ACS Publications. Most Trusted. Most Cited. Most Read
Rhombohedral Potassium–Zinc Hexacyanoferrate as a Cathode Material for Nonaqueous Potassium-Ion Batteries

OR SEARCH CITATIONS

My Activity
Publications

Figure 1Loading Img
Download Hi-Res ImageDownload to MS-PowerPointCite This:Inorg. Chem. 2019, 58, 5, 3065-3072
    Article

    Rhombohedral Potassium–Zinc Hexacyanoferrate as a Cathode Material for Nonaqueous Potassium-Ion Batteries
    Click to copy article linkArticle link copied!

    • Jongwook W. Heo
      Jongwook W. Heo
      Department of Energy Science and Engineering, Daegu Gyeongbuk Institute of Science and Technology, Daegu 42988, Republic of Korea
      More by Jongwook W. Heo
    • Munseok S. Chae
      Munseok S. Chae
      Department of Energy Science and Engineering, Daegu Gyeongbuk Institute of Science and Technology, Daegu 42988, Republic of Korea
      More by Munseok S. Chae
    • Jooeun Hyoung
      Jooeun Hyoung
      Department of Energy Science and Engineering, Daegu Gyeongbuk Institute of Science and Technology, Daegu 42988, Republic of Korea
      More by Jooeun Hyoung
    • Seung-Tae Hong*
      Seung-Tae Hong
      Department of Energy Science and Engineering, Daegu Gyeongbuk Institute of Science and Technology, Daegu 42988, Republic of Korea
      *E-mail: [email protected]. Phone: +82 53 785 6409.
      More by Seung-Tae Hong
      Orcidhttp://orcid.org/0000-0002-5768-121X
    Other Access OptionsSupporting Information (1)

    Inorganic Chemistry

    Cite this: Inorg. Chem. 2019, 58, 5, 3065–3072
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.inorgchem.8b03081
    Published February 15, 2019
    Copyright © 2019 American Chemical Society
    Request reuse permissions

    Abstract

    Click to copy section linkSection link copied!
    Abstract Image

    Rhombohedral potassium–zinc hexacyanoferrate K1.88Zn2.88[Fe(CN)6]2(H2O)5 (KZnHCF) synthesized using a precipitation method is demonstrated as a high-voltage cathode material for potassium-ion batteries (PIBs), exhibiting an initial discharge capacity of 55.6 mAh g–1 with a discharge voltage of 3.9 V versus K/K+ and a capacity retention of ∼95% after 100 cycles in a nonaqueous electrolyte. All K ions are extracted from the structure upon the initial charge process. However, only 1.61 out of 1.88 K ions per formula unit are inserted back into the structure upon discharge, and it becomes the reversible ion of the second cycle onward. Despite the large ionic size of K, the material exhibits a lattice-volume change (∼3%) during a cycle, which is exceptionally small among the cathode materials for PIBs. The distinct feature of the material seems to come from the unique porous framework structure built by ZnN4 and FeC6 polyhedra linked via the C≡N bond and a Zn/Fe atomic ratio of 3/2, resulting in high structural stability and cycle performance.

    Copyright © 2019 American Chemical Society

    Subjects

    what are subjects

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. Add or change your institution or let them know you’d like them to include access.

    Supporting Information

    Click to copy section linkSection link copied!

    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.8b03081.

    • In situ XRD cell scheme, TGA, ICP results, SEM and TEM images, elemental mappings, and Rietveld results for KZnHCF, K0.79ZnHCF, and ZnHCF, electrochemical test results for an irregular-shaped phase of KZnHCF, XRD patterns for KZnHCF after 100 cycles, and ex situ XRD patterns for KxZnHCF (x = 1.88, 0.79, and 0) (PDF)

    Accession Codes

    CCDC 1871922 and 1871923 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    Click to copy section linkSection link copied!
    Citation Statements
    Explore this article's citation statements on scite.ai
    powered by  Scite

    This article is cited by 45 publications.

