a proton or metal cation. The compounds bind to each other via an SS bond by an electrochemical oxidation reaction,
M + - - S-R- S-S-R-S-S-R-S - -M +
Polymerized in the form of The polymer thus formed returns to the original monomer by an electrochemical reduction reaction. In a secondary battery, this reaction is used for a charge / discharge reaction.
また、単体硫黄を電極材料に用いることも提案されている（特許文献３参照）。しかし、どちらの場合も高容量化は可能であるが、サイクル特性が低いという問題がある。これは、硫黄系材料の酸化還元反応におけるジスルフィド結合の解列・再結合では、再結合する頻度が低くなるためである。また、一度解列すると再結合する頻度が低いということは、たとえ理論的に高いエネルギー密度を有していたとしても、すべての反応可能な部位が反応できないことを意味する。これでは、実際には高エネルギー密度を有する材料とは言えない。
以上のように、硫黄系材料を電極材料に用いた軽量で高エネルギー密度な電気化学素子においては、酸化還元反応に伴い、硫黄系材料の構造変化が起こるため、サイクル特性が低いという問題がある。本発明は、この点を鑑みたものであり、軽量で高エネルギー密度な電気化学素子のサイクル特性の改善を目的とする。 As described above, in a light-weight, high-energy-density electrochemical element using a sulfur-based material as an electrode material, the structural change of the sulfur-based material occurs with the oxidation-reduction reaction, and thus the cycle characteristics are low. . The present invention has been made in view of this point, and has as its object to improve the cycle characteristics of a lightweight and high energy density electrochemical device.
本発明は、酸化還元反応に伴う電子移動を電気エネルギーとして取り出す電気化学素子であって、正極と、負極と、電解質とからなり、前記正極および前記負極より選ばれる少なくとも一方が、一般式（１）： The present invention relates to an electrochemical device for extracting electron transfer accompanying an oxidation-reduction reaction as electric energy, comprising a positive electrode, a negative electrode, and an electrolyte, wherein at least one selected from the positive electrode and the negative electrode has a general formula (1) ):
（式中、Ｒ1およびＲ2は、それぞれ独立に鎖状または環状の脂肪族基であり、Ｒ1とＲ2は同じであっても異なっていてもよく、Ｘ1〜Ｘ4は、それぞれ独立に硫黄原子、酸素原子またはテルル原子であり、Ｘ1〜Ｘ4は同じであっても異なっていてもよく、前記脂肪族基は、酸素原子、窒素原子、硫黄原子、ケイ素原子、リン原子およびホウ素原子よりなる群から選ばれる１種以上を含むことができる。）で表される構造を有する化合物を含むことを特徴とする電気化学素子に関する。 (Wherein, R 1 and R 2 are each independently a chain or cyclic aliphatic group, R 1 and R 2 may be the same or different, and X 1 to X 4 are each independently X 1 to X 4 may be the same or different, independently of a sulfur atom, an oxygen atom or a tellurium atom, and the aliphatic group is an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom And at least one selected from the group consisting of boron atoms.)
一般式（１）において、前記脂肪族基としては、特に制限はないが、炭素数１〜６の脂肪族基が好ましい。特に、一般式（１）の構造が、２つの環状π電子系グループを二重結合で繋いだ構造となるように、脂肪族基を選択することが好ましい。
一般式（１）で表される構造を有する化合物には、一般式（２）：
In the general formula (1), the aliphatic group is not particularly limited, but is preferably an aliphatic group having 1 to 6 carbon atoms. In particular, it is preferable to select an aliphatic group so that the structure of the general formula (1) becomes a structure in which two cyclic π-electron groups are connected by a double bond.
The compound having the structure represented by the general formula (1) includes a compound represented by the general formula (2):
（式中、Ｒ3〜Ｒ6は、それぞれ独立に鎖状または環状の脂肪族基、水素原子、ヒドロキシル基、シアノ基、アミノ基、ニトロ基またはニトロソ基であり、Ｒ3〜Ｒ6は同じであっても異なっていてもよく、前記脂肪族基は、酸素原子、窒素原子、硫黄原子、ケイ素原子、リン原子、ホウ素原子およびハロゲン原子よりなる群から選ばれる１種以上を含むことができる。）で表される化合物を用いることができる。
一般式（１）で表される構造を有する化合物には、また、一般式（３）：
(Wherein, R 3 to R 6 are each independently a chain or cyclic aliphatic group, a hydrogen atom, a hydroxyl group, a cyano group, an amino group, a nitro group or a nitroso group, and R 3 to R 6 are the same. And the aliphatic group may include one or more selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom and a halogen atom. ) Can be used.
The compound having the structure represented by the general formula (1) also includes a compound represented by the general formula (3):
（式中、Ｒ7およびＲ8は、それぞれ独立に鎖状または環状の脂肪族基、水素原子、ヒドロキシル基、シアノ基、アミノ基、ニトロ基またはニトロソ基であり、Ｒ7とＲ8は同じであっても異なっていてもよく、Ｘは、イオウ原子、酸素原子またはテルル原子であり、前記脂肪族基は、酸素原子、窒素原子、イオウ原子、ケイ素原子、リン原子、ホウ素原子およびハロゲン原子よりなる群から選ばれる１種以上を含むことができる。）で表される化合物を用いることができる。
一般式（１）で表される構造を有する化合物には、また、一般式（４）：
(Wherein, R 7 and R 8 are each independently a chain or cyclic aliphatic group, a hydrogen atom, a hydroxyl group, a cyano group, an amino group, a nitro group or a nitroso group, and R 7 and R 8 are the same. And X is a sulfur atom, an oxygen atom or a tellurium atom, and the aliphatic group is an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, and a halogen atom. At least one member selected from the group consisting of :).
The compound having the structure represented by the general formula (1) includes a compound represented by the general formula (4):
（式中、ＸおよびＹは、それぞれ独立に硫黄原子、酸素原子またはメチレン基であり、ＸとＹは同じであっても異なっていてもよい。）で表される化合物を用いることができる。
一般式（１）で表される構造を有する化合物には、また、一般式（５）：
(Wherein, X and Y are each independently a sulfur atom, an oxygen atom or a methylene group, and X and Y may be the same or different.).
The compound having the structure represented by the general formula (1) also includes a compound represented by the general formula (5):
（式中、Ｒ9およびＲ10は、それぞれ独立に鎖状または環状の脂肪族基、水素原子、ヒドロキシル基、シアノ基、アミノ基、ニトロ基またはニトロソ基であり、Ｒ9とＲ10は同じであっても異なっていてもよく、前記脂肪族基は、酸素原子、窒素原子、イオウ原子、ケイ素原子、リン原子、ホウ素原子およびハロゲン原子よりなる群から選ばれる１種以上を含むことができ、ｎは１以上である。）で表される化合物を用いることができる。
一般式（１）で表される構造を有する化合物には、また、化学式（６）：
(Wherein R 9 and R 10 are each independently a chain or cyclic aliphatic group, a hydrogen atom, a hydroxyl group, a cyano group, an amino group, a nitro group or a nitroso group, and R 9 and R 10 are the same. And the aliphatic group may include one or more selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, and a halogen atom. , N is 1 or more.).
The compound having the structure represented by the general formula (1) also includes a compound represented by the chemical formula (6):
で表される化合物を用いることができる。
一般式（２）、（３）および（５）において、前記脂肪族基としては、例えば、アルキル基、シクロアルキル基、アルコキシ基、ヒドロキシアルキル基、チオアルキル基、アルデヒド基、カルボン酸基、ハロゲン化アルキル基などが挙げられる。
Can be used.
In the general formulas (2), (3) and (5), examples of the aliphatic group include an alkyl group, a cycloalkyl group, an alkoxy group, a hydroxyalkyl group, a thioalkyl group, an aldehyde group, a carboxylic acid group, and a halogenated group. And an alkyl group.
一般式（１）で表される構造を有する化合物には、また、一般式（１）で表される構造を複数有する高分子化合物を用いることができる。前記高分子化合物は、ポリアセチレン鎖を主鎖として有することが好ましい。前記高分子化合物は膜を形成していることが好ましい。膜の厚さは１０〜３００μｍであることが好ましい。このような膜は、化学合成や式（１）の構造を有する低分子化合物の電解重合などによって得ることができる。 高分子 As the compound having the structure represented by the general formula (1), a polymer compound having a plurality of structures represented by the general formula (1) can be used. The polymer compound preferably has a polyacetylene chain as a main chain. Preferably, the polymer compound forms a film. The thickness of the film is preferably from 10 to 300 μm. Such a film can be obtained by chemical synthesis, electrolytic polymerization of a low molecular compound having the structure of the formula (1), or the like.
本発明の電気化学素子において、前記電解質は、溶媒および前記溶媒に拡散するアニオンとカチオンからなり、前記化合物は、酸化還元反応に伴い、前記カチオンおよび／またはアニオンと配位結合を形成する能力を有することが好ましい。前記カチオンは、リチウムイオンであることが好ましい。 In the electrochemical device according to the aspect of the invention, the electrolyte may include a solvent and an anion and a cation that diffuse into the solvent, and the compound may have a capability of forming a coordination bond with the cation and / or an anion with a redox reaction. It is preferred to have. The cation is preferably a lithium ion.
本発明の電気化学素子において、前記正極は、一般式（１）で表される構造を有する化合物を正極活物質として含み、前記負極は、炭素材料を負極活物質として含むことが好ましい。また、本発明の電気化学素子において、前記正極は、前記化合物を正極活物質として含み、前記負極は、リチウム金属、リチウム含有複合窒化物およびリチウム含有複合チタン酸化物よりなる群から選ばれる少なくとも１種を負極活物質として含むことが好ましい。 In the electrochemical device of the present invention, it is preferable that the positive electrode includes a compound having a structure represented by the general formula (1) as a positive electrode active material, and the negative electrode includes a carbon material as a negative electrode active material. In the electrochemical device of the present invention, the positive electrode contains the compound as a positive electrode active material, and the negative electrode has at least one selected from the group consisting of lithium metal, lithium-containing composite nitride, and lithium-containing composite titanium oxide. It is preferable to include a seed as a negative electrode active material.
