JP6801602B2 - Non-aqueous electrolyte secondary battery - Google Patents
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Description
本開示は、非水電解質二次電池に関する。 The present disclosure relates to a non-aqueous electrolyte secondary battery.
特開２０１７−１０８１９号公報（特許文献１）には、炭酸リチウムおよびリン酸リチウムを含有した正極板と、フルオロスルホン酸リチウムを含有する非水電解質とを備える非水電解質二次電池（以下、「非水電解質二次電池」を単に「電池」とも記す）が開示されている。 Japanese Unexamined Patent Publication No. 2017-10819 (Patent Document 1) describes a non-aqueous electrolyte secondary battery (hereinafter, referred to as a non-aqueous electrolyte secondary battery) comprising a positive electrode plate containing lithium carbonate and lithium phosphate and a non-aqueous electrolyte containing lithium fluorosulfonate. A "non-aqueous electrolyte secondary battery" is also simply referred to as a "battery").
特許文献１において炭酸リチウムおよびリン酸リチウムを含有した正極板と、フルオロスルホン酸リチウムを含有する非水電解質とを用いる理由は、電池の低温出力特性および高温保存特性を良好にしつつ、過充電状態となっても異常な挙動が生じない信頼性の高い電池を得るためである。 The reason for using the positive electrode plate containing lithium carbonate and lithium phosphate in Patent Document 1 and the non-aqueous electrolyte containing lithium fluorosulfonate is that the battery is in an overcharged state while improving the low temperature output characteristics and high temperature storage characteristics of the battery. This is to obtain a highly reliable battery that does not cause abnormal behavior even if it becomes.
特許文献１によると、正極活物質合剤層に炭酸リチウムおよびリン酸リチウムが含有されることにより、異常時に炭酸リチウムにより電流遮断機構の作動に必要な量のガスが短時間で発生し、過充電状態での電解質の酸化分解が抑制され、電解質の酸化分解等に起因する発熱が抑制される。 According to Patent Document 1, since lithium carbonate and lithium phosphate are contained in the positive electrode active material mixture layer, the amount of gas required for the operation of the current cutoff mechanism is generated in a short time by lithium carbonate in an abnormal situation, which is excessive. Oxidative decomposition of the electrolyte in the charged state is suppressed, and heat generation due to oxidative decomposition of the electrolyte is suppressed.
しかしながら特許文献１に開示されている電池は、電流遮断機構が正常に作動することが必須の要件となっている。したがって、仮に電流遮断機構に異常がある際には、電池の発熱が抑制されない懸念がある。すなわち、特許文献１において開示されている電池は、過充電状態等における電池の発熱抑制において、改善の余地がある。 However, in the battery disclosed in Patent Document 1, it is an indispensable requirement that the current cutoff mechanism operates normally. Therefore, if there is an abnormality in the current cutoff mechanism, there is a concern that the heat generation of the battery will not be suppressed. That is, the battery disclosed in Patent Document 1 has room for improvement in suppressing heat generation of the battery in an overcharged state or the like.
本開示の目的は、電池の過充電時における熱安定性の向上、およびＬｉ析出耐性の向上が両立された電池を提供することにある。 An object of the present disclosure is to provide a battery in which both improvement in thermal stability during overcharging of the battery and improvement in Li precipitation resistance are achieved.
以下、本開示の技術的構成および作用メカニズムが説明される。ただし本開示の作用メカニズムは推定を含んでいる。作用メカニズムの正否により、特許請求の範囲が限定されるべきではない。 Hereinafter, the technical configuration and the mechanism of action of the present disclosure will be described. However, the mechanism of action of the present disclosure includes estimation. The scope of claims should not be limited by the correctness of the mechanism of action.
本開示に係る非水電解質二次電池は、正極、負極、および非水電解質を含む非水電解質二次電池である。正極は正極合材層を含み、正極合材層はリン酸リチウム（Ｌｉ３ＰＯ４）を含む正極合材層を含む。非水電解質はフルオロスルホン酸リチウム（ＦＳＯ３Ｌｉ）を含む。非水電解質二次電池の正極の初期充電容量（ＣＰ）に対する負極の初期充電容量（ＣＮ）の比で定義される対向容量比（ＣＮ／ＣＰ）は、１．７９以上１．９６以下である。 The non-aqueous electrolyte secondary battery according to the present disclosure is a non-aqueous electrolyte secondary battery including a positive electrode, a negative electrode, and a non-aqueous electrolyte. The positive electrode includes a positive electrode mixture layer, and the positive electrode mixture layer includes a positive electrode mixture layer containing lithium phosphate (Li 3 PO 4 ). Non-aqueous electrolytes include lithium fluorosulfonate (FSO 3 Li). Counter capacity ratio defined by the ratio of non-aqueous negative electrode initial charging capacity to the initial charge capacity of the positive electrode (C P) of electrolyte secondary cell (C N) (C N / C P) is 1.79 or more 1. It is 96 or less.
