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JP2023081688A - All-solid-state lithium-ion battery and evaluation method for all-solid-state lithium-ion battery - Google Patents

All-solid-state lithium-ion battery and evaluation method for all-solid-state lithium-ion battery Download PDF

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JP2023081688A
JP2023081688A JP2021195611A JP2021195611A JP2023081688A JP 2023081688 A JP2023081688 A JP 2023081688A JP 2021195611 A JP2021195611 A JP 2021195611A JP 2021195611 A JP2021195611 A JP 2021195611A JP 2023081688 A JP2023081688 A JP 2023081688A
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誠 木村
Makoto Kimura
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JX Nippon Mining and Metals Corp
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Abstract

To provide an all-solid-state lithium-ion battery and an evaluation method for an all-solid-state lithium-ion battery stably having good battery characteristics.SOLUTION: An all-solid-state lithium-ion battery includes a solid electrolyte layer composed of a sulfide-based solid electrolyte, a positive electrode layer, and a negative electrode layer, and the positive electrode layer is composed of a positive electrode mixture layer having a coating density of 10 to 25 mg/cm2.SELECTED DRAWING: Figure 1

Description

本発明は、全固体リチウムイオン電池及び全固体リチウムイオン電池の評価方法に関する。 TECHNICAL FIELD The present invention relates to an all-solid lithium ion battery and an evaluation method for an all-solid lithium ion battery.

近年におけるパソコン、ビデオカメラ、及び携帯電話等の情報関連機器や通信機器等の急速な普及に伴い、その電源として利用される電池の開発が重要視されている。該電池の中でも、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。また、車載用等の動力源やロードレベリング用といった大型用途におけるリチウム二次電池についても、高エネルギー密度、電池特性向上が求められている。 2. Description of the Related Art In recent years, with the rapid spread of information-related equipment and communication equipment such as personal computers, video cameras, and mobile phones, the development of batteries used as power sources for these devices has been emphasized. Among these batteries, lithium ion batteries are attracting attention because of their high energy density. High energy density and improved battery characteristics are also required for lithium secondary batteries used in large-scale applications such as power sources for vehicles and load leveling.

ただ、リチウムイオン電池の場合は、電解液は有機化合物が大半であり、たとえ難燃性の化合物を用いたとしても火災に至る危険性が全くなくなるとは言いきれない。こうした液系リチウムイオン電池の代替候補として、電解質を固体とした全固体リチウムイオン電池が近年注目を集めている。その中でも、固体電解質としてＬｉ2Ｓ－Ｐ2Ｓ5などの硫化物やそれにハロゲン化リチウムを添加した全固体リチウムイオン電池が主流となりつつある（非特許文献１）。 However, in the case of lithium-ion batteries, most of the electrolytes are organic compounds, and even if flame-retardant compounds are used, the risk of fire cannot be completely eliminated. In recent years, all-solid-state lithium-ion batteries with a solid electrolyte have been attracting attention as a candidate to replace such liquid-type lithium-ion batteries. Among them, all-solid-state lithium ion batteries in which sulfides such as Li 2 SP 2 S 5 and lithium halides are added as solid electrolytes are becoming mainstream (Non-Patent Document 1).

Ｊｏｕｒｎａｌ ｏｆ Ｔｈｅ Ｅｌｅｃｔｒｏｃｈｅｍｉｃａｌ Ｓｏｃｉｅｔｙ，１６４（２０１７）Ａ２４７４．Journal of The Electrochemical Society, 164 (2017) A2474.

硫化物系固体電解質を有する全固体リチウムイオン電池は、硫化物系固体電解質層と、正極層と、負極層とを含む。これら各構成要素についは、電池特性の改善を狙い、従来種々の組成が開発・研究されている。一方で、当該全固体リチウムイオン電池における各構成要素の組成以外にも、電池特性を向上させる要因が考えられ、このような観点からも未だ開発の余地がある。 An all-solid lithium ion battery having a sulfide-based solid electrolyte includes a sulfide-based solid electrolyte layer, a positive electrode layer, and a negative electrode layer. For each of these constituent elements, various compositions have been developed and researched in the past with the aim of improving battery characteristics. On the other hand, factors other than the composition of each component in the all-solid-state lithium ion battery can be considered to improve the battery characteristics, and there is still room for development from this point of view.

また、所定の硫化物系固体電解質を用いた全固体リチウムイオン電池を作製し、その電池特性を評価する際に、当該全固体リチウムイオン電池の最も優れた電池特性を引き出すような構成に設計することが望まれるが、この点についても未だ開発の余地がある。 In addition, when producing an all-solid lithium ion battery using a predetermined sulfide-based solid electrolyte and evaluating the battery characteristics, the configuration is designed to bring out the best battery characteristics of the all-solid lithium ion battery. However, there is still room for development in this respect as well.

本発明は、このような課題に鑑み、良好な電池特性を安定して有する全固体リチウムイオン電池及び全固体リチウムイオン電池の評価方法を提供することを目的とする。 In view of such problems, an object of the present invention is to provide an all-solid-state lithium ion battery that stably has good battery characteristics and a method for evaluating the all-solid-state lithium ion battery.

上記知見を基礎にして完成した本発明は一側面において、硫化物系固体電解質で構成された固体電解質層と、正極層と、負極層とを含み、前記正極層が、１０～２５ｍｇ／ｃｍ2の塗工密度の正極合材層で構成された、全固体リチウムイオン電池である。 In one aspect, the present invention completed based on the above findings includes a solid electrolyte layer made of a sulfide-based solid electrolyte, a positive electrode layer, and a negative electrode layer, and the positive electrode layer has a thickness of 10 to 25 mg/cm 2 . It is an all-solid-state lithium-ion battery composed of a positive electrode mixture layer with a coating density of .

本発明の全固体リチウムイオン電池は一実施形態において、前記正極合材層が、正極活物質、硫化物系固体電解質で構成された固体電解質及び導電助剤を含む。 In one embodiment of the all-solid-state lithium ion battery of the present invention, the positive electrode mixture layer contains a positive electrode active material, a solid electrolyte composed of a sulfide-based solid electrolyte, and a conductive aid.

