JP2023016671A - 全固体電池用正極活物質、その製造方法、およびこれを含む全固体電池 - Google Patents
全固体電池用正極活物質、その製造方法、およびこれを含む全固体電池 Download PDFInfo
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- JP2023016671A JP2023016671A JP2021205991A JP2021205991A JP2023016671A JP 2023016671 A JP2023016671 A JP 2023016671A JP 2021205991 A JP2021205991 A JP 2021205991A JP 2021205991 A JP2021205991 A JP 2021205991A JP 2023016671 A JP2023016671 A JP 2023016671A
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- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
- C01B35/10—Compounds containing boron and oxygen
- C01B35/1027—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
- C01B35/10—Compounds containing boron and oxygen
- C01B35/12—Borates
- C01B35/121—Borates of alkali metal
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
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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
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- H01M10/052—Li-accumulators
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
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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
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- H01M10/058—Construction or manufacture
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
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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
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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
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- 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
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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Abstract
Description
Lia1Nix1M1 y1M2 1-x1-y1O2
一実施形態では、リチウムニッケル系複合酸化物を含む全固体電池用正極活物質であって、複数の1次粒子が凝集されて形成され前記1次粒子の少なくとも一部分が放射状配列構造を有する2次粒子、前記2次粒子の表面に存在する第1ボロンコーティング部、および前記2次粒子内部の1次粒子の表面に存在する第2ボロンコーティング部を含む、全固体電池用正極活物質を提供する。
Lia1Nix1M1 y1M2 1-x1-y1O2
Lia2Nix2Coy2M3 1-x2-y2O2
Lia3Nix3Coy3M4 z3M5 1-x3-y3-z3O2
一実施形態では、リチウム原料、ニッケル系水酸化物、およびボロン原料を混合し熱処理することを含む全固体電池用正極活物質の製造方法を提供する。
