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ChemSusChem · 2022 ·Vol. 15 ·期 19 ·e202201121 · IF 9.14

Tailoring the Boron Configurations in B-doped Na3V2(PO4)3@Carbon for Fast and Durable Sodium Storage

Dong Yan,Shuhao Xiao,Xinyan Li,Rui Wu,Jinxia Jiang,Xiaobin Niu,Jun Song Chen

Graphical Balancing act : Boron-doped Na 3 V 2 (PO 4 ) 3 is synthesized through a facile electrospinning method. NVP@carbon with a balanced content of BCO 2 and BC 2 O exhibits the best sodium storage properties. BC 2 O mainly improves the sodium diffusion and BCO 2 enhances the structural stability. Na 3 V 2 (PO 4 ) 3 (NVP) is a widely studied cathode material for sodium-ion batteries because of its high ionic conductivity and attractive charge/discharge plateau (3.4 V vs. Na/Na + ). However, its poor electronic conductivity and severe volume expansion during sodium storage need to be addressed before its intensive application could be realized. Herein, boron-doped NVP was synthesized through a facile electrospinning method. By adding boric acid into the reaction mixture during electrospinning followed by carbonization, boron could be directly inserted into the carbon matrix, giving rise to B-doped carbon nanofiber wrapped NVP. By tuning the doping amount, the boron-containing configurations could be facilely manipulated, playing different roles in promoting the sodium storage properties of the composite. Based on the calculation results, BC 2 O enhanced sodium diffusion by lowering the energy barrier, while BCO 2 improved the structural stability. Due to these specific functionalities of the configurations, the as-prepared composite with a balanced amount of BC 2 O and BCO 2 demonstrated superior sodium storage capacity of 113 mAh g −1 at 1 C, outstanding long cycling performance of 103 mAh g −1 at 10 C, and retained 91 mAh g −1 after 1500 cycles. This gave rise to a capacity loss of only 0.08‰ per cycle, much better than the undoped counterpart.

✓ 已验证 DOI PubMed 高影响因子
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ADVANCED POWDER TECHNOLOGY · 2020 · IF 4.217

Synthesis and electrochemical performance of Li1+xTi2−xFex(PO4)3/C anode for aqueous lithium ion battery

Weiwen Meng,Cong Li,Meng Yao,Zhangxing He,Xianwen Wu,Zhen Jiang,Lei Dai,Ling Wang

Aqueous lithium ion batteries (ALIBs) exhibit great application prospects in energy storage system, and the anode materials is the key to the extensive development of ALIBs. In this study, Li 1+x Ti 2−x Fe x (PO 4 ) 3 /C (x = 0, 0.05, 0.10, 0.30) composites as anode for ALIBs were synthesized via sol-gel method. The effect of Fe doping on LiTi 2 (PO 4 ) 3 /C properties was assessed by electrochemical measurements. In all of these composites, Li 1.1 Ti 1.9 Fe 0.1 (PO 4 ) 3 /C (LCF-10) presents the best electrochemical properties. LCF-10 exhibits discharge capacity with 120.0 and 80.2 mAh g −1 at 0.5 and 15C, severally, increasing by 1.2 and 1.3 times compared with the original LiTi 2 (PO 4 ) 3 /C. Besides, LCF-10 demonstrates remarkable cycling performance, whose discharge capacity retention can keep 70.2% at 5 C for 1000 cycles. Our study demonstrates that Fe doping for LiTi 2 (PO 4 ) 3 lattice can efficiently enhance electrochemical properties of LiTi 2 (PO 4 ) 3 /C composite.

✓ 已验证 DOI 高影响因子
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JOURNAL OF ALLOYS AND COMPOUNDS · 2022 · IF 6.371

Effect of TeO2 sintering aid on the microstructure and electrical properties of Li1.3Al0.3Ti1.7(PO4)3 solid electrolyte

