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International Journal of Applied Ceramic Technology · 2023 ·Vol. 20 ·期 4 ·2125-2130 · IF 2.1

Rapid crystallization of Li1.5Al0.5Ge1.5(PO4)3 glass ceramics via ultra-fast high-temperature sintering (UHS)

Jinghua Wu,Milad Kermani,Lei Cao,Bohan Wang,Zhiquan Dai,Le Fu,Chunfeng Hu,Salvatore Grasso

Lithium aluminum germanium phosphate solid electrolyte is a promising candidate for all-solid-state batteries. The currently available processing techniques based on melting-quenching require a rather lengthy crystallization step lasting up to 8 hours. In this work, the newly emerged ultra-fast high-temperature sintering (UHS) was proposed to achieve in a single step reactive consolidation of powder mixture (GeO 2 , Al(PO 3 ) 3 , LiPO 3 ) and crystallization of the electrolyte within 16 minutes. Samples produced using UHS had a better phase purity, reduced Li loss, and improved ionic conductivity when compared to the counterparts prepared using conventional crystallization at 850°C for 6 h. In fact, specimens prepared by UHS achieved a crystallinity of 90% and ionic conductivity as high as 1.31 × 10 −4 S cm −1 .

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JOURNAL OF SOL-GEL SCIENCE AND TECHNOLOGY · 2022 ·Vol. 103 ·期 1 ·205-213 · IF 2.606

Facile synthesis of pure Na3V2(PO4)3 powder via a two-stage carbothermal reduction strategy

Zhao Qian,Yang Wensheng,Zhang Qin,Qiu Liren,Zhou Min,Lu Shengshang,Tao Benfu,Wang Xinhai,Xie Quan,Ruan Yunjun

Sodium super ion conductor (NASICON) structure materials, known for fast diffusion channels for Na + , are promising solid electrolyte materials for sodium-ion batteries (SIBs). However, the high carbon content in the NASICON electrolyte materials originated from the carbothermal reduction (CR) reaction will cause short-circuit and self-discharge of the batteries. Herein, we developed a facile and straightforward two-stage calcining strategy to prepare Na 3 V 2 (PO 4 ) 3 (NVP) with high purity and crystallinity. By precisely controlling the dosage of reducing agent and heat temperature, the purity of NVP can reach 99.97%. Moreover, the NVP film was prepared by the as-synthesized pure NVP powder via fast hot-pressing sinter, whose Vickers hardness is (5.0 ± 0.4) × 10 2 HV and relative density is 99.05%. This study provides a safe and facile strategy to prepare high-purity NVP powder and high-quality NVP films, which is of great significance in exploring NVP as a solid electrolyte for SIBs. Graphical abstract

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RSC Advances · 2020 ·Vol. 10 ·期 2 ·620-625 · IF 3.119

Suppressing H2 evolution by using a hydrogel for reversible Na storage in Na3V2(PO4)3

Xianying Fan,Xiaoyu Gao,Xuan Zhang,Guijia Cui,Huichao Lu,Zhixin Xu,Jun Yang

We report a low-cost hydrogel electrolyte by adding 3 wt% poly(acrylate sodium) (PAAS) into 1 M Na2SO4 aqueous electrolyte, which achieves a widened electrochemical stability window (ESW) of 2.45 V on stainless steel current collector from 2.12 V in 1 M Na2SO4 aqueous electrolytes (AE). Moreover, the H2 evolution potential reaches −1.75 V vs. Ag/AgCl on titanium current collector. The results reveal that the polymer network structure of PAAS has the ability to interact with water molecules and thus the hydrogen evolution reaction can be limited effectively, which broadens the ESW of aqueous electrolyte and allows the reversible Na-ion intercalation/deintercalation of Na3V2(PO4)3 as an anode material in aqueous electrolyte reported for the first time.