本発明は別の一側面において、硫化物系固体電解質で構成された固体電解質層と、正極層と、負極層とを含む全固体リチウムイオン電池において、前記正極層が、１０～２５ｍｇ／ｃｍ2の塗工密度の正極合材層で構成されているか否かを判定することで、前記全固体リチウムイオン電池の電池特性を評価する、全固体リチウムイオン電池の評価方法である。 In another aspect of the present invention, an all-solid lithium ion battery including a solid electrolyte layer made of a sulfide-based solid electrolyte, a positive electrode layer, and a negative electrode layer, wherein the positive electrode layer has a thickness of 10 to 25 mg/cm 2 . A method for evaluating an all-solid-state lithium-ion battery, which evaluates the battery characteristics of the all-solid-state lithium-ion battery by determining whether or not it is composed of a positive electrode mixture layer having a coating density of .

本発明によれば、良好な電池特性を安定して有する全固体リチウムイオン電池及び全固体リチウムイオン電池の評価方法を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the evaluation method of the all-solid-state lithium ion battery which has favorable battery characteristics stably, and an all-solid-state lithium ion battery can be provided.

本発明の実施形態に係る全固体リチウムイオン電池の模式図である。1 is a schematic diagram of an all-solid-state lithium-ion battery according to an embodiment of the present invention; FIG.

次に本発明を実施するための形態を、図面を参照しながら詳細に説明する。本発明は以下の実施形態に限定されるものではなく、本発明の趣旨を逸脱しない範囲で、当業者の通常の知識に基づいて、適宜設計の変更、改良等が加えられることが理解されるべきである。 Embodiments for carrying out the present invention will now be described in detail with reference to the drawings. It is understood that the present invention is not limited to the following embodiments, and that design changes, improvements, etc., can be made as appropriate based on the ordinary knowledge of those skilled in the art without departing from the scope of the present invention. should.

＜全固体リチウムイオン電池＞
図１に、本発明の実施形態に係る全固体リチウムイオン電池の模式図を示す。全固体リチウムイオン電池は、硫化物系固体電解質で構成された固体電解質層と、正極層と、負極層とを含む。 <All-solid-state lithium-ion battery>
FIG. 1 shows a schematic diagram of an all solid state lithium ion battery according to an embodiment of the present invention. An all-solid lithium ion battery includes a solid electrolyte layer made of a sulfide-based solid electrolyte, a positive electrode layer, and a negative electrode layer.

（固体電解質層）
本発明の実施形態に係る全固体リチウムイオン電池の固体電解質層は、硫化物系固体電解質で構成されている。硫化物系固体電解質としては、特に限定されず、公知のものを用いることができるが、電池特性をより向上させる観点から、アルジロダイト（Ａｒｇｙｒｏｄｉｔｅ）型構造を有する硫化物系固体電解質であるのが好ましい。硫化物系固体電解質が、アルジロダイト型構造を有していることは、例えば、ＣｕＫα線を用いたＸ線回折測定により確認できる。アルジロダイト型構造は、２θ＝２４．６±１．０°及び２８．７±１．０°に強い回折ピークを有する。なお、アルジロダイト型構造の回折ピークは、例えば、２θ＝１５．０±１．０°、１７．３±１．０°、３０．０±１．０°、４２．８±１．５°又は４５．５±１．５°にも現れることがある。本実施形態の硫化物系固体電解質は、これらのピークを有していてもよい。また、アルジロダイト型構造を有する硫化物系固体電解質は、その一部に非晶質成分が含まれていてもよく、アルジロダイト型構造以外の構造や原料を含んでいてもよい。また、硫化物系固体電解質としては、Ｌｉ3ＰＳ4ガラス（Ｌｉ2Ｓ－ＰｓＳ5系ガラス）、Ｌｉ7Ｐ3Ｓ11ガラスセラミックスやＬＧＰＳ等であってもよい。 (Solid electrolyte layer)
The solid electrolyte layer of the all-solid lithium ion battery according to the embodiment of the present invention is composed of a sulfide-based solid electrolyte. The sulfide-based solid electrolyte is not particularly limited, and a known one can be used. From the viewpoint of further improving battery characteristics, a sulfide-based solid electrolyte having an argyrodite structure is preferable. . It can be confirmed by, for example, X-ray diffraction measurement using CuKα rays that the sulfide-based solid electrolyte has an aldirodite structure. The aldirodite-type structure has strong diffraction peaks at 2θ=24.6±1.0° and 28.7±1.0°. The diffraction peaks of the aldirodite structure are, for example, 2θ = 15.0 ± 1.0°, 17.3 ± 1.0°, 30.0 ± 1.0°, 42.8 ± 1.5° or It may also appear at 45.5±1.5°. The sulfide-based solid electrolyte of the present embodiment may have these peaks. Moreover, the sulfide-based solid electrolyte having an aldirodite-type structure may partially contain an amorphous component, and may contain structures and raw materials other than the aldirodite-type structure. The sulfide solid electrolyte may be Li 3 PS 4 glass (Li 2 S—PsS 5 glass), Li 7 P 3 S 11 glass ceramics, LGPS, or the like.

本発明の実施形態に係る硫化物系固体電解質の平均粒径は特に限定されないが、０．０１～１００μｍであってもよく、０．１～１００μｍであってもよく、０．１～５０μｍであってもよい。 The average particle size of the sulfide-based solid electrolyte according to the embodiment of the present invention is not particularly limited, but may be 0.01 to 100 μm, may be 0.1 to 100 μm, or may be 0.1 to 50 μm. There may be.

（正極層）
全固体リチウムイオン電池の正極層は、全固体リチウムイオン電池用正極活物質と、固体電解質層で用いた硫化物系固体電解質、または、固体電解質層で用いた硫化物系固体電解質と組成が異なる硫化物系固体電解質とを混合してなる正極合材の層である。 (positive electrode layer)
The positive electrode layer of the all-solid-state lithium ion battery has a different composition from the positive electrode active material for the all-solid-state lithium ion battery, the sulfide-based solid electrolyte used in the solid electrolyte layer, or the sulfide-based solid electrolyte used in the solid electrolyte layer. It is a layer of a positive electrode material mixed with a sulfide-based solid electrolyte.

