蛋黄壳结构FeF3·0.33H2O@N掺杂碳纳米笼正极材料的构筑及其电化学性能

doi:10.15541/jim20230312

摘要/Abstract

摘要：

FeF₃∙0.33H₂O具有理论容量和电压高的特点, 但其导电性差、氧化还原反应过程中体积变化严重导致电化学循环性能不佳, 应用受到限制。本研究采用多巴胺自组装包覆纳米立方Fe₂O₃颗粒, 再经过碳化、HCl刻蚀和HF氟化的策略, 合成了由N掺杂石墨烯外壳和纳米立方FeF₃∙·0.33H₂O内核所构成的蛋黄壳结构复合材料FeF₃∙0.33H₂O@CNBs, 粒径约250 nm, 碳壳厚度为30~40 nm。FeF₃∙0.33H₂O@CNBs在0.2C (1C=237 mA·g^-1)电流密度下充放电初始容量为208 mAh·g^-1, 循环50圈之后容量仍然有173 mAh·g^-1, 每圈容量衰减率仅为0.3%; 而纯FeF₃∙0.33H₂O初始容量只有112 mAh·g^-1, 循环50圈之后只有95 mAh·g^-1。FeF₃∙0.33H₂O@CNBs的循环性能明显优于FeF₃∙0.33H₂O, 同时0.1C~1C充放电结果表明其倍率性能也明显优于FeF₃∙0.33H₂O。这是因为该策略制备的N掺杂石墨烯外壳提供了良好的电子/离子输运性能, 同时碳壳可缓冲和抑制内核FeF₃∙0.33H₂O的体积变化, 其空隙体积对电解液的储液保液性能缩短了离子迁移距离, 提升了Li⁺迁移速率, 从而得到了比文献报道更好的电化学性能。

关键词: 锂离子电池, 电极材料, 氟化铁, 蛋黄壳结构

Abstract:

FeF₃∙0.33H₂O possesses the characteristics of high theoretical capacity and high voltage, but its electrochemical cycling performance is unsatisfactory due to its poor conductivity and serious volume change during redox reaction, resulting in limited application. In this study, by using the strategies of dopamine self-assembly coating, carbonization, HCl etching and HF fluorination, the yolk-shell structured composite FeF₃∙0.33H₂O@carbon nanoboxes (FeF₃∙0.33H₂O@CNBs) composed of N-doped graphene shell and nanocube FeF₃∙0.33H₂O core was synthesized. Its particle size is about 250 nm and thickness of carbon shell is 30-40 nm. FeF₃∙0.33H₂O@CNBs displays an initial charge-discharge capacity of 208 mAh·g^-1 at a current density of 0.2C(1C=237 mA·g^-1). After 50 cycles, the capacity remains 173 mAh·g^-1, and the capacity attenuation rate per cycle is only 0.3%. In comparison, the initial capacity of bare FeF₃∙0.33H₂O is 112 mAh·g^-1, and after 50 cycles, only 95 mAh·g^-1 reserves, indicating superior cycle performance of FeF₃·0.33H₂O@CNBs. Furthermore, charging and discharging results at 0.1C-1C show that the rate performance is also significantly better than bare FeF₃∙0.33H₂O. It’s due to that N-doped graphene shell prepared by this strategy provides good electron/ion transport performance. At the same time, the carbon shell can not only buffer and inhibit the volume change of the core FeF₃∙0.33H₂O, but also shorten the ion migration distance and improve the Li⁺ migration rate on the electrolyte storage and retention performance of the electrolyte. As a result, the electrochemical performances are better than those of previous literature.

Key words: lithium ion battery, cathode material, iron fluoride, yolk-shell structure

中图分类号:

O646

程节, 周月, 罗薪涛, 高美婷, 骆思妃, 蔡丹敏, 吴雪垠, 朱立才, 袁中直. 蛋黄壳结构FeF₃·0.33H₂O@N掺杂碳纳米笼正极材料的构筑及其电化学性能[J]. 无机材料学报, 2024, 39(3): 299-305.

CHENG Jie, ZHOU Yue, LUO Xintao, GAO Meiting, LUO Sifei, CAI Danmin, WU Xueyin, ZHU Licai, YUAN Zhongzhi. Construction and Electrochemical Properties of Yolk-shell Structured FeF₃·0.33H₂O@N-doped Graphene Nanoboxes[J]. Journal of Inorganic Materials, 2024, 39(3): 299-305.