    1. Ju-Hyeon Lee, Jin-Gyu Bae, Min Sung Kim, Jeong Yeon Heo, Hyeon Jeong Lee, Ji Hoon Lee. Effect of the Interaction between Transition Metal Redox Center and Cyanide Ligand on Structural Evolution in Prussian White Cathodes. ACS Nano 2024, 18 (3) , 1995-2005. https://doi.org/10.1021/acsnano.3c08271
    2. Xuanjin Chen, Chunxiu Hua, Kaicheng Zhang, Haohao Sun, Shan Hu, Zelang Jian. Control of Gradient Concentration Prussian White Cathodes for High-Performance Potassium-Ion Batteries. ACS Applied Materials & Interfaces 2023, 15 (40) , 47125-47134. https://doi.org/10.1021/acsami.3c11278
    3. Anoopkumar V, Bibin John, Mercy TD. Potassium-Ion Batteries: Key to Future Large-Scale Energy Storage?. ACS Applied Energy Materials 2020, 3 (10) , 9478-9492. https://doi.org/10.1021/acsaem.0c01574
    4. Gan Li, Ting Wang, Yating Xue, Huifang Li, Dahuan Liu. Construction of low-vacancy hexagonal Prussian blue analogues for efficient rubidium recovery. Separation and Purification Technology 2025, 359 , 130842. https://doi.org/10.1016/j.seppur.2024.130842
    5. Long Cheng, Yuanyi Luo, Hao Wang, Zhiyue Zhou, Mengkai Yang, Chen Li, Yujie Zheng, Meng Li, Lei Wang, Kuan Sun. Optimized synthesis and electrochemical behaviors of Prussian blue analogues cathodes for potassium-ion batteries. Materials Reports: Energy 2025, 355 , 100331. https://doi.org/10.1016/j.matre.2025.100331
    6. Waseem Muneer, M. Imtiaz Khan, Said Karim Shah, Arif Ullah, Javed Iqbal, M. Arif Khan. Advances in prussian blue analogues: A comprehensive review on synthesis methods and battery applications. Materials Chemistry and Physics 2025, 332 , 130248. https://doi.org/10.1016/j.matchemphys.2024.130248
    7. Zihao Zhou, Yutao Dong, Yuan Ma, Hehe Zhang, Fanbo Meng, Yanjiao Ma, Yuping Wu. Innovative High‐Entropy Strategy Extending Traditional Metal Substitution for Optimizing Prussian Blue Analogues in Rechargeable Batteries. SusMat 2025, 29 https://doi.org/10.1002/sus2.265
    8. Yuhan Wu, Lin Li, Yusheng Wu. Potassium-ion battery cathode—Prussian blue analogs. 2025, 43-64. https://doi.org/10.1016/B978-0-443-13891-1.00003-0
    9. Pengfei Dai, Jiangfeng Huang, Xin Cao, Jianwei Zhao, Liang Xue, Yawen Tang, Ping Wu. Central metal coordination environment optimization enhances Na diffusion and structural stability in Prussian blue analogues. Energy Storage Materials 2025, 74 , 103890. https://doi.org/10.1016/j.ensm.2024.103890
    10. Yunjiang Gu, Yonglin Lu, Pengfei Dai, Xin Cao, Yiming Zhou, Yawen Tang, Zhiwei Fang, Ping Wu. Self-assembled high-entropy Prussian blue analogue nanosheets enabling efficient sodium storage. Journal of Colloid and Interface Science 2025, 677 , 307-313. https://doi.org/10.1016/j.jcis.2024.07.211
    11. Leonhard Karger, Saravanakumar Murugan, Liping Wang, Zhirong Zhao-Karger, Aleksandr Kondrakov, Florian Strauss, Torsten Brezesinski. Garnet-Type Zinc Hexacyanoferrates as Lithium, Sodium, and Potassium Solid Electrolytes. Batteries 2024, 10 (10) , 365. https://doi.org/10.3390/batteries10100365
    12. Kuo Sun, Shao‐Hua Luo, Ningyuan Du, Yu Wei, Shengxue Yan. Research progress of lithium manganese iron phosphate cathode materials: From preparation to modification. Electroanalysis 2024, 36 (8) https://doi.org/10.1002/elan.202400120
