Hollow Core-Shelled Na4Fe2.4Ni0.6(PO4)2P2O7 with Tiny-Void Space Capable Fast-Charge and Low-Temperature Sodium Storage
Xinran Qi
Department of Chemistry, College of Science, Hebei Agriculture University, Baoding, 071001 P.R. China
State Key Laboratory of Metastable Materials Science and Technology, Hebei Key Laboratory of Nano-biotechnology, Yanshan University, Qinhuangdao, 066004 China
These authors contributed equally to this work.
Contribution: Methodology (equal), Writing - original draft (lead)
Search for more papers by this authorHanghang Dong
Institute for Carbon Neutralization, College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, Zhejiang, 325035 China
These authors contributed equally to this work.
Contribution: Data curation (lead)
Search for more papers by this authorHao Yan
Department of Chemical Engineering, School of Environmental and Chemical Engineering, Shanghai University, Shanghai, 200444 P. R. China
Contribution: Formal analysis (equal)
Search for more papers by this authorBaoxiu Hou
Department of Chemistry, College of Science, Hebei Agriculture University, Baoding, 071001 P.R. China
Contribution: Investigation (equal)
Search for more papers by this authorHaiyan Liu
Department of Chemistry, College of Science, Hebei Agriculture University, Baoding, 071001 P.R. China
Contribution: Funding acquisition (equal)
Search for more papers by this authorNingzhao Shang
Department of Chemistry, College of Science, Hebei Agriculture University, Baoding, 071001 P.R. China
Contribution: Methodology (equal)
Search for more papers by this authorCorresponding Author
Prof. Longgang Wang
State Key Laboratory of Metastable Materials Science and Technology, Hebei Key Laboratory of Nano-biotechnology, Yanshan University, Qinhuangdao, 066004 China
Contribution: Funding acquisition (equal), Project administration (equal)
Search for more papers by this authorCorresponding Author
Prof. Jianjun Song
College of Physics, Qingdao University, Qingdao, 266071 China
Contribution: Writing - review & editing (equal)
Search for more papers by this authorCorresponding Author
Prof. Shuangqiang Chen
Institute for Carbon Neutralization, College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, Zhejiang, 325035 China
Department of Chemical Engineering, School of Environmental and Chemical Engineering, Shanghai University, Shanghai, 200444 P. R. China
Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Nankai University, Tianjin, 300071 China
Contribution: Resources (equal), Software (supporting), Writing - review & editing (lead)
Search for more papers by this authorShulei Chou
Institute for Carbon Neutralization, College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, Zhejiang, 325035 China
Contribution: Writing - review & editing (equal)
Search for more papers by this authorCorresponding Author
Prof. Xiaoxian Zhao
Department of Chemistry, College of Science, Hebei Agriculture University, Baoding, 071001 P.R. China
Contribution: Funding acquisition (lead), Supervision (lead), Writing - original draft (equal), Writing - review & editing (lead)
Search for more papers by this authorXinran Qi
Department of Chemistry, College of Science, Hebei Agriculture University, Baoding, 071001 P.R. China
State Key Laboratory of Metastable Materials Science and Technology, Hebei Key Laboratory of Nano-biotechnology, Yanshan University, Qinhuangdao, 066004 China
These authors contributed equally to this work.
Contribution: Methodology (equal), Writing - original draft (lead)
Search for more papers by this authorHanghang Dong
Institute for Carbon Neutralization, College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, Zhejiang, 325035 China
These authors contributed equally to this work.
