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摘要: 鈉金屬因其成本低、自然豐度高、氧化還原電位低和理論比容量高等優點,被認為是高能電池的理想負極材料。然而,鈉金屬在充放電過程中易發生體積膨脹和產生鈉枝晶,導致電池性能不斷惡化,并引發安全隱患,嚴重阻礙了鈉金屬電池在實際中的應用。為了解決上述問題,國內外已進行了大量探索。其中,構建三維導電載體可以有效降低局部電流密度和成核能,抑制枝晶生長和減緩體積膨脹,在未來應用方面具有巨大的潛力。本文綜述了近年來利用三維導電載體來提高鈉金屬負極電化學循環穩定性的研究進展并對三維導電載體進行了總結和分類。最后,從基礎研究和實際應用兩個方面討論了三維導電載體材料在鈉金屬負極中的發展前景和未來研究方向。Abstract: Sodium is considered an ideal anode material for high-energy batteries because of its low cost, high natural abundance, low redox potential (?2.71 V vs SHE), and high theoretical specific capacity (1166 mA·h·g?1). However, due to the high reactivity, sodium rapidly reacts with the electrolyte to form an unstable solid electrolyte interface (SEI) layer during stripping/plating cycling. In addition, due to the large size change of sodium, the SEI layer repeatedly breaks and reassembles, resulting in the continuous consumption of sodium and electrolyte, as well as low coulombic efficiency and rapid capacity loss. Simultaneously, due to an uneven electric field distribution on sodium, numerous sodium dendrites generate during the repeated plating/stripping cycles. The growing Na dendrites easily pierce the separator, causing a short circuit and a series of safety issues. The above issues lead to the deterioration of battery performance and safety risks, thus considerably hindering the application of sodium metal batteries. Various studies have been conducted to solve these issues, including electrolyte engineering, artificial SEI layers, current collector and interlayer engineering, solid-state electrolyte engineering, and three-dimensional (3D) frameworks for sodium metal. Among various improvement strategies, the construction of a 3D conductive framework can effectively reduce the local current density, decrease nuclear energy, inhibit Na dendrite growth, and impede volume expansion, thus having a great potential in future applications. In this study, the current research progress in using various 3D conductive frameworks to improve the cycling stability of a sodium metal battery is reviewed, including carbon-based, metal-based, and MXene-based frameworks. Simultaneously, the pros and cons of different 3D conductive framework technologies in recent years are summarized and classified, and the electrochemical performance parameters of different 3D conductive frameworks for sodium metal batteries are compared. Finally, the development prospect and direction of 3D conductive frameworks in sodium metal anodes are discussed from basic research and practical applications. This review provides deeper insights into building more comprehensive and efficient sodium metal anodes. The 3D conductive framework technology can remarkably improve the cycle life and safety of a sodium metal battery. Multistrategy joint research methods will facilitate the practical applications of a sodium metal battery. Further exploration of the deposition behavior of sodium metal is required in the future, and we believe that it can definitely achieve commercial applications with continuous efforts.
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Key words:
- sodium metal battery /
- anode /
- Na dendrite /
- volume expansion /
- three-dimensional conductive framework
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圖 1 (a) Na@rGO復合負極的合成過程示意圖[54]; (b) Na@rGO的表面SEM圖像[54]; (c) Na/Na和Na@rGO/Na@rGO 對稱電池的恒流充放電循環[54]; (d) Cu箔、rGO和PRGO薄膜上Na金屬的沉積示意圖[56]; (e) Na金屬在PRGO薄膜上沉積的力學模擬[56]; (f) 在1 mA·cm?2、1 mA·h·cm?2條件下,三種不同載體對稱電池的恒流充放電循環[56]