图/表 12

图1 蛋黄壳结构FeF3·0.33H2O@CNBs复合材料的制备流程图

Fig. 1 Schematic illustration on FeF3·0.33H2O@CNBs preparation

图2 (a)Fe2O3@CNB, (b) FeF3·0.33H2O@CNB和FeF3·0.33H2O的XRD图谱

Fig. 2 XRD patterns of (a) Fe2O3@CNB, (b) FeF3·0.33H2O@CNB and FeF3·0.33H2O

图3 蛋黄壳结构FeF3∙0.33H2O@CNB材料的(a)Raman光谱图和(b)热重曲线

Fig. 3 (a) Raman spectrum and (b) TG curve of yolk-shell FeF3∙0.33H2O@CNB

图4 FeF3·0.33H2O@CNBs的(a)XPS总谱图, 以及高分辨(b)Fe2p, (c) F1s, (d)C1s, (e)N1s XPS谱图

Fig. 4 (a) XPS survey spectrum and high-resolution (b) Fe2p, (c) F1s, (d) C1s, (e) N1s XPS spectra of FeF3·0.33H2O@CNBs

图5 (a, b)Fe2O3纳米立方体, (c, d)核壳结构Fe2O3@C以及(e, f)蛋黄壳结构FeF3·0.33H2O@CNBs的TEM照片

Fig. 5 TEM images of (a, b) cubic Fe2O3 nano-particle, (c, d) core-shell Fe2O3@C and (e, f) yolk-shell FeF3·0.33H2O@CNB

图6 Li/FeF3·0.33H2O@CNBs电池的循环伏安曲线

Fig. 6 CV curves of Li/FeF3·0.33H2O@CNBs cell

图7 FeF3·0.33H2O@CNBs和纯FeF3·0.33H2O作为正极材料的锂离子电池的电化学性能

Fig. 7 Electrochemical performances of FeF3·0.33H2O@CNBs and bare FeF3·0.33H2O as cathodes of lithium ion cell (a) Voltage-capacity curves of FeF3·0.33H2O@CNBs at 0.2C; (b) Voltage-capacity curves of bare FeF3·0.33H2O at 0.2C; (c) Cycling and (d) rate performances of FeF3·0.33H2O@CNBs and bare FeF3·0.33H2O. Colorful figures are available on website

图8 FeF3·0.33H2O@CNBs和纯FeF3·0.33H2O电极的电化学阻抗

Fig. 8 Electrochemical impedance spectra of FeF3·0.33H2O@CNBs and bare FeF3·0.33H2O (a) Nyquist plots; (b) Relationship between Z′ and ω−1/2 in low-frequency region

图S1 FeF3·0.33H2O@CNBs复合材料的N2吸脱附曲线和孔径分布图

Fig. S1 N2 adsorption-desorption isotherms and corresponding pore size distribution of FeF3·0.33H2O@CNBs

图S2 Li/Fe2O3@CNBs电池的电化学性能

Fig. S2 Electrochemical performance of the Li/Fe2O3@CNBs cell(a) Voltage-capacity curves at 0.1C; (b) Cycling performance at 0.5C

表S1 本工作与文献报道FeF3·0.33H2O类正极材料的性能对比

Table S1 Performance comparison of FeF3·0.33H2O based cathode materials of lithium ion battery in this work and literature

Material	Particle size	Voltage range/V	Discharge density	Initial discharge capacity/(mAh·g^-1)	(Reversible capacity/ (mAh·g^-1))/cycle number	Ref.
FeF₃·0.33H₂O@CNBs	250 nm	2.0-4.5	0.2C	208	173.4/50	This work
FeF₃·0.33H₂O/C	1-1.7 µm	2.0-4.5	1C	187.1	172.3/50	[4]
FeF₃·0.33H₂O@CNHs	80-100 nm	1.5-4.5	1C	155	154/50	[5]
FeF₃·0.33H₂O/MWCNTs	30 nm	2.0-4.3	0.1C	186	116/50	[6]
FeF₃·0.33H₂O@rGO	400 nm	2.0-4.5	0.1C	205	183.8/60	[7]
FeF₃·0.33H₂O/C	1-5 µm	1.5-4.5	1C	276.4	193.5/50	[8]
Co/Ni dual-doped FeF₃·0.33H₂O	200 nm	1.5-4.5	5C	200.1	177.8/400	[9]
FeF₃·0.33H₂O/rGO	150 nm	1.8-4.5	0.5C	208.3	133.1/100	[3]

表S2 FeF3·0.33H2O@CNBs和纯FeF3·0.33H2O的Li+扩散系数

Table S2 Li-ion diffusion coefficients of FeF3·0.33H2O@CNBs and bare FeF3·0.33H2O

Sample	R_s/Ω	R_ct/Ω	D_Li⁺ /(m²·s^-1)
FeF₃·0.33H₂O@CNBs	3.39	46.0	1.84×10^-14
FeF₃·0.33H₂O	8.78	112.6	2.74×10^-15

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蛋黄壳结构FeF₃·0.33H₂O@N掺杂碳纳米笼正极材料的构筑及其电化学性能

Construction and Electrochemical Properties of Yolk-shell Structured FeF₃·0.33H₂O@N-doped Graphene Nanoboxes

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