CERAMICS INTERNATIONAL
·
2023
·
IF 5.2
Xingrui Pu,Xing Cheng,Qiaohong Yan,Yueming Lin,Rentai Yan,Ruize Yang,Xiaohong Zhu
The need to develop safe solid-state lithium batteries has stimulated intense research efforts for Li + solid electrolytes. However, the low conductivity limits the development of NASICON LiZr 2 (PO 4 ) 3 (LZP) electrolyte. Here, the doping effects of Ta on the structure, surface morphologies and electrochemical properties of Li 1- x Zr 2- x Ta x (PO 4 ) 3 (LZTP, x = 0, 0.01, 0.02, 0.04, 0.06 and 0.08) solid electrolyte were analyzed. LZTP was prepared using a simple solid-state reaction route, followed by sintering at 1200 °C for 12 h. A proper content of Ta 5+ substitution for Zr 4+ is beneficial to stabilize the high conductive rhombohedral (α) phase of LZP at room temperature. Doping Ta 5+ is conducive to unblocking of Li + at the M1 site and facilitates the occupation of Li + at the M2 site, thereby expanding the pathway for Li + conduction. Rietveld refinement data demonstrated that the Zr–O and P–O bond lengths ( d Zr-O and d P-O ) increased with a decrease in Zr–O–P bond angles ( θ Zr-O-P ) as x rose. The distortions in the ZrO 6 octahedron may weaken the coulomb attraction in Li + -O 2- , resulting in a lower activation energy ( E a ) and a higher Li + conductivity. The highest room-temperature conductivity (6.06 × 10 −5 S cm −1 ) was obtained at x = 0.06, which reached 1.5 × 10 −4 S cm −1 at 50 °C. The E a was found to decrease from 0.388 eV ( x = 0) to 0.306 eV ( x = 0.06). In addition, Ta doping resulted in improved connectivity and reduced pore formation, which also contributed to the decrease in resistance. The Raman spectrum demonstrated that some phonon modes of bending vibration in PO 4 were degenerate and external modes became too weak to be observed or even disappeared as Ta content increased. This change in the modes also had an impact on the Li + conductivity. Overall, the LZTP-0.06 appears to be a promising candidate for the solid electrolyte.
研究领域:
材料科学
·
电化学
·
固态电池
✓ 已验证
产品关联
DOI
高影响因子
MATERIALS CHEMISTRY AND PHYSICS
·
2024
·
IF 4.3
Mingxuan Zong,Yanjiang Zhang,Jianquan Liang,Xinghai Li,Qi Qi,Kangyi Chen,Li Zhao,Changsong Dai
The recently discovered Na 3 MnTi(PO 4 ) 3 cathode material has an extremely high theoretical capacity, but its poor cycling performance makes it challenging to apply. In this work, a series of NASICON-type Na 3+x MnV x Ti 1-x (PO 4 ) 3 /C (x = 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.8, 1) cathode materials were prepared by sol-gel method for sodium-ion batteries. X-ray diffraction (XRD) indicates that vanadium doping has increased the cell spacing within the material and the cell volume. From the results of X-ray photoelectron spectroscopy (XPS) and Energy dispersive X-ray spectroscopy (EDS) mapping images, it is shown that vanadium has been successfully doped into the material. Among them, the Na 3·3 MnV 0·3 Ti 0·7 (PO 4 ) 3 /C delivers an outstanding specific capacity (121.7 mAh g −1 at 0.1C, C = 135 mA g −1 ) and Na 3·4 MnV 0·4 Ti 0·6 (PO 4 ) 3 /C shows an excellent capacity retention (80.88 % after 1500 cycles at 1C). Notably, the coulombic efficiency of both materials during cycling is close to 100 %, indicating that these materials have great practical application value.
