JP2017112057A - シリコン系粒子およびそれを含むリチウムイオン二次電池用負極活物質並びにそれらの製造方法 - Google Patents
シリコン系粒子およびそれを含むリチウムイオン二次電池用負極活物質並びにそれらの製造方法 Download PDFInfo
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- JP2017112057A JP2017112057A JP2015247754A JP2015247754A JP2017112057A JP 2017112057 A JP2017112057 A JP 2017112057A JP 2015247754 A JP2015247754 A JP 2015247754A JP 2015247754 A JP2015247754 A JP 2015247754A JP 2017112057 A JP2017112057 A JP 2017112057A
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- active material
- silicon
- negative electrode
- lithium ion
- ion secondary
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Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
Description
「シリコン系粒子スラリーの作製」
平均粒子径(D50)が7μmのケミカルグレードの金属Si(純度3N)をメタノールに20重量%混合し、直径0.3mmのジルコニアビーズを用いたバッチ式微粉砕湿式ビーズミルを37時間実施した。このビーズミルはジルコニア製容器内で行い、容器には窒素を3L/min送り込み、不活性雰囲気で行った。
日本黒鉛工業製の酸処理黒鉛EXP−80MTを酸処理黒鉛を振動粉末供給器に入れ、10L/分の流量の窒素ガスに乗せて電気ヒーターで850℃に加熱した長さ1m、内径11mmのムライト管に通し、端面から大気に放出し、亜硫酸等のガスを上部に排気、下部に膨張黒鉛をステンレス容器で捕集した。この膨張黒鉛は約40倍に膨張し、外観はコイル状、SEM観察で黒鉛層が剥離したアコーディオン状であることが確認された。
得られたリチウムイオン二次電池用負極活物質を95.5重量%(固形分全量中の含有量。以下同じ。)に対して、導電助剤としてアセチレンブラック0.5重量%と、バインダとしてカルボキシメチルセルロース(CMC)1.5重量%とスチレンブタジエンゴム(SBR)2.5重量%、水を混合して負極合剤含有スラリーを調製した。
評価用セルは、グローブボックス中でスクリューセルに上記負極、24mmφのポリプロピレン製セパレータ、21mmφのガラスフィルター、18mmφで厚み0.2mmの金属リチウムおよびその基材のステンレス箔を、各々、電解液にディップした後、この順に積層し、最後に蓋をねじ込み作製した。電解液はエチレンカーボネートとジエチルカーボネートを体積比1対1の混合溶媒とし、LiPF6を1.2mol/Lの濃度になるように溶解させ、これにフルオロエチレンカーボネートを2体積%添加したものを使用した。評価用セルは、さらにシリカゲルを入れた密閉ガラス容器に入れて、シリコンゴムの蓋を通した電極を充放電装置(北斗電工製SM−8)に接続した。
評価用セルは25℃の恒温室にて、サイクル試験した。充電は、2mAの定電流で0.01Vまで充電後、0.01Vの定電圧で電流値が0.2mAになるまで行った。また放電は、2mAの定電流で1.5Vの電圧値まで行った。初回放電容量と初回充放電効率は、初回充放電試験の結果とした。
シリコン系粒子スラリーの作製時に、窒素を送り込まずに大気雰囲気でバッチ式微粉砕湿式ビーズミルを行った以外は実施例1と同様の方法でリチウムイオン二次電池用負極活物質の作製を行った。このシリコン系粒子は、平均粒子径(D50)が0.22μm、D90が0.30μm、BET比表面積が86m2/g、LECO社製TC436インパルス炉溶融−赤外吸収法による酸素量10.1重量%、酸素量をBET比表面積で割った値0.12であった。このシリコン系粒子スラリーに対して実施例1と同様の方法でリチウムイオン二次電池用負極活物質の作製、リチウムイオン二次電池用負極の作製、評価用セルの作製、評価を行った。
12 リチウムイオン二次電池用負極活物質内部のシリコン系粒子
Claims (8)
- 平均粒径(D50)が0.01〜0.6μm、D90が0.01〜1.0μmであり、BET法による比表面積が40〜300m2/g、酸素含有量(重量%)を比表面積(m2/g)で割った値が0.1以下であることを特徴とするシリコン系粒子。
- 請求項1に記載のシリコン系粒子を10〜80重量%、炭素質物を90〜5重量%、黒鉛を0〜80重量%含むことを特徴とするリチウムイオン二次電池用負極活物質。
- 平均粒径(D50)が1〜40μm、BET法による比表面積が5〜120m2/gであり、炭素質物で活物質表面が覆われていることを特徴とする請求項2に記載のリチウムイオン二次電池用負極活物質。
- 該黒鉛は、ICP発光分光分析法による26元素(Al、Ca、Cr、Fe、K、Mg、Mn、Na、Ni、V、Zn、Zr、Ag、As、Ba、Be、Cd、Co、Cu、Mo、Pb、Sb、Se、Th、Tl、U)の不純物半定量値より求めた純度が99.9%以上(1000ppm以下)で酸素フラスコ燃焼法によるイオンクロマトグラフィー(IC)測定法によるS量が0.3重量%以下、及び/又は黒鉛のBET法による比表面積が40m2/g以下であることを特徴とする請求項2又は3に記載のリチウムイオン二次電池用負極活物質。
- シリコン系粒子が、炭素質物と共に0.2μm以下の厚みの黒鉛薄層の間に挟まれた構造であり、その構造が積層および/または網目状に広がっており、該黒鉛薄層が活物質粒子の表面付近で湾曲して活物質粒子を覆っていることを特徴とする請求項2〜4のいずれか1項に記載のリチウムイオン二次電池用負極活物質。
- シリコン系粒子が平均粒径(D50)0.5〜100μmの粒子をビーズミルにより不活性雰囲気中で粉砕して製造することを特徴とする請求項1に記載のシリコン系粒子の製造方法。
- 請求項1に記載のシリコン系粒子と炭素前駆体、さらに必要に応じて黒鉛を混合する工程と、造粒・圧密化する工程と、粉砕および球形化処理して複合粒子を形成する工程と、該複合粒子を不活性ガス雰囲気中で焼成する工程とを含むことを特徴とする請求項2に記載のリチウムイオン二次電池用負極活物質の製造方法。
- 前記複合粒子を不活性雰囲気中で焼成する工程の温度が、600〜1000℃であることを特徴とする請求項7に記載のリチウムイオン二次電池用負極活物質の製造方法。
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WO2020129499A1 (ja) * | 2018-12-21 | 2020-06-25 | 株式会社トクヤマ | シリコン微粒子及びその製造方法 |
WO2021193737A1 (ja) * | 2020-03-27 | 2021-09-30 | 株式会社トクヤマ | 多孔質シリコン微粒子およびその製造方法 |
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