本発明は、また、上述の一般式（１）〜（６）のいずれかで表される構造を有する化合物を少なくとも１種含む電気化学素子用電極活物質に関する。
本発明は、さらに、酸化還元反応に伴う電子移動を電気エネルギーとして取り出す電気化学素子であって、正極と、負極と、電解質とからなり、前記正極および前記負極より選ばれる少なくとも一方が、一般式（１）で表される構造を有する化合物およびそれを担持する基材を含み、前記基材と一般式（１）で表される構造を有する化合物とが、化学結合により結合されている電気化学素子に関する。
The present invention also relates to an electrode active material for an electrochemical device including at least one compound having a structure represented by any of the above general formulas (1) to (6).
The present invention is further an electrochemical device that takes out electron transfer accompanying an oxidation-reduction reaction as electric energy, comprising a positive electrode, a negative electrode, and an electrolyte, wherein at least one selected from the positive electrode and the negative electrode has a general formula Electrochemistry comprising a compound having a structure represented by (1) and a substrate supporting the compound, wherein the substrate and a compound having a structure represented by the general formula (1) are bonded by a chemical bond. Related to the element.
前記化学結合は、共有結合および配位結合よりなる群から選択される少なくとも１種であることが好ましい。前記共有結合は、Ｓｉ−Ｏ結合、Ｔｉ−Ｏ結合およびアミド結合よりなる群から選択される少なくとも１種を含むことがこのましい。前記配位結合は、金属−硫黄結合であることが好ましい。前記基材には、金属、金属酸化物、粘土層間化合物、炭素化合物、珪素化合物、樹脂などを用いることができる。 The chemical bond is preferably at least one selected from the group consisting of a covalent bond and a coordination bond. The covalent bond preferably includes at least one selected from the group consisting of a Si-O bond, a Ti-O bond, and an amide bond. The coordination bond is preferably a metal-sulfur bond. Metals, metal oxides, clay interlayer compounds, carbon compounds, silicon compounds, resins, and the like can be used for the base material.
本発明は、さらに、前記化合物および前記化合物を担持する基材を含み、前記基材と前記化合物とが、化学結合により結合されている電気化学素子用電極活物質に関する。 The present invention further relates to an electrode active material for an electrochemical element, comprising the compound and a substrate supporting the compound, wherein the substrate and the compound are bonded by a chemical bond.
本発明によれば、一般式（１）で表される構造を有する化合物を電極活物質に用いることから、軽量かつ高エネルギー密度でサイクル特性に優れた電気化学素子を得ることができる。 According to the present invention, since the compound having the structure represented by the general formula (1) is used as the electrode active material, an electrochemical device that is lightweight, has high energy density, and has excellent cycle characteristics can be obtained.
本発明の電気化学素子は、酸化還元反応に伴う電子移動を電気エネルギーとして取り出す電気化学素子であって、正極と、負極と、電解質とからなり、前記正極および前記負極より選ばれる少なくとも一方が、一般式（１）： The electrochemical element of the present invention is an electrochemical element that takes out electron transfer accompanying an oxidation-reduction reaction as electric energy, and includes a positive electrode, a negative electrode, and an electrolyte, and at least one selected from the positive electrode and the negative electrode, General formula (1):
（式中、Ｒ1およびＲ2は、それぞれ独立に鎖状または環状の脂肪族基であり、Ｒ1とＲ2は同じであっても異なっていてもよく、Ｘ1〜Ｘ4は、それぞれ独立に硫黄原子、酸素原子またはテルル原子であり、Ｘ1〜Ｘ4は同じであっても異なっていてもよく、前記脂肪族基は、酸素原子、窒素原子、硫黄原子、ケイ素原子、リン原子およびホウ素原子よりなる群から選ばれる１種以上を含むことができる。）で表される構造を有する化合物（以下、活物質化合物ともいう）からなることを特徴とする。活物質化合物は、電池内において酸化還元反応を行い、電子の授受を行う。 (Wherein, R 1 and R 2 are each independently a chain or cyclic aliphatic group, R 1 and R 2 may be the same or different, and X 1 to X 4 are each independently X 1 to X 4 may be the same or different, independently of a sulfur atom, an oxygen atom or a tellurium atom, and the aliphatic group is an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom And at least one selected from the group consisting of boron atoms) (hereinafter also referred to as an active material compound). The active material compound undergoes an oxidation-reduction reaction in the battery to exchange electrons.
活物質化合物は、その構造を大きく変化させることなく酸化還元反応を行うことができる。その機構は以下のとおりである。
活物質化合物は、構造対称性を有し、平面構造を有する。また、活物質化合物は、分子の中心に炭素−炭素二重結合を有し、かつ、硫黄、酸素などのカルコゲン元素を含む環状構造を有する。カルコゲン元素は孤立電子対を有する。そのため、分子上にπ電子共役電子雲が形成される。この分子上に広がったπ電子共役電子雲は、電子の授受が可能である。電子の授受は、活物質化合物の酸化・還元反応として進行する。
The active material compound can perform an oxidation-reduction reaction without largely changing the structure. The mechanism is as follows.
The active material compound has a structural symmetry and a planar structure. The active material compound has a carbon-carbon double bond at the center of the molecule and has a cyclic structure containing a chalcogen element such as sulfur or oxygen. The chalcogen element has a lone pair of electrons. Therefore, a π electron conjugated electron cloud is formed on the molecule. The π-electron conjugated electron cloud spread over the molecule can transfer electrons. The transfer of electrons proceeds as an oxidation / reduction reaction of the active material compound.
例えば、還元反応（放電反応）時には、活物質化合物が還元され、電解質中のカチオンが、還元された分子に配位する。その後の酸化反応（充電反応）時には、活物質化合物に配位していたカチオンが脱離する。この反応を電池反応として用いることができる。また、酸化反応（充電反応）時に活物質化合物が酸化される場合には、電解質のアニオンが、酸化された分子に配位する。その後の還元反応（放電反応）時には、活物質化合物に配位していたアニオンが脱離する。 For example, during a reduction reaction (discharge reaction), the active material compound is reduced, and cations in the electrolyte are coordinated with the reduced molecule. During the subsequent oxidation reaction (charging reaction), the cation coordinated to the active material compound is eliminated. This reaction can be used as a battery reaction. When the active material compound is oxidized during the oxidation reaction (charging reaction), the anion of the electrolyte coordinates to the oxidized molecule. During the subsequent reduction reaction (discharge reaction), anions coordinated to the active material compound are eliminated.
このような一連の酸化還元反応において、活物質化合物は、結合の解裂・再結合といった大きな構造変化を起こさないと考えられる。酸化還元反応に伴って前記化合物の分子が大きく構造変化すると、次の反応を行う際にも分子の構造変化が必要となり、このとき大きなエネルギーが必要となる。そのため反応性は低下する。従って、酸化還元反応に伴う大きな構造変化がないことは、反応を効率的に行い得ることを示している。 に お い て In such a series of oxidation-reduction reactions, it is considered that the active material compound does not cause a large structural change such as bond cleavage / recombination. If the molecule of the compound undergoes a large structural change in association with the oxidation-reduction reaction, the structural change of the molecule is required even when performing the next reaction, and a large amount of energy is required at this time. As a result, the reactivity decreases. Therefore, the absence of a large structural change accompanying the oxidation-reduction reaction indicates that the reaction can be performed efficiently.
以上のように、本発明では、分子上に広がったπ電子共役部位を酸化還元反応部位とする化合物を電極活物質に用いている。上記反応機構では、酸化還元反応に伴って活物質の骨格の大きな構造変化は起こらない。従って、酸化還元反応の繰り返しによる活物質の構造的な劣化が抑制されるため、優れた充放電サイクル特性が得られる。 As described above, in the present invention, a compound having a π electron conjugate site spread on a molecule as an oxidation-reduction reaction site is used as an electrode active material. In the above reaction mechanism, a large structural change of the skeleton of the active material does not occur with the oxidation-reduction reaction. Accordingly, structural deterioration of the active material due to repetition of the oxidation-reduction reaction is suppressed, so that excellent charge / discharge cycle characteristics can be obtained.
さらに、上記反応機構では、通常の有機硫黄系化合物が起こすような結合・解裂反応と比べて、速い反応速度を期待できる。反応速度が速くなると、電池特性としては優れたレート特性を期待できることから、急速充放電にも有利である。 Furthermore, in the above reaction mechanism, a higher reaction rate can be expected as compared with the binding / cleavage reaction that occurs with ordinary organic sulfur compounds. When the reaction rate is increased, excellent rate characteristics can be expected as battery characteristics, which is advantageous for rapid charging and discharging.
本発明においては、一般式（１）で表される構造を有する化合物のなかでも、特にテトラチアフルバレン構造を有する化合物を好ましく用いることができる。また、一般式（１）で表される構造を有する限り、低分子化合物から高分子化合物まで用いることができる。これらは単独で用いてもよく、２種以上を組み合わせて用いてもよい。 に お い て In the present invention, among the compounds having a structure represented by the general formula (1), a compound having a tetrathiafulvalene structure can be particularly preferably used. Further, as long as it has the structure represented by the general formula (1), it can be used from low molecular weight compounds to high molecular weight compounds. These may be used alone or in combination of two or more.
本発明において、高分子化合物とは、低分子化合物が重合してなる分子量１００００以上の化合物を言う。高分子化合物は、低分子化合物に比べて電解液などに溶解しにくい性質を有する。従って、高分子化合物を電極活物質として用いた場合には、電解液への活物質の溶出が抑えられ、サイクル特性の安定性が、さらに高められる。 高分子 In the present invention, the high molecular compound means a compound having a molecular weight of 10,000 or more obtained by polymerizing a low molecular compound. The polymer compound has a property that it is harder to dissolve in an electrolytic solution or the like than the low molecular compound. Therefore, when the polymer compound is used as the electrode active material, elution of the active material into the electrolytic solution is suppressed, and the stability of cycle characteristics is further enhanced.