Xiangchao Zhao,Yuansong Luo,Xiujian Zhao

NASICON-type solid electrolyte Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 (LATP) has become an excellent substitute for organic liquid electrolytes due to its high ionic conductivity and exceptional air stability. However, its application is limited by its poor sintering characteristics and high grain boundary resistance. In this study, TeO 2 was introduced into LATP as a sintering aid to promote its sintering, and its properties were measured by XRD , SEM, XPS, EIS and dilatometry . The results show that the addition of TeO 2 can form eutectic liquid phase in LATP ceramic pellets during sintering, thus effectively promoting particle sintering. Not only the grain size was greatly increased, but also grain boundary and pore defects were reduced. With the help of TeO 2 , the performance of LATP is greatly improved when sintered at only 750 °C, the relative density and total ionic conductivity reached 90.64% and 0.207 mS/cm, respectively. The highest total ionic conductivity of 0.279 mS/cm and the highest relative density of 93.81% were obtained when sintered at 800 ℃ and 950 ℃, respectively. However, due to the volatilization of Li and Te at high temperature, the relative density and total ionic conductivity of LATP with TeO 2 added sintered at high temperature have only a small increase compared to that without addition. In conclusion, this study provides a feasible scheme for improving LATP performance.

✓ 已验证 DOI 高影响因子
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Journal of Materials Chemistry A · 2019 ·Vol. 7 ·期 24 ·14681-14688 · IF 10.733

Electrospun Li3V2(PO4)3 nanocubes/carbon nanofibers as free-standing cathodes for high-performance lithium-ion batteries

Yi Peng,Rou Tan,Jianmin Ma,Qiuhong Li,Taihong Wang,Xiaochuan Duan

Lithium vanadium phosphate Li3V2(PO4)3 (LVP)-based cathodes have attracted much attention in pursuit of high-performance lithium-ion batteries (LIBs). In this study, an ionic liquid (IL) has been introduced into the electrospinning process for the first time, successfully leading to the formation of free-standing cathodes built up of LVP nanocubes embedded in N-doped carbon nanofibers (LVP-NC/NCNF). In particular, the IL plays multiple roles in the resulting free-standing cathodes: (i) the IL improves the feasibility of the PAN-based electrospinning system for preparing electrode materials due to its good solubility, resulting in a self-supporting substrate conductive network with good mechanical properties and electrical conductivity; (ii) the IL can act as a structure-directing agent to induce the formation of (100) facet-oriented LVP nanocubes, giving rise to a convenient lithium-ion transport path; and (iii) the IL adsorbed on the surface of LVP nanocubes can form a N-doped dual-phase carbon coating layer during the heat-treatment process, further enhancing the electronic conductivity of the entire electrode. As a result, LVP-NC/NCNF free-standing electrodes exhibit an outstanding electrochemical performance including a high specific capacity, stable cycling performance and superior rate capability. Specially, the LVP-NC/NCNF free-standing cathodes deliver a high discharge capacity of 143.6 mA h g−1 at 5C for a prolonged cycling life of over 1000 cycles. It is highly expected that this facile IL-assisted electrospinning method can be expanded to other polyanion-based cathodes, thus presenting new opportunities for the design and fabrication of high-performance free-standing electrodes for LIBs.

✓ 已验证 DOI 高影响因子
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JOURNAL OF POWER SOURCES · 2021 · IF 9.127

Interface regulation enabling three-dimensional Li1.3Al0.3Ti1.7(PO4)3-reinforced composite solid electrolyte for high-performance lithium batteries

Yingmin Jin,Xin Zong,Xuebai Zhang,Chaojun Liu,Dong Li,Zhenggang Jia,Gen Li,Xuanguang Zhou,Junhua Wei,Yueping Xiong

Composite solid electrolyte (CSE) consisting of Li + conductive fillers and polymer matrix has become attractive for high energy-density lithium batteries . Current researches focus on the “ceramic in polymer”-type CSE due to the severe agglomeration of ceramic particles. Consequently, the destroyed percolation network impedes the further improvement in ionic conductivity . In this work, we report a novel structural design of ceramic-enriched CSE consisting of three-dimensional (3D) interconnected Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 (LATP), polyvinylidene fluoride (PVDF) and LiN(SO 2 ) 2 (CF 3 ) 2 (LiTFSI). The 3D LATP network is constructed through the surface functionalization of LATP particles by polymethyl methacrylate (PMMA). Owing to the intermolecular interaction between PMMA and PVDF, the incorporation of PMMA-coated LATP (denoted as LATP@PMMA) enables the uniform distribution of ceramic phase and generates interconnected LATP network. Noticeably, such an electrolyte maximizes the utilization of inorganic fillers through the facile treatment of zero-dimensional materials, which is comparable to those 3D template-derived fillers. Furthermore, continuous Li + conduction pathways through LATP framework and LATP/PVDF interphase are guaranteed by the enhanced affinity of LATP towards PVDF matrix and the intrinsic Li +  complexation capability of PMMA. Remarkable cycling performances of the LiNi 0.5 Co 0.2 Mn 0.3 O 2 /LATP@PMMA-PVDF/Li batteries confirm the feasibility of 3D ceramic-enriched composite electrolyte in the application of solid-state lithium batteries.

