AI Chat Paper
Note: Please note that the following content is generated by AMiner AI. SciOpen does not take any responsibility related to this content.
{{lang === 'zh_CN' ? '文章概述' : 'Summary'}}
{{lang === 'en_US' ? '中' : 'Eng'}}
Chat more with AI
Powered by AMiner. Clicking this button will take you away from SciOpen.
Home Nano Research Article
Article Link
Cite
EndNote(RIS) BibTeX
Collect
Submit Manuscript
Show Outline
Outline
Show full outline
Hide outline
Outline
Show full outline
Hide outline
Research Article

Active cation-integration high-entropy Prussian blue analogues cathodes for efficient Zn storage

Jiangyuan Xing1,§, Yongsheng Zhang1,§, Yang Jin2, Qianzheng Jin2( )
School of Chemical Engineering, Zhengzhou University, Zhengzhou 450001, China
School of Electrical Engineering, Zhengzhou University, Zhengzhou 450001, China

§ Jiangyuan Xing and Yongsheng Zhang contributed equally to this work.

Show Author Information

Graphical Abstract

Herein, the high-entropy strategy is applied to Mn-based Prussian blue analogues to increase the structural stability in aqueous Zn-ion batteries. The as-prepared high-entropy Prussian blue analogue (HE-PBA) materials incorporate five transition metal elements of Mn, Co, Ni, Fe and Cu into the nitrogen-coordinated -M- lattice sites leading to an increased configuration entropy. Consequently, HE-PBA electrode showed the remarkable cycling stability than other PBAs electrodes.

Abstract

Mn-based Prussian blue analogues (Mn-PBAs), featuring a three-dimensional (3D) metal-organic framework and multiple redox couples, have gained wide interests in Zn-ion batteries (ZIBs). However, owing to the Jahn-Teller distortion and disproportionation reaction of Mn3+, these materials suffer from poor electrochemical performances and inferior structural stability. Herein, we prepare a typical high-entropy Prussian blue analogue (HE-PBA) with increased configuration entropy through integrating five transition metal elements of Mn, Co, Ni, Fe and Cu into the nitrogen-coordinated -M- lattice sites. Consequently, the HE-PBA presents enhanced uptake of Zn2+ with 80 mAh·g−1 compared to those medium-entropy PBAs, low-entropy PBAs and conventional PBAs, which can be assigned to “cocktail” effect of multiple transition metal active redox couples. Furthermore, a phase transition process from monoclinic phase to rhombohedral phase occurs in HE-PBA cathode, resulting in a stable structure of MN6 (M = Mn, Co, Fe, Ni, Cu) and ZnN4 co-linked to FeC6 through the cyanide ligands. Additionally, the advantages of entropy-driven stability are also confirmed by the calculated reduction energy and the density of states between HE-PBA and KMn[Fe(CN)6] (KMnHCF). This work not only presents a high-performance HE-PBA cathode in ZIBs, but also introduces a novel concept of high entropy benefiting for designing advanced materials.

Keywords

high-entropy materialsPrussian blue analoguesphase transformationsecondary batterieszinc-ion batteries

Electronic Supplementary Material

Download File(s)
12274_2022_5020_MOESM1_ESM.pdf (7.9 MB)

References

[1]

Cao, L. S.; Li, D.; Pollard, T.; Deng, T.; Zhang, B.; Yang, C. Y.; Chen, L.; Vatamanu, J.; Hu, E. Y.; Hourwitz, M. J. et al. Fluorinated interphase enables reversible aqueous zinc battery chemistries. Nat. Nanotechnol. 2021, 16, 902–910.
Crossref Google Scholar
[2]

Liang, Y. L.; Dong, H.; Aurbach, D.; Yao, Y. Current status and future directions of multivalent metal-ion batteries. Nat. Energy 2020, 5, 646–656.
Crossref Google Scholar
[3]

Zhang, Q.; Luan, J. Y.; Tang, Y. G.; Ji, X. B.; Wang, H. Y. Interfacial design of dendrite-free zinc anodes for aqueous zinc-ion batteries. Angew. Chem., Int. Ed. 2020, 59, 13180–13191.
Crossref Google Scholar
[4]

