JP2017162633A - Nonaqueous secondary battery - Google Patents

Nonaqueous secondary battery Download PDF

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JP2017162633A
JP2017162633A JP2016045198A JP2016045198A JP2017162633A JP 2017162633 A JP2017162633 A JP 2017162633A JP 2016045198 A JP2016045198 A JP 2016045198A JP 2016045198 A JP2016045198 A JP 2016045198A JP 2017162633 A JP2017162633 A JP 2017162633A
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negative electrode
mixture layer
electrode mixture
secondary battery
positive electrode
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丈主 加味根
Tomokazu Kamine
丈主 加味根
岸見　光浩
Mitsuhiro Kishimi
光浩 岸見
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Maxell Holdings Ltd
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Hitachi Maxell Ltd
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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
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    • Y02E60/10—Energy storage using batteries

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Abstract

PROBLEM TO BE SOLVED: To provide a nonaqueous secondary battery superior in high-temperature storage suitability.SOLUTION: A nonaqueous secondary battery of the invention comprises: a negative electrode having a negative electrode mixture layer including a negative electrode active material and a current collector; a positive electrode; a separator; and a nonaqueous electrolyte solution containing a lithium salt and an organic solvent. The negative electrode mixture layer has, on its surface, a particulate deposit of 10-500 nm in average particle diameter. According to X-ray photoelectron spectroscopic analysis on the surface of the negative electrode mixture layer, a peak coming from boron at 190-195 eV, a peak coming from carbon at 280-292 eV, a peak coming from oxygen at 526-536 eV and a peak coming from fluorine at 682-690 eV are observed. The nonaqueous electrolyte solution contains lithium bis oxalate borate, or vinylene carbonate.SELECTED DRAWING: Figure 5

Description

本発明は、高温貯蔵特性に優れた非水二次電池に関するものである。   The present invention relates to a non-aqueous secondary battery having excellent high-temperature storage characteristics.

リチウムイオン二次電池などの非水二次電池は、高電圧、高容量であることから、各種携帯機器の電源として広く採用されている。また、近年では電動工具などのパワーツールや電気自動車、電動式自転車などのように、中型や大型での用途も広がりを見せている。   Non-aqueous secondary batteries such as lithium ion secondary batteries are widely used as power sources for various portable devices because of their high voltage and high capacity. In recent years, the use of medium-sized and large-sized tools such as power tools such as electric tools, electric vehicles, and electric bicycles has been spreading.

非水二次電池は、民生用途としてまず普及し、現時点では車載用や産業用としても広がりを見せつつある。こうした状況下で、非水二次電池には各種の電池特性の向上が望まれている。   Non-aqueous secondary batteries are first widespread for consumer use, and at present, they are spreading for in-vehicle use and industrial use. Under these circumstances, non-aqueous secondary batteries are desired to improve various battery characteristics.

非水二次電池の特性を改善する手法の一つに、非水電解液の改良が挙げられる。例えば、特許文献１には、特定のラクトン類を含有する非水電解液を用いて、非水二次電池の連続充電特性などを改善する技術が提案されている。なお、特許文献１に記載の技術では、抵抗の高い被膜が正極表面で厚く形成されることを防止するために、非水電解液中の特定のラクトン類を非常に少ない量に制限している。   One method for improving the characteristics of the non-aqueous secondary battery is to improve the non-aqueous electrolyte. For example, Patent Document 1 proposes a technique for improving the continuous charge characteristics of a non-aqueous secondary battery using a non-aqueous electrolyte solution containing a specific lactone. In the technique described in Patent Document 1, specific lactones in the non-aqueous electrolyte are limited to a very small amount in order to prevent a high-resistance film from being formed thick on the positive electrode surface. .

他方、特許文献２には、非水溶媒の一部にγ−ブチロラクトン誘導体を使用した非水電解質に、亜リン酸エステルを添加して、負極表面に被膜を形成させて高温環境下における非水二次電池の自己放電特性を高める技術の提案もある。   On the other hand, in Patent Document 2, a non-aqueous electrolyte using a γ-butyrolactone derivative as a part of a non-aqueous solvent is added with a phosphite ester to form a film on the surface of the negative electrode to form a non-aqueous solvent in a high temperature environment. There is also a proposal of a technique for improving the self-discharge characteristics of the secondary battery.

また、特許文献３には、特定の電気容量を有し、かつ金属多孔体からなる集電体を有する正極および負極を備え、負極活物質に表面非晶質黒鉛を含有するリチウムイオン二次電池において、非水電解液溶媒にエチレンカーボネートとγ−ブチロラクトンとを特定の比率で使用することで、安全性を高める技術が提案されている。   Patent Document 3 discloses a lithium ion secondary battery including a positive electrode and a negative electrode having a specific electric capacity and a current collector made of a metal porous body, and containing a surface amorphous graphite as a negative electrode active material. , A technique for improving safety by using ethylene carbonate and γ-butyrolactone in a non-aqueous electrolyte solvent at a specific ratio has been proposed.

特開２００５−３２２６１０号公報（特許請求の範囲、段落［００４６］など）JP 2005-322610 A (Claims, paragraph [0046], etc.) 特開２００４−１４３５１号公報（特許請求の範囲、段落［００１９］など）JP 2004-14351 A (Claims, paragraph [0019], etc.) 特開２００８−１０３１６号公報（特許請求の範囲、段落［００５１］など）JP 2008-10316 A (Claims, paragraph [0051], etc.)

ところで、非水二次電池においては、特に車載用や産業用への適用を考慮すると、例えば、高温環境下に置かれても特性の低下が生じ難いような貯蔵特性を備えることが求められることが想定される。   By the way, non-aqueous secondary batteries are required to have storage characteristics that are unlikely to deteriorate even when placed in a high-temperature environment, especially considering application to in-vehicle and industrial applications. Is assumed.

本発明は、前記事情に鑑みてなされたものであり、その目的は、高温貯蔵特性に優れた非水二次電池を提供することにある。   This invention is made | formed in view of the said situation, The objective is to provide the non-aqueous secondary battery excellent in the high temperature storage characteristic.

前記目的を達成し得た本発明の非水二次電池は、負極活物質を含有する負極合剤層と集電体とを有する負極、正極、セパレータ、並びにリチウム塩および有機溶媒を含有する非水電解液を備えており、前記負極合剤層の表面に、平均粒子径が１０〜５００ｎｍの粒子状堆積物が存在しており、前記負極合剤層の表面をＸ線光電子分光分析したときに、１９０〜１９５ｅＶにホウ素に基づくピークが、２８０〜２９２ｅＶに炭素に基づくピークが、５２６〜５３６ｅＶに酸素に基づくピークが、６８２〜６９０ｅＶにフッ素に基づくピークが、それぞれ観察され、前記非水電解液は、リチウムビスオキサレートボレート、または、ビニレンカーボネートを含有していることを特徴とするものである。   The non-aqueous secondary battery of the present invention that can achieve the above object is a negative electrode having a negative electrode mixture layer containing a negative electrode active material and a current collector, a positive electrode, a separator, and a non-acid containing a lithium salt and an organic solvent. When the surface of the negative electrode mixture layer is provided with a water electrolyte, and a particulate deposit having an average particle size of 10 to 500 nm exists on the surface of the negative electrode mixture layer, and the surface of the negative electrode mixture layer is analyzed by X-ray photoelectron spectroscopy In addition, a peak based on boron is observed at 190 to 195 eV, a peak based on carbon at 280 to 292 eV, a peak based on oxygen at 526 to 536 eV, and a peak based on fluorine at 682 to 690 eV, respectively. The liquid is characterized by containing lithium bisoxalate borate or vinylene carbonate.

本発明によれば、高温貯蔵特性に優れた非水二次電池を提供することができる。   ADVANTAGE OF THE INVENTION According to this invention, the nonaqueous secondary battery excellent in the high temperature storage characteristic can be provided.

本発明の非水二次電池の一例を模式的に表す縦断面図である。It is a longitudinal section showing typically an example of the nonaqueous secondary battery of the present invention. 本発明の非水二次電池に係る正極の一例を模式的に表す平面図である。It is a top view which represents typically an example of the positive electrode which concerns on the nonaqueous secondary battery of this invention. 本発明の非水二次電池に係る負極の一例を模式的に表す平面図である。It is a top view which represents typically an example of the negative electrode which concerns on the nonaqueous secondary battery of this invention. 本発明の非水二次電池に係るセパレータの一例を模式的に表す平面図である。It is a top view which represents typically an example of the separator which concerns on the nonaqueous secondary battery of this invention. 実施例１の非水二次電池に係る負極の負極合剤層の表面の走査型電子顕微鏡写真である。3 is a scanning electron micrograph of the surface of the negative electrode mixture layer of the negative electrode according to the nonaqueous secondary battery of Example 1. FIG. 比較例５の非水二次電池に係る負極の負極合剤層の表面の走査型電子顕微鏡写真である。6 is a scanning electron micrograph of the surface of a negative electrode mixture layer of a negative electrode according to a nonaqueous secondary battery of Comparative Example 5.

非水二次電池では、その充放電反応によって非水電解液の構成成分が分解して正極や負極の表面に堆積し、ＳＥＩ（Ｓｏｌｉｄ Ｅｌｅｃｔｒｏｌｙｔｅ Ｉｎｔｅｒｆａｃｅ）皮膜を形成する。前記ＳＥＩ皮膜は、正極や負極と非水電解液との接触による非水電解液の分解反応を防止する機能を有しているため、このＳＥＩ皮膜が形成されることで、例えば充電状態の電池を長期間保存しても、電池特性の低下が抑制される。   In the non-aqueous secondary battery, the constituent components of the non-aqueous electrolyte are decomposed by the charge / discharge reaction and are deposited on the surfaces of the positive electrode and the negative electrode to form a SEI (Solid Electrolyte Interface) film. Since the SEI film has a function of preventing the decomposition reaction of the non-aqueous electrolyte due to contact between the positive electrode or the negative electrode and the non-aqueous electrolyte, the SEI film is formed, for example, in a charged battery. Even if the battery is stored for a long time, the deterioration of the battery characteristics is suppressed.

ところが、通常の非水二次電池で形成されるＳＥＩ皮膜は耐熱性が低く、電池が高温環境下に置かれると非水電解液中に溶け出してしまうため、その機能が有効に発揮されなくなる。   However, the SEI film formed by a normal non-aqueous secondary battery has low heat resistance, and when the battery is placed in a high-temperature environment, it dissolves into the non-aqueous electrolyte, so that its function cannot be effectively exhibited. .

そこで、本発明の非水二次電池では、負極（その負極合剤層）の表面に特定の平均粒子径の粒子状堆積物を形成し、かつ負極合剤層の表面におけるＸ線光電子分光（ＸＰＳ）分析により求められる前記粒子状堆積物の含有元素として、ホウ素、炭素、酸素およびフッ素が含まれるようにした。更に、前記粒子状堆積物の性状をより良好なものとし、有効に機能させるため、非水電解液に、リチウムビスオキサレートボレート、または、ビニレンカーボネートを含有させるようにした。この場合、負極合剤層表面の前記粒子状堆積物（それにより形成されているＳＥＩ皮膜）の耐熱性が、通常の非水二次電池で形成されているＳＥＩ皮膜に比べて高く、電池が高温に曝されても非水電解液中に溶け出し難いため、その非水電解液の分解防止機能が、より高い温度下でも有効に発揮されることから、非水二次電池の高温貯蔵特性が向上する。   Therefore, in the nonaqueous secondary battery of the present invention, a particulate deposit having a specific average particle diameter is formed on the surface of the negative electrode (the negative electrode mixture layer), and X-ray photoelectron spectroscopy ( The contained elements of the particulate deposits determined by XPS analysis were boron, carbon, oxygen and fluorine. Furthermore, in order to improve the properties of the particulate deposit and to make it function effectively, the non-aqueous electrolyte contains lithium bisoxalate borate or vinylene carbonate. In this case, the heat resistance of the particulate deposit on the surface of the negative electrode mixture layer (the SEI film formed thereby) is higher than that of the SEI film formed by a normal non-aqueous secondary battery, and the battery Since it is difficult to dissolve in the non-aqueous electrolyte even when exposed to high temperatures, the non-aqueous electrolyte's ability to prevent decomposition is effectively demonstrated even at higher temperatures. Will improve.

本発明の非水二次電池は、負極活物質を含有する負極合剤層と集電体とを有し、負極合剤層が集電体の片面または両面に形成された構造の負極を有している。   The non-aqueous secondary battery of the present invention has a negative electrode mixture layer containing a negative electrode active material and a current collector, and has a negative electrode having a structure in which the negative electrode mixture layer is formed on one side or both sides of the current collector. doing.

