JPWO2014092016A1 - Power storage device - Google Patents

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JPWO2014092016A1
JPWO2014092016A1 JP2014552020A JP2014552020A JPWO2014092016A1 JP WO2014092016 A1 JPWO2014092016 A1 JP WO2014092016A1 JP 2014552020 A JP2014552020 A JP 2014552020A JP 2014552020 A JP2014552020 A JP 2014552020A JP WO2014092016 A1 JPWO2014092016 A1 JP WO2014092016A1
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storage device
electricity storage
negative electrode
film
nitroxyl
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基陽 安井
基陽 安井
岩佐　繁之
繁之 岩佐
教徳 西
教徳 西
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/137—Electrodes based on electro-active polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/044—Activating, forming or electrochemical attack of the supporting material
    • H01M4/0445—Forming after manufacture of the electrode, e.g. first charge, cycling
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • 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
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    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

酸化状態において下記式（１）で示されるニトロキシルカチオン部分構造をとり、還元状態において下記式（２）で示されるニトロキシルラジカル部分構造をとり、二つの状態間で電子の授受を行う下記反応式（Ａ）で示される反応を行うニトロキシル化合物を含む正極と、負極と、電解質塩および有機溶媒を含む電解液とを有する蓄電デバイスであって、蓄電デバイス組立て前にあらかじめ１，３−プロパンスルトンおよびビニレンカーボネートの少なくとも１つの分解によって形成された皮膜を有することを特徴とする蓄電デバイスが開示される。本発明に係る蓄電デバイスは、高出力でかつ高温信頼性に優れる。The following reaction takes an nitroxyl cation partial structure represented by the following formula (1) in the oxidized state and a nitroxyl radical partial structure represented by the following formula (2) in the reduced state to transfer electrons between the two states. An electricity storage device having a positive electrode containing a nitroxyl compound that performs the reaction represented by the formula (A), a negative electrode, and an electrolytic solution containing an electrolyte salt and an organic solvent, And an electricity storage device having a film formed by decomposition of at least one of vinylene carbonate. The electricity storage device according to the present invention has high output and high temperature reliability.

Description

本発明は、蓄電デバイスに関し、詳細には高温保管時における電池特性を改善した有機ラジカル電池に関する。   The present invention relates to an electricity storage device, and more particularly to an organic radical battery having improved battery characteristics during high-temperature storage.

近年、ノート型パソコンや携帯電話などの携帯電子機器は、通信機能をはじめ、動画再生機能やカメラ機能など多機能化している。それに伴い、消費電力は増加し、その電源である蓄電デバイスには高い出力が求められている。また、携帯電子機器は様々な場所で使われることが想定されるため、蓄電デバイスには高温環境下における、高い信頼性も求められている。   In recent years, portable electronic devices such as notebook computers and mobile phones have become multifunctional, including communication functions, video playback functions, and camera functions. Accordingly, power consumption increases, and high output is required for the power storage device that is the power source. In addition, since portable electronic devices are assumed to be used in various places, the power storage devices are also required to have high reliability in a high temperature environment.

このような要求に対するものとして、特許文献１及び２には、高出力な蓄電デバイスとして、ニトロキシル化合物を正極中に含有した蓄電デバイスが提案されている（以下、この蓄電デバイスを「有機ラジカル電池」と呼ぶ）。このニトロキシル化合物は、酸化状態においてオキソアンモニウムカチオン部分構造をとり、還元状態においてニトロキシルラジカル部分構造をとり、その２つの状態間で電子の授受が行われ、この反応が正極の電極反応として用いられる。この電極反応は、比較的速く反応が進むため、高出力な電池を得ることができる。   In order to meet such a demand, Patent Documents 1 and 2 propose a power storage device containing a nitroxyl compound in a positive electrode as a high-power power storage device (hereinafter referred to as “organic radical battery”). Called). This nitroxyl compound takes an oxoammonium cation partial structure in an oxidized state, takes a nitroxyl radical partial structure in a reduced state, and transfers electrons between the two states, and this reaction is used as an electrode reaction of a positive electrode. . Since this electrode reaction proceeds relatively quickly, a battery with high output can be obtained.

しかしながら、長期保管した有機ラジカル電池は初期の状態に比べ、内部抵抗が増加するといった課題がある。特許文献３では、サイクル特性に優れ、さらに電気容量や充電状態での保存特性などの電池特性にも優れたリチウム二次電池を提供する方法として、環状カーボネートおよび鎖状カーボネートを主成分とした非水溶媒中に１，３−プロパンスルトン（以下、ＰＳ）または１，４−ブタンスルトンが含有されたリチウム二次電池用非水電解液を含むリチウム二次電池を提案している。特許文献３によれば、電解液中に含有される１，３−プロパンスルトンや１，４−ブタンスルトンが負極表面上での皮膜形成に寄与し、電解液の分解を抑制する効果を有するものと考えられている。   However, the organic radical battery stored for a long time has a problem that the internal resistance increases compared to the initial state. In Patent Document 3, as a method for providing a lithium secondary battery having excellent cycle characteristics and excellent battery characteristics such as electric capacity and storage characteristics in a charged state, a non-carbon carbonate and chain carbonate as a main component are provided. A lithium secondary battery including a non-aqueous electrolyte for a lithium secondary battery in which 1,3-propane sultone (hereinafter referred to as PS) or 1,4-butane sultone is contained in an aqueous solvent is proposed. According to Patent Document 3, 1,3-propane sultone or 1,4-butane sultone contained in the electrolytic solution contributes to film formation on the negative electrode surface and has an effect of suppressing decomposition of the electrolytic solution. It is considered.

また、非水電解質電池の負極表面に被膜を形成させる方法としては、特許文献４に、チタン酸リチウム等の負極活物質を有する負極を備えた非水電解質電池において、ビニレンカーボネートを含有する非水電解質を用い、初期充放電を、充電末の負極電位がリチウム電位に対して０．８Ｖを超える条件で行うことが記載されている。   In addition, as a method for forming a film on the negative electrode surface of a non-aqueous electrolyte battery, Patent Document 4 discloses a non-aqueous electrolyte containing vinylene carbonate in a non-aqueous electrolyte battery including a negative electrode having a negative electrode active material such as lithium titanate. It is described that an initial charge / discharge is performed using an electrolyte under conditions where the negative electrode potential at the end of charging exceeds 0.8 V with respect to the lithium potential.

特開２００２−３０４９９６号公報JP 2002-304996 A 特開２００９−２３８６１２号公報JP 2009-238612 A 特開２０００−００３７２４号公報JP 2000-003724 A 特開２００８−０９１３２７号公報JP 2008-091327 A

しかしながら、発明者による検討によれば、特許文献３および特許文献４に記載されるように、有機ラジカル電池の電解液に１，３−プロパンスルトンやビニレンカーボネートを添加しただけでは、高温保管時に内部抵抗が増加するといった課題があった。   However, according to studies by the inventor, as described in Patent Document 3 and Patent Document 4, the addition of 1,3-propane sultone or vinylene carbonate to the electrolyte solution of the organic radical battery can cause internal damage during high-temperature storage. There was a problem that resistance increased.

本発明の目的は、この課題を解決し、高温保管時における内部抵抗増加を抑制した高出力の蓄電デバイスを提供することにある。   An object of the present invention is to solve this problem and provide a high-output power storage device that suppresses an increase in internal resistance during high-temperature storage.

本発明の一態様は、酸化状態において下記式（１）で示されるニトロキシルカチオン部分構造をとり、還元状態において下記式（２）で示されるニトロキシルラジカル部分構造をとり、二つの状態間で電子の授受を行う下記反応式（Ａ）で示される反応を行うニトロキシル化合物を含む正極と、負極と、電解質塩および有機溶媒を含む電解液とを有する蓄電デバイスであって、
前記負極が、蓄電デバイス組立て前に、あらかじめ１，３−プロパンスルトンおよびビニレンカーボネートの少なくとも１つの分解によって形成された皮膜を有することを特徴とする蓄電デバイスに関する。One embodiment of the present invention takes a nitroxyl cation partial structure represented by the following formula (1) in the oxidized state and a nitroxyl radical partial structure represented by the following formula (2) in the reduced state, and between the two states An electrical storage device having a positive electrode including a nitroxyl compound that performs a reaction represented by the following reaction formula (A) that performs transfer of electrons, a negative electrode, and an electrolytic solution that includes an electrolyte salt and an organic solvent,
The negative electrode has a film formed by decomposition of at least one of 1,3-propane sultone and vinylene carbonate in advance before assembly of the power storage device.