Contribution: Data curation (lead)
Search for more papers by this authorHao Yan
Department of Chemical Engineering, School of Environmental and Chemical Engineering, Shanghai University, Shanghai, 200444 P. R. China
Contribution: Formal analysis (equal)
Search for more papers by this authorBaoxiu Hou
Department of Chemistry, College of Science, Hebei Agriculture University, Baoding, 071001 P.R. China
Contribution: Investigation (equal)
Search for more papers by this authorHaiyan Liu
Department of Chemistry, College of Science, Hebei Agriculture University, Baoding, 071001 P.R. China
Contribution: Funding acquisition (equal)
Search for more papers by this authorNingzhao Shang
Department of Chemistry, College of Science, Hebei Agriculture University, Baoding, 071001 P.R. China
Contribution: Methodology (equal)
Search for more papers by this authorCorresponding Author
Prof. Longgang Wang
State Key Laboratory of Metastable Materials Science and Technology, Hebei Key Laboratory of Nano-biotechnology, Yanshan University, Qinhuangdao, 066004 China
Contribution: Funding acquisition (equal), Project administration (equal)
Search for more papers by this authorCorresponding Author
Prof. Jianjun Song
College of Physics, Qingdao University, Qingdao, 266071 China
Contribution: Writing - review & editing (equal)
Search for more papers by this authorCorresponding Author
Prof. Shuangqiang Chen
Institute for Carbon Neutralization, College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, Zhejiang, 325035 China
Department of Chemical Engineering, School of Environmental and Chemical Engineering, Shanghai University, Shanghai, 200444 P. R. China
Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Nankai University, Tianjin, 300071 China
Contribution: Resources (equal), Software (supporting), Writing - review & editing (lead)
Search for more papers by this authorShulei Chou
Institute for Carbon Neutralization, College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, Zhejiang, 325035 China
Contribution: Writing - review & editing (equal)
Search for more papers by this authorCorresponding Author
Prof. Xiaoxian Zhao
Department of Chemistry, College of Science, Hebei Agriculture University, Baoding, 071001 P.R. China
Contribution: Funding acquisition (lead), Supervision (lead), Writing - original draft (equal), Writing - review & editing (lead)
Search for more papers by this authorGraphical Abstract
Hollow core–shell Na4Fe2.4Ni0.6(PO4)2P2O7 with tiny-void space was synthesized by one-step spray drying and calcination for the first time due to the different viscosity, coordination ability, ratios, and shrinkage rates between CA and PVP, which ensures high energy density and relieves volume expansion, combining with regulation on Na+ diffusion path and energy barrier by doping Ni to achieve fast charging and low-temperature sodium storage.
Abstract
Iron-based mixed polyanion phosphate Na4Fe3(PO4)2P2O7 (NFPP) is recognized as a promising cathode for Sodium-ion Batteries (SIBs) due to its low cost and environmental friendliness. However, its inherent low conductivity and sluggish Na+ diffusion limit fast charge and low-temperature sodium storage. This study pioneers a scalable synthesis of hollow core–shelled Na4Fe2.4Ni0.6(PO4)2P2O7 with tiny-void space (THoCS-0.6Ni) via a one-step spray-drying combined with calcination process due to the different viscosity, coordination ability, molar ratios, and shrinkage rates between citric acid and polyvinylpyrrolidone. This unique structure with interconnected carbon networks ensures rapid electron transport and fast Na+ diffusion, as well as efficient space utilization for relieving volume expansion. Incorporating regulation of lattice structure by doping Ni heteroatom to effectively improve intrinsic electron conductivity and optimize Na+ diffusion path and energy barrier, which achieves fast charge and low-temperature sodium storage. As a result, THoCS-0.6Ni exhibits superior rate capability (86.4 mAh g−1 at 25 C). Notably, THoCS-0.6Ni demonstrates exceptional cycling stability at −20 °C with a capacity of 43.6 mAh g−1 after 2500 cycles at 5 C. This work provides a universal strategy to design the hollow core–shelled structure with tiny-void space cathode materials for reversible batteries with fast-charge and low-temperature Na-storage features.
Conflict of Interests
The authors declare no conflict of interest.
Open Research
Data Availability Statement
The data that support the findings of this study are available from the corresponding author upon reasonable request.
Supporting Information
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References
- 1W. Zhang, H. Li, Z. Zhang, M. Xu, Y. Lai, S. L. Chou, Small 2020, 16, 2001524.
- 2Z. Gu, X. Wang, Y. Heng, K. Zhang, H. Liang, J. Yang, E. Ang, P. Wang, Y. You, F. Du, X. Wu, Sci. Bull. 2023, 68, 2302–2306.