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APPLIED SURFACE SCIENCE · 2019 · IF 5.155

5LiFe0.9Mn0.1PO4∙4Li3V2(PO4)3/C composites as high capacity cathode materials for lithium-ion batteries

Wei Zhao,Xunhui Xiong,Yingbang Yao,Bo Liang,Ye Fan,Shengguo Lu,Tao Tao

The construction of high capacity cathode materials consisting of two active components, LiFe x Mn 1-x PO 4 and Li 3 V 2 (PO 4 ) 3 , is rarely reported. Herein, 5LiFe 0.9 Mn 0.1 PO 4 ∙4Li 3 V 2 (PO 4 ) 3 /C (LFMVP/C) composites are synthesized by a simple two-step process, including ball milling and heat-treatment. The electrochemical reactivity of the composites with lithium is evaluated. The cathode assembled with LFMVP/C shows better electrochemical performance than that of the single active component (LiFePO 4 , LiMnPO 4, or Li 3 V 2 (PO 4 ) 3 ) during charging and discharging in the potential range of 2.4 and 4.8 V. It delivers the specific capacities of 195, 173, and 158 mAh∙g −1 at 0.1C, 0.5C, and 2C, and retains 88% of the initial discharge capacity after 100 cycles at 0.1 C. Compared with the single active component (LiFePO 4 , LiMnPO 4, or Li 3 V 2 (PO 4 ) 3 ), the lithium-ion diffusion coefficient of the composite composed of two active components (LFMVP/C) is higher.

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Journal of Materials Chemistry A · 2022 ·Vol. 10 ·期 19 ·10625-10637 · IF 14.511

3D porous spheroidal Na4Mn0.9Ce0.1V(PO4)3@CeO2/C cathode for high-energy Na ion batteries

Kun Wang,Xiaobing Huang,Tao Zhou,Dan Sun,Haiyan Wang,Zhi Zhang

The NASICON-type Na4MnV(PO4)3 (NMVP) possesses potential as a cathode material in SIBs, and is known for its stable 3D Na+ superconductive framework, high voltage platform, and relatively low cost and toxicity. Nevertheless, the intrinsic poor electronic conductivity and Jahn–Teller effect from Mn3+ during cycling limit its further application. Herein, to address such issues, a well-designed 3D porous spheroidal Ce3+-doped NMVP@CeO2/C cathode was constructed via a simple spraying drying-assisted route. As proved, the synergistic effect of Ce3+ doping in the crystal framework and CeO2 surface coating was achieved simultaneously, which greatly improved the electronic conductivity, facilitated the ion diffusion transfer and stabilized the crystalline structure. As a result, the as-prepared sample delivered superior discharge performance (50.3 mA h g−1 at 50C) and long circular life (91.0 mA h g−1 after 2000 cycles at 5C with 86.7% capacity retention). Furthermore, the reversible biphasic reaction for cathodes was confirmed by Galvanostatic intermittent titration technique (GITT) and ex situ XRD. The DFT calculation revealed the influence of Ce3+-doping on the crystalline framework and electrochemical properties. Finally, the optimized NMVP cathode also showed great potential for practical utilization through the successful assembly of full cells.

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SURFACE & COATINGS TECHNOLOGY · 2024 · IF 5.3

One-step in-situ construction of Mg0.5Ti2(PO4)3 coating and cation doped modified LiNi0.5Mn1.5O4

Dongjia Li,Bo Xiao,Xinyi Dai,Chao Wang,Yawei Wei,Haijun Chen,Yi Mai,Fuzhong Wu,Jiexi Wang

Amid the fast growth of lithium-ion batteries, LiNi 0.5 Mn 1.5 O 4 (LNMO) with a 4.7 V working voltage and cost advantages has gained significant attention. The instability of LNMO structure during high-voltage cycling leads to significant side reactions with the electrolyte, hindering its commercial development. Our study introduces a co-crystallization calcination strategy to enhance the optimization of LNMO. This study utilized a straightforward wet chemistry approach to combine the precursor of NASICON-type solid electrolyte Mg 0.5 Ti 2 (PO 4 ) 3 (MTP) with the precursor of LNMO. Subsequently, a MTP coating was formed in-situ on the surface of LNMO through a single-step calcination process. Co-crystallization and calcination processes limit LNMO particle secondary growth, shorten Li + diffusion path , achieve Mg 2+ and Ti 4+ co-doping, enhance structural stability , and result in triple modification, leading to a significant improvement in electrochemical performance . Among them, LNMO with a 1 % molar ratio modified by MTP reaches 81.7 % of the initial capacity after 500 cycles at room temperature and 84.3 % after 180 cycles at 55 °C. Under identical conditions, unmodified samples have 39.3 % and 76.3 %, respectively. Our research explores a novel application of NASICON-type solid electrolytes in modifying LNMO cathode material .

