JP2018010880A - Negative electrode, nonaqueous electrolyte secondary battery and battery pack - Google Patents
Negative electrode, nonaqueous electrolyte secondary battery and battery pack Download PDFInfo
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Abstract
Description
実施形態は、負極、非水電解質二次電池及び電池パックに係わる。 Embodiments relate to a negative electrode, a non-aqueous electrolyte secondary battery, and a battery pack.
負極活物質として炭素質材料を、正極活物質としてニッケル、コバルト、マンガン等を含有する層状酸化物用いた非水電解質電池（主にリチウムイオン二次電池）が各種電子機器といった小型の物から、電気自動車など大型の物まで、幅広い分野の電源として既に実用化されている。利用者からのさらなる小型化、軽量化、長時間使用、寿命への要求は強く、電池の容量密度をさらに向上させ、繰り返し性能を高めることが強く要望されている。しかしながら、従来の炭素質材料では、充放電容量の向上に限界があり、また高容量と目される低温焼成炭素では物質の密度が小さいため、単位体積あたりの充放電容量を大きくすることが難しい。このため、高容量電池の実現には新しい負極物質の開発が必要である。 Non-aqueous electrolyte batteries (mainly lithium ion secondary batteries) using a carbonaceous material as a negative electrode active material and a layered oxide containing nickel, cobalt, manganese, etc. as a positive electrode active material are used in various electronic devices. It has already been put into practical use as a power source in a wide range of fields, from large vehicles such as electric vehicles. There are strong demands from users for further miniaturization, weight reduction, long-time use, and longevity, and there is a strong demand to further improve the capacity density of the battery and to improve the repetition performance. However, with conventional carbonaceous materials, there is a limit to the improvement of charge / discharge capacity, and low-temperature calcined carbon, which is considered to have a high capacity, has a low material density, so it is difficult to increase the charge / discharge capacity per unit volume. . Therefore, the development of a new negative electrode material is necessary to realize a high capacity battery.
炭素質材料よりも高容量が得られる負極材料として、アルミニウム（Ａｌ）、シリコン（Ｓｉ）、ゲルマニウム（Ｇｅ）、スズ（Ｓｎ）、アンチモン（Ｓｂ）、などの単体金属を用いることが提案されている。特に、Ｓｉを負極材料として用いると、単位重量（１ｇ）当り４２００ｍＡｈという高容量が得られる。しかしながら、これら単体金属からなる負極では、Ｌｉの吸蔵放出を繰り返すことにより、元素のミクロ的な微粉化が生じるため、高い充放電サイクル特性を得られない。 It has been proposed to use a single metal such as aluminum (Al), silicon (Si), germanium (Ge), tin (Sn), antimony (Sb), etc., as a negative electrode material capable of obtaining a higher capacity than a carbonaceous material. Yes. In particular, when Si is used as the negative electrode material, a high capacity of 4200 mAh per unit weight (1 g) can be obtained. However, in the negative electrode made of these simple metals, the element is micronized by repeating the insertion and extraction of Li, so that high charge / discharge cycle characteristics cannot be obtained.
これらの問題を解決するために、アモルファス状のスズ酸化物、シリコン酸化物などは高容量化と高いサイクル特性を両立させることができ、さらには特許文献１のように、炭素材を複合させることでさらなる改良が可能となる。一方で改良された高容量のスズ酸化物、シリコン酸化物を用いても依然充電時の体積膨張および放電時の収縮による電池に与える負荷はかなり大きい。具体的には、集電体で用いる銅箔が激しく変形して、初回充電時に内部短絡が起こりやすい、あるいは繰り返しの使用により箔に穴が開いたりするため、安全性が大きく損なわれる。 In order to solve these problems, amorphous tin oxide, silicon oxide, etc. can achieve both high capacity and high cycle characteristics, and furthermore, as in Patent Document 1, a carbon material can be combined. Further improvements are possible. On the other hand, even if improved high-capacity tin oxide and silicon oxide are used, the load applied to the battery due to volume expansion during charging and contraction during discharging is still considerable. Specifically, the copper foil used in the current collector is severely deformed, so that an internal short circuit is likely to occur during the initial charge, or a hole is opened in the foil by repeated use, so that safety is greatly impaired.
サイクル特性に優れる負極、非水電解質二次電池及び電池パックを提供することを目的とする。 An object is to provide a negative electrode, a non-aqueous electrolyte secondary battery, and a battery pack that are excellent in cycle characteristics.
実施形態の負極は、負極集電体と負極集電体上に負極活物質層を有し、負極の引っ張り強さが４００Ｎ／ｍｍ２以上１２００Ｎ／ｍｍ２以下で、負極集電体と負極活物質層との剥離強度が１．５Ｎ／ｃｍ以上４Ｎ／ｃｍ以下であり、負極活物質層は、シリコン、シリコン含有酸化物およびスズ含有酸化物からなる群より選ばれる１種以上を含む。 The negative electrode of the embodiment has an anode active material layer on the negative electrode current collector and the anode current collector on the tensile strength of the negative electrode 400 N / mm 2 or more 1200 N / mm 2 or less, the negative electrode current collector and the anode active The peel strength from the material layer is 1.5 N / cm or more and 4 N / cm or less, and the negative electrode active material layer contains one or more selected from the group consisting of silicon, silicon-containing oxides, and tin-containing oxides.
（第１実施形態）
第１実施形態に係る非水電解質二次電池を説明する。
第１実施形態に係る非水電解質二次電池は、外装材と、外装材内に収納された正極と、外装材内に正極と空間的に離間して、例えばセパレータを介在して収納された活物質を含む負極と、外装材内に充填された非水電解質とを具備する。
(First embodiment)
The nonaqueous electrolyte secondary battery according to the first embodiment will be described.
The non-aqueous electrolyte secondary battery according to the first embodiment is housed in an exterior material, a positive electrode accommodated in the exterior material, and spatially separated from the positive electrode in the exterior material, for example, via a separator. A negative electrode containing an active material; and a non-aqueous electrolyte filled in an exterior material.
実施形態に係る非水電解質二次電池１００の一例を示した図１、図２を参照してより詳細に説明する。図１は、外装材１０２がラミネートフィルムからなる扁平型非水電解質二次電池１００の断面図模式図であり、図２は、図１のＡ部の拡大断面図である。なお、各図は説明のための模式図であり、その形状や寸法、比などは実際の装置と異なる個所があるが、これらは以下の説明と公知の技術を参酌して適宜、設計変更することができる。 This will be described in more detail with reference to FIGS. 1 and 2 showing an example of the nonaqueous electrolyte secondary battery 100 according to the embodiment. FIG. 1 is a schematic cross-sectional view of a flat type nonaqueous electrolyte secondary battery 100 in which the exterior material 102 is made of a laminate film, and FIG. 2 is an enlarged cross-sectional view of a portion A in FIG. Each figure is a schematic diagram for explanation, and its shape, dimensions, ratio, etc. are different from the actual device, but these are appropriately changed in consideration of the following explanation and known technology. be able to.
扁平状の捲回電極群１０１は、２枚の樹脂層の間にアルミニウム箔を介在したラミネートフィルムからなる外装材１０２内に収納されている。扁平状の捲回電極群１０１は、外側から負極３、セパレータ１０４、正極１０５、セパレータ１０４の順で積層した積層物を渦巻状に捲回し、プレス成型することにより形成される。最外殻の負極３は、図２に示すように負極集電体１０３ａの内面側の片面に負極層１０３ｂを形成した構成を有する。その他の負極３は、負極集電体１０３ａの両面に負極層１０３ｂを形成して構成されている。負極層１０３ｂ中の活物質は、第１実施形態に係る電池用活物質を含む。正極１０５は、正極集電体１０５ａの両面に正極層１０５ｂを形成して構成されている。 The flat wound electrode group 101 is accommodated in an exterior material 102 made of a laminate film in which an aluminum foil is interposed between two resin layers. The flat wound electrode group 101 is formed by winding a laminate of the negative electrode 3, the separator 104, the positive electrode 105, and the separator 104 in this order from the outside in a spiral shape and press-molding. As shown in FIG. 2, the outermost negative electrode 3 has a configuration in which a negative electrode layer 103b is formed on one surface on the inner surface side of the negative electrode current collector 103a. The other negative electrode 3 is configured by forming a negative electrode layer 103b on both surfaces of a negative electrode current collector 103a. The active material in the negative electrode layer 103b includes the battery active material according to the first embodiment. The positive electrode 105 is configured by forming a positive electrode layer 105b on both surfaces of a positive electrode current collector 105a.