Figure 1. (a) Schematic of the preparation of Na@rGO composites[54]; (b) top-view SEM images of Na@rGO[54]; (c) galvanostatic cycling of symmetric Na/Na and Na@rGO/Na@rGO cells after 300 cycles[54]; (d) schematic of Na nucleation and growth on Cu foil, planar rGO film, and flexible PRGO film, respectively[56]; (e) tension schematics for Na plating on PRGO films through mechanical simulation[56]; (f) symmetric cell patterns of Na plating on three matrices with the capacity limitation of 1 mA·h·cm?2 at the current density of 1 mA·cm?2[56]
圖 2 (a) 氮摻雜石墨烯立方體 (PN-G) 復合結構的制備示意圖[58]; (b) 鈉在NG-NF電極上的成核和生長過程,以及在1 mA·cm?2、1 mA·h·cm?2條件下,Na、BNF@Na和NGNF@Na對稱電池的恒電流充放電曲線[59]; 鈉金屬在 (c) rGO載體和 (d) NaF/SnO2@rGO載體的沉積示意圖[60]
Figure 2. (a) Schematic of N-doped graphene microcube (PN-G) preparation[58]; (b) schematic of the Na nucleation and growth process on the NG-NF electrode and voltage profiles of Na plating/stripping in three symmetric cells (Na foil, BNF@Na, and NGNF@Na cells) at 1 mA·cm?2 for 1 mA·h·cm?2 [59]; schematic of the Na deposition process: (c) nonuniform or irregular growth of Na metal on rGO or scaffolds; (d) guided uniform Na plating in NaF/SnO2@rGO[60]
圖 3 (a) 通過3D打印制備的NVP@C-rGO正極/Na@rGO/CNT負極的全電池示意圖[61]; (b) 全電池在電流密度為電流密度為100 mA·g?1時的循環性能[61]; (c) Na@rGO/CNT電極在電流密度為2 mA·cm?2、容量為1 mA·h·cm?2時的恒電充放曲線上[62]; (d)裸鈉和CNT-Na復合電極上的初始鈉成核示意[62]; (e)裸鈉和CNT-Na對稱電池的恒電流循環曲線 (1 mA·h·cm?2, 0.5 mA·cm?2)[62]
Figure 3. (a) Schematic of the 3D-printed microlattice sodium ion full batteries with NVP@C-rGO as the cathode and Na@rGO/CNT as the anode[61]; (b) cycling performance at a current density of 100 mA·g?1[61]; (c) cycling performance of the Na@rGO/CNT electrodes at a high current density of 2 mA·cm?2 with a capacity limitation of 1 mA·h·cm?2[62]; (d) schematic of initial Na nucleation on bare Na and CNT-Na composite electrodes; (e) galvanostatic cycling profiles of the Na/Na symmetric cells with bare Na and CNT-Na electrodes (1 mA·h·cm?2, 0.5 mA·cm?2) [62]
圖 4 (a) 鈉金屬在Na/NSCNT負極上的沉積示意圖[63]; (b) 鈉與Al、Cu、CNT、NCNT、SCNT、NSCNT的結合能(Eb)[63]; (c) 電流密度為0.05 mA·cm?2時,不同集流體的初始成核能[63]; (d) 在電流密度為1 mA·cm?2、沉積容量為1 mA·h·cm?2時,Cu、Al、CNT和NSCNT的庫侖效率[63]; (e) 在Of?CNT載體中,鈉金屬均勻沉積示意圖[64]
Figure 4. (a) Schematic of the Na striping/plating on the Na/NSCNT anode[63]; (b) binding energies of Na atoms with Al, Cu, CNT, NCNT, SCNT, and NSCNT[63]; (c) the potential-capacity profiles during Na nucleation on different current collectors at a current density of 0.05 mA·cm?2[63]; (d) coulombic efficiencies of Na plating/stripping on Cu foil, Al foil, CNT paper, and NSCNT paper at a current density of 1 mA·cm?2 with a capacity of 1 mA·h·cm?2 [63]; (e) schematic of the Na striping/plating on Of?CNT skeleton[64]
圖 5 (a) 鈉-碳氈 (Na/C)復合電極的制備[67]; (b) 鈉金屬在Cu、純泡沫鎳 (CNF) 和D-HCF電極上的初始成核能[71]; (c) 不同電流密度下D-HCF的初始成核能[71]; (d,e) 8.0 mA·h·cm?2的鈉金屬沉積在Cu箔和D-HCF上的光學照片[71];(f) 利用生物質廢棄椰衣制備3D O-CCF載體的示意圖[19]; (g) 金屬鈉封裝在碳納米薄片中的示意圖[76]; (h) 鈉金屬沉積后石墨化碳微球的SEM圖像[76]; (i) Au/CF載體的制備示意圖[77]
Figure 5. (a) Fabrication of the Na/C composite anode[67]; (b) the initial voltage profiles on planar Cu, pure nickel foam (CNF), and D-HCF electrode[71]; (c) the initial voltage profiles on D-HCF at various current densities [71]; optical photos of Na deposition on (d) planar Cu and (e) D-HCF with an aerial loading of 8.0 mA·h·cm?2[71]; (f) fabrication schematic of 3D O-CCF matrix from biomass waste coconut coat[19]; (g) schematic of the encapsulated Na configuration where most nanoscale metallic Na is embedded inside the graphitized nanosheets[76]; (h) SEM image of the GCMs after Na deposition[76]; (i) fabrication schematic of the Au/CF host[77]