高分子化合物としては、ポリアセチレン鎖を主鎖として有する化合物が好ましい。また、一分子内に一般式（１）で表される構造を２個以上含むことが好ましい。ポリアセチレン鎖の分子量は１００００〜２０００００であることが好ましい。
活物質化合物の好ましい具体例としては、例えば、化学式（６）：
As the polymer compound, a compound having a polyacetylene chain as a main chain is preferable. Further, it is preferable that two or more structures represented by the general formula (1) are included in one molecule. The molecular weight of the polyacetylene chain is preferably 10,000 to 200,000.
Preferred specific examples of the active material compound include, for example, a chemical formula (6):
で表される化合物、化学式（７）： A compound represented by the following chemical formula (7):
で表される化合物、化学式（８）： A compound represented by the following formula, chemical formula (8):
で表される化合物、化学式（９）： A compound represented by the following formula, chemical formula (9):
で表される化合物、化学式（１０）： A compound represented by the following formula, chemical formula (10):
で表される化合物、化学式（１１）： A compound represented by the following chemical formula (11):
で表される化合物、化学式（１２）： A compound represented by the following formula, chemical formula (12):
で表される化合物、化学式（１３）： A compound represented by the following formula, chemical formula (13):
で表される化合物、化学式（１４）： A compound represented by the following chemical formula (14):
で表される化合物、化学式（１５）： A compound represented by the following chemical formula (15):
で表される化合物、化学式（１６）： A compound represented by the following chemical formula (16):
で表される化合物、化学式（１７）： A compound represented by the following chemical formula (17):
で表される化合物等を挙げることができる。これらは単独で用いてもよく、２種以上を組み合わせて用いてもよい。
活物質化合物は、電気化学素子のなかでも、特に二次電池の電極活物質として用いるのに適しているが、一次電池、電解コンデンサ、各種センサ、エレクトロクロミック素子等の電極にも用いることができる。
And the like. These may be used alone or in combination of two or more.
The active material compound is particularly suitable for use as an electrode active material of a secondary battery among electrochemical devices, but can also be used for electrodes of a primary battery, an electrolytic capacitor, various sensors, an electrochromic device, and the like. .
二次電池においては、一般式（１）で表される構造を有する化合物は、正極と負極の両方に用いてもよく、どちらか一方に用いてもよい。どちらか一方の電極に前記化合物を用いる場合には、他方の電極活物質には、二次電池の活物質として従来から用いられている材料を特に限定なく用いることができる。 に お い て In the secondary battery, the compound having the structure represented by the general formula (1) may be used for both the positive electrode and the negative electrode, or may be used for either one. When the compound is used for one of the electrodes, a material conventionally used as an active material for a secondary battery can be used for the other electrode active material without any particular limitation.
正極活物質として一般式（１）で表される構造を有する化合物を用いる場合には、負極活物質として、例えば、グラファイト、非晶質炭素などの炭素材料、リチウム金属、リチウム含有複合窒化物、リチウム含有チタン酸化物、Ｓｎと炭素との複合物、Ｓｎと他の金属との複合物等を用いることができる。また、負極活物質として一般式（１）で表される構造を有する化合物を用いる場合には、正極活物質として、例えば、ＬｉＣｏＯ2、ＬｉＮｉＯ2、ＬｉＭｎ2Ｏ4などの金属酸化物等を用いることができる。 When a compound having a structure represented by the general formula (1) is used as the positive electrode active material, examples of the negative electrode active material include carbon materials such as graphite and amorphous carbon, lithium metal, and lithium-containing composite nitride. A lithium-containing titanium oxide, a composite of Sn and carbon, a composite of Sn and another metal, or the like can be used. When a compound having a structure represented by the general formula (1) is used as the negative electrode active material, a metal oxide such as LiCoO 2 , LiNiO 2 , and LiMn 2 O 4 is used as the positive electrode active material. be able to.
一般式（１）で表される構造を有する化合物を電極活物質に用いた場合、電極抵抗を低減する目的で、カーボンブラック、グラファイト、アセチレンブラック等の炭素材料、ポリアニリン、ポリピロール、ポリチオフェンなどの導電性高分子等を導電補助剤として電極活物質に混合させてもよい。また、イオン伝導補助剤として、ポリエチレンオキシドなどからなる固体電解質、ポリメタクリル酸メチルなどからなるゲル電解質を電極活物質に混合させてもよい。 When a compound having the structure represented by the general formula (1) is used as an electrode active material, a carbon material such as carbon black, graphite, and acetylene black, and a conductive material such as polyaniline, polypyrrole, and polythiophene are used for the purpose of reducing electrode resistance. A conductive polymer or the like may be mixed with the electrode active material as a conductive auxiliary. Further, a solid electrolyte made of polyethylene oxide or the like or a gel electrolyte made of polymethyl methacrylate or the like may be mixed with the electrode active material as an ion conduction aid.
電極内物質の構成材料の結着性を向上させるために、結着剤を用いてもよい。結着剤としては、ポリフッ化ビニリデン、フッ化ビニリデン−ヘキサフルオロプロピレン共重合体、フッ化ビニリデン−テトラフルオロエチレン共重合体、ポリテトラフルオロエチレン、スチレン−ブタジエン共重合体、ポリプロピレン、ポリエチレン、ポリイミド等を用いることができる。 結 A binder may be used to improve the binding property of the constituent material of the substance in the electrode. As the binder, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, polytetrafluoroethylene, styrene-butadiene copolymer, polypropylene, polyethylene, polyimide, etc. Can be used.
正極集電体または負極集電体には、ニッケル、アルミニウム、金、銀、銅、ステンレス鋼、アルミニウム合金等からなる金属箔、金属メッシュ等を用いることができる。集電体上にカーボンなどを塗布することにより、電極の抵抗値を減少させたり、集電体に触媒効果をもたせたり、集電体と活物質と化学的または物理的に結合させたりしてもよい。 金属 A metal foil, a metal mesh, or the like made of nickel, aluminum, gold, silver, copper, stainless steel, an aluminum alloy, or the like can be used for the positive electrode current collector or the negative electrode current collector. By coating the current collector with carbon, etc., the resistance of the electrode can be reduced, the current collector can have a catalytic effect, or the current collector and the active material can be chemically or physically bonded. Is also good.
正極と負極の間にセパレータを介在させる場合には、セパレータに電解液を含浸させる。電解液は、溶媒および前記溶媒に溶解した溶質からなることが好ましい。電解液自体をゲル化させてセパレータとしての機能を持たせてもよい。この場合、ポリアクリロニトリル、アクリレート単位またはメタクリレート単位を含む重合体、エチレンとアクリロニトリルとの共重合体等のマトリックスに電解液を含浸させることが好ましい。マトリックスには架橋高分子を用いることが好ましい。 (4) When a separator is interposed between the positive electrode and the negative electrode, the separator is impregnated with an electrolytic solution. The electrolytic solution preferably comprises a solvent and a solute dissolved in the solvent. The electrolytic solution itself may be gelled to have a function as a separator. In this case, it is preferable to impregnate the electrolyte with a matrix such as polyacrylonitrile, a polymer containing acrylate units or methacrylate units, or a copolymer of ethylene and acrylonitrile. It is preferable to use a crosslinked polymer for the matrix.
電解液の溶質としては、リチウム、ナトリウム、カリウムなどのアルカリ金属またはマグネシウムなどのアルカリ土類金属のハロゲン化物、過塩素酸塩およびトリフロロメタンスルホン酸塩に代表される含フッ素化合物の塩等が好ましい。具体的には、例えば、フッ化リチウム、塩化リチウム、過塩素酸リチウム、トリフロロメタンスルホン酸リチウム、四ホウフッ化リチウム、ビストリフロロメチルスルホニルイミドリチウム、チオシアン酸リチウム、過塩素酸マグネシウム、トリフロロメタンスルホン酸マグネシウム、四ホウフッ化ナトリウムなどが挙げられる。これらは単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Examples of the solute of the electrolyte include halides of alkali metals such as lithium, sodium and potassium or alkali earth metals such as magnesium, salts of fluorine-containing compounds represented by perchlorates and trifluoromethanesulfonates, and the like. preferable. Specifically, for example, lithium fluoride, lithium chloride, lithium perchlorate, lithium trifluoromethanesulfonate, lithium tetrafluorofluoride, lithium bistrifluoromethylsulfonylimide, lithium thiocyanate, magnesium perchlorate, trifluoromethane Examples include magnesium sulfonate and sodium tetrafluoroborate. These may be used alone or in combination of two or more.
電解液の溶媒としては、例えば、エチレンカーボネート、プロピレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、メチルエチルカーボネート、γ−ブチロラクトン、テトラヒドロフラン、ジオキソラン、スルホラン、ジメチルホルムアミド等の有機溶媒が好ましく用いられる。 有機 As the solvent for the electrolytic solution, for example, organic solvents such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, γ-butyrolactone, tetrahydrofuran, dioxolan, sulfolane, and dimethylformamide are preferably used.
電解液の代わりに固体電解質を用いてもよい。固体電解質としては、Ｌｉ2Ｓ−ＳｉＳ2、Ｌｉ2Ｓ−Ｐ2Ｏ5、Ｌｉ2Ｓ−Ｂ2Ｓ5、Ｌｉ2Ｓ−Ｐ2Ｓ5−ＧｅＳ2、ナトリウム／アルミナ（Ａｌ2Ｏ3）、無定形または低相転移温度（Ｔｇ）のポリエーテル、無定形フッ化ビニリデン−６フッ化プロピレンコポリマー、異種高分子のブレンド体、ポリエチレンオキサイドなどが挙げられる。 A solid electrolyte may be used instead of the electrolytic solution. Examples of the solid electrolyte include Li 2 S—SiS 2 , Li 2 S—P 2 O 5 , Li 2 S—B 2 S 5 , Li 2 S—P 2 S 5 —GeS 2 , sodium / alumina (Al 2 O 3) ), Amorphous or low phase transition temperature (Tg) polyethers, amorphous vinylidene fluoride-6-propylene copolymers, blends of different polymers, polyethylene oxide, and the like.