Figure 2014092016
Figure 2014092016

さらに本発明の一態様は、酸化状態において下記式（１）で示されるニトロキシルカチオン部分構造をとり、還元状態において下記式（２）で示されるニトロキシルラジカル部分構造をとり、二つの状態間で電子の授受を行う下記反応式（Ａ）：   Furthermore, one embodiment of the present invention has a nitroxyl cation partial structure represented by the following formula (1) in an oxidized state and a nitroxyl radical partial structure represented by the following formula (2) in a reduced state, The following reaction formula (A) for transferring and receiving electrons:

Figure 2014092016
で示される反応を行うニトロキシル化合物を含む正極と、負極と、電解質塩および有機溶媒を含む電解液とを有する蓄電デバイスの製造方法であって、
蓄電デバイス組立て前にあらかじめ、皮膜形成前の負極に１，３−プロパンスルトンおよびビニレンカーボネートの少なくとも１つの分解による皮膜形成処理を行うことを特徴とする蓄電デバイスの製造方法に関する。
Figure 2014092016
 A method for producing an electricity storage device comprising a positive electrode containing a nitroxyl compound that performs the reaction represented by: a negative electrode; and an electrolyte solution containing an electrolyte salt and an organic solvent,
The present invention relates to a method for producing an electricity storage device, characterized in that a film formation treatment by decomposition of at least one of 1,3-propane sultone and vinylene carbonate is performed in advance on the negative electrode before film formation before assembling the electricity storage device.

本発明の実施形態によれば、高出力でかつ高温信頼性に優れた蓄電デバイスを提供することができる。   According to the embodiment of the present invention, it is possible to provide an electricity storage device having high output and excellent high-temperature reliability.

本発明の実施形態によるラミネート型蓄電デバイスの斜視図である。1 is a perspective view of a laminate type electricity storage device according to an embodiment of the present invention. 本発明の実施形態によるラミネート型蓄電デバイスの断面図である。It is sectional drawing of the lamination type electrical storage device by embodiment of this invention. 本発明の実施形態によるＬｉプレドープ用セルの断面図である。It is sectional drawing of the cell for Li pre dope by embodiment of this invention.

次に、本発明の好適な実施形態について説明する。尚、以下の説明において、１，３−プロパンスルトンを「ＰＳ」、ビニレンカーボネートを「ＶＣ」と略称することがある。本発明における「負極」は、皮膜形成処理された後の、ＰＳおよびＶＣの少なくとも１つの分解によって形成された皮膜を有する「皮膜形成処理済の負極」であるが、用語「負極」が「皮膜形成処理前の負極」または「皮膜形成処理をしない負極」を意味する場合もある。これらは、用語「負極」が使用される文脈から理解される。   Next, a preferred embodiment of the present invention will be described. In the following description, 1,3-propane sultone may be abbreviated as “PS” and vinylene carbonate may be abbreviated as “VC”. The “negative electrode” in the present invention is a “negative electrode after film formation treatment” having a film formed by decomposition of at least one of PS and VC after the film formation treatment. It may mean “negative electrode before forming treatment” or “negative electrode without film forming treatment”. These are understood from the context in which the term “negative electrode” is used.

本発明の実施形態による蓄電デバイスは、上記ニトロキシル化合物を正極活物質として含む正極と、負極と、電解質塩および有機溶媒を含む電解液とを有する。蓄電デバイス組立て前にあらかじめ負極にＰＳおよび／またはＶＣの分解による皮膜形成処理を行う。皮膜形成処理を行うにはＰＳおよび／またはＶＣを添加した電解液を用いる。負極は、リチウムイオンを可逆的に吸蔵放出可能な材料を負極活物質として含むことができ、電解質塩としてリチウム塩を用いることができ、有機溶媒として非プロトン性溶媒を用いることができる。   An electricity storage device according to an embodiment of the present invention includes a positive electrode including the nitroxyl compound as a positive electrode active material, a negative electrode, and an electrolytic solution including an electrolyte salt and an organic solvent. Before assembling the electricity storage device, a film formation process is performed on the negative electrode in advance by decomposing PS and / or VC. In order to perform the film forming treatment, an electrolytic solution to which PS and / or VC is added is used. The negative electrode can include a material capable of reversibly occluding and releasing lithium ions as a negative electrode active material, a lithium salt can be used as an electrolyte salt, and an aprotic solvent can be used as an organic solvent.

蓄電デバイスの通常保管時の最高温度を例えば４０℃と想定すると、４０℃での長時間保存における内部抵抗の増加を抑制することができる。   Assuming that the maximum temperature during normal storage of the electricity storage device is 40 ° C., for example, an increase in internal resistance during long-term storage at 40 ° C. can be suppressed.

発明者の検討によれば、従来技術ではＰＳ等を添加した電解液を用いて蓄電デバイスを組立てた後に充放電を行ってＰＳ等の分解による皮膜を形成しているのに対し、ＰＳおよび／またはＶＣの分解による皮膜形成を蓄電デバイス組立て前にあらかじめ行うことにより、高温保管特性が向上する。これは、皮膜形成をあらかじめ行うことで、蓄電デバイス中の電解液に含まれる未反応のＰＳおよび／またはＶＣの残存量を少なく、または無くし、高温保管時における皮膜の成長を抑える効果があるものと考えられる。   According to the inventor's study, in the prior art, an electric storage device is assembled using an electrolytic solution to which PS or the like is added, and then a charge and discharge are performed to form a film by decomposition of PS or the like. Alternatively, the film formation by the decomposition of VC is performed in advance before assembly of the electricity storage device, so that the high temperature storage characteristics are improved. This has the effect of suppressing the growth of the film during high-temperature storage by reducing or eliminating the remaining amount of unreacted PS and / or VC contained in the electrolyte in the electricity storage device by forming the film in advance. it is conceivable that.

本実施形態による蓄電デバイスは、電気化学的に蓄えられたエネルギーを電力の形で取り出すことができるものであり、一次電池、二次電池、キャパシタやコンデンサ等の電気容量デバイス等に適用できる。   The electricity storage device according to the present embodiment can extract electrochemically stored energy in the form of electric power, and can be applied to an electric capacity device such as a primary battery, a secondary battery, a capacitor and a capacitor.

まず、電極の作製に用いる材料について説明する。   First, materials used for manufacturing the electrode will be described.

［１］電極の材料
［１−１］正極活物質
本発明の実施形態による蓄電デバイスにおける正極活物質としては、酸化状態において式（１）で示されるニトロキシルカチオン部分構造（Ｎ−オキソ−アンモニウムカチオン部分構造）をとり、還元状態において式（２）で示されるニトロキシルラジカル部分構造をとるニトロキシル化合物を用いる。このニトロキシル化合物は、これらの２つの状態間で電子の授受を行う反応式（Ａ）で示される酸化還元反応を行うことができる。本実施形態による蓄電デバイスは、この酸化還元反応を正極の電極反応として用いる。[1] Electrode Material [1-1] Positive Electrode Active Material As the positive electrode active material in the electricity storage device according to the embodiment of the present invention, the nitroxyl cation partial structure (N-oxo-ammonium represented by the formula (1) in the oxidized state is used. A nitroxyl compound having a cation partial structure) and a nitroxyl radical partial structure represented by the formula (2) in a reduced state is used. This nitroxyl compound can perform an oxidation-reduction reaction represented by the reaction formula (A) in which electrons are transferred between these two states. The electricity storage device according to the present embodiment uses this oxidation-reduction reaction as the electrode reaction of the positive electrode.

Figure 2014092016
このニトロキシル化合物の構造としては特に限定されないが、電解液に対する溶解性の観点から、ニトロキシル高分子化合物であることが好ましい。
Figure 2014092016
 The structure of the nitroxyl compound is not particularly limited, but is preferably a nitroxyl polymer compound from the viewpoint of solubility in the electrolytic solution.

このニトロキシル高分子化合物としては、酸化状態において下記式（Ｉａ）で示される環状ニトロキシル構造を側鎖に含むポリマーであることが好ましい。   The nitroxyl polymer compound is preferably a polymer containing a cyclic nitroxyl structure represented by the following formula (Ia) in the side chain in an oxidized state.

Figure 2014092016
（式中、Ｒ１〜Ｒ４はそれぞれ独立に炭素数１〜４のアルキル基を表し、Ｘは５〜７員環を形成する２価の基を表す。但し、Ｘがポリマーの側鎖の一部を構成することにより、式（Ｉａ）で示される環状ニトロキシル構造がポリマーの一部となっている。）
Ｒ１〜Ｒ４は、それぞれ独立に炭素数１〜４のアルキル基を表し、エチル基、メチル基が好ましく、ラジカルの安定性の点でメチル基が特に好ましい。
Figure 2014092016
 (In the formula, R 1 to R 4 each independently represents an alkyl group having 1 to 4 carbon atoms, and X represents a divalent group forming a 5- to 7-membered ring, provided that X represents a side chain of the polymer. (By constituting a part, the cyclic nitroxyl structure represented by the formula (Ia) becomes a part of the polymer.)
R 1 to R 4 each independently represents an alkyl group having 1 to 4 carbon atoms, preferably an ethyl group or a methyl group, and particularly preferably a methyl group in terms of radical stability.