Nix11M11 y11M12 1-x11-y11(OH)2
Nix12Coy12M13 1-x12-y12(OH)2
Nix13Coy13M14 z13M15 1-x13-y13-z13(OH)2
一実施形態では、前述の正極活物質を含む正極、負極および前記正極と前記負極の間に位置する固体電解質層を含む全固体電池を提供する。前記全固体電池は、全固体二次電池と表現することもできる。
全固体電池用正極は、集電体、およびこの集電体上に位置する正極活物質層を含むことができる。前記正極活物質層は前述の正極活物質を含み、バインダー、導電材、分散材および/または固体電解質をさらに含むことができる。
全固体電池用負極は、一例として、集電体、およびこの集電体上に位置する負極活物質層を含むことができる。前記負極活物質層は負極活物質を含み、バインダー、導電材、および/または固体電解質をさらに含むことができる。
前記固体電解質層300は固体電解質を含み、前記固体電解質は硫化物系固体電解質、酸化物系固体電解質などの無機固体電解質であるか、または固体高分子電解質であり得る。
1.正極活物質前駆体の製造
後述の共沈法を通じてニッケル系水酸化物であるNi0.91Co0.09(OH)2を合成する。金属原料としてはニッケル硫酸塩およびコバルト硫酸塩を使用する。反応システムは有効反応体積85.5Lの回分式(Batch)反応器を使用し、共沈物以外の溶液の連続的除去が可能な濃縮システムを使用する。
まず、反応器に濃度が0.25Mであるアンモニア水を入れる。攪拌動力4.5kW/m3、反応温度50℃で金属原料および錯化剤をそれぞれ107ml/minおよび25ml/minの速度で投入しながら反応を始める。pHを維持するためにNaOHを投入しながら6時間反応を実施する。反応の結果得られた粒子の大きさが6時間まで持続減少することを確認してコアを形成した後、2段階を次の通り実施する。
反応温度50℃を維持しながら金属原料および錯化剤をそれぞれ142ml/minおよび33ml/minの速度で変更投入して錯化剤の濃度が0.30Mで維持されるようにする。pHを維持するためにNaOHを投入しながら15時間反応させる。この時、攪拌動力を1段階より低い3.5kW/m3に下げて反応を行う。このような反応を実施して得られたコアおよび表面層を含む生成物粒子の平均サイズが3.5μm~3.8μmであることを確認して反応を終了する。
得られた結果物を洗浄した後、約150℃で24時間熱風乾燥して、ニッケル系水酸化物Ni0.91Co0.09(OH)2を得る。
得られたニッケル系水酸化物とLiOHを1:1のモル比で混合し、前記ニッケル系水酸化物に対してホウ酸1.0モル%を混合して、酸素雰囲気725℃で10時間熱処理することによって、ボロン化合物が内部粒界および表面にコーティングされた正極活物質(LiNi0.91Co0.09O2)を得る。
得られた正極活物質85重量%、リチウムアルジロダイト型固体電解質Li6PS5Cl 13.5重量%、バインダー1.0重量%、炭素ナノチューブ導電材0.4重量%、および分散剤0.1重量%をイソブチルイソブチレート(isobutyl isobutyrate、IBIB)溶媒に入れて2mmジルコニアボールを添加し、シンキー混合機で攪拌してスラリーを製造する。製造されたスラリーを正極集電体に塗布し乾燥して正極を準備する。
アルジロダイト型固体電解質Li6PS5Clにバインダー溶液としてイソブチルイソブチレート(isobutyl isobutyrate、IBIB)を投入して混合する。この時、前記混合物をシンキー混合機(Thinky mixer)で攪拌して適切な粘度に調節する。粘度調節後、2mmジルコニアボールを添加し、シンキー混合機で再び攪拌してスラリーを製造する。前記スラリーを離型PETフィルム上にキャスティングし常温乾燥して、固体電解質層を製造する。
負極は析出型負極であって、触媒であるAgが担持されたカーボンを負極集電体の上にスラリーで塗布し乾燥して負極を準備する。
準備した正極、負極、および固体電解質層を裁断し、正極の上に固体電解質層を積層した後、その上に負極を積層した。これをパウチ形態に密封して、500MPaで30分間高温でWIP(Warm Isostatic Press)して全固体電池を製造する。
前記実施例1の正極活物質前駆体の製造で金属原料として硝酸アルミニウムをさらに使用してNi0.945Co0.04Al0.015(OH)2を収得し、これを正極活物質前駆体として使用し、実施例1の正極活物質の製造で、ホウ酸を0.5モル%添加し700℃で熱処理することを除いては、実施例1と同様の方法で正極活物質および全固体電池を製造する。
