JP5701868B2 - アルカリ金属超イオン伝導セラミック - Google Patents
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Description
製造、分析および試験されたナトリウム欠損NaSICON型材料は、表1に示された複数の材料処方を含んでいるが、これらに限定されない。表1は、比較のために、ナトリウム欠損ではない幾つかのNaSICON型材料も含んでいる。
幾つかの異なるNaSICON膜の組成物をLLW(低レベル放射能汚染ナトリウム塩ベース廃棄物)模擬薬剤および苛性の水酸化ナトリウム水溶液に電界の影響を与えずに暴露した。暴露試験は、約60℃にて168時間(一週間)、3つの異なる水溶液中、すなわち、15質量%の水酸化ナトリウム水溶液(基準の電解液の組成物)、Na:K比がおおよそ50:1である放射性模擬水溶液“AP104”、および、Na:K比を7:1にするように十分なKOHが加えられ、膜が実際のLLWにおいて暴露されうる最高のK濃度を模した、同じ“AP104”水溶液中で行われた。結果は以下の表2に示されており、15質量%の水酸化ナトリウム水溶液と比較すると、腐食レベルは、ほとんどの場合、50:1の水溶液において著しく低い。
NaSICON型薄膜電解セルは、LLW模擬薬剤を模倣するAP104が混合されたナトリウム塩陽極液流および50質量%の水酸化ナトリウム陰極液中で操作された。2つのE−04薄膜電解セルを操作して、混合ナトリウム塩を含む水溶液流からNaOHを再利用し合成した。約2400時間に亘るセル作動中のセル電圧(V)及び電流密度(mA/cm2)が図3に示されている。セル電圧は、3ボルトの一定電圧に維持されていた。
ナトリウム欠乏NaSICON型材料のさらなる例が、上述の例1及び2に開示された手続に従って、製造、分析および試験される。その例は、上に開示された式より大きなyおよび/またはzの値を有する、表5に示した幾つかの材料式を含んでいるが、これらに限定されない。
1. Hong, H.Y.P., Crystal structures and crystal chemistry in the system Na1+xZr2SixP3-xO12. Materials Research Bulletin, 1976. 11(2): p. 173-182.
2. Miyajima, Y., et al., Solubility range and ionic conductivity of large trivalent ion doped Na1+xMxZr2-xP3O12 (M: In, Yb, Er, Y, Dy, Tb, Gd) solid electrolytes. Solid State Ionics, 1999. 124(3-4): p. 201-211.
3. Fan, R.-q., W.-j. Wang, and F.-x. Chen, Synthesis and characterization of sodium fast ion conductors in Na1+2x+yAlxEuyTi2-x-ySixP3-xO12 system. 2002. 30(1): p. 102-105.
4. Tillement, O., et al., Mixed conductivity of the NASICON phase Na2+x+yZr1-yFeIIxFeII11-x+y(PO4)3, Solid State Ionics, 1991. 44(3-4): p. 299-303.
5. Mariappan, CR. and G. Govindaraj, Frequency dependent electrical properties of the Na3Fe2P3O12 and Na4FeCdP3O12 NASICON material. 2002: p. 629-636.
6. Fuentes, R.O., et al., Submicrometric NASICON ceramics with improved electrical conductivity obtained from mechanically activated precursors. Journal of the European Ceramic Society, 2005. 25(4): p. 455-462.
7. Fuentes, R.O., et al., Influence of microstructure on the electrical properties of NASICON materials. Solid State Ionics, 2001. 140(1-2): p. 173-179.
8. Fuentes, R.O., et al., Reaction of NASICON with water. Solid State Ionics, 2001. 139(3-4): p. 309-314.
9. Fuentes, R., et al., Optimised NASICON ceramics for Na+ sensing. Ionics, 2002. 8(5): p. 383-390.
10. Smirnova, O.A., et al., Stability and Thermal Expansion of Na+-Conducting Ceramics. Journal of Electroceramics, 2003. 11(3): p. 179-189.
11. Clearfield, A., et al., Preparation of sodium zirconium phosphates of the type Na1+4xZr2-x(PO4)3, Materials Research Bulletin, 1983. 18(12): p. 1561-1567.