正極合材層がリン酸リチウムを含むことにより、電池の過充電時等の異常時において、電池が発熱した際の熱安定性が向上するものと考えられる。ここで、本明細書の「熱安定性が向上」とは、たとえば電池の過充電時において、セパレーターが反応を抑止するためにシャットダウンした際に、電池の温度上昇が抑制されている状態をいう。非水電解質がフルオロスルホン酸リチウムを含むことにより、Ｌｉ析出耐性が向上するものと考えられる。ここで、本明細書の「Ｌｉ析出耐性が向上」とは、たとえば充放電を繰り返しＬｉが析出しやすい条件下においても、Ｌｉの析出が抑制されている状態をいう。正極の初期充電容量（ＣＰ）に対する負極の初期充電容量（ＣＮ）の比で定義される対向容量比（ＣＮ／ＣＰ）を、１．７９以上１．９６以下とすることにより、電池の過充電時における熱安定性の向上と、Ｌｉ析出耐性の向上とが両立された電池が提供されると期待される。なお、本明細書の「正極の初期充電容量（ＣＰ）」は、正極に含まれる正極活物質の質量（ｇ）と、当該正極活物質の単位質量当たりの理論容量（Ａｈ／ｇ）との積によって算出され、「負極の初期充電容量（ＣＮ）」は、負極に含まれる負極活物質の質量（ｇ）と、当該負極活物質の単位質量当たりの理論容量（Ａｈ／ｇ）との積によって算出される。 It is considered that the inclusion of lithium phosphate in the positive electrode mixture layer improves the thermal stability when the battery generates heat in an abnormal situation such as when the battery is overcharged. Here, the term "improved thermal stability" as used herein means a state in which the temperature rise of the battery is suppressed when the separator shuts down to suppress the reaction, for example, when the battery is overcharged. .. It is considered that the Li precipitation resistance is improved when the non-aqueous electrolyte contains lithium fluorosulfonate. Here, the term "improved Li precipitation resistance" as used herein means a state in which the precipitation of Li is suppressed even under the condition that Li is easily precipitated by repeating charging and discharging, for example. Counter capacity ratio defined by the ratio of the initial charge capacity of the negative electrode with respect to the initial charge capacity of the positive electrode (C P) (C N) and (C N / C P), by 1.79 or more 1.96 or less, It is expected that a battery having both improved thermal stability during overcharging of the battery and improved Li precipitation resistance will be provided. The "initial charge capacity ( CP ) of the positive electrode" in the present specification is the mass (g) of the positive electrode active material contained in the positive electrode and the theoretical capacity (Ah / g) per unit mass of the positive electrode active material. The "initial charge capacity ( CN ) of the negative electrode" is calculated by the product of the mass (g) of the negative electrode active material contained in the negative electrode and the theoretical capacity (Ah / g) per unit mass of the negative electrode active material. Is calculated by the product of.
以下、本開示の実施形態（以下「本実施形態」と記される）が説明される。ただし、以下の説明は、本開示の発明の範囲を限定するものではない。 Hereinafter, embodiments of the present disclosure (hereinafter referred to as “the present embodiment”) will be described. However, the following description does not limit the scope of the invention of the present disclosure.
＜非水電解質二次電池の構成＞
本開示の非水電解質二次電池は、以下で説明する正極、負極および非水電解質を含む限り、従来公知の構成を備えることができる。従来公知の構成とは、たとえば正極と、負極と、正極と負極との間に配置されたセパレータとを有する電極群を備え、この電極群が非水電解質と共に電池ケースに配置される構成等をいう。電極群は、扁平に巻回した形態（巻回電極群）とすることができる。
<Structure of non-aqueous electrolyte secondary battery>
The non-aqueous electrolyte secondary battery of the present disclosure can have a conventionally known configuration as long as it includes a positive electrode, a negative electrode and a non-aqueous electrolyte described below. The conventionally known configuration includes, for example, a configuration in which an electrode group having a positive electrode, a negative electrode, and a separator arranged between the positive electrode and the negative electrode is provided, and the electrode group is arranged in a battery case together with a non-aqueous electrolyte. Say. The electrode group can be in a flatly wound form (wound electrode group).
＜正極＞
本実施形態に係る正極は正極合材層を含み、正極合材層はリン酸リチウムを含む。すなわち、正極はリン酸リチウムを含む正極合材層を含む。加えて、正極の初期充電容量（ＣＰ）に対する後述する負極の初期充電容量（ＣＮ）との比で定義される対向容量比（ＣＮ／ＣＰ）は、１．７９以上１．９６以下である。本実施形態における正極は、リン酸リチウムを含む正極合材層を含み、上述の対向容量比（ＣＮ／ＣＰ）が１．７９以上１．９６以下である限り、従来公知の構成を備えることができる。従来公知の構成とは、たとえば正極集電体と、正極集電体の主面上に形成された正極合材層とを含む構成である。正極集電体は、たとえばアルミニウム（Ａｌ）箔等であってもよい。正極集電体は、たとえば１０〜３０μｍの厚さを有してもよい。
<Positive electrode>
The positive electrode according to the present embodiment includes a positive electrode mixture layer, and the positive electrode mixture layer contains lithium phosphate. That is, the positive electrode includes a positive electrode mixture layer containing lithium phosphate. In addition, counter capacity ratio defined by the ratio of the initial charge capacity of the negative electrode to be described later (C N) to the initial charge capacity of the positive electrode (C P) (C N / C P) is 1.79 or more 1.96 It is as follows. The positive electrode in the present embodiment includes a positive-electrode mixture layer containing a lithium phosphate, unless opposed capacity ratio of the above (C N / C P) is 1.79 or more 1.96 or less, and a conventionally known configuration be able to. The conventionally known configuration is, for example, a configuration including a positive electrode current collector and a positive electrode mixture layer formed on the main surface of the positive electrode current collector. The positive electrode current collector may be, for example, an aluminum (Al) foil or the like. The positive electrode current collector may have a thickness of, for example, 10 to 30 μm.
