JP4379267B2 - Negative electrode member of lithium secondary battery provided with organic electrolyte and lithium secondary battery provided with organic electrolyte - Google Patents

Negative electrode member of lithium secondary battery provided with organic electrolyte and lithium secondary battery provided with organic electrolyte Download PDF

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JP4379267B2
JP4379267B2 JP2004258461A JP2004258461A JP4379267B2 JP 4379267 B2 JP4379267 B2 JP 4379267B2 JP 2004258461 A JP2004258461 A JP 2004258461A JP 2004258461 A JP2004258461 A JP 2004258461A JP 4379267 B2 JP4379267 B2 JP 4379267B2
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lithium secondary
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進啓 太田
伸之 奥田
宏行 植木
寛彦 井原
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Sumitomo Electric Industries Ltd
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この発明は、高安全性かつ高容量でサイクル特性に優れたリチウム二次電池の負極部材およびそれを用いたリチウム二次電池に関するものである。   The present invention relates to a negative electrode member of a lithium secondary battery having high safety, high capacity, and excellent cycle characteristics, and a lithium secondary battery using the same.

リチウムイオン二次電池の体積及び重量容量密度を向上させることを目的として、従来のグラファイト内へのリチウムイオンのインターカレーションを利用する方法ではなく、リチウム金属の状態で負極電極に蓄積する方法が検討されているが、この方法は、リチウム金属と有機電解液が反応し、充放電時にリチウムが樹枝状晶となって析出するデンドライト成長が起こり、そのために負極の利用効率が低下してサイクル寿命が短くなるほか、正極との内部短絡を引き起こし、最終的には爆発に至る危険性がある。   For the purpose of improving the volume and weight capacity density of a lithium ion secondary battery, a method of accumulating in a negative electrode in the state of lithium metal is used instead of a conventional method using intercalation of lithium ions into graphite. Although this method has been studied, this method involves dendritic growth in which lithium metal reacts with the organic electrolyte, and lithium is deposited in the form of dendritic crystals during charge and discharge. In addition to shortening, there is a risk of internal explosion with the positive electrode and eventually explosion.

このデンドライト成長を抑えるための手法として、リチウム金属の表面にポリマー膜やフッ化物膜、炭酸化合物膜、酸化物膜、酸窒化物膜、硫化物膜等の固体電解質膜を形成することが従来検討されており、下記特許文献１〜４にこれらの膜が開示されている。   As a method for suppressing this dendrite growth, it has been studied in the past to form a solid electrolyte film such as a polymer film, a fluoride film, a carbonate compound film, an oxide film, an oxynitride film, or a sulfide film on the surface of lithium metal These films are disclosed in Patent Documents 1 to 4 below.

リチウム金属層は、単位体積および重量当たりの電池容量を上げる目的から、その厚みを２０μｍ以下、好ましくは５μｍ程度に抑える必要があるが、この厚み領域になるとリチウムの自立箔では機械的強度が弱すぎて使用できず、従って、強度のある銅箔等の集電体を基材にしてその上にリチウム箔を貼り合わせること、あるいは蒸着法等の気相堆積法で基材上にリチウム金属層を形成することが必要になる。   For the purpose of increasing the battery capacity per unit volume and weight, the lithium metal layer needs to have a thickness of 20 μm or less, preferably about 5 μm. However, in this thickness region, the lithium self-supporting foil has low mechanical strength. Therefore, the lithium metal layer is deposited on the base material by vapor deposition such as vapor deposition method such as using a strong current collector such as copper foil as a base material and bonding the lithium foil on the base material. It is necessary to form.

従来、リチウムイオン二次電池の負極の基材には、銅箔等の電気伝導体が使用されている。   Conventionally, an electrical conductor such as a copper foil has been used for a base material of a negative electrode of a lithium ion secondary battery.

