硬碳作為一種非晶態碳材料，其微觀結構具有無序分佈的類石墨層片、豐富的邊緣和表面缺陷以及獨特的納米孔洞結構。作為鈉離子電池負極材料時，硬碳在充放電過程中呈現出雙電壓區域特征：一個是在較寬電壓范圍的斜坡區（約1.1 V至0.1 V），另一個是低電壓范圍的平臺區（約0 .1 V至0 V）。由於平臺區容量對應的電壓與鈉金屬的沉積電位相近，硬碳在高電壓斜坡區與低電壓平臺區共存的儲鈉特征，使其被視為實現高功率快速充放電的一大挑戰。此外，鑒於硬碳材料結構上的復雜性和性能多樣性，關於其儲鈉的具體機制仍存在爭議，並未形成統一理論。截至目前，盡管硬碳負極在快充性能方面具有潛力，但在基於安時級規模電池的實際應用上，即能夠支持大電流快速充電且保持良好循環穩定性的鈉離子電池研究報道仍相對較少。
圖1 鈉離子電池快充性能與滿充態表面溫度
最近，中國科學院物理研究所/北京凝聚態物理國傢研究中心胡勇勝研究員、陸雅翔副研究員與荷蘭代爾夫特理工大學Marnix Wagemaker教授等合作，在基於硬碳負極的安時級鈉離子電池快充機制研究中取得進展。該研究團隊通過控制碳化溫度成功制備出具有不同微觀結構的硬碳球材料，並在Ah級圓柱型電池中進行評測。他們開發的26700型圓柱鈉離子電池，具備6.5C的快速充放電能力，能在約9分鐘內充滿83%的容量，並實現3000次連續充放電循環（100%充放電深度），滿充態電池表面溫度的峰值僅為44.3°C左右。這種電池所采用的硬碳負極，通過其精準納米楔形孔的設計（~1 nm孔徑），展示了優異的快充性能和高面積容量（約2.2 mAh/cm²），同時避免了金屬鈉的析出問題。
圖2 鋰/鈉在硬碳中存儲的電化學曲線
該研究引入鋰作為“探針”比較研究硬碳的儲鋰和儲鈉行為，通過過放電實驗獲得形核過電勢之前未被充分認識的容量，發現了鋰鈉電化學行為的異同：即兩者在0 V以下都有隱藏的平臺容量，儲鋰隱藏的容量更多，原因在於嵌鈉相對於嵌鋰約有30-40 mV略正的平臺電位。之後分別研究了斜坡區和平臺區的儲鋰和儲鈉行為。
對斜坡區而言，發現Li和Na的斜坡容量比為1.8，這與文獻統計的結果一致。同時我們註意到鈉離子和鋰離子的投影面積比例也恰好為1.8，這預示著Li和Na在斜坡區的存儲活性位點相同。通過DFT模擬Li/Na在石墨層邊緣的吸附，發現無論是鋰還是鈉，都傾向於選擇相同的吸附位點。由於Li離子尺寸較小，在同樣的表面區域，可容納更多。之後我們采用程序升溫脫附結合質譜（TPD-MS）技術量化碳缺陷濃度，根據活性表面積計算出的斜坡區貢獻容量與實驗數據相符。這些都證實了斜坡區容量對應Li/Na在相同缺陷位點的吸附。
圖3 硬碳負極存儲機制的定量化分析
對平臺區而言，構建楔形孔模型模擬出電壓曲線。發現鈉化開始於邊緣和空位等缺陷，之後為孔隙填充階段，每層碳內表面與1-2層Na層接觸。根據DFT優化的Na-Na和Li-Li平均距離（3.57 Å和2.84 Å），以及平臺容量與封閉孔體積呈正相關，成功預測了鋰、鈉的平臺容量。Bader電荷分析顯示完全鈉化狀態下約20%價電子轉移至碳基質，說明鈉以準金屬狀態存在；盡管鋰與鈉的反應路徑相似，但能夠適應更小的孔徑。聯苯-DME化學探針和電子順磁共振測試進一步證實了封閉孔內鋰、鈉處於準金屬態而非金屬態。分子動力學模擬顯示，在納米尺度上，楔形孔內鈉層對擴散無明顯阻礙，兩個鈉原子可在1-3皮秒時間內協同形成偶極子並進行快速單向運動，表明在當前結構下快速擴散的可能性。
圖4 納米楔形孔的動力學分析
該研究還揭示了孔隙尺寸對硬碳材料中儲鈉和儲鋰性能的關鍵作用，指出理想的孔徑大小約在1 nm左右，有利於減少負極表面暴露引發的能量損耗，並能有效促進快速充電過程。類似於欠電位沉積（UPD）機制，在孔隙內部形成的2-3層鈉原子或3-4層鋰原子的吸附結構，能夠與碳基底發生相互作用，從而降低系統的能量勢壘，實現接近零沉積電位的理想狀態。這種微觀結構特征確保了在電化學反應過程中硬碳與堿金屬離子間形成穩定的接觸界面，進而闡明了硬碳作為高性能、快充型鈉離子電池負極材料的內在機制。
該研究工作不僅展示了基於無定形碳負極的安時級鈉離子電池的快充特性，還明晰了鈉在無定形碳中的存儲位置、存儲狀態和擴散方式問題，為低成本、高性能鈉離子電池碳負極材料的設計制備打下了堅實的科學基礎。
相關研究成果以“Origin of fast charging in hard carbon anodes”為題發表在國際能源領域頂級期刊Nature Energy上。中國科學院物理研究所李鈺琦博士為該論文第一作者，中國科學院物理研究所胡勇勝研究員，陸雅翔副研究員和荷蘭代爾夫特理工大學Wagemaker教授為共同通訊作者。
編輯：7號機
