High-Entropy and Component Stoichiometry Tuning Strategies Boost the Sodium-Ion Storage Performance of Cobalt-Free Prussian Blue Analogues Cathode Materials
Prussian blue analogs (PBAs) are appealing cathode materials for sodium-ion batteries because of their low material cost, facile synthesis methods, rigid open framework, and high theoretical capacity. However, the poor electrical conductivity, unavoidable presence of [Fe(CN)<sub>6</sub>]...
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2024-09-01
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| author | Yuan-Ting Lin Bai-Tong Niu Zi-Han Wang Yu-Xi Li Yun-Peng Xu Shi-Wei Liu Yan-Xin Chen Xiu-Mei Lin |
| author_facet | Yuan-Ting Lin Bai-Tong Niu Zi-Han Wang Yu-Xi Li Yun-Peng Xu Shi-Wei Liu Yan-Xin Chen Xiu-Mei Lin |
| author_sort | Yuan-Ting Lin |
| collection | DOAJ |
| description | Prussian blue analogs (PBAs) are appealing cathode materials for sodium-ion batteries because of their low material cost, facile synthesis methods, rigid open framework, and high theoretical capacity. However, the poor electrical conductivity, unavoidable presence of [Fe(CN)<sub>6</sub>] vacancies and crystalline water within the framework, and phase transition during charge–discharge result in inferior electrochemical performance, particularly in terms of rate capability and cycling stability. Here, cobalt-free PBAs are synthesized using a facile and economic co-precipitation method at room temperature, and their sodium-ion storage performance is boosted due to the reduced crystalline water content and improved electrical conductivity via the high-entropy and component stoichiometry tuning strategies, leading to enhanced initial Coulombic efficiency (ICE), specific capacity, cycling stability, and rate capability. The optimized HE-HCF of Fe<sub>0.60</sub>Mn<sub>0.10</sub>-hexacyanoferrate (referred to as Fe<sub>0.60</sub>Mn<sub>0.10</sub>-HCF), with the chemical formula Na<sub>1.156</sub>Fe<sub>0.599</sub>Mn<sub>0.095</sub>Ni<sub>0.092</sub>Cu<sub>0.109</sub>Zn<sub>0.105</sub> [Fe(CN)<sub>6</sub>]<sub>0.724</sub>·3.11H<sub>2</sub>O, displays the most appealing electrochemical performance of an ICE of 100%, a specific capacity of around 115 and 90 mAh·g<sup>−1</sup> at 0.1 and 1.0 A·g<sup>−1</sup>, with 66.7% capacity retention observed after 1000 cycles and around 61.4% capacity retention with a 40-fold increase in specific current. We expect that our findings could provide reference strategies for the design of SIB cathode materials with superior electrochemical performance. |
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| language | English |
| publishDate | 2024-09-01 |
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| spelling | doaj-art-8aa49d7d6f984b5ab6ef679b04f1bddd2025-08-20T02:16:54ZengMDPI AGMolecules1420-30492024-09-012919455910.3390/molecules29194559High-Entropy and Component Stoichiometry Tuning Strategies Boost the Sodium-Ion Storage Performance of Cobalt-Free Prussian Blue Analogues Cathode MaterialsYuan-Ting Lin0Bai-Tong Niu1Zi-Han Wang2Yu-Xi Li3Yun-Peng Xu4Shi-Wei Liu5Yan-Xin Chen6Xiu-Mei Lin7College of Chemistry, Chemical Engineering and Environment, Minnan Normal University, Zhangzhou 363000, ChinaCollege of Chemistry, Chemical Engineering and Environment, Minnan Normal University, Zhangzhou 363000, ChinaCollege of Energy, Xiamen University, Xiamen 361005, ChinaState Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, iChEM, Xiamen University, Xiamen 361005, ChinaDepartment of Physic, Xiamen University, Xiamen 361005, ChinaCollege of Chemistry, Chemical Engineering and Environment, Minnan Normal University, Zhangzhou 363000, ChinaState Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, ChinaCollege