一方、リチウム金属上に固体電解質膜を形成してデンドライト成長を抑制する手法においては、負極の作製過程やハンドリング工程などにおいて加水分解性の強いリチウム金属層および硫化物系固体電解質の部分的劣化が起こる可能性があり、固体電解質膜による被覆効果が発揮されなくなることが想定される。そのような事態が起こると、劣化部において固体電解質膜を破壊してデンドライト成長が起こり、サイクル寿命の低下を招く。また、基材に電気伝導性の材質を使用している場合には負極に電子が供給され続けるため、その部分で充放電が集中する可能性が高くなる。さらには、デンドライト成長の進行により正極との内部短絡を引き起し、最終的には爆発に至る危険性を有している。
ＵＳ５，３１４，７６５（ｃｌａｉｍ１参照） ＵＳ６，０２５，０９４（ｃｌａｉｍ１および４参照） 特開２０００−３４０２５７（請求項６および７参照） 特開２００２−３２９５２４（請求項１および９参照） On the other hand, in the method of suppressing dendrite growth by forming a solid electrolyte film on lithium metal, the lithium metal layer and sulfide-based solid electrolyte, which are highly hydrolyzable, are partially degraded in the negative electrode fabrication process and handling process. It may occur, and it is assumed that the coating effect by the solid electrolyte membrane is not exhibited. When such a situation occurs, the solid electrolyte membrane is destroyed in the deteriorated portion to cause dendrite growth, leading to a reduction in cycle life. In addition, when an electrically conductive material is used for the base material, electrons continue to be supplied to the negative electrode, so that there is a high possibility that charge and discharge concentrate at that portion. Furthermore, there is a risk of causing an internal short circuit with the positive electrode due to the progress of dendrite growth, and finally an explosion.
US 5,314,765 (see claim 1) US 6,025,094 (see claim 1 and 4) JP 2000-340257 (see claims 6 and 7) JP 2002-329524 A (refer to claims 1 and 9)

この発明は、かかる不具合を解消してリチウム二次電池用負極部材のサイクル特性と安全性を高めることを課題としている。   This invention makes it a subject to eliminate such a malfunction and to improve the cycling characteristics and safety | security of the negative electrode member for lithium secondary batteries.

発明者等は、基材として電気的絶縁体を使用することにより、基材上にリチウム金属膜と固体電解質膜を形成したリチウム二次電池負極部材におけるデンドライトの集中的成長の技術的課題が解決されることを見いだした。特に、基材として有機高分子材料を使用することによりデンドライト成長の抑制効果を高めることができる。   The inventors solved the technical problem of dendrite intensive growth in the negative electrode member of a lithium secondary battery in which a lithium metal film and a solid electrolyte film were formed on the base material by using an electrical insulator as the base material. I found out that In particular, the use of an organic polymer material as the substrate can enhance the effect of suppressing dendrite growth.

また、金属基材上に電気的絶縁体層を設けてこれを基材とする構造でも同一課題を解決することができる。この発明は、かかる構造の有機電解液を備えたリチウム二次電池の負極部材を提供するものである。金属基材は、銅、鉄、ステンレス、ニッケル、アルミニウムの何れであってもよい。また、電気的絶縁体層は有機高分子材料をコーティングして形成されるものでよく、この場合、基材のベースとなる部分が金属箔であるので負極の機械的強度も十分に確保することができる。 Further, the same problem can be solved even with a structure in which an electrical insulator layer is provided on a metal substrate and this is used as a substrate. This invention provides the negative electrode member of the lithium secondary battery provided with the organic electrolyte solution of such a structure. The metal substrate may be any of copper, iron, stainless steel, nickel, and aluminum. In addition, the electrical insulator layer may be formed by coating an organic polymer material. In this case, since the base portion of the base material is a metal foil, the mechanical strength of the negative electrode must be sufficiently ensured. Can do.

有機高分子材料としては、ポリエチレン、ポリプロピレン等のポリビニールが通常使用されるが、ポリイミド、ポリアミド、ポリエステル、ポリエーテル、ポリウレタン、またはポリカーボネートでもよく、これ等を使用しても発明の目的を達成することができる。   Polyvinyl such as polyethylene and polypropylene is usually used as the organic polymer material, but polyimide, polyamide, polyester, polyether, polyurethane, or polycarbonate may be used, and even if these are used, the object of the invention is achieved. be able to.