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(min-width:1024px){body:not(.pages_skin_pc) .wx-root,body:not(.pages_skin_pc) body{--appmsgExtra-BG: #F7F7F7}}@media screen and (min-width:1024px){body:not(.pages_skin_pc) .wx-root[data-weui-theme=dark],body:not(.pages_skin_pc) body[data-weui-theme=dark]{--weui-BG-0: #111;--weui-BG-1: #1e1e1e;--weui-BG-2: #191919;--weui-BG-3: #202020;--weui-BG-4: #404040;--weui-BG-5: #2c2c2c;--weui-FG-0: rgba(255, 255, 255, .8);--weui-FG-HALF: rgba(255, 255, 255, .6);--weui-FG-1: rgba(255, 255, 255, .5);--weui-FG-2: rgba(255, 255, 255, .3);--weui-FG-3: rgba(255, 255, 255, .1);--weui-FG-4: rgba(255, 255, 255, .15);--weui-FG-5: rgba(255, 255, 255, .1);--weui-RED: #fa5151;--weui-ORANGERED: #ff6146;--weui-ORANGE: #c87d2f;--weui-YELLOW: #cc9c00;--weui-GREEN: #74a800;--weui-LIGHTGREEN: #3eb575;--weui-BRAND: #07c160;--weui-BLUE: #10aeff;--weui-INDIGO: #1196ff;--weui-PURPLE: #8183ff;--weui-WHITE: rgba(255, 255, 255, .8);--weui-LINK: #7d90a9;--weui-TEXTGREEN: #259c5c;--weui-FG: #fff;--weui-BG: #000;--weui-TAG-TEXT-RED: rgba(250, 81, 81, .6);--weui-TAG-BACKGROUND-RED: rgba(250, 81, 81, .1);--weui-TAG-TEXT-ORANGE: rgba(250, 157, 59, .6);--weui-TAG-BACKGROUND-ORANGE: rgba(250, 157, 59, .1);--weui-TAG-TEXT-GREEN: rgba(6, 174, 86, .6);--weui-TAG-BACKGROUND-GREEN: rgba(6, 174, 86, .1);--weui-TAG-TEXT-BLUE: rgba(16, 174, 255, .6);--weui-TAG-BACKGROUND-BLUE: rgba(16, 174, 255, .1);--weui-TAG-TEXT-BLACK: rgba(255, 255, 255, .5);--weui-TAG-BACKGROUND-BLACK: rgba(255, 255, 255, .05)}}@media screen and (min-width:1024px){body:not(.pages_skin_pc) .wx-root[data-weui-theme=dark],body:not(.pages_skin_pc) body[data-weui-theme=dark]{--appmsgExtra-BG: #121212}}@media screen and (min-width:1024px){body:not(.pages_skin_pc)body:not(.pages_skin_pc){background:#191919;background:var(--weui-BG-2)}}@media screen and (min-width:1024px) and (prefers-color-scheme:nodark){body:not(.pages_skin_pc) .wx-root[data-weui-mode=care]:not([data-weui-theme=light]),body:not(.pages_skin_pc) 