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INTEGRATED FERROELECTRICS · 2021 · IF 0.836

Realizing Hybrid Ion Storage of NASICON-Structured Na3V2(PO4)3 Prepared by Microwave Irradiation Route

Ji Yan,Zhen Li,Xiao-Kai Ma,Xin-Bo Chang,Fu-Jun Liu,Yong Zhang,Li-Zhen Wang

NASICON Na3V2(PO4)3 was investigated as cathode material in hybrid ion batteries using Li as counter and LiPF6 as electrolyte. The highly efficient and homogeneous heating merits of microwave irradiation facilitates the Na3V2(PO4)3 achieving excellent crystal structure, uniform carbon coating, as well as ideal particle size. After microwave irradiation, a specific capacity of 96.5 mAh g−1 is obtained for the first intercalation of lithium ion into Na3V2(PO4)3 at 0.1 C rate. For long-term cycling stability, the capacity retention reaches 84.4% at 5 C rate after 500 cycles. The unique intercalation/extraction characteristic promises Na3V2(PO4)3 an ideal candidate material for next-generation hybrid ion storage system.

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JOURNAL OF ALLOYS AND COMPOUNDS · 2018 · IF 3.779

Lithium storage performance improvement of NaTi2(PO4)3 with nitrogen-doped carbon derived from polyaniline

Zhi Zhou,Simin Gu,Yongli Zhang,Fangfang Wu,Nan Zhou

NASICON-type NaTi 2 (PO 4 ) 3 has been acknowledged as a promising anode for energy storage due to high ion conductivity and low cost. Nevertheless, intrinsic low electrical conductivity of NaTi 2 (PO 4 ) 3 and low stability in aqueous electrolyte limit its further applications in aqueous lithium rechargeable battery. In this paper, polyaniline as carbon and nitrogen sources was employed to synthesize nitrogen-doped carbon coated NaTi 2 (PO 4 ) 3 (NTP-P) composite by sol-gel approach and following calcination treatment. The loose and carbon-coated structure endows NTP-P with good structure stability and improved electrochemical kinetics . Compared with glucose-derived carbon-coated NaTi 2 (PO 4 ) 3 composite, NTP-P exhibits superior rate and cycling performance. NTP-P with proper carbon content delivers the discharge capacity of 119.4 and 83.4 mAh g −1 at rate of 0.2 and 15 C, and its capacity retention can maintain 85.8% after 1000 cycles at 5 C. This research reveals that the integration of carbon coating and nitrogen doping by using polyaniline give an excellent method to enhance the electrochemical properties of electrode materials.

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APPLIED SURFACE SCIENCE · 2024 · IF 6.3

Optimizing the crystal structure and electrochemical properties of Na4MnCr(PO4)3 by trace La doping

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.

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JOURNAL OF ELECTROANALYTICAL CHEMISTRY · 2023 · IF 4.5

Effect of Zr4+ doping on the electrochemical properties of Na3MnTi(PO4)3/C cathode materials

Qi Qi,Xiaodong Li,Jianquan Liang,Kangyi Chen,Mingxuan Zong,Xinghai Li,Li Zhao,Changsong Dai

NASICON structural materials have the advantages of structural stability, high ion conductivity, and high working potential, which have attracted widespread attention as cathode for sodium-ion batteries. Although the three-electron reaction in the NASICON structure Na 3 MnTi(PO 4 ) 3 increases the specific capacity of the material, poor electronic conductivity remains a key factor restricting its practical application. Herein, Na 3 Mn 1-x Zr x Ti(PO 4 ) 3 /C (x = 0, 0.01, 0.03, 0.05, 0.07 and 0.1), a typical three-dimensional NASICON structure cathode material for sodium-ion batteries, was synthesized by the sol-gel method. Through powder X-ray diffraction, the Zr 4+ doping in the Na 3 MnTi(PO 4 ) 3 (NMTP) structure was verified. It was found that doping trace amounts of Zr at the Mn site can not only reduce the Jahn-Teller effect caused by Mn 3+ , but also strengthen the Zr-O bond compared to the Mn-O bond, making the crystal structure more stable by reducing the proportion of Mn. According to the findings of the EIS test, a suitable amount of Zr doping can enhance the electronic conductivity and Na ion diffusion coefficient of NMTP/C electrode materials, weaken polarization phenomena, increase electrode reaction rate, and significantly improve the rate performance and cycling performance of Na 3 Mn 1-x Zr x Ti(PO 4 ) 3 material. The Na 3 Mn 1-x Zr x Ti(PO 4 ) 3 /C sample prepared has high initial capacity of 124mAh/g, a capacity retention rate of 86 % after 200 cycles at 0.2C, and a capacity retention rate of 84 % after 500 cycles at 1C. This proves that the material still exhibits excellent cycling stability and structural stability after high current cycling. More importantly, the Na 3 Mn 0.95 Zr 0.05 Ti(PO 4 ) 3 (Zr5-NMTP)//Hard carbon full battery also exhibits ideal electrochemical performance.