捲回電極群１０１の外周端近傍において、負極端子１０６は最外殻の負極１０３の負極集電体１０３ａに電気的に接続され、正極端子１０７は内側の正極１０５の正極集電体１０５ａに電気的に接続されている。これらの負極端子１０６及び正極端子１０７は、外装材１０２の開口部から外部に延出されている。例えば液状非水電解質は、外装材１０２の開口部から注入されている。外装材１０２の開口部を負極端子６及び正極端子１０７を挟んでヒートシールすることにより捲回電極群１０１及び液状非水電解質を完全密封している。
実施形態では、電極群として、巻回電極群１０１を示したが、正極と負極とをその間にセパレータを介在させながら交互に積層した構造を有する積層型電極群を用いることも可能である。巻回電極群の方が、その本実施形態の効果をより得ることができる。
In the vicinity of the outer peripheral end of the wound electrode group 101, the negative electrode terminal 106 is electrically connected to the negative electrode current collector 103 a of the outermost negative electrode 103, and the positive electrode terminal 107 is electrically connected to the positive electrode current collector 105 a of the inner positive electrode 105. Connected. The negative electrode terminal 106 and the positive electrode terminal 107 are extended to the outside from the opening of the exterior material 102. For example, the liquid non-aqueous electrolyte is injected from the opening of the exterior material 102. The wound electrode group 101 and the liquid non-aqueous electrolyte are completely sealed by heat-sealing the opening of the exterior material 102 with the negative electrode terminal 6 and the positive electrode terminal 107 interposed therebetween.
In the embodiment, the wound electrode group 101 is shown as the electrode group. However, it is also possible to use a stacked electrode group having a structure in which positive electrodes and negative electrodes are alternately stacked with a separator interposed therebetween. The effect of this embodiment can be obtained more with the wound electrode group.
負極端子１０６は、例えばＡｌまたはＭｇ、Ｔｉ、Ｚｎ、Ｍｎ、Ｆｅ、Ｃｕ、Ｓｉ等の元素を含むアルミニウム合金が挙げられる。負極端子１０６は、負極集電体１０３ａとの接触抵抗を低減するために、負極集電体１０３ａと同様の材料であることが好ましい。 Examples of the negative electrode terminal 106 include Al or an aluminum alloy containing an element such as Mg, Ti, Zn, Mn, Fe, Cu, and Si. The negative electrode terminal 106 is preferably made of the same material as the negative electrode current collector 103a in order to reduce the contact resistance with the negative electrode current collector 103a.
正極端子１０７は、リチウムイオン金属に対する電位が３Ｖから４．２５Ｖの範囲における電気的安定性と導電性とを備える材料を用いることができる。具体的には、ＡｌまたはＭｇ、Ｔｉ、Ｚｎ、Ｍｎ、Ｆｅ、Ｃｕ、Ｓｉ等の元素を含むアルミニウム合金が挙げられる。正極端子１０７は、正極集電体１０５ａとの接触抵抗を低減するために、正極集電体１０５ａと同様の材料であることが好ましい。 The positive electrode terminal 107 can be made of a material having electrical stability and conductivity in the range of the potential with respect to the lithium ion metal in the range of 3V to 4.25V. Specifically, an aluminum alloy containing an element such as Al or Mg, Ti, Zn, Mn, Fe, Cu, and Si can be given. The positive electrode terminal 107 is preferably made of a material similar to that of the positive electrode current collector 105a in order to reduce contact resistance with the positive electrode current collector 105a.
以下、非水電解質二次電池１００の構成部材である外装材、正極、負極、電解質、セパレータについて詳細に説明する。
１）外装材
外装材１０２は、厚さ０．５ｍｍ以下のラミネートフィルムから形成される。或いは、外装材１０２には厚さ１．０ｍｍ以下の金属製容器が用いられる。金属製容器は、厚さ０．５ｍｍ以下であることがより好ましい。
外装材１０２の形状は、扁平型（薄型）、角型、円筒型、コイン型、及びボタン型から選択できる。外装材１０２の例には、電池寸法に応じて、例えば携帯用電子機器等に積載される小型電池用外装材、二輪乃至四輪の自動車等に積載される大型電池用外装材などが含まれる。
Hereinafter, the exterior material, the positive electrode, the negative electrode, the electrolyte, and the separator, which are constituent members of the nonaqueous electrolyte secondary battery 100, will be described in detail.
1) Exterior material The exterior material 102 is formed from a laminate film having a thickness of 0.5 mm or less. Alternatively, a metal container having a thickness of 1.0 mm or less is used for the exterior material 102. The metal container is more preferably 0.5 mm or less in thickness.
The shape of the exterior material 102 can be selected from a flat type (thin type), a square type, a cylindrical type, a coin type, and a button type. Examples of the exterior material 102 include, for example, a small battery exterior material loaded on a portable electronic device, a large battery exterior material loaded on a two- to four-wheeled vehicle, etc. .
ラミネートフィルムは、樹脂層間に金属層を介在した多層フィルムが用いられる。金属層は、軽量化のためにアルミニウム箔若しくはアルミニウム合金箔が好ましい。樹脂層は、例えばポリプロピレン（ＰＰ）、ポリエチレン（ＰＥ）、ナイロン、ポリエチレンテレフタレート（ＰＥＴ）等の高分子材料を用いることができる。ラミネートフィルムは、熱融着によりシールを行って外装材の形状に成形することができる。 As the laminate film, a multilayer film in which a metal layer is interposed between resin layers is used. The metal layer is preferably an aluminum foil or an aluminum alloy foil for weight reduction. For the resin layer, for example, a polymer material such as polypropylene (PP), polyethylene (PE), nylon, polyethylene terephthalate (PET) can be used. The laminate film can be molded into the shape of an exterior material by sealing by heat sealing.
金属製容器は、アルミニウムまたはアルミニウム合金等から作られる。アルミニウム合金は、マグネシウム、亜鉛、ケイ素等の元素を含む合金が好ましい。合金中に鉄、銅、ニッケル、クロム等の遷移金属が含まれる場合、その量は１００質量ｐｐｍ以下にすることが好ましい。 The metal container is made of aluminum or an aluminum alloy. The aluminum alloy is preferably an alloy containing elements such as magnesium, zinc, and silicon. When transition metals such as iron, copper, nickel, and chromium are included in the alloy, the amount is preferably 100 ppm by mass or less.
２）正極１０５
正極は、活物質を含む正極活物質層１０５ｂが正極集電体１０５ａの片面もしくは両面に担持された構造を有する。
前記正極活物質層１０５ｂの片面の厚さは１．０μｍ以上１５０μｍ以下の範囲であることが電池の大電流放電特性とサイクル寿命の保持の点から望ましい。従って正極集電体の両面に担持されている場合は正極活物質層１０５ｂの合計の厚さは２０μｍ以上３００μm以下の範囲となることが望ましい。片面のより好ましい範囲は３０μｍ以上１２０μｍ以下である。この範囲であると大電流放電特性とサイクル寿命は向上する。
2) Positive electrode 105
The positive electrode has a structure in which a positive electrode active material layer 105b containing an active material is supported on one surface or both surfaces of the positive electrode current collector 105a.
The thickness of one surface of the positive electrode active material layer 105b is preferably in the range of 1.0 μm or more and 150 μm or less from the viewpoint of maintaining large current discharge characteristics and cycle life of the battery. Therefore, when the positive electrode current collector is supported on both surfaces, the total thickness of the positive electrode active material layer 105b is preferably in the range of 20 μm to 300 μm. A more preferable range on one side is 30 μm or more and 120 μm or less. Within this range, large current discharge characteristics and cycle life are improved.
正極活物質層１０５ｂは、正極活物質の他に導電剤を含んでいてもよい。
また、正極活物質層１０５ｂは正極材料同士を結着する結着剤を含んでいてもよい。
正極活物質としては、種々の酸化物、例えば二酸化マンガン、リチウムマンガン複合酸化物、リチウム含有ニッケルコバルト酸化物（例えばＬｉＣｏＯ２）、リチウム含有ニッケルコバルト酸化物（例えばＬｉＮｉ０．８ＣＯ０．２Ｏ２）、リチウムマンガン複合酸化物（例えばＬｉＭｎ２Ｏ４、ＬｉＭｎＯ２）を用いると高電圧が得られるために好ましい。
The positive electrode active material layer 105b may contain a conductive agent in addition to the positive electrode active material.
The positive electrode active material layer 105b may include a binder that binds the positive electrode materials to each other.
Examples of the positive electrode active material include various oxides such as manganese dioxide, lithium manganese composite oxide, lithium-containing nickel cobalt oxide (eg, LiCoO 2 ), lithium-containing nickel cobalt oxide (eg, LiNi 0.8 CO 0.2 O). 2 ) and a lithium manganese composite oxide (for example, LiMn 2 O 4 , LiMnO 2 ) are preferable because a high voltage can be obtained.