前記実施例1の正極活物質の製造でホウ酸を添加しないことを除いては実施例1と同様の方法で正極活物質を製造する。エタノールに前記正極活物質、リチウムエトキシド(lithium ethoxide)およびジルコニウムプロポキシド(zirconium propoxide)を混合して、外気との接触がなく有機溶媒の回収が可能な噴霧乾燥を通じて活物質表面にLi2O・ZrO2形態の緩衝層(Buffer Layer)を形成する。その後、実施例1と同様の方法で正極および全固体電池を製造する。
下記の方法で正極活物質前駆体を製造し、正極活物質の製造でホウ酸を添加しないことを除いては実施例1と同様の方法で正極活物質および全固体電池を製造する。
前記実施例1の正極活物質の製造でホウ酸を添加せずボロン化合物がコーティングされていないLiNi0.91Co0.09O2活物質を製造した後、従来の方法で正極活物質にボロン化合物をコーティングする。即ち、LiNi0.91Co0.09O2とホウ酸1.0モル%を混合して酸素雰囲気350℃で8時間2次熱処理することによって、ボロン化合物が表面にコーティングされた正極活物質を得る。これを正極活物質として使用したことを除いては実施例1と同様の方法で正極および全固体電池を製造する。
図5は実施例1の正極活物質前駆体の破断面に関する写真であって、中心に気孔層があり、表面部は1次粒子が2次粒子の表面方向に配向された放射状であることを特徴とする。また、表面が多孔性(porous)であり収縮が容易であって、図6~図7のように、活物質を製造した後、小さな1次粒子が放射状に配向された構造を維持することを確認した。
図9はToF-SIMS(Time-of-Flight Secondary Ion Mass Spectrometry)分析写真であり、図10はToF-SIMS分析の質量スペクトル結果であり、図11はX線光電子分光分析(XPS;X-ray Photoelectron Spectroscopy)結果である。
実施例1で製造した正極活物質に対してICP(Inductively Coupled Plasma)発光分光分析を実施してボロンの含量を測定する。この正極活物質10gを蒸留水100gに入れ30分間攪拌してフィルターで正極活物質を濾す。このような水洗過程を通じて正極活物質の表面に存在するボロンは全て除去される。回収された正極活物質を130℃で24時間乾燥した後、再びICP発光分光分析を実施して、正極活物質に残っているボロンの量を測定し、これを正極活物質内部、即ち、粒界に存在するボロンの量として表示する。また、水洗前のボロンの量から水洗後のボロンの量を引いた値、即ち、水洗過程を通じて除去されたボロンの量を正極活物質の表面に存在するボロンの量として表示する。下記表1で、単位ppmは10-4重量%を意味することができ、正極活物質全体重量に対するボロンの重量の比率を意味することができる。
実施例および比較例で製造した全固体電池を45℃で0.1Cの定電流で上限電圧4.25Vまで充電した後、放電終止電圧2.5Vまで0.1Cで放電して初期放電容量を測定し、その結果を表2に示した。表2を参照すれば、一実施形態による正極活物質を使用せずバッファー層を形成しない比較例2の場合、初期放電容量が顕著に低く、実施例1の場合、バッファー層を形成した比較例1と比べてもさらに高い初期容量を実現するということを確認できる。また、単純に2次粒子表面にのみボロンをコーティングする比較例3ではボロンが抵抗として作用して充電および放電容量が同時に低くなると理解できる。
前記評価例4で初期充放電を経た実施例および比較例の全固体電池に対して45℃で2.5V~4.25Vの電圧範囲において0.33Cで充電および0.33Cで放電することを150回繰り返して寿命特性を評価し、その結果を図12に示した。図12を参照すれば、比較例2と3の場合、急激な寿命の低下が現れ、実施例1および2の場合、従来の方法でバッファー層を形成した比較例1より優れた水準で容量を維持した。したがって、実施例1および2の寿命特性が優れているということを確認できる。
12:2次粒子の内部
13:1次粒子
14:2次粒子の外部
100:全固体電池
200:正極
201:正極集電体
203:正極活物質層
300:固体電解質層
400:負極
401:負極集電体
403:負極活物質層
400’:析出型負極
404:リチウム金属層
405:負極触媒層
500:弾性層
Claims (21)
- リチウムニッケル系複合酸化物を含む全固体電池用正極活物質であって、
複数の1次粒子が凝集されて形成され前記1次粒子の少なくとも一部分が放射状に配列された2次粒子、
前記2次粒子の表面に存在する第1ボロンコーティング部、および
前記2次粒子内部の1次粒子の表面に存在する第2ボロンコーティング部を含む、全固体電池用正極活物質。 - 第1ボロンコーティング部と第2ボロンコーティング部はそれぞれ、ボロン酸化物、リチウムボロン酸化物、またはこれらの組み合わせを含む、請求項1に記載の全固体電池用正極活物質。
- 第1ボロンコーティング部の重量は第2ボロンコーティング部の重量より大きい、請求項1に記載の全固体電池用正極活物質。