正極合材は、さらに導電助剤を含んでもよい。当該導電助剤としては、炭素材料、金属材料、または、これらの混合物を用いることができる。導電助剤は、例えば、炭素、ニッケル、銅、アルミニウム、インジウム、銀、コバルト、マグネシウム、リチウム、クロム、金、ルテニウム、白金、ベリリウム、イリジウム、モリブデン、ニオブ、オスニウム、ロジウム、タングステン及び亜鉛からなる群より選択される少なくとも１種の元素を含んでもよい。導電助剤は、好ましくは、導電性が高い炭素単体、炭素、ニッケル、銅、銀、コバルト、マグネシウム、リチウム、ルテニウム、金、白金、ニオブ、オスニウム又はロジウムを含む金属単体、混合物又は化合物である。炭素材料としては、例えば、ケッチェンブラック、アセチレンブラック、デンカブラック、サーマルブラック、チャンネルブラック等のカーボンブラック、黒鉛、炭素繊維、活性炭等を用いることができる。 The positive electrode mixture may further contain a conductive aid. A carbon material, a metal material, or a mixture thereof can be used as the conductive aid. Conductive agents include, for example, carbon, nickel, copper, aluminum, indium, silver, cobalt, magnesium, lithium, chromium, gold, ruthenium, platinum, beryllium, iridium, molybdenum, niobium, osnium, rhodium, tungsten and zinc. It may contain at least one element selected from the group. The conductive aid is preferably a highly conductive carbon single substance, carbon, nickel, copper, silver, cobalt, magnesium, lithium, ruthenium, gold, platinum, niobium, osnium or rhodium containing metal simple substance, mixture or compound. . As the carbon material, for example, carbon black such as ketjen black, acetylene black, denka black, thermal black and channel black, graphite, carbon fiber, activated carbon and the like can be used.

本発明の実施形態に係る全固体リチウムイオン電池の正極層は、１０～２５ｍｇ／ｃｍ2の塗工密度の正極合材層で構成されている。正極合材層の塗工密度が１０ｍｇ／ｃｍ2以上であると、全固体リチウムイオン電池充電後抵抗の増大を抑制することができ、抵抗のばらつきが小さくなり、全固体リチウムイオン電池の電池特性の安定した測定が可能となる。正極合材層の塗工密度が２５ｍｇ／ｃｍ2以下であると、固体電解質内のリチウムイオンの移動が律速になることを抑制することができるため、放電容量やレート特性が良好となる。このように、全固体リチウムイオン電池の正極層は、１０～２５ｍｇ／ｃｍ2の塗工密度の正極合材層で構成されていることで、全固体リチウムイオン電池が、良好な放電容量、抵抗、レート特性、及び容量維持率を安定的に得ることができる。本発明の実施形態に係る全固体リチウムイオン電池の正極層は、１２～１８ｍｇ／ｃｍ2の塗工密度の正極合材層で構成されているのがより好ましい。 The positive electrode layer of the all-solid-state lithium ion battery according to the embodiment of the present invention is composed of a positive electrode mixture layer with a coating density of 10 to 25 mg/cm 2 . When the coating density of the positive electrode mixture layer is 10 mg/cm 2 or more, the increase in resistance after charging of the all-solid lithium ion battery can be suppressed, the variation in resistance is reduced, and the battery characteristics of the all-solid lithium ion battery are improved. can be stably measured. When the coating density of the positive electrode mixture layer is 25 mg/cm 2 or less, it is possible to suppress the movement of lithium ions in the solid electrolyte from becoming rate-determining, resulting in good discharge capacity and rate characteristics. In this way, the positive electrode layer of the all-solid-state lithium-ion battery is composed of the positive-electrode mixture layer with a coating density of 10 to 25 mg/cm 2 , so that the all-solid-state lithium ion battery has good discharge capacity and resistance. , rate characteristics, and capacity retention rate can be stably obtained. More preferably, the positive electrode layer of the all-solid-state lithium ion battery according to the embodiment of the present invention is composed of a positive electrode mixture layer with a coating density of 12 to 18 mg/cm 2 .

正極合材層の塗工密度は、正極合材層の質量をその塗工面積で除することで得られる。 The coating density of the positive electrode mixture layer is obtained by dividing the mass of the positive electrode mixture layer by its coating area.

全固体リチウムイオン電池の正極層の平均厚みについては特に限定されず、目的に応じて適宜設計することができる。全固体リチウムイオン電池の正極層の平均厚みは、例えば、１μｍ～１００μｍであってもよく、１μｍ～１０μｍであってもよい。 The average thickness of the positive electrode layer of the all-solid lithium ion battery is not particularly limited, and can be appropriately designed according to the purpose. The average thickness of the positive electrode layer of the all-solid lithium ion battery may be, for example, 1 μm to 100 μm, or may be 1 μm to 10 μm.

次に、全固体リチウムイオン電池の正極層の形成方法について説明する。正極層は正極合材層で構成するため、まず、正極合材を準備する。正極合材は、所望の組成を有するリチウムイオン電池用正極活物質、硫化物系固体電解質、導電助剤及びバインダーを所定の質量比で混合する。このとき、スラリーの固形分が５０～８０質量％となるように、溶媒を加えて正極合材スラリーとする。ここで、硫化物系固体電解質は、固体電解質層で用いた硫化物系固体電解質、または、固体電解質層で用いた硫化物系固体電解質と組成が異なる硫化物系固体電解質を用いることができる。溶媒は、アニソール、ヘプタン、テトラリン等の公知のものを用いることができる。
次に、正極合材スラリーを、後述の正極集電体の表面に塗工する。このとき、正極集電体の表面との間にギャップを３００～６００μｍ有するアプリケーターを用いて、５～５０ｍｍ／ｓの速さで当該アプリケーターを移動させて、正極集電体の表面に正極合材スラリーを塗工する。
次に、正極合材スラリーを表面に塗工した正極集電体を乾燥させて溶媒を除去することで、正極集電体の表面に正極合材層を形成する。 Next, a method for forming the positive electrode layer of the all-solid lithium ion battery will be described. Since the positive electrode layer is composed of the positive electrode mixture layer, first, the positive electrode mixture is prepared. The positive electrode mixture is prepared by mixing a positive electrode active material for lithium ion batteries having a desired composition, a sulfide-based solid electrolyte, a conductive aid and a binder at a predetermined mass ratio. At this time, a solvent is added so that the solid content of the slurry becomes 50 to 80% by mass to obtain the positive electrode mixture slurry. Here, the sulfide-based solid electrolyte may be the sulfide-based solid electrolyte used in the solid electrolyte layer, or a sulfide-based solid electrolyte having a different composition from the sulfide-based solid electrolyte used in the solid electrolyte layer. Known solvents such as anisole, heptane, and tetralin can be used as the solvent.
Next, the positive electrode mixture slurry is applied to the surface of a positive electrode current collector which will be described later. At this time, an applicator having a gap of 300 to 600 μm with respect to the surface of the positive electrode current collector is used, and the applicator is moved at a speed of 5 to 50 mm/s to apply the positive electrode mixture to the surface of the positive electrode current collector. Apply slurry.
Next, the positive electrode current collector having the surface coated with the positive electrode mixture slurry is dried to remove the solvent, thereby forming a positive electrode mixture layer on the surface of the positive electrode current collector.

