JP2017084500A - All-solid battery system - Google Patents
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Abstract
Description
本発明は、容量維持率を維持しつつ、全固体電池の充電時における負極活物質層の発熱を抑制した全固体電池システムに関する。 The present invention relates to an all solid state battery system that suppresses heat generation of a negative electrode active material layer during charging of an all solid state battery while maintaining a capacity retention rate.
現在、種々の電池の中でも、エネルギー密度が高いという観点から、リチウムイオン電池が注目を浴びている。その中でも、電解液を固体電解質に置換した全固体電池が特に注目を浴びている。これは、全固体電池が電解液を用いる二次電池と異なり、電解液を用いないことから、過充電に起因する電解液の分解等を生じることがないこと、並びに高いサイクル特性及びエネルギー密度を有していることを理由とする。 Currently, among various batteries, lithium ion batteries are attracting attention from the viewpoint of high energy density. Among them, all-solid-state batteries in which the electrolytic solution is replaced with a solid electrolyte are particularly attracting attention. This is because, unlike a secondary battery using an electrolyte solution, an all-solid battery does not use an electrolyte solution, it does not cause decomposition of the electrolyte solution due to overcharge, and has high cycle characteristics and energy density. It is because of having it.
リチウムイオン電池に一般的に使用される負極活物質としては、グラファイト、ソフトカーボン、又はハードカーボンのような炭素系負極活物質が挙げられる。近年では、炭素系負極活物質に替えて、より容量の大きい合金系負極活物質が研究されている。その中でも、特に容量が大きいことからケイ素が特に注目されている。 Examples of the negative electrode active material generally used for lithium ion batteries include carbon-based negative electrode active materials such as graphite, soft carbon, and hard carbon. In recent years, instead of a carbon-based negative electrode active material, an alloy-based negative electrode active material having a larger capacity has been studied. Among them, silicon is particularly attracting attention because of its particularly large capacity.
全固体電池を充放電した場合に、全固体電池が発熱することが知られている。そのため、全固体電池の充電時に、電池の発熱を抑制する方法が求められている。 It is known that an all solid state battery generates heat when the all solid state battery is charged and discharged. Therefore, there is a need for a method for suppressing battery heat generation when charging an all-solid battery.
また、ケイ素粒子を負極活物質として用いた電池は、炭素系負極活物質等を負極活物質として用いた電池と比較して、容量維持率が低いことが知られている。この原因としては、充放電に伴いケイ素粒子が膨張・収縮することで、ケイ素粒子が粉砕され、また、ケイ素粒子と他の負極活物質層材料との間に空隙が生じることによって、全固体電池の内部の抵抗が増大することが挙げられる。そのため、ケイ素粒子の充電量を制御することにより、容量維持率の低下を防止する技術が研究されている。 Further, it is known that a battery using silicon particles as a negative electrode active material has a lower capacity retention rate than a battery using a carbon-based negative electrode active material or the like as a negative electrode active material. The cause of this is that the silicon particles expand and contract with charge / discharge, so that the silicon particles are pulverized, and voids are generated between the silicon particles and the other negative electrode active material layer material. It is mentioned that the internal resistance increases. Therefore, a technique for preventing a decrease in capacity retention rate by controlling the charge amount of silicon particles has been studied.
例えば、特許文献１では、ケイ素粒子を負極活物質とする焼結体を負極活物質層として用いた非水系リチウムイオン電池において、充放電に伴うケイ素粒子の膨張収縮に起因して生じる容量維持率の低下を防止するために、満充電時のケイ素１ｇあたりの充電量を２００〜８００ｍＡｈとする技術を開示している。
For example, in
また、特許文献２では、表面を炭素層で被覆したケイ素粒子からなる負極活物質層材料を用いたリチウムイオン電池において、容量維持率の低下を防止するために、ケイ素粒子の充電量を、１５００ｍＡｈ／ｇ以下とする技術を公開している。
Further, in
特許文献１及び２の技術では、リチウムイオン電池の容量維持率の低下を抑制するために、ケイ素の充電量を少なくしている。ケイ素粒子の充電量を少なくした場合、電池の充電量を一定の値にするために、より多くのケイ素粒子を必要とする。そのため、負極活物質層の重量が増加する。
In the techniques of
本発明者は、全固体電池の充放電において、ケイ素粒子１ｍｇあたりの充電量が０．４７ｍＡｈ以上である場合、負極活物質層材料１ｍｇあたりの発熱量が一定となることを見出した。 The present inventor has found that, in charge / discharge of an all-solid battery, when the charge amount per 1 mg of silicon particles is 0.47 mAh or more, the calorific value per 1 mg of the negative electrode active material layer material becomes constant.
したがって、本発明は、負極活物質としてケイ素粒子を用いた全固体電池の充電時の発熱量を抑えつつ、容量維持率の低下を抑制した全固体電池システムを提供することを目的とする。 Therefore, an object of the present invention is to provide an all solid state battery system that suppresses a decrease in capacity retention rate while suppressing a calorific value during charging of an all solid state battery using silicon particles as a negative electrode active material.
本発明の全固体電池システムは、正極活物質層、固体電解質層、及び負極活物質層をこの順で有する全固体電池、並びに全固体電池の充電量を制御する制御装置を有する全固体電池システムであって、負極活物質層が、固体電解質、及び負極活物質としてのケイ素粒子を有し、かつ制御装置が、ケイ素粒子の最大充電量が１．１ｍＡｈ／ｍｇ以上１．５ｍＡｈ／ｍｇ以下であるようにして、全固体電池の充電量を制御する。 An all solid state battery system of the present invention includes an all solid state battery having a positive electrode active material layer, a solid electrolyte layer, and a negative electrode active material layer in this order, and an all solid state battery system having a control device for controlling the charge amount of the all solid state battery. The negative electrode active material layer has a solid electrolyte and silicon particles as the negative electrode active material, and the controller has a maximum charge amount of the silicon particles of 1.1 mAh / mg or more and 1.5 mAh / mg or less. In a manner, the charge amount of the all solid state battery is controlled.
本発明によれば、負極活物質としてケイ素粒子を用いた全固体電池の充電時の発熱量を抑えつつ、容量維持率の低下を抑制した全固体電池システムを提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the all-solid-state battery system which suppressed the fall of the capacity | capacitance maintenance factor can be provided, suppressing the emitted-heat amount at the time of charge of the all-solid-state battery using the silicon particle as a negative electrode active material.
以下、本発明の実施の形態について詳述する。なお、本発明は、以下の実施の形態に限定されるのではなく、発明の本旨の範囲内で種々変形して実施できる。 Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the invention.
