JP2007042603A - Nonaqueous electrolyte secondary battery - Google Patents

Nonaqueous electrolyte secondary battery Download PDF

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JP2007042603A
JP2007042603A JP2006155956A JP2006155956A JP2007042603A JP 2007042603 A JP2007042603 A JP 2007042603A JP 2006155956 A JP2006155956 A JP 2006155956A JP 2006155956 A JP2006155956 A JP 2006155956A JP 2007042603 A JP2007042603 A JP 2007042603A
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aqueous electrolyte
secondary battery
electrolyte secondary
carbon fiber
group
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Masami Ootsuki
正珠 大月
Shinichi Toyosawa
真一 豊澤
Masahito Yoshikawa
雅人 吉川
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Bridgestone Corp
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Bridgestone Corp
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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

<P>PROBLEM TO BE SOLVED: To provide a high-safety nonaqueous electrolyte secondary battery having large battery capacity, wherein a volume change of a negative electrode accompanying a charge and discharge cycle is suppressed to have an excellent cycle characteristic. <P>SOLUTION: In this nonaqueous electrolyte secondary battery having a positive electrode, the negative electrode and a nonaqueous electrolytic solution, the negative electrode is a carbon electrode carrying metal fine particles on three-dimensional continuous carbon fiber, and the nonaqueous electrolytic solution contains a phosphazene compound and a supporting salt. Preferably, the three-dimensional continuous carbon fiber is one obtained by baking a fibrillar polymer obtained by oxidizing and polymerizing a compound having an aromatic ring in non-oxidizing atmosphere. Preferably, the metal fine particle is carried on the three-dimensional continuous carbon fiber by a reduction method of a metal ion. Preferably, the metal configuring the metal fine particle is a metal capable of storing and desorbing lithium. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は、非水電解液二次電池、特に、安全性が高い上、電池容量が大きく、充放電サイクルに伴う負極の体積変化が抑制されており、優れたサイクル特性を有する非水電解液二次電池に関するものである。   The present invention relates to a non-aqueous electrolyte secondary battery, in particular, a non-aqueous electrolyte having excellent cycle characteristics, which is highly safe, has a large battery capacity, and suppresses a change in volume of the negative electrode accompanying a charge / discharge cycle. The present invention relates to a secondary battery.

昨今、携帯用端末やモバイル通信機器として広く普及したリチウムイオン電池やキャパシタが、ハイブリッド自動車や燃料電池自動車の補助電源として、あるいは定置用大型電源としても注目を集めており、広く研究が行われている。中でも、リチウムイオン電池は、現存する二次電池の中でも最もエネルギー密度が大きいことから、更なる広範囲な適用に期待がかかっている。   Recently, lithium-ion batteries and capacitors, which have been widely used as portable terminals and mobile communication devices, are attracting attention as auxiliary power sources for hybrid vehicles and fuel cell vehicles, or as large-scale power sources for stationary use. Yes. In particular, lithium ion batteries have the highest energy density among existing secondary batteries, and are expected to be used in a wider range of applications.

上記リチウムイオン電池には、一般に、エステル化合物やエーテル化合物等の非プロトン性有機溶媒に支持塩を溶解させてなる非水電解液が用いられるが、非プロトン性有機溶媒は、例えば、電池が異常に発熱した際に、気化・分解してガスを発生したり、発生したガス及び熱により電池の破裂・発火を引き起こしたり、短絡時に生じる火花が引火する等の危険性が高い。これに対して、非水電解液にホスファゼン化合物を添加して、非水電解液に不燃性、難燃性又は自己消火性を付与して、短絡等の非常時に電池が発火・引火する危険性を大幅に低減したリチウムイオン電池が開発されている（特許文献１参照）。   The lithium ion battery generally uses a non-aqueous electrolyte solution in which a supporting salt is dissolved in an aprotic organic solvent such as an ester compound or an ether compound. The aprotic organic solvent is, for example, an abnormal battery. When it generates heat, it is highly dangerous to vaporize and decompose to generate gas, to cause the battery to rupture or ignite due to the generated gas and heat, and to cause sparks to ignite when short-circuited. On the other hand, adding a phosphazene compound to the non-aqueous electrolyte to impart non-flammability, flame retardancy or self-extinguishing properties to the non-aqueous electrolyte may cause the battery to ignite or ignite in the event of an emergency such as a short circuit Lithium ion batteries have been developed that significantly reduce (see Patent Document 1).

また、上記リチウムイオン電池は、リチウムイオンを電気化学的に吸蔵・離脱可能な層状構造の正極（例えば、ＬｉＣｏＯ2）と同特性を有する負極（例えば、黒鉛）がリチウムイオンを溶解した電解液を介して対向した構造を有する電池であり、一般に、正極と負極との短絡を防止するために電解液を透過しうる多孔質ポリマー膜が両極材の間に配置された構造を有している。上記電極系の場合、充電によってリチウムイオンが負極層間で還元され電気を蓄えた状態、例えば、Ｃ6Ｌｉとなって固定される。この際、正極からはＬｉが放出され、例えば、Ｌｉ0.44ＣｏＯ2のような構造をとる。このように非常に高い還元状態となった負極と、非常に高い酸化状態になった正極とを外部負荷の下で放電すると、非常に電圧が高く、且つ高容量の電気を取り出すことができる。 Further, the lithium ion battery includes an electrolyte in which lithium ions are dissolved in a negative electrode (for example, graphite) having the same characteristics as a positive electrode (for example, LiCoO 2 ) having a layered structure capable of electrochemically inserting and extracting lithium ions. In general, the battery has a structure in which a porous polymer film capable of permeating an electrolyte solution is disposed between both electrode materials in order to prevent a short circuit between the positive electrode and the negative electrode. In the case of the above electrode system, the lithium ions are reduced between the negative electrode layers by charging and stored in a state where electricity is stored, for example, C 6 Li and fixed. At this time, Li is released from the positive electrode, and takes a structure such as Li 0.44 CoO 2 , for example. As described above, when the negative electrode in a very high reduction state and the positive electrode in a very high oxidation state are discharged under an external load, a very high voltage and high capacity electricity can be taken out.

ところで、上記リチウムイオン電池は、１９９２年に市場に投入され、その後２０００年まで年率にして30％以上の急成長を見せた電池である。市場投入当時のリチウムイオン電池の電池容量は、１８６５０型電池にして800mAh程度であったが、２００５年現在ではその容量は2500mAhに達しており、実に3倍の容量向上が実現された。この電池容量の向上は、主に負極の単位重量あたりの容量の向上によってもたらされたものであるが、負極の黒鉛の容量も限界に近づいており、現在、大きなブレークスルー技術の開発が嘱望されている。   By the way, the lithium ion battery is a battery that was put on the market in 1992 and has rapidly grown to 30% or more until 2000. The battery capacity of the lithium-ion battery at the time of market introduction was about 800 mAh for a 18650 type battery. However, as of 2005, the capacity reached 2500 mAh, and the capacity was actually tripled. This increase in battery capacity is mainly due to the increase in capacity per unit weight of the negative electrode, but the capacity of graphite in the negative electrode is approaching its limit, and the development of a large breakthrough technology is currently envy. Has been.

このように負極容量設計がほぼ限界にきており、新たな負極の出現が望まれているリチウムイオン電池において、近年、ＳｉやＳｎ等のリチウムイオンを電気化学的に大量に吸蔵・脱離できる金属が注目されている。なお、黒鉛の吸蔵・脱離能力が372mAh/gであるのに対し、これら金属の吸蔵・脱離能力は約3000〜4000mAh/gに上ることが知られている。   Thus, in the lithium ion battery in which the negative electrode capacity design has almost reached its limit, and a new negative electrode is desired, in recent years, lithium ions such as Si and Sn can be electrochemically occluded and desorbed in large quantities. Metal is drawing attention. It is known that the occlusion / desorption ability of these metals is about 3000 to 4000 mAh / g, whereas the occlusion / desorption ability of graphite is 372 mAh / g.

しかしながら、これら金属は、リチウムの吸蔵・脱離に伴う体積膨張・収縮が極めて大きく、例えば、Ｓｉの場合は吸蔵によりその体積が200％となるため、充放電サイクルが進むにつれＣｕ等からなる集電体から剥離してしまい、電極として機能しなくなるという大きな間題点を抱えている。   However, these metals have extremely large volume expansion / contraction due to insertion / extraction of lithium. For example, in the case of Si, the volume becomes 200% by occlusion. It has a big problem that it peels off from the electric body and does not function as an electrode.

これに対して、金属状のシリコン等をそのまま用いるのではなく、表面にカーボンをコーティンクしたシリコン粒子を使用する等して、異種物質で膨張・収縮に伴う体積変化を吸収する試みも見られるが、依然として本質的な問題の解決には至っていない。   On the other hand, there is an attempt to absorb volume change due to expansion / contraction with a different substance by using silicon particles coated with carbon on the surface instead of using metallic silicon or the like as it is. Still, the essential problem has not been solved.

特開平６−１３１０８号公報JP-A-6-13108 T. Ishiharaら，The 44th Battery Symposium in Japan，2003，1D14，"Anodic Property of n-type Si coated with C Filament"T. Ishihara et al., The 44th Battery Symposium in Japan, 2003, 1D14, "Anodic Property of n-type Si coated with C Filament"

そこで、本発明の目的は、上記従来技術の問題を解決し、安全性が高いことに加え、電池容量が大きく、充放電サイクルに伴う負極の体積変化が抑制されており、優れたサイクル特性を有する非水電解液二次電池を提供することにある。   Accordingly, the object of the present invention is to solve the above-mentioned problems of the prior art, and in addition to high safety, the battery capacity is large, the volume change of the negative electrode accompanying charge / discharge cycles is suppressed, and excellent cycle characteristics are achieved. It is in providing the nonaqueous electrolyte secondary battery which has.

本発明者らは、上記目的を達成するために鋭意検討した結果、非水電解液二次電池において、３次元連続状で網目構造を有する炭素繊維に金属微粒子を担持してなる炭素材電極を負極として用いることで、負極中の金属微粒子が大量のリチウムを吸蔵・脱離できるため、電池容量が大幅に向上し、また、負極中の炭素繊維の網目構造の空隙が担持された金属微粒子の体積膨張を吸収するため、充放電サイクルにより金属微粒子が膨張・収縮しても、負極全体としての体積変化が抑制され、サイクル特性が大幅に向上し、更に、非水電解液にホスファゼン化合物を添加することで、電解液の発火・引火の危険性が大幅に低減され、電池の安全性が大幅に向上することを見出し、本発明を完成させるに至った。   As a result of intensive studies to achieve the above object, the present inventors have found a carbon material electrode in which metal fine particles are supported on carbon fibers having a three-dimensional continuous network structure in a non-aqueous electrolyte secondary battery. By using it as a negative electrode, the metal fine particles in the negative electrode can absorb and desorb a large amount of lithium, so that the battery capacity is greatly improved, and the metal fine particles carrying the voids of the carbon fiber network structure in the negative electrode are supported. In order to absorb volume expansion, even if the metal fine particles expand / contract due to the charge / discharge cycle, the volume change of the negative electrode as a whole is suppressed, cycle characteristics are greatly improved, and phosphazene compounds are added to the non-aqueous electrolyte. Thus, the present inventors have found that the risk of ignition and ignition of the electrolyte is greatly reduced and the safety of the battery is greatly improved, and the present invention has been completed.

即ち、本発明の非水電解液二次電池は、正極と、負極と、非水電解液とを備え、前記負極が３次元連続状炭素繊維に金属微粒子を担持してなる炭素材電極であって、前記非水電解液がホスファゼン化合物と支持塩とを含むことを特徴とする。ここで、負極として用いる炭素材電極は、３次元連続状炭素繊維と、該炭素繊維上に担持された金属微粒子とからなり、３次元連続状炭素繊維が導電体として機能する一方、金属微粒子がリチウム吸蔵体として機能する。   That is, the non-aqueous electrolyte secondary battery of the present invention is a carbon material electrode comprising a positive electrode, a negative electrode, and a non-aqueous electrolyte, wherein the negative electrode carries metal fine particles on a three-dimensional continuous carbon fiber. The non-aqueous electrolyte contains a phosphazene compound and a supporting salt. Here, the carbon material electrode used as the negative electrode is composed of three-dimensional continuous carbon fiber and metal fine particles supported on the carbon fiber, while the three-dimensional continuous carbon fiber functions as a conductor, Functions as a lithium occlusion body.