導電剤としてはアセチレンブラック、カーボンブラック、黒鉛などを挙げることができる。
結着材の具体例としては例えばポリテトラフルオロエチレン（ＰＴＦＥ）、ポリ弗化ビニリデン（ＰＶｄＦ）、エチレン−プロピレン−ジエン共重合体（ＥＰＤＭ）、スチレン−ブタジエンゴム（ＳＢＲ）等を用いることができる。
Examples of the conductive agent include acetylene black, carbon black, and graphite.
Specific examples of the binder include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), ethylene-propylene-diene copolymer (EPDM), styrene-butadiene rubber (SBR), and the like. .
正極活物質、導電剤および結着剤の配合割合は、正極活物質８０質量％以上９５質量％以下、導電剤３質量％以上１８質量％以下、結着剤２質量％以上７質量％以下の範囲にすることが、良好な大電流放電特性とサイクル寿命を得られるために好ましい。 The mixing ratio of the positive electrode active material, the conductive agent and the binder is 80% by mass to 95% by mass of the positive electrode active material, 3% by mass to 18% by mass of the conductive agent, and 2% by mass to 7% by mass of the binder. The range is preferable because good large current discharge characteristics and cycle life can be obtained.
集電体としては、多孔質構造の導電性基板かあるいは無孔の導電性基板を用いることができる。集電体の厚さは５μｍ以上２０μｍであることが望ましい。この範囲であると電極強度と軽量化のバランスがとれるからである。 As the current collector, a conductive substrate having a porous structure or a non-porous conductive substrate can be used. The thickness of the current collector is preferably 5 μm or more and 20 μm. This is because within this range, the electrode strength and weight reduction can be balanced.
正極１０５は、例えば活物質、導電剤及び結着剤を汎用されている溶媒に懸濁してスラリーを調製し、このスラリーを集電体５ａに塗布し、乾燥し、その後、プレスを施すことにより作製される。正極５はまた活物質、導電剤及び結着剤をペレット状に形成して正極層１０５ｂとし、これを集電体１０５ａ上に形成することにより作製されてもよい。 The positive electrode 105 is prepared by, for example, preparing a slurry by suspending an active material, a conductive agent, and a binder in a commonly used solvent, applying the slurry to the current collector 5a, drying, and then applying a press. Produced. The positive electrode 5 may also be manufactured by forming an active material, a conductive agent, and a binder in the form of a pellet to form the positive electrode layer 105b and forming it on the current collector 105a.
３）負極１０３
負極１０３は、負極材料を含む負極活物質層１０３ａが負極集電体１０３ｂの片面もしくは両面に担持された構造を有する。
3) Negative electrode 103
The negative electrode 103 has a structure in which a negative electrode active material layer 103a containing a negative electrode material is supported on one surface or both surfaces of a negative electrode current collector 103b.
負極１０３において引っ張り強さ、電極剥離強度が適当な関係にあるとき、負極１０３の充放電時における変形を抑制させつつ、負極活物質層１０３ａの剥離を抑制させることができる。ここで負極活物質層１０３ａとは負極活物質や導電助剤、結着材などを含む層を指す。また、負極活物質層１０３ａと負極集電体１０３ｂを含めた層を負極１０３と定義する。負極１０３の引っ張り強さが４００Ｎ／ｍｍ２以上、１２００Ｎ／ｍｍ２以下の範囲を有すると、負極活物質の充放電前後における体積膨張変化率が大きくても負極１０３の変形を抑制する観点から好ましい。なお、引っ張り強さとは、二次電池の電極を作製し、非水電解質を注入する前にＪＩＳ Ｚ ２２４１−２０１１に準拠した方法によって、測定された数値である。注入後、充放電を実施した後も測定することができる。この場合、非水電解質二次電池を作製した後、メチルエチルカーボネートで３０分間洗浄し、２４時間室温にて真空乾燥させた電極でも測定することができる。負極１０３の引っ張り強さが４００Ｎ／ｍｍ２未満の場合、体積膨張変化を吸収できず、負極１０３の変形が起こりやすい。一方、負極１０３の引っ張り強さが１２００Ｎ／ｍｍ２を超える負極１０３の変形は防げるものの、負極集電体１０３ｂ表面と負極活物質層１０３ａ表面の間で剥離が起こりやすくなる。上記と同様の理由により、さらに好ましい負極１０３の引っ張り強さの範囲は４００Ｎ／ｍｍ２以上、１０００Ｎ／ｍｍ２以下である。 When the tensile strength and the electrode peeling strength are in an appropriate relationship in the negative electrode 103, the negative electrode active material layer 103a can be prevented from peeling while the deformation of the negative electrode 103 during charging and discharging is suppressed. Here, the negative electrode active material layer 103a refers to a layer containing a negative electrode active material, a conductive additive, a binder, and the like. A layer including the negative electrode active material layer 103 a and the negative electrode current collector 103 b is defined as the negative electrode 103. Tensile strength of the negative electrode 103 is 400 N / mm 2 or more, to have a 1200 N / mm 2 or less in the range of, preferably from the viewpoint of suppressing the deformation of the volumetric expansion rate of change is larger in the negative electrode 103 in the charging and discharging before and after the negative electrode active material . In addition, tensile strength is a numerical value measured by the method based on JISZ2241-2011 before producing the electrode of a secondary battery and inject | pouring a nonaqueous electrolyte. It can be measured even after charging and discharging. In this case, the measurement can also be made with an electrode prepared after producing a non-aqueous electrolyte secondary battery, washed with methyl ethyl carbonate for 30 minutes, and vacuum-dried at room temperature for 24 hours. When the tensile strength of the negative electrode 103 is less than 400 N / mm 2 , the volume expansion change cannot be absorbed, and the negative electrode 103 is easily deformed. On the other hand, although the deformation of the negative electrode 103 in which the tensile strength of the negative electrode 103 exceeds 1200 N / mm 2 can be prevented, peeling tends to occur between the surface of the negative electrode current collector 103b and the surface of the negative electrode active material layer 103a. For the same reason as described above, a more preferable range of the tensile strength of the negative electrode 103 is 400 N / mm 2 or more and 1000 N / mm 2 or less.
負極１０３の引っ張り強さは、負極集電体１０３ｂそのものの引っ張り強度だけでなく、負極活物質層１０３ａ内の結着剤量やプレス密度、その後の熱処理条件で引っ張り強さを調整することができる。例えば、プレス密度を下げて、熱処理温度を２５℃から５０℃程度下げることで引張強度は下がりにくく、逆にプレス密度を上げて、熱処理温度を高くすると引張強度が下がりやすい。また、熱処理の時間によっても変化する。 The tensile strength of the negative electrode 103 can be adjusted not only by the tensile strength of the negative electrode current collector 103b itself but also by the amount of binder in the negative electrode active material layer 103a, the press density, and the subsequent heat treatment conditions. . For example, lowering the press density and lowering the heat treatment temperature from about 25 ° C. to about 50 ° C. makes it difficult for the tensile strength to decrease. Conversely, increasing the press density and raising the heat treatment temperature tends to lower the tensile strength. It also changes depending on the heat treatment time.
負極１０３の変形を抑制しつつ、剥離を防ぐためには引っ張り強さに加えて、負極活物質層１０３ａと負極集電体１０３ｂの剥離強度、つまり電極剥離強度が１．５Ｎ／ｃｍ以上４Ｎ／ｃｍ以下であることが好ましい。電極剥離強度が１．５Ｎ／ｃｍ未満の場合、充電時に負極活物質の体積膨張変化が大きく剥離しやすい。一方、電極剥離強度が４Ｎ／ｃｍをこえると、負極１０３自体が硬く、もろくなりやすくなり、電池作製において支障をきたしやすい。好ましい電極剥離強度の範囲は２Ｎ／ｃｍ以上３．５Ｎ／ｃｍ以下である。 In order to prevent peeling while suppressing deformation of the negative electrode 103, in addition to the tensile strength, the peel strength between the negative electrode active material layer 103a and the negative electrode current collector 103b, that is, the electrode peel strength is 1.5 N / cm or more and 4 N / cm. The following is preferable. When the electrode peel strength is less than 1.5 N / cm, the volume expansion change of the negative electrode active material is large at the time of charging and is easily peeled off. On the other hand, when the electrode peel strength exceeds 4 N / cm, the negative electrode 103 itself is hard and fragile, which is liable to hinder battery fabrication. The range of preferable electrode peeling strength is 2 N / cm or more and 3.5 N / cm or less.
