Strategy of Sb-substitution is carried out on the template structure Na4Sn0.67M0.33S4(M=Si,Ge),which affords a series of quinary sulfide-based sodium fast ionic conductors formulated as Na4-x[Sn0.67M0.33]1-xSbxS4(M=Si...Strategy of Sb-substitution is carried out on the template structure Na4Sn0.67M0.33S4(M=Si,Ge),which affords a series of quinary sulfide-based sodium fast ionic conductors formulated as Na4-x[Sn0.67M0.33]1-xSbxS4(M=Si,x=0.1,0.2,0.3;M=Ge,x=0.2.).Among them,the highest ambient ionic conductivity(1.75×10^-4 S cm^-1)is achieved when M=Si and x=0.2.The new fast ionic conductor Na3.8[Sn0.67Si0.33]0.8Sb0.2S4 is isostructural to its structure template Na4Sn0.67Si0.33S4 and thus crystallizes in the space group of I41/acd.It is shown that the incorporation of Sb improves the ionic conductivity.The study of lattice parameters shows that the improvement of the ion conductivity by Sbsubstitution is mainly due to the enlarged crystal lattice.Furthermore,using Na3.8[Sn0.67Si0.33]0.8Sb0.2S4as solid electrolytes,room temperature all-solid-state sodium battery of Se0.05S0.95@pPAN/Na3Sn is realized,which proves the novel fast ionic conductor a potential candidate to apply in sodium solid state battery.This work not only extends the scope of Na4[Sn0.67Si0.33]S4,the I41/acd space group template,but also deepens the understanding of the lattice size effect on the structure and property relationship by aliovalent substitution.展开更多
钠离子电池因储量丰富、成本低廉而成为可替代锂离子电池的储能设备之一,尤其是在大规模储能领域展现出了广阔的应用前景。然而,类似锂离子电池,以可燃的液态电解质作为离子传输媒介的钠离子电池也不可避免地面临着安全性的挑战。固态...钠离子电池因储量丰富、成本低廉而成为可替代锂离子电池的储能设备之一,尤其是在大规模储能领域展现出了广阔的应用前景。然而,类似锂离子电池,以可燃的液态电解质作为离子传输媒介的钠离子电池也不可避免地面临着安全性的挑战。固态电解质的使用不仅可以大幅提升电池系统的安全性,与金属负极匹配更能进一步实现电池能量密度同步提升。在各类固态电解质中,无机固态电解质以高离子电导率和离子迁移数、高力学性能及稳定性等诸多优势而备受瞩目。尽管如此,在全固态钠电池的实际应用中,不同类型的无机固态电解质材料仍面临离子电导率低、化学与电化学稳定性差等不同困境。因此,无机固态电解质材料的研究和开发是实现固态钠电池应用的必经之路。本文介绍了离子在固体中的迁移机制,并综述了氧化物、硫化物以及络合氢化物钠离子固态电解质的研究进展,重点强调不同结构电解质离子电导率的提升策略和提高化学及电化学稳定性的方法,包括通过离子掺杂提升离子电导率,调控晶界处化学组分或利用低熔点添加剂降低钠的快离子导体(natrium super ionic conductor,NASICON)型电解质的晶界电阻,解决硫化物型电解质的空气敏感问题,开发新型硫化物超离子导体,降低络合氢化物的有序-无序相变温度同时提高室温离子电导率等。最后对固态电解质面临的关键挑战和未来发展趋势进行总结和展望。展开更多
This work focuses on the H2 sensing performance of the sensor with buried Au sensing electrode and spi- nel-type oxide CoCrMnO4 insensitive reference electrode within sodium super ionic conductor（NASICON） film. The ...This work focuses on the H2 sensing performance of the sensor with buried Au sensing electrode and spi- nel-type oxide CoCrMnO4 insensitive reference electrode within sodium super ionic conductor（NASICON） film. The sensor showed the highest response to H2 gas on the insensitive material sintering at 800 ~C. Compared with those of the traditional structure device, the sensitivity and selectivity of the sensor using buried sensing electrode were greatly improved, giving a response of-177 mV in 9x10 5 g/L H2, which was about 3.5 times higher than that of sensors with traditional structure. Moreover, the AV value of the sensing device exhibited linear relationship to the logarithm of H2 concentration and the sensitivity（slope） was -135 mV/decade. A sensing mechanism related to the mixed potential was proposed for the present sensor.展开更多