負極合剤層は、その表面に平均粒子径が１０〜５００ｎｍの粒子状堆積物が存在している。そして、負極合剤層の表面をＸＰＳ分析したときに、１９０〜１９５ｅＶにホウ素に基づくピークが、２８０〜２９２ｅＶに炭素に基づくピークが、５２６〜５３６ｅＶに酸素に基づくピークが、６８２〜６９０ｅＶにフッ素に基づくピークが、それぞれ観察される。   The negative electrode mixture layer has a particulate deposit having an average particle diameter of 10 to 500 nm on the surface thereof. When the surface of the negative electrode mixture layer was analyzed by XPS, a peak based on boron at 190 to 195 eV, a peak based on carbon at 280 to 292 eV, a peak based on oxygen at 526 to 536 eV, and a fluorine peak at 682 to 690 eV Each of the peaks based on is observed.

負極合剤層においては、前記ＸＰＳ分析において観察される前記炭素に基づくピーク、酸素に基づくピークおよびフッ素に基づくピークのピーク強度を、それぞれＩａ、ＩｂおよびＩｃとしたときに、Ｉｃ／（Ｉａ＋Ｉｂ）≧０．３であることが好ましい。すなわち、負極合剤層の表面には、前記の粒子状堆積物がある程度以上の量存在し、かつ前記ピークの強度比が前記の値を満たすことにより、ＳＥＩ皮膜の耐熱性がより優れたものとなる。   In the negative electrode mixture layer, Ic / (Ia + Ib) where Ia, Ib, and Ic are peak intensities of the carbon-based peak, the oxygen-based peak, and the fluorine-based peak observed in the XPS analysis, respectively. It is preferable that ≧ 0.3. That is, the surface of the negative electrode mixture layer has a certain amount or more of the particulate deposits, and the peak intensity ratio satisfies the above value, so that the heat resistance of the SEI film is more excellent. It becomes.

前記粒子状堆積物の平均粒子径は、粒子径が小さすぎると耐熱皮膜としての効果が得られ難くなることから、１０ｎｍ以上であり、５０ｎｍ以上であることが好ましい。また、粒子径が大きすぎると、抵抗増大の要因となり充放電の阻害要因となり得ることから、前記粒子状堆積物の平均粒子径は、５００ｎｍ以下であり、４００ｎｍ以下であることが好ましい。   The average particle size of the particulate deposit is 10 nm or more, and preferably 50 nm or more, because if the particle size is too small, it is difficult to obtain the effect as a heat-resistant film. In addition, if the particle size is too large, it may cause an increase in resistance and may cause a charge / discharge inhibition factor. Therefore, the average particle size of the particulate deposit is preferably 500 nm or less, and preferably 400 nm or less.

本明細書でいう前記粒子状堆積物の平均粒子径は、負極合剤層の表面を、走査型電子顕微鏡（ＳＥＭ）を用いて３万倍の倍率で観察し、粒子状堆積物１００個の粒子径の平均値（数平均値）として求められる値である。なお、個々の粒子状堆積物の粒子径は、平面視で粒子に外接する円を描いたときの円の直径として求めればよい。   As used herein, the average particle size of the particulate deposits is determined by observing the surface of the negative electrode mixture layer at a magnification of 30,000 using a scanning electron microscope (SEM). It is a value obtained as an average value (number average value) of particle diameters. In addition, what is necessary is just to obtain | require the particle diameter of each particulate deposit as a diameter of a circle | round | yen when drawing the circle | round | yen which circumscribes particle | grains by planar view.

本明細書でいう負極合剤層の表面のＸＰＳ分析は、例えば以下の条件下で行うことができる。アルゴン雰囲気に保たれたグローブボックス内で電池を解体し、取り出した負極をジエチルカーボネートに一晩浸漬する。その後、負極を乾燥し、カーボンテープで試料台に貼付け、アルゴン雰囲気を保ったまま、トランスファーベッセルを用いて前記試料台を測定装置に導入し測定を行う。装置には、例えばＵＬＶＡＣ−ＰＨＩ社製「Ｑｕａｎｔｅｒａ ＳＸＭ」を用いることができる。測定条件は、励起源：軟Ｘ線ＡｌＫα（１４８６．６ｅＶ）、分析領域：φ１００μｍ、光電子検出角（ＴＯＡ）：４５ｄｅｇで測定し、ピーク分割を行って各ピークの原子比を算出する。なお、後記の実施例における負極合剤層の表面のＸＰＳ分析は、前記の条件で行った。   The XPS analysis of the surface of the negative electrode mixture layer in the present specification can be performed, for example, under the following conditions. The battery is disassembled in a glove box kept in an argon atmosphere, and the taken-out negative electrode is immersed in diethyl carbonate overnight. Thereafter, the negative electrode is dried, attached to the sample table with carbon tape, and the sample table is introduced into a measuring apparatus using a transfer vessel while the argon atmosphere is maintained, and measurement is performed. As the apparatus, for example, “Quantera SXM” manufactured by ULVAC-PHI can be used. Measurement conditions are as follows: excitation source: soft X-ray AlKα (1486.6 eV), analysis region: φ100 μm, photoelectron detection angle (TOA): 45 deg, and peak division is performed to calculate the atomic ratio of each peak. In addition, the XPS analysis of the surface of the negative mix layer in the Example mentioned later was performed on the said conditions.

負極活物質には、従来から知られている非水二次電池の負極に使用されている負極活物質、すなわち、Ｌｉイオンを吸蔵放出可能な活物質を用いることができる。このような負極活物質の具体例としては、例えば、黒鉛（天然黒鉛；熱分解炭素類、メソフェーズカーボンマイクロビーズ、炭素繊維などの易黒鉛化炭素を２８００℃以上で黒鉛化処理した人造黒鉛；など）、易黒鉛化炭素（ソフトカーボン）、難黒鉛化炭素（ハードカーボン）、熱分解炭素類、コークス類、ガラス状炭素類、有機高分子化合物の焼成体、メソフェーズカーボンマイクロビーズ、炭素繊維、活性炭などの炭素材料；リチウムと合金化可能な金属（Ｓｉ、Ｓｎなど）や、これらの金属を含む材料（合金、酸化物など）；チタン酸リチウム、スピネルマンガンリチウムなどのリチウム含有複合酸化物；などの粒子が挙げられる。負極には、前記例示の負極活物質のうち、１種のみを使用してもよく、２種以上を併用してもよい。なお、前記例示の負極活物質の中でも、前記粒子状堆積物の作用がより明確となることから、炭素材料が好ましく用いられる。   As the negative electrode active material, a conventionally known negative electrode active material used for a negative electrode of a non-aqueous secondary battery, that is, an active material capable of occluding and releasing Li ions can be used. Specific examples of such a negative electrode active material include, for example, graphite (natural graphite; artificial graphite obtained by graphitizing graphitized carbon such as pyrolytic carbons, mesophase carbon microbeads, and carbon fibers at 2800 ° C. or higher; ), Graphitizable carbon (soft carbon), non-graphitizable carbon (hard carbon), pyrolytic carbons, cokes, glassy carbons, fired organic polymer compounds, mesophase carbon microbeads, carbon fibers, activated carbon Carbon materials such as: metals that can be alloyed with lithium (Si, Sn, etc.), materials containing these metals (alloys, oxides, etc.); lithium-containing composite oxides such as lithium titanate and spinel manganese lithium; Particles. In the negative electrode, only one type of the above illustrated negative electrode active materials may be used, or two or more types may be used in combination. Among the above-described negative electrode active materials, a carbon material is preferably used because the action of the particulate deposit becomes clearer.

負極合剤層には、通常、バインダを含有させる。負極合剤層に係るバインダとしては、ポリフッ化ビニリデン（ＰＶＤＦ）などのフッ素樹脂、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）、アクリル樹脂などが挙げられる。   The negative electrode mixture layer usually contains a binder. Examples of the binder related to the negative electrode mixture layer include fluororesins such as polyvinylidene fluoride (PVDF), styrene butadiene rubber (SBR), carboxymethyl cellulose (CMC), and acrylic resins.

前記のアクリル樹脂としては、ブチルアクリレートとアクリル酸との共重合体（ブチルアクリレート由来のユニットとアクリル酸由来のユニットとを分子内に有する共重合体）などが挙げられ、このような樹脂を負極合剤層のバインダに使用することがより好ましい。このようなバインダを使用することで、負極の耐熱性を向上させ得るため、電池の高温貯蔵特性をより高めることができる。   Examples of the acrylic resin include a copolymer of butyl acrylate and acrylic acid (a copolymer having a butyl acrylate-derived unit and an acrylic acid-derived unit in the molecule). It is more preferable to use it for the binder of the mixture layer. By using such a binder, the heat resistance of the negative electrode can be improved, so that the high-temperature storage characteristics of the battery can be further improved.

負極合剤層には導電助剤を含有させてもよい。負極合剤層に係る導電助剤としては、天然黒鉛（鱗片状黒鉛など）、人造黒鉛などの黒鉛（黒鉛質炭素材料）；アセチレンブラック；ケッチェンブラック、チャンネルブラック、ファーネスブラック、ランプブラック、サーマルブラックなどのカ−ボンブラック；炭素繊維（カーボンナノファイバーを含む）；カーボンナノチューブ；などの炭素材料などが挙げられる。   You may make the negative mix layer contain a conductive support agent. Conductive aids for the negative electrode mixture layer include natural graphite (such as flaky graphite), graphite such as artificial graphite (graphitic carbon material); acetylene black; ketjen black, channel black, furnace black, lamp black, thermal Carbon materials such as carbon black such as black; carbon fibers (including carbon nanofibers); carbon nanotubes;

負極は、例えば、負極活物質や必要に応じて使用されるバインダおよび導電助剤などを、水やＮ−メチル−２−ピロリドン（ＮＭＰ）などの有機溶媒といった溶媒に分散させて負極合剤含有組成物を調製し（ただし、バインダは溶媒に溶解していてもよい）、これを集電体の片面または両面に塗布し乾燥して負極合剤層を形成する方法で製造することができる。また、負極合剤層の形成後に、例えば、負極合剤層の密度を調整するために、カレンダ処理などのプレス処理を施してもよい。   The negative electrode contains, for example, a negative electrode active material, a binder used as necessary, and a conductive additive dispersed in a solvent such as water or an organic solvent such as N-methyl-2-pyrrolidone (NMP). The composition can be prepared (however, the binder may be dissolved in a solvent), applied to one or both sides of the current collector and dried to form a negative electrode mixture layer. Further, after the formation of the negative electrode mixture layer, for example, in order to adjust the density of the negative electrode mixture layer, a press treatment such as a calender treatment may be performed.

負極に係る集電体としては、銅製やニッケル製の箔、パンチングメタル、網、エキスパンドメタルなどを用い得るが、通常、銅箔が用いられる。この負極集電体は、高エネルギー密度の電池を得るために負極全体を薄くする場合、厚みの上限は３０μｍであることが好ましく、機械的強度を確保するために厚みの下限は５μｍであることが望ましい。   As the current collector for the negative electrode, a foil made of copper or nickel, a punching metal, a net, an expanded metal, or the like can be used, but a copper foil is usually used. In the negative electrode current collector, when the entire negative electrode is thinned in order to obtain a battery having a high energy density, the upper limit of the thickness is preferably 30 μm, and the lower limit of the thickness is 5 μm to ensure mechanical strength. Is desirable.

負極合剤層においては、負極活物質の含有量（複数種の負極活物質を使用する場合は、それらの合計量。）は９０〜９８質量％であることが好ましく、バインダの含有量は２〜１０質量％であることが好ましい。また、負極合剤層に導電助剤を含有させる場合には、活物質層における導電助剤の含有量は、２〜１０質量％であることが好ましい。更に、負極合剤層の厚み（集電体の両面に負極合剤層を有する場合は、片面あたりの厚み）は、２０〜１００μｍであることが好ましい。   In the negative electrode mixture layer, the content of the negative electrode active material (the total amount thereof when a plurality of types of negative electrode active materials are used) is preferably 90 to 98% by mass, and the binder content is 2 It is preferable that it is -10 mass%. Moreover, when making a negative mix layer contain a conductive support agent, it is preferable that content of the conductive support agent in an active material layer is 2-10 mass%. Furthermore, the thickness of the negative electrode mixture layer (when the negative electrode mixture layer is provided on both sides of the current collector, the thickness per one surface) is preferably 20 to 100 μm.

負極には、電池内の他の部材と電気的に接続するためのリード体を、常法に従って形成してもよい。   A lead body for electrically connecting to other members in the battery may be formed on the negative electrode according to a conventional method.

非水二次電池に係る正極には、例えば、正極活物質、バインダおよび導電助剤などを含有する正極合剤層を、集電体の片面または両面に有する構造のものが使用される。   As the positive electrode related to the nonaqueous secondary battery, for example, one having a structure in which a positive electrode mixture layer containing a positive electrode active material, a binder, a conductive additive and the like is provided on one side or both sides of a current collector is used.

