3DP rGO/diamane 微晶格气凝胶，用于增强型钠金属电池负极

摘要：金属钠阳极在高能量密度钠电池方面具有巨大潜力。然而，由于体积变化大和枝晶生长不可控，阻碍了其实际应用。为了解决这些问题，本文，郑州大学张壮飞副教授、Ye Wang、新加坡科技与设计大学Yang Hui Ying教授等在《ADVANCED SCIENCE》期刊

1成果简介

金属钠阳极在高能量密度钠电池方面具有巨大潜力。然而，由于体积变化大和枝晶生长不可控，阻碍了其实际应用。为了解决这些问题，本文，郑州大学张壮飞副教授、Ye Wang、新加坡科技与设计大学Yang Hui Ying教授等在《ADVANCED SCIENCE》期刊发表名为“3D Printed Sodiophilic Reduced Graphene Oxide/Diamane Microlattice Aerogel for Enhanced Sodium Metal Battery Anodes”的论文，研究采用直接墨水写入（DIW）三维打印（3DP）方法，构建了一种三维（3D）分层多孔亲水还原氧化石墨烯/二烷（rGO/diamane）微晶格气凝胶。

熔融 Na 扩散到 rGO/diamane 主机中，形成 Na@rGO/diamane 阳极，可提供 78.60 mAh cm-2 （1090.94 mAh g-1）的超高容量。得益于均匀的离子分布和均一分布的亲硅二元胺，Na@rGO/二元胺阳极实现了无树枝状沉积形态，在 1 mA cm-2 的条件下，1 mAh cm-2 的循环寿命超过 7200 h。此外，Na@rGO/二烷阳极还提高了在 60 °C高温下的长期稳定性，在 1 mA cm-2 和 1 mAh cm-2 的条件下可延长 400 小时的使用寿命。值得注意的是，当与 Na3V2(PO4)3@碳（NVP@C）阴极和 Na@rGO/diamane 阳极集成时，整个电池具有持续的使用寿命，可维持超过 2000 次循环，容量保持率达 95.72%。这项研究为应用二甘醇开发稳定、高性能的钠金属电池提供了新的视角。

2图文导读

图1、a) Schematic illustration of 3D printed rGO/diamane microlattice electrode with a hierarchical porous frame serves as sodium metal anode host. b) Binding energies of diamane-Na and graphene-Na calculated by DFT simulation.

图2、a) Schematic diagram of the synthesis processes of the 3DP Na@rGO/diamane anode. b,c) SEM and d) TEM images of 3DP rGO/diamane-30 microlattice aerogel. e) XRD patterns, f) N2 adsorption/desorption isotherms, and g) reduced storage modulus of 3DP rGO, rGO/diamane-10, 30, and 50 electrodes.

图3、Electrochemical performance evaluation of Na, 3DP Na@rGO, and Na@rGO/diamane anodes. a) Rate capabilities of the symmetric cells based on Na, 3DP Na@rGO, and Na@rGO/diamane anodes. Long-term Na deposition performance of the Na, 3DP Na@rGO, and Na@rGO/diamane anodes at b) 1 mA cm−2 with 1 mAh cm−2 and c) 5 mA cm−2 with 10 mAh cm−2. Inserts in b) are the related magnified voltage profiles at 10, 340, 1100, and 7250 h. d) Stripping curve to evaluate the specific capacity of 3DP Na@rGO/diamane anode at 2 mA cm−2. e) Comparison of representative electrochemical performance of carbon-based nanomaterials for Na metal anodes. f) EIS curves and g) corresponding diffusion coefficients of bare Na, 3DP Na@rGO, and Na@rGO/diamane electrodes after 10 cycles. h) Tafel curves of bare Na, 3DP Na@rGO, and Na@rGO/diamane electrodes.

图4、In-situ optical microscopy images of Na deposited on a) Na foil, b) 3DP Na@rGO, and c) Na@rGO/diamane electrodes at 5 mA cm−2 for 60 min. Surface current density distribution on d) Na, e) 3DP Na@rGO and f) 3DP Na@rGO/diamane anodes. XPS depth profiles of g) F 1s, h) O 1s, and i) C 1s of 3DP rGO/diamane electrode after 10 cycles at 2 mA cm−2 with 1 mAh cm−2. j) The content comparison of the organic and inorganic species at different depths.

图5、a) Deposition/stripping curves at different temperatures from 30 to 90 °C at 4 mA cm−2 with 4 mAh cm−2. b) Long-term cycling performance at 1 mA cm−2 with 1 mAh cm−2 at 60 °C. c) 3DP Na@rGO/diamane deposition morphology evolution measured by in-situ optical microscopy at 5 mA cm−2 for 1 h at 60 °C. d) High-resolution XPS: F 1s and C 1s profiles of the 3DP rGO/diamane electrode after 10 cycles at 60 °C. e) Schematic illustration of the 3DP Na@rGO/diamane anode with porous framework to enhance the performance of Na metal anode with a robust SEI layer.

图6、Electrochemical performance evaluation of 3DP NVP@C-rGO||3DP Na@rGO/diamane full cell. a) Schematic diagram. b) Rate capability. c) Cycling performance and corresponding CE at 1 C. d) Galvanostatic charge–discharge (GCD) curves at the 1st, 500th, 1000th, and 2000th cycles at 1 C. e) Cycling performance at 1 C with the corresponding CE at 60 °C. f) Performance comparison with various 2D nanomaterial-based Na metal batteries.

3小结

综上所述，利用 DIW 三维打印技术成功制备了分层 3DP rGO/二烷微晶格气凝胶，并将其用作 Na 金属阳极的宿主。3DP rGO/二烷烃微晶格气凝胶在宏观和微观层面都具有分层多孔结构，可显著扩大比表面积并降低局部电流密度。此外，均匀分布在 rGO 片材上的二元胺纳米片是引导 Na 金属成核和均匀沉积的活性位点，可实现无树枝状形态。凭借多孔性和亲电性的优势，3DP Na@rGO/diamane 阳极可提供 78.60 mAh cm-2 （1090.94 mAh g-1）的超高areal容量，并能在 1 mA cm-2 与 1 mAh cm-2 的条件下保持超过 7200 小时的稳定循环。它还能在 5 mA cm-2 和 10 mAh cm-2 条件下连续工作超过 1600 小时，这表明它在高电流密度和大面积容量条件下具有强大的稳定性。此外，3DP Na@rGO/diamane 即使在 60 °C 的较高工作温度下也能增强长期稳定性，在 1 mA cm-2 和 1 mAh cm-2 的条件下可维持 400 小时的循环寿命。最后，3DP NVP@C-rGO||3DP Na@rGO/diamane 全电池显示出超过 2000 次循环的超长循环寿命，并且在 1 C 下每循环 0.0027% 的低容量衰减率。

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