隨著再生能源的蓬勃發展與電動車的普及，電池技術的開發尤為重要，其中鋰金屬電池(Lithium Metal Batteries， LMB)因具備最高理論容量(3860 mAh/g)與最低還原電位(-3.04 V 與標準氫電極相比)而備受關注，然而鋰金屬的固有特性導致其在充放電過程中，容易因為不均勻的鋰沉積而形成枝晶，這不僅會造成嚴重的容量衰減，長期運行後更可能引發安全問題。近期研究指出，將人工固體電解質界面膜（Artificial Solid Electrolyte Interphase，ASEI）引入三維鋰載體(Lithium host)中是一項極具前景的策略。相較於單一功能的改善，這種雙功能的引導機制能顯著增強界面穩定性，有效抑制枝晶生長，進而提升電化學性能。 本論文分成三個部分(1) 噴塗法製備氟化石墨烯球的三維結構：為進一步擴大鋰的儲存空間並建構高效的鋰離子傳輸通道，本研究採用噴塗法製備純氟化石墨烯球三維結構。相較於前期研究所採用的電泳沉積法，由於純氟化石墨烯球難以均勻沉積於銅箔表面，需搭配片層輔助沉積，而本研究利用噴塗法則可有效將純氟化石墨烯球均勻塗覆於銅箔表面，成功構築三維結構。其結果顯示氟化石墨烯球的含量越多(Spray-H)，可提供更大的鋰儲存空間及更多鋰離子傳輸路徑，可實現超過400小時的循環壽命並於第 215 次循環時仍維持 88.47 %的庫倫效率。(2)適中氧含量下不同F/N比對氮氟共摻雜石墨烯的協同效應：在先前實驗室的工作中，我們已經初步討論氧含量對於氮氟共摻雜石墨烯的影響，其中我們發現適中氧含量下可以生成較多的Li2O，有效降低成核過電位及較佳的循環穩定性，本研究將接續此部分，探討在適中氧含量下不同F/N比對氮氟共摻雜石墨烯的協同效應，結果顯示，高氮含量促進Li3N的生成，降低成核過電位至62 mV，與最低的總介面阻抗(541.4 Ω)，顯示Li3N能有效改善鋰離子的傳輸，低氮含量則因保有FG基材表面片層間的結合力以及優化的F/N比例，該比例使得SEI層在機械強度(LiF)和Li⁺傳輸(Li3N)之間達到良好的平衡，在循環表現中能穩定超過450小時，第 257 圈的庫倫效率達 93.8%，且修飾層的厚度變化（~4.83 μm）與膨脹率（46.36 %）均為最低。全電池測試(NMC-622//FOMNL)中，第30 次循環後比容量仍超過150 mAh/g，於40 次循環後容量保持率為62 %。(3)梯度結構於雙功能陽極修飾層之研究：本研究採用兩階段製程成功製備梯度結構，並藉由循環前SEM觀察證實梯度結構已成功建構。接著度分析結果顯示，利用EPD沉積FG可獲得良好的接著強度，其中Cu/Au/FG和Cu/Bi/FG的剝離強度分別為2.7 N cm⁻¹和2.9 N cm⁻¹。此外於半電池的測試中顯示，單層金屬擁有最低的成核過電位(Au~49.2 mV、Bi~58.2 mV)，顯示不論是Au與Bi接有良好的親鋰性，其中Bi的梯度結構擁有最佳的循環穩定性(在126 圈時庫倫效率為70.99 %)，顯示梯度結構由下層Bi提供良好的親鋰性，可降低鋰成核能障並引導均勻鋰沉積；上層FG則可作為保護層，降低Bi於長時間循環過程中的流失與劣化，使親鋰性金屬得以持續發揮作用。同時，Bi的導入亦彌補了純FG親鋰性不足的缺點。;With the rapid development of renewable energy and the widespread adoption of electric vehicles， the development of advanced battery technologies has become increasingly important. Among various energy storage systems，lithium metal batteries (LMB) have attracted significant attention because of their ultrahigh theoretical capacity (3860 mAh g⁻¹) and the lowest reduction potential (−3.04 V vs. the standard hydrogen electrode). However， the intrinsic properties of lithium metal often lead to non-uniform lithium deposition during cycling， resulting in lithium dendrite growth. This not only causes severe capacity fading but also raises serious safety concerns during long-term operation. Recently， introducing an artificial solid electrolyte interphase (ASEI) into a three-dimensional lithium host has been considered a promising strategy. Compared with a single-function design， this dual-functional approach can significantly improve interfacial stability， effectively suppress dendrite growth， and enhance the overall electrochemical performance. This study is divided into three parts:(1)3D fluorinated graphene ball structure fabricated by spray coating: To further enlarge the lithium storage space and construct efficient lithium-ion transport pathways， a 3D F-ball structure was fabricated using a spray-coating method.Compared with the electrophoretic deposition (EPD) method adopted in previous studies， where pure F-ball could not be uniformly deposited on the Cu foil without the assistance of graphene sheets， the spray-coating method enabled homogeneous deposition of pure FG spheres onto the Cu substrate， successfully constructing a three-dimensional architecture. The results indicate that a higher F-ball content (Spray-H) provides a larger lithium storage space and more lithium-ion transport pathways， achieving a stable cycling life exceeding 400 h while maintaining a Coulombic efficiency of 88.47% after 215 cycles.