- 3M. Chen, Q. Liu, S. W. Wang, E. Wang, X. Guo, S. L. Chou, Adv. Energy Mater. 2019, 9, 1803609.
- 4X. Liu, Y. Cao, J. Sun, Adv. Energy Mater. 2022, 12, 2202532.
- 5Y.-F. Liu, K. Han, D.-N. Peng, L.-Y. Kong, Y. Su, H.-W. Li, H.-Y. Hu, J.-Y. Li, H.-R. Wang, Z.-Q. Fu, InfoMat 2023, 5, e12422.
- 6Z. Gu, Y. Heng, J. Guo, J. Cao, X. Wang, X. Zhao, Z. Sun, S. Zheng, H. Liang, B. Li, X. Wu, Nano Res. 2023, 16, 439–448.
- 7M.-Y. Wang, X.-X. Zhao, J.-Z. Guo, X.-J. Nie, Z.-Y. Gu, X. Yang, X.-L. Wu, Green Energy & Environ. 2022, 7, 763–771.
- 8X. Yin, S. Sarkar, S. Shi, Q. A. Huang, H. Zhao, L. Yan, Y. Zhao, J. Zhang, Adv. Funct. Mater. 2020, 30, 1908445.
- 9X. Ma, X. Wu, P. Shen, ACS Appl. Energ. Mater. 2018, 1, 6268.
- 10Z. Xiao, X. Dai, D. Jiang, H. Xie, X. Liu, M. Wu, D. Liu, Y. Li, Z. Qian, R. Wang, Adv. Funct. Mater. 2023, 33, 2304766.
- 11W. Ren, M. Qin, Y. Zhou, H. Zhou, J. Zhu, J. Pan, J. Zhou, X. Cao, S. Liang, Energy Storage Mater. 2023, 54, 776–783.
- 12F. Xiong, S. Tan, X. Yao, Q. An, L. Mai, Mater. Today 2021, 45, 169–190.
- 13P. Lu, Y. Xia, G. Sun, D. Wu, S. Wu, W. Yan, X. Zhu, J. Lu, Q. Niu, S. Shi, Z. Sha, L. Chen, H. Li, F. Wu, Nat. Commun. 2023, 14, 4077.
- 14Z. Wang, Z. Mu, T. Ma, W. Yan, D. Wu, M. Yang, J. Peng, Y. Xia, S. Shi, L. Chen, H. Li, F. Wu, Adv. Mater. 2024, 36, 2310395.
- 15Y. Wu, J. Xu, P. Lu, J. Lu, L. Gan, S. Wang, R. Xiao, H. Li, L. Chen, F. Wu, Adv. Energy Mater. 2023, 13, 2301336.
- 16F. Xiong, J. Li, C. Zuo, X. Zhang, S. Tan, Y. Jiang, Q. An, P. K. Chu, L. Mai, Adv. Funct. Mater. 2023, 33, 2211257.
- 17X. Li, Y. Zhang, B. Zhang, K. Qin, H. Liu, Z. Ma, J. Power Sources 2022, 521, 230922.
- 18J. Gao, H. Chen, Y. Mei, L. Ni, H. Wang, J. Huang, N. Hong, B. Song, Y. Tian, W. Deng, G. Zou, H. Hou, X. Ji, Nano Energy 2023, 115, 108747.
- 19H. Li, T. Jin, X. Chen, Y. Lai, Z. Zhang, W. Bao, L. Jiao, Adv. Energy Mater. 2018, 8, 1801418.
- 20H. Zhang, L. Wang, L. Ma, Y. Liu, B. Hou, N. Shang, S. Zhang, J. Song, S. Chen, X. Zhao, Adv. Sci. 2024, 11, 2306168.
- 21H. Zhang, S. Zhang, L.-j. Yu, L. Ma, H. Liu, S. Zhang, J. Wang, Y. Tang, X. Zhao, Angew. Chem. Int. Ed. 2024, 136, e202400285.
