JP6873404B2 - ナトリウム二次電池用負極活性物質 - Google Patents
ナトリウム二次電池用負極活性物質 Download PDFInfo
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- JP6873404B2 JP6873404B2 JP2017532467A JP2017532467A JP6873404B2 JP 6873404 B2 JP6873404 B2 JP 6873404B2 JP 2017532467 A JP2017532467 A JP 2017532467A JP 2017532467 A JP2017532467 A JP 2017532467A JP 6873404 B2 JP6873404 B2 JP 6873404B2
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- negative electrode
- active material
- electrode active
- storage device
- power storage
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Images
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Description
Xa=100−Xc(%)
表1〜14は本発明の実施例(No.1〜86)及び比較例(No.87、88)を示す。
表1〜14に示す各組成となるように、原料として各種酸化物、炭酸塩原料等を用いて原料粉末を調製した。原料粉末を白金ルツボに投入し、電気炉を用いて大気中にて1200〜1500℃で60分間の溶融を行った。次いで、溶融ガラスを一対の回転ローラー間に流し出し、急冷しながら成形し、厚み0.1〜2mmのフィルム状の溶融固化体を得た。フィルム状溶融固化体をボールミルで粉砕した後、空気分級することで、平均粒子径2μmの粉末状の負極活物質を得た。なお、No.81、82の試料については、溶融固化体をボールミルで粉砕して得られた粉体をバーナーの火炎中に直接噴霧した後、急冷させ、さらにジェットミルで粉砕することで平均粒子径2μmの粉末状の負極活物質を得た。
No.1〜67、87、88の試料については、負極活物質粉末に対し、導電助剤として導電性カーボンブラック(SuperC65、Timcal社製)、結着剤としてポリフッ化ビニリデンを、負極活物質粉末:導電助剤:結着剤=92:3:5(質量比)となるように秤量し、N−メチルピロリドン(NMP)に分散した後、自転・公転ミキサーで十分に撹拌してスラリー化し、負極材料を得た。No.68〜86の試料については、負極活物質粉末:導電助剤:結着剤=85:5:10(質量比)となるように秤量し、同様の方法で負極材料を得た。
ナトリウムイオン二次電池(NIB)用試験電池は以下のようにして作製した。上記で得られた負極を、銅箔面を下に向けてコインセルの下蓋に載置し、その上に70℃で8時間減圧乾燥した直径16mmのポリプロピレン多孔質膜からなるセパレータ、及び、対極である金属ナトリウムを積層し、試験電池を作製した。電解液としては、1M NaPF6溶液/EC:DEC=1:1(EC=エチレンカーボネート、DEC=ジエチルカーボネート)を用いた。なお試験電池の組み立ては露点温度−70℃以下の環境で行った。
ナトリウムイオン二次電池用試験電池については、30℃で開回路電圧から0.5VまでCC(定電流)充電を行い、単位質量当たりの負極活物質へ充電された電気量(初回充電容量)を求めた。次に、0.5Vから2.5VまでCC放電させ、単位質量当たりの負極活物質から放電された電気量(初回放電容量)を求めた。但し、No.69〜86については、開回路電圧から0.01Vまで充電を行うことにより初回充電容量を求め、次に0.01Vから2.5VまでCC放電させて初回放電容量を求めた。なお、Cレートは0.1Cとした。
表15、16は本発明の実施例(No.89〜93)を示す。
No.89〜91については、メタリン酸ソーダ(NaPO3)、酸化チタン(TiO2)、炭酸ソーダ(Na2CO3)、シリカ(SiO2)、オルトリン酸(H3PO4)を原料とし、モル%で、Na2O 20%、TiO2 40%、SiO2 35%、P2O5 5%の組成となるように原料粉末を調合し、1250℃にて45分間、大気雰囲気中にて溶融を行った。No.92、93については、表16に示す各組成となるように、原料として各種酸化物、炭酸塩原料等を用いて原料粉末を調合し、1350℃にて60分間、大気雰囲気中にて溶融を行った。その後、溶融物を一対の回転ローラー間に流し出し、急冷しながら成形し、厚み0.1〜1mmのフィルム状のガラスを得た。このフィルム状ガラスに対し、φ20mmのZrO2玉石を使用したボールミル粉砕を5時間行い、目開き120μmの樹脂製篩に通過させ、平均粒子径3〜15μmのガラス粗粉末を得た。さらに、このガラス粗粉末に対し、粉砕助剤にエタノールを用い、φ3mmのZrO2玉石を使用したボールミル粉砕を80時間行うことで、平均粒子径0.6μmのガラス粉末(負極活物質前駆体粉末)を得た。XRD測定の結果、ガラス粉末は非晶質であることが確認された。