of Chemistry, Chemical Engineering and Environment, Minnan Normal University, Zhangzhou 363000, ChinaPrussian blue analogs (PBAs) are appealing cathode materials for sodium-ion batteries because of their low material cost, facile synthesis methods, rigid open framework, and high theoretical capacity. However, the poor electrical conductivity, unavoidable presence of [Fe(CN)<sub>6</sub>] vacancies and crystalline water within the framework, and phase transition during charge–discharge result in inferior electrochemical performance, particularly in terms of rate capability and cycling stability. Here, cobalt-free PBAs are synthesized using a facile and economic co-precipitation method at room temperature, and their sodium-ion storage performance is boosted due to the reduced crystalline water content and improved electrical conductivity via the high-entropy and component stoichiometry tuning strategies, leading to enhanced initial Coulombic efficiency (ICE), specific capacity, cycling stability, and rate capability. The optimized HE-HCF of Fe<sub>0.60</sub>Mn<sub>0.10</sub>-hexacyanoferrate (referred to as Fe<sub>0.60</sub>Mn<sub>0.10</sub>-HCF), with the chemical formula Na<sub>1.156</sub>Fe<sub>0.599</sub>Mn<sub>0.095</sub>Ni<sub>0.092</sub>Cu<sub>0.109</sub>Zn<sub>0.105</sub> [Fe(CN)<sub>6</sub>]<sub>0.724</sub>·3.11H<sub>2</sub>O, displays the most appealing electrochemical performance of an ICE of 100%, a specific capacity of around 115 and 90 mAh·g<sup>−1</sup> at 0.1 and 1.0 A·g<sup>−1</sup>, with 66.7% capacity retention observed after 1000 cycles and around 61.4% capacity retention with a 40-fold increase in specific current. We expect that our findings could provide reference strategies for the design of SIB cathode materials with superior electrochemical performance.https://www.mdpi.com/1420-3049/29/19/4559high-entropycomponent stoichiometry tuningprussian blue analogues (PBAS)cobalt-free cathode materialssodium-ion batteries |
| spellingShingle | Yuan-Ting Lin Bai-Tong Niu Zi-Han Wang Yu-Xi Li Yun-Peng Xu Shi-Wei Liu Yan-Xin Chen Xiu-Mei Lin High-Entropy and Component Stoichiometry Tuning Strategies Boost the Sodium-Ion Storage Performance of Cobalt-Free Prussian Blue Analogues Cathode Materials Molecules high-entropy component stoichiometry tuning prussian blue analogues (PBAS) cobalt-free cathode materials sodium-ion batteries |
| title | High-Entropy and Component Stoichiometry Tuning Strategies Boost the Sodium-Ion Storage Performance of Cobalt-Free Prussian Blue Analogues Cathode Materials |
| title_full | High-Entropy and Component Stoichiometry Tuning Strategies Boost the Sodium-Ion Storage Performance of Cobalt-Free Prussian Blue Analogues Cathode Materials |
| title_fullStr | High-Entropy and Component Stoichiometry Tuning Strategies Boost the Sodium-Ion Storage Performance of Cobalt-Free Prussian Blue Analogues Cathode Materials |
| title_full_unstemmed | High-Entropy and Component Stoichiometry Tuning Strategies Boost the Sodium-Ion Storage Performance of Cobalt-Free Prussian Blue Analogues Cathode Materials |
| title_short | High-Entropy and Component Stoichiometry Tuning Strategies Boost the Sodium-Ion Storage Performance of Cobalt-Free Prussian Blue Analogues Cathode Materials |
| title_sort | high entropy and component stoichiometry tuning strategies boost the sodium ion storage performance of cobalt free prussian blue analogues cathode materials |
| topic | high-entropy component stoichiometry tuning prussian blue analogues (PBAS) cobalt-free cathode materials sodium-ion batteries |
| url | https://www.mdpi.com/1420-3049/29/19/4559 |
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