✓ 已验证 DOI 高影响因子
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CERAMICS INTERNATIONAL · 2021 · IF 4.527

Effect of SnO–P2O5–MgO glass addition on the ionic conductivity of Li1.3Al0.3Ti1.7(PO4)3 solid electrolyte

Jingrui Kang,Rui Gu,Xu Guo,Jing Li,Hongchen Sun,Leiyang Zhang,Ruiyi Jing,Li Jin,Xiaoyong Wei

NASICON-type structured compounds Li 1+ x M x Ti 2- x (PO 4 ) 3 (M = Al, Fe, Y, etc.) have captured much attention due to their air stability, wide electrochemical window and high lithium ion conductivity. Especially, Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 (LATP) is a potential solid electrolyte due to its high ionic conductivity . However, its actual density usually has a certain gap with the theoretical density, leading the poor ionic conductivity of LATP. Herein, LATP solid electrolyte with series of SnO–P 2 O 5 –MgO (SPM, 0.4 wt%, 0.7 wt%, 1.0 wt%, 1.3 wt%) glass addition was successfully synthesized to improve the density and ionic conductivity. The SPM addition change Al/Ti–O bond and P–O bond distances, leading to gradual shrinkage of octahedral AlO 6 and tetrahedral PO 4 . The bulk conductivity of the samples increases gradually with SPM glass addition from 0.4 wt% to 1.3 wt%. Both SPM and the second-phase LiTiPO 5 , caused by glass addition, are conducive to the improvement of compactness. The relative density of LATP samples increases first from 0 wt% to 0.7 wt%, and then decreases from 0.7 wt% to 1.3 wt% with SPM glass addition. The grain boundary conductivity also changes accordingly. Especially, the highest ionic conductivity of 2.45 × 10 −4  S cm −1 , and a relative density of 96.72% with a low activation energy of 0.34 eV is obtained in LATP with 0.7 wt% SPM. Increasing the density of LATP solid electrolyte is crucial to improve the ionic conductivity of electrolytes and SPM glass addition can promote the development of dense oxide ceramic electrolytes.

✓ 已验证 DOI 高影响因子
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CERAMICS INTERNATIONAL · 2021 · IF 4.527

Sc3+-doping effects on porous Li3V2(PO4)3/C cathode with superior rate performance and cyclic stability

Nali Li,Yong Yu,Yanwei Tong,Tiantian Liu,Xuefeng Zhang

An enhanced sol-gel combustion method was used to synthesize different porous Sc 3+ -doped Li 3 V 2-x Sc x (PO 4 ) 3 /C (x = 0.00, 0.05, 0.10 and 0.15) compounds. The substitution of Sc 3+ into the V 3+ sites of Li 3 V 2-x Sc x (PO 4 ) 3 /C expands the lattice volume along with the enlargement of Li + diffusion channel, which is beneficial for Li + transportation and ionic conductivity improvement. Besides, the Sc 3+ doping content exhibits a great impact on the morphology of Li 3 V 2-x Sc x (PO 4 ) 3 /C composite. The pristine Li 3 V 2 (PO 4 ) 3 /C are constituted of porous particles and nanorods , and the ratio of nanorods to particles can be controlled by adjusting the amount of Sc 3+ doping since the ratio of nanorods to particles decreases with increasing Sc 3+ doping content. When Sc 3+ doping content increases to a certain level (x = 0.15, Li 3 V 1.85 Sc 0.15 (PO 4 ) 3 /C), the nanorods are hardly seen. Li 3 V 1.90 Sc 0.10 (PO 4 ) 3 /C with higher tapped density, better reversibility, smaller resistance and larger Li + diffusion coefficient demonstrates outstanding rate performance and cyclic stability, together with high specific discharge capacities of 130.2 and 92.9 mAh g −1 at 0.5 and 20 C, respectively. Furthermore, a superior specific discharge capacity of 85.8 mAh g −1 was retained at 20 C following 1000 cycles. Overall, a novel approach for the preparation of high-performance Li 3 V 2-x Sc x (PO 4 ) 3 /C cathodes with different morphologies for lithium-ion batteries is provided.