活物質化合物は、化学結合を介して基材に担持させることができる。この場合、活物質化合物は、その誘導体であってもよい。化学結合は、共有結合であっても、配位結合であってもよい。活物質化合物を基材に担持することにより、電極（特に正極）活物質としての安定性が向上し、電池のサイクル特性を向上させることが可能となる。共有結合としては、Ｓｉ−Ｏ結合、Ｔｉ−Ｏ結合、アミド結合およびペプチド結合が好ましく、配位結合としては、金属−硫黄結合が好ましい。 The active material compound can be supported on the substrate via a chemical bond. In this case, the active material compound may be a derivative thereof. The chemical bond may be a covalent bond or a coordinate bond. By supporting the active material compound on the base material, the stability of the electrode (particularly, the positive electrode) as the active material is improved, and the cycle characteristics of the battery can be improved. The covalent bond is preferably a Si-O bond, a Ti-O bond, an amide bond, or a peptide bond, and the coordination bond is preferably a metal-sulfur bond.
基材には、金属、金属酸化物、粘土層間化合物、炭素材料、珪素化合物、樹脂類などを用いることができる。なお、金属には、アルミニウム、チタン、ニッケル、ステンレス鋼、金、銀、銅、白金、パラジウムなどを用いることが好ましく、金属酸化物には、ガラス、アルミナ、チタニアなどを用いることが好ましい。また、炭素材料には、カーボンブラック、グラファイト、アセチレンブラックなどを用いることができる。これらは表面水酸基、カルボキシル基等の官能基の量を多くする表面処理を行ってもよい。また、樹脂類には、フッ素樹脂、カーボン系樹脂、シリコーン樹脂、アミド樹脂、導電性樹脂などを用いることが好ましい。導電性樹脂としては、ポリアニリン、ポリピロール、ポリチオフェンなどが好ましい。 金属 A metal, a metal oxide, a clay interlayer compound, a carbon material, a silicon compound, a resin, or the like can be used for the base material. In addition, it is preferable to use aluminum, titanium, nickel, stainless steel, gold, silver, copper, platinum, palladium, and the like for the metal, and it is preferable to use glass, alumina, titania, and the like for the metal oxide. As the carbon material, carbon black, graphite, acetylene black, or the like can be used. These may be subjected to a surface treatment for increasing the amount of functional groups such as surface hydroxyl groups and carboxyl groups. Further, as the resins, it is preferable to use a fluorine resin, a carbon-based resin, a silicone resin, an amide resin, a conductive resin, or the like. As the conductive resin, polyaniline, polypyrrole, polythiophene, and the like are preferable.
Ｓｉ−Ｏ結合やＴｉ−Ｏ結合は、例えばＲnＳｉＸ(4-n)で表される有機珪素化合物やＲnＴｉＸ(4-n) で表される有機チタン化合物（Ｒは、それぞれ独立に有機基であり、Ｘは、それぞれ独立にハロゲン原子、アルコキシ基またはアシロキシ基であり、ｎは１〜３の整数である。）と、基材上に存在する水酸基との脱ハロゲン化水素または脱アルコール反応によって形成される。 The Si—O bond and the Ti—O bond are, for example, an organic silicon compound represented by R n SiX (4-n) or an organic titanium compound represented by R n TiX (4-n) (R is each independently X is an organic group, each independently represents a halogen atom, an alkoxy group or an acyloxy group, and n is an integer of 1 to 3) and a hydroxyl group present on the base material. It is formed by an alcohol reaction.
例えば有機珪素化合物であるＲＳｉＣｌ3の場合、
Ｒ−ＳｉＣｌ3 + ３ＲＯＨ → Ｒ−Ｓｉ（ＯＲ）3 + ３ＨＣｌ
の反応により、Ｓｉ−Ｏ結合が形成される。従って、基材表面上には、多くの水酸基が存在することが好ましい。なお、上記のような脱ハロゲン化水素反応は、ガラス表面の疎水化処理に多用されており、例えば疎水化処理により樹脂との接着性を改善したガラス繊維を用いてガラス繊維強化樹脂が製造されている。
For example, in the case of RSiCl 3 which is an organic silicon compound,
R-SiCl 3 + 3ROH → R-Si (OR) 3 + 3HCl
Form a Si—O bond. Therefore, it is preferable that many hydroxyl groups exist on the substrate surface. The dehydrohalogenation reaction as described above is frequently used for a hydrophobic treatment of a glass surface.For example, a glass fiber reinforced resin is manufactured using glass fibers having improved adhesion with a resin by the hydrophobic treatment. ing.
ここで、ＲnＳｉＸ(4-n)で表される有機珪素化合物やＲnＴｉＸ(4-n) で表される有機チタン化合物として、Ｒが一般式（１）で表される構造を有する有機基である化合物を用いることにより、基体上に一般式（１）で表される構造を有する化合物を担持させることができる。実際には、Ｒが一般式（１）で表される構造を有する有機基であるＲnＳｉＸ(4-n)やＲnＴｉＸ(4-n)を溶媒に溶解させ、溶液に基材を浸漬させることにより、縮合反応が進行して、簡単に基体上に一般式（１）で表される構造を有する化合物を担持させることができる。 Here, as an organosilicon compound represented by R n SiX (4-n) or an organotitanium compound represented by R n TiX (4-n) , R has a structure represented by the general formula (1). By using a compound that is an organic group, a compound having a structure represented by the general formula (1) can be supported on a substrate. In fact, by dissolving R is a an organic group having a structure represented by the general formula (1) R n SiX (4 -n) or R n TiX (4-n) in a solvent, the substrate in solution By immersion, the condensation reaction proceeds, and the compound having the structure represented by the general formula (1) can be easily carried on the substrate.
基材表面上の置換基と、一般式（１）で表される構造を有する化合物の置換基とを選択することにより、様々な化学結合を形成することができる。例えば、基材表面上にアミノ基を、一般式（１）で表される構造を有する化合物の置換基としてカルボキシル基を選択する場合には、アミノ基とカルボキシル基との間でアミド結合が形成される。アミノ基およびカルボキシル基は、基材および一般式（１）で表される構造を有する化合物のどちらに存在していてもよい。 様 々 Various chemical bonds can be formed by selecting a substituent on the substrate surface and a substituent of the compound having the structure represented by the general formula (1). For example, when an amino group is selected on the surface of a base material and a carboxyl group is selected as a substituent of a compound having a structure represented by the general formula (1), an amide bond is formed between the amino group and the carboxyl group. Is done. The amino group and the carboxyl group may be present on either the substrate or the compound having the structure represented by the general formula (1).
次に、金属−硫黄結合は、金属と、チオール基との反応によって形成することができる。チオール基は、金属に配位・吸着し、金属−硫黄結合を形成することが知られている。この反応を利用して、チオールは、金属表面上に自己集合膜を形成する。活物質化合物に置換基としてチオール基を持たせ、これを金属と接触させると、配位反応が進行し、金属−硫黄結合が形成される。基材には、金属の他に、金属イオンを表面に有する樹脂、炭素材料等を用いることもできる。 Second, a metal-sulfur bond can be formed by the reaction of a metal with a thiol group. Thiol groups are known to coordinate and adsorb to metals to form metal-sulfur bonds. Utilizing this reaction, thiol forms a self-assembled film on the metal surface. When the active material compound has a thiol group as a substituent and is brought into contact with a metal, a coordination reaction proceeds, and a metal-sulfur bond is formed. In addition to the metal, a resin having a metal ion on the surface, a carbon material, or the like can be used for the substrate.
活物質化合物と基材との間の化学結合としては、上記のほかに、炭素−炭素単結合、炭素−炭素二重結合、炭素−カルコゲン原子結合、硫黄−硫黄結合、金属−炭素結合などが挙げられる。
基材に担持された活物質化合物を電極活物質として用いる場合、電極構成材料の結着性を向上させるために、結着剤を用いてもよい。基材に担持された活物質化合物に結着剤等を添加して、ペレット状に成形することもできる。
As the chemical bond between the active material compound and the substrate, in addition to the above, a carbon-carbon single bond, a carbon-carbon double bond, a carbon-chalcogen atom bond, a sulfur-sulfur bond, a metal-carbon bond, and the like. No.
When the active material compound supported on the base material is used as the electrode active material, a binder may be used to improve the binding property of the electrode constituent material. A binder or the like may be added to the active material compound supported on the base material to form a pellet.
次に、本発明について実施例に基づいて詳細に説明する。
各実施例では、コイン型電池を作製して電極活物質の評価を行った。評価方法は通常の二次電池の評価方法と同様とした。以下に、試験電極の作製方法、コイン型電池の作製方法および電池の特性評価について順次に説明する。
Next, the present invention will be described in detail based on examples.
In each of the examples, a coin-type battery was manufactured and the electrode active material was evaluated. The evaluation method was the same as the evaluation method for ordinary secondary batteries. Hereinafter, a method of manufacturing a test electrode, a method of manufacturing a coin-type battery, and evaluation of characteristics of a battery will be sequentially described.