    13. Yifan Xu, Yichen Du, Han Chen, Jing Chen, Tangjing Ding, Dongmei Sun, Dong Ha Kim, Zhiqun Lin, Xiaosi Zhou. Recent advances in rational design for high-performance potassium-ion batteries. Chemical Society Reviews 2024, 53 (13) , 7202-7298. https://doi.org/10.1039/D3CS00601H
    14. Julen Beitia, Isabel Ahedo, Juan Ignacio Paredes, Eider Goikolea, Idoia Ruiz de Larramendi. Exploring Zinc-Doped Manganese Hexacyanoferrate as Cathode for Aqueous Zinc-Ion Batteries. Nanomaterials 2024, 14 (13) , 1092. https://doi.org/10.3390/nano14131092
    15. Chao Li, Hong Yan, Hanlu Yang, Min Yue, Shujun Li, Kuaibing Wang. Recent Advances on Pristine MOF‐Based Electrodes for PIBs: Characteristics, Potassium Storage Mechanisms, and Optimization Strategies. Batteries & Supercaps 2024, 13 https://doi.org/10.1002/batt.202400193
    16. Jiayi Cao, Yutao Xue, Zhenyuan Ji, Jinrui Pu, Xiaoping Shen, Lirong Kong, Aihua Yuan. CoNi hexacyanoferrate nanoparticles anchored on carbon nanotubes as superior cathode materials for rechargeable aqueous zinc-ion batteries. Journal of Energy Storage 2024, 86 , 111413. https://doi.org/10.1016/j.est.2024.111413
    17. Xinyue Li, Xiaolin Zhang, Junmin Xu, Zhixia Duan, Yue Xu, Xiaosheng Zhang, Lingling Zhang, Ye Wang, Paul K. Chu. Potassium‐Rich Iron Hexacyanoferrate/Carbon Cloth Electrode for Flexible and Wearable Potassium‐Ion Batteries. Advanced Science 2024, 11 (5) https://doi.org/10.1002/advs.202305467
    18. Jiayi Liu, Zhongrong Shen, Can-Zhong Lu. Research progress of Prussian blue and its analogues for cathodes of aqueous zinc ion batteries. Journal of Materials Chemistry A 2024, 12 (5) , 2647-2672. https://doi.org/10.1039/D3TA06641J
    19. Wenli Shu, Chunhua Han, Xuanpeng Wang. Prussian Blue Analogues Cathodes for Nonaqueous Potassium‐Ion Batteries: Past, Present, and Future. Advanced Functional Materials 2024, 34 (1) https://doi.org/10.1002/adfm.202309636
    20. Yue Bai, Ke'er YuChi, Xu Liu, Shinuo Tian, Shujie Yang, Xi Qian, Bin Ma, Minghao Fang, Yan'gai Liu, Zhaohui Huang, Xin Min. Progress of Prussian Blue and Its Analogues as Cathode Materials for Potassium Ion Batteries. European Journal of Inorganic Chemistry 2023, 26 (25) https://doi.org/10.1002/ejic.202300246
    21. Qingyi Song, Zongyou Li, Songjie Gan, Wenshuai Dong, Wei Wang, Jianguo Zhang, Qiyao Yu. Progress and challenges of Prussian blue analogs for potassium-ion batteries: a perspective on redox-active transition metals. Journal of Materials Chemistry A 2023, 11 (4) , 1532-1550. https://doi.org/10.1039/D2TA08573A
    22. Yueyue Yuan, Junmin Xu, Xinyue Li, Xin Li, Xinchang Wang, Xinjian Li, Shuge Dai. High-quality Prussian blue analogues K2Zn3[Fe(CN)6]2 crystals as a stable and high rate cathode material for potassium-ion batteries. Journal of Alloys and Compounds 2022, 923 , 166457. https://doi.org/10.1016/j.jallcom.2022.166457
    23. Shabnam Amin, Seyed Abolhasan Alavi, Hasan Aghayan, Hassan Yousefnia. Synthesis and characterization of a novel nanocomposite ([(SBA-15)-(Cu(BTC)]-[KZn(Fe(CN)6)]) for cesium removal from aqueous media and optimization condition using central composite design. Microporous and Mesoporous Materials 2022, 345 , 112250. https://doi.org/10.1016/j.micromeso.2022.112250