Huang, J. T.; Zhou, J.; Liang, S. Q. Guest pre-intercalation strategy to boost the electrochemical performance of aqueous zinc-ion battery Cathodes. Acta Phys. Chim. Sin. 2021, 37, 27–49.
Crossref Google Scholar
[5]

He, Y. N.; Xu, Y. F.; Zhang, M.; Xu, J. Z.; Chen, B. B.; Zhang, Y. X.; Bao, J. C.; Zhou, X. S. Confining ultrafine SnS nanoparticles in hollow multichannel carbon nanofibers for boosting potassium storage properties. Sci. Bull. 2022, 67, 151–160.
Crossref Google Scholar
[6]

Liao, J. Y.; Chen, C. L.; Hu, Q.; Du, Y. C.; He, Y. N.; Xu, Y. F.; Zhang, Z. Z.; Zhou, X. S. A low-strain phosphate cathode for high-rate and ultralong cycle-life potassium-ion batteries. Angew. Chem., Int. Ed. 2021, 60, 25575–25582.
Crossref Google Scholar
[7]

Gao, W. L.; Michalicka, J.; Pumera, M. Hierarchical atomic layer deposited V2O5 on 3D printed nanocarbon electrodes for high-performance aqueous zinc-ion batteries. Small 2022, 18, 2105572.
Crossref Google Scholar
[8]

Tian, Y. P.; Ju, M. M.; Bin, X. Q.; Luo, Y. J.; Que, W. X. Long cycle life aqueous rechargeable battery Zn/Vanadium hexacyanoferrate with H+/Zn2+ coinsertion for high capacity. Chem. Eng. J. 2022, 430, 132964.
Crossref Google Scholar
[9]

Cao, T.; Zhang, F.; Chen, M. J.; Shao, T.; Li, Z.; Xu, Q. J.; Cheng, D. H.; Liu, H. M.; Xia, Y. Y. Cubic manganese potassium hexacyanoferrate regulated by controlling of the water and defects as a high-capacity and stable cathode material for rechargeable aqueous zinc-ion batteries. ACS Appl. Mater. Interfaces 2021, 13, 26924–26935.
Crossref Google Scholar
[10]

Jia, X. X.; Liu, C. F.; Neale, Z. G.; Yang, J. H.; Cao, G. Z. Active materials for aqueous zinc ion batteries: Synthesis, crystal structure, morphology, and electrochemistry. Chem. Rev. 2020, 120, 7795–7866.
Crossref Google Scholar
[11]

Liao, Y. X.; Chen, H. C.; Yang, C.; Liu, R.; Peng, Z. W.; Cao, H. J.; Wang, K. K. Unveiling performance evolution mechanisms of MnO2 polymorphs for durable aqueous zinc-ion batteries. Energy Stor. Mater. 2022, 44, 508–516.
Crossref Google Scholar
[12]

Jin, Y.; Zou, L. F.; Liu, L. L.; Engelhard, M. H.; Patel, R. L.; Nie, Z. M.; Han, K. S.; Shao, Y. Y.; Wang, C. M.; Zhu, J. et al. Joint charge storage for high-rate aqueous zinc-manganese dioxide batteries. Adv. Mater. 2019, 31, 1900567.
Crossref Google Scholar
[13]

Zhong, C.; Liu, B.; Ding, J.; Liu, X. R.; Zhong, Y. W.; Li, Y.; Sun, C. B.; Han, X. P.; Deng, Y. D.; Zhao, N. Q. et al. Decoupling electrolytes towards stable and high-energy rechargeable aqueous zinc-manganese dioxide batteries. Nat. Energy 2020, 5, 440–449.
Crossref Google Scholar
[14]

Zhang, Y. R.; Chen, A. B.; Sun, J. Promise and challenge of vanadium-based cathodes for aqueous zinc-ion batteries. J. Energy Chem. 2021, 54, 655–667.
Crossref Google Scholar
[15]

Wan, F.; Niu, Z. Q. Design strategies for vanadium-based aqueous zinc-ion batteries. Angew. Chem., Int. Ed. 2019, 58, 16358–16367.
Crossref Google Scholar
[16]

Feng, Z. Y.; Sun, J. J.; Liu, Y. Y.; Jiang, H. M.; Cui, M.; Hu, T.; Meng, C. G.; Zhang, Y. F. Engineering interlayer space of vanadium oxide by pyridinesulfonic acid-assisted intercalation of polypyrrole enables enhanced aqueous zinc-ion storage. ACS Appl. Mater. Interfaces 2021, 13, 61154–61165.
Crossref Google Scholar
[17]