研究领域:
材料科学
·
电化学
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能源存储
·
无机固体化学
·
电池技术
✓ 已验证
DOI
高影响因子
Journal of Energy Chemistry
·
2022
·
IF 13.599
Tao Huang,Wei Xiong,Xue Ye,Zhencheng Huang,Yuqing Feng,Jianneng Liang,Shenghua Ye,Jishou Piao,Xinzhong Wang,Yongliang Li,Xiangzhong Ren,Chao Chen,Shaoluan Huang,Xiaoping Ouyang,Qianling Zhang,Jianhong Liu
The isolated inorganic particles within composite polymer electrolytes (CPEs) are not correlated to the Li + transfer network, resulting in the polymer dominating the low ionic conductivity of CPEs. Therefore, we developed novel quasi-solid-state CPEs of a Ce-doped Na super ion conductors (NASICON) Na 1.3+ x Al 0.3 Ce x Ti 1.7− x (PO 4 ) 3 (NCATP) chemically coupled poly(vinylidene fluoride-hexafluoropropylene) (PVDF-HFP)/Li-bis(trifluoromethanes-ulfonyl)imide (LiTFSI) matrix. A strong interaction between Ce 3+ from NCATP and TFSI − anion from the polymer matrix contributes to the fast Li + transportation at the interface. The PVDF-HFP/NCATP CPEs exhibit an ionic conductivity of 2.16 × 0 −3 S cm −1 and a Li + transference number of 0.88. A symmetric Li/Li cell with NCATP-integrated CPEs at 0.1 mA cm −2 presents outstanding cycling stability over 2000 h at 25 °C. The quasi-solid-state Li metal batteries of Li/CPEs/LiFePO 4 at 2 C after 400 cycles and Li/CPEs/LiCoO 2 at 0.2 C after 120 cycles deliver capacities of 100 and 152 mAh g −1 at 25 °C, respectively.
研究领域:
材料科学
·
电化学
·
能源存储
✓ 已验证
DOI
高影响因子
CERAMICS INTERNATIONAL
·
2023
·
IF 5.2
Ziqiang Xu,Bowen Fu,Xin Hu,Jintian Wu,Teng Li,Hongyu Yang,Kashif Khan,Mengqiang Wu,Zixuan Fang
The urgent need for high-performance sodium batteries has drawn great attention to the development of novel solid-state electrolyte systems. However, it is still a great challenge to obtain excellent ionic conductivity and interfacial stability performance for most solid-state electrolytes. In this study, a new NASICON-type solid-state electrolyte Na 3.1+x Zr 2−x Sc x Si 2.1 P 0.9 O 12 (donated as NZSSP, x = 0, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3) was successfully prepared by solid-phase method. Due to the aliovalent substitution of Sc 3+ /Si 4+ , the phase transition or unwanted rhombohedral phase is effectively suppressed, the Na + transport channel bottlenecks are greatly enlarged, and the concentration of Na + is largely increased, giving rise to the significant improvement of the ionic conductivity and stability of NZSSP solid-state electrolyte. The Na 3.35 Zr 1.75 Sc 0.25 Si 2.1 P 0.9 O 12 solid-state electrolyte has an ultra-high ionic conductivity of 4.92 mS cm −1 at room temperature. Meanwhile, it shows an excellent sodium plating/stripping stability by the optimization of the Na + transport channel. The critical current density of the Na//Na 3.35 Zr 1.75 Sc 0.25 Si 2.1 P 0.9 O 12 //Na symmetric battery is achieved up to 1.0 mA cm −2 , and it can stably cycle for nearly 3000 h at 0.1 mA cm −2 or 1000 h at 0.5 mA cm −2 at room temperature. A detailed analysis of these aliovalent dual element substitution samples has been performed, and the mechanism of the conductivity enhancement is discussed systematically. This study can provide a feasible method to improve the ionic conductivity and electrochemical stability of NZSP materials and paves a way for the application of all-solid-state sodium batteries .
研究领域:
材料科学
·
能源存储
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Energy Materials
·
2025
·
IF 5.5
Hongjie Chen,Yixuan Su,Yucong Chen,Minghan Bao,Mingjun Wu,Junyang Chen,Weitao Chen,Qiang Ru
The inherent low electronic conductivity of NASICON-type Na4MnV(PO4)3 (NMVP) impedes its use in advanced energy storage. Herein, we address this challenge by introducing a citric acid-derived carbon coating to elevate the material’s conductivity and electrochemical performance. By precisely tailoring the configuration of the carbon layer, we fabricated Na4MnV(PO4)3 encapsulated by a carbon coating (NMVP@C) and constructed a 3D hierarchical architecture with incorporated V(III) and Mn(II) states, which prompts the reversible redox reaction, augments Na+ storage capability, and mitigates volume expansion during cycling. The optimal cathode manifests superior rate capability and a long life span with 107.5 mA h g–1 at 1 C and 82.5% capacity retention over 5000 cycles at 20 C. The hard carbon//NMVP@C full cell confirms practical applicability with good electrochemical performance. This work underscores the pivotal interplay among the carbon layer, Na+ mobility, and structural integrity in NASICON cathodes, offering a pathway to develop high-performance and cost-effective cathode materials for sodium-ion batteries.
