Progress on Transition Metal Ions Dissolution Suppression Strategies in Prussian Blue Analogs for Aqueous Sodium-/Potassium-Ion Batteries

doi:10.1007/s40820-024-01355-y

Abstract

Abstract:

Aqueous sodium-ion batteries (ASIBs) and aqueous potassium-ion batteries (APIBs) present significant potential for large-scale energy storage due to their cost-effectiveness, safety, and environmental compatibility. Nonetheless, the intricate energy storage mechanisms in aqueous electrolytes place stringent requirements on the host materials. Prussian blue analogs (PBAs), with their open three-dimensional framework and facile synthesis, stand out as leading candidates for aqueous energy storage. However, PBAs possess a swift capacity fade and limited cycle longevity, for their structural integrity is compromised by the pronounced dissolution of transition metal (TM) ions in the aqueous milieu. This manuscript provides an exhaustive review of the recent advancements concerning PBAs in ASIBs and APIBs. The dissolution mechanisms of TM ions in PBAs, informed by their structural attributes and redox processes, are thoroughly examined. Moreover, this study delves into innovative design tactics to alleviate the dissolution issue of TM ions. In conclusion, the paper consolidates various strategies for suppressing the dissolution of TM ions in PBAs and posits avenues for prospective exploration of high-safety aqueous sodium-/potassium-ion batteries.

Key words: Prussian blue analogs, Transition metal ions dissolution, Suppression strategies, Aqueous sodium-ion batteries, Aqueous potassium-ion batteries

Wenli Shu, Junxian Li, Guangwan Zhang, Jiashen Meng, Xuanpeng Wang, Liqiang Mai. Progress on Transition Metal Ions Dissolution Suppression Strategies in Prussian Blue Analogs for Aqueous Sodium-/Potassium-Ion Batteries[J]. Nano-Micro Letters, 2024, 16(1): 128-.

Wenli Shu, Junxian Li, Guangwan Zhang, Jiashen Meng, Xuanpeng Wang, Liqiang Mai. [J]. Nano-Micro Letters, 2024, 16(1): 128-.

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URL: https://www.qk.sjtu.edu.cn/nml/EN/10.1007/s40820-024-01355-y

https://www.qk.sjtu.edu.cn/nml/EN/Y2024/V16/I1/128

Figures/Tables 10

Fig. 1 a The amount of sodium and potassium in the earth's crust compared to other elements [18]. Copyright 2018, Wiley-VCH. b The comparison of ionic radius and Stokes radius of Li⁺, Na⁺, K⁺, Mg²⁺, and Al³⁺ in water [19]. Copyright 2020, American Chemical Society. c The number of publications on ASIBs and APIBs over the past decade (as of Sept. 2023, generated by Web of Science using the keywords ‘Aqueous sodium-ion batteries’ and ‘Aqueous potassium-ion batteries’). d The development of PBAs as electrode materials for ASIBs and APIBs. e Schematic representation of Mn and Fe dissolution, migration, and deposition processes in aqueous batteries in PBA cathodes