本発明の非水電解液二次電池の好適例においては、前記３次元連続状炭素繊維が、芳香環を有する化合物を酸化重合して得られるフィブリル状ポリマーを非酸化性雰囲気中で焼成して得たものである。ここで、前記芳香環を有する化合物としては、アニリン、ピロール、チオフェン、及びそれらの誘導体からなる群から選択される少なくとも一種の化合物が好ましい。また、前記酸化重合としては、電解酸化重合が好ましい。   In a preferred example of the non-aqueous electrolyte secondary battery of the present invention, the three-dimensional continuous carbon fiber is obtained by firing a fibril polymer obtained by oxidative polymerization of a compound having an aromatic ring in a non-oxidizing atmosphere. It is obtained. Here, the compound having an aromatic ring is preferably at least one compound selected from the group consisting of aniline, pyrrole, thiophene, and derivatives thereof. The oxidative polymerization is preferably electrolytic oxidative polymerization.

本発明の非水電解液二次電池に用いる炭素材電極は、金属イオンの還元法により前記金属微粒子が前記３次元連続状炭素繊維上に担持されていることが好ましい。ここで、前記金属イオンの還元法としては、電気メッキ（電解メッキ）が好ましい。電気メッキの場合、印加電圧や電圧印加法を変化させることが容易であるため、金属担持量やその大きさ、形状を制御し易い。   In the carbon material electrode used in the non-aqueous electrolyte secondary battery of the present invention, the metal fine particles are preferably supported on the three-dimensional continuous carbon fiber by a metal ion reduction method. Here, as the metal ion reduction method, electroplating (electrolytic plating) is preferable. In the case of electroplating, since it is easy to change the applied voltage and the voltage application method, it is easy to control the amount of metal carried, its size and shape.

本発明の非水電解液二次電池に用いる炭素材電極において、前記金属微粒子を構成する金属は、リチウムを吸蔵・脱離可能な金属であることが好ましい。ここで、該金属微粒子は、Ｓｎ、Ｓｉ、Ｐｂ、Ａｌ、Ａｕ、Ｐｔ、Ｉｎ、Ｚｎ、Ｃｄ、Ａｇ及びＭｇからなる群から選択される少なくとも一種の金属を含むことが好ましく、Ｓｎを含むことが特に好ましい。   In the carbon material electrode used for the non-aqueous electrolyte secondary battery of the present invention, the metal constituting the metal fine particles is preferably a metal capable of inserting and extracting lithium. Here, the metal fine particles preferably include at least one metal selected from the group consisting of Sn, Si, Pb, Al, Au, Pt, In, Zn, Cd, Ag, and Mg, and include Sn. Is particularly preferred.

本発明の非水電解液二次電池に用いる炭素材電極は、前記３次元連続状炭素繊維の空隙の50体積％以下が前記金属微粒子で充填されていることが好ましい。この場合、充放電サイクルにおいて、炭素繊維上に担持された金属微粒子が膨張しても、炭素材電極全体としての膨張が十分に防止されている。   In the carbon material electrode used for the nonaqueous electrolyte secondary battery of the present invention, it is preferable that 50% by volume or less of the voids of the three-dimensional continuous carbon fiber are filled with the metal fine particles. In this case, even if the metal fine particles supported on the carbon fiber expand in the charge / discharge cycle, the expansion of the entire carbon material electrode is sufficiently prevented.

本発明の非水電解液二次電池において、前記ホスファゼン化合物としては、下記式(I)：
［式中、Ｒ1は、それぞれ独立して一価の置換基又はハロゲン元素を表し；Ｙ1は、それぞれ独立して２価の連結基、２価の元素又は単結合を表し；Ｘは、炭素、ケイ素、ゲルマニウム、スズ、窒素、リン、ヒ素、アンチモン、ビスマス、酸素、硫黄、セレン、テルル及びポロニウムからなる群から選ばれる元素の少なくとも１種を含む置換基を表す］で表される鎖状ホスファゼン化合物、及び下記式(II)：
(ＮＰＲ2 2)n ・・・ (II)
［式中、Ｒ2はそれぞれ独立して一価の置換基又はハロゲン元素を表し；ｎは３〜１５を表す］で表される環状ホスファゼン化合物が好ましい。ここで、前記ホスファゼン化合物としては、リンに直接ハロゲンが結合しているホスファゼン化合物がより好ましく、更には、当該ハロゲンがフッ素であり、その個数が１個以上であるホスファゼン化合物が特に好ましい。 In the non-aqueous electrolyte secondary battery of the present invention, the phosphazene compound includes the following formula (I):
[Wherein, R 1 each independently represents a monovalent substituent or a halogen element; Y 1 each independently represents a divalent linking group, a divalent element or a single bond; Chain representing a substituent containing at least one element selected from the group consisting of carbon, silicon, germanium, tin, nitrogen, phosphorus, arsenic, antimony, bismuth, oxygen, sulfur, selenium, tellurium and polonium] Phosphazene compound and the following formula (II):
(NPR 2 2 ) n ... (II)
A cyclic phosphazene compound represented by the formula: wherein R 2 each independently represents a monovalent substituent or a halogen element; n represents 3 to 15 is preferable. Here, as the phosphazene compound, a phosphazene compound in which a halogen is directly bonded to phosphorus is more preferable, and a phosphazene compound in which the halogen is fluorine and the number thereof is 1 or more is particularly preferable.

また、本発明の非水電解液二次電池の非水電解液は、更に非プロトン性有機溶媒を含むことが好ましい。該非プロトン性有機溶媒は、負極と反応することなく、非水電解液の粘度を低く抑えることができる。   Moreover, it is preferable that the non-aqueous electrolyte of the non-aqueous electrolyte secondary battery of the present invention further contains an aprotic organic solvent. The aprotic organic solvent can keep the viscosity of the non-aqueous electrolyte low without reacting with the negative electrode.

本発明によれば、非水電解液がホスファゼン化合物を含有し且つ３次元連続状炭素繊維に金属微粒子を担持してなる炭素材電極を負極とし、電解液の発火・引火の危険性が大幅に低減されている上、負極中の金属微粒子の利用率が高いため電池容量が大きく、且つ該金属微粒子が電気化学反応に伴って体積変化しても負極全体として体積変化することがなく、優れたサイクル特性を有する非水電解液二次電池を提供することができる。   According to the present invention, the non-aqueous electrolyte contains a phosphazene compound and the carbon material electrode formed by supporting metal fine particles on a three-dimensional continuous carbon fiber is used as the negative electrode, and the risk of ignition and ignition of the electrolyte is greatly increased. In addition, the battery capacity is large due to the high utilization rate of the metal fine particles in the negative electrode, and even if the volume of the metal fine particles changes due to the electrochemical reaction, the volume of the negative electrode as a whole does not change and is excellent. A nonaqueous electrolyte secondary battery having cycle characteristics can be provided.

以下に、本発明を詳細に説明する。本発明の非水電解液二次電池は、正極と、負極と、非水電解液とを備え、前記負極が３次元連続状炭素繊維に金属微粒子を担持してなる炭素材電極であって、前記非水電解液がホスファゼン化合物と支持塩とを含むことを特徴とする。なお、本発明の非水電解液二次電池は、必要に応じて、セパレーター等の非水電解液二次電池の技術分野で通常使用されている他の部材を備えることができる。   The present invention is described in detail below. The non-aqueous electrolyte secondary battery of the present invention is a carbon material electrode comprising a positive electrode, a negative electrode, and a non-aqueous electrolyte, wherein the negative electrode carries metal fine particles on a three-dimensional continuous carbon fiber, The non-aqueous electrolyte contains a phosphazene compound and a supporting salt. In addition, the nonaqueous electrolyte secondary battery of this invention can be equipped with the other member normally used in the technical field of nonaqueous electrolyte secondary batteries, such as a separator, as needed.

＜負極＞
本発明の非水電解液二次電池に負極として用いる炭素材電極は、３次元連続状炭素繊維に金属微粒子を担持してなる。該炭素材電極を構成する３次元連続状炭素繊維は、３次元連続状であるため、導電性が高く、金属微粒子上で起こる酸化・還元反応に伴う電子を効果的に集電体に伝導することができる。そのため、該炭素材電極には、特に外部から導電体を追加付与する必要はない。また、上記炭素材電極においては、金属が微粒子状に担持されているため、金属の比表面積、即ち、反応面積が大きい。そのため、該炭素材電極は、大電流での充電や放電特性にも優れる。更に、上記炭素材電極においては、３次元連続状炭素繊維が３次元網目構造を有し、該網目構造が金属微粒子の電気化学反応に伴う体積変化を効率よく吸収するため、炭素材電極全体としての体積変化が殆どなく、隣接する集電体等と剥離することがない。そのため、本発明の非水電解液二次電池は、充放電サイクル特性に優れる。 <Negative electrode>
The carbon material electrode used as the negative electrode in the nonaqueous electrolyte secondary battery of the present invention is formed by supporting metal fine particles on a three-dimensional continuous carbon fiber. Since the three-dimensional continuous carbon fiber constituting the carbon material electrode is three-dimensional continuous, it has high conductivity and effectively conducts electrons accompanying oxidation / reduction reactions occurring on the metal fine particles to the current collector. be able to. Therefore, it is not necessary to add a conductor to the carbon material electrode from the outside. In the carbon material electrode, since the metal is supported in fine particles, the specific surface area of the metal, that is, the reaction area is large. Therefore, the carbon material electrode is excellent in charging and discharging characteristics at a large current. Furthermore, in the carbon material electrode, since the three-dimensional continuous carbon fiber has a three-dimensional network structure, and the network structure efficiently absorbs the volume change accompanying the electrochemical reaction of the metal fine particles, There is almost no change in volume, and there is no separation from adjacent current collectors. Therefore, the nonaqueous electrolyte secondary battery of the present invention is excellent in charge / discharge cycle characteristics.

また更に、電気メッキで金属微粒子を３次元連続状炭素繊維上に析出させた場合には、金属微粒子が炭素繊維と接触した状態で析出するため、金属微粒子と炭素繊維との接触性が優れる。その結果、炭素材電極における金属の利用効率の向上が達成される上、非水電解液二次電池の内部抵抗を低減することもできる。   Furthermore, when the metal fine particles are deposited on the three-dimensional continuous carbon fiber by electroplating, the metal fine particles are deposited in contact with the carbon fibers, so that the contact between the metal fine particles and the carbon fibers is excellent. As a result, the metal utilization efficiency in the carbon material electrode can be improved and the internal resistance of the non-aqueous electrolyte secondary battery can be reduced.

上記３次元連続状炭素繊維は、例えば、芳香環を有する化合物を酸化重合してフィブリル状ポリマーを生成させた後、該フィブリル状ポリマーを非酸化性雰囲気中で焼成することで得られる。上記芳香環を有する化合物としては、ベンゼン環を有する化合物、芳香族複素環を有する化合物を挙げることができる。ここで、ベンゼン環を有する化合物としては、アニリン及びアニリン誘導体が好まく、芳香族複素環を有する化合物としては、ピロール、チオフェン及びこれらの誘導体が好ましい。これら芳香環を有する化合物は、一種単独で用いても、二種以上の混合物として用いてもよい。   The three-dimensional continuous carbon fiber can be obtained, for example, by oxidizing a compound having an aromatic ring to produce a fibril polymer, and then firing the fibril polymer in a non-oxidizing atmosphere. Examples of the compound having an aromatic ring include a compound having a benzene ring and a compound having an aromatic heterocyclic ring. Here, aniline and aniline derivatives are preferred as the compound having a benzene ring, and pyrrole, thiophene and derivatives thereof are preferred as the compound having an aromatic heterocycle. These compounds having an aromatic ring may be used alone or as a mixture of two or more.

上記芳香環を有する化合物を酸化重合して得られるフィブリル状ポリマーは、直径が30nm〜数百nmで、好ましくは40nm〜500nmであり、長さが0.5μm〜100mmで、好ましくは1μm〜10mmである。   The fibrillar polymer obtained by oxidative polymerization of the compound having an aromatic ring has a diameter of 30 nm to several hundreds of nm, preferably 40 nm to 500 nm, and a length of 0.5 μm to 100 mm, preferably 1 μm to 10 mm. is there.

上記酸化重合法としては、電解酸化重合法及び化学的酸化重合法等の種々の方法が利用できるが、中でも電解酸化重合法が好ましい。また、酸化重合においては、原料の芳香環を有する化合物と共に、酸を混在させることが好ましい。この場合、酸の負イオンがドーパントとして合成されるフィブリル状ポリマー中に取り込まれ、導電性に優れるフィブリル状ポリマーが得られ、このフィブリル状ポリマーを用いることにより炭素繊維の導電性を更に向上させることができる。   As the oxidative polymerization method, various methods such as an electrolytic oxidative polymerization method and a chemical oxidative polymerization method can be used. Among them, the electrolytic oxidative polymerization method is preferable. Moreover, in oxidative polymerization, it is preferable to mix an acid with the compound which has a raw material aromatic ring. In this case, the negative ion of the acid is taken into the fibril polymer synthesized as a dopant to obtain a fibril polymer excellent in conductivity, and the conductivity of the carbon fiber is further improved by using this fibril polymer. Can do.