研究领域:
材料科学
·
能源存储
✓ 已验证
产品关联
DOI
高影响因子
Nature Communications
·
2025
·Vol. 16
·期 1
·1-11
·
IF 15.7
Hou Jingrong,Chen Tsung‐Yi,Ait Tamerd Mohamed,Liu Jie,Huang Wei-Hsiang,Hadouchi Mohammed,Zhu Yiming,Shi Xinyue,Guo Shasha,Yang Menghao,Shi Yongchao,Tang Mingxue,Ma Jiwei
Cycling positive electrode materials with high voltages and long lifetimes remains a challenge. On the one hand, operating electrodes at high voltages is usually accompanied by severe structural distortions and irreversible reactions. On the other hand, the significant volume variation upon Na + insertion/extraction limits the long cycling life. Here, we report a defective positive electrode material with a chemical formula of Na 3.2 □ 0.8 Co 0.5 Fe 0.5 V(PO 3.9 F 0.1 ) 3 (□ represents Na vacancy) through fluorine doping with activated reversible and fast Na + intercalation/deintercalation to increase the energy and power densities. Notably, this positive electrode material achieves a high reversible specific capacity of 151 mAh g −1 and prominent rate performance ranging from 1.5–4.2 V vs. Na + /Na, as well as a long lifespan of 6000 cycles under a high rate of 5 A g −1 with a capacity retention of ~94%, due to the activated cationic defect sites which reduces the transport barrier at the Na(1) site. This approach is expected to be applied to the rational design of polyanionic materials for batteries.
研究领域:
材料科学
·
电化学
·
储能
·
电池技术
·
无机化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2023
·
IF 9.9
Yuxiang Chen,Xiangyue Liao,Peng Wang,Ji Chen,Xiaoqin Zhang,Xingqiao Wu,Sean C. Smith,Dunmin Lin,Xin Tan,Qiaoji Zheng
The stable three-dimensional framework and high operating voltage of sodium superionic conductor (NASICON)-type Na 3 V 2 (PO 4 ) 3 has the potential to work with long cycle life and high-rate performance; however, it suffers from the poor intrinsic electronic conductivity and low energy density . Herein, Ga 3+ is introduced into Na 3 V 2 (PO 4 ) 3 to activate the V 4+ /V 5+ redox couple at a high potential of 4.0 V for enhancing energy density of the materials (Na 3 V 2-x Ga x (PO 4 ) 3 ). After the partial substitution of Ga 3+ for V 3+ , three redox couples (V 2+ /V 3+ , V 3+ /V 4+ and V 4+ /V 5+ ) of V are reversibly converted in the voltage range of 1.4–4.2 V, suggesting multi-electrons (>2e − ) involved in the reversible reaction, and simultaneously the electronic conductivity of the materials is effectively enhanced. As a result, the cathode with x = 0.75 exhibits excellent electrochemical properties: in the voltage range of 2.2–4.2 V, delivering an initial capacity of 105 mAh/g at 1C with a capacity retention rate of 92.3% after 400 cycles, and providing a stable reversible capacity of 88.3 mAh/g at 40C; and in the voltage range of 1.4–4.2 V, presenting the reversible capacity 152.3 mAh/g at 1C (497.6 Wh kg −1 ), and cycling stably for 1000 cycles at 20C with a capacity decay of 0.02375% per cycle. It is found that the Na 3 V 2-x Ga x (PO 4 ) 3 cathodes possess the sodium storage mechanism of single-phase and bi-phase reactions. This investigation presents a useful strategy to enhance the energy density and cycling life of NASICON-structured polyanionic phosphates by activating high-potential V 4+ /V 5+ redox couple.
