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通过疏水相互作用增强的快速镁离子传导性异丙胺硼氢化镁

Fast magnesium ion conducting isopropylamine magnesium borohydride enhanced by hydrophobic interactions.

作者信息

Kristensen Lasse G, Amdisen Mads B, Skov Lasse N, Jensen Torben R

机构信息

Interdisciplinary Nanoscience Center (iNANO) and Department of Chemistry, University of Aarhus, Langelandsgade 140, DK-8000 Aarhus C, Denmark.

出版信息

Phys Chem Chem Phys. 2022 Aug 3;24(30):18185-18197. doi: 10.1039/d1cp05063j.

Abstract

New materials for the next generation of electrochemical energy storage devices such as batteries are of extreme importance. Here we investigate the structure, ionic conductivity and thermal properties of isopropylamine magnesium borohydride based composites with different compositions, Mg(BH)·(CH)CHNH, = 0.5, 0.9, 1.25, 1.5, 1.75, 2.5, 3.1. Three new compounds are discovered, = 1, 2, and 3 and the monoclinic structure of Mg(BH)·2(CH)CHNH (2/) is investigated in detail. This structure consists of neutral complexes [Mg(BH)((CH)CHNH)] di-hydrogen bonded to form layers and these layers are connected by hydrophobic interactions the isopropyl moieties. The orthorhombic unit cell of Mg(BH)·(CH)CHNH was also determined, = 9.78, = 12.17 and = 17.24 Å. In general, the samples are thermally stable up to 50 °C where they started to become softer, and at 70 °C isopropylamine release and melting started. The highest Mg ionic conductivity was that of Mg(BH)·1.5(CH)CHNH, (Mg) = 2.7 × 10 S cm at 45 °C, with an activation energy of = 1.22 eV. Furthermore, reversible stripping/plating of Mg was displayed at 45 °C, with an oxidative stability of 1.2 V Mg/Mg. The addition of MgO nanoparticles (75 wt%) improves the mechanical and thermal stability, and decreases the activation energy, to = 0.56 eV. Thereby the Mg conductivity is increased at low temperature. This suggests that the hydrophobic interactions contribute to the high ionic conductivity in the solid state, which opens a new avenue for design and discovery of electrolyte materials.

摘要

用于下一代电化学储能设备(如电池)的新材料至关重要。在此,我们研究了不同组成的异丙胺硼氢化镁基复合材料Mg(BH₄)ₓ·(C₃H₇NH₂)ₙ(x = 0.5、0.9、1.25、1.5、1.75、2.5、3.1)的结构、离子电导率和热性能。发现了三种新化合物,x = 1、2和3,并详细研究了Mg(BH₄)₂·2(C₃H₇NH₂)(2/1)的单斜结构。该结构由中性络合物[Mg(BH₄)(C₃H₇NH₂)]通过双氢键形成层状结构,这些层通过异丙基部分的疏水相互作用相连。还确定了Mg(BH₄)·(C₃H₇NH₂)的正交晶胞,a = 9.78、b = 12.17和c = 17.24 Å。一般来说,样品在高达50°C时热稳定,此时它们开始变软,在70°C时异丙胺开始释放和熔化。最高的Mg离子电导率是Mg(BH₄)·1.5(C₃H₇NH₂)的,在45°C时σ(Mg) = 2.7 × 10⁻³ S cm⁻¹,活化能Eₐ = 1.22 eV。此外,在45°C时显示出Mg的可逆脱嵌/沉积,氧化稳定性为1.2 V vs Mg/Mg²⁺。添加75 wt%的MgO纳米颗粒提高了机械和热稳定性,并将活化能降低至Eₐ =

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