本発明の全固体電池システムは、正極活物質層、固体電解質層、及び負極活物質層をこの順で有する全固体電池、並びに全固体電池の充電量を制御する制御装置を有する全固体電池システムであって、負極活物質層が、固体電解質、及び負極活物質としてのケイ素粒子を有し、かつ制御装置が、ケイ素粒子の最大充電量が１．１ｍＡｈ／ｍｇ以上１．５ｍＡｈ／ｍｇ以下であるようにして、全固体電池の充電量を制御する。 An all solid state battery system of the present invention includes an all solid state battery having a positive electrode active material layer, a solid electrolyte layer, and a negative electrode active material layer in this order, and an all solid state battery system having a control device for controlling the charge amount of the all solid state battery. The negative electrode active material layer has a solid electrolyte and silicon particles as the negative electrode active material, and the controller has a maximum charge amount of the silicon particles of 1.1 mAh / mg or more and 1.5 mAh / mg or less. In a manner, the charge amount of the all solid state battery is controlled.
図１は、本発明の全固体電池システムの一例の略図である。本発明の全固体電池値システムは、全固体電池（６）及び全固体電池（６）を制御する制御装置（１００）を有する。全固体電池は、正極集電体（１）、正極活物質層（２）、固体電解質層（３）、負極活物質層（４）、及び負極集電体（５）を有している。なお、図１は本発明の全固体電池システムの構成を限定するものではない。 FIG. 1 is a schematic diagram of an example of an all solid state battery system of the present invention. The all solid state battery value system of the present invention has an all solid state battery (6) and a control device (100) for controlling the all solid state battery (6). The all solid state battery includes a positive electrode current collector (1), a positive electrode active material layer (2), a solid electrolyte layer (3), a negative electrode active material layer (4), and a negative electrode current collector (5). In addition, FIG. 1 does not limit the structure of the all-solid-state battery system of this invention.
原理によって限定されるものではないが、本発明の作用原理は以下のとおりであると考える。 Although not limited by the principle, it is considered that the operation principle of the present invention is as follows.
負極活物質としてケイ素粒子を有する全固体電池を充電すると、全固体電池の負極活物質層が発熱する。この発熱は、ケイ素粒子１ｍｇあたりの充電量が大きいほど大きくなる。しかし、ケイ素粒子１ｍｇあたりの充電量を０．４７ｍＡｈ以上にした場合、負極活物質層材料１ｍｇあたりの発熱量は一定となる（図２参照）。 When an all solid state battery having silicon particles as a negative electrode active material is charged, the negative electrode active material layer of the all solid state battery generates heat. This heat generation increases as the charge amount per 1 mg of silicon particles increases. However, when the charge amount per 1 mg of silicon particles is 0.47 mAh or more, the calorific value per 1 mg of the negative electrode active material layer material is constant (see FIG. 2).
負極活物質層の重さは、負極活物質の総量に比例する。そのため、一定の充電量までを充電する場合、ケイ素粒子１ｍｇあたりの充電量が大きいほど必要なケイ素粒子の総量が減少するため、必要となる負極活物質層の重さはケイ素粒子１ｍｇあたりの充電量に反比例して減少する（図３参照）。 The weight of the negative electrode active material layer is proportional to the total amount of the negative electrode active material. Therefore, when charging up to a certain charge amount, the larger the charge amount per 1 mg of silicon particles, the smaller the total amount of necessary silicon particles, so the required weight of the negative electrode active material layer is the charge per 1 mg of silicon particles. It decreases in inverse proportion to the amount (see FIG. 3).
よって、一定の充電量まで充電する場合、ケイ素粒子１ｍｇあたりの充電量が０．４７ｍＡｈ以上であれば、ケイ素粒子１ｍｇあたりの充電量の大きさと、負極活物質層の発熱量の大きさは、反比例の関係にあるといえる。したがって、この範囲では、ケイ素粒子１ｍｇあたりの充電量を大きくし、例えば１．１ｍＡｈ／ｍｇ以上にすれば、負極活物質層の発熱量を減少できる（図４参照）。 Therefore, when charging to a certain charge amount, if the charge amount per 1 mg of silicon particles is 0.47 mAh or more, the magnitude of the charge amount per 1 mg of silicon particles and the magnitude of the calorific value of the negative electrode active material layer are: It can be said that the relationship is inversely proportional. Therefore, in this range, if the charge amount per 1 mg of silicon particles is increased, for example, 1.1 mAh / mg or more, the calorific value of the negative electrode active material layer can be reduced (see FIG. 4).
もっとも、ケイ素粒子１ｍｇあたりの充電量を大きくすると、ケイ素粒子の充放電における膨張収縮率が大きくなり、充放電においてケイ素粒子が粉砕されやすくなる。そのため、ケイ素粒子１ｍｇの充電量が大きくなると、容量維持率が低下する（図５参照）。したがって、ケイ素粒子１ｍｇあたりの充電量を小さく、例えば１．５ｍＡｈ／ｍｇ以下にすれば、容量維持率の低下を抑制することができる。 However, when the charge amount per 1 mg of silicon particles is increased, the expansion / contraction rate in charging / discharging of the silicon particles is increased, and the silicon particles are easily pulverized in charging / discharging. Therefore, when the charge amount of 1 mg of silicon particles increases, the capacity retention rate decreases (see FIG. 5). Therefore, if the charge amount per 1 mg of silicon particles is small, for example, 1.5 mAh / mg or less, it is possible to suppress a decrease in capacity maintenance rate.
本発明では、ケイ素粒子１ｍｇあたりの充電量を調節して、負極活物質層の充放電時の発熱を抑えつつ、容量維持率の低下を抑えた。なお、本発明の全固体電池システムにおける、ケイ素粒子の最大充電量の範囲は、実施例に記載の方法によって求めた。 In the present invention, the amount of charge per 1 mg of silicon particles is adjusted to suppress the heat generation during charging / discharging of the negative electrode active material layer, and the decrease in capacity retention rate is suppressed. In addition, the range of the maximum charge amount of the silicon particles in the all solid state battery system of the present invention was determined by the method described in the examples.
＜全固体電池システム＞
本発明の全固体電池システムは、正極活物質層、固体電解質層、及び負極活物質層をこの順で有する全固体電池、並びに全固体電池の充電量を制御する制御装置を有する。負極活物質層は、負極活物質としてケイ素粒子を有する。
<All-solid battery system>
The all-solid-state battery system of this invention has a control apparatus which controls the charge amount of an all-solid-state battery which has a positive electrode active material layer, a solid electrolyte layer, and a negative electrode active material layer in this order, and an all-solid-state battery. The negative electrode active material layer has silicon particles as the negative electrode active material.