研究领域:
材料科学
·
电化学
·
能源存储
✓ 已验证
DOI
高影响因子
ELECTROCHIMICA ACTA
·
2025
·
IF 5.6
Kaidi Gao,Qiao Hu,Yu Xia,Guangming Han,Jianfeng Yao
NASICON-type Na 3 V 2 (PO 4 ) 3 (NVP) has been identified as an ideal cathode for sodium-ion batteries (SIBs) because of its ultra-fast Na + diffusion and very stable structure. However, it still suffers from significant problems such as a low operating voltage plateau (3.4 V, vs. Na + /Na), inferior electronic conductivity and unsatisfactory energy density (370 Wh kg −1 ), thereby hampering the commercialization of NVP. Herein, a series of Al 3+ /Ga 3+ co-doping Na 3 V 2 (PO 4 ) 3 cathodes were successfully prepared through a facile solid-state reaction process. The substitution of Al 3+ /Ga 3+ for V 3+ in Na 3 V 2–2x Al x Ga x (PO 4 ) 3 ( x = 0, 0.1 and 0.2) effectively activates the electrons outside of V and achieves an extra redox couple V 4+ /V 5+ for high-voltage (3.9 V, vs. Na + /Na) reactions. Moreover, the presence of Ga in this series of electrode materials increases the proportion of sp 2 -type carbon. The optimized Na 3 V 1.8 Al 0.1 Ga 0.1 (PO 4 ) 3 material possesses high ionic/electronic conductivity and superior electrochemical performance: the energy density is enhanced by approximately 13.1 % at 0.1 C (from 345.4 Wh kg −1 for NVP to 390.7 Wh kg −1 for Na 3 V 1.8 Al 0.1 Ga 0.1 (PO 4 ) 3 ), and the power density is increased by approximately 135 % at 30 C (from 2574 W kg −1 for NVP to 6039 W kg −1 for Na 3 V 1.8 Al 0.1 Ga 0.1 (PO 4 ) 3 ). Furthermore, Na 3 V 1.8 Al 0.1 Ga 0.1 (PO 4 ) 3 exhibits excellent cycling stability with 93.4 % capacity retention after 350 cycles at 1 C. Ex-situ XPS and electrochemistry investigations imply the high reversibility of the V 3+ /V 4+ /V 5+ redox reaction in Na 3 V 1.8 Al 0.1 Ga 0.1 (PO 4 ) 3 . This work proposes a novel strategy to modulate the electronic structure of NVP by co-doping with Al 3+ and Ga 3+ to achieve reversible multi-redox activity (V 3+ /V 4+ /V 5+ ) in NASICON-type NVP, thus providing a viable approach for advancing ultrafast high-energy sodium storage.
研究领域:
材料科学
·
电化学
·
储能技术
·
固态化学
✓ 已验证
产品关联
DOI
高影响因子
Functional Materials Letters
·
2024
·
IF 1.2
Hui Wang,Nairan Li
The instability of lithium metal and insoluble discharging products, Li 2 O 2 , has been a formidable challenge that hinders the widespread implementation of lithium-air batteries (LABs). Hybrid electrolyte-based LABs have been proposed as one of the most promising strategies to solve these issues. However, the complex device designs together with a suitable solid electrolyte membrane is one of the key parameters that determine the battery run. Herein, we present a novel approach featuring a three-phase “organic-solid-aqueous” hybrid electrolyte for LABs, incorporating a NASICON-based solid electrolyte and zinc single atoms catalysts. It is clarified that Li 1 . 3 Al 0 . 3 Ti 1 . 7 ( PO 4 ) 3 (LATP) shows much-enhanced stability compared with the pulverization of Li 1 . 3 Al 0 . 3 Ge 1 . 7 ( PO 4 ) 3 (LAGP) by the reduction of Ge upon the Li + transport across. Combined with the bifunction of Zn SAs/CNF catalysts in ORR/OER, the 4 e − pathway has been proven to be established as a primary contributor to the battery’s high efficiency, which can well run over 100 h in the ambient air at room temperature. These innovative methodologies and insights hold promise for advancing the practical application of safe LABs and may extend to various air battery technologies.