Ｘは、具体的には、−ＣＨ２ＣＨ２−、−ＣＨ２ＣＨ２ＣＨ２−、−ＣＨ２ＣＨ２ＣＨ２ＣＨ２−、−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨＣＨ２−、−ＣＨ＝ＣＨＣＨ２ＣＨ２−、−ＣＨ２ＣＨ＝ＣＨＣＨ２−が挙げられ、その中で、隣接しない−ＣＨ２−は、−Ｏ−、−ＮＨ−または−Ｓ−によって置き換えられていてもよく、−ＣＨ＝は−Ｎ＝によって置き換えられていてもよい。また、環を構成する原子に結合した水素原子は、アルキル基、ハロゲン原子、＝Ｏ、エーテル基、エステル基、シアノ基、アミド基等により置換されていてもよい。X is specifically, -CH 2 CH 2 -, - CH 2 CH 2 CH 2 -, - CH 2 CH 2 CH 2 CH 2 -, - CH = CH -, - CH = CHCH 2 -, - CH ═CHCH 2 CH 2 —, —CH 2 CH═CHCH 2 —, in which non-adjacent —CH 2 — may be replaced by —O—, —NH— or —S—, -CH = may be replaced by -N =. The hydrogen atom bonded to the atoms constituting the ring may be substituted with an alkyl group, a halogen atom, ═O, an ether group, an ester group, a cyano group, an amide group, or the like.

特に、好ましい環状ニトロキシル構造は、２，２，６，６−テトラメチルピペリジノキシルラジカル（又はカチオン）、２，２，５，５−テトラメチルピロリジノキシルラジカル（又はカチオン）、２，２，５，５−テトラメチルピロリノキシルラジカル（カチオン）から選ばれるものであり、２，２，６，６−テトラメチルピペリジノキシルラジカル（又はカチオン）、２，２，５，５−テトラメチルピロリジノキシルラジカル（又はカチオン）がより好ましい。   Particularly preferred cyclic nitroxyl structures are 2,2,6,6-tetramethylpiperidinoxyl radical (or cation), 2,2,5,5-tetramethylpyrrolidinoxyl radical (or cation), 2,2 , 5,5-tetramethylpyrrolinoxyl radical (cation), 2,2,6,6-tetramethylpiperidinoxyl radical (or cation), 2,2,5,5-tetra A methylpyrrolidinoxyl radical (or cation) is more preferred.

式（Ｉａ）で示される環状ニトロキシル構造は、式（Ｉｂ）に示すように、Ｘ中の環員を構成する−ＣＨ２−、−ＣＨ＝または−ＮＨ−から水素を取った残基Ｘ’によってポリマーに結合することができる。The cyclic nitroxyl structure represented by the formula (Ia) is, as shown in the formula (Ib), a residue X ′ obtained by removing hydrogen from —CH 2 —, —CH═ or —NH— constituting the ring member in X. Can be attached to the polymer.

Figure 2014092016
ニトロキシル高分子化合物の主鎖として用いられるポリマーとしては特に制限はなく、式（Ｉａ）で示される環状ニトロキシル構造が側鎖に存在できるものであればよい。
Figure 2014092016
 The polymer used as the main chain of the nitroxyl polymer compound is not particularly limited as long as the cyclic nitroxyl structure represented by the formula (Ia) can be present in the side chain.

ニトロキシル高分子化合物は、通常のポリマーに、式（Ｉｂ）の基が付加したもの、またはポリマーの一部の原子または基が式（Ｉｂ）の基によって置換されたものを挙げることができる。式（Ｉｂ）の環状構造を構成する原子が直接ではなく、適当な２価の基を中間に介してポリマー（主鎖）に結合していてもよい。例えば、Ｘ’とポリマーの主鎖の原子とが、エステル結合（−ＣＯＯ−）やエーテル結合（−Ｏ−）等の２価基を介して結合することができる。   Examples of the nitroxyl polymer compound include those obtained by adding a group of the formula (Ib) to a normal polymer, or those obtained by substituting some atoms or groups of the polymer with a group of the formula (Ib). The atoms constituting the cyclic structure of the formula (Ib) may be bonded to the polymer (main chain) via an appropriate divalent group in the middle instead of directly. For example, X ′ and the main chain atom of the polymer can be bonded via a divalent group such as an ester bond (—COO—) or an ether bond (—O—).

ニトロキシル高分子化合物の主鎖として用いられるポリマーとしては、電気化学的な耐性に優れている点で、ポリエチレン、ポリプロピレン等のポリアルキレン系ポリマー；ポリ（メタ）アクリル酸；ポリ（メタ）アクリルアミド系ポリマー；ポリ（メタ）アクリレート系ポリマー；ポリスチレン系ポリマーが好ましい。   As the polymer used as the main chain of the nitroxyl polymer compound, polyalkylene polymers such as polyethylene and polypropylene; poly (meth) acrylic acid; poly (meth) acrylamide polymers are excellent in electrochemical resistance. Poly (meth) acrylate polymer; polystyrene polymer is preferred.

このようなニトロキシル高分子化合物のなかでも、特に安定性の高い、下記式（３）〜（７）のいずれかで示されるものが好ましい。   Among such nitroxyl polymer compounds, those having high stability and those represented by any of the following formulas (3) to (7) are preferable.

Figure 2014092016
（式中、ｎは１以上の整数である。）
式（３）〜（５）に示したニトロキシル高分子化合物は、２，２，６，６−テトラメチルピペリジノキシルラジカル（又はカチオン）を側鎖に有し、式（６）、（７）に示したニトロキシル高分子化合物は、２，２，５，５−テトラメチルピロリジノキシルラジカル（又はカチオン）を側鎖に有する高分子化合物である。これらのニトロキシル高分子化合物は、高分子の側鎖に立体障害性の安定ラジカルを持つ化合物である。
Figure 2014092016
 (In the formula, n is an integer of 1 or more.)
The nitroxyl polymer compound represented by the formulas (3) to (5) has a 2,2,6,6-tetramethylpiperidinoxyl radical (or cation) in the side chain, and the formulas (6), (7 The nitroxyl polymer compound shown in (2) is a polymer compound having a 2,2,5,5-tetramethylpyrrolidinoxyl radical (or cation) in the side chain. These nitroxyl polymer compounds are compounds having a sterically hindered stable radical in the side chain of the polymer.

ニトロキシル高分子化合物の分子量は、電解液に対する溶解性の観点から、１０００以上であることが好ましく、さらには１００００以上であることがより好ましい。分子量は大きいほうが好ましいが、平均分子量が５００万以下のものを用いることができる。ニトロキシル高分子化合物の骨格構造としては、鎖状、分岐状、網目状のいずれでもよく、架橋剤で架橋した構造でもよい。   The molecular weight of the nitroxyl polymer compound is preferably 1000 or more, and more preferably 10,000 or more, from the viewpoint of solubility in the electrolytic solution. A higher molecular weight is preferred, but one having an average molecular weight of 5 million or less can be used. The skeleton structure of the nitroxyl polymer compound may be any of a chain, a branch, and a network, and may be a structure crosslinked with a crosslinking agent.

また、ニトロキシル高分子化合物は、単独で用いることができるが、二種類以上を混合して用いてもよい。   Moreover, although a nitroxyl polymer compound can be used independently, you may mix and use 2 or more types.

また、本実施形態における正極中には、その他の正極活物質を含んでもよい。その他の正極活物質としては、例えばＬｉＭｎＯ２等のリチウムマンガン系酸化物、ＬｉＣｏＯ２等のリチウムコバルト系酸化物、ＬｉＮｉＯ２等のリチウムニッケル系酸化物、ＬｉＦｅＰＯ４等のリチウム鉄系酸化物、ＬｉｘＶ２Ｏ５（０＜ｘ＜２）等のリチウムバナジウム系酸化物が挙げられる。The positive electrode in the present embodiment may contain other positive electrode active materials. Other positive electrode active materials include, for example, lithium manganese oxides such as LiMnO 2 , lithium cobalt oxides such as LiCoO 2 , lithium nickel oxides such as LiNiO 2 , lithium iron oxides such as LiFePO 4 , Li x V 2 O 5 (0 < x <2) lithium vanadium-based oxide and the like.

ニトロキシル高分子化合物の添加効果を十分に得る点から、正極活物質中のニトロキシル高分子化合物の含有量は、５０質量％以上が好ましく、８０質量％以上がより好ましい。   In view of sufficiently obtaining the effect of adding the nitroxyl polymer compound, the content of the nitroxyl polymer compound in the positive electrode active material is preferably 50% by mass or more, and more preferably 80% by mass or more.

［１−２］負極活物質
本実施形態による蓄電デバイスにおける負極活物質としては、リチウムイオンを可逆的に吸蔵放出可能な材料（リチウムイオンを充電時に吸蔵し、放電時に放出できる材料）を用いることができる。このような負極活物質としては、金属酸化物、グラファイト等の炭素材料等を用いることができる。これらの材料の形状としては特に限定されるものではなく、例えば、薄膜状のもの、粉末を固めたもの、繊維状のもの、フレーク状のものが挙げられる。また、これらの負極活物質は、単独、もしくは組み合わせて使用できる。[1-2] Negative electrode active material As the negative electrode active material in the electricity storage device according to the present embodiment, a material capable of reversibly occluding and releasing lithium ions (a material capable of occluding and releasing lithium ions during charging and discharging during discharging) is used. Can do. As such a negative electrode active material, carbon materials such as metal oxides and graphite can be used. The shape of these materials is not particularly limited, and examples thereof include a thin film, a powdered product, a fiber, and a flake. These negative electrode active materials can be used alone or in combination.