実施形態における電極剥離強度とは、サイカス（ＳＡＩＣＡＳ：Ｓｕｒｆａｃｅ Ａｎｄ Ｉｎｔｅｒｆａｃｉａｌ Ｃｕｔｔｉｎｇ Ａｎａｌｙｓｉｓ Ｓｙｓｔｅｍ）法の試験によって測定された切削強度である。これは試料表面に対して深さ位置を制御しつつ微細で鋭利な切り刃による切削を行い、刃にかかる応力を計測する手法である。電極集電体と電極活物質層の界面の切削測定値には、集電体表面を切り刃が接することによる摩擦抵抗が含まれる。電極剥離強度である切削強度は、電極活物質層界面の切削測定値から摩擦抵抗を除いた値とする。刃の深さ位置を、電極集電体と電極活物質層の界面に固定する事によりその界面の切削強度を測定することができる。この時、切り刃は電極集電体方向に一定の所要の荷重が印加されている。一定の所要の荷重は、電極集電体と電極活物質層の界面に切り刃の先端が当たり続ける力であり、電極集電体に対する電極活物質層の切削（剥離）強度が求められる。 The electrode peeling strength in the embodiment is a cutting strength measured by a test of SAICAS (Surface And Interfacial Cutting Analysis System) method. This is a method of measuring the stress applied to the blade by cutting with a fine and sharp cutting blade while controlling the depth position with respect to the sample surface. The measured cutting value at the interface between the electrode current collector and the electrode active material layer includes frictional resistance due to the cutting blade coming into contact with the current collector surface. The cutting strength, which is the electrode peel strength, is a value obtained by removing the frictional resistance from the measured cutting value at the electrode active material layer interface. By fixing the depth position of the blade to the interface between the electrode current collector and the electrode active material layer, the cutting strength at the interface can be measured. At this time, a certain required load is applied to the cutting blade in the direction of the electrode current collector. The constant required load is a force that keeps the tip of the cutting blade hitting the interface between the electrode current collector and the electrode active material layer, and the cutting (peeling) strength of the electrode active material layer with respect to the electrode current collector is required.
より具体的な電極剥離強度（切削強度）の求め方について説明する。切削強度測定装置サイカス（登録商標）ＤＮ−ＧＳ型（ダイプラ・ウインテス（株）製）を用いて、切削強度を測定した。切り刃には、ボラゾン材質のセラミック刃を使用し、刃幅が１．０ｍｍのセラミック製のものを用い、刃角は、すくい角度２０度、にげ角度１０度、速度は２μｍ／秒の一定速度で測定した。測定温度が室温（２５℃）で、試料温度も室温（２５℃）で行った。測定は、０．５Ｎの定荷重モードで行った。 A more specific method for obtaining the electrode peel strength (cutting strength) will be described. The cutting strength was measured using a cutting strength measuring device Cycus (registered trademark) DN-GS type (manufactured by Daipura Wintes Co., Ltd.). The cutting blade is a ceramic blade made of borazon, and the blade width is 1.0 mm. The blade angle is a rake angle of 20 degrees, a bald angle of 10 degrees, and the speed is constant at 2 μm / second. Measured at speed. The measurement temperature was room temperature (25 ° C.), and the sample temperature was also room temperature (25 ° C.). The measurement was performed in a constant load mode of 0.5N.
負極活物質層１０３ａの電極剥離強度は、引っ張り強度と同じく、負極活物質層１０３ａ内の結着剤量やプレス密度、その後の熱処理条件で調製することができる。具体的には、結着剤量を増加させると電極剥離強度が高くなりやすく、減少させると下がりやすい。またプレス密度を高くすると電極剥離強度が高くなりやすいが、一定レベルを超えると下がりやすい。熱処理温度は、４５０℃を極大とし、それ以下でも以上でも下がる傾向がある。 Similarly to the tensile strength, the electrode peel strength of the negative electrode active material layer 103a can be adjusted by the amount of binder in the negative electrode active material layer 103a, the press density, and subsequent heat treatment conditions. Specifically, when the amount of the binder is increased, the electrode peel strength is likely to be increased, and when it is decreased, it is likely to be decreased. Further, when the press density is increased, the electrode peel strength tends to increase, but when it exceeds a certain level, it tends to decrease. The heat treatment temperature has a maximum of 450 ° C., and tends to decrease even below or above.
２５℃環境下にて、０．２Ｃレート、４．２Ｖで充電した負極と、０．２Ｃレートで２．０Ｖで放電した負極１０３の密度の比率（充電時の密度）／（放電時の密度）が０．２５以上０．９以下であることが好ましい。ここで指す密度とは負極活物質層１０３ａの密度を指す。ここでの０．２Ｃレートでの充電とは、初回の電池容量（０．２Ｃレート）を基準としてＣレートを算出し（たとえば０．２Ｃレートで３Ａｈ容量であれば、Ｃ＝３Ａとする）、４．２Ｖまで０．２Ｃレートで定電流充電を実施し、その後、定電圧にて電流が０．０５Ｃに収束するまでの充電を指す。密度の比率が０．２５未満の場合、体積膨張変化が大きすぎて負極１０３の変形を抑制することが困難になるか、負極活物質層１０３ａの剥離が顕著になる。一方、密度の比率が０．９を超える場合、そもそも強度の強い負極集電体１０３ｂを使う必要がない。さらに好ましい密度の比率の範囲は０．３以上０．８５以下である。 Ratio of density of negative electrode 103 charged at 0.2 C rate and 4.2 V and negative electrode 103 discharged at 2.0 V at 0.2 C rate in a 25 ° C. environment (density during charging) / (density during discharge) ) Is preferably 0.25 or more and 0.9 or less. The density indicated here refers to the density of the negative electrode active material layer 103a. Here, charging at 0.2C rate means calculating C rate based on the initial battery capacity (0.2C rate) (for example, if 3Ch capacity at 0.2C rate, C = 3A) It refers to charging until constant current charging is performed at a 0.2 C rate up to 4.2 V, and then the current converges to 0.05 C at a constant voltage. When the density ratio is less than 0.25, it is difficult to suppress deformation of the negative electrode 103 because the volume expansion change is too large, or peeling of the negative electrode active material layer 103a becomes remarkable. On the other hand, when the density ratio exceeds 0.9, it is not necessary to use the negative electrode current collector 103b having high strength in the first place. A more preferable range of the density ratio is 0.3 or more and 0.85 or less.
負極活物質層１０３ａの単位面積あたりの質量は、１０ｇ／ｍ２以上１５０ｇ／ｍ２以下であることが好ましい。
ここで負極活物質層１０３ａの単位面積あたりの質量とは、負極集電体１０３ｂの両側に負極活物質層１０３ａが塗布されている場合は、どちらか片側あたりの負極活物質層１０３ａを指す。負極活物質層１０３ａの単位面積あたりの質量が１０ｇ／ｍ２未満の場合、そもそも強度の強い集電体を使う必要がない。また、負極活物質層１０３ａの単位面積あたりの質量が１５０ｇ／ｍ２を超えると結着を保ちつつ負極集電体１０３ｂの変形を抑制することが難しい。より好ましい負極活物質層１０３ａの単位面積あたりの質量の範囲は２０ｇ／ｍ２以上１００ｇ／ｍ２以下である。
The mass per unit area of the negative electrode active material layer 103a is preferably 10 g / m 2 or more and 150 g / m 2 or less.
Here, the mass per unit area of the negative electrode active material layer 103a refers to the negative electrode active material layer 103a per one side when the negative electrode active material layer 103a is applied on both sides of the negative electrode current collector 103b. When the mass per unit area of the negative electrode active material layer 103a is less than 10 g / m 2 , it is not necessary to use a strong current collector. Further, when the mass per unit area of the negative electrode active material layer 103a exceeds 150 g / m 2 , it is difficult to suppress deformation of the negative electrode current collector 103b while maintaining binding. A more preferable range of the mass per unit area of the negative electrode active material layer 103a is 20 g / m 2 or more and 100 g / m 2 or less.
負極集電体１０３ｂの厚さが５μｍ以上２５μｍ以下であることが好ましい。
負極集電体１０３ｂの厚さが５μｍ未満の場合、電池作製にあたり負極集電体１０３ｂが切れやすかったり、充放電にともなう負極集電体１０３ｂの変形を抑制できなくなったりする恐れがある。負極集電体１０３ｂの厚さが２５μｍを超えると、電池の体積容量が小さくなる。好ましい負極集電体１０３ｂの厚さは、７μｍ以上２０μｍ以下である。
The thickness of the negative electrode current collector 103b is preferably 5 μm or more and 25 μm or less.