（ｉ）試験電極の作製方法
ガス精製装置を備えたドライボックスを用い、アルゴンガス雰囲気下において以下の操作を行った。電極活物質として化学式（７）：
(I) Manufacturing method of test electrode The following operation was performed under an argon gas atmosphere using a dry box equipped with a gas purification device. Chemical formula (7) as an electrode active material:
で表される化合物（テトラチアフルバレン：一般式（２）においてＲ3〜Ｒ6が水素原子の化合物）３０ｍｇと、導電補助剤としてアセチレンブラック３０ｍｇとを均一になるまで混合し、溶剤としてＮ−メチル−２−ピロリドンを１ｍＬ加えた。得られた混合物に、活物質と導電補助剤とを結着させる目的で、結着剤としてポリフッ化ビニリデン５ｍｇを加え、均一になるまで混合し、黒色のスラリーを得た。これをアルミニウム箔集電体上にキャストし、室温にて１時間真空乾燥を行った。乾燥後、これを１３．５ｍｍの円盤上に打ち抜いて試験電極とした。 (Tetrathiafulvalene: a compound in which R 3 to R 6 are hydrogen atoms in the general formula (2)) and 30 mg of acetylene black as a conductive auxiliary are mixed until uniform, and N- 1 mL of methyl-2-pyrrolidone was added. To the obtained mixture, 5 mg of polyvinylidene fluoride as a binder was added and mixed until uniform to obtain a black slurry, in order to bind the active material and the conductive auxiliary. This was cast on an aluminum foil current collector and vacuum dried at room temperature for 1 hour. After drying, this was punched out on a 13.5 mm disk to form a test electrode.
（ii）コイン型電池の作製方法
上記方法で作製した試験電極を正極に用いて、リチウム金属（厚さ：３００μｍ）を負極とするコイン型電池を以下の手順で作製した。得られたコイン型電池の縦断面図を図１に示す。まず、ケース１１の内面に試験電極１２を配置し、試験電極（正極）１２の上に多孔質ポリエチレンシートからなるセパレータ１３を設置した。次に、電解液をケース１１内に注液した。電解液には、エチレンカーボネートとジエチルカーボネートとの重量比１：１の混合溶媒に、１モル／Ｌの濃度で６フッ化リン酸リチウム（ＬｉＰＦ6）を溶解したものを用いた。また、内面に金属リチウム（負極）１４が圧着され、周縁部に封止リング１５を装着した封口板１６を準備した。そして、金属リチウム１４を試験電極１２と対面させてケース１１を封口板１６で封口し、プレス機でケース１１の開口端部を封止リング１５にかしめて、評価用のコイン型電池を得た。
(Ii) Manufacturing Method of Coin-Type Battery Using the test electrode manufactured by the above method as a positive electrode, a coin-type battery using lithium metal (thickness: 300 μm) as a negative electrode was manufactured in the following procedure. FIG. 1 shows a vertical sectional view of the obtained coin-type battery. First, the
（iii）電池の特性評価
作製したコイン型電池の定電流充放電を、電流値０．１３３ｍＡ、電圧範囲２．５Ｖ〜４．５Ｖで行い、１、５０、１００および３００サイクル目の放電容量をそれぞれ求めた。また、リチウムの酸化還元電位（Ｌｉ／Ｌｉ+）に対する平均放電電圧を求めた。平均放電電圧は、１サイクル目の放電時の電圧の平均値を用いた。なお、３００サイクル目まで放電電圧にほとんど変化はなかった。２段階の放電反応により放電カーブが階段状になっている場合にも、全体の平均値を求めた。結果を表１に示す。
(Iii) Evaluation of battery characteristics Constant current charging and discharging of the manufactured coin-type battery was performed at a current value of 0.133 mA and a voltage range of 2.5 V to 4.5 V. I asked for each. Further, the average discharge voltage with respect to the oxidation-reduction potential (Li / Li + ) of lithium was determined. The average value of the voltage at the time of the discharge in the first cycle was used as the average discharge voltage. The discharge voltage hardly changed until the 300th cycle. Even when the discharge curve was stepwise due to the two-step discharge reaction, the average value of the whole was determined. Table 1 shows the results.
また、充放電レート特性を評価した。ここでは、作製したコイン型電池の定電流充放電を、電流値０．６６５、１．３３または２．６６ｍＡ、電圧範囲２．５Ｖ〜４．５Ｖで行い、各電流値における５０サイクル目の放電容量をそれぞれ求めた。結果を表２に示す。 In addition, the charge / discharge rate characteristics were evaluated. Here, constant current charge / discharge of the manufactured coin-type battery was performed at a current value of 0.665, 1.33 or 2.66 mA, and a voltage range of 2.5 V to 4.5 V, and the discharge at the 50th cycle at each current value was performed. The capacities were determined respectively. Table 2 shows the results.
《比較例１》
試験電極の活物質として有機硫黄系化合物である２，５−ジメルカプト−１，３，４−チアジアゾール（以下、ＤＭｃＴ）（Aldrich社製）を用いたこと以外、実施例１と同様にしてコイン型電池を作製し、同様に評価した。結果を表１および２に示す。
<< Comparative Example 1 >>
Coin-shaped in the same manner as in Example 1, except that 2,5-dimercapto-1,3,4-thiadiazole (hereinafter, DMcT) (manufactured by Aldrich), which is an organic sulfur compound, was used as the active material of the test electrode. A battery was prepared and evaluated in the same manner. The results are shown in Tables 1 and 2.
化学式（７）で表される化合物の代わりに、化学式（８）： 代 わ り Instead of the compound represented by the chemical formula (7), the chemical formula (8):
で表される化合物（テトラメチルテトラチアフルバレン：一般式（２）においてＲ3〜Ｒ6がメチル基の化合物）を用いたこと以外、実施例１と同様にしてコイン型電池を作製し、同様に評価した。結果を表１および２に示す。 (Tetramethyltetrathiafulvalene: a compound in which R 3 to R 6 are methyl groups in the general formula (2)) except that a coin-type battery was produced in the same manner as in Example 1; Was evaluated. The results are shown in Tables 1 and 2.
化学式（７）で表される化合物の代わりに、化学式（９）： 代 わ り Instead of the compound represented by the chemical formula (7), the chemical formula (9):
で表される化合物（一般式（２）においてＲ3〜Ｒ6がチオメチル基の化合物）を用いたこと以外、実施例１と同様にしてコイン型電池を作製し、同様に評価した。結果を表１および２に示す。 (In the general formula (2), a coin-type battery was prepared and evaluated in the same manner as in Example 1, except that a compound in which R 3 to R 6 were thiomethyl groups). The results are shown in Tables 1 and 2.
化学式（７）で表される化合物の代わりに、化学式（１０）： 代 わ り Instead of the compound represented by the chemical formula (7), the chemical formula (10):
で表される化合物（一般式（３）においてＲ7およびＲ8が水素原子、Ｘがイオウ原子の化合物）を用いたこと以外、実施例１と同様にしてコイン型電池を作製し、同様に評価した。結果を表１および２に示す。 (In the general formula (3), a compound in which R 7 and R 8 are a hydrogen atom and X is a sulfur atom) was used to produce a coin-type battery in the same manner as in Example 1. evaluated. The results are shown in Tables 1 and 2.
化学式（７）で表される化合物の代わりに、化学式（１１）： 代 わ り Instead of the compound represented by the chemical formula (7), the chemical formula (11):
で表される化合物（一般式（３）においてＲ7およびＲ8が水素原子、Ｘが酸素原子の化合物）を用いたこと以外、実施例１と同様にしてコイン型電池を作製し、同様に評価した。結果を表１および２に示す。 (In the general formula (3), a compound in which R 7 and R 8 are a hydrogen atom and X is an oxygen atom) was used to produce a coin-type battery in the same manner as in Example 1. evaluated. The results are shown in Tables 1 and 2.
化学式（７）で表される化合物の代わりに、化学式（１２）： 代 わ り Instead of the compound represented by the chemical formula (7), the chemical formula (12):
で表される化合物（一般式（３）においてＲ7およびＲ8がヒドロキシメチル基、Ｘがイオウ原子の化合物）を用いたこと以外、実施例１と同様にしてコイン型電池を作製し、同様に評価した。結果を表１および２に示す。 (In the general formula (3), a compound in which R 7 and R 8 are hydroxymethyl groups and X is a sulfur atom) was used to produce a coin-type battery in the same manner as in Example 1. Was evaluated. The results are shown in Tables 1 and 2.
化学式（７）で表される化合物の代わりに、化学式（１３）： 代 わ り Instead of the compound represented by the chemical formula (7), the chemical formula (13):
で表される化合物（一般式（４）においてＸおよびＹがそれぞれ炭素原子の化合物）を用いたこと以外、実施例１と同様にしてコイン型電池を作製し、同様に評価した。結果を表１および２に示す。 (In the general formula (4), a coin-type battery was prepared and evaluated in the same manner as in Example 1 except that X and Y were each a carbon atom.) The results are shown in Tables 1 and 2.
化学式（７）で表される化合物の代わりに、化学式（１４）： 代 わ り Instead of the compound represented by the chemical formula (7), the chemical formula (14):
で表される化合物（一般式（４）においてＸおよびＹがそれぞれイオウ原子の化合物）を用いたこと以外、実施例１と同様にしてコイン型電池を作製し、同様に評価した。結果を表１および２に示す。 (In the general formula (4), each of X and Y is a sulfur atom), a coin-type battery was produced in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Tables 1 and 2.
化学式（７）で表される化合物の代わりに、化学式（１５）： 代 わ り Instead of the compound represented by the chemical formula (7), the chemical formula (15):
で表される化合物（一般式（４）においてＸが酸素原子、Ｙがイオウ原子の化合物）を用いたこと以外、実施例１と同様にしてコイン型電池を作製し、同様に評価した。結果を表１および２に示す。 (In the general formula (4), a compound in which X is an oxygen atom and Y is a sulfur atom) was used to produce a coin-type battery in the same manner as in Example 1, and was similarly evaluated. The results are shown in Tables 1 and 2.