この点について更に詳述すると、例えば、重合原料としてアニリンを用いた場合、アニリンをＨＢＦ4を混在させた状態で酸化重合して得られるポリアニリンは、通常下記式（Ａ）〜（Ｄ）：
に示した４種のポリアニリンが混在した状態、即ち、ベンゾノイド＝アミン状態（式Ａ）、ベンゾノイド＝アンモニウム状態（式Ｂ）、ドープ＝セミキノンラジカル状態（式Ｃ）及びキノイド＝ジイミン状態（式Ｄ）の混合状態になる。ここで、上記各状態の混合比率は特に制限されるものではないが、ドープ＝セミキノンラジカル状態（式Ｃ）を多く含んでいる方がキノイド＝ジイミン状態（式Ｄ）が大部分であるよりも得られる炭素繊維の残炭率及び導電率が高くなる。従って、ドープ＝セミキノンラジカル状態（式Ｃ）を多く含むポリアニリンを得るためには、重合時に酸を混在させることが好ましい。なお、重合の際に混在させる酸としては、上記ＨＢＦ4に限定されるものではなく、種々のものを使用することができ、ＨＢＦ4の他、Ｈ2ＳＯ4、ＨＣｌ、ＨＣｌＯ4等を例示することができる。ここで、該酸の濃度は、0.1〜3mol/Lの範囲が好ましく、0.5〜2.5mol/Lの範囲が更に好ましい。 More specifically, for example, when aniline is used as a polymerization raw material, polyaniline obtained by oxidative polymerization of aniline in a state where HBF 4 is mixed is usually represented by the following formulas (A) to (D):
In the state where the four polyanilines shown in FIG. 4 are mixed, that is, benzonoid = amine state (formula A), benzonoid = ammonium state (formula B), dope = semiquinone radical state (formula C) and quinoid = diimine state (formula D) ). Here, the mixing ratio of each of the above states is not particularly limited, but the quinoid = diimine state (formula D) is mostly contained when the dope = semiquinone radical state (formula C) is contained in a large amount. Further, the carbon residue and conductivity of the carbon fiber obtained are increased. Therefore, in order to obtain polyaniline containing a large amount of dope = semiquinone radical state (formula C), it is preferable to mix an acid during polymerization. As the acid to be mixed in the polymerization, is not limited to the above HBF 4, can be used various ones, other HBF 4, H 2 SO 4, HCl, illustrate HClO 4, etc. can do. Here, the concentration of the acid is preferably in the range of 0.1 to 3 mol / L, and more preferably in the range of 0.5 to 2.5 mol / L.

上記ドープ＝セミキノンラジカル状態（式Ｃ）の含有割合（ドーピングレベル）は適宜調節することができ、この含有割合（ドーピングレベル）を調節することにより、得られる炭素繊維の残炭率及び導電率を制御することができ、ドーピングレベルを高くすることにより得られる炭素繊維の残炭率及び導電率が共に高くなる。なお、特に限定されるものではないが、このドープ＝セミキノンラジカル状態（式Ｃ）の含有割合（ドーピングレベル）は、通常0.01〜50％の範囲とすることが好ましい。   The content ratio (doping level) of the dope = semiquinone radical state (formula C) can be adjusted as appropriate, and by adjusting the content ratio (doping level), the residual carbon ratio and conductivity of the carbon fiber obtained. It is possible to control the residual carbon ratio and conductivity of the carbon fiber obtained by increasing the doping level. Although not particularly limited, the content ratio (doping level) of the dope = semiquinone radical state (formula C) is usually preferably in the range of 0.01 to 50%.

電解酸化重合によりフィブリル状ポリマーを得る場合には、芳香環を有する化合物を含む溶液中に作用極及び対極となる一対の電極板を浸漬し、両極間に前記芳香環を有する化合物の酸化電位以上の電圧を印加するか、または該芳香環を有する化合物が重合するのに充分な電圧が確保できるような条件の電流を通電すればよく、これにより作用極上にフィブリル状ポリマーが生成する。この電解酸化重合法によるフィブリル状ポリマーの合成方法の一例を挙げると、作用極及び対極としてステンレススチール、白金、カーボン等の良導電性物質からなる板や多孔質材などを用い、これらをＨ2ＳＯ4、ＨＢＦ4等の酸及び芳香環を有する化合物を含む電解溶液中に浸漬し、両極間に0.1〜1000mA/cm2、好ましくは0.2〜100mA/cm2の電流を通電して、作用極側にフィブリル状ポリマーを重合析出させる方法などが例示される。ここで、芳香環を有する化合物の電解溶液中の濃度は、0.05〜3mol/Lの範囲が好ましく、0.25〜1.5mol/Lの範囲が更に好ましい。また、電解溶液には、上記成分に加え、ｐＨを調製するために可溶性塩等を適宜添加してもよい。 In the case of obtaining a fibrillated polymer by electrolytic oxidation polymerization, a pair of electrode plates serving as a working electrode and a counter electrode are immersed in a solution containing a compound having an aromatic ring, and the oxidation potential of the compound having an aromatic ring between both electrodes is exceeded. Or a current having such a condition that a voltage sufficient to polymerize the compound having an aromatic ring may be applied, whereby a fibril polymer is formed on the working electrode. Using this and an example of a method of synthesizing fibrillar polymer by electrolytic oxidative polymerization method, stainless steel as a working electrode and a counter electrode, platinum, and good conductivity made of a material plate or a porous material such as carbon, these and H 2 SO 4, was immersed in an electrolyte solution containing a compound having an acid and an aromatic ring of HBF 4, etc., 0.1~1000mA / cm 2 between the electrodes, preferably by passing current of 0.2~100mA / cm 2, a working electrode Examples thereof include a method of polymerizing and depositing a fibrillated polymer on the side. Here, the concentration of the compound having an aromatic ring in the electrolytic solution is preferably in the range of 0.05 to 3 mol / L, and more preferably in the range of 0.25 to 1.5 mol / L. Moreover, in addition to the said component, you may add a soluble salt etc. to an electrolyte solution suitably in order to adjust pH.

上述のように、炭素繊維のドーピングレベルを調節することにより、得られる炭素繊維の導電率及び残炭率を制御することができるが、ドーピングレベルの調節は、得られたフィブリル状ポリマーを何らかの方法で還元すればよく、その手法に特に制限はない。具体例としては、アンモニア水溶液又はヒドラジン水溶液などに浸漬する方法、電気化学的に還元電流を付加する方法などが挙げられる。この還元レベルによりフィブリル状ポリマーに含まれるドーパント量の制御を行うことができ、この場合、還元処理によってフィブリル状ポリマー中のドーパント量は減少する。また、重合時において酸濃度を制御することにより重合過程でドーピングレベルをある程度調節することもできるが、ドーピングレベルが大きく異なる種々のサンプルを得ることは難しく、このため上記還元法が好適に採用される。なお、このように含有割合を調節したドーパントは、後述する焼成処理後も、その焼成条件を制御することによって得られる炭素繊維中に保持され、これにより炭素繊維の導電率及び残炭率が制御される。   As described above, by adjusting the doping level of the carbon fiber, it is possible to control the conductivity and the residual carbon ratio of the obtained carbon fiber. There is no particular limitation on the method. Specific examples include a method of immersing in an aqueous ammonia solution or an aqueous hydrazine solution, a method of electrochemically applying a reduction current, and the like. The amount of dopant contained in the fibril-like polymer can be controlled by this reduction level. In this case, the amount of dopant in the fibril-like polymer is reduced by the reduction treatment. Although the doping level can be adjusted to some extent during the polymerization process by controlling the acid concentration during the polymerization, it is difficult to obtain various samples with greatly different doping levels. Therefore, the above reduction method is preferably employed. The In addition, the dopant which adjusted the content rate in this way is hold | maintained in the carbon fiber obtained by controlling the baking conditions also after the baking process mentioned later, and, thereby, the electrical conductivity and residual carbon rate of carbon fiber are controlled. Is done.

上記のようにして作用極上に得られたフィブリル状ポリマーを、水や有機溶剤等の溶媒で洗浄し、乾燥させた後、非酸化性雰囲気中で焼成して炭化することで、フィブリル状で３次元連続状の炭素繊維が得られる。ここで、乾燥方法としては、特に制限されるものではないが、風乾、真空乾燥の他、流動床乾燥装置、気流乾燥機、スプレードライヤー等を使用した方法を例示することができる。また、焼成条件としては、特に限定されるものではなく、最適導電率となるように設定すればよいが、特に高導電率を必要とする場合は、温度500〜3000℃、好ましくは600〜2800℃で、0.5〜6時間とすることが好ましい。なお、非酸化性雰囲気としては、窒素雰囲気、アルゴン雰囲気、ヘリウム雰囲気等を挙げることができ、場合によっては水素雰囲気とすることもできる。   The fibrillated polymer obtained on the working electrode as described above is washed with a solvent such as water or an organic solvent, dried, and then baked and carbonized in a non-oxidizing atmosphere. A dimensionally continuous carbon fiber is obtained. Here, the drying method is not particularly limited, and examples thereof include a method using a fluidized bed drying device, an air dryer, a spray dryer, etc., in addition to air drying and vacuum drying. In addition, the firing conditions are not particularly limited, and may be set so as to obtain an optimum conductivity. Particularly, when high conductivity is required, the temperature is 500 to 3000 ° C., preferably 600 to 2800. The temperature is preferably 0.5 to 6 hours at ° C. Note that examples of the non-oxidizing atmosphere include a nitrogen atmosphere, an argon atmosphere, and a helium atmosphere, and in some cases, a hydrogen atmosphere can also be used.

上記炭素繊維は、直径が30nm〜数百nm、好ましくは40nm〜500nmであり、長さが0.5μm〜100mm、好ましくは1μm〜10mmであり、表面抵抗が106〜10-2Ω、好ましくは104〜10-2Ωである。また、該炭素繊維は、残炭率が95〜30％、好ましくは90〜40％である。該炭素繊維は、カーボン全体が３次元に連続した構造を有するため、粒状カーボンよりも導電性が高い。 The carbon fiber has a diameter of 30 nm to several hundred nm, preferably 40 nm to 500 nm, a length of 0.5 μm to 100 mm, preferably 1 μm to 10 mm, and a surface resistance of 10 6 to 10 −2 Ω, preferably 10 4 to 10 −2 Ω. The carbon fiber has a residual carbon ratio of 95 to 30%, preferably 90 to 40%. Since the carbon fiber has a structure in which the entire carbon is three-dimensionally continuous, the carbon fiber has higher conductivity than the granular carbon.

上記炭素材電極の金属微粒子を構成する金属としては、リチウムを吸蔵・脱離可能な金属が好ましく、Ｓｎ、Ｓｉ、Ｐｂ、Ａｌ、Ａｕ、Ｐｔ、Ｉｎ、Ｚｎ、Ｃｄ、Ａｇ及びＭｇ等が更に好ましく、Ｓｎがより一層好ましい。これら金属は、一種単独で用いてもよいし、二種以上の合金として用いてもよい。ここで、炭素繊維上に担持される金属微粒子の粒径は、0.5〜20nmの範囲が好ましい。また、金属微粒子の担持率は、炭素繊維1gに対して0.05〜5gの範囲が好ましい。更に、上記炭素材電極においては、３次元連続状炭素繊維の空隙の50体積％以下が金属微粒子で充填されていることが好ましい。この場合、充放電サイクルにおいて、炭素繊維上に担持された金属微粒子が膨張・収縮しても、負極全体としての体積変化が十分に防止されている。   As the metal constituting the metal fine particles of the carbon material electrode, a metal capable of inserting and extracting lithium is preferable, and Sn, Si, Pb, Al, Au, Pt, In, Zn, Cd, Ag, Mg, and the like are further included. Preferably, Sn is even more preferable. These metals may be used individually by 1 type, and may be used as 2 or more types of alloys. Here, the particle size of the metal fine particles supported on the carbon fiber is preferably in the range of 0.5 to 20 nm. Further, the supporting rate of the metal fine particles is preferably in the range of 0.05 to 5 g with respect to 1 g of carbon fiber. Furthermore, in the carbon material electrode, it is preferable that 50% by volume or less of the voids of the three-dimensional continuous carbon fiber is filled with metal fine particles. In this case, in the charge / discharge cycle, even if the metal fine particles supported on the carbon fiber expand and contract, the volume change of the negative electrode as a whole is sufficiently prevented.