- 第1ボロンコーティング部と第2ボロンコーティング部の総量に対して、第1ボロンコーティング部は70重量%~98重量%含まれ、第2ボロンコーティング部は2重量%~30重量%含まれる、請求項1に記載の全固体電池用正極活物質。
- 第1ボロンコーティング部の含量は、前記正極活物質に対して0.02重量%~0.3重量%である、請求項1に記載の全固体電池用正極活物質。
- 第2ボロンコーティング部の含量は、前記正極活物質に対して0.001重量%~0.05重量%である、請求項1に記載の全固体電池用正極活物質。
- 第1ボロンコーティング部と第2ボロンコーティング部の総量は、前記正極活物質に対して0.1モル%~3モル%である、請求項1に記載の全固体電池用正極活物質。
- 第1ボロンコーティング部と第2ボロンコーティング部の総量は、前記正極活物質に対して0.1モル%~1.5モル%である、請求項7に記載の全固体電池用正極活物質。
- 前記1次粒子はプレート形状を有し、前記プレート形状の1次粒子のうちの少なくとも一部は長軸が放射状方向に配列されたものである、請求項1に記載の全固体電池用正極活物質。
- 前記プレート形状の1次粒子の平均長さは150nm~500nmであり、平均厚さは100nm~200nmであり、平均厚さと平均長さの比は1:2~1:5である、請求項9に記載の全固体電池用正極活物質。
- 前記2次粒子は、不規則多孔性構造を含む内部と、放射状配列構造を含む外部とを含有するものである、請求項1に記載の全固体電池用正極活物質。
- 前記2次粒子の内部は外部よりさらに大きな気孔サイズを有し、
前記2次粒子内部の気孔サイズは150nm~1μmであり、
前記2次粒子外部の気孔サイズは150nm未満である、請求項1に記載の全固体電池用正極活物質。 - 前記2次粒子は、表面から内部の中心部側に、大きさが150nm未満であり深さが表面から150nm以下である開孔を含む、請求項1に記載の全固体電池用正極活物質。
- 前記リチウムニッケル系複合酸化物は、下記化学式1で表されるものである、請求項1に記載の全固体電池用正極活物質:
[化学式1]
Lia1Nix1M1 y1M2 1-x1-y1O2
上記化学式1中、0.9≦a1≦1.8、0.3≦x1≦1、0≦y1≦0.7であり、M1およびM2はそれぞれ独立して、Al、B、Ba、Ca、Ce、Co、Cr、Cu、F、Fe、Mg、Mn、Mo、Nb、P、S、Si、Sr、Ti、V、W、Zrおよびこれらの組み合わせから選択される。 - リチウム原料、ニッケル系水酸化物、およびボロン原料を混合し熱処理して、請求項1~14のうちのいずれか一項による正極活物質を得ることを含む、全固体電池用正極活物質の製造方法。
- 前記ボロン原料の含量は前記ニッケル系水酸化物100モル%に対して0.1モル%~3モル%である、請求項15に記載の全固体電池用正極活物質の製造方法。
- 前記熱処理は650℃~850℃の温度で5時間~20時間行われる、請求項15に記載の全固体電池用正極活物質の製造方法。
- 請求項1~14のうちのいずれか一項による正極活物質を含む正極、負極、および前記正極と前記負極の間に位置する固体電解質層を含む、全固体電池。
- 前記正極は集電体および前記集電体上に位置する正極活物質層を含み、前記正極活物質層は前記正極活物質および固体電解質を含み、
前記固体電解質は前記正極活物質層全体重量に対して0.1重量%~35重量%で含まれる、請求項18に記載の全固体電池。 - 前記負極は、集電体および前記集電体上に位置する負極活物質層または負極触媒層を含む、請求項18に記載の全固体電池。
- 前記負極は集電体および前記集電体上に位置する負極触媒層を含み、
前記集電体と前記負極触媒層の間に、初期充電時に形成されるリチウム金属層を含む、請求項18に記載の全固体電池。
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WO2021034020A1 (ko) * | 2019-08-22 | 2021-02-25 | 주식회사 포스코 | 양극 활물질, 이의 제조 방법, 및 이를 포함하는 리튬 이차 전지 |
JP2021077643A (ja) * | 2019-11-11 | 2021-05-20 | 三星エスディアイ株式会社Samsung SDI Co., Ltd. | 全固体二次電池 |
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JP2021077643A (ja) * | 2019-11-11 | 2021-05-20 | 三星エスディアイ株式会社Samsung SDI Co., Ltd. | 全固体二次電池 |
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