(Li2O安定化β”アルミナ)
組成式:Na1.6Li0.34Al10.66O17のLi2O安定化β”アルミナ(Ionotec社製)を乾式研磨して、厚み0.2mmに加工することにより固体電解質シートを得た。また、得られた固体電解質シートを遊星ボールミルを用いて粉砕し、目開き10μmの篩に通過させることで、別途、固体電解質粉末(平均粒子径13μm)を作製した。
炭酸ナトリウム(Na2CO3)、酸化アルミニウム(Al2O3)及び酸化マグネシウム(MgO)を原料とし、モル%で、Na2O 13.0%、Al2O3 80.2%、及びMgO 6.8%となるように原料粉末を調合し、エタノール中でφ5mmのAl2O3玉石を使用したボールミルで粉砕及び混合を10時間行った。得られた粉末を、厚み0.2mmのシート状に成形後、40MPaの圧力で等方加圧成形した後、大気雰囲気中1640℃にて1時間熱処理を行うことにより、MgO安定化β”アルミナからなる固体電解質シートを得た。
メタリン酸ナトリウム(NaPO3)、イットリア安定ジルコニア((ZrO2)0.97(Y2O3)0.03)、炭酸ナトリウム(Na2CO3)及び二酸化ケイ素(SiO2)を原料とし、モル%で、Na2O 25.3%、ZrO2 31.6%、Y2O3 1.0%、P2O5 8.4%、SiO2 33.7%となるように原料粉末を調合し、エタノール中でφ5mmのAl2O3玉石を使用したボールミルで粉砕及び混合を10時間行った。得られた粉末を、厚み0.2mmのシート状に成形後、40MPaの圧力で等方加圧成形した後、大気雰囲気中1250℃にて2時間熱処理を行うことにより、NASICON結晶からなる固体電解質シートを得た。
上記で得られた負極活物質前駆体粉末、固体電解質粉末、及び、導電性炭素としてアセチレンブラック(TIMCAL社製 SUPER C65)をそれぞれ表15、16に記載の割合で秤量し、遊星ボールミルを用いて、300rpmで30分間混合した。得られた混合粉末100質量部に、10質量部のポリプロピレンカーボネート(住友精化株式会社製)を添加し、さらにN−メチルピロリドンを30質量部添加して、自転・公転ミキサーを用いて十分に撹拌し、スラリー化した。
作製した試験電池について、60℃で開回路電圧から0.01VまでのCC(定電流)充電を行い初回充電容量を求めた。次に、放電は0.01Vから2.5VまでCC放電を行い初回放電容量を求めた。なお本試験では、Cレートは0.01Cとし、「放電容量維持率」は初回放電容量に対する10サイクル目の放電容量の割合で評価した。結果を表15、16に示す。また、No.92、93の試料を用いた固体型ナトリウムイオン二次電池用試験電池の初回充放電曲線を図11、12に示す。
Claims (4)
- 酸化物換算のモル%で、TiO2 1〜95%、P2O5+SiO2+B2O3+Al2O3+R´O(R´はMg、Ca、Sr、Ba及びZnから選択される少なくとも一種) 5〜75%(ただし、B 2 O 3 0.1〜50%である場合を除く)を含有し、非晶質相を10質量%以上含有することを特徴とするナトリウムイオン二次電池用負極活物質。
- さらに、R2O(RはLi、Na及びKから選択される少なくとも一種) 1〜70%を含有することを特徴とする請求項1に記載のナトリウムイオン二次電池用負極活物質。
- 非晶質相からなることを特徴とする請求項1または2に記載のナトリウムイオン二次電池用負極活物質。
- 請求項1〜3のいずれか一項に記載のナトリウムイオン二次電池用負極活物質を含有することを特徴とするナトリウムイオン二次電池用負極材料。
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JPH1140150A (ja) * | 1997-07-17 | 1999-02-12 | Sanyo Electric Co Ltd | リチウム二次電池 |
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WO2011083861A1 (ja) * | 2010-01-08 | 2011-07-14 | 三菱化学株式会社 | リチウム二次電池正極材料用粉体及びその製造方法、並びにそれを用いたリチウム二次電池用正極及びリチウム二次電池 |
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JP2014154236A (ja) * | 2013-02-05 | 2014-08-25 | Seiko Epson Corp | 電極複合体の製造方法 |
JP6222433B2 (ja) | 2013-08-08 | 2017-11-01 | 日本電気硝子株式会社 | 蓄電デバイス用負極活物質の製造方法 |
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