12. Rudolf, P. R., et al., The crystal structure of a nonstoichiometric NASICON Materials Research Bulletin, 1985. 20(6): p. 643-651.
13. Von Alpen, U., M. F. Bell, and H.H. Hofer, Compositional dependence of the electrochemical and structural parameters in the Nasicon system (Na1+xSixZr2P3-xO12), Solid State Ionics, 1981. 3-4: p. 215-218.
14. Delmas, C, A. Nadiri, and J.L. Soubeyroux, The NASICON-type titanium phosphates ATi2(PO4)3 (A = lithium, sodium) as electrode materials. Solid State Ionics, 1988. 28-30(Pt. 1): p. 419-23.
15. Tillement, O., et al., Crystal chemistry and electrical study of sodium niobium titanium phosphate (NaxNbTi(PO4)3), Solid State Ionics, 1991. 48(3-4): p. 249-55.
16. Tillement, O., et al., Electrochemical studies of mixed valence Nasicon. Solid State Ionics, 1992. 53-56(Pt. 1): p. 391-9.
17. Znaidi, L., S. Launay, and M. Quarton, Crystal chemistry and electrical properties of Na1+xScNb(PO4)3 phases. Solid State Ionics, 1997. 93(3,4): p. 273-277.
18. Stratichuk, D. A., et al., Insertion of Li, Na, K, Rb, and Cs in the unfilled structure of Nb2(PO4)3. Zhurnal Neorganicheskoi Khimii, 2001. 46(9): p. 1449-1452.
19. Patoux, S., et al., Structural and Electrochemical Studies of Rhombohedral Na2TiM(PO4)3 and Li1.6Na0.4TiM(PO4)3 (M = Fe, Cr) Phosphates. 2003. 15(10): p. 2084-2093
Claims (8)
- ナトリウムイオン伝導度を与え以下の一般式を有するナトリウムイオン伝導性セラミック材料。
Na1+x+y−zYyZr2−ySixP3−xO12−(z/2)
ここで、2.0≦x≦2.4、0.0≦y≦0.12および0.25≦z≦0.9である。 - 2.2≦x≦2.4である、請求項1に記載のナトリウムイオン伝導性セラミック材料。
- 0.25≦z≦0.3である、請求項1に記載のナトリウムイオン伝導性セラミック材料。
- xは2.2、yは0.05およびzは0.9である、請求項1に記載のナトリウムイオン伝導性セラミック材料。
- xは2.3、yは0.0およびzは0.9である、請求項1に記載のナトリウムイオン伝導性セラミック材料。
- xは2.3、yは0.05およびzは0.8である、請求項1に記載のナトリウムイオン伝導性セラミック材料。
- xは2.4、yは0.0およびzは0.9である、請求項1に記載のナトリウムイオン伝導性セラミック材料。
- xは2.4、yは0.0およびzは0.8である、請求項1に記載のナトリウムイオン伝導性セラミック材料。
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US12/492,834 US8246863B2 (en) | 2009-06-26 | 2009-06-26 | Alkali metal super ionic conducting ceramic |
US12/492,834 | 2009-06-26 | ||
PCT/US2010/038877 WO2010151468A2 (en) | 2009-06-26 | 2010-06-16 | Alkali metal super ionic conducting ceramic |
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US (1) | US8246863B2 (ja) |
EP (3) | EP3760603A1 (ja) |
JP (1) | JP5701868B2 (ja) |
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CN103204903A (zh) * | 2003-05-21 | 2013-07-17 | 贝林格尔.英格海姆国际有限公司 | 丙型肝炎抑制剂化合物 |
US7941244B2 (en) * | 2007-09-25 | 2011-05-10 | Amazon Technologies, Inc. | Stow and sortation system |
US9957622B2 (en) | 2009-07-23 | 2018-05-01 | Field Upgrading Limited | Device and method of obtaining diols and other chemicals using decarboxylation |
US9206515B2 (en) | 2009-07-23 | 2015-12-08 | Ceramatec, Inc. | Method of producing coupled radical products via desulfoxylation |
US8506789B2 (en) * | 2009-07-23 | 2013-08-13 | Ceramatec, Inc. | Method of producing coupled radical products |
US9051656B2 (en) * | 2009-07-23 | 2015-06-09 | Ceramatec, Inc. | Electrochemical synthesis of aryl-alkyl surfacant precursor |