正極合剤層に係る正極活物質については特に制限はなく、従来から知られている非水電解質二次電池の正極活物質として使用されているものと同じもの、すなわち、Ｌｉイオンを吸蔵放出可能な正極活物質を用いることができる。具体的には、例えば、Ｌｉ１＋ｘＭ１Ｏ２（−０．１＜ｘ＜０．１、Ｍ１：Ｃｏ、Ｎｉ、Ｍｎ、Ａｌ、Ｍｇなど）で表される層状構造のリチウム含有遷移金属酸化物、ＬｉＭｎ２Ｏ４やその元素の一部を他元素で置換したスピネル構造のリチウムマンガン酸化物、ＬｉＭ２ＰＯ４（Ｍ２：Ｃｏ、Ｎｉ、Ｍｎ、Ｆｅなど）で表されるオリビン型化合物などのリチウム含有複合酸化物などが挙げられる。前記層状構造のリチウム含有遷移金属酸化物の具体例としては、ＬｉＣｏＯ２やＬｉＮｉ１−ａＣｏａ−ｂＡｌｂＯ２（０．１≦ａ≦０．３、０．０１≦ｂ≦０．２、０＜ａ−ｂ）などのほか、少なくともＮｉ、ＣｏおよびＭｎを含む酸化物（ＬｉＮｉ１／３Ｃｏ１／３Ｍｎ１／３Ｏ２、ＬｉＮｉ５／１２Ｃｏ１／６Ｍｎ５／１２Ｏ２、ＬｉＮｉ１／２Ｃｏ２／１０Ｍｎ３／１０Ｏ２、ＬｉＮｉ３／５Ｃｏ１／５Ｍｎ１／５Ｏ２など）などを例示することができる There is no particular limitation on the positive electrode active material related to the positive electrode mixture layer, and the same as that used as the positive electrode active material of the conventionally known non-aqueous electrolyte secondary battery, that is, Li ion can be occluded and released. Any positive electrode active material can be used. Specifically, for example, a lithium-containing transition metal having a layered structure represented by Li 1 + x M 1 O 2 (−0.1 <x <0.1, M 1 : Co, Ni, Mn, Al, Mg, etc.) Olivine type represented by oxide, LiMn 2 O 4 and spin manganese lithium manganese oxide in which some of its elements are substituted with other elements, LiM 2 PO 4 (M 2 : Co, Ni, Mn, Fe, etc.) Examples thereof include lithium-containing composite oxides such as compounds. Specific examples of the lithium-containing transition metal oxide having a layered structure include LiCoO 2 and LiNi 1-a Co ab Al b O 2 (0.1 ≦ a ≦ 0.3, 0.01 ≦ b ≦ 0. 2, 0 <ab), etc., and at least Ni, Co, and Mn-containing oxides (LiNi 1/3 Co 1/3 Mn 1/3 O 2 , LiNi 5/12 Co 1/6 Mn 5/12 O 2 , LiNi 1/2 Co 2/10 Mn 3/10 O 2 , LiNi 3/5 Co 1/5 Mn 1/5 O 2, etc.).

正極合剤層に係るバインダには、負極合剤層に含有させ得るものとして先に例示した各種のバインダと同じものや、ポリアミドイミド（ＰＡＩ）、ポリイミド（ＰＩ）などが好ましいものとして挙げられる。   As the binder relating to the positive electrode mixture layer, the same ones as those exemplified above as those which can be contained in the negative electrode mixture layer, polyamideimide (PAI), polyimide (PI) and the like are preferable.

正極合剤層に係る導電助剤には、負極合剤層に含有させ得るものとして先に例示したものと同じものが使用できる。   The same thing as what was illustrated previously as what can be contained in a negative mix layer can be used for the conductive support agent which concerns on a positive mix layer.

正極は、例えば、正極活物質、バインダおよび導電助剤を、ＮＭＰなどの有機溶媒などの溶媒に分散させて正極合剤含有組成物を調製し（ただし、バインダは溶媒に溶解していてもよい）、これを集電体の片面または両面に塗布し乾燥して正極合剤層を形成する方法で製造することができる。また、正極合剤層の形成後に、必要に応じてカレンダ処理を施してもよい。   For the positive electrode, for example, a positive electrode active material, a binder, and a conductive additive are dispersed in a solvent such as an organic solvent such as NMP to prepare a positive electrode mixture-containing composition (however, the binder may be dissolved in the solvent). ), Which is applied to one or both sides of the current collector and dried to form a positive electrode mixture layer. Moreover, you may perform a calendar process as needed after formation of a positive mix layer.

正極に係る集電体には、従来から知られている非水二次電池の正極に使用されているものと同様のものが使用でき、例えば、厚みが１０〜３０μｍのアルミニウム箔が好ましい。   As the current collector for the positive electrode, the same one as used for the positive electrode of a conventionally known non-aqueous secondary battery can be used. For example, an aluminum foil having a thickness of 10 to 30 μm is preferable.

正極合剤層の厚み（集電体の両面に正極合剤層が形成されている場合には、片面あたりの厚み。）は、３０〜９５μｍであることが好ましい。また、正極合剤層においては、正極活物質の含有量は８５〜９８質量％であることが好ましく、バインダの含有量は１〜１０質量％であることが好ましく、導電助剤の含有量は１〜１０質量％であることが好ましい。   The thickness of the positive electrode mixture layer (when the positive electrode mixture layer is formed on both sides of the current collector, the thickness per side) is preferably 30 to 95 μm. In the positive electrode mixture layer, the content of the positive electrode active material is preferably 85 to 98% by mass, the content of the binder is preferably 1 to 10% by mass, and the content of the conductive auxiliary agent is It is preferable that it is 1-10 mass%.

正極には、電池内の他の部材と電気的に接続するためのリード体を、常法に従って形成してもよい。   A lead body for electrical connection with other members in the battery may be formed on the positive electrode according to a conventional method.

非水二次電池において、前記の負極と前記の正極とは、例えば、セパレータを介して重ね合わせた積層体（積層電極体）や、この積層体を更に渦巻状に巻回した巻回体（巻回電極体）の形態で使用される。   In the non-aqueous secondary battery, the negative electrode and the positive electrode include, for example, a laminated body (laminated electrode body) stacked with a separator interposed therebetween, or a wound body obtained by further winding this laminated body in a spiral shape ( Used in the form of a wound electrode body).

セパレータには、８０℃以上（より好ましくは１００℃以上）１７０℃以下（より好ましくは１５０℃以下）において、その孔が閉塞する性質（すなわち、シャットダウン機能）を有していることが好ましく、通常の非水二次電池などで使用されているセパレータ、例えば、ポリエチレン（ＰＥ）やポリプロピレン（ＰＰ）などのポリオレフィン製の微多孔膜を用いることができる。セパレータを構成する微多孔膜は、例えば、ＰＥのみを使用したものやＰＰのみを使用したものであってもよく、また、ＰＥ製の微多孔膜とＰＰ製の微多孔膜との積層体であってもよい。また、耐熱性の優れている（分解温度２００℃以上）セルロースやポリイミド製の不織布を用いてもよい。   The separator preferably has a property (that is, a shutdown function) that closes the pores at 80 ° C. or higher (more preferably 100 ° C. or higher) and 170 ° C. or lower (more preferably 150 ° C. or lower). Separator used in non-aqueous secondary batteries, for example, a microporous membrane made of polyolefin such as polyethylene (PE) or polypropylene (PP) can be used. The microporous film constituting the separator may be, for example, one using only PE or one using PP, or a laminate of a PE microporous film and a PP microporous film. There may be. Moreover, you may use the nonwoven fabric made from a cellulose or a polyimide excellent in heat resistance (decomposition temperature 200 degreeC or more).

非水二次電池に係る非水電解液には、リチウム塩および有機溶媒を含有し、このリチウム塩が有機溶媒に溶解した溶液が使用される。   As the non-aqueous electrolyte solution for the non-aqueous secondary battery, a solution containing a lithium salt and an organic solvent and dissolving the lithium salt in the organic solvent is used.

負極合剤層の表面において、ホウ素、炭素、酸素およびフッ素を含有する前記の粒子状堆積物を形成するには、α位に置換基を有するラクトン類を有機溶媒として含有し、ＬｉＢＦ４をリチウム塩として含有する非水電解液を使用すればよい。 In order to form the particulate deposit containing boron, carbon, oxygen and fluorine on the surface of the negative electrode mixture layer, a lactone having a substituent at the α-position is contained as an organic solvent, and LiBF 4 is added to lithium. What is necessary is just to use the nonaqueous electrolyte solution contained as a salt.

α位に置換基を有するラクトン類は１５０℃以上の高い沸点を有しているため、電池が高温環境下に置かれても揮発し難く、非水電解液の組成の変動や外装体の膨れによる電池特性の低下を抑制できる。また、ＬｉＢＦ４も耐熱性が高いリチウム塩である。よって、前記の非水電解液を使用することで、負極合剤層の表面に耐熱性に優れたＳＥＩ皮膜が形成されることのみならず、これらの理由によっても、電池の高温貯蔵特性が向上する。 Since the lactone having a substituent at the α-position has a high boiling point of 150 ° C. or higher, it is difficult to volatilize even when the battery is placed in a high temperature environment, and the composition of the non-aqueous electrolyte changes and the outer body swells. It is possible to suppress a decrease in battery characteristics due to. LiBF 4 is also a lithium salt with high heat resistance. Therefore, by using the non-aqueous electrolyte, not only the SEI film having excellent heat resistance is formed on the surface of the negative electrode mixture layer, but also the high temperature storage characteristics of the battery are improved for these reasons. To do.

なお、α位に置換基を有するラクトン類以外にも、１５０℃以上の沸点を有する高沸点溶媒は知られているが、一般に高沸点溶媒はポリオレフィン製のセパレータなどの非水二次電池に通常使用されているセパレータへの浸透性が低いことから、非水電解液のセパレータへの浸透性を高めるために別の溶媒（一般に沸点が低い）を併用する必要がある。これに対し、α位に置換基を有するラクトン類は前記のような非水二次電池に通常使用されているセパレータへの浸透性が良好であるため、これを使用した非水電解液を用いることで、例えば電池の負荷特性を損なうことなく、耐熱性を高めることができる。   In addition to lactones having a substituent at the α-position, high-boiling solvents having a boiling point of 150 ° C. or higher are known. Generally, high-boiling solvents are generally used for non-aqueous secondary batteries such as polyolefin separators. Since the permeability to the separator used is low, it is necessary to use another solvent (generally having a low boiling point) in order to increase the permeability of the non-aqueous electrolyte into the separator. On the other hand, since lactones having a substituent at the α-position have good permeability to separators usually used in non-aqueous secondary batteries as described above, non-aqueous electrolytes using them are used. Thus, for example, the heat resistance can be enhanced without impairing the load characteristics of the battery.

α位に置換基を有するラクトン類は、例えば５員環のもの（環を構成する炭素数が４つのもの）が好ましい。また、前記ラクトン類のα位の置換基は、１つであってもよく、２つであってもよい。   The lactone having a substituent at the α-position is preferably, for example, a 5-membered ring (having 4 carbon atoms constituting the ring). In addition, the α-position substituent of the lactone may be one or two.

前記置換基としては、炭化水素基、ハロゲン基（フルオロ基、クロロ基、ブロモ基、ヨード基）などが挙げられる。炭化水素基としては、アルキル基、アリール基などが好ましく、その炭素数は１以上１５以下（より好ましくは６以下）であることが好ましい。前記置換基が炭化水素基の場合、メチル基、エチル基、プロピル基、ブチル基、フェニル基などが更に好ましい。   Examples of the substituent include a hydrocarbon group and a halogen group (fluoro group, chloro group, bromo group, iodo group) and the like. As a hydrocarbon group, an alkyl group, an aryl group, etc. are preferable, and it is preferable that the carbon number is 1 or more and 15 or less (more preferably 6 or less). When the substituent is a hydrocarbon group, a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, and the like are more preferable.

α位に置換基を有するラクトン類の具体例としては、α−メチル−γ−ブチロラクトン、α−エチル−γ−ブチロラクトン、α−プロピル−γ−ブチロラクトン、α−ブチル−γ−ブチロラクトン、α−フェニル−γ−ブチロラクトン、α−フルオロ−γ−ブチロラクトン、α−クロロ−γ−ブチロラクトン、α−ブロモ−γ−ブチロラクトン、α−ヨード−γ−ブチロラクトン、α，α−ジメチル−γ−ブチロラクトン、α，α−ジエチル−γ−ブチロラクトン、α，α−ジフェニル−γ−ブチロラクトン、α−エチル−α−メチル−γ−ブチロラクトン、α−メチル−α−フェニル−γ−ブチロラクトン、α，α−ジフルオロ−γ−ブチロラクトン、α，α−ジクロロ−γ−ブチロラクトン、α，α−ジブロモ−γ−ブチロラクトン、α，α−ジヨード−γ−ブチロラクトンなどが挙げられ、これらのうちの１種のみを用いてもよく、２種以上を併用してもよい。   Specific examples of lactones having a substituent at the α-position include α-methyl-γ-butyrolactone, α-ethyl-γ-butyrolactone, α-propyl-γ-butyrolactone, α-butyl-γ-butyrolactone, α-phenyl. -Γ-butyrolactone, α-fluoro-γ-butyrolactone, α-chloro-γ-butyrolactone, α-bromo-γ-butyrolactone, α-iodo-γ-butyrolactone, α, α-dimethyl-γ-butyrolactone, α, α -Diethyl-γ-butyrolactone, α, α-diphenyl-γ-butyrolactone, α-ethyl-α-methyl-γ-butyrolactone, α-methyl-α-phenyl-γ-butyrolactone, α, α-difluoro-γ-butyrolactone , Α, α-dichloro-γ-butyrolactone, α, α-dibromo-γ-butyrolactone, α, α-diiodo-γ-butyrolac Emissions, and the like, may be used only one of these may be used in combination of two or more.

