JP2023548097A - 全固体リチウム二次電池およびその製造方法 - Google Patents
全固体リチウム二次電池およびその製造方法 Download PDFInfo
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- JP2023548097A JP2023548097A JP2023525602A JP2023525602A JP2023548097A JP 2023548097 A JP2023548097 A JP 2023548097A JP 2023525602 A JP2023525602 A JP 2023525602A JP 2023525602 A JP2023525602 A JP 2023525602A JP 2023548097 A JP2023548097 A JP 2023548097A
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- Prior art keywords
- solid
- negative electrode
- secondary battery
- active material
- lithium secondary
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Links
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Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
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Abstract
Description
本発明の一実施形態による全固体リチウム二次電池は、正極活物質層と、負極活物質層と、前記正極活物質層と前記負極活物質層との間に配置された固体電解質層とを含み、前記負極活物質層は、炭素構造体および銀ナノ粒子を含み、前記炭素構造体は、少なくとも一つ以上の中空型粒子を含み、前記中空型粒子は、中空(Hollow)および前記中空を囲む炭素質のシェルを含むことができる。
前記全固体リチウム二次電池は、負極活物質層を含むことができる。具体的には、前記全固体リチウム二次電池は、負極を含むことができ、前記負極は、負極集電体および負極活物質層を含むことができる。
前記炭素構造体は、正極活物質層から伝達されたリチウムイオンが負極集電体上で容易に析出および貯蔵されるようにする移動経路の役割を果たすことができる。
前記銀ナノ粒子は、リチウム親和性(Lithiophilic)の特性があることから、リチウムイオンと容易に合金をなすことができる。これにより、銀ナノ粒子は、正極活物質層から伝達されたリチウムイオンと合金を形成して、負極活物質層内へのリチウムイオンの吸蔵および拡散を促進することができる。
前記負極活物質層は、負極バインダーをさらに含むことができる。前記負極バインダーは、ポリビニリデンフルオライド(PVdF)、ポリビニルアルコール(PVA)、カルボキシメチルセルロース(CMC)、デンプン、ヒドロキシプロピルセルロース、ポリビニルピロリドン、ポリテトラフルオロエチレン(PTFE)、ポリテトラフルオロエチレン、ポリエチレン、ポリプロピレン、エチレン-プロピレン-ジエンモノマー(EPDM)、スチレン-ブタジエンゴム(SBR)、およびフッ素ゴムからなる群から選択される少なくとも1種を含むことができる。
前記全固体リチウム二次電池は、正極活物質層を含むことができる。具体的には、前記全固体リチウム二次電池は、正極を含むことができ、前記正極は、正極活物質層を含むか、前記正極活物質層からなることができる。
前記全固体リチウム二次電池は、固体電解質層を含むことができる。
本発明の他の実施形態による全固体リチウム二次電池の製造方法は、銀イオンと炭素構造体の混合物に対して、銀イオンを還元して、前記炭素構造体および前記炭素構造体上に配置された銀ナノ粒子を含む乾燥混合粉末を形成する第1ステップと、前記乾燥混合粉末を含む負極スラリーを介して負極集電体上に負極活物質層を形成する第2ステップとを含むことができる。ここで、前記全固体リチウム二次電池は、上述の実施形態の全固体リチウム二次電池と同一であることができる。また、前記負極活物質層は、上述の実施形態の負極活物質層と同一であることができる。