(2) Synergistic effect of different F/N ratios in N、F co-doped graphene under moderate oxygen content: In our previous work， the influence of oxygen content on N、F co-doped graphene was preliminarily investigated， and it was found that a moderate oxygen content promoted the formation of Li₂O， thereby reducing the nucleation overpotential and improving cycling stability. Building upon this work， the present study further investigated the synergistic effects of different F/N ratios under moderate oxygen content. The results reveal that a higher nitrogen content promotes the formation of Li₃N， reducing the nucleation overpotential to 62 mV and achieving the lowest total interfacial resistance (541.4 Ω)， indicating that Li₃N effectively facilitates lithium-ion transport. In contrast， the low-nitrogen sample preserved the interlayer bonding of the FG framework and maintained an optimized F/N ratio， enabling the SEI to achieve an optimal balance between mechanical strength provided by LiF and lithium-ion conductivity provided by Li₃N. Consequently， this sample exhibited the best cycling performance， sustaining stable cycling for over 450 h with a Coulombic efficiency of 93.8% after 257 cycles. In addition， it exhibited the smallest coating thickness variation (~4.83 μm) and the lowest expansion ratio (46.36%). In full-cell tests using an NMC-622 cathode (NMC-622//FOMNL)， the discharge capacity remained above 150 mAh g⁻¹ after 30 cycles， with a capacity retention of 62% after 40 cycles.(3)Gradient structure for a dual-functional anode modifier:In this study， a gradient structure was successfully fabricated through a two-step process， and its successful construction was confirmed by pre-cycling SEM observations. Adhesion analysis demonstrated that the EPD of FG provided excellent adhesion strength， with peel strengths of 2.7 and 2.9 N cm⁻¹ for the Cu/Au/FG and Cu/Bi/FG electrodes， respectively. Half-cell measurements further revealed that the single-metal interlayers exhibited the lowest nucleation overpotentials (Au: ~49.2 mV; Bi: ~58.2 mV)， indicating the excellent lithiophilicity of both Au and Bi. Among the gradient-structured electrodes， the Bi-based gradient structure exhibited the best cycling stability， achieving a Coulombic efficiency of 70.99% after 126 cycles. These results indicate that the bottom Bi interlayer provides superior lithiophilicity， effectively reducing the Li nucleation energy barrier and promoting uniform Li deposition， while the top FG layer serves as a protective layer that suppresses the loss and degradation of Bi during prolonged cycling， thereby enabling the lithiophilic metal to maintain its functionality. Furthermore， the incorporation of Bi compensates for the insufficient lithiophilicity of pristine FG.