非水電解液の有機溶媒には、α位に置換基を有するラクトン類のみを用いてもよいが、他の有機溶媒を共に使用する場合には、１５０℃以上の沸点を有する高沸点溶媒（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、スルホラン、トリメチルホスフェート、トリエチルホスフェートなど）を使用することが好ましく、鎖状カーボネート（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など）など沸点が１５０℃未満である溶媒の割合は、例えば３０質量％以下のように少なくすることが好ましい。   As the organic solvent of the non-aqueous electrolyte, only lactones having a substituent at the α-position may be used. However, when other organic solvents are used together, a high-boiling solvent having a boiling point of 150 ° C. or higher ( It is preferable to use ethylene carbonate, propylene carbonate, γ-butyrolactone, sulfolane, trimethyl phosphate, triethyl phosphate, etc.), and solvents having a boiling point of less than 150 ° C., such as chain carbonates (dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, etc.) It is preferable to reduce the ratio of, for example, 30% by mass or less.

有機溶媒にα位に置換基を有するラクトン類の、非水電解液における全有機溶媒中の割合は、３０〜１００質量％であることが好ましい。   The proportion of the lactone having a substituent at the α-position in the organic solvent in the total organic solvent in the non-aqueous electrolyte is preferably 30 to 100% by mass.

また、非水電解液のリチウム塩には、ＬｉＢＦ４のみを用いてもよいが、ＬｉＢＦ４とともに他のリチウム塩を使用してもよい。ＬｉＢＦ４とともに用い得る他のリチウム塩としては、ＬｉＣｌＯ４、ＬｉＡｓＦ６、ＬｉＳｂＦ６などの無機リチウム塩；ＬｉＣＦ３ＳＯ３、ＬｉＣＦ３ＣＯ２、Ｌｉ２Ｃ２Ｆ４（ＳＯ３）２、ＬｉＣ（ＣＦ３ＳＯ２）３、ＬｉＣｎＦ２ｎ＋１ＳＯ３（ｎ≧２）、ＬｉＮ（ＦＳＯ２）２〔ＬｉＦＳＩ〕、ＬｉＮ（ＣＦ３ＳＯ２）２〔ＬｉＴＦＳＩ〕、ＬｉＮ（Ｃ２Ｆ５ＳＯ２）２、リチウムビスオキサレートボレート（ＬｉＢＯＢ）などの有機リチウム塩；が挙げられる。 Further, only LiBF 4 may be used as the lithium salt of the non-aqueous electrolyte, but other lithium salts may be used together with LiBF 4 . Other lithium salts that can be used with LiBF 4 include inorganic lithium salts such as LiClO 4 , LiAsF 6 , LiSbF 6 ; LiCF 3 SO 3 , LiCF 3 CO 2 , Li 2 C 2 F 4 (SO 3 ) 2 , LiC ( CF 3 SO 2 ) 3 , LiC n F 2n + 1 SO 3 (n ≧ 2), LiN (FSO 2 ) 2 [LiFSI], LiN (CF 3 SO 2 ) 2 [LiTFSI], LiN (C 2 F 5 SO 2 ) 2 , organolithium salts such as lithium bisoxalate borate (LiBOB).

特に、非水二次電池には、リチウム塩として、ＬｉＢＦ４とともにＬｉＢＯＢを含有する非水電解液を使用することがより好ましい。この場合には、負極合剤層の表面に形成される前記の粒子状堆積物において、形成されるＳＥＩ皮膜の性状が良好なものとなって耐熱性がより向上する。 In particular, in a non-aqueous secondary battery, it is more preferable to use a non-aqueous electrolyte containing LiBOB together with LiBF 4 as a lithium salt. In this case, in the particulate deposit formed on the surface of the negative electrode mixture layer, the properties of the SEI film formed are favorable, and the heat resistance is further improved.

電池に使用する非水電解液におけるリチウム塩の濃度（リチウム塩を複数種使用する場合には、それらの合計濃度）は、０．６ｍｏｌ／Ｌ以上であることが好ましく、０．９ｍｏｌ／Ｌ以上であることがより好ましく、また、１．８ｍｏｌ／Ｌ以下であることが好ましく、１．６ｍｏｌ／Ｌ以下であることがより好ましい。   The concentration of the lithium salt in the non-aqueous electrolyte used in the battery (when multiple types of lithium salts are used, the total concentration thereof) is preferably 0.6 mol / L or more, and 0.9 mol / L or more More preferably, it is preferably 1.8 mol / L or less, and more preferably 1.6 mol / L or less.

また、電池に使用する非水電解液におけるＬｉＢＦ４の濃度は、負極合剤層の表面において、前記の粒子状堆積物を形成し、かつ前記ピークの強度比Ｉｃ／（Ｉａ＋Ｉｂ）を前記の値に調整することを容易にする観点から、０．３ｍｏｌ／Ｌ以上であることが好ましく、０．６ｍｏｌ／Ｌ以上であることがより好ましい。なお、非水電解液のリチウム塩には、ＬｉＢＦ４のみを用いてもよいことから、電池に使用する非水電解液におけるＬｉＢＦ４の濃度は、先に記載したリチウム塩濃度の好適上限値を満たす範囲で設定すればよい。 The concentration of LiBF 4 in the non-aqueous electrolyte used for the battery is such that the particulate deposit is formed on the surface of the negative electrode mixture layer and the peak intensity ratio Ic / (Ia + Ib) is the above value. From the viewpoint of facilitating the adjustment, it is preferably 0.3 mol / L or more, and more preferably 0.6 mol / L or more. In addition, since only LiBF 4 may be used for the lithium salt of the non-aqueous electrolyte, the concentration of LiBF 4 in the non-aqueous electrolyte used for the battery is the preferred upper limit of the lithium salt concentration described above. What is necessary is just to set in the range to satisfy.

更に、リチウム塩にＬｉＢＦ４とＬｉＢＯＢとを併用する場合には、ＬｉＢＯＢの使用による前記の効果を良好に確保する観点から、電池に使用する非水電解液が含有するＬｉＢＦ４とＬｉＢＯＢとの合計を１００ｍｏｌ％としたときに、ＬｉＢＯＢの割合は、１ｍｏｌ％以上であることが好ましく、５ｍｏｌ％以上であることがより好ましい（すなわち、非水電解液が含有するＬｉＢＦ４とＬｉＢＯＢとの合計を１００ｍｏｌ％としたときに、ＬｉＢＦ４の割合は、９９ｍｏｌ％以下であることが好ましく、９５ｍｏｌ％以下であることがより好ましい）。なお、ＬｉＢＯＢは非水電解液溶媒への溶解性が比較的低いため、電池に使用する非水電解液が含有するＬｉＢＦ４とＬｉＢＯＢとの合計を１００ｍｏｌ％としたときに、ＬｉＢＯＢの割合は、１８ｍｏｌ％以下であることが好ましく、１５ｍｏｌ％以下であることがより好ましい（すなわち、非水電解液が含有するＬｉＢＦ４とＬｉＢＯＢとの合計を１００ｍｏｌ％としたときに、ＬｉＢＦ４の割合は、８２ｍｏｌ％以上であることが好ましく、８５ｍｏｌ％以上であることがより好ましい）。 Furthermore, when LiBF 4 and LiBOB are used in combination with the lithium salt, the total of LiBF 4 and LiBOB contained in the non-aqueous electrolyte used in the battery from the viewpoint of ensuring the above-described effects due to the use of LiBOB. the when the 100 mol%, the proportion of LiBOB is, 100 mol preferably at least 1 mol%, more preferably at least 5 mol% (i.e., the sum of LiBF 4 and LiBOB to the nonaqueous electrolyte solution contains %, The ratio of LiBF 4 is preferably 99 mol% or less, and more preferably 95 mol% or less). Since LiBOB has relatively low solubility in a non-aqueous electrolyte solvent, when the total amount of LiBF 4 and LiBOB contained in the non-aqueous electrolyte used in the battery is 100 mol%, the ratio of LiBOB is: is preferably not more than 18 mol%, more preferably not more than 15 mol% (i.e., the sum of LiBF 4 and LiBOB to the nonaqueous electrolyte solution contains when a 100 mol%, the proportion of LiBF 4 is, 82 mol % Or more, and more preferably 85 mol% or more).

また、非水電解液には、電池の安全性や充放電サイクル性を向上させたり、高温貯蔵特性を更に向上させたりする目的で、ビニレンカーボネート（ＶＣ）、４−フルオロ−１，３−ジオキソラン−２−オン（ＦＥＣ）などのハロゲン置換された環状カーボネート、トリエチルホスホノアセテート（ＴＥＰＡ）などのホスホノアセテート類、ジフェニルジスルフィド、シクロヘキシルベンゼン、ビフェニル、フルオロベンゼン、ｔ−ブチルベンゼン、プロパンスルトンなどの添加剤を適宜加えることもできる。   Non-aqueous electrolytes include vinylene carbonate (VC) and 4-fluoro-1,3-dioxolane for the purpose of improving battery safety and charge / discharge cycleability and further improving high-temperature storage characteristics. Such as halogenated cyclic carbonates such as 2-one (FEC), phosphonoacetates such as triethylphosphonoacetate (TEPA), diphenyl disulfide, cyclohexylbenzene, biphenyl, fluorobenzene, t-butylbenzene, propane sultone, etc. Additives can also be added as appropriate.

なかでも、ＶＣを含有する非水電解液を使用することがより好ましく、この場合にも、ＬｉＢＯＢを含有する場合と同様に、負極合剤層の表面に形成されるＳＥＩ皮膜の耐熱性がより良好となり、電池の高温貯蔵特性が更に向上する。   In particular, it is more preferable to use a non-aqueous electrolyte containing VC. In this case, as in the case of containing LiBOB, the heat resistance of the SEI film formed on the surface of the negative electrode mixture layer is higher. As a result, the high-temperature storage characteristics of the battery are further improved.

ＶＣを含有する非水電解液を使用する場合、電池に使用する非水電解液におけるＶＣの含有量は、その使用による前記の効果をより良好に確保する観点から、１．０質量％以上であることが好ましく、２．０質量％以上であることがより好ましい。ただし、非水電解液中のＶＣの量が多すぎると、負極合剤層の表面に形成されるＳＥＩ皮膜が厚くなりすぎて、電池の内部抵抗の増大を引き起こす虞があることから、これを抑制するために、電池に使用する非水電解液におけるＶＣの含有量は、１０質量％以下であることが好ましく、７．５質量％以下であることがより好ましい。   When using a non-aqueous electrolyte containing VC, the content of VC in the non-aqueous electrolyte used for the battery is 1.0% by mass or more from the viewpoint of better securing the above-described effect due to its use. It is preferable that it is 2.0% by mass or more. However, if the amount of VC in the non-aqueous electrolyte is too large, the SEI film formed on the surface of the negative electrode mixture layer becomes too thick, which may increase the internal resistance of the battery. In order to suppress it, the content of VC in the nonaqueous electrolytic solution used in the battery is preferably 10% by mass or less, and more preferably 7.5% by mass or less.

更に、非水電解液は、ポリマーなどの公知のゲル化剤を加えてゲル状（ゲル状電解質）として用いてもよい。   Furthermore, the non-aqueous electrolyte may be used in the form of a gel (gel electrolyte) by adding a known gelling agent such as a polymer.

非水二次電池の形態としては、スチール缶やアルミニウム缶などを外装缶として使用した筒形（角筒形や円筒形など）やコイン形などが挙げられる。また、金属を蒸着したラミネートフィルムを外装体としたソフトパッケージ電池とすることもできる。   Examples of the form of the non-aqueous secondary battery include a cylindrical shape (such as a rectangular tube shape or a cylindrical shape) using a steel can, an aluminum can, or the like as an outer can, or a coin shape. Moreover, it can also be set as the soft package battery which used the laminated film which vapor-deposited the metal as an exterior body.