When the thickness of the negative electrode current collector 103b is less than 5 μm, the negative electrode current collector 103b may be easily cut during battery production, or deformation of the negative electrode current collector 103b due to charge / discharge may not be suppressed. When the thickness of the negative electrode current collector 103b exceeds 25 μm, the volume capacity of the battery becomes small. A preferable thickness of the negative electrode current collector 103b is 7 μm or more and 20 μm or less.
負極活物質層１０３ａ内の負極活物質に少なくともシリコン、シリコン含有酸化物、スズ、スズ含有酸化物を１種類以上含むことが好ましい。 The negative electrode active material in the negative electrode active material layer 103a preferably contains at least one kind of silicon, silicon-containing oxide, tin, and tin-containing oxide.
負極活物質層１０３ａ内の負極活物質は、少なくともシリコン、シリコン含有酸化物、スズ、スズ含有酸化物の１種類以上が好ましい。シリコン含有酸化物は、ＳｉＯｘ（０＜ｘ≦２）を指し、ＳｉＯｘの表面にＳｉが析出している形態でも構わない。スズ含有酸化物はＳｎＯｘ（０＜ｘ≦２）を指し、同様にＳｎが析出している形態でも構わない。また、活物質自体のサイクル性能改善のため、微少量の異種元素を置換していても構わない。さらに、これらのシリコン含有酸化物およびスズ含有酸化物の周りがカーボンで被覆されていても構わない。 The negative electrode active material in the negative electrode active material layer 103a is preferably at least one of silicon, silicon-containing oxide, tin, and tin-containing oxide. The silicon-containing oxide refers to SiO x (0 <x ≦ 2), and Si may be deposited on the surface of SiO x . Tin-containing oxide refers to SnO x (0 <x ≦ 2), and similarly, Sn may be deposited. In addition, in order to improve the cycle performance of the active material itself, a minute amount of different elements may be substituted. Furthermore, these silicon-containing oxides and tin-containing oxides may be covered with carbon.
負極導電剤は、通常、炭素質材料が使用される。炭素質材料は、アルカリ金属の吸蔵性と導電性との両特性の高いものがあればよい。炭素質材料の例は、アセチレンブラックまたはカーボンブラックを含み、結晶性の高いグラファイトでも構わない。 A carbonaceous material is usually used for the negative electrode conductive agent. The carbonaceous material only needs to have high properties of both alkali metal occlusion and conductivity. Examples of the carbonaceous material may include acetylene black or carbon black, and may be graphite having high crystallinity.
結着剤の例は、ポリテトラフルオロエチレン（ＰＴＦＥ）、ポリフッ化ビニリデン（ＰＶｄＦ）、フッ素系ゴム、エチレン-ブタジエンゴム（ＳＢＲ）、ポリプロピレン（ＰＰ）、ポリエチレン（ＰＥ）、カルボキシメチルセルロース（ＣＭＣ）、ポリイミド（ＰＩ）、ポリアクリルイミド（ＰＡＩ）を含む。 Examples of the binder include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), fluorine-based rubber, ethylene-butadiene rubber (SBR), polypropylene (PP), polyethylene (PE), carboxymethyl cellulose (CMC), Includes polyimide (PI) and polyacrylimide (PAI).
負極活物質層１０３ａ中の負極活物質、導電剤および結着剤の配合割合は、負極活物質が７０質量％以上９５質量％、導電剤が０質量％以上２５質量％以下、結着剤が２質量％以上１０質量％にすることが好ましい。最終的に負極層内のシリコン元素およびスズ元素は炭素元素に対する原子比が５％以上８０％以下であることが好ましい。 The mixing ratio of the negative electrode active material, the conductive agent, and the binder in the negative electrode active material layer 103a is such that the negative electrode active material is 70% by mass to 95% by mass, the conductive agent is 0% by mass to 25% by mass, and the binder is It is preferable to make it 2 mass% or more and 10 mass%. Finally, the atomic ratio of silicon element and tin element in the negative electrode layer to the carbon element is preferably 5% or more and 80% or less.
４）電解質
電解質としては非水電解液、電解質含浸型ポリマー電解質、高分子電解質、あるいは無機固体電解質を用いることができる。
非水電解液は、非水溶媒に電解質を溶解することにより調製される液体状電解液で、電極群中の空隙に保持される。
非水溶媒としては、プロピレンカーボネート（ＰＣ）やエチレンカーボネート（ＥＣ）とＰＣやＥＣより低粘度である非水溶媒（以下第２溶媒と称す）との混合溶媒を主体とする非水溶媒を用いることが好ましい。
4) Electrolyte As the electrolyte, a non-aqueous electrolyte, an electrolyte-impregnated polymer electrolyte, a polymer electrolyte, or an inorganic solid electrolyte can be used.
The non-aqueous electrolyte is a liquid electrolyte prepared by dissolving an electrolyte in a non-aqueous solvent, and is held in the voids in the electrode group.
As the non-aqueous solvent, a non-aqueous solvent mainly composed of a mixed solvent of propylene carbonate (PC) or ethylene carbonate (EC) and a non-aqueous solvent having a viscosity lower than that of PC or EC (hereinafter referred to as a second solvent) is used. It is preferable.
第２溶媒としては、例えば鎖状カーボンが好ましく、中でもジメチルカーボネート（ＤＭＣ）、メチルエチルカーボネート（ＭＥＣ）、ジエチルカーボネート（ＤＥＣ）、プロピオン酸エチル、プロピオン酸メチル、γ−ブチロラクトン（ＢＬ）、アセトニトリル（ＡＮ）、酢酸エチル（ＥＡ）、トルエン、キシレンまたは、酢酸メチル（ＭＡ）等が挙げられる。これらの第２溶媒は、単独または２種以上の混合物の形態で用いることができる。特に、第２溶媒はドナー数が１６．５以下であることがより好ましい。 As the second solvent, for example, chain carbon is preferable, among which dimethyl carbonate (DMC), methyl ethyl carbonate (MEC), diethyl carbonate (DEC), ethyl propionate, methyl propionate, γ-butyrolactone (BL), acetonitrile ( AN), ethyl acetate (EA), toluene, xylene or methyl acetate (MA). These second solvents can be used alone or in the form of a mixture of two or more. In particular, the second solvent preferably has a donor number of 16.5 or less.
第２溶媒の粘度は、２５℃において２．８ｃｍｐ以下であることが好ましい。混合溶媒中のエチレンカーボネートまたはプロピレンカーボネートの配合量は、体積比率で１．０％以上８０％以下であることが好ましい。より好ましいエチレンカーボネートまたはプロピレンカーボネートの配合量は体積比率で２０％以上７５％以下である。 The viscosity of the second solvent is preferably 2.8 cmp or less at 25 ° C. The blending amount of ethylene carbonate or propylene carbonate in the mixed solvent is preferably 1.0% or more and 80% or less by volume ratio. More preferable blending amount of ethylene carbonate or propylene carbonate is 20% or more and 75% or less by volume ratio.
非水電解液に含まれる電解質としては、例えば過塩素酸リチウム（ＬｉＣｌＯ４）、六弗化リン酸リチウム（ＬｉＰＦ６）、ホウ弗化リチウム（ＬｉＢＦ４）、六弗化砒素リチウム（ＬｉＡｓＦ６）、トリフルオロメタスルホン酸リチウム（ＬｉＣＦ３ＳＯ３）、ビストリフルオロメチルスルホニルイミドリチウム［ＬｉＮ（ＣＦ３ＳＯ２）２］等のリチウム塩（電解質）が挙げられる。中でもＬｉＰＦ６、ＬｉＢＦ４を用いるのが好ましい。
電解質の非水溶媒に対する溶解量は、０．５ｍｏｌ／Ｌ以上２．０ｍｏｌ／Ｌ以下とすることが望ましい。
Examples of the electrolyte contained in the non-aqueous electrolyte include lithium perchlorate (LiClO 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium borofluoride (LiBF 4 ), and lithium arsenic hexafluoride (LiAsF 6 ). And lithium salts (electrolytes) such as lithium trifluorometasulfonate (LiCF 3 SO 3 ) and lithium bistrifluoromethylsulfonylimide [LiN (CF 3 SO 2 ) 2 ]. Of these, LiPF 6 and LiBF 4 are preferably used.
The amount of electrolyte dissolved in the non-aqueous solvent is desirably 0.5 mol / L or more and 2.0 mol / L or less.