《正極合材層》
正極合材層は、リン酸リチウムを含む。正極合材層はリン酸リチウムに加え、従来公知の構成として正極活物質、導電材、およびバインダを含む。正極合材層は、たとえば８０〜９８重量％の正極活物質、１〜１５重量％以下の導電材、および１〜５重量％以下のバインダを含み、かつ、上記正極活物質１００質量部に対して、１〜５質量部のリン酸リチウムを含んでもよい。正極合材層は、たとえば３０〜２００μｍの厚さを有してもよい。
<< Positive electrode mixture layer >>
The positive electrode mixture layer contains lithium phosphate. In addition to lithium phosphate, the positive electrode mixture layer contains a positive electrode active material, a conductive material, and a binder as conventionally known configurations. The positive electrode mixture layer contains, for example, 80 to 98% by weight of the positive electrode active material, 1 to 15% by weight or less of the conductive material, and 1 to 5% by weight or less of the binder, and is based on 100 parts by mass of the positive electrode active material. It may contain 1 to 5 parts by mass of lithium phosphate. The positive electrode mixture layer may have a thickness of, for example, 30 to 200 μm.
（正極活物質、導電材およびバインダ）
正極活物質、導電材およびバインダは特に限定されるべきではない。正極活物質は、たとえばＬｉＣｏＯ２、ＬｉＮｉＯ２、ＬｉＮｉ１／３Ｃｏ１／３Ｍｎ１／３Ｏ２（ＮＣＭ）、ＬｉＭｎＯ２、ＬｉＭｎ２Ｏ４、ＬｉＦｅＰＯ４等であってもよい。導電材は、たとえばアセチレンブラック（ＡＢ）、ファーネスブラック、気相成長炭素繊維（ＶＧＣＦ）、黒鉛等であってもよい。バインダは、たとえばポリフッ化ビニリデン（ＰＶｄＦ）、スチレンブタジエンラバー（ＳＢＲ）、ポリテトラフルオロエチレン（ＰＴＦＥ）等であってもよい。
(Positive electrode active material, conductive material and binder)
The positive electrode active material, the conductive material and the binder should not be particularly limited. The positive electrode active material may be, for example, LiCoO 2 , LiNiO 2 , LiNi 1/3 Co 1/3 Mn 1/3 O 2 (NCM), LiMnO 2 , LiMn 2 O 4 , LiFePO 4, or the like. The conductive material may be, for example, acetylene black (AB), furnace black, vapor-grown carbon fiber (VGCF), graphite or the like. The binder may be, for example, polyvinylidene fluoride (PVdF), styrene butadiene rubber (SBR), polytetrafluoroethylene (PTFE), or the like.
＜負極＞
本実施形態における負極においては、上述した正極の初期充電容量（ＣＰ）に対する負極の初期充電容量（ＣＮ）との比で定義される対向容量比（ＣＮ／ＣＰ）は、１．７９以上１．９６以下である。本実施形態における負極は、上述の対向容量比（ＣＮ／ＣＰ）が１．７９以上１．９６以下である限り、従来公知の構成を備えることができる。従来公知の構成とは、たとえば負極集電体および負極合材層を含む構成である。負極集電体は、たとえば銅（Ｃｕ）箔等でよい。負極集電体は、たとえば５〜２０μｍ程度の厚さを有してもよい。負極合材層は、負極集電体の表面に形成されている。負極合材層は、たとえば１０〜１５０μｍ程度の厚さを有してもよい。負極合材層は、負極活物質およびバインダ材等を含有する。負極合材層は、たとえば９５〜９９質量％の負極活物質、および１〜５質量％のバインダを含有する。負極の比表面積は、３．０ｍ２／ｇ〜５．５ｍ２／ｇであることが好ましい。
<Negative electrode>
In the negative electrode in the present embodiment, counter capacity ratio defined by the ratio of the initial charge capacity of the negative electrode with respect to the initial charge capacity of the positive electrode described above (C P) (C N) (C N / C P) is 1. It is 79 or more and 1.96 or less. Negative in this embodiment, as long as counter capacity ratio of above (C N / C P) is 1.79 or more 1.96 or less may be provided with a conventional configuration. The conventionally known configuration is, for example, a configuration including a negative electrode current collector and a negative electrode mixture layer. The negative electrode current collector may be, for example, copper (Cu) foil or the like. The negative electrode current collector may have a thickness of, for example, about 5 to 20 μm. The negative electrode mixture layer is formed on the surface of the negative electrode current collector. The negative electrode mixture layer may have a thickness of, for example, about 10 to 150 μm. The negative electrode mixture layer contains a negative electrode active material, a binder material, and the like. The negative electrode mixture layer contains, for example, 95 to 99% by mass of the negative electrode active material and 1 to 5% by mass of the binder. The specific surface area of the negative electrode is preferably 3.0m 2 /g~5.5m 2 / g.