- 22T. Ma, Z. Wang, D. Wu, P. Lu, X. Zhu, M. Yang, J. Peng, L. Chen, H. Li, F. Wu, Energy Environ. Sci. 2023, 16, 2142–2152.
- 23L. Zhang, X. He, S. Wang, N. Ren, J. Wang, J. Dong, F. Chen, Y. Li, Z. Wen, C. Chen, ACS Appl. Mater. Interfaces 2021, 13, 25972–25980.
- 24W. Yan, Z. Mu, Z. Wang, Y. Huang, D. Wu, P. Lu, J. Lu, J. Xu, Y. Wu, T. Ma, M. Yang, X. Zhu, Y. Xia, S. Shi, L. Chen, H. Li, F. Wu, Nat. Energy 2023, 8, 800–813.
- 25T. Yuan, Y. Wang, J. Zhang, X. Pu, X. Ai, Z. Chen, H. Yang, Y. Cao, Nano Energy 2019, 56, 160.
- 26H. Kim, I. Park, D. Seo, S. Lee, S. Kim, W. Kwon, Y. Park, C. Kim, S. Jeon, K. Kang, J. Am. Chem. Soc. 2012, 134, 10369–10372.
- 27H. Li, Y. Bai, F. Wu, Q. Ni, C. Wu, ACS Appl. Mater. Interfaces 2016, 8, 27779–27787.
- 28M. Chen, W. Hua, J. Xiao, D. Cortie, W. Chen, E. Wang, Z. Hu, Q. Gu, X. Wang, S. Indris, Nat. Commun. 2019, 10, 1480.
- 29R. Essehli, B. El Bali, S. Benmokhtar, H. Fuess, I. Svoboda, S. Obbade, J. Alloys Compd. 2010, 493, 654–660.
- 30H. Song, K. Kim, J. Kim, S. Hong, D. Kim, Chem. Commun. 2017, 53, 9316–9319.
- 31J. Sang, X. Zhang, K. Liu, G. Cao, R. Guo, S. Zhang, Z. Wu, Y. Zhang, R. Hou, Y. Shen, Adv. Funct. Mater. 2023, 33, 2211640.
- 32X. Li, J. Zhang, Y. Zhang, B. Zhang, H. Liu, Q. Xu, Y. Xia, Chem. Eng. Sci. 2022, 260, 117951.
- 33W. Shen, C. Wang, Q. Xu, H. Liu, Y. Wang, Adv. Energy Mater. 2015, 5, 1400982.
- 34C. Shu, Z. Gan, Y. Hou, T. Zhu, J. Ma, W. Tang, Y. Wu, Energy Environ. Mater. 2021, 4, 81.
- 35J. Zhang, L. Tang, Y. Zhang, X. Li, Q. Xu, H. Liu, Z. Ma, J. Power Sources 2021, 498, 229907.
- 36Q. Peng, Y. Lu, S. Qi, M. Liang, D. Xu, W. Sun, L. Lv, Y. Wei, S. Chen, Y. Wang, ACS Appl. Energ. Mater. 2022, 5, 3199.
- 37X. Li, Y. Meng, X. Chen, Y. Wang, D. Xiao, Ind. Eng. Chem. Res. 2022, 61, 9311–9321.
- 38X. Ma, D. Wang, R. Xu, Y. Lai, X. Yu, Y. Liu, ChemSusChem 2021, 14, 5424–5433.
- 39X. Ao, W. Zhang, Z. Li, J. Li, L. Soule, X. Huang, W. Chiang, H. Chen, C. Wang, M. Liu, ACS Nano 2019, 13, 11853–11862.
- 40J. Yang, Z. Qiu, C. Zhao, W. Wei, W. Chen, Z. Li, Y. Qu, J. Dong, J. Luo, Z. Li, Y. Wu, Angew. Chem. Int. Ed. 2018, 57, 14095–14100.
- 41X. Ge, H. Li, J. Li, C. Guan, X. Wang, L. He, S. Li, Y. Lai, Z. Zhang, Small 2023, 19, 2302609.