（負極層）
全固体リチウムイオン電池の負極層は、公知の全固体リチウムイオン電池用負極活物質を層状に形成したものであってもよい。また、当該負極層は、公知の全固体リチウムイオン電池用負極活物質と、本発明の実施形態に係る硫化物系固体電解質または別の硫化物系固体電解質とを混合してなる負極合材を層状に形成したものであってもよい。 (Negative electrode layer)
The negative electrode layer of the all-solid-state lithium ion battery may be formed by layering a known negative-electrode active material for all-solid-state lithium ion batteries. In addition, the negative electrode layer is a negative electrode mixture obtained by mixing a known negative electrode active material for an all-solid lithium ion battery and the sulfide-based solid electrolyte according to the embodiment of the present invention or another sulfide-based solid electrolyte. It may be formed in layers.

負極層は、正極層と同様に、導電助剤を含んでもよい。当該導電助剤は、正極層において説明した材料と同じ材料を用いることができる。負極活物質としては、例えば、炭素材料、具体的には、人造黒鉛、黒鉛炭素繊維、樹脂焼成炭素、熱分解気相成長炭素、コークス、メソカーボンマイクロビーズ（ＭＣＭＢ）、フルフリルアルコール樹脂焼成炭素、ポリアセン、ピッチ系炭素繊維、気相成長炭素繊維、天然黒鉛及び難黒鉛化性炭素等、または、その混合物を用いることができる。また、負極材としては、例えば、金属リチウム、金属インジウム、金属アルミ、金属ケイ素等の金属自体や他の元素、化合物と組み合わせた合金を用いることができる。 The negative electrode layer, like the positive electrode layer, may contain a conductive aid. The same material as the material described for the positive electrode layer can be used for the conductive aid. Examples of negative electrode active materials include carbon materials such as artificial graphite, graphite carbon fiber, resin baked carbon, pyrolytic vapor growth carbon, coke, mesocarbon microbeads (MCMB), furfuryl alcohol resin baked carbon. , polyacene, pitch-based carbon fiber, vapor-grown carbon fiber, natural graphite, non-graphitizable carbon, etc., or a mixture thereof. As the negative electrode material, for example, metals such as metallic lithium, metallic indium, metallic aluminum, and metallic silicon, or alloys in which they are combined with other elements or compounds can be used.

全固体リチウムイオン電池の負極層の平均厚みについては特に限定されず、目的に応じて適宜選択することができる。全固体リチウムイオン電池の負極層の平均厚みは、例えば、１μｍ～１００μｍであってもよく、１μｍ～１０μｍであってもよい。 The average thickness of the negative electrode layer of the all-solid lithium ion battery is not particularly limited, and can be appropriately selected depending on the purpose. The average thickness of the negative electrode layer of the all-solid-state lithium ion battery may be, for example, 1 μm to 100 μm, or may be 1 μm to 10 μm.

全固体リチウムイオン電池の負極層の形成方法については特に限定されず、目的に応じて適宜選択することができる。全固体リチウムイオン電池の負極層の形成方法としては、例えば、負極活物質のターゲット材料を用いたスパッタリング、または、負極活物質を圧縮成形する方法、負極活物質を蒸着する方法などが挙げられる。 The method for forming the negative electrode layer of the all-solid-state lithium ion battery is not particularly limited, and can be appropriately selected depending on the purpose. Methods for forming the negative electrode layer of the all-solid-state lithium ion battery include, for example, sputtering using a target material for the negative electrode active material, compression molding of the negative electrode active material, and vapor deposition of the negative electrode active material.

本発明の実施形態に係る硫化物系固体電解質によって形成された全固体リチウムイオン電池の固体電解質層の平均厚みについては特に限定されず、目的に応じて適宜設計することができる。全固体リチウムイオン電池の固体電解質層の平均厚みは、例えば、１μｍ～５００μｍであってもよく、５０μｍ～１００μｍであってもよい。 The average thickness of the solid electrolyte layer of the all-solid-state lithium-ion battery formed from the sulfide-based solid electrolyte according to the embodiment of the present invention is not particularly limited, and can be appropriately designed according to the purpose. The average thickness of the solid electrolyte layer of the all-solid-state lithium ion battery may be, for example, 1 μm to 500 μm, or may be 50 μm to 100 μm.

全固体リチウムイオン電池の固体電解質層の形成方法については特に限定されず、目的に応じて適宜選択することができる。全固体リチウムイオン電池の固体電解質層の形成方法としては、例えば、固体電解質のターゲット材料を用いたスパッタリング、または、固体電解質を圧縮成形する方法などが挙げられる。 The method for forming the solid electrolyte layer of the all-solid lithium ion battery is not particularly limited, and can be appropriately selected depending on the purpose. Methods for forming the solid electrolyte layer of the all-solid-state lithium ion battery include, for example, sputtering using a solid electrolyte target material and compression molding of the solid electrolyte.

全固体リチウムイオン電池を構成するその他の部材については特に限定されず、目的に応じて適宜選択することができ、例えば、正極集電体、負極集電体、及び、電池ケースなどが挙げられる。全固体リチウムイオン電池の形態については、特に限定されないが、例えば、正極集電体／正極層／固体電解質／負極層／負極集電体の順に積層された構成を有してもよく、さらにこれらを電池ケースで囲んだ構成を有していてもよい。 Other members constituting the all-solid-state lithium ion battery are not particularly limited, and can be appropriately selected according to the purpose. Examples thereof include a positive electrode current collector, a negative electrode current collector, and a battery case. The form of the all-solid-state lithium-ion battery is not particularly limited. may be surrounded by a battery case.