［１−３］導電性付与剤
正極および負極を形成する際に、インピーダンスを低下させる目的で、導電性付与剤を添加してもよい。導電性付与剤としては、グラファイト、カーボンブラック、アセチレンブラック等の炭素質微粒子や活性炭等の炭素材料、カーボンナノチューブ等の炭素繊維、ポリアニリン、ポリピロール、ポリチオフェン、ポリアセチレン、ポリアセン、ポリフェニレン等の導電性高分子が挙げられる。[1-3] Conductivity imparting agent When forming the positive electrode and the negative electrode, a conductivity imparting agent may be added for the purpose of reducing impedance. Conductivity-imparting agents include carbonaceous fine particles such as graphite, carbon black and acetylene black, carbon materials such as activated carbon, carbon fibers such as carbon nanotubes, conductive polymers such as polyaniline, polypyrrole, polythiophene, polyacetylene, polyacene, and polyphenylene. Is mentioned.

［１−４］結着剤
正極および負極を形成する際に、結着剤を用いることもできる。結着剤を用いることにより、活物質同士、活物質と導電性付与剤との間、活物質や導電付与剤と集電体との間の結びつきを強めることができる。このような結着剤としては、ポリテトラフルオロエチレン（ＰＴＦＥ）、ポリフッ化ビニリデン、ビニリデンフロライド−ヘキサフルオロプロピレン共重合体、ビニリデンフロライド−テトラフルオロエチレン共重合体、スチレン−ブタジエン共重合ゴム、ポリプロピレン、ポリエチレン、ポリイミド、部分カルボキシ化セルロース、各種ポリウレタン等の樹脂バインダーが挙げられる。[1-4] Binder A binder can also be used when forming the positive electrode and the negative electrode. By using the binder, it is possible to strengthen the connection between the active materials, between the active material and the conductivity imparting agent, and between the active material or the conductivity imparting agent and the current collector. Examples of such a binder include polytetrafluoroethylene (PTFE), polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, styrene-butadiene copolymer rubber, Examples thereof include resin binders such as polypropylene, polyethylene, polyimide, partially carboxylated cellulose, and various polyurethanes.

［１−５］集電体
正極活物質又は負極活物質を含む電極材料は、集電体上に設けることができる。集電体としては、ニッケルやアルミニウム、銅、アルミニウム合金、ステンレス、炭素等からなる箔、シート、平板等を用いることができる。[1-5] Current Collector An electrode material containing a positive electrode active material or a negative electrode active material can be provided on the current collector. As the current collector, a foil, a sheet, a flat plate, or the like made of nickel, aluminum, copper, aluminum alloy, stainless steel, carbon, or the like can be used.

［２］蓄電デバイスの基本構造、構成部材および蓄電デバイスの製造方法
図１に本実施形態によるラミネート型蓄電デバイスの一例の斜視図を示し、図２に断面図を示す。これらの図に示されるように、蓄電デバイス１０７は、正極１０１、この正極に対向する負極１１０（皮膜形成処理済の負極）、正極と負極との間に挟まれたセパレータ１０５を含む積層構造を有し、この積層構造は外装用フィルム１０６で覆われ、外装用フィルム１０６の外部へ、電極リード１０４が引き出されている。この蓄電デバイス内へは電解液が注入されている。以下に、蓄電デバイスの構成部材と製造方法についてさらに詳細に説明する。[2] Basic structure of power storage device, constituent member, and method for manufacturing power storage device FIG. 1 is a perspective view of an example of a laminate type power storage device according to the present embodiment, and FIG. As shown in these drawings, the electricity storage device 107 has a laminated structure including a positive electrode 101, a negative electrode 110 (a negative electrode subjected to film formation treatment) facing the positive electrode, and a separator 105 sandwiched between the positive electrode and the negative electrode. The laminated structure is covered with an exterior film 106, and the electrode leads 104 are drawn out of the exterior film 106. An electrolytic solution is injected into the electricity storage device. Below, the structural member and manufacturing method of an electrical storage device are demonstrated in detail.

［２−１］正極
正極１０１は、正極活物質を含み、必要に応じてさらに導電性付与剤、結着剤を含み、一方の集電体１０３上に形成されている。[2-1] Positive Electrode The positive electrode 101 includes a positive electrode active material, and further includes a conductivity imparting agent and a binder as necessary, and is formed on one current collector 103.

［２−２］負極
負極は、負極活物質を含み、必要に応じてさらに導電性付与剤、結着剤を含み、他方の集電体１０３上に形成されている。本実施形態の負極１１０は、皮膜形成処理がされている。[2-2] Negative Electrode The negative electrode includes a negative electrode active material, and further includes a conductivity imparting agent and a binder as necessary, and is formed on the other current collector 103. The negative electrode 110 of this embodiment is subjected to a film formation process.

［２−３］セパレータ
正極１０１と負極１１０との間には、これらを絶縁分離する絶縁性の多孔質セパレータ１０５が設けられる。セパレータ１０５としては、ポリエチレン、ポリプロピレン等からなる多孔質樹脂フィルム、セルロース膜、不繊布等を用いることができる。[2-3] Separator An insulating porous separator 105 is provided between the positive electrode 101 and the negative electrode 110 to insulate and separate them. As the separator 105, a porous resin film made of polyethylene, polypropylene, or the like, a cellulose film, a non-woven cloth, or the like can be used.

［２−４］電解液
電解液は、正極と負極との間で荷電担体の輸送を行うものであり、正極１０１、負極１１０及びセパレータ１０５に含浸している。電解液としては、２０℃で１０−５〜１０−１Ｓ／ｃｍのイオン伝導性を有しているものを用いることができ、電解質塩を有機溶媒に溶解した非水電解液を用いることができる。電解液の溶媒としては、非プロトン性有機溶媒を用いることができる。[2-4] Electrolytic Solution The electrolytic solution transports charge carriers between the positive electrode and the negative electrode, and impregnates the positive electrode 101, the negative electrode 110, and the separator 105. As the electrolytic solution, one having an ion conductivity of 10 −5 to 10 −1 S / cm at 20 ° C. can be used, and a nonaqueous electrolytic solution in which an electrolyte salt is dissolved in an organic solvent is used. it can. As the solvent for the electrolytic solution, an aprotic organic solvent can be used.

電解質塩としては、例えばＬｉＰＦ６、ＬｉＣｌＯ４、ＬｉＢＦ４、ＬｉＣＦ３ＳＯ３、ＬｉＮ（ＣＦ３ＳＯ２）２（以下「ＬｉＴＦＳＩ」）、ＬｉＮ（Ｃ２Ｆ５ＳＯ２）２（以下「ＬｉＢＥＴＩ」）、Ｌｉ（ＣＦ３ＳＯ２）３Ｃ、Ｌｉ（Ｃ２Ｆ５ＳＯ２）３Ｃ等の通常の電解質材料を用いることができる。Examples of the electrolyte salt include LiPF 6 , LiClO 4 , LiBF 4 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 (hereinafter “LiTFSI”), LiN (C 2 F 5 SO 2 ) 2 (hereinafter “LiBETI”). ), Li (CF 3 SO 2 ) 3 C, Li (C 2 F 5 SO 2 ) 3 C, or other ordinary electrolyte materials can be used.

有機溶媒としては、例えばエチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート等の環状カーボネート；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等の鎖状カーボネート；γ−ブチロラクトン等のγ−ラクトン類；テトラヒドロフラン、ジオキソラン等の環状エーテル類；ジメチルホルムアミド、ジメチルアセトアミド、Ｎ−メチル−２−ピロリドン等のアミド類が挙げられる。他の有機溶媒としては、環状カーボネート及び鎖状カーボネートの少なくとも一方を混合することが好ましい。   Examples of the organic solvent include cyclic carbonates such as ethylene carbonate, propylene carbonate, and butylene carbonate; chain carbonates such as dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate; γ-lactones such as γ-butyrolactone; cyclics such as tetrahydrofuran and dioxolane. Ethers; amides such as dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone and the like. As another organic solvent, it is preferable to mix at least one of a cyclic carbonate and a chain carbonate.

［２−５］外装用フィルム
外装用フィルム１０６としてはアルミラミネートフィルム等を用いることができる。外装用フィルム以外の外装体としては、金属ケースや樹脂ケースが挙げられる。蓄電デバイスの外形としては、円筒型、角型、コイン型、シート型が挙げられる。[2-5] Exterior Film An aluminum laminate film or the like can be used as the exterior film 106. Examples of the exterior body other than the exterior film include a metal case and a resin case. Examples of the outer shape of the electricity storage device include a cylindrical shape, a square shape, a coin shape, and a sheet shape.

［２−６］Ｌｉプレドープ用セルの作製例
電極活物質および結着剤を含む電極材料と溶媒からなるスラリーを調製し、このスラリーを集電体上に塗布し、乾燥し、プレスして、負極（皮膜形成処理前）を得ることができる。[2-6] Preparation Example of Li Pre-Dope Cell A slurry made of an electrode material containing an electrode active material and a binder and a solvent is prepared, and this slurry is applied onto a current collector, dried and pressed. A negative electrode (before film formation treatment) can be obtained.

