P修饰提高Fe-N-C的氧反应活性用于高稳定的锌-空气电池

doi:10.1016/S1872-2067(23)64432-8

催化学报 ›› 2023, Vol. 49: 141-151.DOI: 10.1016/S1872-2067(23)64432-8

P修饰提高Fe-N-C的氧反应活性用于高稳定的锌-空气电池

张光颖^a, 刘旭^b, 张欣欣^a, 梁志坚^a, 邢耕宇^a, 蔡斌^a, 沈迪^a, 王蕾^a^,^*(), 付宏刚^a^,^*()

^a黑龙江大学功能无机材料化学教育部重点实验室, 黑龙江哈尔滨 150080
^b东北农业大学文理学院化学系, 黑龙江哈尔滨 150030

收稿日期:2023-01-22 接受日期:2023-03-23 出版日期:2023-06-18 发布日期:2023-06-05
通讯作者: ^*电子信箱: wanglei0525@hlju.edu.cn (王蕾),fuhg@hlju.edu.cn, fuhg@vip.sina.com (付宏刚).
基金资助:
国家自然科学基金(U20A20250);国家自然科学基金(22179034)

Phosphate-decorated Fe-N-C to promote electrocatalytic oxygen reaction activities for highly stable zinc-air batteries

Guangying Zhang^a, Xu Liu^b, Xinxin Zhang^a, Zhijian Liang^a, Gengyu Xing^a, Bin Cai^a, Di Shen^a, Lei Wang^a^,^*(), Honggang Fu^a^,^*()

^aKey Laboratory of Functional Inorganic Material Chemistry, Ministry of Education, Heilongjiang University, Harbin 150080, Heilongjiang, China
^bDepartment of Chemistry, College of Arts and Science, Northeast Agricultural University, Harbin 150030, Heilongjiang, China

Received:2023-01-22 Accepted:2023-03-23 Online:2023-06-18 Published:2023-06-05
Contact: ^*E-mail: wanglei0525@hlju.edu.cn (L. Wang), fuhg@hlju.edu.cn, fuhg@vip.sina.com (H. Fu).
Supported by:
National Natural Science Foundation of China(U20A20250);National Natural Science Foundation of China(22179034)

摘要/Abstract

摘要：

生物质碳基材料具有可调的微观结构、丰富的表面活性中心、优良的导电和导热性能以及较大的比表面积, 已经成为新能源领域的重要基础材料. 然而, 应用于锌-空气电池中时, 碳基材料高电位下的碳腐蚀问题严重影响了电池的稳定性, 因此, 开发具有低过电位的析氧反应(OER)催化剂来降低充电电压是解决该问题的关键. 本课题组采用一种低温磷化策略制备了具有低OER过电位的P修饰的Fe₃O₄/Fe₂N和生物质碳复合催化剂(P-Fe₃O₄/Fe₂N@NPC), 其具有较好的双功能氧反应活性, 氧还原反应(ORR)的半波电位为0.86 V, 仅需要280 mV的OER过电位就可以达到10 mA cm^‒2的电流密度. 以P-Fe₃O₄/Fe₂N@NPC作为正极组装的锌-空气电池表现出低的充放电电压差和长期稳定性, 在目前报道的碳基催化剂应用于锌-空气电池中具有很大优势. 此外, 采用X射线光电子能谱(XPS)、拉曼光谱和氧气程序升温脱附(O₂-TPD)等技术研究了磷化对催化剂的结构和催化性能带来的差异原因, 并利用密度泛函理论(DFT)计算研究了催化剂的OER反应机制.

XPS测试结果表明, P-Fe₃O₄/Fe₂N@NPC的P 2p轨道观察到P‒M键、P‒C键和P‒O键, 证实P在碳纳米结构中的成功修饰. Fe 2p XPS谱显示, P的掺入使Fe 2p峰向低结合能方向移动, 这表明P的表面改性改变了金属Fe物种的表面电子构型. 此外, 拉曼光谱结果表明, P掺杂后样品的I_D/I_G值增加, 说明结构中具有更多的缺陷, 为ORR反应提供更多的催化活性位. O₂-TPD结果表明, 两种催化剂在低温区域(<500 ^oC)表现为表面缺陷上的化学吸附氧, 在高温区域(>500 ^oC)表现为晶格氧释放, 这说明了催化剂中都存在表面氧空位. 与P-Fe₃O₄/Fe₂N@NPC的脱附氧物种相关的峰值温度低于Fe₃O₄/Fe₂N@NPC, 证明P修饰可以使催化剂具有更好的吸附/脱附氧能力, 进一步降低了吸附氧分子的活化能垒.

利用DFT计算分析了OER活性增强的原因. DOS结果显示, 与位于E_V在‒0.543 eV的Fe₃O₄/Fe₂N模型的Fe-3d-t_2g相比, 引入P的P-Fe₃O₄和P-Fe₂N模型分别正移到‒0.442和‒0.493 eV (E_V= 0为E_F(费米能级)), 更接近E_F. 这表明, 在电化学反应过程中, 表面P的修饰促进了Fe位点的电子转移能力. 不同模型OER/ORR过程中间体的自由能结果表明, OER的速率决定步骤为*OOH→O₂, P-Fe₃O₄和P-Fe₂N模型的速率决定步骤自由能分别为2.25和1.02 eV, 比Fe₃O₄ (2.36 eV)和Fe₂N(1.25 eV)模型更低, 说明P改性降低了驱动OER所需的最小过电位. 综上, P修饰可以调节Fe位点的电子结构, 促进氧中间物的吸附和解吸, 从而改善OER的性能.