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Journal of Materials Chemistry A · 2022 ·Vol. 10 ·期 21 ·11340-11353 · IF 14.511

Unraveling the modified regulation of ternary substitution on Na3V2(PO4)3 for sodium ion batteries

Shiqi Sun,Yanjun Chen,Qiang Bai,Que Huang,Changcheng Liu,Shengnan He,Yaxiong Yang,Yanzhong Wang,Li Guo

The emergence of three-dimensional Na3V2(PO4)3 (NVP) has attracted a lot of attention due to its high reversible capacity and long voltage platform. Unfortunately, its popularization and application are limited by its poor intrinsic conductivity. Herein, a convenient sol–gel method is proposed to synthesize potassium/lanthanum/silicon co-substituted NVP. The potassium ions are responsible for extension along the c axis while the other two ions facilitate the expansion of the crystal structure along the other directions. Accordingly, the ternary substitution reduces the resistance existing in the neighboring coordination environment and improves the stability of the crystal framework by enlarging the migration channels for Na+. Significantly, with the simultaneous function of ternary substitution, slight lattice distortions occur in the bulk and more active sites for reversible de-intercalation of Na+ emerge, favorably supplementing the discharge capacity during the period of structural phase transition. Moreover, first-principles calculations demonstrate that the introduction of three heteroatoms could decrease the gap between the conductive and valence bands and reduce the energy barrier for sodium migration. The optimized Na3.03V1.93La0.07(PO4)2.9(SiO4)0.1 possesses a superior sodium storage property in both half- and full-cells. This work reveals the distinctive advantages of ternary substitution on the NVP system through theoretical and experimental methods, contributing to further exploration of other cathode materials.

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CERAMICS INTERNATIONAL · 2017 ·Vol. 43 ·期 12 ·9327-9333 · IF 2.986

High-performance LiTi2(PO4)3@carbon anode using double carbon sources for aqueous lithium ion battery

Nan Zhou,Shengxiong Huang,Tao Hong,Wei Luo,Yun Tian,Xiangyang Lu,Zhi Zhou

In this paper, LiTi 2 (PO 4 ) 3 @carbon composite as anode for aqueous lithium ion battery has been successfully synthesized by in-situ carbon coating method using oxalic acid and glucose as double carbon sources. XRD results confirm the rhombohedral NASICON-type LiTi 2 (PO 4 ) 3 structure of the as-prepared composite. The LiTi 2 (PO 4 ) 3 @carbon composite using double carbon sources (LTP-OG-10) disperses well, and the coated carbon layer has the appropriate thickness of 3–7   nm, which result in proper balance of the good electrical conductivity and the fast kinetics of diffusion of lithium ions . LTP-OG-10 exhibits better electrochemical performance compared with those using oxalic acid (LTP-O) or glucose (LTP-G) single carbon source. LTP-OG-10 anode delivers the discharge capacity of 112.5 mA   h g −1 , 96.8 mA   h g −1 , and 54.2 mA   h g −1 at 0.2   C, 5   C and 20   C, respectively, much larger than that of LTP-O and LTP-G. Moreover, LTP-OG-10 demonstrated excellent cycling performance, with the capacity retention of 71.1% after 400 cycles at 0.2   C, 22.9% higher than that of LTP-G. The good electrochemical properties of LTP-OG-10 is mainly ascribed to the increase of defects, high-quality and appropriate thickness of carbon layer. Our study reveals that preparing LiTi 2 (PO 4 ) 3 @carbon composite using double carbon sources is an efficient approach to enhance its electrochemical properties.

研究领域: 材料科学 · 电化学 · 能源存储 · 无机非金属材料 · 功能材料
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