本発明の非水二次電池の一例を模式的の表す縦断面図を図１に示す。図１に示す非水二次電池１はコイン形（ボタン形を含む）の形態を有するものである。この非水二次電池１においては、複数の正極５および複数の負極６Ａ、６Ｂを、セパレータ７を介して、それらの平面が電池の扁平面に略平行（平行を含む）となるように積層した積層電極体と、非水電解液（図示しない）とが、外装缶２、封口板３および絶縁ガスケット４により形成される空間（密閉空間）内に収容されている。封口板３は、外装缶２の開口部に絶縁ガスケット４を介して嵌合しており、外装缶２の開口端部が内方に締め付けられ、これにより絶縁ガスケット４が封口板３に当接することで、外装缶２の開口部が封口されて電池内部が密閉構造となっている。外装缶２および封口板３は、ステンレス鋼などの金属製であり、絶縁ガスケット４は、ＰＰなどの絶縁性を有する樹脂製である。   FIG. 1 is a longitudinal sectional view schematically showing an example of the nonaqueous secondary battery of the present invention. A non-aqueous secondary battery 1 shown in FIG. 1 has a coin shape (including a button shape). In this non-aqueous secondary battery 1, a plurality of positive electrodes 5 and a plurality of negative electrodes 6A and 6B are laminated via separators 7 so that their planes are substantially parallel (including parallel) to the flat surface of the battery. The laminated electrode body and the non-aqueous electrolyte (not shown) are accommodated in a space (sealed space) formed by the outer can 2, the sealing plate 3, and the insulating gasket 4. The sealing plate 3 is fitted to the opening of the outer can 2 via an insulating gasket 4, and the opening end of the outer can 2 is tightened inward, whereby the insulating gasket 4 contacts the sealing plate 3. Thus, the opening of the outer can 2 is sealed, and the inside of the battery has a sealed structure. The outer can 2 and the sealing plate 3 are made of a metal such as stainless steel, and the insulating gasket 4 is made of an insulating resin such as PP.

図１の電池では、外装缶２が正極端子を兼ね、封口板３が負極端子を兼ねているが、本発明の電池においては、例えば電極体の構成に応じて、外装缶が負極端子を兼ね、封口板が正極端子を兼ねていてもよい。   In the battery of FIG. 1, the outer can 2 also serves as the positive electrode terminal, and the sealing plate 3 also serves as the negative electrode terminal. However, in the battery of the present invention, the outer can also serves as the negative electrode terminal, for example, depending on the configuration of the electrode body. The sealing plate may also serve as the positive electrode terminal.

非水二次電池１が有する積層電極体では、負極６Ａ、６Ｂと正極５とが、セパレータ７を介して交互に積層されている。積層電極体の上下両端に配されている負極６Ｂは、負極集電体６２の片面に負極合剤層６１を有しており、その他の箇所に配されている負極６Ａは、負極集電体６２の両面に負極合剤層６１を有している。また、正極５も、正極集電体５２の両面に正極合剤層５１を有している。   In the laminated electrode body included in the nonaqueous secondary battery 1, the negative electrodes 6 </ b> A and 6 </ b> B and the positive electrode 5 are alternately laminated via the separators 7. The negative electrode 6B disposed on the upper and lower ends of the laminated electrode body has the negative electrode mixture layer 61 on one surface of the negative electrode current collector 62, and the negative electrode 6A disposed on the other part is composed of the negative electrode current collector. The negative electrode mixture layer 61 is provided on both surfaces of 62. The positive electrode 5 also has a positive electrode mixture layer 51 on both surfaces of the positive electrode current collector 52.

積層電極体を構成する全ての正極５からは正極タブ部５ｂが引き出されており、全ての正極タブ部５ｂは、溶接などにより一体化した上で外装缶２の内面に溶接されるなどして電気的に接続している。   The positive electrode tab portions 5b are drawn from all the positive electrodes 5 constituting the laminated electrode body, and all the positive electrode tab portions 5b are integrated by welding or the like and then welded to the inner surface of the outer can 2. Electrically connected.

また、積層電極体を構成する全ての負極６Ａ、６Ｂからは負極タブ部６ｂが引き出されており、全ての負極タブ部６ｂは、溶接などにより一体化している。そして、図中上側の負極６Ｂの負極集電体６２の露出面が、封口板３の内面と接することで、全ての負極６Ａ、６Ｂが、封口板３と電気的に接続している。   Further, negative electrode tab portions 6b are drawn out from all the negative electrodes 6A and 6B constituting the laminated electrode body, and all the negative electrode tab portions 6b are integrated by welding or the like. The exposed surface of the negative electrode current collector 62 of the upper negative electrode 6B in the drawing is in contact with the inner surface of the sealing plate 3, so that all the negative electrodes 6A and 6B are electrically connected to the sealing plate 3.

図中下側の負極６Ｂの負極集電体６２の露出面と、外装缶２の内面との間には、ポリエチレンテレフタレート（ＰＥＴ）やポリイミドなどで形成されたテープなどからなる絶縁シール８が配されている。   Between the exposed surface of the negative electrode current collector 62 of the lower negative electrode 6B in the drawing and the inner surface of the outer can 2 is an insulating seal 8 made of tape formed of polyethylene terephthalate (PET) or polyimide. Has been.

なお、図１は、本発明の非水二次電池の一例を模式的に表すものであって、本発明の非水二次電池は、前記の通り、図１に示されるコイン形のものに限定される訳ではなく、また、非水二次電池が有する電極体の構成および構造も、図１に示されるものに限定される訳ではない。   FIG. 1 schematically shows an example of the non-aqueous secondary battery of the present invention. As described above, the non-aqueous secondary battery of the present invention is the coin-shaped one shown in FIG. The configuration and structure of the electrode body included in the nonaqueous secondary battery are not limited to those shown in FIG.

なお、非水二次電池の製造に際しては、通常、正極および負極を含む電極体、並びに非水電解液を外装体に収容し、その外装体の封止前または封止後に予備充電やエージングを行う活性化処理（化成処理）が施されるが、この活性化処理によって非水電解液中の成分が反応し、負極合剤層の表面において、前記の粒子状堆積物が形成される（すなわち、ＳＥＩ皮膜が形成される）。また、製品となった電池において充放電を行うことによっても、負極合剤層の表面において、前記の粒子状堆積物が形成される。   When manufacturing a non-aqueous secondary battery, normally, an electrode body including a positive electrode and a negative electrode, and a non-aqueous electrolyte solution are accommodated in an exterior body, and pre-charging or aging is performed before or after the exterior body is sealed. The activation treatment (chemical conversion treatment) to be performed is performed. By this activation treatment, the components in the non-aqueous electrolyte react and the particulate deposit is formed on the surface of the negative electrode mixture layer (that is, , SEI film is formed). Moreover, the particulate deposits are also formed on the surface of the negative electrode mixture layer by charging / discharging the battery as a product.

本発明の非水二次電池は、高温貯蔵特性に優れていることから、前記特性を生かして車載用や産業用の蓄電池などに好適に使用できるほか、従来から知られているリチウムイオン二次電池などの非水二次電池が適用されている用途と同じ用途にも使用することができる。   Since the non-aqueous secondary battery of the present invention is excellent in high-temperature storage characteristics, it can be suitably used for in-vehicle or industrial storage batteries by taking advantage of the above characteristics, as well as conventionally known lithium ion secondary batteries. It can also be used for the same applications as non-aqueous secondary batteries such as batteries.

以下、実施例に基づいて本発明を詳細に述べる。ただし、下記実施例は、本発明を制限するものではない。   Hereinafter, the present invention will be described in detail based on examples. However, the following examples do not limit the present invention.

実施例１
＜正極の作製＞
正極活物質としてＬｉＣｏＯ２を、導電助剤としてカーボンブラックを、バインダとしてＰＶＤＦを、それぞれ用いて正極を作製した。まず、ＬｉＣｏＯ２：９３質量部とカーボンブラック：３質量部とを混合し、得られた混合物とＰＶＤＦ：４質量部を予めＮＭＰに溶解させておいたバインダ溶液とを混合して正極合剤含有ペーストを調製した。得られた正極合剤含有ペーストを厚さ１５μｍのアルミニウム箔からなる正極集電体の両面にアプリケータにより塗布した。なお、正極合剤含有ペーストの塗布に際しては、塗布部と未塗布部とが５ｃｍおきに連続するように、かつ表面で塗布部とした箇所は、裏面でも塗布部となるようにした。続いて、塗布した正極合剤含有ペーストを乾燥して正極合剤層を形成し、その後、ロールプレスし、所定の大きさに切断して、帯状の正極シートを得た。なお、この正極シートは、幅を４０ｍｍとし、正極合剤層形成部の厚みが１４０μｍとなるようにした。 Example 1
<Preparation of positive electrode>
A positive electrode was prepared using LiCoO 2 as a positive electrode active material, carbon black as a conductive additive, and PVDF as a binder. First, LiCoO 2 : 93 parts by mass and carbon black: 3 parts by mass were mixed, and the resulting mixture was mixed with a binder solution in which 4 parts by mass of PVDF was previously dissolved in NMP to contain a positive electrode mixture. A paste was prepared. The obtained positive electrode mixture-containing paste was applied to both surfaces of a positive electrode current collector made of an aluminum foil having a thickness of 15 μm by an applicator. When applying the positive electrode mixture-containing paste, the application part and the non-application part were continuously arranged every 5 cm, and the part that was the application part on the front surface was also the application part on the back surface. Subsequently, the applied positive electrode mixture-containing paste was dried to form a positive electrode mixture layer, and then roll-pressed and cut into a predetermined size to obtain a belt-like positive electrode sheet. The positive electrode sheet had a width of 40 mm, and the positive electrode mixture layer forming portion had a thickness of 140 μm.

前記の帯状の正極シートを、正極合剤層形成部が本体部（円弧の部分の直径１５．１ｍｍ）となり、正極合剤層未形成部が集電タブ部（幅３．５ｍｍ）となるように打ち抜いて、図２に示す形状の正極を得た。図２は、打ち抜き後の前記正極を模式的に表す平面図である。正極５は、集電体の両面に正極合剤層５１を形成している本体部５ａと、本体部５ａから突出した幅狭の正極タブ部（集電タブ部）５ｂとを有している。   In the belt-like positive electrode sheet, the positive electrode mixture layer forming portion becomes the main body portion (arc portion diameter 15.1 mm), and the positive electrode mixture layer non-formed portion is the current collecting tab portion (width 3.5 mm). The positive electrode having the shape shown in FIG. 2 was obtained. FIG. 2 is a plan view schematically showing the positive electrode after punching. The positive electrode 5 has a main body part 5a in which the positive electrode mixture layer 51 is formed on both surfaces of the current collector, and a narrow positive electrode tab part (current collection tab part) 5b protruding from the main body part 5a. .

＜負極の作製＞
負極活物質として黒鉛を、バインダとしてＰＶＤＦを、それぞれ用いて負極を作製した。前記黒鉛：９４質量部とＰＶＤＦ：６質量部と予めＮＭＰに溶解させておいたバインダ溶液とを混合して、負極合剤含有ペーストを調製した。得られた負極合剤含有ペーストを厚さ１０μｍの銅箔からなる負極集電体の片面または両面にアプリケータにより塗布した。なお、負極合剤含有ペーストの塗布に際しては、塗布部と未塗布部とが５ｃｍおきに連続するように、かつ集電体の両面に塗布したものでは、表面で塗布部とした箇所は、裏面でも塗布部となるようにした。続いて、塗布した負極合剤含有ペーストを乾燥して負極合剤層を形成し、その後、ロールプレスし、所定の大きさに切断して、帯状の負極シートを得た。なお、この負極シートは、幅を４０ｍｍとし、負極合剤層形成部の厚みを、集電体の両面に形成したものでは１９０μｍ、集電体の片面に形成したものでは１００μｍとなるようにした。 <Production of negative electrode>
A negative electrode was prepared using graphite as the negative electrode active material and PVDF as the binder. The graphite: 94 parts by mass, PVDF: 6 parts by mass, and a binder solution previously dissolved in NMP were mixed to prepare a negative electrode mixture-containing paste. The obtained negative electrode mixture-containing paste was applied to one or both sides of a negative electrode current collector made of a copper foil having a thickness of 10 μm by an applicator. In addition, when applying the negative electrode mixture-containing paste, when the coated part and the non-coated part are continuously applied every 5 cm and are applied to both sides of the current collector, the place where the coated part is the surface is the back side However, it was made to become an application part. Subsequently, the applied negative electrode mixture-containing paste was dried to form a negative electrode mixture layer, and then roll-pressed and cut into a predetermined size to obtain a strip-shaped negative electrode sheet. The negative electrode sheet had a width of 40 mm, and the thickness of the negative electrode mixture layer forming portion was 190 μm when formed on both sides of the current collector, and 100 μm when formed on one side of the current collector. .

前記の帯状の負極シートを、負極合剤層形成部が本体部（円弧の部分の直径１６．３ｍｍ）となり、負極合剤層未形成部が集電タブ部となるように打ち抜くことにより、図３に示す形状であって、集電体の片面に負極合剤層を有する負極と、集電体の両面に負極合剤層を有する負極とを得た。なお、集電体の片面に負極合剤層を有する負極のうち、外装缶側に配置される負極については、前記の帯状の負極の集電体の露出面に、厚みが１００μｍのＰＥＴフィルムを貼り付けた後に打ち抜いた。   By punching out the belt-like negative electrode sheet so that the negative electrode mixture layer forming portion is the main body portion (arc portion diameter 16.3 mm) and the negative electrode mixture layer non-forming portion is the current collecting tab portion, 3, a negative electrode having a negative electrode mixture layer on one side of the current collector and a negative electrode having a negative electrode mixture layer on both sides of the current collector were obtained. Of the negative electrodes having a negative electrode mixture layer on one side of the current collector, for the negative electrode disposed on the outer can side, a PET film having a thickness of 100 μm is placed on the exposed surface of the current collector of the strip-shaped negative electrode. Punched after pasting.