化学式（７）で表される化合物の代わりに、化学式（１６）： 代 わ り Instead of the compound represented by the chemical formula (7), the chemical formula (16):
で表される化合物（一般式（５）においてＲ9およびＲ10がヒドロキシメチル基、ｎ＝３の化合物）を用いたこと以外、実施例１と同様にしてコイン型電池を作製し、同様に評価した。結果を表１および２に示す。 (Wherein R 9 and R 10 in the general formula (5) are hydroxymethyl groups, n = 3), and a coin-type battery was prepared in the same manner as in Example 1. evaluated. The results are shown in Tables 1 and 2.
化学式（７）で表される化合物の代わりに、化学式（６）： 代 わ り Instead of the compound represented by the chemical formula (7), the chemical formula (6):
で表される化合物を用いたこと以外、実施例１と同様にしてコイン型電池を作製し、同様に評価した。結果を表１および２に示す。 A coin-type battery was prepared and evaluated in the same manner as in Example 1, except that the compound represented by the following formula was used. The results are shown in Tables 1 and 2.
［評価結果の考察］
表１の結果から、有機硫黄系化合物を電極活物質に用いた比較例１では、初期放電時には２００ｍＡｈ／ｇの容量が得られたものの、５０サイクル目には５０ｍＡｈ／ｇまで減少し、１００サイクル目にはわずか１０ｍＡｈ／ｇ程度の容量しか得られなかった。一方、一般式（１）で表される構造を有する化合物を電極活物質に用いた実施例１〜実施例１１では、いずれも３．５Ｖ付近の高い平均放電電圧が得られ、３００サイクル目でもほとんど放電容量の減少が観察されなかった。
[Consideration of evaluation results]
From the results in Table 1, in Comparative Example 1 in which an organic sulfur-based compound was used as the electrode active material, a capacity of 200 mAh / g was obtained during the initial discharge, but decreased to 50 mAh / g at the 50th cycle, and 100 cycles. The eye only had a capacity of about 10 mAh / g. On the other hand, in Examples 1 to 11 in which the compound having the structure represented by the general formula (1) was used as the electrode active material, a high average discharge voltage of about 3.5 V was obtained, and even in the 300th cycle. Almost no decrease in discharge capacity was observed.
比較例１で用いた有機硫黄系化合物は、その充放電反応機構がＳ−Ｓ結合の解列・再結合反応に基づいている。この反応は反応頻度が低いこと、充放電反応により分子構造が大きく変化することから、再結合性は低くなる。そのため、サイクル初期では高い放電容量が得られたものの、１００サイクル目には、ほとんど放電容量が得られなくなってしまったと考えられる。以上より、Ｓ−Ｓ結合の解列・再結合反応に基づく反応機構を有する化合物をそのままの状態で電極活物質に用いても、高いサイクル特性が得られないことがわかる。 有機 The organic sulfur-based compound used in Comparative Example 1 has a charge / discharge reaction mechanism based on an SS bond disconnection / recombination reaction. In this reaction, the recombination property is low because the reaction frequency is low and the molecular structure is largely changed by the charge / discharge reaction. Therefore, it is considered that although a high discharge capacity was obtained at the beginning of the cycle, almost no discharge capacity was obtained at the 100th cycle. From the above, it can be seen that even if a compound having a reaction mechanism based on the SS bond dissociation / recombination reaction is used as it is as an electrode active material, high cycle characteristics cannot be obtained.
一方、本発明の実施例１〜１１で用いた一般式（１）で表される構造を有する化合物は、３００サイクル経過後においても、ほとんど放電容量が減少することはなかった。これらの化合物は、充放電反応において、分子上にアニオンやカチオンが配位するだけであり、分子構造の大きな変化を起こさないことから、サイクル経過に伴う化合物自身の劣化が起こらなかったためと考えられる。 On the other hand, the compounds having the structure represented by the general formula (1) used in Examples 1 to 11 of the present invention hardly reduced the discharge capacity even after 300 cycles. It is considered that these compounds only coordinate anions and cations on the molecules during the charge / discharge reaction, and do not cause a significant change in the molecular structure. .
以上の結果から、一般式（１）で表される構造を有する化合物を電極活物質とする電気化学素子は、高いサイクル特性を有することがわかる。また、表２の結果から明らかなように、一般式（１）で表される構造を有する化合物を電極活物質とする電気化学素子は、高い充放電レート特性を有することがわかった。 From the above results, it can be seen that the electrochemical element using the compound having the structure represented by the general formula (1) as an electrode active material has high cycle characteristics. Further, as is clear from the results in Table 2, it was found that the electrochemical element using the compound having the structure represented by the general formula (1) as an electrode active material had high charge / discharge rate characteristics.
次に、一般式（１）で表される構造を複数有する高分子化合物を電極活物質に用いた実施例について説明する。ここでは、ポリアセチレン鎖を主鎖として有し、テトラチアフルバレン構造を有する化合物として、化学式（１７）： Next, an example in which a polymer compound having a plurality of structures represented by the general formula (1) is used as an electrode active material will be described. Here, as a compound having a polyacetylene chain as a main chain and having a tetrathiafulvalene structure, a compound having a chemical formula (17):
で表される化合物を用いた。３０ｍｇの化学式（７）で表される化合物の代わりに、４０ｍｇの化学式（１７）で表される化合物を用いたこと以外、実施例１と同様にしてコイン型電池を作製した。そして、作製したコイン型電池の定電流充放電を、電流値０．１３３ｍＡ、電圧範囲２．５Ｖ〜４．５Ｖで行い、１、５０、１００および３００サイクル目の放電容量をそれぞれ実施例１と同様に求めた。結果を表３に示す。表３の結果より、一般式（１）で表される構造を複数有する高分子化合物を電極活物質に用いた電気化学素子も、高いサイクル特性を示すことがわかる。 The compound represented by was used. A coin-type battery was produced in the same manner as in Example 1, except that 40 mg of the compound represented by the chemical formula (17) was used instead of 30 mg of the compound represented by the chemical formula (7). Then, a constant current charge / discharge of the manufactured coin-type battery was performed at a current value of 0.133 mA and a voltage range of 2.5 V to 4.5 V, and the discharge capacities at the 1, 50, 100, and 300th cycles were the same as those in Example 1. I asked similarly. Table 3 shows the results. From the results in Table 3, it can be seen that an electrochemical element using a polymer compound having a plurality of structures represented by the general formula (1) as an electrode active material also shows high cycle characteristics.
次に、負極としてリチウム含有複合窒化物を用いた実施例について説明する。以下に示す負極を用いたこと以外は、実施例１と同様にしてコイン型電池を作製した。正極には、実施例１で作製したものと同じ試験電極を用いた。そして、作製したコイン型電池の定電流充放電を、電流値０．１３３ｍＡ、電圧範囲２．５Ｖ〜４．５Ｖで行い、１、５０、１００および３００サイクル目の放電容量をそれぞれ実施例１と同様に求めた。結果を表４に示す。 Next, an example using a lithium-containing composite nitride as the negative electrode will be described. A coin-type battery was produced in the same manner as in Example 1, except that the following negative electrode was used. The same test electrode as that prepared in Example 1 was used for the positive electrode. Then, a constant current charge / discharge of the manufactured coin-type battery was performed at a current value of 0.133 mA and a voltage range of 2.5 V to 4.5 V, and the discharge capacities at the 1, 50, 100, and 300th cycles were the same as those in Example 1. I asked similarly. Table 4 shows the results.
ここで、リチウム含有複合窒化物は、Ｌｉ／Ｃｏのモル比が２．６／０．４のリチウムコバルト合金を銅製の容器に入れ、窒素雰囲気中、８００℃２時間保持することにより、前記合金を窒素と反応させて調製した。反応後、得られた黒灰色の窒化物を粉末状に粉砕し、負極活物質として用いた。 Here, the lithium-containing composite nitride is obtained by placing a lithium-cobalt alloy having a molar ratio of Li / Co of 2.6 / 0.4 in a copper container and maintaining the same in a nitrogen atmosphere at 800 ° C. for 2 hours. Was reacted with nitrogen. After the reaction, the obtained black-gray nitride was pulverized into a powder and used as a negative electrode active material.
得られた負極活物質の粉末Ｘ線回折測定をＣｕＫα線を用いて行ったところ、窒化リチウム（Ｌｉ3Ｎ）と同じ六方晶に基づく回折パターンが観測された。このことから、Ｃｏが窒化リチウムの結晶構造に取り込まれた状態の、単一相の固溶体が得られていることが確認された。合成したリチウム含有複合窒化物の組成はＬｉ2.6Ｃｏ0.4Ｎであった。 When the powder X-ray diffraction measurement of the obtained negative electrode active material was performed using CuKα radiation, a diffraction pattern based on the same hexagonal crystal as lithium nitride (Li 3 N) was observed. From this, it was confirmed that a single-phase solid solution in which Co was incorporated in the crystal structure of lithium nitride was obtained. The composition of the synthesized lithium-containing composite nitride was Li 2.6 Co 0.4 N.
Ｌｉ2.6Ｃｏ0.4Ｎの粉末、炭素粉末、および結着剤としてのポリテトラフルオロエチレン粉末を、重量比１００：２５：５で充分に混合して、負極合剤を得た。この負極合剤を銅シート上に塗布し、圧延し、得られた極板を直径１３．５ｍｍの円盤状に打ち抜いて負極とした。 Powder Li 2.6 Co 0.4 N, carbon powder, and polytetrafluoroethylene powder as a binder, the weight ratio of 100: 25: thoroughly mixed with 5 to obtain a negative electrode mixture. This negative electrode mixture was applied on a copper sheet, rolled, and the obtained electrode plate was punched into a disk having a diameter of 13.5 mm to obtain a negative electrode.