＜制御装置＞
本発明の全固体電電池システムは、全固体電池の充電量を制御する制御装置を有する。この制御装置は、全固体電池の充放電においてケイ素粒子の最大充電量が１．１ｍＡｈ／ｍｇ以上１．５ｍＡｈ／ｍｇ以下になるようにして、全固体電池の充電量を制御する。この制御装置は、全固体電池の充放電においてケイ素粒子の最大充電量を所定の範囲に制御することができる装置であれば、特に限定されない。
<Control device>
The all-solid-state battery system of this invention has a control apparatus which controls the charge amount of an all-solid-state battery. This control device controls the charge amount of the all-solid-state battery so that the maximum charge amount of the silicon particles is 1.1 mAh / mg or more and 1.5 mAh / mg or less in the charge / discharge of the all-solid-state battery. The control device is not particularly limited as long as it is a device that can control the maximum charge amount of the silicon particles within a predetermined range in charging / discharging of the all solid state battery.
ケイ素粒子の最大充電量を制御する方法としては、例えば、全固体電池が有する負極活物質としてのケイ素粒子の含有量が既知であれば、充電上限電圧を調節することによって制御することができる。したがって、この制御装置としては、例えば、全固体電池の充電時において、全固体電池の電圧が一定の電圧まで到達したかを判定し、一定の電圧まで到達した場合に充電を終了させることができるものが挙げられる。 As a method for controlling the maximum charge amount of the silicon particles, for example, if the content of silicon particles as the negative electrode active material of the all-solid battery is known, it can be controlled by adjusting the charge upper limit voltage. Therefore, for example, when the all-solid battery is charged, the control device can determine whether the voltage of the all-solid battery has reached a certain voltage, and can terminate the charging when the voltage reaches a certain voltage. Things.
なお、ケイ素粒子の充電量とは、負極活物質としてケイ素粒子を有する全固体電池を充電したときの充電量の値であり、充電によって負極活物質としてのケイ素粒子にドープされたリチウムの量に対応している。 The charged amount of silicon particles is the value of the charged amount when an all solid state battery having silicon particles as a negative electrode active material is charged, and is the amount of lithium doped into the silicon particles as the negative electrode active material by charging. It corresponds.
＜全固体電池＞
本発明の全固体電池は、正極活物質層、固体電解質層、及び負極活物質層をこの順で有する。
<All solid battery>
The all solid state battery of the present invention has a positive electrode active material layer, a solid electrolyte layer, and a negative electrode active material layer in this order.
１．正極活物質層
本発明における正極活物質層は、正極活物質、並びに随意にバインダー、導電助剤、及び固体電解質を有する。
1. Positive electrode active material layer The positive electrode active material layer in the present invention includes a positive electrode active material, and optionally, a binder, a conductive additive, and a solid electrolyte.
正極活物質としては、リチウム二次電池の正極活物質材料として用いられる材料であれば特に限定されない。例えば、コバルト酸リチウム、ニッケル酸リチウム、ニッケルコバルトマンガン酸リチウム、マンガン酸リチウム、異種元素置換Ｌｉ−Ｍｎスピネル、チタン酸リチウム、若しくはＬｉＭＰＯ４（ＭがＦｅ、Ｍｎ、Ｃｏ、Ｎｉから選ばれる一種類以上）で表される組成のリン酸金属リチウム等、又はこれらの組み合わせを挙げることができる。 The positive electrode active material is not particularly limited as long as it is a material used as a positive electrode active material for a lithium secondary battery. For example, lithium cobalt acid, lithium nickel acid, lithium nickel cobalt manganese oxide, one type lithium manganate, heterogeneous element substituted Li-Mn spinel, lithium titanate, or the LiMPO 4 (M is Fe, Mn, Co, chosen from Ni And lithium metal phosphate having a composition represented by the above), or a combination thereof.
固体電解質としては、全固体電池の固体電解質として用いられる硫化物固体電解質を用いることができる。例えば、Ｌｉ２Ｓ−ＳｉＳ２、ＬｉＩ−Ｌｉ２Ｓ−ＳｉＳ２、ＬｉＩ−Ｌｉ２Ｓ−Ｐ２Ｓ５、ＬｉＩ−Ｌｉ２Ｓ−Ｐ２Ｓ５、ＬｉＩ−ＬｉＰＯ４−Ｐ２Ｓ５、Ｌｉ２Ｓ−Ｐ２Ｓ５などが挙げられる。
As the solid electrolyte, a sulfide solid electrolyte used as a solid electrolyte of an all-solid battery can be used. For example, Li 2 S-SiS 2, LiI-Li 2 S-
バインダーとしては、特に限定されないが、ポリマー樹脂、例えば、ポリフッ化ビニリデン（ＰＶＤＦ）、ポリテトラフルオロエチレン（ＰＴＦＥ）、ポリイミド（ＰＩ）、ポリアミド（ＰＡ）、ポリアミドイミド（ＰＡＩ）、ブタジエンゴム（ＢＲ）、スチレンブタジエンゴム（ＳＢＲ）、ニトリル−ブタジエンゴム（ＮＢＲ）、スチレン−エチレン−ブチレン−スチレンブロック共重合体（ＳＥＢＳ）、若しくはカルボキシメチルセルロース（ＣＭＣ）等、又はこれらの組み合わせを挙げることができる。 The binder is not particularly limited, but a polymer resin such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyimide (PI), polyamide (PA), polyamideimide (PAI), butadiene rubber (BR) Styrene-butadiene rubber (SBR), nitrile-butadiene rubber (NBR), styrene-ethylene-butylene-styrene block copolymer (SEBS), carboxymethyl cellulose (CMC), or a combination thereof.
導電助剤としては、ＶＧＣＦ、アセチレンブラック、ケッチェンブラック、カーボンナノチューブ（ＣＮＴ）、又はカーボンナノファイバー（ＣＮＦ）等の炭素材料の他、ニッケル・アルミニウム・ステンレス鋼等の金属、又はこれらの組み合わせを上げることができる。 Conductive aids include carbon materials such as VGCF, acetylene black, ketjen black, carbon nanotube (CNT), or carbon nanofiber (CNF), metals such as nickel, aluminum, and stainless steel, or combinations thereof. Can be raised.
２．固体電解質層
固体電解質層は上記正極活物質層において記載した電解質を利用することができる。固体電解質層の厚さは、例えば、０．１μｍ以上３００μｍ以下であり、特に、０．１μｍ以上１００μｍ以下であってよい。
2. Solid electrolyte layer The electrolyte described in the said positive electrode active material layer can be utilized for a solid electrolyte layer. The thickness of the solid electrolyte layer is, for example, not less than 0.1 μm and not more than 300 μm, and particularly not less than 0.1 μm and not more than 100 μm.