Table 1 Electrochemical properties of the PBAs for ASIBs and APIBs

Work electrode	Counter electrode	Electrolyte	Discharge capacity (mAh g⁻¹)	Rate capability (mAh g⁻¹)	Cycling performance	References
Aqueous sodium-ion batteries
Na₂Mn[Fe(CN)₆]	KMn[Cr(CN)₆]	17 M NaClO₄	40 at 1 C	25 at 30 C	N/A	[30]
Na₂CoFe(CN)₆	AC	1 M Na₂SO₄ + 1 wt% CoSO₄	110.8 at 2 C	61 at 20 C	69.2%@10 C after 2000 cycles	[60]
Na_1.85Co[Fe(CN)₆]_0.99·2.5H₂O	Activated carbon (AC)	1 M Na₂SO₄	128 at 1 C	61 at 20 C	90%@5 C after 800 cycles	[61]
Na_1.24Mn[Fe(CN)₆]_0.8·1.28H₂O	NaTi₂(PO₄)₃	17 M NaClO₄	117 at 2.0 mA cm⁻²	56 at 20 mA cm⁻²	N/A	[93]
Na₂MnFe(CN)₆	NaTi₂(PO₄)₃/C	32 M KAc and 8 M NaAc	57 at 0.1 A g⁻¹	41 at 1 A g⁻¹	N/A	[95]
Na_1.88Mn[Fe(CN)6]_0.97·1.35H₂O	NaTiOPO₄	9 M NaOTF + 22 M TEAOTF	41 at 0.25 C	N/A	76%@1 C after 800 cycles	[96]
Na₂Mn[Fe(CN)₆]	Pt	1 M Na₂SO₄ + 1 M ZnSO₄ + SDS	137 at 0.5 C	100 at 30 C	74%@5 C after 2000 cycles	[97]
Na_1.58Fe_0.07Mn_0.97Fe(CN)₆ ·2.65H₂O	PTCDI	17.6 M NaClO₄ + 0.33 M Na₄Fe(CN)₆	157 at 0.5 A g⁻¹	53 at 10 A g⁻¹	73.4%@2 A g⁻¹ after 15,000 cycles	[98]
[Ni(en)₂]₃[Fe(CN)₆]₂	Pt	0.5 M Na₂SO₄	36.5 at 0.1 A g⁻¹	N/A	60.7%@1 A g⁻¹ after 500 cycles	[100]
K_0.01Cr₃[Cr(CN)₆]₂⋅3.8H₂O	MnFe PBA	17 M NaClO₄	52.8 at 1 C	23 at 150 C	93.01%@30 C after 500 cycles	[101]
V/Fe PBA	Pt	0.5 M Na₂SO₄ + 5 M H₂SO₄	90 at 1.2 C	54 at 32 C	79%@16 C after 250 cycles	[102]
Na_1.65Co_0.55Mn_0.45[Fe(CN)₆]_0.87	AC	1 M NaNO₃	112.82 at 1 C	N/A	80%@1 C after 100 cycles	[105]
Na₂Mn_0.2Co_0.2Ni_0.2Cu_0.2Zn_0.2[Fe(CN)₆]	NaTi₂(PO₄)₃@C	1 M Na₂SO₄	75 at 0.5 C	57.1 at 10 C	87%@1 C after 5000 cycles	[109]
HQ-PB NCs	Pt	1 M Na₂SO₄	126.1 at 0.25 A g⁻¹	83.3 at 3 A g⁻¹	96.3%@1.25 A g⁻¹ after 200 cycles	[115]
Na_1.17Fe[Fe(CN)₆]·0.35H₂O	AC	17 M NaClO₄	75 at 1 C	67 at 10 C	90%@10 C after 18,000 cycles	[123]
