JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2024
·
IF 9.4
Qing Zhu,Jinxin Wu,Wenhao Li,Xiuli Hu,Ningchen Tian,Liqing He,Yanwei Li
Na superionic conductor ( NASICON)-structured Na 4 MnCr(PO 4 ) 3 (NMCP) possessing unique three-electron transfer process renders admirable energy density for sodium ion batteries (SIBs). However, the current issues like its sluggish Na + diffusion kinetics, deficient intrinsic conductivity, and unsatisfactory structural stability, hinder its practical application. Herein, a selective replacement of O elements in PO 4 group by Cl anions in the NMCP system was developed to significantly enhance its electrochemical performance. The results affirm that the enhanced performance of Cl doped samples can be attributed to the enlargement of cell size, the creation of Na vacancies and the weakness of Na2 O bond after Cl doping. The as-prepared Na 3.85 □ 0.15 MnCr(PO 3.95 Cl 0.05 ) 3 /C (NMCPC − 15/C) cathode delivers a high capacity (128.0 mAh/g at 50 mA g −1 ) and excellent rate performance (73.0 mAh/g at 1000 mA g −1 ) in contrast to NMCP/C that merely provides 105.2 mAh/g at 50 mA g −1 and reduces to 47.4 mAh/g at 1000 mA g −1 . Meanwhile, NMCPC − 15/C shows a capacity retention of 60.7 % at 1000 mA g −1 after 500 cycles, while only 37.1 % for NMCP/C in the same test conditions. Moreover, the satisfactory performance and energy density of NMCPC − 15/C||hard carbon (HC) full cell confirm the potential practicality of NMCPC − 15. Therefore, chloride ions doping into NMCP has practical application prospects in the preparation of high-performance cathode materials and our work also offers new inspiration to apply anion doping strategies in promoting the performance of the other NASICON-structured cathodes for SIBs.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
APPLIED SURFACE SCIENCE
·
2024
·
IF 6.3
Keyi Sun,Yuxuan Liu,Wenbin Fei,Yian Wang,Huazhang Guo,Kexin Rao,Mengting Deng,Yulei Sui,Ling Wu
Na 4 MnCr(PO 4 ) 3 , a manganese-based NASICON-type phosphate cathode material, is attracted considerable attention due to its high voltage and energy density. However, its practical application is hindered by poor electronic conductivity and inferior sodium ion diffusion kinetics. In this study, trace La 3+ is utilized to optimize the lattice structure of Na 4 MnCr(PO 4 ) 3 due to its unique energy level structure. La 3+ doping significantly enhances the local environment of the Mn-O bond and stabilizes the lattice structure by improving covalency, thereby mitigating Mn dissolution during charge–discharge cycles. Additionally, the large ionic radius of La 3+ promotes the sodium ion transport kinetics by expanding the cell volume and facilitating rapid sodium storage. As a result, the optimal Na 4 MnCr 0.995 La 0.005 (PO 4 ) 3 /C sample demonstrates an impressive initial discharge specific capacity of 124.5 mAh g −1 at 0.1C and superior cycling stability with a capacity retention of 70.2 % after 500 cycles at 5C. Furthermore, density functional theory calculations indicate that La 3+ doping can enhance conductivity and reduce the energy barrier for sodium ion diffusion. This study presents an effective and cost-efficient doping strategy for modifying high-energy density NASICON-type phosphate cathode materials, showing promising potential in the field of sodium ion batteries.
研究领域:
材料科学
·
电化学
·
能源存储
·
无机固体化学
·
计算材料学
✓ 已验证
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2025
·
IF 8.2
Xiangyu Han,Jiaqi Wang,Yongguang Liu,Lei Dai,Ling Wang,Shan Liu
All-solid-state sodium-ion batteries (ASSIBs) with inorganic solid electrolytes can achieve high safety and high energy density when paired with a high-voltage cathode. However, the slow charge transfer and chemical instability between the high-voltage cathode and rigid electrolyte seriously restrict its development. Herein, a high energy density Na4MnCr(PO4)3-based ASSIBs have been achieved by using a simple low-temperature brazing strategy. The in situ generated secondary phase can not only achieve close contact and rapid charge transfer between the Na4MnCr(PO4)3 cathode and electrolyte but also change the interface electric field distribution and reduce interface side reactions effectively. This strategy is simple and easy to implement and has important guidance for the development of other high-energy all-solid-state batteries.