３．負極活物質層
負極活物質層は、負極活物質、並びに随意に導電助剤、バインダー、及び固体電解質を有している。負極活物質としては、ケイ素粒子が用いられる。導電助剤、バインダー、及び固体電解質としては、上記正極活物質層において記載したものを用いることができる。
3. Negative electrode active material layer The negative electrode active material layer includes a negative electrode active material, and optionally a conductive additive, a binder, and a solid electrolyte. Silicon particles are used as the negative electrode active material. As a conductive support agent, a binder, and a solid electrolyte, what was described in the said positive electrode active material layer can be used.
４．製造方法
本発明の全固体電池システムに用いられる全固体電池は、当業者にとって公知であるいかなる方法によっても作製することができ、また当業者にとって公知でない方法によっても作製することができる。
4). Manufacturing Method The all-solid-state battery used in the all-solid-state battery system of the present invention can be manufactured by any method known to those skilled in the art, and can also be manufactured by methods not known to those skilled in the art.
作製方法を限定する趣旨ではないが、具体的な作製方法の例としては、例えば、正極集電体、正極活物質層、固体電解質層、負極活物質層、及び負極集電体を、この順番になるように積層し、プレスすることにより作製することができる。 Although not intended to limit the manufacturing method, examples of specific manufacturing methods include, for example, a positive electrode current collector, a positive electrode active material layer, a solid electrolyte layer, a negative electrode active material layer, and a negative electrode current collector in this order. It can be produced by laminating and pressing.
なお、正極活物質層、固体電解質層、及び負極活物質層は、例えば、上記正極活物質層、固体電解質層、負極活物質層において記載したそれぞれの材料を分散媒に分散し、これらの材料を混合したスラリーをそれぞれ金属箔上に塗工し、乾燥させることによって作製することができる。 The positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer are prepared by, for example, dispersing the respective materials described in the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer in a dispersion medium. Each of the slurries mixed can be coated on a metal foil and dried.
下記の方法により、本発明の全固体電池システムにおける全固体電池の最大充電量の範囲を求めた。具体的には、ケイ素粒子１ｍｇあたりの充電量に対する負極活物質層の発熱量の関係から、最大充電時のケイ素粒子の充電量の下限を求め（下記の例１参照）、ケイ素粒子１ｍｇあたりの充電量に対する容量維持率の関係から、最大充電時のケイ素粒子の充電量の上限を求めた（下記の例２参照）。 The range of the maximum charge amount of the all solid state battery in the all solid state battery system of the present invention was determined by the following method. Specifically, from the relationship between the calorific value of the negative electrode active material layer with respect to the charge amount per 1 mg of silicon particles, the lower limit of the charge amount of the silicon particles at the maximum charge is obtained (see Example 1 below), From the relationship between the capacity retention rate and the charge amount, the upper limit of the charge amount of the silicon particles at the maximum charge was determined (see Example 2 below).
＜＜例１＞＞
下記の方法により全固体電池を作製し、負極活物質層の発熱量を計算した。この計算に基づき、ケイ素粒子１ｍｇあたりの充電量に対する負極活物質層の発熱量の関係から、最大充電時のケイ素粒子の充電量の下限を求めた。
<< Example 1 >>
An all-solid battery was prepared by the following method, and the calorific value of the negative electrode active material layer was calculated. Based on this calculation, the lower limit of the charge amount of the silicon particles at the maximum charge was obtained from the relationship between the calorific value of the negative electrode active material layer and the charge amount per 1 mg of silicon particles.
＜全固体電池の作製＞
１．硫化物固体電解質の合成
Ｌｉ２Ｓ（日本化学工業製）、Ｐ２Ｓ５（アルドリッチ製）、ＬｉＩ（日宝化学製）、及びＬｉＢｒ（高純度化学製）を出発原料として、Ｌｉ２Ｓを０．５８６ｇ、Ｐ２Ｓ５を０．９４５ｇ、ＬｉＩを０．２８４ｇ、及びＬｉＢｒを０．１８５ｇ秤量し、メノウ乳鉢で５分混合した。その混合物を遊星型ボールミルの容器（４５ｃｃ、ＺｒＯ２製）に投入し、脱水ヘプタン（水分量３０ｐｐｍ以下、４ｇ）を投入し、さらにＺｒＯ２ボール（φ＝５ｍｍ、５３ｇ）を投入し、容器を完全に密閉した。この容器を遊星型ボールミル機（フリッチュ製Ｐ７）に取り付け、台盤回転数５００ｒｐｍで、２０時間メカニカルミリングを行った。その後、１１０℃で１時間乾燥することによりヘプタンを除去し、非晶質硫化物固体電解質を得た。なお、得られた非晶質硫化物固体電解質の組成はモル表記で１０ＬｉＩ・１０ＬｉＢｒ・８０（０．７５Ｌｉ２Ｓ・０．２５Ｐ２Ｓ５）（ｍｏｌ％）であった。
<Preparation of all-solid battery>
1. Synthesis of sulfide solid electrolyte Li 2 S (manufactured by Nippon Kagaku Kogyo), P 2 S 5 (manufactured by Aldrich), LiI (manufactured by Nichibo Chemical), and LiBr (manufactured by high purity chemical) are used as starting materials, and Li 2 S is synthesized. 0.586 g, 0.945 g of P 2 S 5 , 0.284 g of LiI, and 0.185 g of LiBr were weighed and mixed in an agate mortar for 5 minutes. The mixture is put into a planetary ball mill container (45 cc, made of ZrO 2 ), dehydrated heptane (moisture content of 30 ppm or less, 4 g) is added, and ZrO 2 balls (φ = 5 mm, 53 g) are further charged. Completely sealed. This container was attached to a planetary ball mill (P7 made by Fritsch), and mechanical milling was performed for 20 hours at a base plate rotation speed of 500 rpm. Then, heptane was removed by drying at 110 ° C. for 1 hour to obtain an amorphous sulfide solid electrolyte. In addition, the composition of the obtained amorphous sulfide solid electrolyte was 10LiI · 10LiBr · 80 (0.75Li 2 S · 0.25P 2 S 5 ) (mol%) in molar notation.
次に、得られた非晶質硫化物固体電解質０．５ｇを石英管中に真空封入し、１８５℃で熱処理を行った。室温から１８５℃まで１℃／分で昇温し、１８５℃に到達後に１０時間保持した後、自然冷却して、ガラスセラミックスである硫化物固体電解質を得た。 Next, 0.5 g of the obtained amorphous sulfide solid electrolyte was sealed in a quartz tube and heat-treated at 185 ° C. The temperature was raised from room temperature to 185 ° C. at a rate of 1 ° C./min. After reaching 185 ° C. and held for 10 hours, it was naturally cooled to obtain a sulfide solid electrolyte as glass ceramic.
