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广东工业大学/广州大学Small:高熵掺杂协同MXene构筑超稳定高倍率钠硒电池阴极材料

  • 2026-03-14 08:00:12
广东工业大学/广州大学Small:高熵掺杂协同MXene构筑超稳定高倍率钠硒电池阴极材料
【研究背景】
随着可再生能源存储与便携电子技术的发展,对低成本、高性能储能系统的需求日益迫切。钠离子电池因钠资源丰富、成本低廉,成为替代锂离子电池的重要方向。其中,钠硒电池因其高理论容量和良好导电性备受关注,但其实际应用受限于多硒化物穿梭效应和缓慢的反应动力学。为解决这些问题,研究者常将硒限制于多孔碳或极性宿主材料中,但如何在提升导电性的同时增强对多硒化物的化学吸附与催化转化能力,仍是当前研究的核心挑战。
【文章概述】
2026年1月8日,广东工业大学孙志鹏教授/史晓艳副教授及广州大学王家海教授等在期刊Small上发表了题为“Ultrastable and High-Rate Sodium Storage Enabled by High-Entropy Doping in HE-Fe3Se4/Se/MXene Composites”的研究论文。本研究通过高熵掺杂与MXene导电骨架的协同设计,成功构建了高性能的HE‑Fe₃Se₄/Se/MXene复合阴极材料。采用原位生长高熵普鲁士蓝类似物于MXene表面,并通过硒化处理制备最终复合材料。该材料不仅通过高熵掺杂调控电子结构、增强导电性与反应活性位点,还借助MXene的导电网络与机械支撑作用抑制体积应变。实验表明,该复合材料在钠硒电池中表现出优异的倍率性能与循环稳定性,为高功率、长寿命钠硒电池的开发提供了新思路。
【图文导读】

图1:HE‑Fe₃Se₄/Se/MX复合材料的合成路径与物相表征

图1a展示了复合材料的分步合成策略:首先在MXene上原位生长高熵普鲁士蓝类似物(HE‑PBA),随后经高温硒化转化为HE‑Fe₃Se₄/Se/MX。XRD图谱(图1b)显示高熵前驱体硒化后形成Fe₃Se₄与单质Se两相共存,而低熵样品中Se含量显著降低,说明高熵掺杂促进Se的嵌入与稳定。Raman光谱(图1c)中位于261.5 cm⁻¹的峰证实了无定形Se链的存在,且HE‑Fe₃Se₄/Se/MX的峰强最高,与其最高Se负载量一致。TGA曲线(图1d)定量显示Se含量随高熵掺杂与MXene引入逐步提升,进一步验证了高熵结构对Se的稳定作用。

图2:复合材料的微观形貌与元素分布

SEM图像显示(图2a‑c),低熵样品呈不规则团聚颗粒(≈100 nm),而高熵掺杂与MXene复合后颗粒尺寸减小至≈70 nm,分布更均匀。TEM与HRTEM图像(图2d‑e)证实MXene层(晶面间距0.317 nm)、HE‑Fe₃Se₄纳米颗粒(0.208 nm)与Se域(0.250 nm)形成了紧密异质结构。SAED图谱(图2f)呈现多晶衍射环,表明多相共存。EDS面扫描(图2g)证明Fe、Se及掺杂元素(Co、Mn、Ni、Cu)在复合材料中均匀分布,验证了高熵掺杂的成功实现。

图3:HE‑Fe₃Se₄/Se/MX电极的电化学性能

CV曲线(图3a)显示复合材料在0.01–3.0 V范围内呈现多步可逆氧化还原峰,对应Se与Fe₃Se₄的逐步转化与嵌入反应。充放电曲线(图3b)表明HE‑Fe₃Se₄/Se/MX具有最高的比容量和最小的极化。倍率性能测试(图3c)显示其在0.1 A g⁻¹下容量为512 mAh g⁻¹,在30 A g⁻¹下仍保持330 mAh g⁻¹,容量保持率达64.4%。长循环测试(图3d,f)表明在10 A g⁻¹下循环1000次后容量保持337 mAh g⁻¹,每圈衰减率仅0.0106%,显著优于对照样品。