K_0.6Ni_1.2Fe(CN)₆ ·3.6H₂O	NiHCF	1 M NaNO₃	59 at 0.83 C	40 at 41.7 C	100%@8.3 C after 5000 cycles	[127]
Na_1.64Ni[Fe(CN)₆]_0.89·2.82H₂O	5,7,12,14-Pentacenetetrone	17 M NaClO₄	126 at 0.2 A g⁻¹	87.9 at 50 A g⁻¹	80%@2 A g⁻¹ after 2000 cycles	[128]
Na_xCuCNPFe	NaTi₂(PO₄)₃@C@RGO	17 M NaClO₄	45 at 0.025 A g⁻¹	23 at 25 A g⁻¹	N/A	[129]
NaMn_0.8Fe_0.2HCF	AC	2 M NaClO₄ + 92PEG	100 at 0.1 A g⁻¹	N/A	76%@0.2 A g⁻¹ after 10,000 cycles	[130]
Aqueous potassium-ion batteries
K_1.85Fe_0.33Mn_0.67[Fe(CN)₆]_0.98·0.77H₂O	PTCDI	22 M KCF₃SO₃	135 at 0.5 C	94 at 100 C	70%@100 C after 10,000 cycles	[31]
K_1.82Mn[Fe(CN)₆]_0.96·0.47H₂O	PTCDI	0.2 M Fe(CF₃SO₃)₃ and 21 M KCF₃SO₃	160 at 0.3 A g⁻¹	120 at 2.5 A g⁻¹	99.9%@2.5 A g⁻¹ after 130,000 cycles	[32]
CuHCF	AC/PPy	1 M potassium phosphate buffer	54 at 1 C	16.5 at 50 C	100%@10 C after 1000 cycles	[45]
K_0.71Cu[Fe(CN) ₆]_0.72·3.7H₂O	CuHCF	1 M KNO₃ + 0.01 M HNO₃	59.14 at 0.83 C	40.1 at 83 C	83%@17 C after 40,000 cycles	[46]
K₂NiFe(CN)₆·1.2H₂O	Graphite	1 M KNO₃ + 0.01 M HNO₃	77.4 at 5 C	42.1 at 500 C	98.6%@5 C after 5000 cycles	[69]
[Ni(en)₂]₃[Fe(CN)₆]₂	AC	0.5 M K₂SO₄	32.8 at 0.1 A g⁻¹	30 at 5 A g⁻¹	77.2%@0.5 A g⁻¹ after 1000 cycles	[100]
CoFeHCF	AC	1 M KNO₃	119 at 2 A g⁻¹	N/A	51%@2 A g⁻¹ after 4000 cycles	[103]
K_1.66Fe_0.25Co_0.75[Fe(CN)₆]·0.83H₂O	AC	3 M KNO3	97 at 0.02 A g⁻¹	43.4 at 1 A g⁻¹	90.6%@0.2 A g⁻¹ after 1000 cycles	[104]
K₂Fe^II[Fe^II(CN)₆] ·2H₂O	Graphite	0.5 M K₂SO₄	120 at 1.4 C	104 at 14.4 C	85%@21.4 C after 500 cycles	[113]
K_1.93Fe[Fe(CN)₆]_0.97 ·1.82H₂O	AC	0.5 M Na₂SO₄ + 5 M H₂SO₄	142 at 0.075 A g⁻¹	40 at 9 A g⁻¹	88%@1.5 A g⁻¹ after 300 cycles	[116]
Inverse opal PB single crystals	Pt	1 M KNO₃	90 at 20 A g⁻¹	N/A	100%@20 A g⁻¹ after 1000 cycles	[117]
K_0.6Ni_1.2Fe(CN)₆ ·3.6H₂O	NiHCF	1 M KNO₃	59 at 0.83 C	39 at 41.7 C	93%@8.3 C after 5000 cycles	[127]
K₃[Fe(CN)₆]/CNT	Pt	0.1 M KCl	75 at 0.2 A g⁻¹	26 at 2 A g⁻¹	N/A	[131]