５）セパレータ１０４
非水電解液を用いる場合、および電解質含浸型ポリマー電解質を用いる場合においてはセパレータ１０４を用いることができる。セパレータ１０４は多孔質セパレータを用いる。セパレータ１０４の材料としては、例えば、ポリエチレン、ポリプロピレン、またはポリ弗化ピニリデン（ＰＶｄＦ）を含む多孔質フィルム、合成樹脂製不織布等を用いることができる。中でも、ポリエチレンか、あるいはポリプロピレン、または両者からなる多孔質フィルムは、二次電池の安全性を向上できるため好ましい。
5) Separator 104
In the case of using a non-aqueous electrolyte and in the case of using an electrolyte-impregnated polymer electrolyte, the separator 104 can be used. A separator 104 is a porous separator. As a material of the separator 104, for example, a porous film containing polyethylene, polypropylene, or polyvinylidene fluoride (PVdF), a synthetic resin nonwoven fabric, or the like can be used. Among these, a porous film made of polyethylene, polypropylene, or both is preferable because it can improve the safety of the secondary battery.
セパレータ１０４の厚さは、３０μｍ以下にすることが好ましい。厚さが３０μｍを越えると、正負極間の距離が大きくなって内部抵抗が大きくなる恐れがある。また、厚さの下限値は、５μｍにすることが好ましい。厚さを５μｍ未満にすると、セパレータ１０４の強度が著しく低下して内部ショートが生じやすくなる恐れがある。厚さの上限値は、２５μｍにすることがより好ましく、また、下限値は１．０μｍにすることがより好ましい。 The thickness of the separator 104 is preferably 30 μm or less. If the thickness exceeds 30 μm, the distance between the positive and negative electrodes may be increased and the internal resistance may be increased. Further, the lower limit value of the thickness is preferably 5 μm. If the thickness is less than 5 μm, the strength of the separator 104 may be significantly reduced and an internal short circuit is likely to occur. The upper limit value of the thickness is more preferably 25 μm, and the lower limit value is more preferably 1.0 μm.
セパレータ１０４は、１２０℃の条件で１時間おいたときの熱収縮率が２０％以下であることが好ましい。熱収縮率が２０％を超えると、加熱により短絡が起こる可能性が大きくなる。熱収縮率は、１５％以下にすることがより好ましい。 The separator 104 preferably has a heat shrinkage rate of 20% or less when kept at 120 ° C. for 1 hour. If the heat shrinkage rate exceeds 20%, the possibility of a short circuit due to heating increases. The thermal shrinkage rate is more preferably 15% or less.
セパレータ１０４は、多孔度が３０％以上７０％以上の範囲であることが好ましい。これは次のような理由によるものである。多孔度を３０％未満にすると、セパレータ１０４において高い電解質保持性を得ることが困難になる恐れがある。一方、多孔度が７０％を超えると十分なセパレータ１０４強度を得られなくなる恐れがある。多孔度のより好ましい範囲は、３５％以上７０％以下である。 The separator 104 preferably has a porosity in the range of 30% to 70%. This is due to the following reason. If the porosity is less than 30%, it may be difficult to obtain high electrolyte retention in the separator 104. On the other hand, if the porosity exceeds 70%, sufficient separator 104 strength may not be obtained. A more preferable range of the porosity is 35% or more and 70% or less.
セパレータ１０４は、空気透過率が５００秒／１．００ｃｍ３以下であると好ましい。空気透過率が５００秒／１．００ｃｍ３を超えると、セパレータ１０４において高いリチウムイオン移動度を得ることが困難になる恐れがある。また、空気透過率の下限値は、３０秒／１．００ｃｍ３である。空気透過率を３０秒／１．００ｃｍ３未満にすると、十分なセパレータ１０４強度を得られなくなる恐れがあるからである。 The separator 104 preferably has an air permeability of 500 seconds / 1.00 cm 3 or less. If the air permeability exceeds 500 seconds / 1.00 cm 3 , it may be difficult to obtain high lithium ion mobility in the separator 104. The lower limit of the air permeability is 30 seconds / 1.00 cm 3 . This is because if the air permeability is less than 30 seconds / 1.00 cm 3 , sufficient strength of the separator 104 may not be obtained.
空気透過率の上限値は３００秒／１．００ｃｍ３にすることがより好ましく、また、下限値は５０秒／１．００ｃｍ３にするとより好ましい。 The upper limit value of the air permeability is more preferably 300 seconds / 1.00 cm 3 , and the lower limit value is more preferably 50 seconds / 1.00 cm 3 .
（第２実施形態）
次に、上述の非水電解質二次電池を用いた電池パックについて説明する。
第２実施形態に係る電池パックは、上記実施形態に係る非水電解質二次電池（即ち、単電池）を一以上有する。電池パックに複数の単電池が含まれる場合、各単電池は、電気的に直列、並列、或いは、直列と並列に接続して配置される。
図３の概念図及び図４のブロック図を参照して電池パック２００を具体的に説明する。図３に示す電池パック２００では、単電池２０１として図１に示す非水電解質液電池１００を使用している。
(Second Embodiment)
Next, a battery pack using the above-described nonaqueous electrolyte secondary battery will be described.
The battery pack according to the second embodiment includes one or more nonaqueous electrolyte secondary batteries (that is, single cells) according to the above-described embodiment. When the battery pack includes a plurality of single cells, the single cells are electrically connected in series, parallel, or connected in series and parallel.
The battery pack 200 will be specifically described with reference to the conceptual diagram of FIG. 3 and the block diagram of FIG. In the battery pack 200 shown in FIG. 3, the nonaqueous electrolyte battery 100 shown in FIG. 1 is used as the unit cell 201.
複数の単電池２０１は、外部に延出した負極端子２０２及び正極端子２０３が同じ向きに揃えられるように積層され、粘着テープ２０４で締結することにより組電池２０５を構成している。これらの単電池２０１は、図４に示すように互いに電気的に直列に接続されている。 The plurality of unit cells 201 are stacked such that the negative electrode terminal 202 and the positive electrode terminal 203 extending to the outside are aligned in the same direction, and are fastened with an adhesive tape 204 to constitute an assembled battery 205. These unit cells 201 are electrically connected to each other in series as shown in FIG.
プリント配線基板２０６は、負極端子２０２及び正極端子２０３が延出する単電池２０１側面と対向して配置されている。プリント配線基板２０６には、図４に示すようにサーミスタ２０７、保護回路２０８及び外部機器への通電用端子２０９が搭載されている。なお、組電池２０５と対向する保護回路基板２０６の面には組電池２０５の配線と不要な接続を回避するために絶縁板（図示せず）が取り付けられている。 The printed wiring board 206 is disposed to face the side surface of the unit cell 201 from which the negative electrode terminal 202 and the positive electrode terminal 203 extend. As shown in FIG. 4, a thermistor 207, a protection circuit 208, and a terminal 209 for energizing external devices are mounted on the printed wiring board 206. An insulating plate (not shown) is attached to the surface of the protection circuit board 206 facing the assembled battery 205 in order to avoid unnecessary connection with the wiring of the assembled battery 205.
正極側リード２１０は、組電池２０５の最下層に位置する正極端子２０３に接続され、その先端はプリント配線基板２０６の正極側コネクタ２１１に挿入されて電気的に接続されている。負極側リード２１２は、組電池２０５の最上層に位置する負極端子２０２に接続され、その先端はプリント配線基板２０６の負極側コネクタ２１３に挿入されて電気的に接続されている。これらのコネクタ２１１、２１３は、プリント配線基板２０６に形成された配線２１４、２１５を通して保護回路２０８に接続されている。 The positive electrode side lead 210 is connected to the positive electrode terminal 203 located in the lowermost layer of the assembled battery 205, and the tip thereof is inserted into the positive electrode side connector 211 of the printed wiring board 206 to be electrically connected. The negative electrode side lead 212 is connected to the negative electrode terminal 202 located in the uppermost layer of the assembled battery 205, and the tip thereof is inserted into the negative electrode side connector 213 of the printed wiring board 206 to be electrically connected. These connectors 211 and 213 are connected to the protection circuit 208 through wirings 214 and 215 formed on the printed wiring board 206.