上記金属微粒子の炭素繊維上への担持法としては、含浸法、電気メッキ法（電解還元法）、無電解メッキ法（化学メッキ法）、スパッタリング法等が挙げられるが、金属微粒子の担持率の調整が容易な点で、電気メッキ法が好ましい。該電気メッキ法では、メッキしたい金属のイオンを含む溶液を調製し、該溶液に上記炭素繊維を浸漬し、所定の電圧を印加することで、溶液から金属微粒子を炭素繊維上に電気化学的に析出させることにより、炭素繊維表面のみに金属微粒子を析出させることができ、しかも通電電荷量で金属微粒子の析出量を正確に制御することができる。また、金属微粒子析出の際の通電条件（電流密度、直流法かパルス法か、温度、金属イオン濃度、共存イオン種等）を適宜選択することで、析出させる金属微粒子の粒径、形態、付着状況等を変えることもできる。   Examples of the method for supporting the metal fine particles on the carbon fiber include an impregnation method, an electroplating method (electrolytic reduction method), an electroless plating method (chemical plating method), and a sputtering method. The electroplating method is preferable in terms of easy adjustment. In the electroplating method, a solution containing ions of a metal to be plated is prepared, the carbon fiber is immersed in the solution, and a predetermined voltage is applied to electrochemically deposit metal fine particles on the carbon fiber from the solution. By precipitating, metal fine particles can be deposited only on the carbon fiber surface, and the amount of metal fine particles deposited can be accurately controlled by the amount of electric charge. In addition, by appropriately selecting the energization conditions (current density, direct current method or pulse method, temperature, metal ion concentration, coexisting ion species, etc.) at the time of metal fine particle deposition, the particle size, form, and adhesion of the metal fine particles to be deposited You can also change the situation.

例えば、炭素繊維にＳｎ微粒子を担持する場合は、Ｓｎイオンを含む水溶液に炭素繊維を浸漬し、該炭素繊維を通電することで、炭素繊維の表面上にＳｎ微粒子を電気化学的に析出させることができる。この場合においても、通電量によってＳｎ微粒子の析出量をコントロールすることができる。但し、Ｓｎのように表面が酸化し易い金属を電析させて炭素材電極を作製する場合には、金属微粒子表面に生成したＳｎＯ層等を除去するために、ＨＦ処理やＨ2雰囲気下でのアニーリングを施すことが好ましく、これらの処理によって、炭素材電極の性能を向上させることができる。 For example, when Sn fine particles are supported on carbon fibers, the carbon fine particles are immersed in an aqueous solution containing Sn ions, and the carbon fibers are energized to electrochemically precipitate the Sn fine particles on the surface of the carbon fibers. Can do. Even in this case, the precipitation amount of the Sn fine particles can be controlled by the amount of energization. However, in the case of producing a carbon material electrode by depositing a metal whose surface is easily oxidized, such as Sn, in order to remove the SnO layer formed on the surface of the metal fine particles, it can be used under HF treatment or H 2 atmosphere. It is preferable to perform annealing, and the performance of the carbon material electrode can be improved by these treatments.

上記炭素材電極は、特に限定されるものではないが、集電体上で３次元連続状炭素繊維を合成し、更に金属微粒子を担持することで、集電体の塗工工程が省略できる。例えば、銅集電体上に３次元連続状炭素繊維を形成し、該炭素繊維上に電気メッキ等によりスズ等の金属微粒子を担持し、該金属微粒子担持炭素繊維を加熱乾燥した後、プレスすることで、そのまま負極として用いることができる。   Although the said carbon material electrode is not specifically limited, The application | coating process of a collector can be skipped by synthesize | combining a three-dimensional continuous carbon fiber on a collector, and also carry | supporting metal microparticles. For example, a three-dimensional continuous carbon fiber is formed on a copper current collector, metal fine particles such as tin are supported on the carbon fiber by electroplating, and the metal fine particle-supported carbon fiber is heated and dried and then pressed. Therefore, it can be used as a negative electrode as it is.

本発明の非水電解液二次電池の負極の形状としては、特に制限はなく、電極として公知の形状の中から適宜選択することができる。例えば、シート状、円柱形状、板状形状、スパイラル形状等が挙げられる。   There is no restriction | limiting in particular as a shape of the negative electrode of the nonaqueous electrolyte secondary battery of this invention, It can select suitably from well-known shapes as an electrode. For example, a sheet shape, a columnar shape, a plate shape, a spiral shape, and the like can be given.

＜正極＞
本発明の非水電解液二次電池の正極活物質としては、Ｖ2Ｏ5、Ｖ6Ｏ13、ＭｎＯ2、ＭｎＯ3等の金属酸化物、ＬｉＣｏＯ2、ＬｉＮｉＯ2、ＬｉＭｎ2Ｏ4、ＬｉＦｅＯ2及びＬｉＦｅＰＯ4等のリチウム含有複合酸化物、ＴｉＳ2、ＭｏＳ2等の金属硫化物、ポリアニリン等の導電性ポリマー等が好適に挙げられる。上記リチウム含有複合酸化物は、Ｆｅ、Ｍｎ、Ｃｏ及びＮｉからなる群から選択される２種又は３種の遷移金属を含む複合酸化物であってもよく、この場合、該複合酸化物は、ＬｉＦｅxＣｏyＮｉ(1-x-y)Ｏ2（式中、０≦ｘ＜１、０≦ｙ＜１、０＜ｘ＋ｙ≦１）、ＬｉＭｎxＦｅyＯ2-x-y、あるいはＬｉＮｉxＣｏyＭｎ1-x-yＯ2等で表される。これらの中でも、高容量で安全性が高く、更には電解液の濡れ性に優れる点で、ＬｉＣｏＯ2、ＬｉＮｉＯ2、ＬｉＭｎ2Ｏ4、ＬｉＮｉ1/3Ｃｏ1/3Ｍｎ1/3Ｏ2が特に好適である。これら正極活物質は、１種単独で使用してもよく、２種以上を併用してもよい。 <Positive electrode>
As the positive electrode active material of the non-aqueous electrolyte secondary battery of the present invention, metal oxides such as V 2 O 5 , V 6 O 13 , MnO 2 , MnO 3 , LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , LiFeO Preferred examples include lithium-containing composite oxides such as 2 and LiFePO 4 , metal sulfides such as TiS 2 and MoS 2 , and conductive polymers such as polyaniline. The lithium-containing composite oxide may be a composite oxide containing two or three transition metals selected from the group consisting of Fe, Mn, Co, and Ni. In this case, the composite oxide includes: LiFe x Co y Ni (wherein, 0 ≦ x <1,0 ≦ y <1,0 <x + y ≦ 1) (1-xy) O 2, LiMn x Fe y O 2-xy or LiNi x Co y Mn, It is represented by 1-xy O 2 or the like. Among these, LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , LiNi 1/3 Co 1/3 Mn 1/3 O 2 are high in terms of high capacity, high safety, and excellent electrolyte wettability. Particularly preferred. These positive electrode active materials may be used individually by 1 type, and may use 2 or more types together.

上記正極には、必要に応じて導電剤、結着剤を混合することができ、導電剤としてはアセチレンブラック等が挙げられ、結着剤としてはポリフッ化ビニリデン（ＰＶＤＦ）、ポリテトラフルオロエチレン（ＰＴＦＥ）、スチレン・ブタジエンゴム（ＳＢＲ）、カルボキシメチルセルロース（ＣＭＣ）等が挙げられる。これらの添加剤は、従来と同様の配合割合で用いることができる。また、上記正極の形状としては、特に制限はなく、電極として公知の形状の中から適宜選択することができる。例えば、シート状、円柱形状、板状形状、スパイラル形状等が挙げられる。   The positive electrode can be mixed with a conductive agent and a binder as necessary. Examples of the conductive agent include acetylene black, and the binder includes polyvinylidene fluoride (PVDF), polytetrafluoroethylene ( PTFE), styrene / butadiene rubber (SBR), carboxymethyl cellulose (CMC), and the like. These additives can be used at a blending ratio similar to the conventional one. Moreover, there is no restriction | limiting in particular as a shape of the said positive electrode, It can select suitably from well-known shapes as an electrode. For example, a sheet shape, a columnar shape, a plate shape, a spiral shape, and the like can be given.

＜非水電解液＞
本発明の非水電解液二次電池に用いる非水電解液は、ホスファゼン化合物と支持塩とを含み、更に非プロトン性有機溶媒を含むことが好ましい。上記ホスファゼン化合物は、分解して、窒素ガスやリン酸エステル等を発生するため、発生した窒素ガスの作用によって、電解液が燃焼する危険性が低減されると共に、発生したリン酸エステル等の作用によって、電池を構成する高分子材料の連鎖分解が抑制されるため、電池の発火・引火の危険性を効果的に低減することができる。更に、上記ホスファゼン化合物がハロゲンを含む場合、万が一の燃焼時にはハロゲンが活性ラジカルの捕捉剤として機能し、電解液の燃焼の危険性を低減する。また更に、上記ホスファゼン化合物が有機置換基を含む場合、燃焼時にセパレーター上に炭化物（チャー）を生成するため酸素の遮断効果もある。なお、上記非水電解液において、上記ホスファゼン化合物の含有量は、電解液の安全性を向上させる観点から、3体積％以上が好ましく、5体積％以上が更に好ましく、また、電解液の100体積％をホスファゼン化合物とすることもできる。 <Non-aqueous electrolyte>
The non-aqueous electrolyte used in the non-aqueous electrolyte secondary battery of the present invention preferably contains a phosphazene compound and a supporting salt, and further contains an aprotic organic solvent. Since the phosphazene compound decomposes to generate nitrogen gas, phosphate ester, etc., the action of the generated nitrogen gas reduces the risk of the electrolyte solution burning and the action of the generated phosphate ester, etc. Therefore, the chain decomposition of the polymer material constituting the battery is suppressed, so that the risk of ignition and ignition of the battery can be effectively reduced. Further, when the phosphazene compound contains a halogen, the halogen functions as an active radical scavenger in the unlikely event of combustion, and reduces the risk of combustion of the electrolyte. Furthermore, when the phosphazene compound contains an organic substituent, it produces a carbide (char) on the separator during combustion, and has an oxygen blocking effect. In the non-aqueous electrolyte, the content of the phosphazene compound is preferably 3% by volume or more, more preferably 5% by volume or more, and 100% by volume of the electrolyte from the viewpoint of improving the safety of the electrolyte. % Can also be a phosphazene compound.

上記非水電解液に用いるホスファゼン化合物としては、上記式(I)で表される鎖状ホスファゼン化合物及び上記式(II)で表される環状ホスファゼン化合物が好適に挙げられる。また、式(I)又は式(II)で表されるホスファゼン化合物の中でも、25℃（室温）において液体であるものが好ましい。該液状ホスファゼン化合物の25℃における粘度は、300mPa・s（300cP）以下が好ましく、20mPa・s（20cP）以下が更に好ましく、5mPa・s（5cP）以下が特に好ましい。なお、本発明において粘度は、粘度測定計［Ｒ型粘度計Ｍｏｄｅｌ ＲＥ５００-ＳＬ、東機産業(株)製］を用い、1rpm、2rpm、3rpm、5rpm、7rpm、10rpm、20rpm及び50rpmの各回転速度で120秒間づつ測定し、指示値が50〜60％となった時の回転速度を分析条件とし、その際の粘度を測定することによって求めた。ホスファゼン化合物の25℃における粘度が300mPa・sを超えると、支持塩が溶解し難くなり、正極、負極、セパレーター等への濡れ性が低下し、電解液の粘性抵抗の増大によりイオン導電性が著しく低下し、特に氷点以下等の低温条件下での使用において性能不足となる。また、これらのホスファゼン化合物は、液状であるため、通常の液状電解質と同等の導電性を有し、電解液に使用することで、優れたサイクル特性を発現させることができる。また、上記式(I)又は式(II)で表されるホスファゼン化合物の中でも、リンに直接ハロゲンが結合しているホスファゼン化合物が更に好ましく、リンに直接フッ素が結合しているホスファゼン化合物がより一層好ましい。   Preferred examples of the phosphazene compound used in the non-aqueous electrolyte include a chain phosphazene compound represented by the above formula (I) and a cyclic phosphazene compound represented by the above formula (II). Of the phosphazene compounds represented by formula (I) or formula (II), those which are liquid at 25 ° C. (room temperature) are preferred. The viscosity at 25 ° C. of the liquid phosphazene compound is preferably 300 mPa · s (300 cP) or less, more preferably 20 mPa · s (20 cP) or less, and particularly preferably 5 mPa · s (5 cP) or less. In the present invention, the viscosity is measured at 1 rpm, 2 rpm, 3 rpm, 5 rpm, 7 rpm, 10 rpm, 20 rpm and 50 rpm using a viscometer [R-type viscometer Model RE500-SL, manufactured by Toki Sangyo Co., Ltd.] The measurement was performed at a speed of 120 seconds, and the rotation speed when the indicated value reached 50 to 60% was set as an analysis condition, and the viscosity was measured at that time. When the viscosity of the phosphazene compound at 25 ° C exceeds 300 mPa · s, the supporting salt becomes difficult to dissolve, the wettability to the positive electrode, negative electrode, separator, etc. decreases, and the ionic conductivity is remarkably increased by increasing the viscous resistance of the electrolyte. In particular, when used under low temperature conditions such as below freezing point, the performance becomes insufficient. In addition, since these phosphazene compounds are in a liquid state, they have the same conductivity as that of a normal liquid electrolyte, and can exhibit excellent cycle characteristics when used in an electrolytic solution. Among the phosphazene compounds represented by the above formula (I) or formula (II), phosphazene compounds in which halogen is directly bonded to phosphorus are more preferable, and phosphazene compounds in which fluorine is directly bonded to phosphorus are more preferable. preferable.