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.1);--weui-TAG-TEXT-GREEN: rgba(6, 174, 86, .6);--weui-TAG-BACKGROUND-GREEN: rgba(6, 174, 86, .1);--weui-TAG-TEXT-BLUE: rgba(16, 174, 255, .6);--weui-TAG-BACKGROUND-BLUE: rgba(16, 174, 255, .1);--weui-TAG-TEXT-BLACK: rgba(255, 255, 255, .5);--weui-TAG-BACKGROUND-BLACK: rgba(255, 255, 255, .05)}}@media screen and (min-width:1024px) and (prefers-color-scheme:nodark){body:not(.pages_skin_pc) .wx-root:not([data-weui-theme=light]),body:not(.pages_skin_pc) body:not([data-weui-theme=light]){--weui-BG-0: #111;--weui-BG-1: #1e1e1e;--weui-BG-2: #191919;--weui-BG-3: #202020;--weui-BG-4: #404040;--weui-BG-5: #2c2c2c;--weui-FG-0: rgba(255, 255, 255, .8);--weui-FG-HALF: rgba(255, 255, 255, .6);--weui-FG-1: rgba(255, 255, 255, .5);--weui-FG-2: rgba(255, 255, 255, .3);--weui-FG-3: rgba(255, 255, 255, .1);--weui-FG-4: rgba(255, 255, 255, .15);--weui-FG-5: rgba(255, 255, 255, .1);--weui-RED: #fa5151;--weui-ORANGERED: #ff6146;--weui-ORANGE: #c87d2f;--weui-YELLOW: #cc9c00;--weui-GREEN: #74a800;--weui-LIGHTGREEN: #3eb575;--weui-BRAND: #07c160;--weui-BLUE: #10aeff;--weui-INDIGO: #1196ff;--weui-PURPLE: #8183ff;--weui-WHITE: rgba(255, 255, 255, .8);--weui-LINK: #7d90a9;--weui-TEXTGREEN: #259c5c;--weui-FG: #fff;--weui-BG: #000;--weui-TAG-TEXT-RED: rgba(250, 81, 81, .6);--weui-TAG-BACKGROUND-RED: rgba(250, 81, 81, .1);--weui-TAG-TEXT-ORANGE: rgba(250, 157, 59, .6);--weui-TAG-BACKGROUND-ORANGE: rgba(250, 157, 59, .1);--weui-TAG-TEXT-GREEN: rgba(6, 174, 86, .6);--weui-TAG-BACKGROUND-GREEN: rgba(6, 174, 86, .1);--weui-TAG-TEXT-BLUE: rgba(16, 174, 255, .6);--weui-TAG-BACKGROUND-BLUE: rgba(16, 174, 255, .1);--weui-TAG-TEXT-BLACK: rgba(255, 255, 255, .5);--weui-TAG-BACKGROUND-BLACK: rgba(255, 255, 255, .05)}}@media screen and (min-width:1024px) and (prefers-color-scheme:nodark){body:not(.pages_skin_pc) .wx-root:not([data-weui-theme=light]),body:not(.pages_skin_pc) body:not([data-weui-theme=light]){--appmsgExtra-BG: 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