次に、負極としてリチウム含有チタン酸化物を用いた実施例について説明する。以下に示す負極を用いたこと以外は、実施例１と同様にしてコイン型電池を作製した。正極には、実施例１で作製したものと同じ試験電極を用いた。そして、作製したコイン型電池の定電流充放電を、電流値０．１３３ｍＡ、電圧範囲２．５Ｖ〜４．５Ｖで行い、１、５０、１００および３００サイクル目の放電容量をそれぞれ実施例１と同様に求めた。結果を表４に示す。 Next, an example using a lithium-containing titanium oxide as the negative electrode will be described. A coin-type battery was produced in the same manner as in Example 1, except that the following negative electrode was used. The same test electrode as that prepared in Example 1 was used for the positive electrode. Then, a constant current charge / discharge of the manufactured coin-type battery was performed at a current value of 0.133 mA and a voltage range of 2.5 V to 4.5 V, and the discharge capacities at the 1, 50, 100, and 300th cycles were the same as those in Example 1. I asked similarly. Table 4 shows the results.
ここで、リチウム含有チタン酸化物には、ＬｉＴｉ5Ｏ12粉末を用いた。ＬｉＴｉ5Ｏ12の粉末、炭素粉末、および結着剤としてのポリテトラフルオロエチレン粉末を、重量比１００：２５：５で充分に混合して、負極合剤を得た。この負極合剤を銅シート上に塗布し、圧延し、得られた極板を直径１３．５ｍｍの円盤状に打ち抜いて負極とした。 Here, LiTi 5 O 12 powder was used for the lithium-containing titanium oxide. LiTi 5 O 12 powder, carbon powder, and polytetrafluoroethylene powder as a binder were sufficiently mixed in a weight ratio of 100: 25: 5 to obtain a negative electrode mixture. This negative electrode mixture was applied on a copper sheet, rolled, and the obtained electrode plate was punched into a disk having a diameter of 13.5 mm to obtain a negative electrode.
表４の結果より、一般式（１）で表される構造を有する化合物を一方の電極活物質に用い、他方の電極活物質にリチウム含有複合窒化物またはリチウム含有チタン酸化物を用いた電気化学素子も、高いサイクル特性を示すことがわかる。 From the results in Table 4, it was found that the compound having the structure represented by the general formula (1) was used for one electrode active material, and the other electrode active material was lithium-containing composite nitride or lithium-containing titanium oxide. It can be seen that the element also shows high cycle characteristics.
次に、一般式（１）で表される構造を有する化合物を、正極および負極の両方の活物質に用いた実施例について説明する。ここでは、正極活物質として化学式（１３）： Next, an example in which a compound having a structure represented by the general formula (1) is used for both a positive electrode and a negative electrode active material will be described. Here, the chemical formula (13) is used as the positive electrode active material:
で表される化合物を用い、負極活物質として化学式（８）： Using a compound represented by the following formula, a chemical formula (8):
で表される化合物を用いた。正極活物質および負極活物質にこれらを用いたこと以外、実施例１と同様にしてコイン型電池を作製した。すなわち、化学式（７）で表される化合物の代わりに、それぞれ化学式（１３）で表される化合物および化学式（８）で表される化合物を用いて試験電極を作製し、前者の試験電極を正極に、後者の試験電極を負極に用いたコイン型電池を作製した。そして、作製したコイン型電池の定電流充放電を、電流値０．１３３ｍＡ、電圧範囲０．３Ｖ〜０．６Ｖで行い、１、５０、１００および３００サイクル目の放電容量をそれぞれ実施例１と同様に求めた。結果を表５に示す。表５の結果より、両極に一般式（１）で表される化合物を用いた場合にも、高いサイクル特性が得られることがわかる。 The compound represented by was used. A coin-type battery was produced in the same manner as in Example 1, except that these were used as the positive electrode active material and the negative electrode active material. That is, instead of the compound represented by the chemical formula (7), a test electrode was prepared by using a compound represented by the chemical formula (13) and a compound represented by the chemical formula (8), respectively. Then, a coin-type battery using the latter test electrode as a negative electrode was produced. Then, constant current charge / discharge of the manufactured coin-type battery was performed at a current value of 0.133 mA and a voltage range of 0.3 V to 0.6 V, and the discharge capacities at the 1, 50, 100, and 300th cycles were the same as those of Example 1. I asked similarly. Table 5 shows the results. From the results in Table 5, it can be seen that high cycle characteristics can be obtained also when the compound represented by the general formula (1) is used for both electrodes.
次に、一般式（１）で表される構造を有し、かつ、膜を形成している高分子化合物を正極に用いた実施例について説明する。ここでは、化学式（１７）： Next, an example in which a polymer compound having a structure represented by the general formula (1) and forming a film is used for a positive electrode will be described. Here, chemical formula (17):
で表される化合物を電解重合して膜を調製した。具体的には、化学式（１７）で表される化合物をアセトニトリルに溶解して、濃度０．１ｍｏｌ／Ｌの溶液を調製し、その溶液にアルミニウム基板を浸漬して、基板と対極との間に２．０Ｖ（対Ｌｉ／Ｌｉ+）の定電位電解を行った。その結果、基板上に高分子化合物の膜（厚さ４０μｍ）が形成された。 Was electrolytically polymerized to prepare a film. Specifically, a compound represented by the chemical formula (17) is dissolved in acetonitrile to prepare a solution having a concentration of 0.1 mol / L, and an aluminum substrate is immersed in the solution to form a solution between the substrate and the counter electrode. 2.0 V (vs. Li / Li + ) constant potential electrolysis was performed. As a result, a polymer compound film (thickness: 40 μm) was formed on the substrate.
この膜を所定の形状に打ち抜き、これを正極として用いたこと以外、実施例１と同様にしてコイン型電池を作製した。そして、作製したコイン型電池の定電流充放電を、電流値０．１３３ｍＡ、電圧範囲３．０Ｖ〜３．８Ｖで行い、１、５０、１００および３００サイクル目の放電容量をそれぞれ実施例１と同様に求めた。結果を表５に示す。表５の結果より、電解重合により得られた高分子化合物からなる膜を用いても、高いサイクル特性が得られることがわかる。 コ イ ン A coin-type battery was produced in the same manner as in Example 1 except that this film was punched into a predetermined shape and used as a positive electrode. Then, constant current charging / discharging of the manufactured coin-type battery was performed at a current value of 0.133 mA and a voltage range of 3.0 V to 3.8 V, and the discharge capacities at the 1, 50, 100, and 300th cycles were the same as those of Example 1. I asked similarly. Table 5 shows the results. From the results in Table 5, it can be seen that high cycle characteristics can be obtained even when a film made of a polymer compound obtained by electrolytic polymerization is used.
活物質化合物を基材に担持する場合について説明する。
（ｉ）試験電極の作製方法
電極活物質としては、置換基としてアルキルトリメトキシシラン基を有する化学式（１８）：
A case where the active material compound is supported on a substrate will be described.
(I) Method of preparing test electrode Chemical formula (18) having an alkyltrimethoxysilane group as a substituent as an electrode active material:
で表される化合物を用いた。また、基材としては活性炭を用いた。ヘキサデカンとクロロホルムとの体積比４：１の混合溶媒１００重量部と、化学式（１８）で表される化合物を５重量部とを混合し、処理液を調製した。この処理液１００ｍＬに、１２０℃で１０分間オゾン処理を行った活性炭１０ｇを浸漬し、１２時間攪拌を行った。オゾン処理は、活性炭表面上に多く存在する官能基を水酸基に変換する目的で行った。 The compound represented by was used. Activated carbon was used as a substrate. 100 parts by weight of a mixed solvent of hexadecane and chloroform at a volume ratio of 4: 1 and 5 parts by weight of a compound represented by the chemical formula (18) were mixed to prepare a treatment liquid. 10 g of activated carbon subjected to ozone treatment at 120 ° C. for 10 minutes was immersed in 100 mL of this treatment liquid, and stirred for 12 hours. The ozone treatment was performed for the purpose of converting a large number of functional groups on the activated carbon surface into hydroxyl groups.
活性炭を処理液から濾別し、さらにクロロホルム１００ｍＬ中に浸漬して１時間攪拌した。その後、活性炭をクロロホルムから濾別し、再度クロロホルム１００ｍＬ中に浸漬して１時間攪拌を行うことにより、洗浄を行った。洗浄後の活性炭を濾別し、１０時間真空乾燥を行うことにより、電極活物質を担持した活性炭を得た。なお、これらの処理は、すべてアルゴン雰囲気下、湿度−３０度以下の条件下で行った。 (4) The activated carbon was separated from the treatment liquid by filtration, further immersed in 100 mL of chloroform, and stirred for 1 hour. Thereafter, the activated carbon was separated from the chloroform by filtration, immersed again in 100 mL of chloroform, and stirred for 1 hour to perform washing. The activated carbon after the washing was separated by filtration and vacuum-dried for 10 hours to obtain activated carbon supporting an electrode active material. Note that all of these treatments were performed in an argon atmosphere under conditions of a humidity of −30 ° C. or less.
活性炭上に電極活物質が化学結合を介して担持されているかを分光学的手法を用いて確認した。具体的には、電極活物質を担持した活性炭のＩＲ測定を行うと、２５００ｃｍ-1付近にＳ−Ｈに由来するピーク、７５０ｃｍ-1および１２５０ｃｍ-1付近にＣ−Ｓ−Ｃ結合に由来するピーク、３０００ｃｍ-1付近にＣＨ2に由来するピーク、１１００ｃｍ-1付近にＳｉ−Ｏ−Ｓｉ結合に由来するピークがそれぞれ観察された。これらのピークは、活性炭のみの場合には、いずれも観測されなかった。以上より、上記処理によって、活性炭上に電極活物質が化学結合を介して担持されていることが確認された。 Whether the electrode active material was supported on the activated carbon via a chemical bond was confirmed using a spectroscopic technique. Specifically, when the IR measurement of the activated carbon carrying an electrode active material, from the vicinity of 2500 cm -1 peak derived from S-H, the C-S-C bond in the vicinity of 750 cm -1 and 1250 cm -1 A peak derived from CH 2 was observed around 3000 cm −1 , and a peak derived from a Si—O—Si bond was observed around 1100 cm −1 . None of these peaks were observed when only activated carbon was used. From the above, it was confirmed that the electrode active material was supported on the activated carbon via the chemical bond by the above treatment.