式(I)のＲ1は、一価の置換基又はハロゲン元素である限り特に制限はなく、各Ｒ1は、同一でも、異なってもよい。ここで、一価の置換基としては、アルコキシ基、アルキル基、カルボキシル基、アシル基、アリール基等が挙げられ、これらの中でも、ホスファゼン化合物が低粘度となる点で、アルコキシ基が好ましい。一方、ハロゲン元素としては、フッ素、塩素、臭素等が好適に挙げられる。上記アルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基等や、メトキシエトキシ基、メトキシエトキシエトキシ基等のアルコキシ置換アルコキシ基等が挙げられ、これらの中でも、メトキシ基、エトキシ基、メトキシエトキシ基及びメトキシエトキシエトキシ基が好ましく、低粘度・高誘電率の観点から、メトキシ基及びエトキシ基が更に好ましい。また、上記アルキル基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基等が挙げられ、上記アシル基としては、ホルミル基、アセチル基、プロピオニル基、ブチリル基、イソブチリル基、バレリル基等が挙げられ、上記アリール基としては、フェニル基、トリル基、ナフチル基等が挙げられる。これら一価の置換基中の水素元素は、ハロゲン元素で置換されているのが好ましく、該ハロゲン元素としては、フッ素、塩素、臭素が好適であり、フッ素が最も好ましく、次いで塩素が好ましい。 R 1 in the formula (I) is not particularly limited as long as it is a monovalent substituent or a halogen element, and each R 1 may be the same or different. Here, examples of the monovalent substituent include an alkoxy group, an alkyl group, a carboxyl group, an acyl group, and an aryl group. Among these, an alkoxy group is preferable in that the phosphazene compound has low viscosity. On the other hand, preferred examples of the halogen element include fluorine, chlorine, bromine and the like. Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, and alkoxy-substituted alkoxy groups such as methoxyethoxy group and methoxyethoxyethoxy group. Among these, methoxy group, ethoxy group, methoxy group, etc. An ethoxy group and a methoxyethoxyethoxy group are preferable, and a methoxy group and an ethoxy group are more preferable from the viewpoint of low viscosity and high dielectric constant. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Examples of the acyl group include a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, and a valeryl group. Examples of the aryl group include a phenyl group, a tolyl group, and a naphthyl group. The hydrogen element in these monovalent substituents is preferably substituted with a halogen element. As the halogen element, fluorine, chlorine and bromine are preferred, fluorine is most preferred, and chlorine is then preferred.

式(I)のＹ1は、２価の連結基、２価の元素又は単結合である限り特に制限はなく、各Ｙ1は、同一でも、異なってもよい。ここで、２価の連結基としては、ＣＨ2基の他、酸素、硫黄、セレン、窒素、ホウ素、アルミニウム、スカンジウム、ガリウム、イットリウム、インジウム、ランタン、タリウム、炭素、ケイ素、チタン、スズ、ゲルマニウム、ジルコニウム、鉛、リン、バナジウム、ヒ素、ニオブ、アンチモン、タンタル、ビスマス、クロム、モリブデン、テルル、ポロニウム、タングステン、鉄、コバルト、ニッケルからなる群から選ばれる元素の少なくとも１種を含む２価の連結基が挙げられ；２価の元素としては、酸素、硫黄、セレン等が挙げられる。これらの中でも、式(I)のＹ1としては、ＣＨ2基、及び、酸素、硫黄、セレン、窒素からなる群から選ばれる元素の少なくとも１種を含む２価の連結基が好ましい。特に、硫黄及び／又はセレンの元素を含む２価の連結基の場合には、電解液の発火・引火の危険性が著しく低減するため好ましい。 Y 1 of the formula (I), the divalent linking group is not particularly limited as long as it is bivalent element or a single bond, each Y 1 may be the same or different. Here, as the divalent linking group, in addition to the CH 2 group, oxygen, sulfur, selenium, nitrogen, boron, aluminum, scandium, gallium, yttrium, indium, lanthanum, thallium, carbon, silicon, titanium, tin, germanium Divalent containing at least one element selected from the group consisting of zirconium, lead, phosphorus, vanadium, arsenic, niobium, antimony, tantalum, bismuth, chromium, molybdenum, tellurium, polonium, tungsten, iron, cobalt, nickel A divalent element includes oxygen, sulfur, selenium and the like. Among these, Y 1 in the formula (I) is preferably a divalent linking group containing a CH 2 group and at least one element selected from the group consisting of oxygen, sulfur, selenium, and nitrogen. In particular, a divalent linking group containing sulfur and / or selenium is preferable because the risk of ignition and ignition of the electrolyte is remarkably reduced.

式(I)のＸは、炭素、ケイ素、ゲルマニウム、スズ、窒素、リン、ヒ素、アンチモン、ビスマス、酸素、硫黄、セレン、テルル及びポロニウムからなる群から選ばれる元素の少なくとも１種を含む置換基である限り特に制限はない。有害性、環境等への配慮の観点から、式(I)のＸとしては、炭素、ケイ素、窒素、リン、酸素及び硫黄からなる群から選ばれる元素の少なくとも１種を含む置換基が好ましく、下記式(III)、式(IV)又は式(V)：
［式(III)、式(IV)及び式(V)中、Ｒ3、Ｒ4及びＲ5は、それぞれ独立に一価の置換基又はハロゲン元素を表し；Ｙ3、Ｙ4及びＹ5は、それぞれ独立に２価の連結基、２価の元素又は単結合を表し；Ｚは２価の基又は２価の元素を表す］で表される置換基が更に好ましい。 X in formula (I) is a substituent containing at least one element selected from the group consisting of carbon, silicon, germanium, tin, nitrogen, phosphorus, arsenic, antimony, bismuth, oxygen, sulfur, selenium, tellurium and polonium. As long as it is, there is no particular limitation. From the viewpoint of consideration for toxicity, environment, etc., X in formula (I) is preferably a substituent containing at least one element selected from the group consisting of carbon, silicon, nitrogen, phosphorus, oxygen and sulfur, The following formula (III), formula (IV) or formula (V):
[In Formula (III), Formula (IV) and Formula (V), R 3 , R 4 and R 5 each independently represents a monovalent substituent or a halogen element; Y 3 , Y 4 and Y 5 are And each independently represents a divalent linking group, a divalent element or a single bond; and Z represents a divalent group or a divalent element].

式(III)のＲ3、式(IV)のＲ4及び式(V)のＲ5としては、式(I)のＲ1で述べたのと同様の一価の置換基又はハロゲン元素がいずれも好適に挙げられる。また、式(III)の２つのＲ3、並びに式(V)の２つのＲ5は、それぞれ同一でも、異なってもよく、互いに結合して環を形成していてもよい。 R 3 of formula (III), R 5 of formula (IV) R 4 and formula (V), substituent or a halogen element similar monovalent to that described in R 1 of formula (I) is either Are also preferred. Further, two R 3 s in the formula (III) and two R 5 s in the formula (V) may be the same or different, and may be bonded to each other to form a ring.

式(III)のＹ3、式(IV)のＹ4及び式(V)のＹ5としては、式(I)のＹ1で述べたのと同様の２価の連結基又は２価の元素がいずれも好適に挙げられる。同様に、硫黄及び／又はセレンの元素を含む２価の連結基の場合には、電解液の発火・引火の危険性が大きく低減するため特に好ましい。また、Ｙ3、Ｙ4及びＹ5としては、単結合も好ましい。式(III)の２つのＹ3、並びに式(V)の２つのＹ5は、それぞれ同一でも、異なってもよい。 Y 3 of the formula (III), Y 4 and Y 5 of formula (V) of the formula (IV), the divalent linking group or bivalent element similar to that described by Y 1 in the formula (I) Are preferably mentioned. Similarly, a divalent linking group containing sulfur and / or selenium is particularly preferable because the risk of ignition and ignition of the electrolyte is greatly reduced. Y 3 , Y 4 and Y 5 are also preferably single bonds. Two Y 3 in the formula (III) and two Y 5 in the formula (V) may be the same or different.

式(III)のＺは、２価の基又は２価の元素である限り特に制限はない。ここで、２価の基としては、ＣＨ2基、ＣＨＲ基（ここで、Ｒは、アルキル基、アルコキシ基、フェニル基等を表す）、ＮＲ基の他、酸素、硫黄、セレン、ホウ素、アルミニウム、スカンジウム、ガリウム、イットリウム、インジウム、ランタン、タリウム、炭素、ケイ素、チタン、スズ、ゲルマニウム、ジルコニウム、鉛、リン、バナジウム、ヒ素、ニオブ、アンチモン、タンタル、ビスマス、クロム、モリブデン、テルル、ポロニウム、タングステン、鉄、コバルト、ニッケルからなる群から選ばれる元素の少なくとも１種を含む２価の基等が挙げられ；２価の元素としては、酸素、硫黄、セレン等が挙げられる。これらの中でも、式(III)のＺとしては、ＣＨ2基、ＣＨＲ基、ＮＲ基の他、酸素、硫黄、セレンからなる群から選ばれる元素の少なくとも１種を含む２価の基が好ましい。特に、硫黄及び／又はセレンの元素を含む２価の基の場合には、電解液の発火・引火の危険性が大幅に低減するため好ましい。 Z in the formula (III) is not particularly limited as long as it is a divalent group or a divalent element. Here, as the divalent group, CH 2 group, CHR group (where R represents an alkyl group, alkoxy group, phenyl group, etc.), NR group, oxygen, sulfur, selenium, boron, aluminum , Scandium, gallium, yttrium, indium, lanthanum, thallium, carbon, silicon, titanium, tin, germanium, zirconium, lead, phosphorus, vanadium, arsenic, niobium, antimony, tantalum, bismuth, chromium, molybdenum, tellurium, polonium, tungsten , A divalent group containing at least one element selected from the group consisting of iron, cobalt, and nickel; and examples of the divalent element include oxygen, sulfur, and selenium. Among these, Z in the formula (III) is preferably a divalent group containing at least one element selected from the group consisting of oxygen, sulfur and selenium in addition to the CH 2 group, CHR group and NR group. In particular, a divalent group containing an element of sulfur and / or selenium is preferable because the risk of ignition and ignition of the electrolyte is greatly reduced.

これら置換基としては、特に効果的に発火・引火の危険性を低減し得る点で、式(III)で表されるようなリンを含む置換基が特に好ましい。また、置換基が式(IV)で表されるような硫黄を含む置換基である場合には、電解液の小界面抵抗化の点で特に好ましい。   As these substituents, a substituent containing phosphorus as represented by the formula (III) is particularly preferable in that the risk of ignition / flammability can be particularly effectively reduced. Further, when the substituent is a substituent containing sulfur as represented by the formula (IV), it is particularly preferable in terms of reducing the interface resistance of the electrolytic solution.