✓ 已验证 DOI 高影响因子
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JOURNAL OF ALLOYS AND COMPOUNDS · 2020 · IF 4.65

Passion fruit-like structure endows Li3V2(PO4)3@C/CNT composite with superior cyclic stability and rate performance

Yang Xia,Liyue Yu,Chengwei Lu,Jing Zhu,Zhen Xiao,Jun Zhang,Chu Liang,Hui Huang,Yongping Gan,Wenkui Zhang

Monoclinic Li 3 V 2 (PO 4 ) 3 (LVP) fulfills safety requirements including superior chemical and thermal stabilities since the oxygen atoms are firmly anchored in PO 4 3− units, however the low intrinsic electronic conductivity strictly limits its electrochemical performance . Herein, to overcome this problem, a rationally designed passion fruit-like LVP@C/CNT composite constructed with LVP grains as seeds, carbon matrix as pulp, and carbon nanotubes (CNTs) as filaments, has been prepared via a facile spray pyrolysis method. In such unique biomimetic structure, carbon matrix encases LVP to reduce its particle size, which is beneficial to shorten ion pathways; Porous structure scattered around carbon matrix facilitates the rapid penetration of electrolyte; 3D CNT networks afford high-speed electron conduction and remarkable structural stability by forming the bridges between LVP grains. Owing to the multiple merits of this biomimetic structure, the rationally designed LVP@C/CNT composite with 3 wt% CNT exhibits high reversible capacity, superior cyclic stability and remarkable rate capability.

研究领域: 材料科学 · 电化学 · 能源存储 · 纳米复合材料 · 锂离子电池
✓ 已验证 DOI 高影响因子
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JOURNAL OF ALLOYS AND COMPOUNDS · 2021 · IF 5.316

Building a highly functional Li1.3Al0.3Ti1.7(PO4)3/poly (vinylidene fluoride) composite electrolyte for all-solid-state lithium batteries

Yingmin Jin,Chaojun Liu,Zhenggang Jia,Xin Zong,Dong Li,Mengyu Fu,Junhua Wei,Yueping Xiong

Solid-state electrolytes have become a promising approach for rechargeable lithium batteries with enhanced safety and high energy density . However, the rigid nature of ceramic electrolytes would result in the poor interfacial contact, and polymer electrolytes suffer from inferior electrochemical performance and unsatisfied mechanical strength to suppress Li dendrites. In this work, we report a flexible Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 (LATP)-reinforced polyvinylidene fluoride (PVDF)-based solid composite electrolyte with superior performances in terms of high ionic conductivity (1.64 × 10 −3 S cm −1 at room temperature), high lithium transference number (0.45), wide electrochemical window (0–4.76 V) and enhanced tensile strength (14.2 MPa). The existence of LATP permits the utilization of high Li-salt content which increases the charge carrier concentration. Meanwhile, LATP facilitates the Li + conduction process and enhances the mechanical strength, leading to a long-term electrochemical stability of symmetric Li cell for 600 h at 0.2 mA cm −2 . Assembled with LiFePO 4 cathode, the all-solid-state Li battery delivers a high capacity of 153.7 mA h g −1 at 0.3 C with remarkable cycle stability. This work provides a bright future for composite polymer electrolytes in the application of all-solid-state lithium batteries .

研究领域: 材料科学 · 电化学 · 能源存储 · 高分子科学 · 无机非金属材料
✓ 已验证 DOI 高影响因子
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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS · 2023 · IF 5.2

Effects of scandium doping on the electrochemical performance of cathode materials Na3MnTi(PO4)3 for sodium-ion batteries

Kangyi Chen,Qingmo Shi,Yue Wang,Xinghai Li,Yingying Jiang,Haoran Xu,Shilong Guo,Li Zhao,Changsong Dai