２．正極活物質層用粉末の作製
エタノール溶媒に、等モルのＬｉＯＣ２Ｈ５及びＮｂ（ＯＣ２Ｈ５）５を溶解させて作製した組成物を、平均粒径Ｄ５０＝５μｍのＬｉＮｉ１／３Ｃｏ１／３Ｍｎ１／３Ｏ２（日亜化学工業）の表面に、転動流動コーティング装置（ＳＦＰ−０１、株式会社パウレック製）を用いてスプレーコートした。その後、コーティングされたＬｉＮｉ１／３Ｃｏ１／３Ｍｎ１／３Ｏ２を、３５０℃、大気圧下で１時間にわたって熱処理ことにより、ＬｉＮｉ１／３Ｃｏ１／３Ｍｎ１／３Ｏ２の表面にＬｉＮｂＯ３の層を形成し、正極活物質を作製した。
2. Preparation of Powder for Positive Electrode Active Material Layer A composition prepared by dissolving equimolar LiOC 2 H 5 and Nb (OC 2 H 5 ) 5 in an ethanol solvent was used as a LiNi 1/3 Co having an average particle diameter D50 = 5 μm. Spray coating was performed on the surface of 1/3 Mn 1/3 O 2 (Nichia Corporation) using a rolling fluidized coating apparatus (SFP-01, manufactured by POWREC Co., Ltd.). Thereafter, the coated LiNi 1/3 Co 1/3 Mn 1/3 O 2 was heat-treated at 350 ° C. under atmospheric pressure for 1 hour, so that LiNi 1/3 Co 1/3 Mn 1/3 O 2 A layer of LiNbO 3 was formed on the surface to produce a positive electrode active material.
正極活物質５２ｇ、導電助剤としてのＶＧＣＦ１ｇ、硫化物固体電解質２２ｇ、分散媒としての酪酸ブチル（昭和化学）５０ｇ、及びバインダーとしてのＰＶＤＦ１．５ｇを秤量し、十分に混合して正極活物質層用スラリーを作製した。この正極活物質用スラリーをアルミニウム箔上に塗工し、乾燥して正極活物質層用粉末を得た。 Positive electrode active material layer 52 g, VGCF 1 g as conductive additive, sulfide solid electrolyte 22 g, butyl butyrate (Showa Chemical) 50 g as dispersion medium, and PVDF 1.5 g as binder are weighed and mixed well A slurry was prepared. This positive electrode active material slurry was coated on an aluminum foil and dried to obtain a positive electrode active material layer powder.
３．負極活物質層用粉末の作製
負極活物質としてのケイ素粒子（高純度化学）３６ｇ、導電助剤としてのＶＧＣＦ１．５ｇ、硫化物固体電解質２５ｇ、分散媒としての酪酸ブチル（昭和化学）６０ｇ、及びバインダーとしてのＰＶＤＦ１ｇを秤量し、十分に混合して負極活物質層用スラリーを作製した。この負極活物質用スラリーをアルミニウム箔上に塗工し、乾燥して負極活物質層用粉末を得た。
3. Preparation of powder for negative electrode active material layer 36 g of silicon particles (high purity chemistry) as a negative electrode active material, 1.5 g of VGCF as a conductive additive, 25 g of sulfide solid electrolyte, 60 g of butyl butyrate (Showa Chemical) as a dispersion medium, and 1 g of PVDF as a binder was weighed and mixed well to prepare a slurry for negative electrode active material layer. This negative electrode active material slurry was coated on an aluminum foil and dried to obtain a negative electrode active material layer powder.
４．固体電解質層の作製
硫化物固体電解質２５ｇ、バインダー１ｇ、及び分散媒としての脱水へプタン２５ｇを十分に混合して、固体電解質用スラリーを作製した。この固体電解質用スラリーをアルミニウム箔上に塗工し、乾燥させることにより固体電解質層を得た。
4). Production of Solid Electrolyte Layer 25 g of sulfide solid electrolyte, 1 g of binder, and 25 g of dehydrated heptane as a dispersion medium were sufficiently mixed to produce a solid electrolyte slurry. This solid electrolyte slurry was applied onto an aluminum foil and dried to obtain a solid electrolyte layer.
５．電池の組立
固体電解質層をプレスし、その上に所定量秤量した正極活物質層用粉末を設置し、プレスしてペレット１を成形した。負極活物質層用粉末を所定量秤量し、プレスしてペレット２を成形した。ペレット１の固体電解質層上にペレット２を積層し、治具で拘束して全固体電池を作製した。
5. Assembling the Battery The solid electrolyte layer was pressed, a predetermined amount of powder for the positive electrode active material layer was placed thereon, and pressed to form
＜負極活物質としてのケイ素粒子への充電＞
作製した全固体電池について、初期充放電として、４．５５Ｖまで充電し、２．５Ｖまで放電した。その後、作製した全固体電池について、所定電圧まで充電して、負極活物質としてのケイ素粒子への充電とした。このときの充電量を、負極活物質としてのケイ素粒子の重量で除算した値を、ケイ素粒子１ｍｇあたりの充電量とした。なお、作製した複数の全固体電池について、ケイ素粒子１ｍｇあたりの充電量が異なる全固体電池とするため、それぞれ所定電圧を変えて充電を行っている。
<Charging to silicon particles as negative electrode active material>
About the produced all-solid-state battery, it charged to 4.55V as initial stage charge / discharge, and discharged to 2.5V. Then, about the produced all-solid-state battery, it charged to the predetermined voltage and was set as the charge to the silicon particle as a negative electrode active material. A value obtained by dividing the charge amount at this time by the weight of the silicon particles as the negative electrode active material was defined as the charge amount per 1 mg of silicon particles. In addition, about the produced all-solid-state battery, in order to set it as the all-solid-state battery from which the charge amount per 1 mg of silicon particles differs, it charges by changing each predetermined voltage.