基金supported by the National Natural Science Foundation of China(21975087 and 51902116)。
文摘Strategy of Sb-substitution is carried out on the template structure Na4Sn0.67M0.33S4(M=Si,Ge),which affords a series of quinary sulfide-based sodium fast ionic conductors formulated as Na4-x[Sn0.67M0.33]1-xSbxS4(M=Si,x=0.1,0.2,0.3;M=Ge,x=0.2.).Among them,the highest ambient ionic conductivity(1.75×10^-4 S cm^-1)is achieved when M=Si and x=0.2.The new fast ionic conductor Na3.8[Sn0.67Si0.33]0.8Sb0.2S4 is isostructural to its structure template Na4Sn0.67Si0.33S4 and thus crystallizes in the space group of I41/acd.It is shown that the incorporation of Sb improves the ionic conductivity.The study of lattice parameters shows that the improvement of the ion conductivity by Sbsubstitution is mainly due to the enlarged crystal lattice.Furthermore,using Na3.8[Sn0.67Si0.33]0.8Sb0.2S4as solid electrolytes,room temperature all-solid-state sodium battery of Se0.05S0.95@pPAN/Na3Sn is realized,which proves the novel fast ionic conductor a potential candidate to apply in sodium solid state battery.This work not only extends the scope of Na4[Sn0.67Si0.33]S4,the I41/acd space group template,but also deepens the understanding of the lattice size effect on the structure and property relationship by aliovalent substitution.
文摘钠离子电池因储量丰富、成本低廉而成为可替代锂离子电池的储能设备之一,尤其是在大规模储能领域展现出了广阔的应用前景。然而,类似锂离子电池,以可燃的液态电解质作为离子传输媒介的钠离子电池也不可避免地面临着安全性的挑战。固态电解质的使用不仅可以大幅提升电池系统的安全性,与金属负极匹配更能进一步实现电池能量密度同步提升。在各类固态电解质中,无机固态电解质以高离子电导率和离子迁移数、高力学性能及稳定性等诸多优势而备受瞩目。尽管如此,在全固态钠电池的实际应用中,不同类型的无机固态电解质材料仍面临离子电导率低、化学与电化学稳定性差等不同困境。因此,无机固态电解质材料的研究和开发是实现固态钠电池应用的必经之路。本文介绍了离子在固体中的迁移机制,并综述了氧化物、硫化物以及络合氢化物钠离子固态电解质的研究进展,重点强调不同结构电解质离子电导率的提升策略和提高化学及电化学稳定性的方法,包括通过离子掺杂提升离子电导率,调控晶界处化学组分或利用低熔点添加剂降低钠的快离子导体(natrium super ionic conductor,NASICON)型电解质的晶界电阻,解决硫化物型电解质的空气敏感问题,开发新型硫化物超离子导体,降低络合氢化物的有序-无序相变温度同时提高室温离子电导率等。最后对固态电解质面临的关键挑战和未来发展趋势进行总结和展望。
基金Supported by the National Natural Science Foundation of China（Nos.61104203, 61134010, 61327804, 41074172）, the Pro- gram for Changjiang Scholars and Innovative Research Team in University, China（No.IRT13018） and the National High Tech- nology Research and Development Program of China（No.2013AA030902）.
文摘This work focuses on the H2 sensing performance of the sensor with buried Au sensing electrode and spi- nel-type oxide CoCrMnO4 insensitive reference electrode within sodium super ionic conductor（NASICON） film. The sensor showed the highest response to H2 gas on the insensitive material sintering at 800 ~C. Compared with those of the traditional structure device, the sensitivity and selectivity of the sensor using buried sensing electrode were greatly improved, giving a response of-177 mV in 9x10 5 g/L H2, which was about 3.5 times higher than that of sensors with traditional structure. Moreover, the AV value of the sensing device exhibited linear relationship to the logarithm of H2 concentration and the sensitivity（slope） was -135 mV/decade. A sensing mechanism related to the mixed potential was proposed for the present sensor.