図３に本実施形態によるＬｉプレドープ用セルの断面図を示す。   FIG. 3 shows a cross-sectional view of the Li pre-doping cell according to the present embodiment.

一対の外装用フィルムを用意し、得られた負極（皮膜形成処理前）１０２を一方の外装用フィルム１０６上に置き、セパレータ１０５を介してリチウム箔１０８と重ね合わせることで、外装用フィルム上の電極積層体を得ることができる。   A pair of exterior films are prepared, and the obtained negative electrode (before film formation treatment) 102 is placed on one exterior film 106 and overlapped with the lithium foil 108 via the separator 105, whereby the exterior film An electrode laminate can be obtained.

得られた電極積層体を他方の外装用フィルム１０６で覆い、電極リード部を含む３辺を熱融着することができる。   The obtained electrode laminate can be covered with the other exterior film 106, and the three sides including the electrode lead portion can be heat-sealed.

これに１，３−プロパンスルトンおよびビニレンカーボネートの少なくとも１つを添加した電解液を注入し、真空含浸させることができる。電解液を電極およびセパレータの空隙に十分に含浸させた後、残りの４辺目を減圧下で熱融着することができる。結果、ラミネート型のＬｉプレドープ用セル１０９を得ることができる。   An electrolytic solution to which at least one of 1,3-propane sultone and vinylene carbonate is added can be injected and vacuum impregnated. After the electrolyte solution is sufficiently impregnated in the gap between the electrode and the separator, the remaining fourth side can be heat-sealed under reduced pressure. As a result, a laminate-type Li pre-doping cell 109 can be obtained.

ここで、皮膜形成処理を行う際に用いるセルに使用される電解液は、前述の［２−４］電解液の項で説明した電解液に、１，３−プロパンスルトン（ＰＳ）およびビニレンカーボネート（ＶＣ）の少なくとも１つを添加したものである。ＰＳおよびＶＣは、どちらか１種を添加すればよいが、両方を添加してもよい。ＰＳおよびＶＣの添加量が少ないと十分な厚みの皮膜を形成することができず、皮膜形成による効果を十分に得ることができない。また、添加量が多いと皮膜が厚く成長するために、皮膜自体の抵抗がセルの内部抵抗を大きくしてしまう。よって、ＰＳおよびＶＣの添加量（但し、１，３−プロパンスルトンおよびビニレンカーボネートのどちらか１つのみが存在する場合は、その１つのみの添加量）は電解液全体の重量に対して通常０．５〜１５重量％、好ましくは１〜１０重量％、より好ましくは２〜８重量％、さらに好ましくは２〜６重量％である。   Here, the electrolytic solution used in the cell used for the film formation treatment is the same as the electrolytic solution described in the above section [2-4] electrolytic solution, 1,3-propane sultone (PS) and vinylene carbonate. At least one of (VC) is added. Either PS or VC may be added, but both may be added. If the addition amount of PS and VC is small, a film having a sufficient thickness cannot be formed, and the effect of film formation cannot be sufficiently obtained. Moreover, since the film grows thick when the amount added is large, the resistance of the film itself increases the internal resistance of the cell. Therefore, the addition amount of PS and VC (however, in the case where only one of 1,3-propane sultone and vinylene carbonate is present), the addition amount of only one of them is usually relative to the weight of the entire electrolyte. It is 0.5 to 15% by weight, preferably 1 to 10% by weight, more preferably 2 to 8% by weight, and further preferably 2 to 6% by weight.

［２−７］皮膜形成処理の例
Ｌｉプレドープ用セル１０９のセル電圧が０Ｖになるまで放電することにより、負極にＬｉを吸蔵させると同時に、負極表面にＰＳおよび／またはＶＣの分解による皮膜を形成させることができる。これにより、皮膜形成処理済の負極１１０（図３において、負極１０２が示す部位に該当する）を得ることができる。[2-7] Example of film formation treatment By discharging until the cell voltage of the Li pre-doping cell 109 becomes 0 V, Li is occluded in the negative electrode, and at the same time, a film formed by decomposition of PS and / or VC is formed on the negative electrode surface. Can be formed. Thereby, the negative electrode 110 (corresponding to the portion indicated by the negative electrode 102 in FIG. 3) having been subjected to the film formation treatment can be obtained.

なお、負極表面にＰＳおよび／またはＶＣの分解による皮膜を形成させる方法としては、電気化学セル内に電流を流すことにより負極表面に皮膜を形成する方法であれば、金属Ｌｉを対極として放電する方法に限られない。   In addition, as a method of forming a film by decomposing PS and / or VC on the negative electrode surface, discharge is performed using metal Li as a counter electrode as long as the film is formed on the negative electrode surface by passing an electric current through the electrochemical cell. It is not limited to the method.

［２−８］蓄電デバイスの作製例
電極活物質および結着剤を含む電極材料と溶媒からなるスラリーを調製し、このスラリーを集電体上に塗布し、乾燥し、プレスして、正極を得ることができる。[2-8] Production Example of Electric Storage Device A slurry made of an electrode material containing an electrode active material and a binder and a solvent is prepared, and this slurry is applied onto a current collector, dried and pressed to obtain a positive electrode. Can be obtained.

一対の外装用フィルムを用意し、得られた正極１０１を一方の外装用フィルム１０６上に置き、セパレータ１０５を介して皮膜形成処理済負極１１０と重ね合わせることで、外装用フィルム上の電極積層体を得ることができる。   A pair of exterior films are prepared, and the obtained positive electrode 101 is placed on one exterior film 106 and overlapped with the film-forming treated negative electrode 110 via the separator 105, whereby an electrode laminate on the exterior film. Can be obtained.

得られた電極積層体を他方の外装用フィルム１０６で覆い、電極リード部を含む３辺を熱融着することができる。   The obtained electrode laminate can be covered with the other exterior film 106, and the three sides including the electrode lead portion can be heat-sealed.

これに電解液を注入し、真空含浸させることができる。電解液を電極およびセパレータの空隙に十分に含浸させた後、残りの４辺目を減圧下で熱融着することができる。結果、ラミネート型の蓄電デバイス１０７を得ることができる。   An electrolyte can be injected into this and vacuum impregnated. After the electrolyte solution is sufficiently impregnated in the gap between the electrode and the separator, the remaining fourth side can be heat-sealed under reduced pressure. As a result, a laminate-type power storage device 107 can be obtained.

以下、本発明を実施例により具体的に説明するが、本発明はこれらの実施例に限定されるものではない。   EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

（正極の作製）
本実施例で用いたニトロキシル高分子であるポリ（２，２，６，６−テトラメチルピペリジノキシルメタクリレート（ＰＴＭＡ）は、特開２００９−２３８６１２号公報に記載の方法に従って合成した。(Preparation of positive electrode)
Poly (2,2,6,6-tetramethylpiperidinoxyl methacrylate (PTMA), which is a nitroxyl polymer used in this example, was synthesized according to the method described in JP-A-2009-238612.

すなわち、下記記載に従って合成した。   That is, it synthesize | combined according to the following description.

還流管を付けた１００ｍｌナスフラスコ中に、２，２，６，６−テトラメチルピペリジンメタクリレートモノマー２０ｇ（０．０８９ｍｏｌ）を入れ、乾燥テトラヒドロフラン８０ｍｌに溶解させた。そこへ、アゾビスイソブチロニトリル（ＡＩＢＮ）０．２９ｇ（０．００１８７ｍｏｌ）（モノマー／ＡＩＢＮ＝５０／１）を加え、アルゴン雰囲気下７５〜８０℃で攪拌した。６時間反応後、室温まで放冷した。へキサン中でポリマーを析出させて濾別し、減圧乾燥してポリ（２，２，６，６−テトラメチルピペリジンメタクリレート）を得た。次に、得られたポリ（２，２，６，６−テトラメチルピペリジンメタクリレート）１０ｇを乾操ジクロロメタン１００ｍｌに溶解させた。ここへｍ−クロロ過安息香酸１５．２ｇ（０．０８８ｍｏｌ）のジクロロメタン溶液１００ｍｌを室温にて攪拌しながら１時間かけて滴下した。さらに６時間攪拌後、沈殿したｍ−クロロ安息香酸を濾別して除き、濾液を炭酸ナトリウム水溶液および水で洗浄後、ジクロロメタンを留去した。残った固形分を粉砕し、得られた粉末をジエチルカーボネート（ＤＥＣ）で洗浄し、減圧下乾燥させて、ポリ（２，２，６，６−テトラメチルピペリジノキシルメタクリレート）（ＰＴＭＡ）を得た。   In a 100 ml eggplant flask equipped with a reflux tube, 20 g (0.089 mol) of 2,2,6,6-tetramethylpiperidine methacrylate monomer was placed and dissolved in 80 ml of dry tetrahydrofuran. Thereto was added 0.29 g (0.00187 mol) of azobisisobutyronitrile (AIBN) (monomer / AIBN = 50/1), and the mixture was stirred at 75 to 80 ° C. in an argon atmosphere. After reacting for 6 hours, it was allowed to cool to room temperature. The polymer was precipitated in hexane, separated by filtration, and dried under reduced pressure to obtain poly (2,2,6,6-tetramethylpiperidine methacrylate). Next, 10 g of the obtained poly (2,2,6,6-tetramethylpiperidine methacrylate) was dissolved in 100 ml of dry-treated dichloromethane. To this, 100 ml of a dichloromethane solution of 15.2 g (0.088 mol) of m-chloroperbenzoic acid was added dropwise over 1 hour with stirring at room temperature. After further stirring for 6 hours, the precipitated m-chlorobenzoic acid was removed by filtration, and the filtrate was washed with an aqueous sodium carbonate solution and water, and then dichloromethane was distilled off. The remaining solid was pulverized, and the resulting powder was washed with diethyl carbonate (DEC) and dried under reduced pressure to obtain poly (2,2,6,6-tetramethylpiperidinoxyl methacrylate) (PTMA). Obtained.