サーミスタ２０７は、単電池２０５の温度を検出するために用いられ、その検出信号は保護回路２０８に送信される。保護回路２０８は、所定の条件で保護回路２０８と外部機器への通電用端子２０９との間のプラス側配線２１６ａ及びマイナス側配線２１６ｂを遮断できる。所定の条件とは、例えばサーミスタ２０７の検出温度が所定温度以上になったときである。また、所定の条件とは単電池２０１の過充電、過放電、過電流等を検出したときである。この過充電等の検出は、個々の単電池２０１もしくは単電池２０１全体について行われる。個々の単電池２０１を検出する場合、電池電圧を検出してもよいし、正極電位もしくは負極電位を検出してもよい。後者の場合、個々の単電池２０１中に参照極として用いるリチウム電極が挿入される。図３及び図４の場合、単電池２０１それぞれに電圧検出のための配線２１７を接続し、これら配線２１７を通して検出信号が保護回路２０８に送信される。 The thermistor 207 is used to detect the temperature of the unit cell 205, and the detection signal is transmitted to the protection circuit 208. The protection circuit 208 can cut off the plus-side wiring 216a and the minus-side wiring 216b between the protection circuit 208 and the energization terminal 209 to the external device under a predetermined condition. The predetermined condition is, for example, when the temperature detected by the thermistor 207 is equal to or higher than a predetermined temperature. Further, the predetermined condition is when an overcharge, overdischarge, overcurrent, or the like of the unit cell 201 is detected. This detection of overcharge or the like is performed for each single cell 201 or the entire single cell 201. When detecting each single cell 201, the battery voltage may be detected, or the positive electrode potential or the negative electrode potential may be detected. In the latter case, a lithium electrode used as a reference electrode is inserted into each unit cell 201. In the case of FIG. 3 and FIG. 4, a wiring 217 for voltage detection is connected to each single cell 201, and a detection signal is transmitted to the protection circuit 208 through these wirings 217.
正極端子２０３及び負極端子２０２が突出する側面を除く組電池２０５の三側面には、ゴムもしくは樹脂からなる保護シート２１８がそれぞれ配置されている。 Protective sheets 218 made of rubber or resin are disposed on the three side surfaces of the assembled battery 205 excluding the side surfaces from which the positive electrode terminal 203 and the negative electrode terminal 202 protrude.
組電池２０５は、各保護シート２１８及びプリント配線基板２０６と共に収納容器２１９内に収納される。すなわち、収納容器２１９の長辺方向の両方の内側面と短辺方向の内側面それぞれに保護シート２１８が配置され、短辺方向の反対側の内側面にプリント配線基板２０６が配置される。組電池２０５は、保護シート２１８及びプリント配線基板２０６で囲まれた空間内に位置する。蓋３２０は、収納容器２１９の上面に取り付けられている。 The assembled battery 205 is stored in the storage container 219 together with each protective sheet 218 and the printed wiring board 206. That is, the protective sheet 218 is disposed on each of the inner side surface in the long side direction and the inner side surface in the short side direction of the storage container 219, and the printed wiring board 206 is disposed on the inner side surface on the opposite side in the short side direction. The assembled battery 205 is located in a space surrounded by the protective sheet 218 and the printed wiring board 206. The lid 320 is attached to the upper surface of the storage container 219.
なお、組電池２０５の固定には粘着テープ２０４に代えて、熱収縮テープを用いてもよい。この場合、組電池の両側面に保護シートを配置し、熱収縮テープを周回させた後、熱収縮テープを熱収縮させて組電池を結束させる。 Note that a heat shrink tape may be used instead of the adhesive tape 204 for fixing the assembled battery 205. In this case, protective sheets are arranged on both side surfaces of the assembled battery, the heat shrinkable tape is circulated, and then the heat shrinkable tape is heat shrunk to bind the assembled battery.
図３、図４では単電池２０１を直列接続した形態を示したが、電池容量を増大させるためには並列に接続しても、または直列接続と並列接続を組み合わせてもよい。組み上がった電池パックをさらに直列、並列に接続することもできる。
以上に記載した本実施形態によれば、上記実施形態における優れた充放電サイクル性能を有する非水電解質二次電池を備えることにより、優れた充放電サイクル性能を有する電池パックを提供することができる。
3 and 4 show a configuration in which the unit cells 201 are connected in series, but in order to increase the battery capacity, they may be connected in parallel, or a combination of series connection and parallel connection may be used. The assembled battery packs can be further connected in series and in parallel.
According to this embodiment described above, a battery pack having excellent charge / discharge cycle performance can be provided by including the nonaqueous electrolyte secondary battery having excellent charge / discharge cycle performance in the above embodiment. .
なお、電池パックの態様は用途により適宜変更される。電池パックの用途は、小型かつ大容量が求められるもの好ましい。具体的には、スマートフォン、デジタルカメラの電源用や、二輪乃至四輪のハイブリッド電気自動車、二輪乃至四輪の電気自動車、アシスト自転車等の車載用が挙げられる。 In addition, the aspect of a battery pack is changed suitably by a use. The battery pack is preferably used for small size and large capacity. Specific examples include power supplies for smartphones and digital cameras, and two-wheel to four-wheel hybrid electric vehicles, two-wheel to four-wheel electric vehicles, and assist bicycles.
以下に具体的な実施例（各実施例で説明する夫々の条件で、図１で説明した電池を具体的に作成した例）を挙げ、その効果について述べる。但し、これらの実施例に限定されるものではない。 Specific examples (examples in which the battery described in FIG. 1 is specifically created under the respective conditions described in each example) will be given and the effects will be described. However, it is not limited to these examples.
（実施例１）
＜正極の作製＞
活物質であるリチウムニッケルマンガンコバルト複合酸化物（ＬｉＮｉ１／３Ｍｎ１／３Ｃｏ１／３Ｏ２）粉末８５質量％とアセチレンブラック１０質量％とポリフッ化ビニリデン（ＰＶｄＦ）５質量％とをＮ−メチルピロリドンに加えて混合してスラリーを調製した。このスラリーを厚さ１５μｍのアルミニウム箔（集電体）に、活物質層の単位面積あたりの質量が２７０ｇ／ｍ２になるように塗布し、乾燥後、プレスすることにより密度３．２５ｇ／ｃｍ３の正極層を有する正極を作製した。
Example 1
<Preparation of positive electrode>
85% by mass of lithium nickel manganese cobalt composite oxide (LiNi 1/3 Mn 1/3 Co 1/3 O 2 ) powder, 10% by mass of acetylene black, and 5% by mass of polyvinylidene fluoride (PVdF), which are active materials, are N -A slurry was prepared by adding to methylpyrrolidone and mixing. The slurry was applied to an aluminum foil (current collector) having a thickness of 15 μm so that the mass per unit area of the active material layer was 270 g / m 2 , dried and pressed to obtain a density of 3.25 g / cm 3. A positive electrode having three positive electrode layers was produced.
＜負極の作製＞
シリコン酸化物粉末（ＳｉＯ）およびシリコン粉末（Ｓｉ）の混合物を８０質量％とハードカーボン粉末１０質量％とポリイミド（ＰＩ）１０質量％をＮＭＰに加えて混合してスラリーを調製した。
このスラリーを厚さ１０μｍのステンレス箔に、活物質層の単位質量が２５ｇ／ｍ２になるように塗布・乾燥した後、密度１．５ｇ／ｃｍ３の電極密度になるように負極をロールプレスにて圧延した。作製した電極群を露点−２０℃のアルゴン雰囲気下、４５０℃にて１日間熱処理を行った。
<Production of negative electrode>
A slurry was prepared by adding 80% by mass of a mixture of silicon oxide powder (SiO) and silicon powder (Si), 10% by mass of hard carbon powder, and 10% by mass of polyimide (PI) to NMP and mixing them.
After applying and drying this slurry onto a stainless steel foil having a thickness of 10 μm so that the unit mass of the active material layer is 25 g / m 2 , the negative electrode is roll-pressed so as to have an electrode density of 1.5 g / cm 3. And rolled. The produced electrode group was heat-treated at 450 ° C. for 1 day in an argon atmosphere with a dew point of −20 ° C.
＜電極群の作製＞
前記正極、ポリエチレン製多孔質フィルムからなるセパレータ、前記負極および前記セパレータをそれぞれこの順序で積層した後、前記負極が最外周に位置するように渦巻き状に巻回して電極群を作製した。
<Production of electrode group>
The positive electrode, a separator made of a polyethylene porous film, the negative electrode, and the separator were each laminated in this order, and then wound in a spiral shape so that the negative electrode was located on the outermost periphery, thereby producing an electrode group.
＜非水電解液の調製＞
エチレンカーボネート（ＥＣ）とメチルエチルカーボネート（ＭＥＣ）とを体積比で１：２になるように混合して混合溶媒とした。この混合溶媒に六フッ化リン酸リチウム（ＬｉＰＦ６）を１．０モル／Ｌ溶解して非水電解液を調製した。
<Preparation of non-aqueous electrolyte>
Ethylene carbonate (EC) and methyl ethyl carbonate (MEC) were mixed at a volume ratio of 1: 2 to obtain a mixed solvent. A non-aqueous electrolyte was prepared by dissolving 1.0 mol / L of lithium hexafluorophosphate (LiPF 6 ) in this mixed solvent.