負極活物質およびバインダは特に限定されるべきではない。負極活物質は、たとえば黒鉛、易黒鉛化性炭素、難黒鉛化性炭素、珪素、酸化珪素、錫、酸化錫等であってもよい。バインダは、たとえばカルボキシメチルセルロース（ＣＭＣ）、スチレンブタジエンゴム（ＳＢＲ）等であってもよい。 Negative electrode active materials and binders should not be particularly limited. The negative electrode active material may be, for example, graphite, graphitizable carbon, non-graphitizable carbon, silicon, silicon oxide, tin, tin oxide or the like. The binder may be, for example, carboxymethyl cellulose (CMC), styrene butadiene rubber (SBR), or the like.
＜非水電解質＞
本開示の非水電解質は、フルオロスルホン酸リチウム（ＦＳＯ３Ｌｉ）を含む。非水電解質中のフルオロスルホン酸リチウムの含有量は、たとえば０．３〜２．０質量％程度であってもよい。本実施形態における非水電解質は、フルオロスルホン酸リチウムを含む限り、従来公知の構成を備えることができる。従来公知の構成とは、非水溶媒、支持塩、および添加剤を含む構成である。非水溶媒は、たとえば環状カーボネートと鎖状カーボネートとの混合物でよい。環状カーボネートと鎖状カーボネートとの混合比は、体積比で、たとえば環状カーボネート：鎖状カーボネート＝１：９〜５：５でよい。環状カーボネートとしては、たとえばエチレンカーボネート（ＥＣ）、プロピレンカーボネート（ＰＣ）、ブチレンカーボネート（ＢＣ）等であってもよい。鎖状カーボネートは、たとえばジメチルカーボネート（ＤＭＣ）、エチルメチルカーボネート（ＥＭＣ）、ジエチルカーボネート（ＤＥＣ）等であってもよい。支持塩は、たとえばヘキサフルオロ燐酸リチウム（ＬｉＰＦ６）、テトラフルオロ硼酸リチウム（ＬｉＢＦ４）等のＬｉ塩でよい。Ｌｉ塩の濃度は、たとえば０．５〜２．０ｍоｌ／Ｌ程度でよい。非水電解質は、ビニレンカーボネート（ＶＣ）、シクロヘキシルベンゼン（ＣＨＢ）等の添加剤を含んでいてもよい。
<Non-aqueous electrolyte>
The non-aqueous electrolytes of the present disclosure include lithium fluorosulfonate (FSO 3 Li). The content of lithium fluorosulfonate in the non-aqueous electrolyte may be, for example, about 0.3 to 2.0% by mass. The non-aqueous electrolyte in the present embodiment can have a conventionally known configuration as long as it contains lithium fluorosulfonate. The conventionally known configuration is a configuration containing a non-aqueous solvent, a supporting salt, and an additive. The non-aqueous solvent may be, for example, a mixture of a cyclic carbonate and a chain carbonate. The mixing ratio of the cyclic carbonate and the chain carbonate may be a volume ratio, for example, cyclic carbonate: chain carbonate = 1: 9 to 5: 5. The cyclic carbonate may be, for example, ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC) or the like. The chain carbonate may be, for example, dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC) or the like. The supporting salt may be a Li salt such as lithium hexafluorophosphate (LiPF 6 ) or lithium tetrafluoroborate (LiBF 4 ). The concentration of the Li salt may be, for example, about 0.5 to 2.0 mL / L. The non-aqueous electrolyte may contain additives such as vinylene carbonate (VC) and cyclohexylbenzene (CHB).
＜セパレータ＞
セパレータは、電気絶縁性の多孔質膜である。セパレータは、正極と負極とを電気的に隔離する。セパレータは、たとえば５〜３０μｍの厚さを有してもよい。セパレータは、たとえば多孔質ポリエチレン（ＰＥ）膜、多孔質ポリプロピレン（ＰＰ）膜等により構成され得る。セパレータは、多層構造を含んでもよい。たとえばセパレータは、多孔質ＰＰ膜、多孔質ＰＥ膜、および多孔質ＰＰ膜がこの順序で積層されることにより構成されていてもよい。セパレータは、その表面に耐熱層を含んでいてもよい。耐熱層は、耐熱材料を含む。耐熱材料としては、たとえばアルミナ等の金属酸化物粒子、ポリイミド等の高融点樹脂等が挙げられる。
<Separator>
The separator is an electrically insulating porous membrane. The separator electrically separates the positive electrode and the negative electrode. The separator may have a thickness of, for example, 5 to 30 μm. The separator may be composed of, for example, a porous polyethylene (PE) film, a porous polypropylene (PP) film, or the like. The separator may include a multi-layer structure. For example, the separator may be composed of a porous PP film, a porous PE film, and a porous PP film laminated in this order. The separator may include a heat-resistant layer on its surface. The heat-resistant layer contains a heat-resistant material. Examples of the heat-resistant material include metal oxide particles such as alumina and a refractory resin such as polyimide.