第1ステップにおいて、前記炭素構造体および前記炭素構造体上に配置された銀ナノ粒子を含む乾燥混合粉末が形成される。前記乾燥混合粉末は、パウダー状の銀ナノ粒子とパウダー状の炭素構造体を混合して製造することができる。これとは異なり、前記乾燥混合粉末は、銀イオン溶液に炭素構造体を混合した後、銀ナノイオンを還元して製造されることもできる。前記銀ナノ粒子を還元する方法は、化学的還元法、電気化学的還元法、光化学的還元法、レーザ還元法、超音波還元法、スパッタリングなどの様々な方法があるが、好ましくは、ポリオールプロセス(Polyol Process)を用いた化学的還元法やマイクロ波を用いたマイクロ波支援ポリオール(microwave-assisted Polyol)方法が使用されることができる。
前記第2ステップでは、前記乾燥混合粉末を含む負極スラリーにより負極集電体上に負極活物質層が形成されることができる。前記負極スラリーは、乾燥混合粉末および負極スラーリ用溶媒を含むことができる。
製造例1:炭素構造体の形成
アセチレンブラックを、Ar雰囲気で、2800℃で6時間熱処理し、中空型粒子が互いに連結されて二次粒子構造を有する製造例1の炭素構造体を製造した。前記炭素構造体は、複数の中空型粒子が互いに結合して二次粒子構造を示しており、前記中空型粒子は、中空および前記中空を囲む炭素質のシェルを含んでいた(図5および図6参照)。
製造例1で使用されたアセチレンブラックより粒径が大きいアセチレンブラックを、Ar雰囲気で、2800℃で6時間熱処理し、中空型粒子が互いに連結されて二次粒子構造を有する製造例2の炭素構造体を製造した。前記炭素構造体は、複数の中空型粒子が互いに結合して二次粒子構造を示しており、前記中空型粒子は、中空および前記中空を囲む炭素質のシェルを含んでいた(図7および図8参照)。
エチレングリコール溶媒に炭素構造体とAgNO3、ポリビニルピロリドンを混合し、NaOHペレットを介してpHが8~14の範囲を満たすように調節した後、24時間撹拌して混合溶液を製造した。超音波装置によりArバブリング(bubbling)を行った混合溶液に対してマイクロ波反応装置(Microwave Reactor)(LG電子社製)のContinuous Wave Mode(2.45GHz、500W)を用いて、10秒間、20秒間、30秒間、1分間、2分間、5分間の時間単位で処理して加熱と冷却を繰り返した。これにより、銀イオンが還元し、炭素構造体上に銀ナノ粒子が配置された。次に、アセトン溶液によりフィルタリングおよび洗浄を行って、100℃の真空オーブンで24時間乾燥し、炭素構造体および炭素構造体上に配置された銀ナノ粒子を含む乾燥混合粉末を取得した(図9参照)。前記銀ナノ粒子の担持量は10重量%であり、銀ナノ粒子の平均粒径は1nmであった。
正極活物質としてLi[Ni0.82Co0.14Mn0.04]O2、固体電解質としてLi6PS6Cl、導電材としてカーボンナノファイバー(VGCF、Showa Denko社製)、およびバインダーとしてポリテトラフルオロエチレンを77:20:1:2の重量比で順に容器に投入した。それぞれの構成を投入する度に、Lab Blenderを使用して、10,000RPMで30秒ずつ10回繰り返してミキシング(mixing)し、正極混合物を製造した。前記混合物に対して二軸混練機(Twin Screw Kneader)(LG電子社製)を使用して、100℃で100rpmでせん断力を印加して高せん断ミキシングを5分間行って正極混合物を製造した。前記正極混合物を100℃で二本ロールミル(Two roll mill)装置(Inoue社製)を使用して、厚さ200μmの自立型フィルム(Free-standing Film)を製造した。次に、前記フィルムをプライマーがコーティングされたアルミニウム集電体(厚さ:20μm)の一面上に位置させ、120℃に維持されるラミネーションロールを使用して、フィルムを集電体に接合させて正極を製造した。
Li6PS6Clの固体電解質とニトリルブタジエンゴム(NBR)を溶媒であるキシレンに混合した後、Thinky Mixerで、2,000RPMで、1分ずつ10回ジルコニアボールとともにミキシングして固体電解質スラリーを製造した。これを離型紙のPETフィルムの上にコーティングし、45℃の真空オーブンで6時間乾燥させて固体電解質層を準備した。ここで、Li6PS6Clの固体電解質とニトリルブタジエンゴム(NBR)の重量比は95:5重量%であり、製造された固体電解質層の厚さは100μmであった。
炭素構造体、AgNO3、ポリビニリデンピロリドンの重量比、pH値、マイクロ波反応装置での反応条件などを制御して、銀ナノ粒子の含量と平均粒径を表1のように調節した以外は、実施例1と同じ方法で全固体リチウム二次電池を製造した。