图4:电化学动力学机理分析

不同扫速下的CV曲线(图4a‑c)显示HE‑Fe₃Se₄/Se/MX的峰位偏移最小,表明极化低、反应动力学快。b值分析(图4e)表明其储能行为以表面电容为主(b≈0.9),而对照样品则更多受扩散控制。EIS图谱(图4g‑i)显示复合材料具有最低的电荷转移电阻(2.53 Ω)和最高的Na⁺扩散系数,证实高熵掺杂与MXene复合显著提升了界面反应与离子传输动力学。第一性计算(图4j‑l)进一步揭示高熵结构优化了电子态分布,并降低了Na⁺迁移能垒。

图5:储钠机制与结构演变研究

通过非原位HRTEM与SAED(图5a‑d)观察到在完全放电态(0.01 V)下生成Na₂Se与Fe纳米晶,充电态(3.0 V)下恢复为Fe₃Se₄与Se,证实了高度可逆的转化反应。原位EIS(图5e)显示在充放电过程中电荷转移电阻随相变动态变化,进一步支持了Se与Fe₃Se₄协同储钠的机制(图5f)。

【结论】
总之,本研究提出了一种高熵掺杂与MXene骨架协同设计的策略,通过调控电子结构增强本征导电性、构建化学吸附位点以锚定多硒化物,并利用MXene的导电网络与机械支撑缓解体积应变,从而实现了高效催化与结构稳定的统一。该复合材料在钠硒电池中展现出卓越的倍率性能(30 A g⁻¹下容量保持330 mAh g⁻¹)与超长循环稳定性(1000圈后每圈衰减仅0.0106%),其性能提升源于高熵诱导的快速离子扩散、表面主导的电容行为以及多相界面的协同催化作用。该工作不仅证实了铁基硒化物作为高效硒载体的可行性,也为高熵工程与导电骨架结合构筑高性能电极提供了新范式,推动钠硒电池向高功率、长寿命储能系统发展。未来可探索该策略在其它多电子转换型电极体系中的普适性,并进一步优化界面工程以提升全电池性能。
【论文信息】

Ultrastable and High‐Rate Sodium Storage Enabled by High‐Entropy Doping in HE‐Fe 3 Se 4 /Se/MXene Composites. Lei Luo;Wei Yin;Lianyi Shao;Junling Xu;Xiaoyan Shi;Jiahai Wang;Zhipeng Sun. ISSN: 1613-6810 , 1613-6829; DOI: 10.1002/smll.202514126. Small : nano micro. , 2026.

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  1. CONNECT:[ UseTime:0.000498s ] mysql:host=127.0.0.1;port=3306;dbname=c460;charset=utf8mb4
  2. SHOW FULL COLUMNS FROM `fenlei` [ RunTime:0.001621s ]
  3. SELECT * FROM `fenlei` WHERE `fid` = 0 [ RunTime:0.000688s ]
  4. SELECT * FROM `fenlei` WHERE `fid` = 63 [ RunTime:0.000822s ]
  5. SHOW FULL COLUMNS FROM `set` [ RunTime:0.001333s ]
  6. SELECT * FROM `set` [ RunTime:0.000654s ]
  7. SHOW FULL COLUMNS FROM `article` [ RunTime:0.001760s ]
  8. SELECT * FROM `article` WHERE `id` = 464951 LIMIT 1 [ RunTime:0.001116s ]
  9. UPDATE `article` SET `lasttime` = 1773695041 WHERE `id` = 464951 [ RunTime:0.022771s ]
  10. SELECT * FROM `fenlei` WHERE `id` = 65 LIMIT 1 [ RunTime:0.000661s ]
  11. SELECT * FROM `article` WHERE `id` < 464951 ORDER BY `id` DESC LIMIT 1 [ RunTime:0.001293s ]
  12. SELECT * FROM `article` WHERE `id` > 464951 ORDER BY `id` ASC LIMIT 1 [ RunTime:0.002514s ]
  13. SELECT * FROM `article` WHERE `id` < 464951 ORDER BY `id` DESC LIMIT 10 [ RunTime:0.004177s ]
  14. SELECT * FROM `article` WHERE `id` < 464951 ORDER BY `id` DESC LIMIT 10,10 [ RunTime:0.002212s ]
  15. SELECT * FROM `article` WHERE `id` < 464951 ORDER BY `id` DESC LIMIT 20,10 [ RunTime:0.002880s ]
0.138961s