关键词: Fe-N-C催化剂, 磷修饰, 氧还原反应, 析氧反应, 锌-空气电池

Abstract:

An obvious challenge for rechargeable Zn-air batteries (ZABs) is the impact of large charge potentials on the oxidation of their cathode catalysts, which accelerates the corrosion of the carbon electrodes, and significantly compromises their stability. It is therefore necessary to design simple methods aimed at facilitating the oxygen evolution reaction (OER) processes of ZABs to suppress the corrosion of their cathode materials. Herein, a biomass-derived N-doped porous carbon material coupled with Fe₃O₄ and Fe₂N nanoparticles and modified with phosphorus (P-Fe₃O₄/Fe₂N@NPC) was designed as an air-cathode to reduce the charging voltage of ZABs. It exhibited excellent ORR/OER bifunctional electrocatalytic activities, and the assembled ZAB displayed an ultra-long service life. DFT calculations showed that the P-modification modulated the electronic state and coordination environment of the active iron atom, thereby significantly enhancing the OER activity of P-Fe₃O₄/Fe₂N@NPC.

Key words: Fe-N-C catalyst, Phosphate-decoration, Oxygen reduction reaction Oxygen evolution reaction, Zinc-air battery

张光颖, 刘旭, 张欣欣, 梁志坚, 邢耕宇, 蔡斌, 沈迪, 王蕾, 付宏刚. P修饰提高Fe-N-C的氧反应活性用于高稳定的锌-空气电池[J]. 催化学报, 2023, 49: 141-151.

Guangying Zhang, Xu Liu, Xinxin Zhang, Zhijian Liang, Gengyu Xing, Bin Cai, Di Shen, Lei Wang, Honggang Fu. Phosphate-decorated Fe-N-C to promote electrocatalytic oxygen reaction activities for highly stable zinc-air batteries[J]. Chinese Journal of Catalysis, 2023, 49: 141-151.

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https://www.cjcatal.com/CN/Y2023/V49/I6/141

图/表 6

Fig. 1. (a) Schematic illustration of the construction of P-Fe3O4/Fe2N@NPC. TEM (b) and HRTEM (c?e) images of P-Fe3O4/Fe2N@NPC. (f) STEM and EDS elemental mapping images of C, N, O, P and Fe elements in P-Fe3O4/Fe2N@NPC.

Fig. 2. XRD patterns (a), Raman spectra (b) and N2 sorption isotherms (c) of Fe3O4/Fe2N@NPC and P-Fe3O4/Fe2N@NPC. Wide XPS spectra (d), high-resolution XPS spectra of Fe 2p (e), P 2p (f), C 1s (g), N 1s (h) and O 1s (i) for Fe3O4/Fe2N@NPC and P-Fe3O4/Fe2N@NPC.

Fig. 3. (a) LSV curves of Fe3O4/Fe2N@NPC, P-Fe3O4/Fe2N@NPC and commercial Pt/C catalysts tested in 0.1 mol L?1 KOH electrolyte at 1600 r min?1 and a sweep rate of 5 mV s-1. (b) ORR Tafel plots of the catalysts. (c) K-L plots of J?1 versus ω?1/2 at potentials of 0.3?0.5 V and the inset shows the LSV curve in the speed range of 400?2025 r min?1. (d) Calculated n and H2O2 yields (%) based on the RRDE of P-Fe3O4/Fe2N@NPC. (e) ORR stability test of P-Fe3O4/Fe2N@NPC before and after 10000 cycles. (f) iR-compensated OER polarization curves of the catalyst in 1 mol L?1 KOH electrolyte. (g) OER Tafel plots. (h) OER stability test of P-Fe3O4/Fe2N@NPC at different current densities, and the inset represents the OER performance before and after 5000 CV cycle. (i) LSV curves of Fe3O4/Fe2N@NPC, P-Fe3O4/Fe2N@NPC in the full OER/ORR region in 0.1 mol L?1 KOH.

Fig. 4. The optimized structures for O2 adsorption on Fe3O4 (a), P-Fe3O4 (b) and Fe2N(c), P-Fe2N (d). (e) Density of states. (f,g) Free energy diagrams of the OER and ORR on Fe3O4, P-Fe3O4, Fe2N and P-Fe2N at potentials of 0 and 1.23 V.

Fig. 5. (a) Schematic diagram of rechargeable ZAB. (b) Specific discharging capacities for liquid state ZABs assembled by P-Fe3O4/Fe2N@NPC and Pt/C+RuO2 at 5 mA cm?2. (c) Cyclic performance of rechargeable ZABs with duration of 10 min per cycle at 10 mA cm?2 for Fe3O4/Fe2N@NPC, P-Fe3O4/Fe2N@NPC and Pt/C+RuO2. (d) Discharge polarization curves and power density curves. (e) The corresponding galvanostatic charge-discharge plots of Fe3O4/Fe2N@NPC and P-Fe3O4/Fe2N@NPC for the 300?312 cycles. (f) The photograph of the battery electrolyte using Fe3O4/Fe2N@NPC (①) and P-Fe3O4/Fe2N@NPC (②) as the air electrode after 10000 cycles.

Fig. 6. (a) Schematic diagram of solid-state ZAB. (b) Open-circuit voltages for solid-state ZABs assembled with P-Fe3O4/Fe2N@NPC by PVA+rGO. (c) Galvanostatic discharge-charge cycling profiles of P-Fe3O4/Fe2N@NPC enabled all-solid-state ZAB by PVA+KOH and PVA+rGO+KOH solid electrolyte at 2 mA cm?2. (d) Photograph of a timepiece is driven by two all-solid-state ZABs in series. (e) Charge-discharge polarization curves for battery tests under different bending degrees at 2 mA cm?2.

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P修饰提高Fe-N-C的氧反应活性用于高稳定的锌-空气电池

Phosphate-decorated Fe-N-C to promote electrocatalytic oxygen reaction activities for highly stable zinc-air batteries

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