高质量水系钠离子电池正极Fe4[Fe(CN)6]3的合成及其电化学性能

doi:10.15541/jim20190076

摘要/Abstract

摘要：

采用水热法合成高质量的Fe₄[Fe(CN)₆]₃(HQ-FeHCF)纳米材料, 并对材料进行X射线衍射(XRD), 扫描电子显微镜(SEM), 透射电子显微镜(TEM)和热重分析测试(TGA)等表征。结果表明：Fe₄[Fe(CN)₆]₃呈规则立方体, 颗粒大小约500 nm, 属面心立方结构。Fe₄[Fe(CN)₆]₃在NaClO₄-H₂O-聚乙二醇电解液中1C、2C、5C、10C、20C、30C和40C的容量分别为124、118、105、94、83、74和64 mAh·g ^-1, 表现出优异的倍率性能; 以5C倍率循环500次, 容量保持率接近100%, 表现出极佳的循环稳定性。以Fe₄[Fe(CN)₆]₃和磷酸钛钠分别为正负极的全电池工作电压高达1.9 V, 能量密度可达126 Wh·kg ^-1; 以5C倍率恒流充放电测试140次后全电池容量保持率为92%, 且库伦效率始终接近100%。

关键词: 水系钠离子电池, 正极材料, 立方结构, 能量密度

Abstract:

High-quality Fe₄[Fe(CN)₆]₃ (HQ-FeHCF) nanocubes were synthesized by a simple hydrothermal method. Its structure, morphology and water content are characterized. Fe₄[Fe(CN)₆]₃ exhibits regular cubic shape with a uniform size of ca. 500 nm, which belongs to the face-centered cubic phase. Fe₄[Fe(CN)₆]₃ shows discharge capacities of 124, 118, 105, 94, 83, 74 and 64 mAh·g ^-1 at 1C, 2C, 5C, 10C, 20C, 30C and 40C rate, respectively, in the aqueous ternary electrolyte of NaClO₄-H₂O-Polyethylene glycol. Its capacity retention remains 100% after 500 charge/discharge cycles at the rate of 5C. The full battery with Fe₄[Fe(CN)₆]₃ as cathode and NaTi₂(PO₄)₃ as anode was fabricated, which delivers a specific energy density of 126 Wh·kg ^-1 (based on the active electrode materials) with a voltage output of 1.9 V. Furthermore, 92% of its initial discharge capacity retains after 140 charge/discharge cycles at a rate of 5C, and its Coulomb efficiency is close to 100%.

Key words: aqueous sodium-ion battery, cathode material, cubic structure, energy density

中图分类号:

TQ174

王武练, 张军, 王秋实, 陈亮, 刘兆平. 高质量水系钠离子电池正极Fe₄[Fe(CN)₆]₃的合成及其电化学性能[J]. 无机材料学报, 2019, 34(12): 1301-1308.

WANG Wu-Lian, ZHANG Jun, WANG Qiu-Shi, CHEN Liang, LIU Zhao-Ping. High-quality Fe₄[Fe(CN)₆]₃ Nanocubes: Synthesis and Electrochemical Performance as Cathode Material for Aqueous Sodium-ion Battery[J]. Journal of Inorganic Materials, 2019, 34(12): 1301-1308.

图/表 11

图1 HQ-FeHCF和LQ-FeHCF的(a)XRD图谱和(b)TG曲线, (a)中插图为HQ-FeHCF晶胞结构示意图

Fig. 1 (a) XRD patterns and (b)TG curves of HQ-FeHCF and LQ-FeHCF with inset in (a) showing crystal structure of HQ-FeHCF

表1 HQ-FeHCF的XRD精修数据

Table 1 Fractional coordinates of HQ-FeHCF determined from Rietveld method

Atom	Wyckoff position	x	Site occupancy
Fe₁	4a	0.0000	0.9790
Fe₂	4b	0.5000	0.8901
C	24e	0.2024	0.9771
N	24e	0.2988	0.9771

表2 LQ-FeHCF的XRD精修数据

Table 2 Fractional coordinates of LQ-FeHCF determined from Rietveld method

Atom	Wyckoff position	x	Site occupancy
Fe₁	4a	0.0000	0.8458
Fe₂	4b	0.5000	0.6262
C	24e	0.2260	0.8420
N	24e	0.3275	0.8420