Li, W. J.; Han, C.; Cheng, G.; Chou, S. L.; Liu, H. K.; Dou, S. X. Chemical properties, structural properties, and energy storage applications of prussian blue analogues. Small 2019, 15, 1900470.
Crossref Google Scholar
[18]

Shi, Y. C.; Chen, Y.; Shi, L.; Wang, K.; Wang, B.; Li, L.; Ma, Y. M.; Li, Y. H.; Sun, Z. H.; Ali, W. et al. An overview and future perspectives of rechargeable zinc batteries. Small 2020, 16, 2000730.
Crossref Google Scholar
[19]

Liu, H. Y.; Wang, J. G.; You, Z. Y.; Wei, C. G.; Kang, F. Y.; Wei, B. Q. Rechargeable aqueous zinc-ion batteries: Mechanism, design strategies and future perspectives. Mater. Today 2021, 42, 73–98.
Crossref Google Scholar
[20]

Yi, H. C.; Qin, R. Z.; Ding, S. X.; Wang, Y. T.; Li, S. N.; Zhao, Q. H.; Pan, F. Structure and properties of prussian blue analogues in energy storage and conversion applications. Adv. Funct. Mater. 2021, 31, 2006970.
Crossref Google Scholar
[21]

Du, G. Y.; Pang, H. Recent advancements in Prussian blue analogues: Preparation and application in batteries. Energy Stor. Mater. 2021, 36, 387–408.
Crossref Google Scholar
[22]

Xu, Y. F.; Du, Y. C.; Yi, Z. Y.; Zhang, Z. Z.; Lai, C. L.; Liao, J. Y.; Zhou, X. S. Coupling Co3[Co(CN)6]2 nanocubes with reduced graphene oxide for high-rate and long-cycle-life potassium storage. J. Energy Chem. 2021, 58, 593–601.
Crossref Google Scholar
[23]

Xu, J. Y.; Xu, Y. F.; Lai, C. L.; Xia, T. T.; Zhang, B. N.; Zhou, X. S. Challenges and perspectives of covalent organic frameworks for advanced alkali-metal ion batteries. Sci. China Chem. 2021, 64, 1267–1282.
Crossref Google Scholar
[24]

Song, M.; Tan, H.; Chao, D. L.; Fan, H. J. Recent advances in Zn-ion batteries. Adv. Funct. Mater. 2018, 28, 1802564.
Crossref Google Scholar
[25]

Li, H. F.; Ma, L. T.; Han, C. P.; Wang, Z. F.; Liu, Z. X.; Tang, Z. J.; Zhi, C. Y. Advanced rechargeable zinc-based batteries: Recent progress and future perspectives. Nano Energy 2019, 62, 550–587.
Crossref Google Scholar
[26]

Tang, B. Y.; Shan, L. T.; Liang, S. Q.; Zhou, J. Issues and opportunities facing aqueous zinc-ion batteries. Energy Environ. Sci. 2019, 12, 3288–3304.
Crossref Google Scholar
[27]

Zeng, Y. X.; Lu, X. F.; Zhang, S. L.; Luan, D. Y.; Li, S.; Lou, X. W. Construction of Co-Mn prussian blue analog hollow spheres for efficient aqueous Zn-ion batteries. Angew. Chem., Int. Ed. 2021, 60, 22189–22194.
Crossref Google Scholar
[28]

Ma, Y. J.; Ma, Y.; Dreyer, S. L.; Wang, Q. S.; Wang, K.; Goonetilleke, D.; Omar, A.; Mikhailova, D.; Hahn, H.; Breitung, B. et al. High-entropy metal-organic frameworks for highly reversible sodium storage. Adv Mater 2021, 33, 2101342.
Crossref Google Scholar
[29]

George, E. P.; Raabe, D.; Ritchie, R. O. High-entropy alloys. Nat. Rev. Mater. 2019, 4, 515–534.
Crossref Google Scholar
[30]