＜電池ケース＞
電池ケースは、たとえば角形（扁平直方体）であってもよいし、円筒形であってもよいし、袋状であってもよい。たとえばアルミニウム（Ａｌ）、Ａｌ合金等の金属が電池ケースを構成する。ただし、電池ケースが所定の密閉性を有する限り、たとえば金属および樹脂の複合材が電池ケースを構成してもよい。金属および樹脂の複合材としては、たとえばアルミラミネートフィルム等が挙げられる。電池ケースは、外部端子、注液孔、ガス排出弁等を備えていてもよい。本開示の電池ケースは、電流遮断機構（ＣＩＤ）を備えていてもよいし、備えていなくてもよい。
<Battery case>
The battery case may be, for example, a square shape (flat rectangular parallelepiped), a cylindrical shape, or a bag shape. For example, a metal such as aluminum (Al) or Al alloy constitutes a battery case. However, as long as the battery case has a predetermined airtightness, for example, a composite material of metal and resin may form the battery case. Examples of the metal and resin composite material include an aluminum laminated film and the like. The battery case may be provided with an external terminal, a liquid injection hole, a gas discharge valve, and the like. The battery case of the present disclosure may or may not be provided with a current cutoff mechanism (CID).
＜用途＞
本開示に係る電池は、たとえばハイブリッド自動車（ＨＶ）、プラグインハイブリッド自動車（ＰＨＶ）、電気自動車（ＥＶ）等の動力電源として用いられる。ただし、本開示に係る非水電解質二次電池の用途は、車載用途に限定されるべきではなく、あらゆる用途に適用可能である。
<Use>
The battery according to the present disclosure is used as a power source for a hybrid vehicle (HV), a plug-in hybrid vehicle (PHV), an electric vehicle (EV), or the like. However, the use of the non-aqueous electrolyte secondary battery according to the present disclosure should not be limited to in-vehicle use, and can be applied to all uses.
以下、実施例が説明される。ただし以下の例は、本開示の範囲を限定するものではない。 Examples will be described below. However, the following examples do not limit the scope of the present disclosure.
＜非水電解液二次電池の製造＞
《実施例１》
１．正極の製造
以下の材料が準備された。
正極活物質：ＮＣＭ
導電材：ＡＢ
バインダ：ＰＶｄＦ
添加剤：リン酸三リチウム（Ｌｉ３ＰＯ４）
溶媒：Ｎ−メチル−ピロリドン（ＮＭＰ）
正極集電箔：Ａｌ箔（厚さ１５μｍ）
<Manufacturing of non-aqueous electrolyte secondary batteries>
<< Example 1 >>
1. 1. Manufacture of positive electrode The following materials were prepared.
Positive electrode active material: NCM
Conductive material: AB
Binder: PVdF
Additive: Trilithium Phosphate (Li 3 PO 4 )
Solvent: N-methyl-pyrrolidone (NMP)
Positive electrode current collector foil: Al foil (
プラネタリミキサにより、ＮＣＭ、Ｌｉ３ＰＯ４、ＡＢ、ＰＶｄＦおよびＮＭＰが混合された。これにより、ペースト状の正極合材（以下、「正極合材ペースト」と記載する）が調製された。正極合材ペーストにおけるＬｉ３ＰＯ４以外の固形分組成は、質量比で「ＮＣＭ：ＡＢ：ＰＶｄＦ＝９１：６：３」とされた。Ｌｉ３ＰＯ４の添加量は、ＮＣＭ１００質量部に対して３質量部とされた。正極合材層用ペーストが正極集電体の表面に塗布され、乾燥された。これにより正極合材層が形成された。以上より、正極が形成された。正極は圧延され、帯状に裁断された。なお、正極の密度は２．３５ｇ／ｃｍ３となるよう調整された。 NCM, Li 3 PO 4 , AB, PVdF and NMP were mixed by a planetary mixer. As a result, a paste-like positive electrode mixture (hereinafter, referred to as “positive electrode mixture paste”) was prepared. The solid content composition other than Li 3 PO 4 in the positive electrode mixture paste was set to "NCM: AB: PVdF = 91: 6: 3" in terms of mass ratio. The amount of Li 3 PO 4 added was 3 parts by mass with respect to 100 parts by mass of NCM. The paste for the positive electrode mixture layer was applied to the surface of the positive electrode current collector and dried. As a result, a positive electrode mixture layer was formed. From the above, the positive electrode was formed. The positive electrode was rolled and cut into strips. The density of the positive electrode was adjusted to 2.35 g / cm 3 .
２．負極の製造
以下の材料が準備された。
負極活物質：粉末黒鉛
増粘材：ＣＭＣ
バインダ：ＳＢＲ
溶媒：イオン交換水
負極集電箔：Ｃｕ箔（厚さ１０μｍ）
2. 2. Manufacture of negative electrode The following materials were prepared.