研究领域:
储能技术
·
电化学
·
材料科学
·
电池技术
·
固态电解质
✓ 已验证
DOI
高影响因子
Science Bulletin
·
2022
·
IF 20.577
Shunshun Zhao,Chuanlin Li,Xixi Zhang,Na Li,Tongkai Wang,Xiaojuan Li,Chenggang Wang,Guangmeng Qu,Xijin Xu
The proposal of hybrid ion batteries, which can integrate the advantages of the single ion battery, opens up a new route for developing high-performance secondary batteries. Herein, we successfully constructed an aqueous hybrid battery comprised of polyanionic-type cathode material (Na 3 V 2 (PO 4 ) 3 , NVP), Zn metal anode, and aqueous Ca 2+ /Zn 2+ hybrid electrolyte. This exciting combination gives full play to not only the excellent diffusion dynamics of Ca 2+ in the NASICON (sodium super ion conductors) structure but also the electrostatic shielding effect of Ca 2+ with low reduction potential that inhibits the formation of zinc dendrites. As results, the NVP//Zn Zn/Ca hybrid battery delivers favorable specific capacity with outstanding rate performance (85.3 mAh g −1 capacity at 1 C, 60.5 mAh g −1 capacity at 20 C), and excellent cycle stability (74 % capacity retention after 1300 cycles).
研究领域:
储能
·
电化学
·
电池技术
·
材料科学
✓ 已验证
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2021
·
IF 9.229
Jiapin Liu,Yun Huang,Zhixing Zhao,Wenhao Ren,Zhuangzhi Li,Chao Zou,Ling Zhao,Zhaomin Tang,Xing Li,Mingshan Wang,Yuanhua Lin,Haijun Cao
The sodium super ion conductor (NASICON) structure materials are essential for sodium-ion batteries (SIBs) due to their robust crystal structure, excellent ionic conductivity, and flexibility to regulate element and valence. However, the poor electronic conductivity and inferior energy density caused by the nature of these materials have always been obstacles to commercialization. Herein, using yeast as a template to derive NASICON structure Na3MnTi(PO4)3 (NMTP) materials (noted as Yeast@NMTP/C) is presented. The Yeast@NMTP/C material retains the microsphere morphology of the yeast template and not only controls the particle size (around 2 μm) to shorten the Na+ diffusion pathways but also improves the electronic conductivity to optimize the electrochemical kinetics. The Yeast@NMTP/C cathode delivers reversible multielectron redox reactions including Ti4+/3+, Mn3+/2+, and Mn4+/3+ and exhibits a high capacity of 108.5 mAh g–1 with a 79.2% capacity retention after 1000 cycles at a 2C rate. The sodium storage mechanism of Yeast@NMTP/C reveals that the addition of Ti4+/3+ redox plays a key role in improving the Na+ diffusion kinetics, and both solid-solution and two-phase reactions take place during the desodiation and sodiation process. Additionally, the high-rate and long-span cycle performance of Yeast@NMTP/C at 10C is ascribed to contribute to pseudocapacitance.
研究领域:
材料科学
·
电化学
·
电池技术
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2020
·
IF 4.65
Congcai Huang,Guanming Yang,Wenhao Yu,Chao Xue,Yanfang Zhai,Weiping Tang,Ning Hu,Zhaoyin Wen,Li Lu,Shufeng Song
As a possible solid electrolyte material for solid-state sodium-based batteries, gallium-substituted Na 3 Zr 2 Si 2 PO 12 in the structure of Nasicon (sodium super ion conductor) has received hardly any attention so far, though Ga 3+ has similar ionic radius close to that of Zr 4+ . Herein, a series of gallium-substituted Na 3 Zr 2 Si 2 PO 12 with formula of Na 3+x Zr 2-x Ga x Si 2 PO 12 (0 ≤ x ≤ 0.4) have been prepared through solid-state synthesis. The electrical, microstructural, and crystallographic performances of the developed solid electrolytes are systematically studied. In particular, the gallium-substituted Na 3.1 Zr 1.9 Ga 0.1 Si 2 PO 12 shows superior ionic conductivity of 1.06 × 10 −3 S cm −1 at 25 °C, which is almost one order of magnitude higher than that of the pristine Na 3 Zr 2 Si 2 PO 12 , as well as low electronic conductivity of 6.17 × 10 −8 S cm −1 and wide electrochemical stability window of 5 V vs. Na/Na + . This work demonstrates a new substituted strategy for exploring Na + -ion solid electrolytes.
研究领域:
材料科学
·
能源存储与转换
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）