この発明の負極部材は、これらの絶縁性基材上に形成したリチウム金属層を負極活物質として働かせ、同時に集電体としても機能させる。   In the negative electrode member of the present invention, the lithium metal layer formed on these insulating base materials functions as a negative electrode active material, and at the same time functions as a current collector.

これにより、不測の事態が生じて固体電解質膜の性能が低下し、局所的なデンドライト成長が発生しても、その部分のリチウム金属が消耗すれば自動的に電子の供給が停止し、その部位で集中的な充放電が繰り返される危険性がなくなる。この発明においては、かかる負極部材を使用したリチウム二次電池も併せて提供する。 As a result, even if an unforeseen situation occurs and the performance of the solid electrolyte membrane deteriorates and local dendrite growth occurs, the supply of electrons automatically stops when the lithium metal in the portion is consumed, This eliminates the risk of repeated intensive charge / discharge. In the present invention, a lithium secondary battery using such a negative electrode member is also provided.

この発明によれば、負極部材の基材を、金属基材上に電気的絶縁体層を設けた部材で形成し、その上にリチウム金属膜と固体電解質膜を設けるので、リチウム金属と有機電解液が反応して起こるデンドライト成長が抑制され、また、局所的なデンドライト成長が仮に生じてもその部位のリチウム金属の消耗により電子の供給が自動的にストップし、これにより、デンドライト成長に起因した短絡が無くなり、エネルギー密度が高くて充放電サイクル特性に優れた安定性、安全性の高いリチウム二次電池が得られる。 According to this invention, the base material of the negative electrode member is formed by a member provided with an electrical insulator layer on a metal base material, and the lithium metal film and the solid electrolyte film are provided thereon. Dendrite growth caused by the reaction of the liquid is suppressed, and even if local dendrite growth occurs, the supply of electrons automatically stops due to the consumption of lithium metal at the site, and this is caused by dendrite growth. A short-circuit is eliminated, and a lithium secondary battery having high stability and safety with high energy density and excellent charge / discharge cycle characteristics is obtained.

〔実施例１〕
図１に示すように、厚さ１０μｍ、直径３０ｍｍの銅箔６を基材にしてその銅箔６の上面に、上面の周辺部０．５ｍｍ幅の部分を残してポリプロピレン膜７をキャスティング法で１μｍ厚にマスク形成した。 [Example 1]
As shown in FIG. 1, using a copper foil 6 having a thickness of 10 μm and a diameter of 30 mm as a base material, a polypropylene film 7 is cast on the upper surface of the copper foil 6 by leaving a peripheral portion of 0.5 mm width on the upper surface by a casting method. A mask was formed to a thickness of 1 μm.

引き続き、上面全面に蒸着法によりリチウム金属膜３を形成した。このリチウム金属膜３の膜厚は５μｍであった。膜厚の測定は触針式段差計を用いて行った。さらに、リチウム金属膜３上に、リチウム（Ｌｉ）−リン（Ｐ）−イオウ（Ｓ）組成の固体電解質膜４を蒸着法により０．２μｍ厚に形成して負極部材５Ａとした。なお、固体電解質膜４は分析の結果、Ｌｉ３４原子％、Ｐ１４原子％、Ｓ５２原子％組成の非晶質体であった。   Subsequently, a lithium metal film 3 was formed on the entire upper surface by vapor deposition. The thickness of this lithium metal film 3 was 5 μm. The film thickness was measured using a stylus step meter. Furthermore, a solid electrolyte film 4 having a lithium (Li) -phosphorus (P) -sulfur (S) composition was formed on the lithium metal film 3 to a thickness of 0.2 μm by a vapor deposition method to obtain a negative electrode member 5A. As a result of analysis, the solid electrolyte membrane 4 was an amorphous body having a composition of Li 34 atomic%, P 14 atomic%, and S 52 atomic%.