- 42A. Zhao, T. Yuan, P. Li, C. Liu, H. Cong, X. Pu, Z. Chen, X. Ai, H. Yang, Y. Cao, Nano Energy 2022, 91, 106680.
- 43Y. Cao, X. Xia, Y. Liu, N. Wang, J. Zhang, D. Zhao, Y. Xia, J. Power Sources 2020, 461, 228130.
- 44X. Pu, H. Wang, T. Yuan, S. Cao, S. Liu, L. Xu, H. Yang, X. Ai, Z. Chen, Y. Cao, Energy Storage Mater. 2019, 22, 330–336.
- 45Q. Tao, H. Ding, X. Tang, K. Zhang, J. Teng, H. Zhao, J. Li, Energy Fuels 2023, 37, 6230–6239.
- 46X. Wang, H. Li, W. Zhang, X. Ge, L. He, L. Zhang, S. Li, N. Wen, J. Guo, Y. Lai, J. Mater. Chem. A 2023, 11, 6978–6985.
- 47Y. Xi, X. Wang, H. Wang, M. Wang, G. Wang, J. Peng, N. Hou, X. Huang, Y. Cao, Z. Yang, D. Liu, X. Pu, G. Cao, R. Duan, W. Li, J. Wang, K. Zhang, K. Xu, J. Zhang, X. Li, Adv. Funct. Mater. 2024, 34, 2309701.
- 48B. Yan, H. Sun, X. Liu, X. Fu, C. Xu, T. Zhang, H. Tao, L. Zhang, X. Li, X. Yang, R. Wang, Energy Environ. Sci. 2024, 17, 3419–3432.
- 49L. Miao, Z. Xiao, D. Shi, M. Wu, D. Liu, Y. Li, X. Liu, Y. Sun, S. Zhong, Z. Qian, R. Wang, Adv. Funct. Mater. 2023, 33, 2306952.
- 50H. Li, M. Xu, C. Gao, W. Zhang, Z. Zhang, Y. Lai, L. Jiao, Energy Storage Mater. 2020, 26, 325–333.
- 51X. Liu, G. Feng, E. Wang, H. Chen, Z. Wu, W. Xiang, Y. Zhong, Y. Chen, X. Guo, B. Zhong, ACS Appl. Mater. Interfaces 2019, 11, 12421–12430.
- 52Y. Fang, L. Xiao, J. Qian, Y. Cao, X. Ai, Y. Huang, H. Yang, Adv. Energy Mater. 2016, 6, 1502197.
- 53Y. Wang, X. Yu, S. Xu, J. Bai, R. Xiao, Y. Hu, H. Li, X. Yang, L. Chen, X. Huang, Nat. Commun. 2013, 4, 2365.
- 54Y. Jiang, Y. Wu, Y. Chen, Z. Qi, J. Shi, L. Gu, Y. Yu, Small 2018, 14, 1703471.
- 55J. Ming, H. Ming, W. Yang, W. Kwak, J. Park, J. Zheng, Y. Sun, RSC Adv. 2015, 5, 8793–8800.
- 56Y. Jiang, Y. Wu, Y. Chen, Z. Qi, J. Shi, L. Gu, Y. Yu, Small 2018, 14, 1703471.
- 57P. Hu, T. Zhu, C. Cai, B. Mai, C. Yang, J. Ma, L. Zhou, H. J. Fan, L. Mai, Adv. Funct. Mater. 2022, 32, 2208051.
- 58J. Zhang, H. Wen, L. Yue, J. Chai, J. Ma, P. Hu, G. Ding, Q. Wang, Z. Liu, G. Cui, Small 2017, 13, 1601530.
- 59J. Gao, Y. Tian, Y. Mei, L. Ni, H. Wang, H. Liu, W. Deng, G. Zou, H. Hou, X. Ji, Chem. Eng. J. 2023, 458, 141385.
- 60H. Wang, Z. Pan, H. Zhang, C. Dong, Y. Ding, Y. Cao, Z. Chen, Small Methods 2021, 5, 2100372.