式(II)のＲ2は、一価の置換基又はハロゲン元素である限り特に制限はない。ここで、一価の置換基としては、アルコキシ基、アリールオキシ基、アルキル基、カルボキシル基、アシル基、アリール基等が挙げられ、これらの中でも、ホスファゼン化合物が低粘度となる点で、アルコキシ基及びアリールオキシ基が好ましい。一方、ハロゲン元素としては、フッ素、塩素、臭素等が好適に挙げられ、これらの中でも、フッ素が特に好ましい。上記アルコキシ基としては、メトキシ基、エトキシ基、メトキシエトキシ基、プロポキシ基等が挙げられ、上記アリールオキシ基としては、フェノキシ基等が挙げられ、これらの中でも、メトキシ基、エトキシ基、メトキシエトキシ基、フェノキシ基が特に好ましい。また、上記アルキル基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基等が挙げられ；上記アシル基としては、ホルミル基、アセチル基、プロピオニル基、ブチリル基、イソブチリル基、バレリル基等が挙げられ；上記アリール基としては、フェニル基、トリル基、ナフチル基等が挙げられる。これら一価の置換基中の水素元素は、ハロゲン元素で置換されているのが好ましく、ハロゲン元素としては、フッ素、塩素、臭素等が好適に挙げられ、フッ素原子で置換された置換基としては、トリフルオロエトキシ基等が挙げられる。 R 2 in formula (II) is not particularly limited as long as it is a monovalent substituent or a halogen element. Here, examples of the monovalent substituent include an alkoxy group, an aryloxy group, an alkyl group, a carboxyl group, an acyl group, and an aryl group. Among these, an alkoxy group is used because the phosphazene compound has low viscosity. And aryloxy groups are preferred. On the other hand, preferred examples of the halogen element include fluorine, chlorine, bromine and the like, and among these, fluorine is particularly preferred. Examples of the alkoxy group include a methoxy group, an ethoxy group, a methoxyethoxy group, and a propoxy group. Examples of the aryloxy group include a phenoxy group. Among these, a methoxy group, an ethoxy group, and a methoxyethoxy group. A phenoxy group is particularly preferred. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group; examples of the acyl group include a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, and a valeryl group. Examples of the aryl group include a phenyl group, a tolyl group, and a naphthyl group. The hydrogen element in these monovalent substituents is preferably substituted with a halogen element. Preferred examples of the halogen element include fluorine, chlorine, bromine and the like. Examples of the substituent substituted with a fluorine atom include And a trifluoroethoxy group.

式(I)〜式(V)におけるＲ1〜Ｒ5、Ｙ1、Ｙ3〜Ｙ5、Ｚを適宜選択することにより、より好適な粘度、添加・混合に適する溶解性等を有するホスファゼン化合物が得られる。これらホスファゼン化合物は、１種単独で使用してもよく、２種以上を併用してもよい。 A phosphazene compound having more suitable viscosity, solubility suitable for addition and mixing, etc., by appropriately selecting R 1 to R 5 , Y 1 , Y 3 to Y 5 , and Z in formulas (I) to (V) Is obtained. These phosphazene compounds may be used alone or in combination of two or more.

また、上記非水電解液に用いる支持塩としては、リチウムイオンのイオン源となる支持塩が好ましい。該支持塩としては、特に制限はないが、例えば、ＬｉＣｌＯ4、ＬｉＢＦ4、ＬｉＰＦ6、ＬｉＣＦ3ＳＯ3、ＬｉＡｓＦ6、ＬｉＣ4Ｆ9ＳＯ3、Ｌｉ(ＣＦ3ＳＯ2)2Ｎ及びＬｉ(Ｃ2Ｆ5ＳＯ2)2Ｎ等のリチウム塩が好適に挙げられる。これらの中でも、不燃性に優れる点で、ＬｉＰＦ6が更に好ましい。これら支持塩は、１種単独で使用してもよく、２種以上を組み合わせて用いてもよい。ここで、非水電解液における支持塩の濃度としては、0.2〜1.5mol/L（Ｍ）の範囲が好ましく、0.5〜1mol/L（Ｍ）の範囲が更に好ましい。支持塩の濃度が0.2mol/L未満では、電解液の導電性を充分に確保することができず、電池の放電特性及び充電特性に支障をきたすことがあり、1.5mol/Lを超えると、電解液の粘度が上昇し、リチウムイオンの移動度を充分に確保できないため、前述と同様に電解液の導電性を充分に確保できず、電池の放電特性及び充電特性に支障をきたすことがある。 Moreover, as a support salt used for the non-aqueous electrolyte, a support salt that is an ion source of lithium ions is preferable. The supporting salt is not particularly limited, and for example, LiClO 4 , LiBF 4 , LiPF 6 , LiCF 3 SO 3 , LiAsF 6 , LiC 4 F 9 SO 3 , Li (CF 3 SO 2 ) 2 N and Li ( Preferable examples include lithium salts such as C 2 F 5 SO 2 ) 2 N. Among these, LiPF 6 is more preferable in terms of excellent nonflammability. These supporting salts may be used alone or in combination of two or more. Here, the concentration of the supporting salt in the nonaqueous electrolytic solution is preferably in the range of 0.2 to 1.5 mol / L (M), and more preferably in the range of 0.5 to 1 mol / L (M). If the concentration of the supporting salt is less than 0.2 mol / L, the conductivity of the electrolyte cannot be sufficiently ensured, and the discharge characteristics and charging characteristics of the battery may be hindered. Since the viscosity of the electrolytic solution increases and the mobility of lithium ions cannot be ensured sufficiently, the conductivity of the electrolytic solution cannot be sufficiently ensured in the same manner as described above, which may hinder battery discharge characteristics and charge characteristics. .

更に、上記非水電解液に用いることができる非プロトン性有機溶媒としては、特に制限はないが、電解液の粘度を低く抑える観点から、エーテル化合物やエステル化合物等が好ましい。具体的には、１,２-ジメトキシエタン（ＤＭＥ）、テトラヒドロフラン（ＴＨＦ）、ジメチルカーボネート（ＤＭＣ）、ジエチルカーボネート（ＤＥＣ）、ジフェニルカーボネート、エチレンカーボネート（ＥＣ）、プロピレンカーボネート（ＰＣ）、γ-ブチロラクトン（ＧＢＬ）、γ-バレロラクトン、エチルメチルカーボネート（ＥＭＣ）、メチルフォルメート（ＭＦ）等が好適に挙げられる。これらの中でも、エチレンカーボネート、プロピレンカーボネート、γ-ブチロラクトン等の環状エステル化合物、ジメチルカーボネート、エチルメチルカーボネート、ジエチルカーボネート等の鎖状エステル化合物、１,２-ジメトキシエタン等の鎖状エーテル化合物が好ましい。特に、環状のエステル化合物は、比誘電率が高く、リチウム塩等の溶解性に優れる点で好適であり、鎖状のエステル化合物及びエーテル化合物は、低粘度であるため電解液の低粘度化の点で好適である。これらは１種単独で使用してもよく、２種以上を併用してもよいが、２種以上を併用するのが好適である。   Furthermore, the aprotic organic solvent that can be used in the nonaqueous electrolytic solution is not particularly limited, but ether compounds and ester compounds are preferable from the viewpoint of keeping the viscosity of the electrolytic solution low. Specifically, 1,2-dimethoxyethane (DME), tetrahydrofuran (THF), dimethyl carbonate (DMC), diethyl carbonate (DEC), diphenyl carbonate, ethylene carbonate (EC), propylene carbonate (PC), γ-butyrolactone (GBL), γ-valerolactone, ethyl methyl carbonate (EMC), methyl formate (MF) and the like are preferable. Among these, cyclic ester compounds such as ethylene carbonate, propylene carbonate, and γ-butyrolactone, chain ester compounds such as dimethyl carbonate, ethyl methyl carbonate, and diethyl carbonate, and chain ether compounds such as 1,2-dimethoxyethane are preferable. In particular, a cyclic ester compound is suitable in that it has a high relative dielectric constant and excellent solubility in lithium salts and the like, and a chain ester compound and an ether compound have a low viscosity. This is preferable in terms of points. These may be used individually by 1 type, may use 2 or more types together, but it is suitable to use 2 or more types together.

＜その他の部材＞
本発明の非水電解液二次電池に使用できる他の部材としては、非水電解液二次電池において、正負極間に、両極の接触による電流の短絡を防止する役割で介在させるセパレーターが挙げられる。セパレーターの材質としては、両極の接触を確実に防止し得、且つ電解液を通したり含んだりできる材料、例えば、ポリテトラフルオロエチレン、ポリプロピレン、ポリエチレン、セルロース系、ポリブチレンテレフタレート、ポリエチレンテレフタレート等の合成樹脂製の不織布、薄層フィルム等が好適に挙げられる。これらの中でも、厚さ20〜50μm程度のポリプロピレン又はポリエチレン製の微孔性フィルム、セルロース系、ポリブチレンテレフタレート、ポリエチレンテレフタレート等のフィルムが特に好適である。本発明では、上述のセパレーターの他にも、通常電池に使用されている公知の各部材が好適に使用できる。 <Other members>
Other members that can be used in the non-aqueous electrolyte secondary battery of the present invention include a separator interposed in the non-aqueous electrolyte secondary battery between positive and negative electrodes to prevent current short-circuit due to contact between both electrodes. It is done. As the material of the separator, it is possible to reliably prevent contact between the two electrodes and to allow the electrolyte to pass through or to contain, for example, synthesis of polytetrafluoroethylene, polypropylene, polyethylene, cellulose, polybutylene terephthalate, polyethylene terephthalate, etc. Preferred examples include resin nonwoven fabrics and thin layer films. Of these, polypropylene or polyethylene microporous films having a thickness of about 20 to 50 μm, cellulose-based films, polybutylene terephthalate, polyethylene terephthalate, and the like are particularly suitable. In the present invention, in addition to the separators described above, known members that are normally used in batteries can be suitably used.

以上に説明した本発明の非水電解液二次電池の形態としては、特に制限はなく、コインタイプ、ボタンタイプ、ペーパータイプ、角型又はスパイラル構造の円筒型電池等、種々の公知の形態が好適に挙げられる。ボタンタイプの場合は、シート状の正極及び負極を作製し、該正極及び負極でセパレーターを挟む等して、非水電解液二次電池を作製することができる。また、スパイラル構造の場合は、例えば、シート状の正極を作製して集電体を挟み、これに、シート状の負極を重ね合わせて巻き上げる等して、非水電解液二次電池を作製することができる。   The form of the non-aqueous electrolyte secondary battery of the present invention described above is not particularly limited, and various known forms such as a coin type, a button type, a paper type, a square type or a spiral type cylindrical battery are available. Preferably mentioned. In the case of the button type, a non-aqueous electrolyte secondary battery can be manufactured by preparing a sheet-like positive electrode and negative electrode and sandwiching a separator between the positive electrode and the negative electrode. In the case of the spiral structure, for example, a non-aqueous electrolyte secondary battery is manufactured by preparing a sheet-like positive electrode, sandwiching a current collector, and stacking and winding up the sheet-like negative electrode on the current collector. be able to.

以下に、実施例を挙げて本発明を更に詳しく説明するが、本発明は下記の実施例に何ら限定されるものではない。   Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

＜３次元連続状炭素繊維の製造例＞
アニリンモノマー 0.5mol/LとＨＢＦ4 1.0mol/Lとを含む酸性水溶液中に、銅製の作用極を設置し、対極として白金板を使用して、室温にて10mA/cm2の定電流で10分間電解重合を行い、ポリアニリンを作用極上に電析させた。得られたポリアニリンをイオン交換水で洗浄し、更に24時間真空乾燥した後、ＳＥＭで観察したところ、フィブリル状ポリアニリンが生成していることを確認した。 <Production example of three-dimensional continuous carbon fiber>
A copper working electrode was placed in an acidic aqueous solution containing 0.5 mol / L of aniline monomer and 1.0 mol / L of HBF 4 , and a platinum plate was used as the counter electrode, with a constant current of 10 mA / cm 2 at room temperature. Electropolymerization was performed for a minute, and polyaniline was electrodeposited on the working electrode. The obtained polyaniline was washed with ion-exchanged water, further vacuum-dried for 24 hours, and then observed with SEM. As a result, it was confirmed that fibrillar polyaniline was produced.

次に、上記ポリアニリンを銅作用極ごとＡｒ雰囲気中3℃/分の昇温速度で950℃まで加熱し、その後950℃で1時間保持して焼成処理した。得られた焼成物をＳＥＭで観察したところ、直径が40〜100nmのフィブリル状で３次元連続状の炭素繊維が、銅作用極上に生成していることを確認した。なお、該炭素繊維は、残炭率が45％で、表面抵抗が1.0Ωであった（三菱油化製, Loresta IP又はHiresta IPで測定）。   Next, the polyaniline was heated to 950 ° C. at a rate of temperature increase of 3 ° C./min in an Ar atmosphere together with the copper working electrode, and then held at 950 ° C. for 1 hour for firing treatment. When the obtained fired product was observed by SEM, it was confirmed that fibril-like and three-dimensional continuous carbon fibers having a diameter of 40 to 100 nm were formed on the copper working electrode. The carbon fiber had a residual carbon ratio of 45% and a surface resistance of 1.0Ω (measured by Mitsubishi Yuka, Loresta IP or Hiresta IP).