圖 6 (a)鈉金屬在CuNW-Cu上循環沉積示意圖[80]; (b) 裸泡沫銅和CuNW-Cu的首次充放電曲線[80]; (c)全電池充放電示意圖[80]; (d) 3D Ni@Cu中鈉金屬的沉積示意圖[79]
Figure 6. (a) Schematic of the Na plating processes on the CuNW-Cu substrate[80]; (b) first charge?discharge profiles of bare Cu foam and CuNW-Cu[80]; (c) illustration of completely charged and discharged states of the full cells[80]; (d) schematic of the Na plating process on 3D Ni@Cu[79]
圖 7 (a) 鈉金屬在CF@ZnO上的成核和沉積過程[82]; (b) CF@ZnO界面局部電流密度分布的多物理場仿真模擬[82]; (c) 鈉在Na15Sn4上的電荷密度[82]; (d) 鈉在純Na、Na2O和Na15Sn4上的結合能[83]; (e) 鈉金屬在Na-Sn合金/Na2O載體上的沉積/溶解示意圖[83]; (f) Na在CNF上的沉積示意圖[75]
Figure 7. (a) Schematic of the Na nucleation and deposition processes on CF@ZnO[82]; (b) COMSOL simulation of the local current density distribution at the substrate/electrolyte interface of CF@ZnO[82]; (c) charge density for Na on Na15Sn4[82]; (d) bar chart on the summary of the calculated binding energy of Na on pure Na, Na2O, and Na15Sn4[83]; (e) Na stripping and plating process on the Na–Sn alloy/Na2O framework[83]; (f) schematic of Na stripping/plating on CNF[75]
圖 8 (a) h-Ti3C2/CNTs的合成示意圖[84]; (b) 鈉原子與碳原子 (CNTs)、氧原子 (h-Ti3C2O) 和氟原子 (h-Ti3C2F)的結合能[84]; (c) 鈉在Cu、CNTs和h-Ti3C2/CNTs載體上的初始成核能[84]; (d) Na//O2電池示意圖[84]; (e) 鈉金屬在CT-Sn(II)@Ti3C2載體上的成核和沉積示意圖[86]; (f) Na3V2(PO4)3//CT-Sn(II)@ Ti3C2/Na全電池示意圖[86]; (g) CT-Sn(II)@Ti3C2對稱電池的倍率性能[86]; (h) Na3V2(PO4)3/Na和Na3V2(PO4)3/CT-Sn(II)@Ti3C2/Na全電池在1C條件下的循環性能[86]
Figure 8. (a) Synthesis of h-Ti3C2/CNTs[84]; (b) corresponding binding energies of a Na atom with C atom (CNTs), O atom (h-Ti3C2O), and F atom (h-Ti3C2F) [84]; (c) nucleation overpotentials for Na plating on Cu, CNTs, and h-Ti3C2/CNTs hosts (at 1 mA·cm?2) [84]; (d) graph of the Na//O2 battery[84]; (e) schematics for the comparison of Na nucleation and deposition in CT-Sn(II)@Ti3C2 matrixes[84]; (f) full-cell configurations of Na3V2(PO4)3//CT-Sn(II)@Ti3C2/Na cells[86]; (g) rate performance of the CT-Sn(II)@Ti3C2 symmetric cell[86]; (h) cycling performance of Na3V2(PO4)3//bare Na and Na3V2(PO4)3//CT-Sn(II)@Ti3C2/Na cells at 1C[86]
表 1 使用不同3D導電載體的鈉金屬電池(SMBs) 的電化學性能
Table 1. Electrochemical performance parameters of different 3D conductive frameworks for SMBs
Ref. Materials Electrolyte Current density/ Capacity/ Time/ Coulombic efficiency/% (mA·cm?2) (mA·h·cm?2) h 19 O-CCF NaPF6 in diglyme 5 5 4000 99.80 54 Na@rGO NaPF6 in diglyme 1 1 600 56 PRGO NaPF6 in EC/DMC 1 1 1000 99.50 58 PN-G NaClO4 in EC/PC 5 3 600 59 NG-NF NaPF6 in diglyme 0.5 1 800 >99 60 NaF/SiO2@rGO NaSO3CF3 in diglyme 1 0.5 3000 99.87 61 rGO/CNT NaPF6 in diglyme 1 1 800 99.50 62 CNT-Na NaClO4 in EC/DMC 0.5 1 700 63 NSCNT NaSO3CF3 in diglyme 1 1 500 99.80 64 Of-CNTs NaPF6 in diglyme 1 1 4000 67 Na/C NaClO4 in EC/PC 1 2 27000 71 D-HCF NaSO3CF3 in diglyme 0.5 1 700 77 Au/CF NaCF3SO3 in diglyme 2 1 1000 99.50 80 CuNW-Cu NaPF6 in diglyme 1 2 1400 97.50 82 CF@ZnO NaPF6 in diglyme 1 3 500 99.50 83 Na-Sn alloy/Na2O NaClO4 in EC/PC 1 1 160 84 h-Ti3C2/CNTs NaCF3SO3 in diglyme 1 1 4000 99.20 86 CT-Sn(II)@Ti3C2 NaPF6 in diglyme 4 4 500 83.70 www.77susu.com -
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