Negative electrode active material: powdered graphite thickener: CMC
Binder: SBR
Solvent: Ion-exchanged water Negative electrode current collector foil: Cu foil (
攪拌装置の攪拌槽に、粉末黒鉛、ＣＭＣ、ＳＢＲおよびイオン交換水を投入し、攪拌することにより、ペースト状の負極合材（以下、「負極合材ペースト」と記載する）が調製された。負極合材ペーストにおいて固形分の配合は、質量比で「粉末黒鉛：ＣＭＣ：ＳＢＲ＝９８：１：１」とされた。負極合材層用ペーストが、負極集電体の表面に塗布され、乾燥された。これにより負極合材層が形成された。以上により、負極が形成された。負極は圧延され、帯状に裁断された。なお、上述の正極合材ペーストの目付量および負極合材ペーストの目付量は、正極の初期充電容量（ＣＰ）に対する負極の初期充電容量（ＣＮ）との比で定義される対向容量比（ＣＮ／ＣＰ）が１．７９となるよう調整された。また、負極のＢＥＴ表面積は、４．０ｍ２／ｇであり、負極の密度は１．２０ｇ／ｃｍ３となるよう調整された。 A paste-like negative electrode mixture (hereinafter referred to as "negative electrode mixture paste") was prepared by putting powdered graphite, CMC, SBR and ion-exchanged water into the stirring tank of the stirring device and stirring the mixture. In the negative electrode mixture paste, the solid content was set to "powdered graphite: CMC: SBR = 98: 1: 1" in terms of mass ratio. The paste for the negative electrode mixture layer was applied to the surface of the negative electrode current collector and dried. As a result, a negative electrode mixture layer was formed. As a result, the negative electrode was formed. The negative electrode was rolled and cut into strips. Incidentally, the basis weight of the basis weight and negative electrode composite paste of the above positive electrode paste, counter capacity ratio defined by the ratio of the initial charge capacity of the negative electrode with respect to the initial charge capacity of the positive electrode (C P) (C N) (C N / C P) is adjusted to be 1.79. The BET surface area of the negative electrode was adjusted to 4.0 m 2 / g, and the density of the negative electrode was adjusted to 1.20 g / cm 3 .
３．非水系電解質の準備
以下の組成を有する電解液が準備された。
溶媒組成：［ＥＣ：ＤＭＣ：ＥＭＣ＝３：４：３（体積比）］
支持塩：ＬｉＰＦ６（１．１ｍоｌ／Ｌ）
添加剤：ＦＳＯ３Ｌｉ（１．０質量％）
3. 3. Preparation of non-aqueous electrolyte An electrolyte solution having the following composition was prepared.
Solvent composition: [EC: DMC: EMC = 3: 4: 3 (volume ratio)]
Supporting salt: LiPF 6 (1.1 mol / L)
Additive: FSO 3 Li (1.0% by mass)
４．非水電解質二次電池の製造
帯状の正極、帯状の負極および帯状のセパレータ（ＰＰ／ＰＥ／ＰＰの三層構造）がそれぞれ準備された。セパレータを挟んで、正極と負極とが対向するように、正極、セパレータ、負極、セパレータの順で積層され、さらに渦巻状に巻回された。これにより電極群が構成された。正極および負極に端子がそれぞれ接続された。電極群がアルミニウムからなる電池ケースに収納された。角型の電池ケースに非水電解質が注入され、電池ケースが密閉された。以上より、非水電解質二次電池が製造された。電池は、角形（奥行１３．５ｍｍ×幅１１０ｍｍ×高さ９１．５ｍｍ）である。電池は、３．０〜４．１Ｖの電圧範囲で４．５Ａｈの容量を有するように設計されている。
4. Manufacture of non-aqueous electrolyte secondary battery A band-shaped positive electrode, a band-shaped negative electrode, and a band-shaped separator (PP / PE / PP three-layer structure) were prepared. The positive electrode, the separator, the negative electrode, and the separator were laminated in this order so that the positive electrode and the negative electrode faced each other with the separator interposed therebetween, and further wound in a spiral shape. This formed a group of electrodes. The terminals were connected to the positive electrode and the negative electrode, respectively. The electrode group was housed in a battery case made of aluminum. Non-aqueous electrolyte was injected into the square battery case, and the battery case was sealed. From the above, a non-aqueous electrolyte secondary battery was manufactured. The battery is square (depth 13.5 mm × width 110 mm × height 91.5 mm). Batteries are designed to have a capacity of 4.5 Ah in the voltage range of 3.0 to 4.1 V.
《実施例２〜４》
下記表１に示されるように、対向容量比（ＣＮ／ＣＰ）が異なるよう正極ペーストの目付量および負極ペーストの目付量を調整したことを除いては、実施例１と同様に電池が製造された。
<< Examples 2 to 4 >>
As shown in Table 1 below, the battery is the same as in Example 1 except that the basis weight of the positive electrode paste and the basis weight of the negative electrode paste are adjusted so that the facing capacity ratios ( CN / CP ) are different. manufactured.