    24. Qianchen Wang, Jingbo Li, Haibo Jin, Sen Xin, Hongcai Gao. Prussian‐blue materials: Revealing new opportunities for rechargeable batteries. InfoMat 2022, 4 (6) https://doi.org/10.1002/inf2.12311
    25. Jihwan Kim, Seong-Hoon Yi, Li Li, Sang-Eun Chun. Enhanced stability and rate performance of zinc-doped cobalt hexacyanoferrate (CoZnHCF) by the limited crystal growth and reduced distortion. Journal of Energy Chemistry 2022, 69 , 649-658. https://doi.org/10.1016/j.jechem.2022.01.034
    26. Jie Feng, Shaohua Luo, Kexing Cai, Shengxue Yan, Qing Wang, Yahui Zhang, Xin Liu. Research progress of tunnel-type sodium manganese oxide cathodes for SIBs. Chinese Chemical Letters 2022, 33 (5) , 2316-2326. https://doi.org/10.1016/j.cclet.2021.09.077
    27. Qingyun Yang, Yanjin Liu, Hong Ou, Xueyi Li, Xiaoming Lin, Akif Zeb, Lei Hu. Fe-Based metal–organic frameworks as functional materials for battery applications. Inorganic Chemistry Frontiers 2022, 9 (5) , 827-844. https://doi.org/10.1039/D1QI01396C
    28. Ashwani Tyagi, Nagmani, Sreeraj Puravankara. Opportunities in Na/K [hexacyanoferrate] frameworks for sustainable non-aqueous Na + /K + batteries. Sustainable Energy & Fuels 2022, 6 (3) , 550-595. https://doi.org/10.1039/D1SE01653A
    29. Jiaqiang ZHANG, Xinlei ZOU, Nengze WANG, Chunyang JIA. Zn-Fe PBA Films by Two-step Electrodeposition Method: Preparation and Performance in Electrochromic Devices. Journal of Inorganic Materials 2022, 37 (9) , 961. https://doi.org/10.15541/jim20210724
    30. Junmin Xu, Yueyue Yuan, Xinyue Li, Xin Li, Xinchang Wang, Xinjian Li, Shuge Dai. High-Quality Prussian Blue Analogues K2zn3[Fe(Cn)6]2 Crystals as a Stable and High Rate Cathode Material for Potassium-Ion Batteries. SSRN Electronic Journal 2022, 12 https://doi.org/10.2139/ssrn.4070211
    31. Jia Lin, R. Chenna Krishna Reddy, Chenghui Zeng, Xiaoming Lin, Akif Zeb, Cheng-Yong Su. Metal-organic frameworks and their derivatives as electrode materials for potassium ion batteries: A review. Coordination Chemistry Reviews 2021, 446 , 214118. https://doi.org/10.1016/j.ccr.2021.214118
    32. Qian Li, Kaixuan Ma, Cheng Hong, Zhen Yang, Chenze Qi, Gongzheng Yang, Chengxin Wang. High-voltage K/Zn dual-ion battery with 100,000-cycles life using zero-strain ZnHCF cathode. Energy Storage Materials 2021, 42 , 715-722. https://doi.org/10.1016/j.ensm.2021.08.017
    33. Yan‐Song Xu, Si‐Jie Guo, Xian‐Sen Tao, Yong‐Gang Sun, Jianmin Ma, Chuntai Liu, An‐Min Cao. High‐Performance Cathode Materials for Potassium‐Ion Batteries: Structural Design and Electrochemical Properties. Advanced Materials 2021, 33 (36) https://doi.org/10.1002/adma.202100409
    34. Yirui Li, Qi Dang, Wenqian Chen, Liang Tang, Ming Hu. Recent Advances in Rechargeable Batteries with Prussian Blue Analogs Nanoarchitectonics. Journal of Inorganic and Organometallic Polymers and Materials 2021, 31 (5) , 1877-1893. https://doi.org/10.1007/s10904-021-01886-6
    35. Guangyu Du, Huan Pang. Recent advancements in Prussian blue analogues: Preparation and application in batteries. Energy Storage Materials 2021, 36 , 387-408. https://doi.org/10.1016/j.ensm.2021.01.006