Table 1 Electrochemical properties of the PBAs for ASIBs and APIBs

Work electrode	Counter electrode	Electrolyte	Discharge capacity (mAh g⁻¹)	Rate capability (mAh g⁻¹)	Cycling performance	References
Aqueous sodium-ion batteries
Na₂Mn[Fe(CN)₆]	KMn[Cr(CN)₆]	17 M NaClO₄	40 at 1 C	25 at 30 C	N/A	[30]
Na₂CoFe(CN)₆	AC	1 M Na₂SO₄ + 1 wt% CoSO₄	110.8 at 2 C	61 at 20 C	69.2%@10 C after 2000 cycles	[60]
Na_1.85Co[Fe(CN)₆]_0.99·2.5H₂O	Activated carbon (AC)	1 M Na₂SO₄	128 at 1 C	61 at 20 C	90%@5 C after 800 cycles	[61]
Na_1.24Mn[Fe(CN)₆]_0.8·1.28H₂O	NaTi₂(PO₄)₃	17 M NaClO₄	117 at 2.0 mA cm⁻²	56 at 20 mA cm⁻²	N/A	[93]
Na₂MnFe(CN)₆	NaTi₂(PO₄)₃/C	32 M KAc and 8 M NaAc	57 at 0.1 A g⁻¹	41 at 1 A g⁻¹	N/A	[95]
Na_1.88Mn[Fe(CN)6]_0.97·1.35H₂O	NaTiOPO₄	9 M NaOTF + 22 M TEAOTF	41 at 0.25 C	N/A	76%@1 C after 800 cycles	[96]
Na₂Mn[Fe(CN)₆]	Pt	1 M Na₂SO₄ + 1 M ZnSO₄ + SDS	137 at 0.5 C	100 at 30 C	74%@5 C after 2000 cycles	[97]
Na_1.58Fe_0.07Mn_0.97Fe(CN)₆ ·2.65H₂O	PTCDI	17.6 M NaClO₄ + 0.33 M Na₄Fe(CN)₆	157 at 0.5 A g⁻¹	53 at 10 A g⁻¹	73.4%@2 A g⁻¹ after 15,000 cycles	[98]
[Ni(en)₂]₃[Fe(CN)₆]₂	Pt	0.5 M Na₂SO₄	36.5 at 0.1 A g⁻¹	N/A	60.7%@1 A g⁻¹ after 500 cycles	[100]
K_0.01Cr₃[Cr(CN)₆]₂⋅3.8H₂O	MnFe PBA	17 M NaClO₄	52.8 at 1 C	23 at 150 C	93.01%@30 C after 500 cycles	[101]
V/Fe PBA	Pt	0.5 M Na₂SO₄ + 5 M H₂SO₄	90 at 1.2 C	54 at 32 C	79%@16 C after 250 cycles	[102]
Na_1.65Co_0.55Mn_0.45[Fe(CN)₆]_0.87	AC	1 M NaNO₃	112.82 at 1 C	N/A	80%@1 C after 100 cycles	[105]
Na₂Mn_0.2Co_0.2Ni_0.2Cu_0.2Zn_0.2[Fe(CN)₆]	NaTi₂(PO₄)₃@C	1 M Na₂SO₄	75 at 0.5 C	57.1 at 10 C	87%@1 C after 5000 cycles	[109]
HQ-PB NCs	Pt	1 M Na₂SO₄	126.1 at 0.25 A g⁻¹	83.3 at 3 A g⁻¹	96.3%@1.25 A g⁻¹ after 200 cycles	[115]
Na_1.17Fe[Fe(CN)₆]·0.35H₂O	AC	17 M NaClO₄	75 at 1 C	67 at 10 C	90%@10 C after 18,000 cycles	[123]