《比較例1〜４》
下記表１に示されるように、対向容量比（ＣＮ／ＣＰ）が異なるよう正極ペーストの目付量および負極ペーストの目付量を調整したことを除いては、実施例１と同様に電池が製造された。
<< Comparative Examples 1 to 4 >>
As shown in Table 1 below, the battery is the same as in Example 1 except that the basis weight of the positive electrode paste and the basis weight of the negative electrode paste are adjusted so that the facing capacity ratios ( CN / CP ) are different. manufactured.
《比較例５》
下記表１に示されるように、非水系電解質にＦＳＯ３Ｌｉを添加しなかったことを除いては、実施例１と同様に電池が製造された。
<< Comparative Example 5 >>
As shown in Table 1 below, a battery was manufactured in the same manner as in Example 1 except that FSO 3 Li was not added to the non-aqueous electrolyte.
《比較例６》
下記表１に示されるように、正極合材層にＬｉ３ＰＯ４を添加しなかったことを除いては、実施例１と同様に電池が製造された。
<< Comparative Example 6 >>
As shown in Table 1 below, a battery was manufactured in the same manner as in Example 1 except that Li 3 PO 4 was not added to the positive electrode mixture layer.
＜過充電耐性の評価試験＞
２５℃の温度下において、各電池をセパレータがシャットダウンするまで、４０Ａの定電流で充電した。そして、セパレーターがシャットダウンしてから２０秒間の、電池ケース表面の温度上昇を測定した。電池ケース表面の温度上昇が小さいほど、過充電時に電池温度の上昇が抑えられたことを示している。すなわち、電池ケース表面の温度上昇が小さいほど、電池の過充電時における熱安定性が優れていることを示す。結果は下記表１の「過充電発熱評価」の欄に示されている。
<Evaluation test of overcharge resistance>
At a temperature of 25 ° C., each battery was charged with a constant current of 40 A until the separator shut down. Then, the temperature rise on the surface of the battery case was measured for 20 seconds after the separator shut down. The smaller the temperature rise on the surface of the battery case, the more the rise in battery temperature was suppressed during overcharging. That is, the smaller the temperature rise on the surface of the battery case, the better the thermal stability when the battery is overcharged. The results are shown in the column of "Overcharge heat generation evaluation" in Table 1 below.
＜Ｌｉ析出耐性の評価試験＞
−１０℃の環境下で「充電→放電」を１サイクルとして３００サイクル実行し、３００サイクル前後での電池容量を測定した。充電電流は２６０Ａとし、充電時間は５秒とし、放電電流は２６Ａとし、放電時間は５０秒とした。３００サイクルの充放電後の電池容量を、３００サイクルの充放電を行う前の電池容量で除することにより、電池容量維持率を算出した。容量維持率が高いほど、Ｌｉ析出耐性が優れていることを示している。結果は下記表１の「Ｌｉ析出耐性評価」の欄に示されている。
<Evaluation test of Li precipitation resistance>
In an environment of −10 ° C., 300 cycles were executed with “charging → discharging” as one cycle, and the battery capacity was measured around 300 cycles. The charging current was 260 A, the charging time was 5 seconds, the discharge current was 26 A, and the discharge time was 50 seconds. The battery capacity retention rate was calculated by dividing the battery capacity after charging and discharging for 300 cycles by the battery capacity before charging and discharging for 300 cycles. The higher the capacity retention rate, the better the Li precipitation resistance. The results are shown in the column of "Li precipitation resistance evaluation" in Table 1 below.
＜結果＞
上記表１に示されるように、実施例１〜４は過充電発熱評価およびＬｉ析出耐性評価が共に優れていた。この結果から、正極がＬｉ３ＰＯ４を含む正極合材層を含み、非水電解質がＦＳＯ３Ｌｉを含み、電池の正極の初期充電容量（ＣＰ）に対する負極の初期充電容量（ＣＮ）の比で定義される対向容量比（ＣＮ／ＣＰ）が１．７９以上１．９６以下である電池は、電池の過充電時における熱安定性の向上、およびＬｉ析出耐性の向上が両立されていることが示された。
<Result>
As shown in Table 1 above, Examples 1 to 4 were excellent in both the overcharge heat generation evaluation and the Li precipitation resistance evaluation. From this result, the positive electrode comprises a positive-electrode mixture layer containing Li 3 PO 4, nonaqueous include electrolyte FSO 3 Li, the initial charge capacity of the negative electrode for the positive electrode initial charging capacity of the battery (C P) (C N) incompatible battery counter capacity ratio defined by the ratio of (C N / C P) is 1.79 or more 1.96 or less, improvement in thermal stability during overcharging of the battery, and improvement in the deposition of Li resistant It was shown that it was done.
表１における実施例１〜４と比較例１〜４との比較、および図１より、正極がＬｉ３ＰＯ４を含む正極合材層を含み、非水電解質がＦＳＯ３Ｌｉを含んでいたとしても、電池の正極の初期充電容量（ＣＰ）に対する負極の初期充電容量（ＣＮ）の比で定義される対向容量比（ＣＮ／ＣＰ）が１．７９以上１．９６以下では無い場合、過充電発熱評価において改善の余地があることが示された。 From the comparison between Examples 1 to 4 and Comparative Examples 1 to 4 in Table 1 and FIG. 1, it is assumed that the positive electrode contains the positive electrode mixture layer containing Li 3 PO 4 and the non-aqueous electrolyte contains FSO 3 Li. also, counter capacity ratio defined by the ratio of the initial charge capacity of the negative electrode for the positive electrode initial charging capacity of the battery (C P) (C N) (C N / C P) is not 1.79 or higher 1.96 or less In this case, it was shown that there is room for improvement in the overcharge heat generation evaluation.