＜発熱量の評価＞
充電した複数の全固体電池を分解して、ペレット２を取出した。ペレット２をパンに詰め、示差走査熱量計（ＤＳＣ）で発熱量を測定した。得られた発熱量をペレット２の重量で除算した値を、負極活物質層材料の単位重量あたりの発熱量とした。
<Evaluation of calorific value>
A plurality of charged all-solid-state batteries were disassembled and the
ケイ素粒子１ｍｇあたりの充電量と負極活物質層材料１ｍｇあたりの発熱量との関係を図２のグラフに表した。図のとおり、負極活物質層材料１ｍｇあたりの発熱量は、ケイ素粒子１ｍｇあたりの充電量が増加するとともに増加した。しかし、ケイ素粒子１ｍｇあたりの充電量が０．４７ｍＡｈ／ｍｇ以上になると、ケイ素粒子１ｍｇあたりの充電量の大きさによらず、負極活物質層材料１ｍｇあたりの発熱量は一定の値（約１０００ｍＪ／ｍｇ）となった。例えば、図２において、ケイ素粒子１ｍｇあたりの充電量が０．４７ｍＡｈ／ｍｇ（例１−１）、０．７ｍＡｈ／ｍｇ（例１−２）、１．１ｍＡｈ／ｍｇ（例１−３）、及び１．８ｍＡｈ／ｍｇ（例１−４）のとき、いずれも負極活物質層材料１ｍｇあたりの発熱量は約１０００ｍＪ／ｍｇであった。 The relationship between the charge amount per 1 mg of silicon particles and the calorific value per 1 mg of the negative electrode active material layer material is shown in the graph of FIG. As shown in the figure, the calorific value per 1 mg of the negative electrode active material layer material increased as the charge amount per 1 mg of silicon particles increased. However, when the charge amount per 1 mg of silicon particles is 0.47 mAh / mg or more, the calorific value per 1 mg of the negative electrode active material layer material is a constant value (about 1000 mJ) regardless of the charge amount per 1 mg of silicon particles. / Mg). For example, in FIG. 2, the charge amount per 1 mg of silicon particles is 0.47 mAh / mg (Example 1-1), 0.7 mAh / mg (Example 1-2), 1.1 mAh / mg (Example 1-3), And 1.8 mAh / mg (Example 1-4), the calorific value per 1 mg of the negative electrode active material layer material was about 1000 mJ / mg.
＜負極活物質層重量の算定＞
正極活物質層の容量を０．１Ａｈと想定して、これをケイ素粒子単位重量当たりの充電容量で除することにより、必要なケイ素粒子の重量を求めた。そして、必要なケイ素粒子の重量を負極活物質層中のケイ素粒子の重量比率で除することにより、必要な負極活物質層の重量を求めた。
<Calculation of negative electrode active material layer weight>
The capacity of the positive electrode active material layer was assumed to be 0.1 Ah, and this was divided by the charge capacity per unit weight of the silicon particles, thereby obtaining the necessary weight of the silicon particles. And the weight of the required negative electrode active material layer was calculated | required by remove | dividing the weight of the required silicon particle by the weight ratio of the silicon particle in a negative electrode active material layer.
ケイ素粒子１ｍｇあたりの充電量が０．４７ｍＡｈ／ｍｇ以上の場合について、ケイ素粒子１ｍｇあたりの充電量と負極活物質層の重量との関係を図３のグラフに表した。図のとおり、ケイ素粒子１ｍｇあたりの充電量が多いほど、負極活物質層の重量は減少した。 In the case where the charge amount per 1 mg of silicon particles is 0.47 mAh / mg or more, the relationship between the charge amount per 1 mg of silicon particles and the weight of the negative electrode active material layer is shown in the graph of FIG. As shown in the figure, the weight of the negative electrode active material layer decreased as the charge amount per 1 mg of silicon particles increased.
＜負極活物質層発熱量の算定＞
負極活物質層材料１ｍｇあたりの発熱量に負極活物質層の重量を乗算し、負極活物質層の発熱量を求めた。また、ケイ素粒子１ｍｇあたりの充電量と負極活物質層の発熱量との関係を図４のグラフに示した。図のとおり、ケイ素粒子１ｍｇあたりの充電量が０．４７ｍＡｈ／ｍｇ以上の場合には、ケイ素粒子１ｍｇあたりの充電量が増加するほど負極活物質層の発熱量は低下した。図から、ケイ素粒子１ｍｇあたりの充電量が１．１ｍＡｈ／ｍｇ（例１−３）より小さい場合には、負極活物質層の発熱量が大きくなりすぎるといえる。
<Calculation of calorific value of negative electrode active material layer>
The calorific value per 1 mg of the negative electrode active material layer material was multiplied by the weight of the negative electrode active material layer to obtain the calorific value of the negative electrode active material layer. Moreover, the relationship between the charge amount per 1 mg of silicon particles and the calorific value of the negative electrode active material layer is shown in the graph of FIG. As shown in the figure, when the charge amount per 1 mg of silicon particles was 0.47 mAh / mg or more, the calorific value of the negative electrode active material layer decreased as the charge amount per 1 mg of silicon particles increased. From the figure, it can be said that when the charge amount per 1 mg of silicon particles is smaller than 1.1 mAh / mg (Example 1-3), the calorific value of the negative electrode active material layer becomes too large.
以上から、最大充電時のケイ素粒子の充電量の下限を１．１ｍＡｈ／ｍｇとした。 From the above, the lower limit of the charged amount of silicon particles during maximum charging was set to 1.1 mAh / mg.
＜＜例２＞＞
下記の方法により、例２−１、例２−２、及び例２−３の全固体電池を作製し、その容量維持率を評価した。この評価に基づき、ケイ素粒子１ｍｇあたりの充電量に対する容量維持率の関係から、最大充電時のケイ素粒子の充電量の上限を求めた。
<< Example 2 >>
By the following method, the all-solid-state batteries of Example 2-1, Example 2-2, and Example 2-3 were produced, and the capacity retention rate was evaluated. Based on this evaluation, the upper limit of the charge amount of the silicon particles at the maximum charge was determined from the relationship of the capacity retention rate with respect to the charge amount per 1 mg of silicon particles.