K_0.6Ni_1.2Fe(CN)₆ ·3.6H₂O	NiHCF	1 M NaNO₃	59 at 0.83 C	40 at 41.7 C	100%@8.3 C after 5000 cycles	[127]
Na_1.64Ni[Fe(CN)₆]_0.89·2.82H₂O	5,7,12,14-Pentacenetetrone	17 M NaClO₄	126 at 0.2 A g⁻¹	87.9 at 50 A g⁻¹	80%@2 A g⁻¹ after 2000 cycles	[128]
Na_xCuCNPFe	NaTi₂(PO₄)₃@C@RGO	17 M NaClO₄	45 at 0.025 A g⁻¹	23 at 25 A g⁻¹	N/A	[129]
NaMn_0.8Fe_0.2HCF	AC	2 M NaClO₄ + 92PEG	100 at 0.1 A g⁻¹	N/A	76%@0.2 A g⁻¹ after 10,000 cycles	[130]
Aqueous potassium-ion batteries
K_1.85Fe_0.33Mn_0.67[Fe(CN)₆]_0.98·0.77H₂O	PTCDI	22 M KCF₃SO₃	135 at 0.5 C	94 at 100 C	70%@100 C after 10,000 cycles	[31]
K_1.82Mn[Fe(CN)₆]_0.96·0.47H₂O	PTCDI	0.2 M Fe(CF₃SO₃)₃ and 21 M KCF₃SO₃	160 at 0.3 A g⁻¹	120 at 2.5 A g⁻¹	99.9%@2.5 A g⁻¹ after 130,000 cycles	[32]
CuHCF	AC/PPy	1 M potassium phosphate buffer	54 at 1 C	16.5 at 50 C	100%@10 C after 1000 cycles	[45]
K_0.71Cu[Fe(CN) ₆]_0.72·3.7H₂O	CuHCF	1 M KNO₃ + 0.01 M HNO₃	59.14 at 0.83 C	40.1 at 83 C	83%@17 C after 40,000 cycles	[46]
K₂NiFe(CN)₆·1.2H₂O	Graphite	1 M KNO₃ + 0.01 M HNO₃	77.4 at 5 C	42.1 at 500 C	98.6%@5 C after 5000 cycles	[69]
[Ni(en)₂]₃[Fe(CN)₆]₂	AC	0.5 M K₂SO₄	32.8 at 0.1 A g⁻¹	30 at 5 A g⁻¹	77.2%@0.5 A g⁻¹ after 1000 cycles	[100]
CoFeHCF	AC	1 M KNO₃	119 at 2 A g⁻¹	N/A	51%@2 A g⁻¹ after 4000 cycles	[103]
K_1.66Fe_0.25Co_0.75[Fe(CN)₆]·0.83H₂O	AC	3 M KNO3	97 at 0.02 A g⁻¹	43.4 at 1 A g⁻¹	90.6%@0.2 A g⁻¹ after 1000 cycles	[104]
K₂Fe^II[Fe^II(CN)₆] ·2H₂O	Graphite	0.5 M K₂SO₄	120 at 1.4 C	104 at 14.4 C	85%@21.4 C after 500 cycles	[113]
K_1.93Fe[Fe(CN)₆]_0.97 ·1.82H₂O	AC	0.5 M Na₂SO₄ + 5 M H₂SO₄	142 at 0.075 A g⁻¹	40 at 9 A g⁻¹	88%@1.5 A g⁻¹ after 300 cycles	[116]
Inverse opal PB single crystals	Pt	1 M KNO₃	90 at 20 A g⁻¹	N/A	100%@20 A g⁻¹ after 1000 cycles	[117]
K_0.6Ni_1.2Fe(CN)₆ ·3.6H₂O	NiHCF	1 M KNO₃	59 at 0.83 C	39 at 41.7 C	93%@8.3 C after 5000 cycles	[127]
K₃[Fe(CN)₆]/CNT	Pt	0.1 M KCl	75 at 0.2 A g⁻¹	26 at 2 A g⁻¹	N/A	[131]