A lately proposed NASICON-structured Na 3 MnTi(PO 4 ) 3 (NMTP) provides a promising solution that enables a large theoretical specific capacity and a high voltage discharge platform. However, it encounters a difficulty in electronic conductivity which obstructs its further implements. Herein, in this work we propose the Sodium-ion battery cathode materials Na 3 Mn 1−x Sc x Ti(PO 4 ) 3 /C with different Sc contents (x = 0, 0.01, 0.03, 0.05, 0.07, 0.1), a potential cathode material for sodium-ion batteries with typical three-dimensional NASICON structure were synthesized by sol-gel method aiming to address the problem. Doping of Sc 3+ in the NMTP structure was proved by powder X-ray diffraction and energy dispersive X-ray spectroscopy techniques . Impedance spectroscopy and galvanostatic intermittent titration technique results suggest that appropriate-proportion doping has dramatically enhanced the electrical conductivity and Na ion migration of the NMTP matrix. Na 3 Mn 0.95 Sc 0.05 Ti(PO 4 ) 3 exhibited a higher initial discharge specific capacity (123 mA h /g at 0.2 C, 111 mA h /g at 1 C) and the highest cycling stability (capacity retention of 93% after 250cycles at 0.2 C, capacity retention of 88% after 500 cycles at 1 C). In addition, Electrochemical Impedance Spectroscopy and X-ray diffraction tests revealed the reasons for the improved cycling stability of the materials due to doping. Furthermore, Na 3 Mn 0.95 Sc 0.05 Ti(PO 4 ) 3 //hard carbon full cells also demonstrates ideal electrochemical properties .

✓ 已验证 DOI 高影响因子
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JOURNAL OF POWER SOURCES · 2015 · IF 6.217

One-pot synthesis of carbon-coated nanosized LiTi2(PO4)3 as anode materials for aqueous lithium ion batteries

Zhantao Liu,Xusong Qin,Hui Xu,Guohua Chen

In this study, a one-pot sintering process incorporating sol–gel preparation route and in-situ carbon coating was proposed for the synthesis of carbon-coated nanosized LiTi 2 (PO 4 ) 3 . Experimental results show that the prepared LiTi 2 (PO 4 ) 3 particles are of high crystallinity and well-coated by turbostratic carbon. Attributed to nanosized particles and enhanced conductivity provided by turbostratic carbon coating, the carbon-coated LiTi 2 (PO 4 ) 3 showed high rate performance and good cycling life in aqueous electrolyte. Particularly, the carbon-coated LiTi 2 (PO 4 ) 3 exhibited initial specific capacities of 103 and 89 mAh g −1 , and retained 80.6% and 97% of the initial capacities after 120 cycles at 1C and 10C in aqueous electrolyte, respectively. The high rate performance and good cycling life of carbon-coated LiTi 2 (PO 4 ) 3 in aqueous electrolyte reveal its potential as negative electrode in aqueous lithium-ion batteries for electric vehicles and industrial-scale energy storage systems .

研究领域: 材料科学 · 电化学 · 能源存储 · 纳米技术 · 无机化学
✓ 已验证 DOI 高影响因子
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JOURNAL OF POWER SOURCES · 2021 · IF 9.127

Gravity-driven Poly(ethylene glycol)@Li1.5Al0.5Ge1.5(PO4)3 asymmetric solid polymer electrolytes for all-solid-state lithium batteries

Shujiao Yang,Zhihua Zhang,Lin Shen,Peng Chen,Zhi Gu,Mingyuan Chang,Yue zhao,Hao He,Xiayin Yao

An asymmetric solid polymer electrolyte (ASPE) is designed as two-in-one layered structure driven by gravity and in-situ polymerization. The rigid layer composed of polymer embedded three-dimensional continuous Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 (LAGP) framework improves the Li + transference number and critical current densities. The soft poly(ethylene glycol) (PEG) layer prepared via thermal polymerization by poly(ethylene glycol) methyl ether methacrylate (PEGMEM) makes good interfacial contact with cathodes. Driven by gravity, the two layers are automatically stratified during the polymerization. By virtue of this structural merit, the Li + transference number of PEG@LAGP ASPE extends to 0.144 (vs. 0.083 of PEG SPE), and symmetric Li/PEG@LAGP ASPE/Li cells can stably cycle over 400 h at current density of 0.5 mA cm −2 under 60 °C. LiFePO 4 /PEG@LAGP ASPE/Li cell exhibits excellent electrochemical performance at 2.5 C (0.5 mA cm −2 ) under 60 °C, reaching to a maximum specific capacity of 130.8 mA h g −1 and a capacity retention of 87.2% after 1000 cycles. Furthermore, the cells operating at high rates or high temperatures also have been demonstrated. This work provides a promising electrolyte design strategy for all-solid-state batteries with superior interface compatibility and long cycle life.

研究领域: 材料科学 · 电化学 · 储能技术 · 高分子科学 · 电池技术
✓ 已验证 DOI 高影响因子
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