（実施例１）
1Ｎの硫酸酸性Ｓｎイオン溶解溶液（Ｓｎ2+：18g/L）に上記の方法で作製した３次元連続状炭素繊維を浸漬し、5Ｃ/cm2で電気メッキを行った。電気メッキの際の電流値は50mAである。得られたＳｎ担持炭素繊維のＳＥＭ写真を図１に示す。該ＳＥＭ写真から、Ｓｎが炭素繊維上に微細に担持されており、基材の３次元連続状炭素繊維の骨格が維持されていることが確認された。その後、該Ｓｎ担持炭素繊維を水洗し、乾燥後、Ａｒ雰囲気下のグローブボックス中で更に乾燥した。また、下記の方法で炭素繊維の空隙の充填率を測定したところ、炭素繊維の空隙の約20体積％がＳｎ微粒子で埋められていることが分かった。 Example 1
The three-dimensional continuous carbon fiber prepared by the above method was immersed in a 1N sulfuric acid Sn ion solution (Sn 2+ : 18 g / L), and electroplated at 5 C / cm 2 . The current value during electroplating is 50 mA. An SEM photograph of the obtained Sn-supported carbon fiber is shown in FIG. From the SEM photograph, it was confirmed that Sn was finely supported on the carbon fiber and the skeleton of the three-dimensional continuous carbon fiber of the base material was maintained. Thereafter, the Sn-supported carbon fiber was washed with water, dried, and further dried in a glove box under an Ar atmosphere. Moreover, when the filling rate of the carbon fiber voids was measured by the following method, it was found that about 20% by volume of the carbon fiber voids were filled with Sn fine particles.

＜炭素繊維の空隙充填率＞
まず、Ｓｎ担持前の炭素繊維についてその嵩密度を求め、真密度との関係から空隙率を求める。この空隙率と未担持の炭素繊維の見かけ体積から空隙の体積を求める。更に、Ｓｎ担持炭素繊維の重量と未担持炭素繊維の重量差からＳｎ担持重量を求め、これをＳｎの真密度で除して、Ｓｎの占有する体積を求める。得られたＳｎ占有体積と先に求めた空隙体積の関係から、Ｓｎ充填率を算出する。 <Carbon fiber void filling factor>
First, the bulk density is calculated | required about the carbon fiber before Sn carrying | support, and the porosity is calculated | required from a relationship with a true density. From the porosity and the apparent volume of the unsupported carbon fiber, the volume of the void is determined. Further, the Sn-supported weight is obtained from the difference between the weight of the Sn-supported carbon fiber and the unsupported carbon fiber, and this is divided by the true density of Sn to determine the volume occupied by Sn. The Sn filling rate is calculated from the relationship between the obtained Sn occupation volume and the previously obtained void volume.

次に、得られたＳｎ担持炭素繊維に有機溶媒（酢酸エチルとエタノールとの50/50質量％混合溶媒）を加えて混練した後、該混練物を厚さ25μmの銅箔（集電体）にドクターブレードで塗工し、更に熱風乾燥（100〜120℃）して、厚さ60μmの負極シートを作製した。   Next, an organic solvent (50/50 mass% mixed solvent of ethyl acetate and ethanol) was added to the obtained Sn-supported carbon fiber and kneaded, and then the kneaded product was copper foil (current collector) having a thickness of 25 μm. The film was coated with a doctor blade and further dried with hot air (100 to 120 ° C.) to prepare a negative electrode sheet having a thickness of 60 μm.

また、ＬｉＣｏＯ2（正極活物質）94質量部に対して、アセチレンブラック（導電剤）3質量部と、ポリフッ化ビニリデン（結着剤）3質量部とを添加し、有機溶媒（酢酸エチルとエタノールとの50/50質量％混合溶媒）で混練した後、該混練物を厚さ25μmのアルミニウム箔（集電体）にドクターブレードで塗工し、更に熱風乾燥（100〜120℃）して、厚さ80μmの正極シートを作製した。 Further, 3 parts by mass of acetylene black (conductive agent) and 3 parts by mass of polyvinylidene fluoride (binder) are added to 94 parts by mass of LiCoO 2 (positive electrode active material), and an organic solvent (ethyl acetate and ethanol) is added. 50/50 mass% mixed solvent) and the kneaded product is applied to a 25 μm thick aluminum foil (current collector) with a doctor blade, and further dried with hot air (100 to 120 ° C.), A positive electrode sheet having a thickness of 80 μm was produced.

更に、エチレンカーボネート（ＥＣ）30体積％、エチルメチルカーボネート（ＥＭＣ）60体積％及びホスファゼン化合物Ａ［上記式(II)において、ｎが３であって、全Ｒ2のうち１つがエトキシ基で、５つがフッ素である環状ホスファゼン化合物］10体積％からなる混合溶液に、ＬｉＰＦ6（支持塩）を1Ｍ（mol/L）の濃度で溶解させて非水電解液を調製した。なお、下記の方法で電解液の安全性を評価したところ、得られた非水電解液は不燃性であった。ここで、ＥＣ及びＥＭＣの混合溶媒（ＥＣ／ＥＭＣ体積比＝１／２）にＬｉＰＦ6を1Ｍの濃度で溶解させて調製した非水電解液の評価結果が燃焼性であったことから、上記ホスファゼン化合物の添加によって電解液の安全性が大幅に向上したことが確認された。 Further, 30% by volume of ethylene carbonate (EC), 60% by volume of ethyl methyl carbonate (EMC) and phosphazene compound A [in the above formula (II), n is 3, and one of all R 2 is an ethoxy group, [Cyclic phosphazene compound in which five are fluorine] LiPF 6 (supporting salt) was dissolved in a mixed solution consisting of 10% by volume at a concentration of 1 M (mol / L) to prepare a nonaqueous electrolytic solution. In addition, when the safety of the electrolytic solution was evaluated by the following method, the obtained nonaqueous electrolytic solution was nonflammable. Here, the evaluation result of the non-aqueous electrolyte prepared by dissolving LiPF 6 at a concentration of 1M in a mixed solvent of EC and EMC (EC / EMC volume ratio = 1/2) was combustible. It was confirmed that the safety of the electrolyte was greatly improved by the addition of the phosphazene compound.

＜電解液の安全性の評価方法＞
ＵＬ（アンダーライティングラボラトリー）規格のＵＬ９４ＨＢ法をアレンジした方法で、大気環境下において着火した炎の燃焼挙動から非水電解液の安全性を評価した。その際、着火性、燃焼性、炭化物の生成、二次着火時の現象についても観察した。具体的には、ＵＬ試験基準に基づき、不燃性石英ファイバーに上記電解液1.0mLを染み込ませて、127mm×12.7mmの試験片を作製して行った。ここで、試験炎が試験片に着火しない場合（燃焼長：0mm）を「不燃性」、着火した炎が25mmラインまで到達せず且つ落下物にも着火が認められない場合を「難燃性」、着火した炎が25〜100mmラインで消火し且つ落下物にも着火が認められない場合を「自己消火性」、着火した炎が100mmラインを超えた場合を「燃焼性」と評価した。 <Method for evaluating safety of electrolyte>
The safety of the non-aqueous electrolyte was evaluated from the combustion behavior of flames ignited in an atmospheric environment by the method of arranging UL94HB method of UL (underwriting laboratory) standard. At that time, ignitability, combustibility, formation of carbides, and secondary ignition phenomena were also observed. Specifically, based on the UL test standard, a non-combustible quartz fiber was impregnated with 1.0 mL of the electrolytic solution, and a test piece of 127 mm × 12.7 mm was produced. Here, when the test flame does not ignite the test piece (combustion length: 0 mm), it is “non-flammable”, and when the ignited flame does not reach the 25 mm line and the fallen object is not ignited, “flame retardant” The case where the ignited flame was extinguished on the 25-100 mm line and the fallen object was not ignited was evaluated as “self-extinguishing”, and the case where the ignited flame exceeded the 100 mm line was evaluated as “combustible”.

次に、上記正極シート及び上記負極シートをそれぞれφ16mmに打ち抜いたものを正極及び負極とし、セルロースセパレーター［日本高度紙工業社製ＴＦ４０３０］を介して正負極を対座させ、上記非水電解液を注入し封口して、4mAh級のリチウムイオン電池（２０１６コイン型）を作製した。   Next, the positive electrode sheet and the negative electrode sheet punched to φ16 mm are used as the positive electrode and the negative electrode, the positive and negative electrodes are faced through a cellulose separator [TF4030 made by Nippon Kogyo Paper Industries Co., Ltd.], and the non-aqueous electrolyte is injected. Then, a 4 mAh-class lithium ion battery (2016 coin type) was produced.

（実施例２）
10Ｃ/cm2で電気メッキを行う以外は、実施例１と同様にして３次元連続状炭素繊維にＳｎを担持した。得られたＳｎ担持炭素繊維のＳＥＭ写真を図２に示す。該ＳＥＭ写真から、Ｓｎが炭素繊維上に微細に担持されており、基材の３次元連続状炭素繊維の骨格が維持されていることが確認された。その後、該Ｓｎ担持炭素繊維を水洗し、乾燥後、Ａｒ雰囲気下のグローブボックス中で更に乾燥した。また、上記の方法で炭素繊維の空隙の充填率を測定したところ、炭素繊維の空隙の約50体積％がＳｎ微粒子で埋められていることが分かった。更に、得られたＳｎ担持炭素繊維を用いて、実施例１と同様にしてリチウムイオン電池を作製した。 (Example 2)
Sn was supported on the three-dimensional continuous carbon fiber in the same manner as in Example 1 except that electroplating was performed at 10 C / cm 2 . The SEM photograph of the obtained Sn carrying | support carbon fiber is shown in FIG. From the SEM photograph, it was confirmed that Sn was finely supported on the carbon fiber and the skeleton of the three-dimensional continuous carbon fiber of the base material was maintained. Thereafter, the Sn-supported carbon fiber was washed with water, dried, and further dried in a glove box under an Ar atmosphere. Further, when the filling rate of the carbon fiber voids was measured by the above method, it was found that about 50% by volume of the carbon fiber voids were filled with Sn fine particles. Furthermore, a lithium ion battery was produced in the same manner as in Example 1 using the obtained Sn-supported carbon fiber.

（実施例３）
25Ｃ/cm2で電気メッキを行う以外は、実施例１と同様にして３次元連続状炭素繊維にＳｎを担持した。得られたＳｎ担持炭素繊維のＳＥＭ写真を図３に示す。該ＳＥＭ写真から、25Ｃ/cm2以上では析出するＳｎが成長し、炭素繊維の３次元空間を壊して巨大化することが分かった。その後、該Ｓｎ担持炭素繊維を水洗し、乾燥後、Ａｒ雰囲気下のグローブボックス中で更に乾燥を実施した。また、上記の方法で炭素繊維の空隙の充填率を測定したところ、炭素繊維の空隙の60体積％がＳｎ微粒子で埋められていることが分かった。更に、得られたＳｎ担持炭素繊維を用いて、実施例１と同様にしてリチウムイオン電池を作製した。 (Example 3)
Sn was supported on a three-dimensional continuous carbon fiber in the same manner as in Example 1 except that electroplating was performed at 25 C / cm 2 . An SEM photograph of the obtained Sn-supported carbon fiber is shown in FIG. From the SEM photograph, it was found that the precipitated Sn grows at 25 C / cm 2 or more, and the three-dimensional space of the carbon fiber is broken and enlarged. Thereafter, the Sn-supported carbon fiber was washed with water, dried, and further dried in a glove box under an Ar atmosphere. Moreover, when the filling rate of the voids of the carbon fiber was measured by the above method, it was found that 60% by volume of the voids of the carbon fiber was filled with Sn fine particles. Furthermore, a lithium ion battery was produced in the same manner as in Example 1 using the obtained Sn-supported carbon fiber.

（比較例１）
ＥＣ及びＥＭＣの混合溶媒（ＥＣ／ＥＭＣ体積比＝１／２）にＬｉＰＦ6を1Ｍの濃度で溶解させて調製した非水電解液を用いる以外は、実施例１と同様にしてリチウムイオン電池を作製した。 (Comparative Example 1)
A lithium ion battery was prepared in the same manner as in Example 1 except that a non-aqueous electrolyte prepared by dissolving LiPF 6 at a concentration of 1M in a mixed solvent of EC and EMC (EC / EMC volume ratio = 1/2) was used. Produced.

（比較例２）
ＥＣ及びＥＭＣの混合溶媒（ＥＣ／ＥＭＣ体積比＝１／２）にＬｉＰＦ6を1Ｍの濃度で溶解させて調製した非水電解液を用いる以外は、実施例２と同様にしてリチウムイオン電池を作製した。 (Comparative Example 2)
A lithium ion battery was prepared in the same manner as in Example 2 except that a nonaqueous electrolyte prepared by dissolving LiPF 6 at a concentration of 1 M in a mixed solvent of EC and EMC (EC / EMC volume ratio = 1/2) was used. Produced.