Fig. 2 a Schematic illustration of the electronic states of TM ions in PBAs. b Schematic diagram of the general crystal structure of MHCF [50]. Copyright 2020, Wiley-VCH. Crystal structure evolution of c FeHCF and CoHCF, d MnHCF, and e CuHCF and NiHCF induced by insertion/extraction of AM ions during redox reactions [57]. Copyright 2022, Elsevier

Fig. 3 a Schematic representation of the dissolution phenomena in aqueous batteries of PBAs observable. The inset in the lower right corner shows the color change of the electrolyte after ten cycles of cycling at 0.3 A g⁻¹ with 1 M KNO₃ as the electrolyte, KMnHCF as the working electrode, and graphite as the counter electrode. b Schematic of critical factors in suppressing TM ions dissolution of PBA in the concentrated electrolyte [79]. Copyright 2022, American Chemical Society

Fig. 4 Strategies for suppressing TM ions dissolution in PBAs

Fig. 5 a XRD Rietveld refinement pattern for the KFeMnHCF-3565. b The typical structure of the K_xFe_yMn_1 −_y[Fe(CN)₆]_w·zH₂O. Charge/discharge curves at 10 C: c KMnHCF and d KFeMnHCF-3565 in 1 M KCF₃SO₃ electrolyte, e KMnHCF and f KFeMnHCF-3565 in 22 M KCF₃SO₃ electrolyte [31]. Copyright 2019, Springer Nature. g Electrochemical voltage window of 9 mol kg^-1 NaOTF and 9 mol kg^-1 NaOTF + 22 mol kg^-1 TEAOTF electrolytes. h Charge/discharge curves of the NaMnHCF cathode and NaTiOPO₄ anode in 9 mol kg^-1 NaOTF and 9 mol kg^-1 NaOTF + 22 mol kg^-1 TEAOTF electrolytes, respectively. i Long cycling of NaMnHCF electrodes in different electrolytes at 1 C. j The dissolving amount of the TM ions (Fe and Mn) after 50 cycles at 1 C [96]. Copyright 2020, Wiley-VCH

Fig. 6 a, b The elemental content, intensity contour map, and image of the chosen cross-sectional area were acquired from the STEM-EELS line scan of the initial electrode and modified electrode. c Ultralong cycling stability of the KMnF in the modified electrolyte [32]. Copyright 2022, Springer Nature. d, e STEM mapping images of fully discharged electrodes in the blank and modified electrolyte. f, g EELS line scans of fully discharged electrodes for 300 cycles of PTCDI||NaFeMnF in blank and modified electrolytes, respectively, at 0.5 A g⁻¹. h Cycling performance of the PTCDI||NaFeMnF at 2 A g⁻¹ [98]. Copyright 2023, Springer Nature

Fig. 7 a, b SEM images and XPS spectra of CoFeHCF in different charge/discharge states. c Corresponding charge/discharge curves. d XRD pattern variations and e the corresponding cell parameters. f Variations in the concentration of Fe/Co in the electrolytes for CoFeHCF during cycles 21 and 22. g Long-term cyclic performance of CoFeHCF at 2 A g⁻¹ [103]. Copyright 2022, Wiley-VCH. h CV curves of NiHCF, M5HCF and medium-entropy PBAs at 2 mV s⁻¹. i Statistic results of R_ct values in DRT analysis. j Cycling performance at 1 C of NiHCF, M5HCF and medium-entropy PBAs cathode in PBAs||NTP@C full cells. k Schematic diagram of the band edges for M5HCF and medium-entropy doped PBAs. l DOS and PDOS plots of M5HCF [109]. Copyright 2023, The Royal Society of Chemistry

Fig. 8 a SEM image of KFeHCF decomposition in ethylene glycol solution. b Rietveld refinement pattern of XRD for KFeHCF. c Refined crystal structure views along different axes. d CV images at different scanning rates. e Cycling performance of KFeHCF at different current densities [113]. Copyright 2017, Wiley-VCH. f, g SEM images of NaCoHCF. h Charge/discharge curves of the NaCoHCF||NaTi₂(PO₄)₃ full cell at 5 C. i Rate and cycling performance [61]. Copyright 2015, Wiley-VCH. j Ex situ XRD patterns of KFe(1.0) electrode collected at various charged states [116]. Copyright 2018, Wiley-VCH

Fig. 9 a Manganese dissolution in the electrolyte after long cycles. SEM and EDS mapping images of separators disassembled from b PBM and c PBM@PBN after 200 cycles, respectively [121]. Copyright 2021, Elsevier. d Schematic illustration of the proposed protective mechanism of CoχB to suppress the Mn dissolution and generation of microcracks of MnHCF. e Ex situ XRD patterns of the MnHCF-5%CoχB electrode during the first charge/discharge process [122]. Copyright 2023, Wiley-VCH. f Schematic illustration of PBM, GO/PBM, and rGO/PBM synthesis procedure. g Raman spectra. h TGA curves. i Cycling performance. j Rate capabilities [126]. Copyright 2021, American Chemical Society

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