正極は、活物質となるＬｉＣｏＯ2粒子、電子伝導性を付与する炭素粒子、及びポリフッ化ビニリデンを有機溶媒と共に混合し、アルミニウム箔上に塗布して作製した。活物質層は、厚みが１００μｍ、容量密度が３ｍＡｈ（ミリアンペア・時）／ｃｍ2、総容量２１ｍＡｈであった。また、正極の直径は３０ｍｍであった。 The positive electrode was prepared by mixing LiCoO 2 particles serving as an active material, carbon particles imparting electron conductivity, and polyvinylidene fluoride together with an organic solvent, and applying the mixture onto an aluminum foil. The active material layer had a thickness of 100 μm, a capacity density of 3 mAh (milliampere · hour) / cm 2 , and a total capacity of 21 mAh. The positive electrode had a diameter of 30 mm.

露点−８０℃以下のアルゴンガス雰囲気下で、前述の負極部材５Ａ、セパレータ（多孔質ポリマーフィルム）、及び正極部材をコイン型セル内に設置し、さらにエチレンカーボネートとプロピレンカーボネートの混合液に電解塩として１モル％のＬｉＰＦ６を溶解させた有機電解液を滴下してリチウム二次電池を１００個作製した。 In an argon gas atmosphere with a dew point of −80 ° C. or lower, the negative electrode member 5A, the separator (porous polymer film), and the positive electrode member are placed in a coin-type cell, and an electrolytic salt is added to a mixed solution of ethylene carbonate and propylene carbonate. As an example, 100 lithium secondary batteries were prepared by dropping an organic electrolyte solution in which 1 mol% of LiPF 6 was dissolved.

その後、この試作品について充放電のサイクル試験を行った。サイクル試験の条件は１０ｍＡ定電流、充電４．２Ｖ、放電３．０Ｖとした。その結果を表１に試料No.１として示す。   After that, a charge / discharge cycle test was performed on this prototype. The conditions for the cycle test were a 10 mA constant current, a charge of 4.2 V, and a discharge of 3.0 V. The results are shown in Table 1 as Sample No. 1.

Figure 0004379267
Figure 0004379267

この結果から判るように、試料No.１は５００サイクル後も１００個すべてが内部短絡を起こしていない。また、容量の低下も見られず、良品の歩留りは１００％であった。   As can be seen from this result, 100 samples No. 1 did not cause an internal short circuit even after 500 cycles. Further, no decrease in capacity was observed, and the yield of non-defective products was 100%.

充放電サイクル試験後、コインセルを分解して負極を取り出し、その負極について走査型電子顕微鏡（ＳＥＭ）による観察とエネルギー分散Ｘ線分析（ＥＤＸ）を行った。
その結果、９５個のリチウム二次電池負極についてはリチウム金属のデンドライト成長は見られず、負極面に固体電解質膜が保持されていることが確認された。 After the charge / discharge cycle test, the coin cell was disassembled, the negative electrode was taken out, and the negative electrode was observed with a scanning electron microscope (SEM) and subjected to energy dispersive X-ray analysis (EDX).
As a result, no dendritic growth of lithium metal was observed for 95 lithium secondary battery negative electrodes, and it was confirmed that the solid electrolyte membrane was held on the negative electrode surface.

また、残りの５個の電池負極については、固体電解質膜が部分的に破壊され、局所的にデンドライト成長が起きていることが観察されたが、初期段階でそのデンドライト成長が停止して発生部位は負極の表面近傍に限られていた。   Further, with respect to the remaining five battery negative electrodes, it was observed that the solid electrolyte membrane was partially destroyed and dendrite growth occurred locally. Was limited to the vicinity of the surface of the negative electrode.

〔比較例１〕
比較試験として、基材として圧延銅箔を用い、その上にリチウム金属膜と固体電解質膜を形成した部材を負極とするリチウム二次電池を１００個作製し、実施例１と同じ条件で充放電のサイクル試験を行った。 [Comparative Example 1]
As a comparative test, 100 lithium secondary batteries using a rolled copper foil as a base material and a member having a lithium metal film and a solid electrolyte film formed thereon as a negative electrode were produced and charged and discharged under the same conditions as in Example 1. The cycle test was conducted.