    36. Munseok S. Chae, Yuval Elias, Doron Aurbach. Tunnel‐Type Sodium Manganese Oxide Cathodes for Sodium‐Ion Batteries. ChemElectroChem 2021, 8 (5) , 798-811. https://doi.org/10.1002/celc.202001323
    37. Fei Wang, Yong Liu, Hui-Jie Wei, Teng-Fei Li, Xun-Hui Xiong, Shi-Zhong Wei, Feng-Zhang Ren, Alex A. Volinsky. Recent advances and perspective in metal coordination materials-based electrode materials for potassium-ion batteries. Rare Metals 2021, 40 (2) , 448-470. https://doi.org/10.1007/s12598-020-01649-1
    38. Bo Wang, Edison Huixiang Ang, Yang Yang, Yufei Zhang, Minghui Ye, Qi Liu, Cheng Chao Li. Post‐Lithium‐Ion Battery Era: Recent Advances in Rechargeable Potassium‐Ion Batteries. Chemistry – A European Journal 2021, 27 (2) , 512-536. https://doi.org/10.1002/chem.202001811
    39. Aijun Zhou, Weijie Cheng, Wei Wang, Qiang Zhao, Jian Xie, Wuxing Zhang, Hongcai Gao, Leigang Xue, Jingze Li. Hexacyanoferrate‐Type Prussian Blue Analogs: Principles and Advances Toward High‐Performance Sodium and Potassium Ion Batteries. Advanced Energy Materials 2021, 11 (2) https://doi.org/10.1002/aenm.202000943
    40. Mengxi Yang, Noel Leon, Baofei Pan, Zhou Yu, Lei Cheng, Chen Liao. Mechanistic Insights in Quinone-Based Zinc Batteries with Nonaqueous Electrolytes. Journal of The Electrochemical Society 2020, 167 (10) , 100536. https://doi.org/10.1149/1945-7111/ab9b0a
    41. Davi Marcelo Soares, Santanu Mukherjee, Gurpreet Singh. TMDs beyond MoS 2 for Electrochemical Energy Storage. Chemistry – A European Journal 2020, 26 (29) , 6320-6341. https://doi.org/10.1002/chem.202000147
    42. Sapna Raghav, Pallavi Jain, Praveen Kumar Yadav, Dinesh Kumar. Alloys for K‐Ion Batteries. 2020, 191-211. https://doi.org/10.1002/9781119654919.ch10
    43. Xianghua Zhang, Dan Yang, Xianhong Rui, Yan Yu, Shaoming Huang. Advanced cathodes for potassium-ion battery. Current Opinion in Electrochemistry 2019, 18 , 24-30. https://doi.org/10.1016/j.coelec.2019.09.002
    44. Tomer Y. Burshtein, Eliyahu M. Farber, Kasinath Ojha, David Eisenberg. Revealing structure–activity links in hydrazine oxidation: doping and nanostructure in carbide–carbon electrocatalysts. Journal of Materials Chemistry A 2019, 7 (41) , 23854-23861. https://doi.org/10.1039/C9TA03357B
    45. Yunpo Sun, Chunli Liu, Jian Xie, Dagao Zhuang, Wenquan Zheng, Xinbing Zhao. Potassium manganese hexacyanoferrate/graphene as a high-performance cathode for potassium-ion batteries. New Journal of Chemistry 2019, 43 (29) , 11618-11625. https://doi.org/10.1039/C9NJ02085C
    Download PDF
    Go to Inorganic Chemistry
    Get e-Alerts
    Get e-Alerts

    Inorganic Chemistry

    Cite this: Inorg. Chem. 2019, 58, 5, 3065–3072
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.inorgchem.8b03081
    Published February 15, 2019
    Copyright © 2019 American Chemical Society
    Request reuse permissions

    Article Views

    2435

    Altmetric

    -

    Citations

    45
    Learn about these metrics

    Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.

    Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.

    The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.