図３は、打ち抜き後の負極を模式的に表す平面図である。負極６Ａ、６Ｂは、集電体の両面に負極合剤層６１を形成しているか（負極６Ａ）または集電体の片面に負極合剤層６１を形成している（負極６Ｂ）本体部６ａと、本体部６ａから突出した幅狭の負極タブ部（集電タブ部）６ｂとを有している。   FIG. 3 is a plan view schematically showing the negative electrode after punching. In the negative electrodes 6A and 6B, the negative electrode mixture layer 61 is formed on both surfaces of the current collector (negative electrode 6A), or the negative electrode mixture layer 61 is formed on one surface of the current collector (negative electrode 6B). And a narrow negative electrode tab portion (current collecting tab portion) 6b protruding from the main body portion 6a.

＜電池用正極とセパレータとの一体化＞
図４に、本実施例で使用したセパレータを模式的に表した平面図を示す。前記の正極の両面に、図４に示す形状のＰＥ製微多孔膜セパレータ（厚み１６μｍ）を配置し、図４に示す箇所を加熱プレス（温度１７０℃、プレス時間２秒）により溶着し、２枚のセパレータに係る主体部の周縁部の一部および張り出し部の周縁部の一部に接合部を形成して、正極とセパレータとを一体化した。 <Integration of battery positive electrode and separator>
FIG. 4 is a plan view schematically showing the separator used in this example. A PE microporous membrane separator (thickness 16 μm) having the shape shown in FIG. 4 is disposed on both surfaces of the positive electrode, and the portions shown in FIG. 4 are welded by a hot press (temperature 170 ° C., press time 2 seconds). A joining part was formed in a part of a peripheral part of a main part concerning a sheet of separator, and a part of a peripheral part of an overhanging part, and a positive electrode and a separator were unified.

図４では、セパレータ７とともに、正極、負極およびセパレータが積層された積層電極体とした場合を想定して、セパレータ７の下に配置される正極５を点線で示し、それらの更に下側に配置される負極に係る集電タブ部６ｂを一点鎖線で示し、積層電極体に係る各構成要素の位置ずれを抑えるための結束テープ９を二点鎖線で示している。また、図４に示す正極５は、積層電極体において、その両側（両面）が一体化されたセパレータ７を介して負極と対向するものであり、図４では図示していないが、積層電極体とした状態では、セパレータ７の上側（図中手前方向）に負極を配置する。   In FIG. 4, assuming that a laminated electrode body in which a positive electrode, a negative electrode, and a separator are laminated together with the separator 7, the positive electrode 5 arranged below the separator 7 is indicated by a dotted line, and arranged further below them. The current collecting tab portion 6b related to the negative electrode is shown by a one-dot chain line, and the binding tape 9 for suppressing the positional deviation of each component related to the laminated electrode body is shown by a two-dot chain line. Moreover, the positive electrode 5 shown in FIG. 4 faces the negative electrode through a separator 7 in which both sides (both sides) are integrated in the laminated electrode body, and although not shown in FIG. In this state, the negative electrode is disposed on the upper side of the separator 7 (frontward in the figure).

図４に示すセパレータ７は、正極５（図中点線で表示）を介してその下側（図中奥行き方向）に配置される他のセパレータと、その周縁部において互いに溶着した接合部７ｃ（図中、格子模様で表示）を有している。すなわち、セパレータ７と、その下側に配置されたセパレータとは、周縁部で互いに溶着されて袋状となっており、その内部に正極５を収容することで、正極とセパレータとが一体化している。   The separator 7 shown in FIG. 4 is joined to another separator disposed on the lower side (in the depth direction in the figure) via the positive electrode 5 (indicated by a dotted line in the figure), and a joint 7c (FIG. Middle). That is, the separator 7 and the separator disposed below the separator 7 are welded to each other at the peripheral edge to form a bag, and the positive electrode 5 and the separator are integrated by accommodating the positive electrode 5 therein. Yes.

なお、図４に示すセパレータ７は、正極５の本体部５ａ全面を覆う主体部７ａ（すなわち、正極５の本体部５ａよりも平面視での面積が大きな主体部７ａ）と、主体部７ａから突出し、正極５の集電タブ部５ｂの、本体部５ａとの境界部を少なくとも含む部分を覆う張り出し部７ｂとを有している。そして、セパレータ７の主体部７ａの周縁部の少なくとも一部に、正極５の両面に配置された２枚のセパレータ（セパレータ７と、正極５の下側に配置されたセパレータ）同士を互いに溶着した接合部７ｃを設けている。また、主体部７ａの周縁部の一部は、セパレータ同士を溶着せずに非溶着部７ｄ、７ｄとして残している。   4 includes a main body portion 7a covering the entire surface of the main body portion 5a of the positive electrode 5 (that is, a main body portion 7a having a larger area in plan view than the main body portion 5a of the positive electrode 5), and the main body portion 7a. It has a protruding portion 7b that protrudes and covers at least a portion of the current collecting tab portion 5b of the positive electrode 5 that includes a boundary portion with the main body portion 5a. Then, two separators (the separator 7 and the separator disposed below the positive electrode 5) disposed on both surfaces of the positive electrode 5 were welded to at least a part of the peripheral portion of the main body portion 7 a of the separator 7. A joint 7c is provided. Moreover, a part of peripheral part of the main-body part 7a is left as the non-welding parts 7d and 7d, without welding separators.

なお、２枚のセパレータに係る接合部の幅は、主体部、張り出し部とも０．３ｍｍとし、張り出し部の周縁部における主体部からの突出方向の長さは０．５ｍｍとした。また、２枚のセパレータの主体部の外縁のうち、９０％の長さ部分を接合部とした。   Note that the width of the joint portion relating to the two separators was 0.3 mm for both the main portion and the overhang portion, and the length in the protruding direction from the main portion at the peripheral portion of the overhang portion was 0.5 mm. Of the outer edges of the main parts of the two separators, 90% of the length was used as the joint.

＜非水電解液の調製＞
α−メチル−γ−ブチロラクトン（ＭＢＬ）とプロピレンカーボネート（ＰＣ）との質量比が５２：４８の混合溶媒に、電解質であるリチウム塩として、ＬｉＢＦ４とＬｉＢ（Ｃ２Ｏ４）２〔ＬｉＢＯＢ〕とを、それぞれ１．０ｍｏｌ／Ｌおよび０．０３ｍｏｌ／Ｌとなる濃度で溶解し、更に、ビニレンカーボネート（ＶＣ）を５．０質量％添加した非水電解液を作製した。 <Preparation of non-aqueous electrolyte>
LiBF 4 and LiB (C 2 O 4 ) 2 [LiBOB] are used as a lithium salt as an electrolyte in a mixed solvent having a mass ratio of α-methyl-γ-butyrolactone (MBL) and propylene carbonate (PC) of 52:48. Were dissolved at concentrations of 1.0 mol / L and 0.03 mol / L, respectively, and a non-aqueous electrolyte solution containing 5.0% by mass of vinylene carbonate (VC) was prepared.

＜電池の組み立て＞
前記のセパレータと一体化した正極３枚と、集電体の両面に負極合剤層を形成した負極２枚と、集電体の片面に負極合剤層を形成した負極２枚（このうち１枚は、集電体の露出面にＰＥＴフィルムを貼り付けたもの）とを用い、集電体の片面に負極合剤層を形成した負極が最外部の電極になるように、正極と負極とを交互に重ね、全体を結束テープで固定して積層電極体とした。 <Battery assembly>
Three positive electrodes integrated with the separator, two negative electrodes having a negative electrode mixture layer formed on both sides of the current collector, and two negative electrodes having a negative electrode mixture layer formed on one side of the current collector (of which 1 The sheet is made by adhering a PET film to the exposed surface of the current collector), and the positive electrode and the negative electrode are formed so that the negative electrode having the negative electrode mixture layer formed on one surface of the current collector becomes the outermost electrode. Are stacked alternately and fixed with a binding tape to obtain a laminated electrode body.

積層電極体の一方の両側に出ている各正極の集電タブ部と、その反対側に出ている各負極の集電タブ部を、それぞれ纏めて溶接して一体化した後、積層電極体の負極のＰＥＴフィルムが外装缶（正極端子）の内面と対向するようにして、積層電極体を外装缶内に入れ、一体化した各正極の集電タブ部を外装缶の内面に溶接した。   After the current collecting tabs of each positive electrode coming out on one side of the laminated electrode body and the current collecting tabs of each negative electrode coming out on the opposite side are welded together and integrated, the laminated electrode body The laminated electrode body was placed in the outer can so that the negative electrode PET film faced the inner surface of the outer can (positive electrode terminal), and the integrated current collecting tab portion of each positive electrode was welded to the inner surface of the outer can.

次に、封口板（負極端子）に絶縁ガスケットを装着し、前記非水電解液を９０ｍｇ（７０μｌ）注入した後、電極体を収容した外装缶を被せ、周囲をかしめて、直径２０ｍｍ、厚み１．６ｍｍで、セパレータの形態が異なる以外は図１に示すものと同様の構造のコイン形非水二次電池を得た。   Next, an insulating gasket is attached to the sealing plate (negative electrode terminal), 90 mg (70 μl) of the non-aqueous electrolyte solution is injected, and an outer can containing the electrode body is covered, and the periphery is caulked to have a diameter of 20 mm and a thickness of 1 A coin-type non-aqueous secondary battery having a structure similar to that shown in FIG.

なお、前記のコイン非水二次電池は、電流値６ｍＡでの放電で、放電容量が３０ｍＡｈとなるように設計したものである。   The coin non-aqueous secondary battery is designed to have a discharge capacity of 30 mAh when discharged at a current value of 6 mA.

作製した電池に対し、６ｍＡの電流で９０％の充電深度（充電電気量：２７ｍＡｈ）となるまで充電し、更に６０℃の恒温槽中で６時間保持することにより活性化処理を行った。その後、一部の電池を分解して負極を取り出し、負極合剤層の表面のＳＥＭ観察を行った。これにより得られたＳＥＭ写真を図５に示す。図５に示す通り、実施例１の非水二次電池に係る負極の負極合剤層の表面には、粒子状堆積物が形成されており、その平均粒子径は１００ｎｍであった。また、負極合剤層の表面のＸＰＳ分析を行ったところ、１９０〜１９５ｅＶにホウ素に基づくピークが、２８０〜２９２ｅＶに炭素に基づくピークが、５２６〜５３６ｅＶに酸素に基づくピークが、６８２〜６９０ｅＶにフッ素に基づくピークが、それぞれ観察された。更に、ＸＰＳ分析により得られた前記の各ピークのピーク強度から求めたホウ素、炭素、酸素およびフッ素の量は、それぞれ、１．６原子％、２３．４原子％、１７．０原子％および１８．３原子％であり、Ｉｃ／（Ｉａ＋Ｉｂ）の値は０．４５であった。   The manufactured battery was charged with a current of 6 mA until the charging depth reached 90% (charged electricity amount: 27 mAh), and further maintained in a thermostatic bath at 60 ° C. for 6 hours to carry out activation treatment. Then, some batteries were disassembled, the negative electrode was taken out, and SEM observation of the surface of the negative electrode mixture layer was performed. The SEM photograph obtained by this is shown in FIG. As shown in FIG. 5, particulate deposits were formed on the surface of the negative electrode mixture layer of the negative electrode according to the nonaqueous secondary battery of Example 1, and the average particle size was 100 nm. Further, when XPS analysis of the surface of the negative electrode mixture layer was performed, a peak based on boron at 190 to 195 eV, a peak based on carbon at 280 to 292 eV, a peak based on oxygen at 526 to 536 eV, and 682 to 690 eV Each peak based on fluorine was observed. Furthermore, the amounts of boron, carbon, oxygen and fluorine obtained from the peak intensities of the respective peaks obtained by XPS analysis were 1.6 atomic%, 23.4 atomic%, 17.0 atomic% and 18 respectively. .3 atomic%, and the value of Ic / (Ia + Ib) was 0.45.

実施例２
非水電解液の調製において、ＭＢＬとＰＣとの質量比が６８：３２の混合溶媒を用い、ＬｉＢＯＢを添加しなかった以外は、実施例１と同様にしてコイン形非水二次電池を作製し、前記と同様の活性化処理を行った。 Example 2
A coin-type non-aqueous secondary battery was produced in the same manner as in Example 1 except that a mixed solvent having a mass ratio of MBL to PC of 68:32 was used and LiBOB was not added. Then, the same activation treatment as described above was performed.