研究领域:
材料科学
·
电化学
·
能源存储
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Advanced Sustainable Systems
·
2023
·Vol. 9
·期 7
·2300233
·
IF 7.1
Sijie Yu,Yuwei Chen,Yangyang Huang,Huabin Sun,Yu Xie,Sihao Du,Wei Luo
NASICON (NAtrium Super Ionic CONductor)-structured Na 4 MnCr(PO 4 ) 3 has attracted attention as a promising cathode for sodium-ion batteries due to its high operating voltage and specific capacity contributed by multielectron reactions. Unfortunately, its intrinsic low electronic conductivity significantly hinders the release of specific capacity and rate capability, preventing its practical application. Herein, a carbon layer with dual conductive networks connected by chain-like Ketjen black (KB) is built on the surface of Na 4 MnCr(PO 4 ) 3 material. This novel Na 4 MnCr(PO 4 ) 3 /C@KB composite material exhibits improved rate capability of 61.2 mAh g −1 at 2 C compared to 19.5 mAh g −1 of Na 4 MnCr(PO 4 ) 3 /C and high reversible capacity of 88.0 mAh g −1 at 1 C with 73% capacity retention after 100 cycles. The enhanced electrochemical performance can be ascribed to an increase of electronic conductivity enabled by the dual conductive 3D network construction and an adequate infiltration of electrolyte by substantial pores existence in carbon layer. A promising dual conductive network design strategy is demonstrated here for improving the performance of NASICON-structured cathodes.
研究领域:
材料科学
·
电化学
·
能源存储
·
无机化学
·
纳米材料
·
固态离子学
✓ 已验证
DOI
高影响因子
Energy Material Advances
·
2023
·
IF 12.9
Zhongyue Wang,Cheng Tang,Zhi Wang,Qing Zhang,Peng Lv,Kehan Yu,Jiajin Zheng,Wei Wei
Developing high-energy cathode for sodium ion batteries (SIBs) that enables 3-electron reaction is the most effective way to reduce high cost and solve range anxiety and safety hazards. Here, a novel NASICON-type Na 4 MnCr(PO 4 ) 3 (NMCP) is synthesized as a high-energy cathode for SIBs. The as-prepared 6.4 wt% carbon-coated NMCP (NMCP@C) cathode annealed at 700 °C delivers a discharge capacity of 107.3 mA h g −1 @0.1C, high rate capability up to 15C, and well capacity retention of 69.3% after 500 cycles at 5C within 1.4 ~ 4.3 V. Meanwhile, it also provides an exciting reversible capacity of 164.3 mA h g −1 @0.1C within 1.4 ~ 4.6 V and an ultrahigh energy density of 523.6 Wh kg −1 . Moreover, high sodium ion diffusion coefficients ( D Na+ , 10 −12 ~ 10 −9 cm 2 s −1 ) demonstrate the superior electrode process kinetics, and both solid solution and 2-phase reactions are involved in the sodium ion extraction/insertion process through ex situ x-ray diffraction analyses. Na 3.3 La 0.3 Zr 1.7 Si 2 PO 12 with 3 wt% Na 2 B 4 O 7 additive (NLZSP(NBO3)) ceramic electrolyte is utilized to assemble NMCP@C//NLZSP(NBO3)//Na solid-state sodium metal batteries for the first time, which reveals an initial discharge capacity of 99.1 mA h g −1 (1.4 ~ 4.3 V) and 121.7 mA h g −1 (1.4 ~ 4.6 V) at 0.1C and an excellent cycling performance (capacity retention of 75.8%/72.6% after 100 cycles at 0.2C) at 30 °C. All these confirm that NMCP@C is a high-energy cathode with great practical potential for all-solid-state SIBs.