（ii）コイン型電池の作製方法
化学式（７）で表される化合物単独の代わりに、こうして得られた基材と電極活物質との複合材料７０ｍｇを用い、導電補助剤としてアセチレンブラック２０ｍｇ、結着剤としてポリフッ化ビニリデン１０ｍｇを用いたこと以外、実施例１と同様にして、コイン型電池を作成した。
(Ii) Manufacturing method of coin-type battery Instead of the compound represented by the chemical formula (7) alone, 70 mg of the composite material of the base material and the electrode active material thus obtained was used, and 20 mg of acetylene black was added as a conductive auxiliary agent. A coin-type battery was prepared in the same manner as in Example 1, except that 10 mg of polyvinylidene fluoride was used as the adhesive.
（iii）電池の特性評価
作製したコイン型電池の充放電試験を、電流値１．０ｍＡで、電圧範囲４．２Ｖから２．５Ｖで繰り返した。充放電は雰囲気温度２０℃で行った。１、５０、１００および３００サイクル目における放電容量（ｍＡｈ／ｇ）を求めた。結果を理論容量とともに表６に示す。
(Iii) Battery Characteristics Evaluation The charge / discharge test of the produced coin-type battery was repeated at a current value of 1.0 mA in a voltage range of 4.2 V to 2.5 V. Charging and discharging were performed at an ambient temperature of 20 ° C. The discharge capacity (mAh / g) at 1, 50, 100 and 300 cycles was determined. The results are shown in Table 6 together with the theoretical capacity.
表６中、理論容量および測定された放電容量は、活物質重量あたりの容量であるが、ここでは活物質重量に基材重量を含めていない。表６の結果から、−Ｓｉ−Ｏ−結合により導電性基材である活性炭上に電極活物質を担持することにより、充放電サイクルに伴う容量劣化がほとんど起こらないことがわかる。本実施例では、３００サイクル経過後にも安定したサイクル特性が確認された。 理論 In Table 6, the theoretical capacity and the measured discharge capacity are capacities per active material weight, but the active material weight does not include the substrate weight. From the results in Table 6, it can be seen that by carrying the electrode active material on the activated carbon, which is the conductive base material, by the -Si-O- bond, the capacity deterioration accompanying the charge / discharge cycle hardly occurs. In this example, stable cycle characteristics were confirmed even after 300 cycles.
化学式（１８）で表される化合物の代わりに、化学式（１９）： 代 わ り Instead of the compound represented by the chemical formula (18), the chemical formula (19):
で表される化合物を用いたこと以外、実施例１７と同様にして、基材と電極活物質との複合材料を作製した。化学式（１９）で表される化合物は、置換基としてアミノ基を有する。このアミノ基は、基材である活性炭上のカルボキシル基とアミド結合を形成することができる。 A composite material of a substrate and an electrode active material was produced in the same manner as in Example 17 except that the compound represented by The compound represented by the chemical formula (19) has an amino group as a substituent. This amino group can form an amide bond with a carboxyl group on activated carbon as a base material.
活性炭上に電極活物質が化学結合を介して担持されているかを分光学的手法を用いて確認した。具体的には、電極活物質を担持した活性炭の場合、３０００ｃｍ-1付近にＮ−Ｈに由来するピーク、８５０ｃｍ-1付近にＣ−Ｎ結合に由来するピーク、３０００ｃｍ-1付近にＣＨ2に由来するピーク、３４００ｃｍ-1付近にＮＨ−ＣＯ結合に由来するピークがそれぞれ観察された。これらのピークは、活性炭のみの場合には、いずれも観測されなかった。以上より、上記処理によって、活性炭上に電極活物質が化学結合を介して担持されていることが確認された。 Whether the electrode active material was supported on the activated carbon via a chemical bond was confirmed using a spectroscopic technique. More specifically, in the case of activated carbon which carries an electrode active material, a peak derived from the N-H in the vicinity of 3000 cm -1, a peak derived from the C-N bond in the vicinity of 850 cm -1, the CH 2 in the vicinity of 3000 cm -1 Derived peaks and peaks derived from NH-CO bonds were observed at around 3400 cm -1 . None of these peaks were observed when only activated carbon was used. From the above, it was confirmed that the electrode active material was supported on the activated carbon via the chemical bond by the above treatment.
こうして得られた複合材料を用いたこと以外、実施例１７と同様にして、コイン型電池を作製し、同様に評価した。結果を理論容量とともに表６に示す。表６の結果から、アミド結合により導電性基材である活性炭上に電極活物質を担持することにより、充放電サイクルに伴う容量劣化がほとんど起こらないことがわかる。本実施例では、３００サイクル経過後にも安定したサイクル特性が確認された。 コ イ ン A coin-type battery was prepared and evaluated in the same manner as in Example 17, except that the thus obtained composite material was used. The results are shown in Table 6 together with the theoretical capacity. From the results in Table 6, it can be seen that by carrying the electrode active material on the activated carbon, which is a conductive base material, through an amide bond, capacity deterioration due to charge / discharge cycles hardly occurs. In this example, stable cycle characteristics were confirmed even after 300 cycles.
（ｉ）試験電極の作製方法
電極活物質としては、置換基としてチオール基を有する化学式（２０）：
(I) Method for preparing test electrode Chemical formula (20) having a thiol group as a substituent as an electrode active material:
で表される化合物を用いた。また、基材としては金微粒子を用いた。金微粒子（平均粒径１０μｍ）１重量％のＮ−メチル−２−ピロリドン（ＮＭＰ）溶液１００重量部と、化学式（２０）で表される化合物を３重量部とを混合し、２５℃で１２時間攪拌を行った。その後、金微粒子をＮＭＰから濾別し、１０時間真空乾燥を行うことにより、電極活物質を担持した金微粒子を得た。なお、これらの処理は、すべてアルゴン雰囲気下、湿度−３０度以下の条件下で行った。 The compound represented by was used. Gold fine particles were used as a substrate. 100 parts by weight of an N-methyl-2-pyrrolidone (NMP) solution containing 1% by weight of gold fine particles (average particle diameter: 10 μm) and 3 parts by weight of a compound represented by the chemical formula (20) were mixed, Stirring was performed for hours. Thereafter, the gold fine particles were separated from the NMP by filtration and vacuum-dried for 10 hours to obtain gold fine particles carrying the electrode active material. Note that all of these treatments were performed in an argon atmosphere under conditions of a humidity of −30 ° C. or less.
金微粒子上に電極活物質が化学結合を介して担持されているかを、ＩＲ測定およびＸＰＳ測定により確認した。具体的には、ＩＲ測定においては、３０００ｃｍ-1付近にＣＨ2に由来すると考えられるピーク、７５０ｃｍ-1および１２５０ｃｍ-1付近にＣ−Ｓ−Ｃ結合に由来すると考えられるピークが観測された。これらのピークは、金微粒子のみの場合には、いずれも観測されなかった。また、ＸＰＳ測定においては、金微粒子のみからは全く観測されなかったＳ（２ｐ）のピークが観測された。以上より、上記処理によって、金微粒子上に電極活物質が化学結合を介して担持されていることが確認された。 Whether the electrode active material was supported on the fine gold particles via a chemical bond was confirmed by IR measurement and XPS measurement. Specifically, in the IR measurement, peaks considered to be derived from CH 2 near 3000 cm −1 and peaks considered to be derived from C—S—C bonds were observed near 750 cm −1 and 1250 cm −1 . None of these peaks were observed when only the fine gold particles were used. In the XPS measurement, a peak of S (2p) was observed, which was not observed at all only from the fine gold particles. From the above, it was confirmed that the electrode active material was supported on the fine gold particles via the chemical bond by the above-described treatment.
こうして得られた金微粒子と電極活物質との複合材料を用いたこと以外、実施例１７と同様にして、コイン型電池を作製し、同様に評価した。結果を理論容量とともに表６に示す。表６の結果から、金-硫黄結合により導電性基材である金微粒子上に電極活物質を担持することにより、充放電サイクルに伴う容量劣化がほとんど起こらないことがわかる。本実施例では、３００サイクル経過後にも安定したサイクル特性が確認された。
実施例１７〜１９は、基材に化学結合を介して電極活物質を担持することにより、高いサイクル特性が得られることを示している。
A coin-type battery was prepared and evaluated in the same manner as in Example 17, except that the composite material of the gold fine particles and the electrode active material thus obtained was used. The results are shown in Table 6 together with the theoretical capacity. From the results in Table 6, it can be seen that by carrying the electrode active material on the gold fine particles as the conductive base material by the gold-sulfur bond, the capacity deterioration accompanying the charge / discharge cycle hardly occurs. In this example, stable cycle characteristics were confirmed even after 300 cycles.
Examples 17 to 19 show that high cycle characteristics can be obtained by supporting an electrode active material on a base material through a chemical bond.
以上のように、本発明は、一般式（１）で表される構造を有する化合物を電極活物質に用いることから、軽量かつ高エネルギー密度でサイクル特性に優れた電気化学素子に適用することができる。 As described above, the present invention uses a compound having the structure represented by the general formula (1) as an electrode active material, and thus can be applied to an electrochemical element that is lightweight, has high energy density, and has excellent cycle characteristics. it can.
１１ ケース
１２ 試験電極
１３ セパレータ
１４ 金属リチウム
１５ 封止リング
１６ 封口板
DESCRIPTION OF
Claims (28)
正極と、負極と、電解質とからなり、
前記正極および前記負極より選ばれる少なくとも一方が、一般式（１）：
A positive electrode, a negative electrode, and an electrolyte,
At least one selected from the positive electrode and the negative electrode has a general formula (1):
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