次に、正極活物質としてＰＴＭＡ２．１ｇ、導電付与剤として炭素材料０．６３ｇ、結着剤としてカルボキシメチルセルロース（ＣＭＣ）０．２４ｇ及びポリテトラフルオロエチレン（ＰＴＦＥ）０．０３ｇ、並びに水１５ｍｌを混合し、ホモジェナイザーで撹拌し、均一なスラリーを調製した。   Next, 2.1 g of PTMA as a positive electrode active material, 0.63 g of a carbon material as a conductivity imparting agent, 0.24 g of carboxymethylcellulose (CMC) and 0.03 g of polytetrafluoroethylene (PTFE) as a binder, and 15 ml of water are mixed. And stirred with a homogenizer to prepare a uniform slurry.

このスラリーを集電体であるアルミ箔上に塗布し、次いで８０℃で５分間乾燥した。さらにロールプレス機により厚さを調整した。これを２２×２４ｍｍの長方形に切り抜き、アルミ電極リードを超音波圧着した。得られた正極の厚さは１４０〜１５０μｍであった。   This slurry was applied on an aluminum foil as a current collector, and then dried at 80 ° C. for 5 minutes. Furthermore, the thickness was adjusted with a roll press. This was cut into a 22 × 24 mm rectangle, and an aluminum electrode lead was ultrasonically bonded. The thickness of the obtained positive electrode was 140 to 150 μm.

（負極（皮膜形成処理前）の作製）
グラファイト粉末（粒径６μｍ）１３．５ｇ、ポリフッ化ビニリデン１．３５ｇ、カーボンブラック０．１５ｇ、及びＮ−メチルピロリドン３０ｇを混合し、ホモジェナイザーで撹拌し、均一なスラリーを調製した。(Preparation of negative electrode (before film formation treatment))
13.5 g of graphite powder (particle size 6 μm), 1.35 g of polyvinylidene fluoride, 0.15 g of carbon black, and 30 g of N-methylpyrrolidone were mixed and stirred with a homogenizer to prepare a uniform slurry.

このスラリーを集電体である銅メッシュ上に塗布し、次いで１２０℃で５分間乾燥した。さらにロールプレス機により厚さを調整した。これを２２×２４ｍｍの長方形に切り抜き、ニッケル電極リードを超音波圧着した。得られた負極（皮膜形成処理前）の厚さは５０〜６０μｍであった。   This slurry was applied onto a copper mesh as a current collector, and then dried at 120 ° C. for 5 minutes. Furthermore, the thickness was adjusted with a roll press. This was cut into a 22 × 24 mm rectangle, and a nickel electrode lead was ultrasonically bonded. The thickness of the obtained negative electrode (before film formation treatment) was 50 to 60 μm.

（実施例１）
一対の外装用フィルムを用意し、得られた負極を一方の外装用フィルム上に置き、セパレータを介してリチウム箔と重ね合わせることで、外装用フィルム上の電極積層体を得た。得られた電極積層体を他方の外装用フィルムで覆い、電極リード部を含む３辺を熱融着した。これにＰＳを２重量％添加した濃度１ｍｏｌ／ｌのＬｉＰＦ６支持塩を含むエチレンカーボネート／ジエチルカーボネート＝３／７（ｖ／ｖ）の混合電解液を注入し、電極中によく含浸させた。電解液を電極およびセパレータの空隙に十分に含浸させた後、残りの４辺目を減圧下で熱融着した。結果、ラミネート型のＬｉプレドープ用セルを得た。Example 1
A pair of exterior films were prepared, and the obtained negative electrode was placed on one exterior film and overlapped with a lithium foil via a separator to obtain an electrode laminate on the exterior film. The obtained electrode laminate was covered with the other exterior film, and three sides including the electrode lead part were heat-sealed. A mixed electrolyte solution of ethylene carbonate / diethyl carbonate = 3/7 (v / v) containing LiPF 6 supporting salt with a concentration of 1 mol / l to which 2% by weight of PS was added was injected and well impregnated in the electrode. After the electrolyte solution was sufficiently impregnated in the gap between the electrode and the separator, the remaining four sides were thermally fused under reduced pressure. As a result, a laminate-type Li pre-doping cell was obtained.

Ｌｉプレドープ用セルのセル電圧が０Ｖになるまで放電することにより、負極にＬｉを吸蔵させると同時に、負極表面にＰＳの分解による皮膜を形成させた。これにより、皮膜形成処理済負極を得た。   By discharging until the cell voltage of the Li pre-doping cell became 0 V, Li was occluded in the negative electrode, and at the same time, a film by decomposition of PS was formed on the negative electrode surface. As a result, a film-formed negative electrode was obtained.

一対のアルミラミネートフィルムを用意し、一方のアルミラミネートフィルム上に、正極、ポリプロピレン多孔質フィルムセパレータ、皮膜形成処理済負極の順で積層し、電極積層体を得た。この電極積層体を他方のアルミラミネートフィルムで覆い、電極リード部を含む３辺を熱融着した。これに電解液を注入し、電極中によく含浸させた。次に、残りの４辺目を減圧下にて熱融着した。結果、ラミネート型の蓄電デバイスを得た。蓄電デバイスに用いた電解液は、濃度１ｍｏｌ／ｌのＬｉＰＦ６支持塩を含むエチレンカーボネート／ジエチルカーボネート＝３／７（ｖ／ｖ）の混合電解液である。A pair of aluminum laminate films were prepared, and a positive electrode, a polypropylene porous film separator, and a film-formed negative electrode were laminated in this order on one aluminum laminate film to obtain an electrode laminate. This electrode laminate was covered with the other aluminum laminate film, and three sides including the electrode lead portion were heat-sealed. An electrolytic solution was injected into this, and the electrode was well impregnated. Next, the remaining four sides were heat-sealed under reduced pressure. As a result, a laminate-type electricity storage device was obtained. The electrolytic solution used for the electricity storage device is a mixed electrolytic solution of ethylene carbonate / diethyl carbonate = 3/7 (v / v) containing a LiPF 6 supporting salt having a concentration of 1 mol / l.

（実施例２）
Ｌｉプレドープ用セルに用いた電解液中にＰＳを４重量％添加したこと以外は、実施例１と同様にして蓄電デバイスを作製した。(Example 2)
An electricity storage device was produced in the same manner as in Example 1 except that 4% by weight of PS was added to the electrolytic solution used in the Li pre-doping cell.

（実施例３）
Ｌｉプレドープ用セルに用いた電解液中にＰＳを８重量％添加したこと以外は、実施例１と同様にして蓄電デバイスを作製した。(Example 3)
An electricity storage device was produced in the same manner as in Example 1 except that 8% by weight of PS was added to the electrolytic solution used in the Li pre-doping cell.

（実施例４）
Ｌｉプレドープ用セルに用いた電解液中にＶＣを２重量％添加したこと以外は、実施例１と同様にして蓄電デバイスを作製した。Example 4
An electricity storage device was produced in the same manner as in Example 1 except that 2% by weight of VC was added to the electrolytic solution used in the Li pre-doping cell.

（実施例５）
Ｌｉプレドープ用セルに用いた電解液中にＶＣを４重量％添加したこと以外は、実施例１と同様にして蓄電デバイスを作製した。(Example 5)
An electricity storage device was produced in the same manner as in Example 1 except that 4% by weight of VC was added to the electrolytic solution used in the Li pre-doping cell.

（実施例６）
Ｌｉプレドープ用セルに用いた電解液中にＶＣを８重量％添加したこと以外は、実施例１と同様にして蓄電デバイスを作製した。(Example 6)
An electricity storage device was produced in the same manner as in Example 1 except that 8% by weight of VC was added to the electrolytic solution used in the Li pre-doping cell.

（比較例１）
Ｌｉプレドープ用セルに用いた電解液中にＰＳおよびＶＣのどちらも添加しないことにより、負極にＰＳおよび／またはＶＣの分解による皮膜形成を行っていないこと以外は、実施例１と同様にして蓄電デバイスを作製した。(Comparative Example 1)
Electricity storage was carried out in the same manner as in Example 1 except that neither PS nor VC was added to the electrolyte used for the Li pre-doping cell, and no film was formed on the negative electrode by decomposition of PS and / or VC. A device was fabricated.