✓ 已验证
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2024
·
IF 8.3
Suo Chen,Jie Hou,Xin He,Qingyuan Wang,Wei Wang,Min Zhou,Kangli Wang,Kai Jiang
Manganese-based NASICON-type compounds are promising as high-energy-density cathodes for sodium-ion batteries. However, the structural defects of Mn ions inside the crystal framework reduce the sodium storage capacity, voltage plateau, and cyclic stability of the cathodes. Here, a strategy to inhibit the Mn ion defects of Na4MnCr(PO4)3 has been proposed by using different phosphate sources. It is found that Na4MnCr(PO4)3 prepared with NH4H2PO4 (NMCP-N) exhibits less noticeable voltage hysteresis than that of Na4MnCr(PO4)3 prepared with H3PO4 (NMCP-H), indicating that the site occupation defects of Mn ions in the Na4MnCr(PO4)3 crystal structure are successfully suppressed, as confirmed by theoretical calculations and structural refinements. In the case of NMCP-N, a capacity of 109.7 mAh g–1 is delivered at 0.01 A g–1, and 54.2% capacity retention can be kept after 500 cycles at 0.5 A g–1, which is much better than that of the counterpart of NMCP-H (a lower capacity of 96.1 mAh g–1 and poorer cyclability of only 22.8% capacity retention after 500 cycles), showing that the structure defects strongly affect the sodium storage properties of Na4MnCr(PO4)3 cathodes. This work provides an effective strategy to manipulate the structure defects of Mn-based NASICON-type cathode materials to enhance their electrochemistry.
研究领域:
材料科学
·
电化学
·
储能
·
电池技术
✓ 已验证
DOI
高影响因子
SOLID STATE IONICS
·
2024
·
IF 3
Shengping Deng,Chongran Song,Shiyu Li,Ying Bai
NASICON-type Na 4 MnCr(PO 4 ) 3 (NMCP) has gained significant attention due to its prominent capacity and voltage platform. However, poor intrinsic electron conductivity severely obstructed its wider application. Here, the NMCP was decorated through structurally integrated with the high conductive carbon nanotubes (CNTs) component via the sol-gel method. The CNTs additive was tightly implanted NMCP bulk, providing fast electron transfer rates, further reduced charge transfer resistance and ohmic resistance , and improving the electrochemical properties of NMCP during the reversible intercalation/deintercalation of Na + . Finally, the as-prepared rambutan-like NMCP/C@CNTs could release a high reversible capability of 118.7 mAh g −1 at 0.1C and exhibit long durability over 500 cycles at a high rate of 10C. The pseudocapacitance contributions were investigated, and the Na storage mechanism was also demonstrated through in-situ synchrotron X-ray diffraction. The assembled NMCP/C@CNTs//HC full cell could deliver a high energy density of 364.4 Wh kg −1 . The encouraging electrochemical performance of the full cell will promote the development of sodium ion secondary batteries for large-scale applications in the future.