图2 (a~b)HQ-FeHCF和(c~d)LQ-FeHCF的SEM照片

Fig. 2 SEM images of (a-b) HQ-FeHCF and (c-d) LQ-FeHCF

图3 (a)HQ-FeHCF和(b)LQ-FeHCF的TEM照片

Fig. 3 TEM images of (a) HQ-FeHCF and (b) LQ-FeHCF

图4 (a)HQ-FeHCF和LQ-FeHCF在Na-H2O-PEG电解液中以1 mV·s-1的扫速测得的循环伏安曲线; (b)HQ-FeHCF和LQ-FeHCF在1C倍率下的充放电曲线; (c)HQ-FeHCF和LQ-FeHCF的倍率性能; (d)HQ-FeHCF和LQ-FeHCF的循环性能

Fig. 4 (a) Cyclic voltammogram (CV) curves of HQ-FeHCF and LQ-FeHCF at the sweep rate of 1 mV·s-1 in the electrolyte of Na-H2O-PEG; (b) Charge and discharge curves of HQ-FeHCF and LQ-FeHCF at 1C; (c) Rate performance of HQ-FeHCF and LQ-FeHCF; (d) Cycling performance of HQ-FeHCF and LQ-FeHCF

图5 循环(a~b) 100次和(c~d) 500次后 HQ-FeHCF的SEM照片

Fig. 5 SEM images of HQ-FeHCF after (a-b)100 and (c-d) 500 cycles

图6 循环500次后HQ-FeHCF和LQ-FeHCF的TG曲线

Fig. 6 TG curves of HQ-FeHCF and LQ-FeHCF after 500 cycles

图7 不同荷电状态下HQ-FeHCF的XRD图谱

Fig. 7 Ex situ XRD patterns of HQ-FeHCF material at various states of charge and discharge

图8 (a)HQ-FeHCF和NaTi2(PO4)在Na-H2O-PEG电解液中以1 mV·s-1的扫速测得的循环伏安曲线; (b)1C倍率下正极、负极和全电池的衡流充放电曲线;全电池的(c)倍率性能和(d)循环性能

Fig. 8 (a) Cyclic voltammogram (CV) curves of HQ-FeHCF and NaTi2(PO4) at the sweep rate of 1 mV·s-1 in the electrolyte of Na-H2O-PEG; (b) Galvanostatic charge-discharge profiles at 1C for full cell, cathode, and anodein the electrolyte of Na-H2O-PEG; (c) Rate performance and (d) cycling performance of full cell

表3 不同水系钠离子全电池的能量密度对比

Table 3 Energy density of different aqueous sodium-ion batteries

Cathode	Anode	Energy density/ (Wh·kg^-1)	Ref.
Na_0.44MnO₂	NaTi₂(PO₄)₃	33	[39]
Na₂Ni[Fe(CN)₆]	NaTi₂(PO₄)₃	43	[13]
Na₂Cu[Fe(CN)₆]	NaTi₂(PO₄)₃	48	[40]
NaMnO₂	NaTi₂(PO₄)₃	30	[12]
K_0.27MnO₂	NaTi₂(PO₄)₃	55	[41]
NaFePO₄	NaTi₂(PO₄)₃	61	[42]
Na₂VTi(PO₄)₃	NaTi₂(PO₄)₃	68	[43]
Na₃MnTi(PO₄)₃	NaTi₂(PO₄)₃	82	[44]
Na_0.66Mn_0.66Ti_0.34O₂	NaTi₂(PO₄)₃	76	[45]
Na₂Ni_0.4Co_0.6[Fe(CN)₆]	NaTi₂(PO₄)₃	121	[46]
Fe₄[Fe(CN)₆]₃	NaTi₂(PO₄)₃	126	This work

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高质量水系钠离子电池正极Fe₄[Fe(CN)₆]₃的合成及其电化学性能

High-quality Fe₄[Fe(CN)₆]₃ Nanocubes: Synthesis and Electrochemical Performance as Cathode Material for Aqueous Sodium-ion Battery

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