(1)負極の製造
前記実施例1で炭素構造体の代わりに、カーボンブラック(PRINTEX、Orion Engineered Carbons社製)を使用し、カーボンブラック、AgNO3、ポリビニリデンピロリドンの重量比、pH値、マイクロ波反応装置での反応条件などを制御して、銀ナノ粒子の含量と平均粒径を表1のように調節した以外は、実施例1と同じ方法で全固体リチウム二次電池を製造した。
(1)負極および正極の製造
実施例1と同じ方法で負極および正極を製造した。
次に、前記製造された負極および正極とその間に厚さ15μmのポリエチレン系セパレータを配置してモノセルを製造した後、前記モノセルに電解液(エチレンカーボネート(EC)/エチルメチルカーボネート(EMC)=1/2(体積比)、リチウムヘキサフルオロホスフェート(LiPF61モル))を注入し、リチウム二次電池を製造した。
炭素構造体、AgNO3、ポリビニリデンピロリドンの重量比、pH値、マイクロ波反応装置での反応条件などを制御して、銀ナノ粒子の含量と平均粒径を表1のように調節した以外は、比較例3と同じ方法でリチウム二次電池を製造した。
実施例および比較例の電池それぞれを加圧治具に装着し、四角の角部に位置したボルト/ナットを1N・mの同一圧力で締結してモノセルを準備した。60℃で下記の条件で1回充電および1回放電させた時に、1回目の充電容量に対する1回目の放電容量の割合で初期充電/放電効率を評価した(表3参照)。
放電条件:3.0Vまで0.1C CC放電
実施例および比較例の電池それぞれを、60℃で、下記の条件で充放電を行った後、50サイクル(cycle)での容量維持率(%)を評価した。1回目の充電/放電時の放電容量を100%として基準とした。
放電条件:3.0Vまで0.33C CC放電
Claims (15)
- 正極活物質層、負極活物質層、および前記正極活物質層と前記負極活物質層との間に配置された固体電解質層を含み、
前記負極活物質層は、炭素構造体および銀ナノ粒子を含み、
前記炭素構造体は、少なくとも一つ以上の中空型粒子を含み、
前記中空型粒子は、中空および前記中空を囲む炭素質のシェルを含む、全固体リチウム二次電池。 - 前記銀ナノ粒子は、前記炭素構造体の表面上に配置されている、請求項1に記載の全固体リチウム二次電池。
- 前記シェルの厚さは、1nm~15nmである、請求項1に記載の全固体リチウム二次電池。
- 前記炭素構造体の比表面積は、10m2/g~300m2/gである、請求項1に記載の全固体リチウム二次電池。
- 前記中空型粒子の平均粒径は、5nm~100nmである、請求項1に記載の全固体リチウム二次電池。
- 前記炭素構造体に対してラマンスペクトル測定を行う際、
前記炭素構造体のID/IGは、0.1~1.5である、請求項1に記載の全固体リチウム二次電池。 - 前記炭素構造体は、複数の中空型粒子が互いに結合した二次粒子形態を有する、請求項1に記載の全固体リチウム二次電池。
- 前記炭素構造体は、前記負極活物質層内に50重量%~98重量%含まれる、請求項1に記載の全固体リチウム二次電池。
- 前記銀ナノ粒子の平均粒径は、1nm~100nmである、請求項1に記載の全固体リチウム二次電池。
- 前記負極活物質層において、
前記銀ナノ粒子は、前記炭素構造体および前記銀ナノ粒子の全重量に対して1重量%~40重量%含まれる、請求項1に記載の全固体リチウム二次電池。 - 前記炭素構造体と前記銀ナノ粒子の重量比は、99:1~60:40である、請求項1に記載の全固体リチウム二次電池。
- 前記負極活物質層は、負極バインダーをさらに含む、請求項1に記載の全固体リチウム二次電池。
- 前記負極活物質層の厚さは、1μm~100μmである、請求項1に記載の全固体リチウム二次電池。
- 負極集電体をさらに含み、
充電状態で、前記負極活物質層と前記負極集電体との間に位置した金属層をさらに含み、
前記金属層は、リチウムを含む、請求項1に記載の全固体リチウム二次電池。 - 銀イオンと炭素構造体の混合物に対して、銀イオンを還元して、前記炭素構造体および前記炭素構造体上に配置された銀ナノ粒子を含む乾燥混合粉末を形成する第1ステップと、
前記乾燥混合粉末を含む負極混合物を介して負極集電体上に負極活物質層を形成する第2ステップとを含む、請求項1に記載の全固体リチウム二次電池の製造方法。
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