＜例２―１＞
１．全固体電池の作製
（１）硫化物固体電解質の合成
Ｌｉ２Ｓ（日本化学工業製）、Ｐ２Ｓ５（アルドリッチ製）、ＬｉＩ（日宝化学製）、及びＬｉＢｒ（高純度化学製）を出発原料として、Ｌｉ２Ｓを０．５８６ｇ、Ｐ２Ｓ５を０．９４５ｇ、ＬｉＩを０．２８４ｇ、及びＬｉＢｒを０．１８５ｇ秤量し、メノウ乳鉢で５分混合した。その混合物を遊星型ボールミルの容器（４５ｃｃ、ＺｒＯ２製）に投入し、脱水ヘプタン（水分量３０ｐｐｍ以下、４ｇ）を投入し、さらにＺｒＯ２ボール（φ＝５ｍｍ、５３ｇ）を投入し、容器を完全に密閉した。この容器を遊星型ボールミル機（フリッチュ製Ｐ７）に取り付け、台盤回転数５００ｒｐｍで、２０時間メカニカルミリングを行った。その後、１１０℃で１時間乾燥することによりヘプタンを除去し、非晶質硫化物固体電解質を得た。なお、得られた非晶質硫化物固体電解質の組成はモル表記で１０ＬｉＩ・１０ＬｉＢｒ・８０（０．７５Ｌｉ２Ｓ・０．２５Ｐ２Ｓ５）（ｍｏｌ％）であった。
<Example 2-1>
1. Production of all-solid-state battery (1) Synthesis of sulfide solid electrolyte Li 2 S (manufactured by Nippon Chemical Industry Co., Ltd.), P 2 S 5 (manufactured by Aldrich), LiI (manufactured by Nichiho Chemical), and LiBr (manufactured by High Purity Chemical) As starting materials, 0.586 g of Li 2 S, 0.945 g of P 2 S 5 , 0.284 g of LiI, and 0.185 g of LiBr were weighed and mixed in an agate mortar for 5 minutes. The mixture is put into a planetary ball mill container (45 cc, made of ZrO 2 ), dehydrated heptane (moisture content of 30 ppm or less, 4 g) is added, and ZrO 2 balls (φ = 5 mm, 53 g) are further charged. Completely sealed. This container was attached to a planetary ball mill (P7 made by Fritsch), and mechanical milling was performed for 20 hours at a base plate rotation speed of 500 rpm. Then, heptane was removed by drying at 110 ° C. for 1 hour to obtain an amorphous sulfide solid electrolyte. In addition, the composition of the obtained amorphous sulfide solid electrolyte was 10LiI · 10LiBr · 80 (0.75Li 2 S · 0.25P 2 S 5 ) (mol%) in molar notation.
次に、得られた非晶質硫化物固体電解質０．５ｇを石英管中に真空封入し、１８５℃で熱処理を行った。室温から１８５℃まで１℃／分で昇温し、１８５℃に到達後に１０時間保持した後、自然冷却して、ガラスセラミックスである硫化物固体電解質を得た。 Next, 0.5 g of the obtained amorphous sulfide solid electrolyte was sealed in a quartz tube and heat-treated at 185 ° C. The temperature was raised from room temperature to 185 ° C. at a rate of 1 ° C./min. After reaching 185 ° C. and held for 10 hours, it was naturally cooled to obtain a sulfide solid electrolyte as glass ceramic.
（２）正極活物質層の作製
エタノール溶媒に、等モルのＬｉＯＣ２Ｈ５及びＮｂ（ＯＣ２Ｈ５）５を溶解させて作製した組成物を、平均粒径Ｄ５０＝５μｍのＬｉＮｉ１／３Ｃｏ１／３Ｍｎ１／３Ｏ２（日亜化学工業）の表面に、転動流動コーティング装置（ＳＦＰ−０１、株式会社パウレック製）を用いてスプレーコートした。その後、コーティングされたＬｉＮｉ１／３Ｃｏ１／３Ｍｎ１／３Ｏ２を、３５０℃、大気圧下で１時間にわたって熱処理ことにより、ＬｉＮｉ１／３Ｃｏ１／３Ｍｎ１／３Ｏ２の表面にＬｉＮｂＯ３の層を形成し、正極活物質を作製した。
(2) Preparation of positive electrode active material layer A composition prepared by dissolving equimolar amounts of LiOC 2 H 5 and Nb (OC 2 H 5 ) 5 in an ethanol solvent was LiNi 1/3 having an average particle diameter D50 = 5 μm. The surface of Co 1/3 Mn 1/3 O 2 (Nichia Corporation) was spray coated using a tumbling fluidized coating apparatus (SFP-01, manufactured by POWREC Co., Ltd.). Thereafter, the coated LiNi 1/3 Co 1/3 Mn 1/3 O 2 was heat-treated at 350 ° C. under atmospheric pressure for 1 hour, so that LiNi 1/3 Co 1/3 Mn 1/3 O 2 A layer of LiNbO 3 was formed on the surface to produce a positive electrode active material.
正極活物質５２ｇ、導電助剤としてのＶＧＣＦ１ｇ、硫化物固体電解質２２ｇ、分散媒としての酪酸ブチル（昭和化学）５０ｇ、及びバインダーとしてのＰＶＤＦ１．５ｇを秤量し、十分に混合して正極活物質層用スラリーを作製した。この正極活物質用スラリーを正極集電体としてのアルミニウム箔上に塗工し、乾燥させることにより正極活物質層を得た。 Positive electrode active material layer 52 g, VGCF 1 g as conductive additive, sulfide solid electrolyte 22 g, butyl butyrate (Showa Chemical) 50 g as dispersion medium, and PVDF 1.5 g as binder are weighed and mixed well A slurry was prepared. This positive electrode active material slurry was coated on an aluminum foil as a positive electrode current collector and dried to obtain a positive electrode active material layer.
（３）負極活物質層の作製
負極活物質としてのケイ素粒子（高純度化学）３６ｇ、導電助剤としてのＶＧＣＦ１．５ｇ、硫化物固体電解質２５ｇ、分散媒としての酪酸ブチル（昭和化学）６０ｇ、及びバインダーとしてのＰＶＤＦ１ｇを秤量し、十分に混合して負極活物質層用スラリーを作製した。この負極活物質用スラリーを負極集電体としての銅箔上に塗工し、乾燥させることにより負極活物質層を得た。
(3) Production of negative electrode active material layer 36 g of silicon particles (high-purity chemistry) as a negative electrode active material, 1.5 g of VGCF as a conductive additive, 25 g of sulfide solid electrolyte, 60 g of butyl butyrate (Showa Chemical) as a dispersion medium, And 1 g of PVDF as a binder was weighed and mixed well to prepare a slurry for negative electrode active material layer. This negative electrode active material slurry was applied onto a copper foil as a negative electrode current collector and dried to obtain a negative electrode active material layer.
（４）固体電解質層の作製
硫化物固体電解質２５ｇ、バインダー１ｇ、及び分散媒としての脱水へプタン２５ｇを十分に混合して、固体電解質用スラリーを作製した。この固体電解質用スラリーをアルミニウム箔上に塗工し、乾燥させることにより固体電解質層を得た。
(4) Production of Solid Electrolyte Layer 25 g of sulfide solid electrolyte, 1 g of binder, and 25 g of dehydrated heptane as a dispersion medium were sufficiently mixed to produce a solid electrolyte slurry. This solid electrolyte slurry was applied onto an aluminum foil and dried to obtain a solid electrolyte layer.