正極集電体の大きさ及び構造については特に限定されず、目的に応じて適宜選択することができる。
正極集電体の材質としては、例えば、ダイス鋼、ステンレス鋼、アルミニウム、アルミニウム合金、チタン合金、銅、金、ニッケルなどが挙げられる。
正極集電体の形状としては、例えば、箔状、板状、メッシュ状などが挙げられる。
正極集電体の平均厚みとしては、例えば、１０μｍ～５００μｍであってもよく、５０μｍ～１００μｍであってもよい。 The size and structure of the positive electrode current collector are not particularly limited, and can be appropriately selected according to the purpose.
Examples of materials for the positive electrode current collector include die steel, stainless steel, aluminum, aluminum alloys, titanium alloys, copper, gold, and nickel.
Examples of the shape of the positive electrode current collector include a foil shape, a plate shape, and a mesh shape.
The average thickness of the positive electrode current collector may be, for example, 10 μm to 500 μm, or may be 50 μm to 100 μm.

負極集電体の大きさ及び構造については特に限定されず、目的に応じて適宜選択することができる。
負極集電体の材質としては、例えば、ダイス鋼、金、インジウム、ニッケル、銅、ステンレス鋼などが挙げられる。
負極集電体の形状としては、例えば、箔状、板状、メッシュ状などが挙げられる。
負極集電体の平均厚みとしては、例えば、１０μｍ～５００μｍであってもよく、５０μｍ～１００μｍであってもよい。 The size and structure of the negative electrode current collector are not particularly limited, and can be appropriately selected according to the purpose.
Examples of materials for the negative electrode current collector include die steel, gold, indium, nickel, copper, and stainless steel.
Examples of the shape of the negative electrode current collector include a foil shape, a plate shape, and a mesh shape.
The average thickness of the negative electrode current collector may be, for example, 10 μm to 500 μm, or may be 50 μm to 100 μm.

電池ケースについては特に限定されず、目的に応じて適宜選択することができ、例えば、従来の全固体電池で使用可能な公知のラミネートフィルムなどが挙げられる。ラミネートフィルムとしては、例えば、樹脂製のラミネートフィルム、樹脂製のラミネートフィルムに金属を蒸着させたフィルムなどが挙げられる。
電池の形状については特に限定されず、目的に応じて適宜選択することができ、例えば、円筒型、角型、ボタン型、コイン型、扁平型などが挙げられる。 The battery case is not particularly limited, and can be appropriately selected according to the purpose. Examples thereof include known laminate films that can be used in conventional all-solid-state batteries. Examples of laminate films include resin laminate films and films obtained by vapor-depositing metal on resin laminate films.
The shape of the battery is not particularly limited, and can be appropriately selected according to the purpose. Examples thereof include cylindrical, square, button, coin, and flat shapes.

＜全固体リチウムイオン電池の評価方法＞
本発明の実施形態に係る全固体リチウムイオン電池の評価方法は、全固体リチウムイオン電池を作製した後、正極層が１０～２５ｍｇ／ｃｍ2の塗工密度の正極合材層で構成されているか否かを判定し、当該判定結果に基づいて、全固体リチウムイオン電池の電池特性を評価する。正極層が１０～２５ｍｇ／ｃｍ2の塗工密度の正極合材層で構成されている場合は、電池特性が良好であると評価し、正極層が１０～２５ｍｇ／ｃｍ2の塗工密度の正極合材層で構成されていない場合は、電池特性が良好ではないと評価することができる。このような構成によれば、全固体リチウムイオン電池の電池特性の評価が簡便化するため、電池評価を効率的に実施することができる。なお、全固体リチウムイオン電池の電池特性としては放電容量、抵抗、レート特性、及び容量維持率が挙げられ、それぞれ確認のために、以下のように評価することができる。 <Method for evaluating all-solid-state lithium-ion battery>
A method for evaluating an all-solid-state lithium ion battery according to an embodiment of the present invention is to determine whether the positive electrode layer is composed of a positive electrode mixture layer with a coating density of 10 to 25 mg/cm 2 after manufacturing an all-solid-state lithium ion battery. or not, and the battery characteristics of the all-solid-state lithium-ion battery are evaluated based on the determination result. When the positive electrode layer is composed of a positive electrode mixture layer with a coating density of 10 to 25 mg/cm 2 , the battery characteristics are evaluated as good, and the positive electrode layer is evaluated to have a coating density of 10 to 25 mg/cm 2 . When the positive electrode mixture layer is not formed, the battery characteristics can be evaluated as not good. According to such a configuration, evaluation of the battery characteristics of the all-solid-state lithium ion battery is simplified, so battery evaluation can be performed efficiently. The battery characteristics of the all-solid-state lithium ion battery include discharge capacity, resistance, rate characteristics, and capacity retention rate, and each can be evaluated as follows for confirmation.

（放電容量の評価）
全固体リチウムイオン電池の放電容量は、初回充電後にインピーダンスを測定し抵抗を求め、続いて放電することで、３０℃初回放電容量として評価することができる。 (Evaluation of discharge capacity)
The discharge capacity of the all-solid-state lithium ion battery can be evaluated as the 30° C. initial discharge capacity by measuring the impedance after the initial charge to determine the resistance, and then discharging.

（抵抗の評価）
全固体リチウムイオン電池の抵抗は、交流インピーダンス測定を０．１Ｈｚ～１ＭＨｚまで行い、得られたＣｏｌｅ－Ｃｏｌｅプロットを解析することで初回充電後抵抗として評価することができる。 (Resistance evaluation)
The resistance of an all-solid-state lithium ion battery can be evaluated as the resistance after initial charge by performing AC impedance measurement from 0.1 Hz to 1 MHz and analyzing the obtained Cole-Cole plot.