＜非水電解質二次電池の調製＞
前記電極群および前記非水電解液を直径１．８ｍｍ、高さ６５０ｍｍのステンレス製の有底円筒状容器内にそれぞれ収納した。つづいて、負極リードの一端を電極群の負極に接続した。負極リードの他端は、負極端子を兼ねる有底円筒状容器に接続した。ひきつづき、中央に正極端子が嵌着された絶縁封口板を用意した。正極リードの一端を正極端子に、その他端を電極群の正極に接続した後、絶縁封口板を容器の上部開口部にかしめ加工することにより円筒形非水電解質二次電池を組み立てた。
得られた二次電池を、０．２Ｃレート、２５℃環境下にて、４．２Ｖで充電し、その後、２Ｖに達するまで０．２Ｃレートで放電した。その後２５℃環境下、４．２Ｖにて充放電を１回繰り返し、容量確認を実施した。
<Preparation of nonaqueous electrolyte secondary battery>
The electrode group and the non-aqueous electrolyte were respectively stored in a bottomed cylindrical container made of stainless steel having a diameter of 1.8 mm and a height of 650 mm. Subsequently, one end of the negative electrode lead was connected to the negative electrode of the electrode group. The other end of the negative electrode lead was connected to a bottomed cylindrical container that also served as a negative electrode terminal. Subsequently, an insulating sealing plate having a positive terminal fitted in the center was prepared. After connecting one end of the positive electrode lead to the positive electrode terminal and the other end to the positive electrode of the electrode group, a cylindrical nonaqueous electrolyte secondary battery was assembled by caulking the insulating sealing plate to the upper opening of the container.
The obtained secondary battery was charged at 4.2 V in a 0.2 C rate and 25 ° C. environment, and then discharged at a 0.2 C rate until 2 V was reached. Thereafter, charging and discharging were repeated once at 4.2 V in a 25 ° C. environment, and the capacity was confirmed.
＜各種値の測定＞
実施例１と同じ条件で作製した非水電解質二次電池を０．２Ｃレートで４．２Ｖと２Ｖに調整したものを、それぞれ露点−５０℃のアルゴン雰囲気内にて解体した。負極の活物質層よりそれぞれ数ｍｇほどかき出して、溶媒にヘキサンを用い、ピクノメータを用いて２５℃における密度測定を実施した。それぞれの密度を算出した後、密度比率（４．２Ｖ時の密度）／（２Ｖ時の密度）を算出したところ、０．５８であった。２Ｖに調製した負極電極を露点―２０℃のドライルーム環境下に持ち出し、活物質層の剥離強度は、サイカスを用いて測定した。その結果２．８Ｎ／ｃｍであった。最後に電極層の引っ張り強度は、引張圧縮試験機を用いて測定を実施した。電極層が切断した荷重から引っ張り強度を算出した結果、引っ張り強度は８６５Ｎ／ｍｍ２であった。一覧を表１にまとめた。
<Measurement of various values>
A non-aqueous electrolyte secondary battery prepared under the same conditions as in Example 1 and adjusted to 4.2 V and 2 V at a 0.2 C rate was disassembled in an argon atmosphere with a dew point of −50 ° C., respectively. About several mg each was scraped from the active material layer of the negative electrode, hexane was used as a solvent, and density measurement was performed at 25 ° C. using a pycnometer. After calculating the respective densities, the density ratio (density at 4.2 V) / (density at 2 V) was calculated to be 0.58. The negative electrode prepared at 2 V was taken out in a dry room environment having a dew point of −20 ° C., and the peel strength of the active material layer was measured using CYCUS. As a result, it was 2.8 N / cm. Finally, the tensile strength of the electrode layer was measured using a tensile / compression tester. As a result of calculating the tensile strength from the load cut by the electrode layer, the tensile strength was 865 N / mm 2 . The list is summarized in Table 1.
（実施例２〜８、比較例１〜２）
負極電極が表１の構成になるように、適宜構成部材、熱処理温度を変更した。また、正極の塗布量を負極活物質あたりの容量、負極塗布量にあわせて調整し、おおよそ１５０ｇ／ｍ２から３００ｇ／ｍ２になるようにする以外は、実施例１と同じ構成にて非水電解質二次電池を作製した。
(Examples 2-8, Comparative Examples 1-2)
The constituent members and the heat treatment temperature were appropriately changed so that the negative electrode had the configuration shown in Table 1. Further, the non-reactive structure is the same as that of Example 1 except that the coating amount of the positive electrode is adjusted in accordance with the capacity per negative electrode active material and the coating amount of the negative electrode so as to be approximately 150 g / m 2 to 300 g / m 2. A water electrolyte secondary battery was produced.
実施例１〜８および、比較例１〜２の電池について、容量確認を実施した後、１Ｃレートにて４．２Ｖ〜２．０Ｖの範囲にてサイクル試験を１０回実施した後、電池を４．２Ｖに調整した。そのまま１週間２５℃環境下で貯蔵し、初回の容量との比較を実施した。その結果を表２に示す。 For the batteries of Examples 1 to 8 and Comparative Examples 1 and 2, the capacity was confirmed, and then the cycle test was performed 10 times in the range of 4.2 V to 2.0 V at the 1C rate, and then the batteries were Adjusted to 2V. The product was stored as it was at 25 ° C. for one week, and compared with the initial capacity. The results are shown in Table 2.
以上の結果より、実施例１〜８に比べて、比較例１〜２の非水電解質二次電池は容量維持率が小さく、つまり自己放電が大きかった。これらの電池について解体して負極の観察をしたところ、負極電極層に大きなシワが生じていたり、活物質層の剥がれが顕著であったり、集電体に小さな穴が開いているものが確認できた。（表２）
以上のように、本発明の条件では、高容量を維持しつつ、かつ体積膨張による集電体の変形を大幅に抑制することが可能である。
From the above result, compared with Examples 1-8, the non-aqueous electrolyte secondary batteries of Comparative Examples 1-2 had a smaller capacity maintenance rate, that is, a larger self-discharge. When these batteries were disassembled and the negative electrode was observed, it was confirmed that there were large wrinkles in the negative electrode layer, significant peeling of the active material layer, and small holes in the current collector. It was. (Table 2)
As described above, under the conditions of the present invention, it is possible to significantly suppress deformation of the current collector due to volume expansion while maintaining a high capacity.
１０１…電極群、１０２…外装材、１０３…負極、１０４…セパレータ、１０５…正極、１０６…負極端子、１０７…正極端子、２００…電池パック、２０１…単電池、２０２…負極端子、２０３…正極端子、２０４…粘着テープ、２０５…組電池、２０６…プリント配線基板、２０７…サーミスタ、２０８…保護回路、２０９…通電用端子、２１０…、極側リード、２１１…正極側コネクタ、２１２…負極側リード、２１３…負極側コネクタ、２１４、２１５…配線、２１６ａ…プラス側配線、２１６ｂ…マイナス側配線、２１７…配線、２１８…保護シート、２１９…収納容器、２２０…蓋 DESCRIPTION OF SYMBOLS 101 ... Electrode group, 102 ... Exterior material, 103 ... Negative electrode, 104 ... Separator, 105 ... Positive electrode, 106 ... Negative electrode terminal, 107 ... Positive electrode terminal, 200 ... Battery pack, 201 ... Single cell, 202 ... Negative electrode terminal, 203 ... Positive electrode Terminals 204, adhesive tape, 205, assembled battery, 206, printed wiring board, 207, thermistor, 208, protection circuit, 209, current-carrying terminals, 210, pole lead, 211, positive connector, 212, negative pole Lead, 213 ... Negative electrode side connector, 214, 215 ... Wiring, 216a ... Positive side wiring, 216b ... Minus side wiring, 217 ... Wiring, 218 ... Protection sheet, 219 ... Storage container, 220 ... Lid
Claims (10)
前記負極の引っ張り強さが４００Ｎ／ｍｍ２以上１２００Ｎ／ｍｍ２以下で、
前記負極集電体と前記負極活物質層との剥離強度が１．５Ｎ／ｃｍ以上４Ｎ／ｃｍ以下であり、
前記負極活物質層は、シリコン、シリコン含有酸化物、スズおよびスズ含有酸化物からなる群より選ばれる１種類以上を含む負極。 A negative electrode current collector and a negative electrode having a negative electrode active material layer on the negative electrode current collector,
Wherein the negative electrode of the tensile strength is 400 N / mm 2 or more 1200 N / mm 2 or less,
The peel strength between the negative electrode current collector and the negative electrode active material layer is 1.5 N / cm or more and 4 N / cm or less,
The negative electrode active material layer is a negative electrode including at least one selected from the group consisting of silicon, silicon-containing oxides, tin, and tin-containing oxides.
The battery pack according to claim 8 or 9, comprising a plurality of the nonaqueous secondary batteries, wherein the nonaqueous electrolyte secondary batteries are electrically connected in series, parallel, or a combination of series and parallel.
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