実施例３
非水電解液の調製において、ＭＢＬとＰＣとの質量比が６８：３２の混合溶媒を用い、ＶＣを添加しなかった以外は実施例１と同様にしてコイン形非水二次電池を作製し、前記と同様の活性化処理を行った。 Example 3
In the preparation of the non-aqueous electrolyte, a coin-type non-aqueous secondary battery was manufactured in the same manner as in Example 1 except that a mixed solvent having a mass ratio of MBL to PC of 68:32 was used and VC was not added. The same activation treatment as described above was performed.

実施例４
非水電解液の調製において、ＭＢＬとＰＣとの質量比が６８：３２の混合溶媒を用いた以外は、実施例１と同様にしてコイン形非水二次電池を作製し、前記と同様の活性化処理を行った。 Example 4
In the preparation of the non-aqueous electrolyte, a coin-type non-aqueous secondary battery was produced in the same manner as in Example 1 except that a mixed solvent having a mass ratio of MBL to PC of 68:32 was used. Activation processing was performed.

実施例５
非水電解液の調製において、ＶＣに代えてプロパンスルトン（ＰＳ）を５．０質量％添加した以外は、実施例３と同様にしてコイン形非水二次電池を作製し、前記と同様の活性化処理を行った。 Example 5
A coin-type non-aqueous secondary battery was prepared in the same manner as in Example 3 except that 5.0% by mass of propane sultone (PS) was added instead of VC in the preparation of the non-aqueous electrolyte. Activation processing was performed.

実施例６
非水電解液の調製において、ＭＢＬとＰＣとの混合溶媒に代えて、ＭＢＬのみを溶媒として用いた以外は、実施例１と同様にしてコイン形非水二次電池を作製し、前記と同様の活性化処理を行った。 Example 6
In the preparation of the non-aqueous electrolyte, a coin-type non-aqueous secondary battery was produced in the same manner as in Example 1 except that only MBL was used as the solvent instead of the mixed solvent of MBL and PC, and the same as described above. The activation treatment was performed.

実施例７
非水電解液の調製において、ＭＢＬとＰＣとエチルメチルカーボネート（ＥＭＣ）との質量比が６９：２２：９の混合溶媒を用いた以外は、実施例１と同様にしてコイン形非水二次電池を作製し、前記と同様の活性化処理を行った。 Example 7
In the preparation of the non-aqueous electrolyte, a coin-type non-aqueous secondary was prepared in the same manner as in Example 1 except that a mixed solvent having a mass ratio of MBL, PC, and ethyl methyl carbonate (EMC) of 69: 22: 9 was used. A battery was prepared and the same activation treatment as described above was performed.

実施例８
セパレータに、セルロース材の不織布を用いた以外は実施例３と同様にしてコイン形非水二次電池を作製し、前記と同様の活性化処理を行った。 Example 8
A coin-type non-aqueous secondary battery was produced in the same manner as in Example 3 except that a cellulose nonwoven fabric was used as the separator, and the same activation treatment as described above was performed.

実施例９
＜正極の作製＞
実施例１で調製した正極合剤含有ペーストを、厚みが１５μｍのアルミニウム箔からなる正極集電体の両面に塗布し、乾燥後、プレス処理を施して正極合剤層を形成し、正極シートを得た。得られた正極シートの正極合剤層の厚みは、集電体の片面あたり６０μｍであった。その後、得られた正極シートを裁断することにより、正極合剤層の形成部分が幅１０５ｍｍ、長さ２００ｍｍであり、更に正極タブとなる正極集電体の露出部を有する正極を得た。 Example 9
<Preparation of positive electrode>
The positive electrode mixture-containing paste prepared in Example 1 was applied to both surfaces of a positive electrode current collector made of an aluminum foil having a thickness of 15 μm, dried, and then subjected to press treatment to form a positive electrode mixture layer. Obtained. The thickness of the positive electrode mixture layer of the obtained positive electrode sheet was 60 μm per one side of the current collector. Thereafter, the obtained positive electrode sheet was cut to obtain a positive electrode having a positive electrode mixture layer forming portion having a width of 105 mm and a length of 200 mm, and further having an exposed portion of a positive electrode current collector serving as a positive electrode tab.

＜負極の作製＞
実施例１で調製した負極合剤含有ペーストを、厚みが１０μｍの銅箔からなる負極集電体の両面に塗布し、乾燥後、プレス処理を施して負極合剤層を形成し、負極シートを得た。得られた負極シートの負極合剤層の厚みは、集電体の片面あたり６０μｍであった。その後、得られた負極シートを裁断することにより、負極合剤層の形成部分が幅１１０ｍｍ、長さ２０５ｍｍであり、更に負極タブとなる負極集電体の露出部を有する負極を得た。 <Production of negative electrode>
The negative electrode mixture-containing paste prepared in Example 1 was applied to both sides of a negative electrode current collector made of a copper foil having a thickness of 10 μm, dried, and then subjected to a press treatment to form a negative electrode mixture layer. Obtained. The thickness of the negative electrode mixture layer of the obtained negative electrode sheet was 60 μm per one side of the current collector. Thereafter, the obtained negative electrode sheet was cut to obtain a negative electrode having a negative electrode mixture layer forming portion having a width of 110 mm and a length of 205 mm, and further having an exposed portion of a negative electrode current collector serving as a negative electrode tab.

＜電池の組み立て＞
前記の正極２０枚と、前記の負極２１枚とを、セパレータ（厚みが２５μｍのポリエチレン製微多孔フィルム）を介して積層し、積層電極体とした。なお、積層電極体の両端は、いずれも負極となるように積層した。次に、前記の積層電極体の各々の正極タブを重ねて正極外部端子（長さ３０ｍｍ、幅２０ｍｍ、厚み０．２ｍｍのアルミニウム板）に超音波溶接し、また、前記の積層電極体の各々の負極タブを重ねて負極外部端子（長さ３０ｍｍ、幅２０ｍｍ、厚み０．２ｍｍの銅板）に超音波溶接した。更に、ポリエステルフィルム／アルミニウムフィルム／変性ポリオレフィンフィルムからなる厚み１５０μｍの三層構造の２枚の金属ラミネートフィルム（矩形で、サイズ１３０ｍｍ×２３０ｍｍ）を用意し、前記変性ポリオレフィンフィルムが内側になるようにして前記積層電極体を間に挟んで重ね、前記正極外部端子および前記負極外部端子の一部が、金属ラミネートフィルムの同一辺から突出するようにして、重ねた金属ラミネートフィルムの３辺を熱シールして封止し、外装体を形成した。これを７０℃で１５時間真空乾燥した後、ラミネートフィルム外装体の封止していない一辺から、実施例４で調製した非水電解液を注入し、減圧状態で前記の一辺を熱シールして、ラミネート形非水二次電池を作製した。なお、ラミネートフィルム外装体の熱シールの幅は、１０ｍｍとした。 <Battery assembly>
20 sheets of the positive electrodes and 21 sheets of the negative electrodes were laminated via a separator (a polyethylene microporous film having a thickness of 25 μm) to obtain a laminated electrode body. In addition, it laminated | stacked so that both ends of a laminated electrode body might become a negative electrode. Next, the respective positive electrode tabs of the multilayer electrode body are overlapped and ultrasonically welded to positive electrode external terminals (aluminum plate having a length of 30 mm, a width of 20 mm, and a thickness of 0.2 mm). The negative electrode tabs were stacked and ultrasonically welded to a negative electrode external terminal (copper plate having a length of 30 mm, a width of 20 mm, and a thickness of 0.2 mm). Furthermore, two metal laminate films (rectangular, size 130 mm × 230 mm) having a thickness of 150 μm and comprising a polyester film / aluminum film / modified polyolefin film are prepared so that the modified polyolefin film is on the inside. The laminated electrode body is overlapped, and the positive electrode external terminal and a part of the negative electrode external terminal protrude from the same side of the metal laminate film, and the three sides of the overlapped metal laminate film are heat-sealed. And sealed to form an outer package. This was vacuum dried at 70 ° C. for 15 hours, and then the non-aqueous electrolyte prepared in Example 4 was injected from the unsealed side of the laminate film outer package, and the one side was heat-sealed in a reduced pressure state. A laminated non-aqueous secondary battery was produced. In addition, the width | variety of the heat seal of a laminate film exterior body was 10 mm.

作製した電池に対し、９０％の充電深度となるまで定電流充電し、更に６０℃の恒温槽中で６時間保持することにより活性化処理を行った。   The produced battery was subjected to an activation treatment by charging at a constant current until the charging depth reached 90%, and further holding in a constant temperature bath at 60 ° C. for 6 hours.

実施例２〜９の非水二次電池についても、実施例１と同様にして、一部の電池を分解して負極を取り出し、負極合剤層の表面のＳＥＭ観察を行った。その結果、負極合剤層の表面に形成されている粒子状堆積物の平均粒子径が、１０〜５００ｎｍの範囲にあることが確認された、また、負極合剤層の表面のＸＰＳ分析を行ったところ、１９０〜１９５ｅＶにホウ素に基づくピークが、２８０〜２９２ｅＶに炭素に基づくピークが、５２６〜５３６ｅＶに酸素に基づくピークが、６８２〜６９０ｅＶにフッ素に基づくピークが、それぞれ観察され、炭素、酸素およびフッ素の各ピークのピーク強度から求めたＩｃ／（Ｉａ＋Ｉｂ）の値は、いずれも０．３以上であった。   For the non-aqueous secondary batteries of Examples 2 to 9, as in Example 1, some of the batteries were disassembled, the negative electrode was taken out, and the surface of the negative electrode mixture layer was observed by SEM. As a result, it was confirmed that the average particle size of the particulate deposit formed on the surface of the negative electrode mixture layer was in the range of 10 to 500 nm, and the XPS analysis of the surface of the negative electrode mixture layer was performed. As a result, a peak based on boron was observed at 190 to 195 eV, a peak based on carbon at 280 to 292 eV, a peak based on oxygen at 526 to 536 eV, and a peak based on fluorine at 682 to 690 eV, respectively. The value of Ic / (Ia + Ib) obtained from the peak intensity of each peak of fluorine and fluorine was 0.3 or more.

比較例１
非水電解液の調製において、ＭＢＬとＰＣとの質量比が５２：４８の混合溶媒を用い、ＬｉＢＯＢおよびＶＣを添加しなかった以外は、実施例１と同様にしてコイン形非水二次電池を作製し、前記と同様の活性化処理を行った。 Comparative Example 1
A coin-type non-aqueous secondary battery was prepared in the same manner as in Example 1 except that a mixed solvent having a mass ratio of MBL to PC of 52:48 was used and LiBOB and VC were not added. The same activation treatment as described above was performed.

活性化処理後の電池の一部を分解して負極を取り出し、負極合剤層の表面のＳＥＭ観察を行ったところ、平均粒子径が５０ｎｍの粒子状堆積物が形成されていた。また、前記負極の負極合剤層の表面のＸＰＳ分析を行ったところ、１９０〜１９５ｅＶにホウ素に基づくピークが、２８０〜２９２ｅＶに炭素に基づくピークが、５２６〜５３６ｅＶに酸素に基づくピークが、６８２〜６９０ｅＶにフッ素に基づくピークがそれぞれ観察され、炭素、酸素およびフッ素の各ピークのピーク強度から求めたＩｃ／（Ｉａ＋Ｉｂ）の値は、０．２８であった。   A part of the battery after the activation treatment was disassembled, the negative electrode was taken out, and SEM observation of the surface of the negative electrode mixture layer was performed. As a result, a particulate deposit having an average particle diameter of 50 nm was formed. Further, when XPS analysis was performed on the surface of the negative electrode mixture layer of the negative electrode, a peak based on boron at 190 to 195 eV, a peak based on carbon at 280 to 292 eV, a peak based on oxygen at 526 to 536 eV, and 682 A peak based on fluorine was observed at ˜690 eV, and the value of Ic / (Ia + Ib) obtained from the peak intensity of each peak of carbon, oxygen and fluorine was 0.28.

比較例２
非水電解液の調製において、ＭＢＬとＰＣとの混合溶媒に代えて、エチレンカーボネート（ＥＣ）とジエチルカーボネート（ＤＥＣ）との質量比が３０：７０の混合溶媒を用いた以外は、実施例２と同様にしてコイン形非水二次電池を作製し、前記と同様の活性化処理を行った。 Comparative Example 2
Example 2 except that a mixed solvent having a mass ratio of ethylene carbonate (EC) and diethyl carbonate (DEC) of 30:70 was used in place of the mixed solvent of MBL and PC in the preparation of the nonaqueous electrolytic solution. In the same manner as above, a coin-type non-aqueous secondary battery was produced, and the same activation treatment as described above was performed.

活性化処理後の電池の一部を分解して負極を取り出し、負極合剤層の表面のＳＥＭ観察を行ったが、平均粒子径が１０ｎｍ以上となる粒子状堆積物は形成されていなかった。   A part of the battery after the activation treatment was disassembled, the negative electrode was taken out, and SEM observation of the surface of the negative electrode mixture layer was performed, but no particulate deposit having an average particle diameter of 10 nm or more was formed.