（レート特性の評価）
全固体リチウムイオン電池のレート特性（％）は、放電レート０．０５Ｃで得られた初期容量（３０℃、充電上限電圧：４．５５Ｖ、放電下限電圧：３．７Ｖ）を測定し、次に放電レート０．２Ｃで得られた高率容量（３０℃、充電上限電圧：４．５５Ｖ、放電下限電圧：３．７Ｖ）を測定し、（高率容量）／（初期容量）の比を百分率として評価することができる。 (Evaluation of rate characteristics)
The rate characteristics (%) of the all-solid-state lithium ion battery are obtained by measuring the initial capacity obtained at a discharge rate of 0.05 C (30 ° C., upper limit charge voltage: 4.55 V, lower limit discharge voltage: 3.7 V), then The high rate capacity obtained at a discharge rate of 0.2 C (30 ° C., upper limit charge voltage: 4.55 V, lower limit discharge voltage: 3.7 V) was measured, and the ratio of (high rate capacity) / (initial capacity) was expressed as a percentage. can be evaluated as

（容量維持率の評価）
全固体リチウムイオン電池の容量維持率は、３０℃で０．２Ｃの放電電流で得られた初期放電容量で、１０サイクル後の放電容量を除することで、１０サイクル容量維持率として評価することができる。 (Evaluation of capacity retention rate)
The capacity retention rate of the all-solid-state lithium ion battery is the initial discharge capacity obtained at a discharge current of 0.2 C at 30 ° C., and the discharge capacity after 10 cycles is divided to evaluate the 10 cycle capacity retention rate. can be done.

以下、本発明及びその利点をより良く理解するための実施例を提供するが、本発明はこれらの実施例に限られるものではない。 The following examples are provided for a better understanding of the invention and its advantages, but the invention is not limited to these examples.

（実施例１）
正極活物質（Ｌｉ（Ｎｉ0.82Ｃｏ0.15Ｍｎ0.03）Ｏ2）と硫化物系固体電解質（７５Ｌｉ2Ｓ－２５Ｐ2Ｓ5）とアセチレンブラックとバインダーとをこの順で６０：３５：５：１．５の質量比で混合し、スラリーの固形分が６５質量％となるようにアニソールを溶媒として加え、マゼルスターで４００秒混合して正極合材スラリーとし、これを正極集電体である厚さ０．０３ｍｍのアルミニウム箔の表面に塗工した。このとき、ギャップが３００μｍのアプリケーターを使用して１５ｍｍ／ｓの移動速度でアプリケーターを移動させることで当該正極合材スラリーを正極集電体表面に塗工した。
次に、正極合材スラリーを表面に塗工した正極集電体を室温で１週間放置することで乾燥させて溶媒を除去することで、正極集電体の表面に正極合材層を形成した。ここで、正極合材層の質量（９．３ｍｇ）をその塗工面積（０．７８５ｃｍ2）で除すると、正極合材層の塗工密度は１１．８ｍｇ／ｃｍ2であった。なお、上述のように正極合材スラリーを室温で放置することで乾燥させたが、より早く乾燥させるために、乾燥機を用いて乾燥させてもよい。
次に、正極合材層の作製の際に用いた硫化物系固体電解質と同組成の硫化物系固体電解質の上に上述の正極合材層を載せて、３３３ＭＰａでプレスして、固体電解質層／正極合材層／正極集電体の積層体を作製した。
次に、固体電解質層の負極側に、金属Ｉｎを３７ＭＰａで圧着して負極層とした。このように作製した積層体をＳＵＳ３０４製の電池試験セルに入れて拘束圧をかけて全固体二次電池とした。また、当該拘束圧をかけて全固体二次電池としたものについて、大気を遮断するために密閉容器に入れた。 (Example 1)
A positive electrode active material (Li(Ni 0.82 Co 0.15 Mn 0.03 )O 2 ), a sulfide-based solid electrolyte (75Li 2 S-25P 2 S 5 ), acetylene black and a binder were mixed in this order at 60:35:5:1. Mix at a mass ratio of 5, add anisole as a solvent so that the solid content of the slurry is 65% by mass, mix for 400 seconds with Mazerustar to make a positive electrode mixture slurry, and this is a positive electrode current collector with a thickness of 0 It was coated on the surface of a .03 mm aluminum foil. At this time, an applicator with a gap of 300 μm was used and moved at a moving speed of 15 mm/s to coat the positive electrode mixture slurry on the surface of the positive electrode current collector.
Next, the positive electrode current collector having the surface coated with the positive electrode mixture slurry was left at room temperature for one week to dry and remove the solvent, thereby forming a positive electrode mixture layer on the surface of the positive electrode current collector. . Here, when the mass (9.3 mg) of the positive electrode mixture layer was divided by the coating area (0.785 cm 2 ), the coating density of the positive electrode mixture layer was 11.8 mg/cm 2 . As described above, the positive electrode mixture slurry was dried by leaving it at room temperature, but in order to dry it more quickly, it may be dried using a dryer.
Next, the above positive electrode mixture layer is placed on a sulfide-based solid electrolyte having the same composition as the sulfide-based solid electrolyte used in producing the positive electrode mixture layer, and pressed at 333 MPa to form a solid electrolyte layer. A laminate of /positive electrode mixture layer/positive electrode current collector was produced.
Next, metal In was pressure-bonded to the negative electrode side of the solid electrolyte layer at 37 MPa to form a negative electrode layer. The laminate thus produced was placed in a battery test cell made of SUS304, and a confining pressure was applied to obtain an all-solid secondary battery. In addition, the all-solid secondary battery obtained by applying the confining pressure was placed in a sealed container to shut off the atmosphere.

（実施例２）
ギャップが４００μｍのアプリケーターを使用して正極合材スラリーを正極集電体表面に塗工することで、正極合材層の質量を１３．７ｍｇ、塗工密度を１７．５ｍｇ／ｃｍ2とした以外は、実施例１と同様にして全固体リチウムイオン電池を作製した。 (Example 2)
The positive electrode mixture slurry was applied to the surface of the positive electrode current collector using an applicator with a gap of 400 μm, except that the mass of the positive electrode mixture layer was 13.7 mg and the coating density was 17.5 mg / cm 2 prepared an all-solid-state lithium ion battery in the same manner as in Example 1.

（実施例３）
ギャップが５００μｍのアプリケーターを使用して正極合材スラリーを正極集電体表面に塗工することで、正極合材層の質量を１７．８ｍｇ、塗工密度を２２．６ｍｇ／ｃｍ2とした以外は、実施例１と同様にして全固体リチウムイオン電池を作製した。 (Example 3)
By applying the positive electrode mixture slurry to the surface of the positive electrode current collector using an applicator with a gap of 500 μm, except that the mass of the positive electrode mixture layer was 17.8 mg and the coating density was 22.6 mg / cm 2 prepared an all-solid-state lithium ion battery in the same manner as in Example 1.