その結果、９７個の電池がほぼ３００〜５００サイクルにて電圧上昇によりサイクルが停止した。また、残り３個については、１００サイクル程度で短絡が生じた。   As a result, 97 batteries stopped at approximately 300 to 500 cycles due to voltage increase. Moreover, about the remaining three, the short circuit occurred in about 100 cycles.

また、充放電サイクル試験後、コインセルを分解して負極を取り出し、その負極について走査型電子顕微鏡（ＳＥＭ）による観察とエネルギー分散Ｘ線分析（ＥＤＸ）を行ったところ、３００サイクル以上の寿命を示した電池の負極についてはリチウム金属のデンドライト成長は見られず、負極面に固体電解質膜が保持されていることが確認されたが、短絡を生じた負極については局所的デンドライト成長が起こり、その成長が正極まで至っていることが確認された。   After the charge / discharge cycle test, the coin cell was disassembled and the negative electrode was taken out. The negative electrode was observed with a scanning electron microscope (SEM) and subjected to energy dispersive X-ray analysis (EDX). It was confirmed that no lithium metal dendrite growth was observed for the negative electrode of the battery, and that the solid electrolyte membrane was retained on the negative electrode surface. Was confirmed to reach the positive electrode.

この発明の負極部材の一例を示す断面図Sectional drawing which shows an example of the negative electrode member of this invention

符号の説明Explanation of symbols

３ リチウム金属膜
４ 固体電解質膜
５Ａ 負極部材
６ 銅箔
７ ポリプロピレン膜 3 Lithium metal film 4 Solid electrolyte film 5A Negative electrode member 6 Copper foil 7 Polypropylene film

Claims (4)

金属基材上にリチウム金属膜を形成し、さらにその上に無機固体電解質膜を形成した有機電解液を備えたリチウム二次電池の負極部材において、前記金属基材とリチウム金属膜の界面に電気的絶縁体層を設け、前記金属基材の周辺部でこの金属基材と前記リチウム金属膜を電気的に接続したことを特徴とする有機電解液を備えたリチウム二次電池の負極部材。 In a negative electrode member of a lithium secondary battery comprising an organic electrolytic solution in which a lithium metal film is formed on a metal base material and an inorganic solid electrolyte film is further formed on the metal base material, an electric current is connected to the interface between the metal base material and the lithium metal film. A negative electrode member for a lithium secondary battery comprising an organic electrolytic solution , wherein an electrical insulator layer is provided, and the metal substrate and the lithium metal film are electrically connected at a peripheral portion of the metal substrate. 電気的絶縁体が有機高分子物質であることを特徴とする請求項１に記載の有機電解液を備えたリチウム二次電池の負極部材。 The negative electrode member of a lithium secondary battery provided with the organic electrolyte according to claim 1 , wherein the electrical insulator is an organic polymer substance. 有機高分子物質が、ポリエチレン、ポリプロピレン、ポリイミド、ポリアミド、ポリエステル、ポリエーテル、ポリウレタン、ポリカーボネートの中のいずれかであることを特徴とする請求項２に記載の有機電解液を備えたリチウム二次電池の負極部材。 3. The lithium secondary battery with an organic electrolyte according to claim 2 , wherein the organic polymer substance is one of polyethylene, polypropylene, polyimide, polyamide, polyester, polyether, polyurethane, and polycarbonate. the negative electrode member. 請求項１に記載の負極部材を用いて構成される有機電解液を備えたリチウム二次電池。 Lithium secondary battery including an organic electrolyte solution constituted by using a negative electrode member according to claim 1.
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CN115832323A (en) * 2021-11-18 2023-03-21 宁德时代新能源科技股份有限公司 Metallic lithium negative electrode, secondary battery, battery module, battery pack, and electric device

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