（５）電池組立
負極活物質層上に固体電解質層を積層し、固体電解質層上のアルミニウム箔を剥離した。その後、固体電解質層上に正極活物質層を積層した。積層した負極活物質層、固体電解質層、及び正極活物質層をプレスして、積層体を作製した。
(5) Battery assembly The solid electrolyte layer was laminated | stacked on the negative electrode active material layer, and the aluminum foil on a solid electrolyte layer was peeled. Thereafter, a positive electrode active material layer was laminated on the solid electrolyte layer. The laminated negative electrode active material layer, solid electrolyte layer, and positive electrode active material layer were pressed to produce a laminate.
集電タブをセル端子と接触させ、作製した積層体と共にアルミニウムラミネートで真空封入することで、全固体電池を完成させた。 The current collecting tab was brought into contact with the cell terminal, and was vacuum-sealed with an aluminum laminate together with the produced laminate, thereby completing an all-solid battery.
２．電池の評価
上記方法により作製した全固体電池に対して、初期充放電として、全固体電池を４．５５Ｖまで充電し、２．５Ｖまで放電した（ＣＣＣＶ充放電、終止電流０．０２ｍＡｈ）。その後、全固体電池を４．４Ｖまで充電し、３Ｖまで放電した。この時の放電容量を測定し、耐久試験前の放電容量とした。
2. Evaluation of Battery The all solid state battery manufactured by the above method was charged to 4.55V and discharged to 2.5V as the initial charge / discharge (CCCV charge / discharge, final current 0.02 mAh). Thereafter, the all solid state battery was charged to 4.4V and discharged to 3V. The discharge capacity at this time was measured and used as the discharge capacity before the durability test.
その後、耐久試験として、電池を６０℃の環境下で、４．１７Ｖまで充電して３．１３７Ｖまで放電する充放電サイクルを、３００サイクル繰り返した。その後、電池を４．４Ｖまで充電し、３Ｖまで放電した。この時の放電容量を測定し、耐久試験後の放電容量とした。 Thereafter, as a durability test, a charge / discharge cycle in which the battery was charged to 4.17 V and discharged to 3.137 V in an environment of 60 ° C. was repeated 300 cycles. Thereafter, the battery was charged to 4.4V and discharged to 3V. The discharge capacity at this time was measured and used as the discharge capacity after the durability test.
耐久試験後の放電容量を耐久試験前の放電容量で除し、１００を乗算した値を、容量維持率とした。 A value obtained by dividing the discharge capacity after the endurance test by the discharge capacity before the endurance test and multiplying by 100 was taken as the capacity retention rate.
＜例２―２及び例２−３＞
負極活物質層の作製において、負極集電体としての銅箔上に塗工する負極活物質層用スラリーの量を変えたことを除いて、例２―１と同様にして全固体電池を作製し、その容量維持率を評価した。
<Example 2-2 and Example 2-3>
In the production of the negative electrode active material layer, an all solid state battery was produced in the same manner as in Example 2-1, except that the amount of the slurry for the negative electrode active material layer applied on the copper foil as the negative electrode current collector was changed. The capacity maintenance rate was evaluated.
＜結果＞ <Result>
１．表の説明
表において、「Ｓｉ１ｍｇあたりの容量」とは、初期充放電後耐久試験前に全固体電池を４．４Ｖまで充電したときの充電量を、負極活物質としてのケイ素粒子の重量で割った値である。
1. Explanation of Table In the table, “capacity per 1 mg of Si” is obtained by dividing the amount of charge when the all-solid-state battery is charged to 4.4 V before the endurance test after the initial charge / discharge by the weight of the silicon particles as the negative electrode active material. Value.
２．考察
表１のとおり、例２―１、例２―２、及び例２―３において作製した全固体電池の、初期充放電後耐久試験前に全固体電池を４．４Ｖまで充電したときの充電量は、それぞれ１．５ｍＡｈ／ｍｇ、０．８ｍＡｈ／ｍｇ、及び０．５ｍＡｈ／ｍｇであった。
2. Discussion As shown in Table 1, charging of all solid state batteries produced in Examples 2-1 and 2-2 and Example 2-3 when the all solid state batteries are charged to 4.4 V before the endurance test after the initial charge / discharge. The amounts were 1.5 mAh / mg, 0.8 mAh / mg, and 0.5 mAh / mg, respectively.
図５は、例２―１、例２―２、例２―３の全固体電池の「Ｓｉ１ｍｇあたりの容量」に対する容量維持率のグラフである。図のとおり、「Ｓｉ１ｍｇあたりの容量」が１．５ｍＡｈ／ｍｇより小さい場合には、容量維持率は約９７％であり、「Ｓｉ１ｍｇあたりの容量」が１．５ｍＡｈ／ｍｇになると、容量維持率は約９３％に低下している。「Ｓｉ１ｍｇあたりの容量」の値がさらに大きくなると、容量維持率はさらに低下すると考えられる。 FIG. 5 is a graph of the capacity retention ratio with respect to “capacity per 1 mg of Si” of the all-solid-state batteries of Examples 2-1 and 2-2 and 2-3. As shown in the figure, when the “capacity per 1 mg of Si” is smaller than 1.5 mAh / mg, the capacity maintenance rate is about 97%, and when the “capacity per 1 mg of Si” becomes 1.5 mAh / mg, the capacity maintenance rate Has dropped to about 93%. As the value of “capacity per 1 mg of Si” further increases, the capacity retention rate is considered to further decrease.
以上から、本発明の全固体電池システムにおける、最大充電時のケイ素粒子の充電量の上限を１．５ｍＡｈ／ｍｇとした。 From the above, in the all solid state battery system of the present invention, the upper limit of the charge amount of the silicon particles at the maximum charge was set to 1.5 mAh / mg.
１ 正極集電体
２ 正極活物質層
３ 固体電解質層
４ 負極活物質層
５ 負極集電体
６ 全固体電池
１０ 制御装置
DESCRIPTION OF
Claims (1)
前記負極活物質層が、固体電解質、及び負極活物質としてのケイ素粒子を有し、かつ
前記制御装置が、前記ケイ素粒子の最大充電量が１．１ｍＡｈ／ｍｇ以上１．５ｍＡｈ／ｍｇ以下であるようにして、前記全固体電池の充電量を制御する、
全固体電池システム。 An all solid state battery system having a positive electrode active material layer, a solid electrolyte layer, and a negative electrode active material layer in this order, and a control device for controlling the charge amount of the all solid state battery,
The negative electrode active material layer has a solid electrolyte and silicon particles as a negative electrode active material, and the control device has a maximum charge amount of the silicon particles of 1.1 mAh / mg or more and 1.5 mAh / mg or less. In this way, the charge amount of the all solid state battery is controlled,
All solid state battery system.
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