（実施例４）
ギャップが６００μｍのアプリケーターを使用して正極合材スラリーを正極集電体表面に塗工することで、正極合材層の質量を１７．２ｍｇ、塗工密度を２２．０ｍｇ／ｃｍ2とした以外は、実施例１と同様にして全固体リチウムイオン電池を作製した。 (Example 4)
By applying the positive electrode mixture slurry to the surface of the positive electrode current collector using an applicator with a gap of 600 μm, except that the mass of the positive electrode mixture layer was 17.2 mg and the coating density was 22.0 mg / cm 2 prepared an all-solid-state lithium ion battery in the same manner as in Example 1.

（比較例１）
ギャップが１００μｍのアプリケーターを使用して正極合材スラリーを正極集電体表面に塗工することで、正極合材層の質量を２．７ｍｇ、塗工密度を３．４ｍｇ／ｃｍ2とした以外は、実施例１と同様にして全固体リチウムイオン電池を作製した。 (Comparative example 1)
By applying the positive electrode mixture slurry to the surface of the positive electrode current collector using an applicator with a gap of 100 μm, the mass of the positive electrode mixture layer was 2.7 mg, and the coating density was 3.4 mg / cm 2 . prepared an all-solid-state lithium ion battery in the same manner as in Example 1.

（比較例２）
ギャップが２００μｍのアプリケーターを使用して正極合材スラリーを正極集電体表面に塗工することで、正極合材層の質量を６．３ｍｇ、塗工密度を８．０ｍｇ／ｃｍ2とした以外は、実施例１と同様にして全固体リチウムイオン電池を作製した。 (Comparative example 2)
The positive electrode mixture slurry was applied to the surface of the positive electrode current collector using an applicator with a gap of 200 μm, except that the mass of the positive electrode mixture layer was 6.3 mg and the coating density was 8.0 mg / cm 2 prepared an all-solid-state lithium ion battery in the same manner as in Example 1.

（比較例３）
ギャップが７００μｍのアプリケーターを使用して正極合材スラリーを正極集電体表面に塗工することで、正極合材層の質量を２９．４ｍｇ、塗工密度を３７．５ｍｇ／ｃｍ2とした以外は、実施例１と同様にして全固体リチウムイオン電池を作製した。 (Comparative Example 3)
The positive electrode mixture slurry was applied to the surface of the positive electrode current collector using an applicator with a gap of 700 μm, except that the mass of the positive electrode mixture layer was 29.4 mg and the coating density was 37.5 mg / cm 2 prepared an all-solid-state lithium ion battery in the same manner as in Example 1.

（比較例４）
ギャップが８００μｍのアプリケーターを使用して正極合材スラリーを正極集電体表面に塗工することで、正極合材層の質量を２５．３ｍｇ、塗工密度を３２．２ｍｇ／ｃｍ2とした以外は、実施例１と同様にして全固体リチウムイオン電池を作製した。 (Comparative Example 4)
The positive electrode mixture slurry was applied to the surface of the positive electrode current collector using an applicator with a gap of 800 μm, except that the mass of the positive electrode mixture layer was 25.3 mg and the coating density was 32.2 mg / cm 2 . prepared an all-solid-state lithium ion battery in the same manner as in Example 1.

（比較例５）
ギャップが１０００μｍのアプリケーターを使用して正極合材スラリーを正極集電体表面に塗工することで、正極合材層の質量を３８．３ｍｇ、塗工密度を４８．７ｍｇ／ｃｍ2とした以外は、実施例１と同様にして全固体リチウムイオン電池を作製した。 (Comparative Example 5)
The positive electrode mixture slurry was applied to the surface of the positive electrode current collector using an applicator with a gap of 1000 μm, except that the mass of the positive electrode mixture layer was 38.3 mg and the coating density was 48.7 mg / cm 2 . prepared an all-solid-state lithium ion battery in the same manner as in Example 1.

（放電容量の評価）
上述のようにして作製したサンプル（全固体リチウムイオン電池）について、初回充電後にインピーダンスを測定し抵抗を求めた。次に、放電して３０℃初回放電容量を得た。 (Evaluation of discharge capacity)
For the sample (all-solid lithium ion battery) produced as described above, the impedance was measured after the initial charge to obtain the resistance. Next, it was discharged to obtain a 30° C. initial discharge capacity.

（抵抗の評価）
上述のようにして作製したサンプル（全固体リチウムイオン電池）について、交流インピーダンス測定を０．１Ｈｚ～１ＭＨｚまで行い、得られたＣｏｌｅ－Ｃｏｌｅプロットを解析して、初回充電後抵抗を求めた。当該初回充電後抵抗の大きさにより、全固体リチウムイオン電池充電後抵抗の増大を抑制することができているかを評価した。 (Resistance evaluation)
For the sample (all-solid-state lithium ion battery) produced as described above, AC impedance measurement was performed from 0.1 Hz to 1 MHz, and the obtained Cole-Cole plot was analyzed to obtain the resistance after the first charge. Based on the magnitude of the resistance after the initial charge, it was evaluated whether an increase in the resistance after the charge of the all-solid-state lithium ion battery could be suppressed.

（レート特性の評価）
上述のようにして作製したサンプル（全固体リチウムイオン電池）について、放電レート０．０５Ｃで得られた初期容量（３０℃、充電上限電圧：４．５５Ｖ、放電下限電圧：３．７Ｖ）を測定し、次に放電レート０．２Ｃで得られた高率容量（３０℃、充電上限電圧：４．５５Ｖ、放電下限電圧：３．７Ｖ）を測定し、（高率容量）／（初期容量）の比を百分率としてレート特性（％）とした。 (Evaluation of rate characteristics)
For the sample (all-solid-state lithium-ion battery) prepared as described above, the initial capacity obtained at a discharge rate of 0.05 C (30 ° C., upper limit charge voltage: 4.55 V, lower limit discharge voltage: 3.7 V) was measured. Then, the high rate capacity obtained at a discharge rate of 0.2 C (30 ° C., upper limit charge voltage: 4.55 V, lower limit discharge voltage: 3.7 V) was measured, and (high rate capacity) / (initial capacity) The rate characteristic (%) was defined as a percentage.