研究领域:
材料科学
·
电化学
·
储能
·
纳米材料
·
电池技术
✓ 已验证
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2023
·
IF 6.2
Qing Zhu,Jinxin Wu,Rui Tong,Wenhao Li,Xiuli Hu,Ningchen Tian,Liqing He,Yanwei Li,Zhenyu Wang
Na 4 MnCr(PO 4 ) 3 (NMCP) has been considered as one kind of privileged cathodes with high energy density for sodium ion batteries (SIBs) due to three-electron redox reaction during the insertion/extraction process. Nevertheless, its practical use is restricted by its low intrinsic conductivity and serious Jahn-Teller distortions. Herein, a facile doping strategy was presented to address the above issues, and the effects of different kinds and quantities of transition metal dopants on electrochemical performance of NMCP were systemically studied. The results reveal that Ni50-NMCP/C has the most effective doping composition, showing a discharge capacity of 143.0 mAh g −1 at 50 mA g −1 and long-term cyclic stability with capacity retention of 55.7 % at 1000 mA g −1 over 500 cycles, higher than those of the pristine NMCP (106.6 mAh g −1 at 50 mA g −1 and 38.8 % capacity retention at 1000 mA g −1 ). The substitution of Ni 2+ for Mn 2+ promotes electron conductivity and structural stability, rendering improved electrochemical performance. Moreover, the promising electrochemical performance of Ni50-NMCP/C//HC full cell demonstrates the anode's potential for use. This study indicates a quick way to understand the effects of elemental doping on NMCP and explore novel high energy and high stability cathodes for SIBs.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
ADVANCED POWDER TECHNOLOGY
·
2024
·
IF 4.2
Jiuxiang Zhang,Xiaoping Zhang,Shengxing Lu,Yian Wang,Yulei Sui,Keyi Sun,Mengting Deng,Wenbin Fei,Ling Wu
Na 4 MnCr(PO 4 ) 3 is a promising cathode material with high redox potential and high energy density, but the intrinsic poor electronic conductivity and substandard structural stability restrict its practical application. Herein, porous Na 4 MnCr(PO 4 ) 3 /C with conductive networks and improved electrochemical properties is synthesized by a facile modified solid-state process using citric acid as a multifunctional additive. The results reveal that citric acid can be used as a grinding aid to make the raw materials mix more evenly and speed up the efficiency of ball milling. Besides, 3D conductive network and porous structure originated from polycondensation and carbonization of citric acid can promote the electrochemical properties of Na 4 MnCr(PO 4 ) 3 /C by enhancing the electronic/ionic conductivity and (de)intercalation reaction kinetics. As expected, the optimal Na 4 MnCr(PO 4 ) 3 /C delivers a high reversible capacity of 130.5 mAh g −1 at 0.1C rate, and exhibits a capacity retention of 82.62% at 10C rate after 500 cycles. In addition, the reversible biphasic reaction of the cathode is confirmed by the constant galvanostatic intermittent titration technique and ex-situ XRD, which shows great potential of the synthesized Na 4 MnCr(PO 4 ) 3 /C for practical applications.
研究领域:
材料科学
·
电化学
·
能源存储
·
无机固体化学
·
纳米材料
✓ 已验证
DOI
高影响因子
Small
·
2020
·Vol. 16
·期 25
·2001524
·
IF 11.459
Wei Zhang,Huangxu Li,Zhian Zhang,Ming Xu,Yanqing Lai,Shu-Lei Chou
Developing high-voltage cathode materials is critical for sodium-ion batteries to boost energy density. NASICON (Na super-ionic conductor)-structured Na x MnM(PO 4 ) 3 materials (M represents transition metal) have drawn increasing attention due to their features of robust crystal framework, low cost, as well as high voltage based on Mn 4+ /Mn 3+ and Mn 3+ /Mn 2+ redox couples. However, full activation of Mn 4+ /Mn 3+ redox couple within NASICON framework is still a great challenge. Herein, a novel NASICON-type Na 4 MnCr(PO 4 ) 3 material with highly reversible Mn 4+ /Mn 3+ redox reaction is discovered. It proceeds a two-step reaction with voltage platforms centered at 4.15 and 3.52 V versus Na + /Na, delivering a capacity of 108.4 mA h g −1 . The Na 4 MnCr(PO 4 ) 3 cathode also exhibits long durability over 500 cycles and impressive rate capability up to 10 C. The galvanostatic intermittent titration technique (GITT) test shows fast Na diffusivity which is further verified by density functional theory calculations. The high electrochemical activity derives from the 3D robust framework structure, fast kinetics, and pseudocapacitive contribution. The sodium storage mechanism of the Na 4 MnCr(PO 4 ) 3 cathode is deeply studied by ex situ X-ray diffraction (XRD) and ex situ X-ray photoelectron spectroscopy (XPS), revealing that both solid-solution and two-phase reactions are involved in the Na + ions extraction/insertion process.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）