（比較例２）
一対の外装用フィルムを用意し、得られた負極（皮膜形成処理前）を一方の外装用フィルム上に置き、セパレータを介してリチウム箔と重ね合わせることで、外装用フィルム上の電極積層体を得た。得られた電極積層体を他方の外装用フィルムで覆い、電極リード部を含む３辺を熱融着した。これに濃度１ｍｏｌ／ｌのＬｉＰＦ６支持塩を含むエチレンカーボネート／ジエチルカーボネート＝３／７（ｖ／ｖ）の混合電解液を注入し、電極中によく含浸させた。電解液を電極およびセパレータの空隙に十分に含浸させた後、残りの４辺目を減圧下で熱融着した。結果、ラミネート型のＬｉプレドープ用セルを得た。(Comparative Example 2)
A pair of exterior films are prepared, and the obtained negative electrode (before film formation treatment) is placed on one exterior film and overlapped with a lithium foil via a separator to form an electrode laminate on the exterior film. Obtained. The obtained electrode laminate was covered with the other exterior film, and three sides including the electrode lead part were heat-sealed. A mixed electrolytic solution of ethylene carbonate / diethyl carbonate = 3/7 (v / v) containing LiPF 6 supporting salt at a concentration of 1 mol / l was poured into the electrode and thoroughly impregnated in the electrode. After the electrolyte solution was sufficiently impregnated in the gap between the electrode and the separator, the remaining four sides were thermally fused under reduced pressure. As a result, a laminate-type Li pre-doping cell was obtained.

Ｌｉプレドープ用セルのセル電圧が０Ｖになるまで放電することにより、負極（皮膜形成処理をしていないもの）にＬｉを吸蔵させた。   By discharging until the cell voltage of the Li pre-doping cell became 0 V, Li was occluded in the negative electrode (those not subjected to film formation treatment).

一対のアルミラミネートフィルムを用意し、一方のアルミラミネートフィルム上に、正極、ポリプロピレン多孔質フィルムセパレータ、負極（皮膜形成処理をしていないもの）の順で積層し、電極積層体を得た。この電極積層体を他方のアルミラミネートフィルムで覆い、電極リード部を含む３辺を熱融着した。これに電解液を注入し、電極中によく含浸させた。次に、残りの４辺目を減圧下にて熱融着した。結果、ラミネート型の蓄電デバイスを得た。蓄電デバイスに用いた電解液は、ＰＳを２重量％添加した濃度１ｍｏｌ／ｌのＬｉＰＦ６支持塩を含むエチレンカーボネート／ジエチルカーボネート＝３／７（ｖ／ｖ）の混合電解液である。A pair of aluminum laminate films were prepared, and a positive electrode, a polypropylene porous film separator, and a negative electrode (those not subjected to film formation treatment) were laminated in this order on one aluminum laminate film to obtain an electrode laminate. This electrode laminate was covered with the other aluminum laminate film, and three sides including the electrode lead portion were heat-sealed. An electrolytic solution was injected into this, and the electrode was well impregnated. Next, the remaining four sides were heat-sealed under reduced pressure. As a result, a laminate-type electricity storage device was obtained. The electrolytic solution used for the electricity storage device is a mixed electrolytic solution of ethylene carbonate / diethyl carbonate = 3/7 (v / v) containing LiPF 6 supporting salt with a concentration of 1 mol / l to which 2% by weight of PS is added.

（比較例３）
Ｌｉプレドープ用セルに用いた電解液中にＰＳおよびＶＣのどちらも添加しないことにより、負極にＰＳおよび／またはＶＣの分解による皮膜形成を行っていないこと、かつ、蓄電デバイスに用いた電解液中にＰＳを４重量％添加することにより、蓄電デバイス作製後にＰＳの分解による皮膜形成を行っていること以外は、実施例１と同様にして蓄電デバイスを作製した。(Comparative Example 3)
By not adding PS and VC to the electrolyte used for the Li pre-doping cell, the negative electrode is not subjected to film formation by decomposition of PS and / or VC, and in the electrolyte used for the electricity storage device By adding 4% by weight of PS, an electricity storage device was produced in the same manner as in Example 1 except that a film was formed by decomposing PS after the electricity storage device was produced.

（比較例４）
Ｌｉプレドープ用セルに用いた電解液中にＰＳおよびＶＣのどちらも添加しないことにより、負極にＰＳおよび／またはＶＣの分解による皮膜形成を行っていないこと、かつ、蓄電デバイスに用いた電解液中にＰＳを８重量％添加することにより、蓄電デバイス作製後にＰＳの分解による皮膜形成を行っていること以外は、実施例１と同様にして蓄電デバイスを作製した。(Comparative Example 4)
By not adding PS and VC to the electrolyte used for the Li pre-doping cell, the negative electrode is not subjected to film formation by decomposition of PS and / or VC, and in the electrolyte used for the electricity storage device By adding 8% by weight of PS, an electricity storage device was produced in the same manner as in Example 1 except that a film was formed by decomposing PS after the electricity storage device was produced.

（比較例５）
Ｌｉプレドープ用セルに用いた電解液中にＰＳおよびＶＣのどちらも添加しないことにより、負極にＰＳおよび／またはＶＣの分解による皮膜形成を行っていないこと、かつ、蓄電デバイスに用いた電解液中にＶＣを２重量％添加することにより、蓄電デバイス作製後にＶＣの分解による皮膜形成を行っていること以外は、実施例１と同様にして蓄電デバイスを作製した。(Comparative Example 5)
By not adding PS and VC to the electrolyte used for the Li pre-doping cell, the negative electrode is not subjected to film formation by decomposition of PS and / or VC, and in the electrolyte used for the electricity storage device By adding 2% by weight of VC, an electricity storage device was produced in the same manner as in Example 1 except that a film was formed by decomposition of VC after the electricity storage device was produced.

（比較例６）
Ｌｉプレドープ用セルに用いた電解液中にＰＳおよびはＶＣのどちらも添加しないことにより、負極にＰＳおよび／またはＶＣの分解による皮膜形成を行っていないこと、かつ、蓄電デバイスに用いた電解液中にＶＣを４重量％添加することにより、蓄電デバイス作製後にＶＣの分解による皮膜形成を行っていること以外は、実施例１と同様にして蓄電デバイスを作製した。(Comparative Example 6)
By adding neither PS nor VC to the electrolyte used for the Li pre-doping cell, no coating is formed on the negative electrode by decomposition of PS and / or VC, and the electrolyte used for the electricity storage device By adding 4% by weight of VC, an electricity storage device was produced in the same manner as in Example 1 except that a film was formed by decomposition of VC after the electricity storage device was produced.

（比較例７）
Ｌｉプレドープ用セルに用いた電解液中にＰＳおよびＶＣのどちらも添加しないことにより、負極にＰＳおよび／またはＶＣの分解による皮膜形成を行っていないこと、かつ、蓄電デバイスに用いた電解液中にＶＣを８重量％添加することにより、蓄電デバイス作製後にＶＣの分解による皮膜形成を行っていること以外は、実施例１と同様にして蓄電デバイスを作製した。(Comparative Example 7)
By not adding PS and VC to the electrolyte used for the Li pre-doping cell, the negative electrode is not subjected to film formation by decomposition of PS and / or VC, and in the electrolyte used for the electricity storage device By adding 8 wt% of VC, an electricity storage device was produced in the same manner as in Example 1 except that a film was formed by decomposition of VC after the electricity storage device was produced.

（内部抵抗の測定とその結果）
実施例１〜６及び比較例１〜７の蓄電デバイスを、４０℃にて、０．５ｍＡの定電流で電圧が４Ｖになるまで充電した後、１０ｍＡで１秒間放電した。再度、０．５ｍＡの定電流で電圧が４Ｖになるまで充電した後、２０ｍＡで１秒間放電した。この充電・放電の繰り返しを、放電電流を３０、４０、・・・、１００ｍＡと変えながら行った。放電直後の電圧を測定し、電流と電圧の関係から内部抵抗を求めた。測定後、０．５ｍＡの定電流で電圧が４Ｖになるまで充電した後、４０℃の恒温槽の中で保管した。１週間後と６週間後に再度、内部抵抗を測定した。(Measurement of internal resistance and results)
The electricity storage devices of Examples 1 to 6 and Comparative Examples 1 to 7 were charged at 40 ° C. with a constant current of 0.5 mA until the voltage reached 4 V, and then discharged at 10 mA for 1 second. The battery was charged again at a constant current of 0.5 mA until the voltage reached 4 V, and then discharged at 20 mA for 1 second. This charging / discharging was repeated while changing the discharge current to 30, 40,..., 100 mA. The voltage immediately after discharge was measured, and the internal resistance was determined from the relationship between current and voltage. After the measurement, the battery was charged at a constant current of 0.5 mA until the voltage reached 4 V, and then stored in a constant temperature bath at 40 ° C. The internal resistance was measured again after 1 week and 6 weeks.