（容量維持率の評価）
上述のようにして作製したサンプル（全固体リチウムイオン電池）について、３０℃で０．２Ｃの放電電流で得られた初期放電容量で、１０サイクル後の放電容量を除することで、１０サイクル容量維持率を測定した。
試験結果を表１に示す。なお、表１の「正極合材層量」及び「塗工密度」の数値は、いずれも小数点以下第２位を四捨五入した数値を示している。 (Evaluation of capacity retention rate)
For the sample (all-solid-state lithium ion battery) prepared as described above, the discharge capacity after 10 cycles was divided by the initial discharge capacity obtained at 30 ° C. and a discharge current of 0.2 C. Retention rate was measured.
Table 1 shows the test results. The numerical values of "amount of positive electrode mixture layer" and "coating density" in Table 1 are both rounded to the second decimal place.

Figure 2023081688000002
Figure 2023081688000002

（評価結果）
実施例１～４は、いずれも正極層が、１０～２５ｍｇ／ｃｍ2の塗工密度の正極合材層で構成されていたため、初回放電容量、初回充電後抵抗、レート特性及び１０サイクル容量維持率のいずれにおいても良好な特性を示した。
また、実施例１～４では、正極合材層の正極活物質としてＬｉ（Ｎｉ0.82Ｃｏ0.15Ｍｎ0.03）Ｏ2の組成を有する正極活物質を、また、正極合材層の硫化物系固体電解質として７５Ｌｉ2Ｓ－２５Ｐ2Ｓ5の組成を有する硫化物系固体電解質を使用したが、正極合材層の正極活物質及び硫化物系固体電解質については、それらの組成によらず、正極合材層の塗工密度を１０～２５ｍｇ／ｃｍ2に制御することによって初回放電容量、初回充電後抵抗、レート特性及び１０サイクル容量維持率という電池特性を向上させることができる。これは、正極合材層の塗工密度が１０ｍｇ／ｃｍ2以上であると、その組成によらず、全固体リチウムイオン電池充電後抵抗の増大を抑制することができ、抵抗のばらつきが小さくなり、全固体リチウムイオン電池の電池特性の安定した測定が可能となるためである。また、正極合材層の塗工密度が２５ｍｇ／ｃｍ2以下であると、その組成によらず、固体電解質内のリチウムイオンの移動が律速になることを抑制することができ、放電容量やレート特性が良好となるためである。
比較例１及び２は、正極合材層の塗工密度が１０ｍｇ／ｃｍ2未満であるため、初回充電後抵抗が不良であった。
比較例３～５は、正極合材層の塗工密度が２５ｍｇ／ｃｍ2を超えているため、初回放電容量、レート特性及び１０サイクル容量維持率の少なくともいずれかが不良であった。 (Evaluation results)
In Examples 1 to 4, the positive electrode layer was composed of a positive electrode mixture layer with a coating density of 10 to 25 mg/cm 2 , so the initial discharge capacity, the resistance after the first charge, the rate characteristics, and the 10-cycle capacity retention were improved. Good characteristics were shown in all the ratios.
In Examples 1 to 4, a positive electrode active material having a composition of Li(Ni 0.82 Co 0.15 Mn 0.03 )O 2 was used as the positive electrode active material for the positive electrode mixture layer, and a sulfide-based solid electrolyte was used for the positive electrode mixture layer. A sulfide-based solid electrolyte having a composition of 75Li 2 S-25P 2 S 5 was used as the material for the positive electrode mixture layer. By controlling the coating density of the layer to 10 to 25 mg/cm 2 , battery characteristics such as initial discharge capacity, resistance after initial charge, rate characteristics, and 10-cycle capacity retention rate can be improved. This is because when the coating density of the positive electrode mixture layer is 10 mg/cm 2 or more, the increase in resistance after charging of the all-solid-state lithium ion battery can be suppressed, regardless of the composition, and the variation in resistance becomes small. This is because it is possible to stably measure the battery characteristics of all-solid-state lithium-ion batteries. In addition, when the coating density of the positive electrode mixture layer is 25 mg/cm 2 or less, regardless of the composition, it is possible to suppress the rate-limiting movement of lithium ions in the solid electrolyte, thereby improving the discharge capacity and rate. This is because the characteristics are improved.
In Comparative Examples 1 and 2, since the coating density of the positive electrode mixture layer was less than 10 mg/cm 2 , the resistance after the initial charge was poor.
In Comparative Examples 3 to 5, since the coating density of the positive electrode mixture layer exceeded 25 mg/cm 2 , at least one of the initial discharge capacity, rate characteristics, and 10-cycle capacity retention rate was poor.

Claims (3)

硫化物系固体電解質で構成された固体電解質層と、正極層と、負極層とを含み、
前記正極層が、１０～２５ｍｇ／ｃｍ2の塗工密度の正極合材層で構成された、全固体リチウムイオン電池。 including a solid electrolyte layer made of a sulfide-based solid electrolyte, a positive electrode layer, and a negative electrode layer,
An all-solid lithium ion battery, wherein the positive electrode layer is composed of a positive electrode mixture layer with a coating density of 10 to 25 mg/cm 2 . 前記正極合材層が、正極活物質、硫化物系固体電解質で構成された固体電解質及び導電助剤を含む、請求項１に記載の全固体リチウムイオン電池。 2. The all-solid lithium ion battery according to claim 1, wherein the positive electrode mixture layer includes a positive electrode active material, a solid electrolyte composed of a sulfide-based solid electrolyte, and a conductive aid. 硫化物系固体電解質で構成された固体電解質層と、正極層と、負極層とを含む全固体リチウムイオン電池において、
前記正極層が、１０～２５ｍｇ／ｃｍ2の塗工密度の正極合材層で構成されているか否かを判定することで、前記全固体リチウムイオン電池の電池特性を評価する、全固体リチウムイオン電池の評価方法。 In an all-solid lithium ion battery including a solid electrolyte layer made of a sulfide-based solid electrolyte, a positive electrode layer, and a negative electrode layer,
The battery characteristics of the all-solid-state lithium-ion battery are evaluated by determining whether the positive-electrode layer is composed of a positive electrode mixture layer with a coating density of 10 to 25 mg/cm 2. All-solid-state lithium ion Battery evaluation method.
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