WO2011011521A2 (en) * | 2009-07-23 | 2011-01-27 | Ceramatec, Inc. | Decarboxylation cell for production of coupled radical products |
US9493882B2 (en) | 2010-07-21 | 2016-11-15 | Ceramatec, Inc. | Custom ionic liquid electrolytes for electrolytic decarboxylation |
EP2601331B1 (en) | 2010-08-05 | 2018-06-20 | Field Upgrading Limited | Method and device for carboxylic acid production |
US8853463B2 (en) | 2011-01-25 | 2014-10-07 | Ceramatec, Inc. | Decarboxylation of levulinic acid to ketone solvents |
ES2724528T3 (es) | 2011-01-25 | 2019-09-11 | Enlighten Innovations Inc | Producción de combustible a partir de sustancias químicas derivadas de biomasa |
WO2013031508A1 (ja) * | 2011-08-31 | 2013-03-07 | 旭硝子株式会社 | リチウムイオン伝導性ガラスセラミックスおよびその製造方法 |
EP2804845A4 (en) * | 2012-01-16 | 2015-08-19 | Ceramatec Inc | LITHIUM ION CONDUCTIVE MATERIALS |
EP2900594B1 (en) * | 2012-09-25 | 2018-01-10 | University of Maryland, College Park | High conductivity nasicon electrolyte for room temperature solid- state sodium ion batteries |
WO2014136650A1 (ja) * | 2013-03-05 | 2014-09-12 | 旭硝子株式会社 | リチウムイオン伝導性ガラスセラミックスの製造方法、リチウムイオン伝導性ガラスセラミックスおよびリチウムイオン二次電池 |
US11888149B2 (en) | 2013-03-21 | 2024-01-30 | University Of Maryland | Solid state battery system usable at high temperatures and methods of use and manufacture thereof |
WO2014153534A1 (en) | 2013-03-21 | 2014-09-25 | University Of Maryland, College Park | Ion-conducting batteries with solid state electrolyte materials |
JP2015026483A (ja) * | 2013-07-25 | 2015-02-05 | トヨタ自動車株式会社 | ナトリウム電池用正極及びナトリウム電池 |
JP6362883B2 (ja) * | 2014-03-13 | 2018-07-25 | エナジー・ストレージ・マテリアルズ合同会社 | 固体イオンキャパシタおよび固体イオンキャパシタの製造方法 |
JP6362882B2 (ja) * | 2014-03-13 | 2018-07-25 | エナジー・ストレージ・マテリアルズ合同会社 | 固体イオンキャパシタ、及びその製造方法 |
US10916819B2 (en) | 2015-09-22 | 2021-02-09 | Enlighten Innovations Inc. | Multi-stage sodium heat engine for electricity and heat production |
JP6649641B2 (ja) * | 2016-09-20 | 2020-02-19 | 株式会社村田製作所 | 固体電解質及び全固体電池 |
CN116895830A (zh) | 2018-02-15 | 2023-10-17 | 马里兰大学派克分院 | 有序多孔固态电解质结构及其制造方法、电化学装置 |
US11569527B2 (en) | 2019-03-26 | 2023-01-31 | University Of Maryland, College Park | Lithium battery |
CN110038452A (zh) * | 2019-04-23 | 2019-07-23 | 东南大学 | 负载银的陶瓷纳米纤维基复合净化膜及其制备方法和应用 |
US11545723B2 (en) | 2019-11-26 | 2023-01-03 | National Technology & Engineering Solutions Of Sandia, Llc | Sodium electrochemical interfaces with NaSICON-type ceramics |
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US8012621B2 (en) * | 2007-11-26 | 2011-09-06 | Ceramatec, Inc. | Nickel-metal hydride battery using alkali ion conducting separator |
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CA2759663C (en) | 2016-01-12 |
EP2445846A2 (en) | 2012-05-02 |
EP3395779A1 (en) | 2018-10-31 |
WO2010151468A3 (en) | 2011-04-07 |
US20100331170A1 (en) | 2010-12-30 |
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WO2010151468A2 (en) | 2010-12-29 |
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