表１に内部抵抗を測定した結果を示す。実施例１、実施例２、実施例３、実施例４、実施例５、実施例６、比較例１、比較例２、比較例３、比較例４、比較例５、比較例６、比較例７の６週間後の内部抵抗はそれぞれ、２．３０Ω、２．０７Ω、２．０６Ω、２．３５Ω、２．０９Ω、２．１０Ω、２．４４Ω、２．３３Ω、２．１１Ω、２．１０Ω、２．３９Ω、２．１２Ω、２．１４Ωであった。この結果から、蓄電デバイス作製前にあらかじめＰＳもしくはＶＣの分解による皮膜形成処理を負極に対して行うことで、高温保管時における蓄電デバイスの内部抵抗の増加を抑えることができた。また、ＰＳもしくはＶＣの添加量が電解液全体の重量の２重量％から４重量％のときは、初期の内部抵抗を抑えつつ高温保管時における内部抵抗の増加を抑えることができ、より望ましいと考えられる。   Table 1 shows the results of measuring the internal resistance. Example 1, Example 2, Example 3, Example 4, Example 5, Example 6, Comparative Example 1, Comparative Example 2, Comparative Example 3, Comparative Example 4, Comparative Example 4, Comparative Example 5, Comparative Example 6, Comparative Example 7 after 6 weeks, the internal resistance is 2.30Ω, 2.07Ω, 2.06Ω, 2.35Ω, 2.09Ω, 2.10Ω, 2.44Ω, 2.33Ω, 2.11Ω, 2.10Ω, respectively. 2.39Ω, 2.12Ω, and 2.14Ω. From this result, it was possible to suppress an increase in internal resistance of the electricity storage device during high-temperature storage by performing a film formation process by decomposing PS or VC on the negative electrode in advance before producing the electricity storage device. Further, when the addition amount of PS or VC is 2 to 4% by weight of the total electrolyte, it is more desirable because it can suppress an increase in internal resistance during high temperature storage while suppressing initial internal resistance. Conceivable.

Figure 2014092016
Figure 2014092016

本発明の実施形態によれば、十分な出力と高温信頼性をもつ蓄電デバイスを提供することができる。そのため、本発明の実施形態による蓄電デバイスは、電気自動車、ハイブリッド電気自動車などの駆動用又は補助用の蓄電源、各種携帯電子機器の電源、ソーラーエネルギーや風力発電等の各種エネルギーの蓄電装置、あるいは家庭用電気器具の蓄電源等に適用できる。   According to the embodiment of the present invention, it is possible to provide an electricity storage device having sufficient output and high temperature reliability. Therefore, the power storage device according to the embodiment of the present invention is a power storage device for driving or auxiliary such as an electric vehicle or a hybrid electric vehicle, a power source for various portable electronic devices, a power storage device for various energy such as solar energy or wind power generation, or It can be applied to a storage power source for household appliances.

１０１ 正極
１０２ 負極（皮膜形成処理前）
１０３ 集電体
１０４ 電極リード
１０５ セパレータ
１０６ 外装用フィルム
１０７ ラミネート型蓄電デバイス
１０８ リチウム箔
１０９ Ｌｉプレドープ用セル
１１０ 皮膜形成処理済負極101 Positive electrode 102 Negative electrode (before film formation treatment)
DESCRIPTION OF SYMBOLS 103 Current collector 104 Electrode lead 105 Separator 106 Exterior film 107 Laminate type electrical storage device 108 Lithium foil 109 Li pre-doping cell 110 Film-formed negative electrode

Claims (7)

酸化状態において下記式（１）で示されるニトロキシルカチオン部分構造をとり、還元状態において下記式（２）で示されるニトロキシルラジカル部分構造をとり、二つの状態間で電子の授受を行う下記反応式（Ａ）で示される反応を行うニトロキシル化合物を含む正極と、負極と、電解質塩および有機溶媒を含む電解液とを有する蓄電デバイスであって、
前記負極が、蓄電デバイス組立て前に、あらかじめ１，３−プロパンスルトンおよびビニレンカーボネートの少なくとも１つの分解によって形成された皮膜を有することを特徴とする蓄電デバイス。
Figure 2014092016
 The following reaction takes an nitroxyl cation partial structure represented by the following formula (1) in the oxidized state and a nitroxyl radical partial structure represented by the following formula (2) in the reduced state to transfer electrons between the two states. An electricity storage device having a positive electrode containing a nitroxyl compound that performs the reaction represented by the formula (A), a negative electrode, and an electrolyte solution containing an electrolyte salt and an organic solvent,
The electricity storage device, wherein the negative electrode has a film formed by decomposition of at least one of 1,3-propane sultone and vinylene carbonate in advance before assembling the electricity storage device.
Figure 2014092016
 前記皮膜は、前記負極が前記蓄電デバイスに組み込まれる前に、１，３−プロパンスルトンおよびビニレンカーボネートの少なくとも１つを添加した電解液を有する電気化学セルに電流を流すことにより形成されたことを特徴とする、請求項１に記載の蓄電デバイス。   The film was formed by passing an electric current through an electrochemical cell having an electrolyte solution to which at least one of 1,3-propane sultone and vinylene carbonate was added before the negative electrode was incorporated into the electricity storage device. The electrical storage device according to claim 1, characterized in that 前記皮膜は、前記負極が前記蓄電デバイスに組み込まれる前に、１，３−プロパンスルトンおよびビニレンカーボネートの少なくとも１つを添加した電解液を有する電気化学セルに、金属Ｌｉを対極として用いて放電することにより形成されたことを特徴とする、請求項１に記載の蓄電デバイス。   The film is discharged using a metal Li as a counter electrode in an electrochemical cell having an electrolytic solution to which at least one of 1,3-propane sultone and vinylene carbonate is added before the negative electrode is incorporated in the electricity storage device. The electricity storage device according to claim 1, wherein the electricity storage device is formed. 酸化状態において下記式（１）で示されるニトロキシルカチオン部分構造をとり、還元状態において下記式（２）で示されるニトロキシルラジカル部分構造をとり、二つの状態間で電子の授受を行う下記反応式（Ａ）：
Figure 2014092016
 で示される反応を行うニトロキシル化合物を含む正極と、負極と、電解質塩および有機溶媒を含む電解液とを有する蓄電デバイスの製造方法であって、
蓄電デバイス組立て前にあらかじめ、皮膜形成前の負極に１，３−プロパンスルトンおよびビニレンカーボネートの少なくとも１つの分解による皮膜形成処理を行うことを特徴とする蓄電デバイスの製造方法。The following reaction takes an nitroxyl cation partial structure represented by the following formula (1) in the oxidized state and a nitroxyl radical partial structure represented by the following formula (2) in the reduced state to transfer electrons between the two states. Formula (A):
Figure 2014092016
 A method for producing an electricity storage device comprising a positive electrode containing a nitroxyl compound that performs the reaction represented by: a negative electrode; and an electrolyte solution containing an electrolyte salt and an organic solvent,
A method for producing an electricity storage device, wherein a film formation treatment by decomposition of at least one of 1,3-propane sultone and vinylene carbonate is performed in advance on a negative electrode before film formation before assembling the electricity storage device. 前記皮膜形成前の負極と１，３−プロパンスルトンおよびビニレンカーボネートの少なくとも１つを添加した電解液を有する電気化学セルに電流を流すことにより、前記皮膜形成処理を行うことを特徴とする、請求項４に記載の蓄電デバイスの製造方法。   The film formation treatment is performed by passing an electric current through an electrochemical cell having an electrolyte solution to which at least one of the negative electrode before formation of the film and 1,3-propane sultone and vinylene carbonate is added. Item 5. A method for producing an electricity storage device according to Item 4. 前記皮膜形成前の負極と１，３−プロパンスルトンおよびビニレンカーボネートの少なくとも１つを添加した電解液を有する電気化学セルに、金属Ｌｉを対極として用いて放電することにより、前記皮膜形成前の負極に皮膜形成処理を行うこと特徴とする、請求項４に記載の蓄電デバイスの製造方法。   The negative electrode before forming the film by discharging to the electrochemical cell having the negative electrode before forming the film and an electrolyte containing at least one of 1,3-propane sultone and vinylene carbonate using metal Li as a counter electrode The method for manufacturing an electricity storage device according to claim 4, wherein a film forming process is performed on the battery. 前記電解液に含まれる１，３−プロパンスルトンおよびビニレンカーボネートの重量（但し、１，３−プロパンスルトンおよびビニレンカーボネートのどちらか１つのみが存在する場合は、その１つのみの重量）が電解液全体の重量に対して１〜１０重量％であることを特徴とする、請求項４〜６のいずれか１項に記載の蓄電デバイスの製造方法。   The weight of 1,3-propane sultone and vinylene carbonate contained in the electrolytic solution (however, when only one of 1,3-propane sultone and vinylene carbonate is present) is the weight of only one of them. It is 1 to 10 weight% with respect to the weight of the whole liquid, The manufacturing method of the electrical storage device of any one of Claims 4-6 characterized by the above-mentioned.
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