（比較例３）
ＥＣ及びＥＭＣの混合溶媒（ＥＣ／ＥＭＣ体積比＝１／２）にＬｉＰＦ6を1Ｍの濃度で溶解させて調製した非水電解液を用いる以外は、実施例３と同様にしてリチウムイオン電池を作製した。 (Comparative Example 3)
A lithium ion battery was prepared in the same manner as in Example 3 except that a non-aqueous electrolyte prepared by dissolving LiPF 6 at a concentration of 1 M in a mixed solvent of EC and EMC (EC / EMC volume ratio = 1/2) was used. Produced.

＜電池のサイクル特性評価＞
上記のようにして得られた各電池に対して、20℃の環境下で、上限電圧4.3Ｖ、下限電圧3.0Ｖ、放電電流50mA、充電電流50mAの条件で充放電を行い、この時の放電容量を既知の電極重量で除することにより初期放電容量（mAh/g）を求めた。更に、同様の充放電条件で50サイクルまで充放電を繰り返して、各サイクル後の放電容量を求め、下記の式：
容量残存率＝各サイクル後の放電容量／初期放電容量×１００（％）
に従って各サイクルの容量残存率を算出し、電池のサイクル特性の指標とした。結果を図４に示す。 <Evaluation of battery cycle characteristics>
Each battery obtained as described above is charged and discharged under the conditions of an upper limit voltage of 4.3 V, a lower limit voltage of 3.0 V, a discharge current of 50 mA, and a charge current of 50 mA in an environment of 20 ° C. The initial discharge capacity (mAh / g) was determined by dividing the capacity by the known electrode weight. Furthermore, charging / discharging was repeated up to 50 cycles under the same charging / discharging conditions to determine the discharge capacity after each cycle, and the following formula:
Capacity remaining rate = discharge capacity after each cycle / initial discharge capacity × 100 (%)
Thus, the capacity remaining rate of each cycle was calculated and used as an index of the battery cycle characteristics. The results are shown in FIG.

図４中の実施例１と比較例１、実施例２と比較例２、実施例３と比較例３の比較から、Ｓｎ担持炭素繊維からなる負極を備えるリチウムイオン電池において、電解液にホスファゼン化合物を含ませることで、電池のサイクル特性が向上することが分る。   From the comparison between Example 1 and Comparative Example 1, Example 2 and Comparative Example 2, and Example 3 and Comparative Example 3 in FIG. 4, in the lithium ion battery comprising the negative electrode made of Sn-supported carbon fiber, the phosphazene compound was used as the electrolyte. It can be seen that by including the battery, the cycle characteristics of the battery are improved.

また、図４から、３次元連続状炭素繊維の空隙の50体積％以下がＳｎ微粒子で埋められたＳｎ担持炭素繊維からなる負極を用いた実施例１及び２のリチウムイオン電池は、特に優れたサイクル特性を有することが分る。   From FIG. 4, the lithium ion batteries of Examples 1 and 2 using the negative electrode made of Sn-supported carbon fiber in which 50% by volume or less of the voids of the three-dimensional continuous carbon fiber were filled with Sn fine particles were particularly excellent. It can be seen that it has cycle characteristics.

一方、３次元連続状炭素繊維の空隙の50体積％超がＳｎ微粒子で埋められたＳｎ担持炭素繊維からなる負極を用いた実施例３のリチウムイオン電池は、サイクル特性が実施例１及び２に比べて悪かったため、金属微粒子の充填率は３次元連続状炭素繊維の空隙の50体積％以下であることが好ましいことが確認された。これは、本発明で用いる３次元連続状炭素繊維は、網目構造を有し、金属微粒子が体積膨張しても、炭素材電極全体としての体積膨張を緩和できるものの、例えば、金属としてＳｎを担持した場合、充放電に伴うＳｎの体積膨張率が200％であるため、Ｓｎを炭素繊維の空隙の50体積％を超えて担持すると、充放電によって炭素繊維の網目構造の一部が壊れ、該部分の導通が遮断されるため、充放電容量が低下したものと思われる。   On the other hand, the lithium ion battery of Example 3 using the negative electrode made of Sn-supported carbon fiber in which more than 50% by volume of the voids of the three-dimensional continuous carbon fiber is filled with Sn fine particles has the cycle characteristics as in Examples 1 and 2. It was confirmed that the filling rate of the metal fine particles was preferably 50% by volume or less of the voids of the three-dimensional continuous carbon fiber because it was worse than that. This is because the three-dimensional continuous carbon fiber used in the present invention has a network structure, and even if the metal fine particles undergo volume expansion, the volume expansion of the carbon material electrode as a whole can be reduced, but for example, Sn is supported as a metal. In this case, since the volume expansion rate of Sn accompanying charging / discharging is 200%, when Sn is supported exceeding 50% by volume of the voids of the carbon fiber, part of the network structure of the carbon fiber is broken by charging / discharging, It seems that the charge / discharge capacity was reduced because the conduction of the portion was interrupted.

実施例１で得られたＳｎ担持炭素繊維のＳＥＭ写真である。2 is a SEM photograph of Sn-supported carbon fibers obtained in Example 1. 実施例２で得られたＳｎ担持炭素繊維のＳＥＭ写真である。4 is a SEM photograph of Sn-supported carbon fibers obtained in Example 2. 実施例３で得られたＳｎ担持炭素繊維のＳＥＭ写真である。4 is a SEM photograph of Sn-supported carbon fibers obtained in Example 3. 実施例及び比較例のリチウムイオン電池のサイクル特性を示すグラフである。It is a graph which shows the cycling characteristics of the lithium ion battery of an Example and a comparative example.

Claims (11)

正極と、負極と、非水電解液とを備える非水電解液二次電池において、
前記負極が３次元連続状炭素繊維に金属微粒子を担持してなる炭素材電極であって、
前記非水電解液がホスファゼン化合物と支持塩とを含むことを特徴とする非水電解液二次電池。 In a non-aqueous electrolyte secondary battery comprising a positive electrode, a negative electrode, and a non-aqueous electrolyte,
The negative electrode is a carbon material electrode in which metal fine particles are supported on a three-dimensional continuous carbon fiber,
The non-aqueous electrolyte secondary battery, wherein the non-aqueous electrolyte contains a phosphazene compound and a supporting salt. 前記３次元連続状炭素繊維が、芳香環を有する化合物を酸化重合して得られるフィブリル状ポリマーを非酸化性雰囲気中で焼成して得たものであることを特徴とする請求項１に記載の非水電解液二次電池。   The three-dimensional continuous carbon fiber is obtained by firing a fibril-like polymer obtained by oxidative polymerization of a compound having an aromatic ring in a non-oxidizing atmosphere. Non-aqueous electrolyte secondary battery. 金属イオンの還元法により前記金属微粒子を前記３次元連続状炭素繊維上に担持したことを特徴とする請求項１又は２に記載の非水電解液二次電池。   The nonaqueous electrolyte secondary battery according to claim 1 or 2, wherein the metal fine particles are supported on the three-dimensional continuous carbon fiber by a metal ion reduction method. 前記金属微粒子を構成する金属がリチウムを吸蔵・脱離可能な金属であることを特徴とする請求項１〜３のいずれかに記載の非水電解液二次電池。   The non-aqueous electrolyte secondary battery according to any one of claims 1 to 3, wherein the metal constituting the metal fine particles is a metal capable of inserting and extracting lithium. 前記金属微粒子が、Ｓｎ、Ｓｉ、Ｐｂ、Ａｌ、Ａｕ、Ｐｔ、Ｉｎ、Ｚｎ、Ｃｄ、Ａｇ及びＭｇからなる群から選択される少なくとも一種の金属を含むことを特徴とする請求項４に記載の非水電解液二次電池。   The metal fine particle includes at least one metal selected from the group consisting of Sn, Si, Pb, Al, Au, Pt, In, Zn, Cd, Ag, and Mg. Non-aqueous electrolyte secondary battery. 前記３次元連続状炭素繊維の空隙の50体積％以下が前記金属微粒子で充填されていることを特徴とする請求項１に記載の非水電解液二次電池。   2. The nonaqueous electrolyte secondary battery according to claim 1, wherein 50% by volume or less of the voids of the three-dimensional continuous carbon fiber is filled with the metal fine particles. 前記芳香環を有する化合物が、アニリン、ピロール、チオフェン、及びそれらの誘導体からなる群から選択される少なくとも一種の化合物であることを特徴とする請求項２に記載の非水電解液二次電池。   The non-aqueous electrolyte secondary battery according to claim 2, wherein the compound having an aromatic ring is at least one compound selected from the group consisting of aniline, pyrrole, thiophene, and derivatives thereof. 前記酸化重合が電解酸化重合であることを特徴とする請求項２に記載の非水電解液二次電池。   The non-aqueous electrolyte secondary battery according to claim 2, wherein the oxidative polymerization is electrolytic oxidative polymerization. 前記金属イオンの還元法が電気メッキであることを特徴とする請求項３に記載の非水電解液二次電池。   The non-aqueous electrolyte secondary battery according to claim 3, wherein the metal ion reduction method is electroplating. 前記ホスファゼン化合物が下記式(I)：
［式中、Ｒ1は、それぞれ独立して一価の置換基又はハロゲン元素を表し；Ｙ1は、それぞれ独立して２価の連結基、２価の元素又は単結合を表し；Ｘは、炭素、ケイ素、ゲルマニウム、スズ、窒素、リン、ヒ素、アンチモン、ビスマス、酸素、硫黄、セレン、テルル及びポロニウムからなる群から選ばれる元素の少なくとも１種を含む置換基を表す］又は下記式(II)：
(ＮＰＲ2 2)n ・・・ (II)
［式中、Ｒ2はそれぞれ独立して一価の置換基又はハロゲン元素を表し；ｎは３〜１５を表す］で表されることを特徴とする請求項１に記載の非水電解液二次電池。 The phosphazene compound has the following formula (I):
[Wherein, R 1 each independently represents a monovalent substituent or a halogen element; Y 1 each independently represents a divalent linking group, a divalent element or a single bond; Represents a substituent containing at least one element selected from the group consisting of carbon, silicon, germanium, tin, nitrogen, phosphorus, arsenic, antimony, bismuth, oxygen, sulfur, selenium, tellurium and polonium] or the following formula (II ):
(NPR 2 2 ) n ... (II)
Wherein, R 2 each independently represent a monovalent substituent or a halogen element; n represents 3 to 15] Non-aqueous electrolyte secondary of claim 1, characterized by being represented by Next battery. 前記非水電解液が、更に非プロトン性有機溶媒を含むことを特徴とする請求項１に記載の非水電解液二次電池。   The non-aqueous electrolyte secondary battery according to claim 1, wherein the non-aqueous electrolyte further contains an aprotic organic solvent.
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Cited By (5)

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JP2010009837A (en) * 2008-06-25 2010-01-14 Furukawa Electric Co Ltd:The Alloy negative electrode material for lithium secondary battery
WO2010089991A1 (en) * 2009-02-04 2010-08-12 独立行政法人産業技術総合研究所 Fiber electrodes for lithium secondary batteries, manufacturing method therefor, and lithium secondary batteries provided with fiber electrodes
JP2012119079A (en) * 2010-11-29 2012-06-21 Hiramatsu Sangyo Kk Negative electrode active material, method of manufacturing negative electrode, negative electrode, and secondary battery
US9281539B2 (en) 2009-07-14 2016-03-08 Kawasakai Jukogyo Kabushiki Kaisha Electrical storage device including fiber electrode, and method of fabricating the same
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010009837A (en) * 2008-06-25 2010-01-14 Furukawa Electric Co Ltd:The Alloy negative electrode material for lithium secondary battery
WO2010089991A1 (en) * 2009-02-04 2010-08-12 独立行政法人産業技術総合研究所 Fiber electrodes for lithium secondary batteries, manufacturing method therefor, and lithium secondary batteries provided with fiber electrodes
JP5283138B2 (en) * 2009-02-04 2013-09-04 独立行政法人産業技術総合研究所 Method for producing fiber positive electrode for lithium secondary battery, fiber negative electrode for lithium secondary battery and method for producing the same, and lithium secondary battery provided with fiber electrode
US9065139B2 (en) 2009-02-04 2015-06-23 National Institute Of Advanced Industrial Science And Technology Fiber electrode for lithium secondary battery, fabrication method therefor, and lithium secondary battery including fiber electrode
US9281539B2 (en) 2009-07-14 2016-03-08 Kawasakai Jukogyo Kabushiki Kaisha Electrical storage device including fiber electrode, and method of fabricating the same
JP2012119079A (en) * 2010-11-29 2012-06-21 Hiramatsu Sangyo Kk Negative electrode active material, method of manufacturing negative electrode, negative electrode, and secondary battery
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