Xie, B. X.; Zuo, P. J.; Wang, L. G.; Wang, J. J.; Huo, H.; He, M. X.; Shu, J.; Li, H. F.; Lou, S. F.; Yin, G. P. Achieving long-life Prussian blue analogue cathode for Na-ion batteries via triple-cation lattice substitution and coordinated water capture. Nano Energy 2019, 61, 201–210.
Crossref Google Scholar
[31]

Oses, C.; Toher, C.; Curtarolo, S. High-entropy ceramics. Nat. Rev. Mater. 2020, 5, 295–309.
Crossref Google Scholar
[32]

Wang, Q. S.; Sarkar, A.; Wang, D.; Velasco, L.; Azmi, R.; Bhattacharya, S. S.; Bergfeldt, T.; Düvel, A.; Heitjans, P.; Brezesinski, T. et al. Multi-anionic and -cationic compounds: New high entropy materials for advanced Li-ion batteries. Energy Environ. Sci. 2019, 12, 2433–2442.
Crossref Google Scholar
[33]

Sarkar, A.; Velasco, L.; Wang, D.; Wang, Q.; Talasila, G.; De Biasi, L.; Kübel, C.; Brezesinski, T.; Bhattacharya, S. S.; Hahn, H. et al. High entropy oxides for reversible energy storage. Nat. Commun. 2018, 9, 3400.
Crossref Google Scholar
[34]

Ma, Y. J.; Ma, Y.; Wang, Q. S.; Schweidler, S.; Botros, M.; Fu, T. T.; Hahn, H.; Brezesinski, T.; Breitung, B. High-entropy energy materials: Challenges and new opportunities. Energy Environ. Sci. 2021, 14, 2883–2905.
Crossref Google Scholar
[35]

Zhao, C. L.; Ding, F. X.; Lu, Y. X.; Chen, L. Q.; Hu, Y. S. High-entropy layered oxide cathodes for sodium-ion batteries. Angew. Chem., Int. Ed. 2020, 59, 264–269.
Crossref Google Scholar
[36]

You, Y.; Wu, X. L.; Yin, Y. X.; Guo, Y. G. High-quality Prussian blue crystals as superior cathode materials for room-temperature sodium-ion batteries. Energy Environ. Sci. 2014, 7, 1643–1647.
Crossref Google Scholar
[37]

Ji, Z.; Han, B.; Liang, H. T.; Zhou, C. G.; Gao, Q.; Xia, K. S.; Wu, J. P. On the Mechanism of the improved operation voltage of rhombohedral nickel hexacyanoferrate as cathodes for sodium-ion batteries. ACS Appl. Mater. Interfaces 2016, 8, 33619–33625.
Crossref Google Scholar
[38]

Li, J. H.; He, L. Z.; Jiang, J. B.; Xu, Z. F.; Liu, M. Q.; Liu, X.; Tong, H. X.; Liu, Z.; Qian, D. Facile syntheses of bimetallic Prussian blue analogues (KxM[Fe(CN)6]·nH2O, M = Ni, Co, and Mn) for electrochemical determination of toxic 2-nitrophenol. Electrochim. Acta 2020, 353, 136579.
Crossref Google Scholar
[39]

Chong, S. K.; Yang, J.; Sun, L.; Guo, S. W.; Liu, Y. N.; Liu, H. K. Potassium nickel iron hexacyanoferrate as ultra-long-life cathode material for potassium-ion batteries with high energy density. ACS Nano 2020, 14, 9807–9818.
Crossref Google Scholar
[40]

Huang, Y. X.; Xie, M.; Wang, Z. H.; Jiang, Y.; Yao, Y.; Li, S. J.; Li, Z. H.; Li, L.; Wu, F.; Chen, R. J. A chemical precipitation method preparing hollow-core-shell heterostructures based on the prussian blue analogs as cathode for sodium-ion batteries. Small 2018, 14, 1801246.
Crossref Google Scholar
[41]

Zhao, C. X.; Liu, B.; Li, X. N.; Zhu, K. X.; Hu, R. S.; Ao, Z. M.; Wang, J. H. A Co-Fe Prussian blue analogue for efficient Fenton-like catalysis: The effect of high-spin cobalt. Chem. Commun. 2019, 55, 7151–7154.
Crossref Google Scholar
[42]

Bie, X. F.; Kubota, K.; Hosaka, T.; Chihara, K.; Komaba, S. Synthesis and electrochemical properties of Na-rich Prussian blue analogues containing Mn, Fe, Co, and Fe for Na-ion batteries. J. Power Sources 2018, 378, 322–330.
Crossref Google Scholar
[43]