表１における実施例１〜４と比較例１〜４との比較、および図２より、正極がＬｉ３ＰＯ４を含む正極合材層を含み、非水電解質がＦＳＯ３Ｌｉを含んでいる場合、電池の正極の初期充電容量（ＣＰ）に対する負極の初期充電容量（ＣＮ）の比で定義される対向容量比（ＣＮ／ＣＰ）が１．７９以上１．９６以下である場合に加え、対向容量比（ＣＮ／ＣＰ）がそれぞれ１．９８および２．０２である比較例３および比較例４においても、良好なＬｉ析出耐性評価が得られることが示された。しかしながら前述の通り、比較例３および比較例４は過充電発熱評価においては改善の余地があるものである。なお。比較例１および２に関しては、Ｌｉ析出耐性評価において改善の余地があることが示されている。 Comparison between Examples 1 to 4 and Comparative Examples 1 to 4 in Table 1 and from FIG. 2, when the positive electrode contains a positive electrode mixture layer containing Li 3 PO 4 and the non-aqueous electrolyte contains FSO 3 Li. If counter capacity ratio defined by the ratio of the initial charge capacity of the negative electrode for the positive electrode initial charging capacity of the battery (C P) (C N) (C N / C P) is 1.79 or more 1.96 or less in addition, also in the counter capacity ratio (C N / C P) is Comparative example 3 and Comparative example 4 is 1.98 and 2.02, respectively, showed that good deposition of Li robustness evaluation is obtained. However, as described above, Comparative Example 3 and Comparative Example 4 have room for improvement in the evaluation of overcharge heat generation. In addition. Regarding Comparative Examples 1 and 2, it is shown that there is room for improvement in the evaluation of Li precipitation resistance.
表１における実施例１〜４と比較例５との比較、および図２より、電池の正極の初期充電容量（ＣＰ）に対する負極の初期充電容量（ＣＮ）の比で定義される対向容量比（ＣＮ／ＣＰ）が１．７９以上１．９６以下であっても、非水系電解質がＦＳＯ３Ｌｉを含んでいなければ、Ｌｉ析出耐性評価において改善の余地があることが示された。 Comparison with Comparative Example 5 and Examples 1-4 in Table 1, and from FIG. 2, counter capacity is defined as the ratio of the initial charge capacity of the negative electrode for the positive electrode initial charging capacity of the battery (C P) (C N) even the ratio (C N / C P) is 1.79 or more 1.96 or less, a non-aqueous electrolyte unless comprise FSO 3 Li, indicated that there is room for improvement in deposition of Li robustness evaluation It was.
表１における実施例１〜４と比較例６との比較、および図１より、電池の正極の初期充電容量（ＣＰ）に対する負極の初期充電容量（ＣＮ）の比で定義される対向容量比（ＣＮ／ＣＰ）が１．７９以上１．９６以下であっても、正極がＬｉ３ＰＯ４を含む正極合材層を含んでいなければ、過充電発熱評価において改善の余地があることが示された。 Comparison with Examples 1-4 in Table 1 as Comparative Example 6, and from Figure 1, the counter capacity is defined as the ratio of the initial charge capacity of the negative electrode for the positive electrode initial charging capacity of the battery (C P) (C N) even the ratio (C N / C P) is 1.79 or more 1.96 or less, if the positive electrode contains a positive-electrode mixture layer containing Li 3 PO 4, is room for improvement in overcharging heating evaluation It was shown to be.
上記の実施形態および実施例はすべての点で例示であって制限的なものではない。特許請求の範囲によって定められる技術的範囲は、特許請求の範囲と均等の意味および範囲内でのすべての変更を含む。 The above embodiments and examples are exemplary in all respects and are not restrictive. The technical scope defined by the claims includes all changes within the meaning and scope equivalent to the claims.
Claims (1)
前記正極は正極合材層を含み、
前記正極合材層はリン酸リチウムを含み、
前記非水電解質はフルオロスルホン酸リチウムを含み、
前記正極の初期充電容量（ＣＰ）に対する前記負極の初期充電容量（ＣＮ）の比で定義される対向容量比（ＣＮ／ＣＰ）が、１．７９以上１．９６以下である、
非水電解質二次電池。 A non-aqueous electrolyte secondary battery containing a positive electrode, a negative electrode, and a non-aqueous electrolyte.
The positive electrode contains a positive electrode mixture layer and contains a positive electrode mixture layer.
The positive electrode mixture layer contains lithium phosphate and contains
The non-aqueous electrolyte contains lithium fluorosulfonate and contains
The counter capacity ratio defined by the ratio of the initial charge capacity of the negative electrode with respect to the initial charge capacity of the positive electrode (C P) (C N) (C N / C P) is 1.79 or more 1.96 or less,
Non-aqueous electrolyte secondary battery.
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