比較例３
非水電解液の調製において、電解質であるリチウム塩として、ＬｉＢＦ４とに代えて、ＬｉＰＦ６を１．２ｍｏｌ／Ｌとなる濃度で溶解した以外は、比較例１と同様にしてコイン形非水二次電池を作製し、前記と同様の活性化処理を行った。 Comparative Example 3
In the preparation of the non-aqueous electrolyte, a coin-shaped non-aqueous solution was prepared in the same manner as in Comparative Example 1 except that LiPF 6 was dissolved at a concentration of 1.2 mol / L instead of LiBF 4 as the lithium salt as the electrolyte. A secondary battery was prepared and subjected to activation treatment similar to that described above.

活性化処理後の電池の一部を分解して負極を取り出し、負極合剤層の表面のＳＥＭ観察を行ったところ、平均粒子径が５０ｎｍの粒子状堆積物が形成されていた。また、前記負極の負極合剤層の表面のＸＰＳ分析を行ったところ、１９０〜１９５ｅＶにホウ素に基づくピークは観察されなかった。   A part of the battery after the activation treatment was disassembled, the negative electrode was taken out, and SEM observation of the surface of the negative electrode mixture layer was performed. As a result, a particulate deposit having an average particle diameter of 50 nm was formed. Moreover, when the XPS analysis of the surface of the negative mix layer of the said negative electrode was conducted, the peak based on boron was not observed at 190-195 eV.

比較例４
非水電解液の調製において、エチレンカーボネート（ＥＣ）とジエチルカーボネート（ＤＥＣ）との質量比が３０：７０の混合溶媒を用いた以外は、比較例１と同様にしてコイン形非水二次電池を作製し、前記と同様の活性化処理を行った。 Comparative Example 4
A coin-type non-aqueous secondary battery was prepared in the same manner as in Comparative Example 1, except that a mixed solvent having a mass ratio of ethylene carbonate (EC) and diethyl carbonate (DEC) of 30:70 was used in the preparation of the non-aqueous electrolyte. The same activation treatment as described above was performed.

活性化処理後の電池の一部を分解して負極を取り出し、負極合剤層の表面のＳＥＭ観察を行ったが、平均粒子径が１０ｎｍ以上となる粒子状堆積物は形成されていなかった。   A part of the battery after the activation treatment was disassembled, the negative electrode was taken out, and SEM observation of the surface of the negative electrode mixture layer was performed, but no particulate deposit having an average particle diameter of 10 nm or more was formed.

比較例５
非水電解液の調製において、ＶＣを２．０質量％添加した以外は、比較例４と同様にしてコイン形非水二次電池を作製し、前記と同様の活性化処理を行った。 Comparative Example 5
A coin-type non-aqueous secondary battery was produced in the same manner as in Comparative Example 4 except that 2.0% by mass of VC was added in the preparation of the non-aqueous electrolyte, and the same activation treatment as described above was performed.

活性化処理後の電池の一部を分解して負極を取り出し、負極合剤層の表面のＳＥＭ観察を行った。これにより得られたＳＥＭ写真を図６に示す。図６に示す通り、比較例５に係る負極の負極合剤層の表面には、平均粒子径が１０ｎｍ以上となる粒子状堆積物は形成されていなかった。なお、前記負極の負極合剤層の表面のＸＰＳ分析を行ったところ、１９０〜１９５ｅＶにホウ素に基づくピークは観察されなかった。また、ＸＰＳ分析により得られた炭素、酸素およびフッ素の各ピークのピーク強度から求めたＩｃ／（Ｉａ＋Ｉｂ）の値は０．１７であった。   A part of the battery after the activation treatment was disassembled, the negative electrode was taken out, and SEM observation of the surface of the negative electrode mixture layer was performed. The SEM photograph obtained by this is shown in FIG. As shown in FIG. 6, no particulate deposit having an average particle diameter of 10 nm or more was formed on the surface of the negative electrode mixture layer of the negative electrode according to Comparative Example 5. In addition, when XPS analysis of the surface of the negative electrode mixture layer of the negative electrode was performed, no peak based on boron was observed at 190 to 195 eV. The value of Ic / (Ia + Ib) obtained from the peak intensity of each peak of carbon, oxygen and fluorine obtained by XPS analysis was 0.17.

実施例および比較例の非水二次電池について、以下の各評価を行った。   The following evaluation was performed about the non-aqueous secondary battery of the Example and the comparative example.

＜高温充放電サイクル特性評価＞
実施例１〜９および比較例１〜５の各非水二次電池について、８５℃の環境下で、１Ｃの電流値で４．２Ｖになるまで定電流充電を行い、引き続いて電流値が０．１Ｃになるまで４．２Ｖで定電圧充電を行った後、２．５Ｖになるまで定電流放電を行う一連の操作を１サイクルとして、これらを５０サイクル実施した。そして、その間の短絡の有無を調べた。 <High-temperature charge / discharge cycle characteristics evaluation>
About each non-aqueous secondary battery of Examples 1-9 and Comparative Examples 1-5, constant current charge was carried out until it became 4.2V by the current value of 1C in the environment of 85 degreeC, and the electric current value was set to 0 continuously. A series of operations for performing constant current discharge at 4.2V until reaching 1C and then performing constant current discharge until reaching 2.5V was taken as one cycle, and these were performed for 50 cycles. And the presence or absence of the short circuit in the meantime was investigated.

＜高温貯蔵特性評価＞
実施例１〜９および比較例１〜５の各非水二次電池について、室温（２５℃）で、１Ｃの電流値で４．２Ｖになるまで定電流充電を行い、引き続いて電流値が０．１Ｃになるまで４．２Ｖで定電圧充電を行った後、２．５Ｖになるまで定電流放電を行い、放電容量（初期容量）を測定した。 <High temperature storage characteristics evaluation>
About each non-aqueous secondary battery of Examples 1-9 and Comparative Examples 1-5, constant current charge was carried out at room temperature (25 degreeC) until it became 4.2V with the electric current value of 1C, and electric current value was set to 0 continuously. After constant voltage charging at 4.2 V until 0.1 C, constant current discharge was performed until 2.5 V, and the discharge capacity (initial capacity) was measured.

次に、初期容量測定時と同じ条件で定電流充電および定電圧充電を行った各電池を、１００℃の恒温槽内で４８時間貯蔵した。その後、各電池を恒温槽から取り出して室温に戻した後に、２．５Ｖになるまで定電流放電を行った後、初期容量測定時と同じ条件で、定電流充電、定電圧充電および定電流放電を行って、放電容量（回復容量）を求めた。   Next, each battery subjected to constant current charging and constant voltage charging under the same conditions as those at the time of initial capacity measurement was stored in a thermostat at 100 ° C. for 48 hours. Then, after each battery is taken out from the thermostat and returned to room temperature, constant current discharge is performed until it reaches 2.5 V, and then constant current charging, constant voltage charging, and constant current discharging are performed under the same conditions as those for initial capacity measurement. The discharge capacity (recovery capacity) was determined.

そして、各電池について、回復容量を初期容量で除した値を百分率で表して容量回復率を求めた。   For each battery, the capacity recovery rate was determined by expressing the value obtained by dividing the recovery capacity by the initial capacity as a percentage.

実施例および比較例の各非水二次電池に用いた非水電解液の構成を表１、２に示し、前記の各評価結果を表３に示す。表３における「高温充放電サイクル特性」の欄では、短絡が生じなかった場合を「○」で示し、短絡が生じた場合を「×」で示す。   Tables 1 and 2 show the configurations of the nonaqueous electrolyte solutions used in the nonaqueous secondary batteries of Examples and Comparative Examples, and Table 3 shows the evaluation results. In the column of “High-temperature charge / discharge cycle characteristics” in Table 3, the case where no short circuit occurred is indicated by “◯”, and the case where a short circuit occurred is indicated by “X”.

表１〜３に示す通り、負極合剤層の表面が適正な性状の負極を有する実施例１〜９の非水二次電池は、高温貯蔵特性評価時の容量維持率が高く、優れた高温貯蔵特性を有しており、また、高温充放電サイクル特性評価時に短絡も認められなかった。   As shown in Tables 1 to 3, the non-aqueous secondary batteries of Examples 1 to 9 having negative electrodes with appropriate properties on the surface of the negative electrode mixture layer have a high capacity retention rate at the time of high-temperature storage property evaluation and an excellent high temperature. It had storage characteristics and no short circuit was observed during the high temperature charge / discharge cycle characteristics evaluation.

これに対し、ＬｉＢＯＢおよびＶＣのいずれも含有しない非水電解液を使用した比較例１の電池、適正なサイズの粒子状堆積物が負極合剤層の表面に形成されていない比較例２、４の電池、負極合剤層の表面にホウ素が認められない比較例３、５の電池は、高温貯蔵時の容量維持率が低く、高温充放電サイクル特性評価時に短絡が生じており、高温貯蔵特性および高温充放電サイクル特性が劣っていた。   On the other hand, the battery of the comparative example 1 using the nonaqueous electrolyte solution which does not contain any of LiBOB and VC, and the comparative examples 2 and 4 in which the particulate deposit of an appropriate size is not formed on the surface of the negative electrode mixture layer The batteries of Comparative Examples 3 and 5 in which no boron is observed on the surface of the negative electrode mixture layer have a low capacity retention rate during high-temperature storage, and a short circuit occurs during the evaluation of the high-temperature charge / discharge cycle characteristics. And the high-temperature charge / discharge cycle characteristics were inferior.

１ 非水二次電池
２ 外装缶
３ 封口板
４ 絶縁ガスケット
５ 正極
５１ 正極合剤層
５２ 正極集電体
５ｂ 正極タブ部
６Ａ、６Ｂ 負極
６１ 負極合剤層
６２ 負極集電体
６ｂ 負極タブ部
７ セパレータ
８ 絶縁シール DESCRIPTION OF SYMBOLS 1 Nonaqueous secondary battery 2 Exterior can 3 Sealing plate 4 Insulation gasket 5 Positive electrode 51 Positive electrode mixture layer 52 Positive electrode collector 5b Positive electrode tab part 6A, 6B Negative electrode 61 Negative electrode mixture layer 62 Negative electrode collector 6b Negative electrode tab part 7 Separator 8 Insulation seal

Claims (4)

負極活物質を含有する負極合剤層と集電体とを有する負極、正極、セパレータ、並びにリチウム塩および有機溶媒を含有する非水電解液を備えた非水二次電池であって、
前記負極合剤層の表面に、平均粒子径が１０〜５００ｎｍの粒子状堆積物が存在しており、
前記負極合剤層の表面をＸ線光電子分光分析したときに、１９０〜１９５ｅＶにホウ素に基づくピークが、２８０〜２９２ｅＶに炭素に基づくピークが、５２６〜５３６ｅＶに酸素に基づくピークが、６８２〜６９０ｅＶにフッ素に基づくピークが、それぞれ観察され、
前記非水電解液は、リチウムビスオキサレートボレート、または、ビニレンカーボネートを含有していることを特徴とする非水二次電池。 A nonaqueous secondary battery comprising a negative electrode having a negative electrode mixture layer containing a negative electrode active material and a current collector, a positive electrode, a separator, and a nonaqueous electrolyte solution containing a lithium salt and an organic solvent,
There is a particulate deposit having an average particle size of 10 to 500 nm on the surface of the negative electrode mixture layer,
When the surface of the negative electrode mixture layer was analyzed by X-ray photoelectron spectroscopy, a peak based on boron at 190 to 195 eV, a peak based on carbon at 280 to 292 eV, a peak based on oxygen at 526 to 536 eV, and 682 to 690 eV Each of the peaks based on fluorine is observed,
The non-aqueous electrolyte includes lithium bisoxalate borate or vinylene carbonate. 前記炭素に基づくピーク、酸素に基づくピークおよびフッ素に基づくピークの強度を、それぞれＩａ、ＩｂおよびＩｃとしたときに、Ｉｃ／（Ｉａ＋Ｉｂ）≧０．３である請求項１に記載の非水二次電池。   2. The non-aqueous two-phase composition according to claim 1, wherein Ic / (Ia + Ib) ≧ 0.3 when the intensity of the peak based on carbon, the peak based on oxygen, and the peak based on fluorine is Ia, Ib, and Ic, respectively. Next battery. 前記非水電解液は、前記有機溶媒としてα位に置換基を有するラクトン類を含有し、かつ前記リチウム塩としてＬｉＢＦ４を含有している請求項１または２に記載の非水二次電池。 3. The non-aqueous secondary battery according to claim 1, wherein the non-aqueous electrolyte contains a lactone having a substituent at the α-position as the organic solvent, and LiBF 4 as the lithium salt. 前記負極合剤層は、前記負極活物質として炭素材料を含有している請求項１〜３のいずれかに記載の非水二次電池。   The non-aqueous secondary battery according to claim 1, wherein the negative electrode mixture layer contains a carbon material as the negative electrode active material.
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