Li, Q.; Ma, K. X.; Yang, G. Z.; Wang, C. X. High-voltage non-aqueous Zn/K1.6Mn1. 2Fe(CN)6 batteries with zero capacity loss in extremely long working duration. Energy Stor. Mater. 2020, 29, 246–253.
Crossref Google Scholar
[44]

Xia, M. T.; Zhang, X. K.; Liu, T. T.; Yu, H. X.; Chen, S.; Peng, N.; Zheng, R. T.; Zhang, J. D.; Shu, J. Commercially available Prussian blue get energetic in aqueous K-ion batteries. Chem. Eng. J. 2020, 394, 124923.
Crossref Google Scholar
[45]

Ma, L. T.; Chen, S. M.; Long, C. B.; Li, X. L.; Zhao, Y. W.; Liu, Z. X.; Huang, Z. D.; Dong, B. B.; Zapien, J. A.; Zhi, C. Y. Achieving high-voltage and high-capacity aqueous rechargeable zinc ion battery by incorporating two-species redox reaction. Adv. Energy Mater. 2019, 9, 1902446.
Crossref Google Scholar
[46]

Tao, Y. Y.; Li, Z.; Tang, L. B.; Pu, X. M.; Cao, T.; Cheng, D. H.; Xu, Q. J.; Liu, H. M.; Wang, Y. G.; Xia, Y. Y. Nickel and cobalt Co-substituted spinel ZnMn2O4@N-rGO for increased capacity and stability as a cathode material for rechargeable aqueous zinc-ion battery. Electrochim. Acta 2020, 331, 135296.
Crossref Google Scholar
[47]

Tang, Y.; Li, W.; Feng, P. Y.; Zhou, M.; Wang, K. L.; Wang, Y. S.; Zaghib, K.; Jiang, K. High-performance manganese hexacyanoferrate with cubic structure as superior cathode material for sodium-ion batteries. Adv. Funct. Mater. 2020, 30, 1908754.
Crossref Google Scholar
[48]

Gao, Y. N.; Yang, H. Y.; Wang, X. R.; Bai, Y.; Zhu, N.; Guo, S. N.; Suo, L. M.; Li, H.; Xu, H. J.; Wu, C. The compensation effect mechanism of Fe-Ni mixed prussian blue analogues in aqueous rechargeable aluminum-ion batteries. ChemSusChem 2020, 13, 732–740.
Crossref Google Scholar
[49]

Xu, Y.; Wan, J.; Huang, L.; Xu, J.; Ou, M. Y.; Liu, Y.; Sun, X. P.; Li, S.; Fang, C.; Li, Q. et al. Dual redox-active copper hexacyanoferrate nanosheets as cathode materials for advanced sodium-ion batteries. Energy Stor. Mater. 2020, 33, 432–441.
Crossref Google Scholar
[50]

Kresse, G.; Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 1996, 54, 11169–11186.
Crossref Google Scholar
[51]

Kresse, G.; Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 1996, 6, 15–50.
Crossref Google Scholar
[52]

Kresse, G.; Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 1999, 59, 1758–1775.
Crossref Google Scholar
[53]

Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 1996, 77, 3865–3868.
Crossref Google Scholar
[54]

Henkelman, G.; Uberuaga, B. P.; Jónsson, H. A climbing image nudged elastic band method for finding saddle points and minimum energy paths. J. Chem. Phys. 2000, 113, 9901–9904.
Crossref Google Scholar
Nano Research
Volume 16 Issue 2,
February 2023
Pages 2486-2494
DOI: 10.1007/s12274-022-5020-0
Cite this article:
Xing J, Zhang Y, Jin Y, et al. Active cation-integration high-entropy Prussian blue analogues cathodes for efficient Zn storage. Nano Research, 2023, 16(2): 2486-2494. https://doi.org/10.1007/s12274-022-5020-0
Topics:
Secondary batteries

1399

Views

35

Crossref

33

Web of Science

34

Scopus

0

CSCD

Altmetrics
Received: 16 July 2022
Revised: 25 August 2022
Accepted: 06 September 2022
Published: 21 October 2022
© Tsinghua University Press 2022
Return