JOURNAL OF MATERIALS SCIENCE
·
2024
·Vol. 59
·期 44
·20671-20685
·
IF 3.5
Wang Jiashuai,Wang Chengdeng,Shi Haofeng,Wang Zhaokun,Wang Zhi,Li Jin peng,Chen Xiangrui,Gao Yan,Bai Zhiming,Yan Xiaoqin
The interface instability between a Li-excess cation disordered rocksalt cathode (DRX) and sulfide solid electrolyte (SE) results in rapid capacity fade. It is well established that cathode coatings are important to mitigate the side reaction at interfaces and therefore increasing the reversible specific capacity of all-solid-state Li batteries (ASSLBs). However, internal mechanism remains blurry, and the effects of the coating layer on electrode/electrolyte interface and capacity degradation have not been fully clarified. In this work, we used various coating materials on Li 1.2 Ni 0.3 Ti 0.3 Nb 0.2 O 2 (LNTNO) cathodes to investigate the behavior of the DRX/SE interfaces. The electrochemical performances are compared of uncoated, Li 2 ZrO 3 -coated, LiNbO 3 -coated, and Li 3 BO 3 (LBO)-coated cathodes in Li 6 PS 5 Cl-based ASSLBs in long charge–discharge processes. The results demonstrate that all coated LNTNO could improve specific capacity and cycle performance. Li 3 BO 3 is identified as a superior coating with good structural stability that exhibits observably large discharge capacity (206 mAh g −1 at 10 mA g −1 ), long cycle life (100 cycles, capacity retention of 78%), as well as outstanding rate property. Combined with ex situ X-ray photoelectron spectroscopy and scanning electron microscope, we can observe the side reactions at cathode/electrolyte interface can be mitigated after the LBO coating layer, enabling fast lithium transport dynamics. This work highlights the critical role of having an appropriate coating layer and offers a promising path to enhance the electrochemical behaviors of ASSLBs. Graphical abstract
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
ACS Applied Energy Materials
·
2024
·
IF 5.4
Tiandong Chen,Luxiang Ma,Hongli Su,Wencheng Pan,Chunxi Hai,Shengde Dong,Yanxia Sun,Qi Xu,Xin He,Yan Zhao,Jitao Chen,Zhiqin Zheng,Yuan Zhou
Despite the high energy density of lithium-rich manganese-based (LR) cathode materials, the practical implementation in batteries has been impeded by the intrinsic issues regarding cycling. Herein, a coherent interface modification strategy is proposed. The LR materials are coated with a lattice-matched Li3BO3 (LBO) layer at the interface. The coating applied to the electrode has two impacts. (1) It reduces interfacial side reactions between the electrode materials and electrolyte, thereby improving structural stability. (2) It mitigates stress between solid particles, which enhances the cycling stability (83% after 500 cycles at 2C) of LR. Furthermore, the LBO coating promotes the development of a spinel-like structure on the electrode materials surface, eliminating unstable oxygen, increasing oxygen vacancy (Ov), consequently enhancing the initial Coulombic efficiency (ICE, 92.18%), and alleviating particle breakage (Young’s moduli of LR@S@LBO is 3.26 ± 1.6 GPa) after optimization. Theoretical calculations show that Ov and spinel can improve the diffusion of Li+ and the structural stability of LR materials. This work shows great potential for the rational design of high-energy-density electrode materials.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2024
·
IF 9.4
Min Xu,Junjie Lu,Zhefei Sun,Ming Yang,Bifu Sheng,Minfeng Chen,Jizhang Chen,Qiaobao Zhang,Xiang Han
Single crystalline Ni-rich layered oxide cathodes show high energy density and low cost, have been regarded as one of the most promising candidates for next generation lithium-ion batteries (LIBs). Extending the cycling voltage window will significantly improve the energy density, however, suffers from bulk structural and interfacial chemistry degradation, leading to rapidly cycle performance deterioration. Here, we propose a dual-modification strategy to synthesize La doping and Li 3 BO 3 (LBO) coating layers modified LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811) by a facile one-step heating treatment processing. In-situ EIS and XRD, ex-situ XPS techniques are applied to demonstrate that the La diffused amorphous domains and Li 3 BO 3 passivating layers dampen the lattice distortion, enhance the interfacial chemistry behavior as well as lithium ion transportation kinetics. Specifically, surface La doping amorphous domains successfully suppress the intense lattice stress and volume changes induced by the phase transitions during lithiation/delithiation, thus avoiding the intergranular crack and enhancing the mechanical stability of the material. Moreover, the LBO layer formed by the consumption of residual lithium prevents successive parasitic reactions at the interface as well as provides rapid Li-ion diffusion channels. Furthermore, the coating layer also diminishes the residual lithium compounds, increasing the atmosphere stability and safety of LIBs. Consequently, the La doping and LBO coating NCM811 exhibits an exceptional initial specific capacity (230.6 mAh/g) at 0.5C under a high cutoff voltage of 4.8 V, and a 73.8 % capacity retention following 100 cycles. In addition, a superior specific capacity of 133.8 mAh/g is provided even at a high current density (4C). Our work paves a promising road to tackle the integral structure deterioration and interfacial instability of Ni-rich cathodes.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
JOURNAL OF POWER SOURCES
·
2021
·
IF 9.127
Yu Ye,Lei Gao,Zhi Deng,Kangdi Niu,Ruo Zhao,Juncao Bian,Haibin Lin,Jinlong Zhu,Yusheng Zhao
Lithium-rich anti-perovskite materials, with their high theoretical Li + conductivity and relatively low energy barrier for Li + transport, are highly promising as an electrolyte contender in all-solid-state lithium-metal batteries. Their current performance is however compromised by the grain boundary to result in low Li + conductivity and high activation energy . Herein, a composite electrolyte is prepared by introducing the glassy Li 3 BO 3 into the Li 2 OHCl to serve as a bridge to connect the Li 2 OHCl grains together to lower the impact from the grain boundary. The Li + conductivity of Li 2 OHCl can be improved by the presence of 10 wt% Li 3 BO 3 , and its impact on the lithium metal growth behavior is also investigated. It is found that the lithium-metal battery with Li 3 BO 3 /Li 2 OHCl prefers the deposition of lithium metal particles with larger size than that in the battery with Li 2 OHCl. Consequently, the lithium-metal symmetric cell with 10 wt% Li 3 BO 3 /Li 2 OHCl is able to display excellent cycling for over 1800 h at 0.1 mA cm −2 . The batteries with 10 wt% Li 3 BO 3 /Li 2 OHCl are also able to improve the cycle stability and rate performance. The results of this study provide the direct experimental proof of the effect of grain boundary in Li 2 OHCl on the battery performance.
研究领域:
材料科学
·
电化学
·
电池技术
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2016
·
IF 3.014
Yufei Ma,Yuan Li,Ting Liu,Xin Zhao,Lu Zhang,Shumin Han,Yijing Wang
LiBH 4 is considered a promising hydrogen storage material for automotive applications ; however, its usage is limited because of unfavorable reversibility and sluggish kinetics. In this paper, we have improved the hydrogen storage properties of LiBH 4 by doping with a porous Li 3 BO 3 additive, which was prepared by a solid state synthesis method . The LiBH 4 –33 wt% Li 3 BO 3 composite was prepared via mechanical milling. The composite exhibited an acceptable hydrogenation/dehydrogenation rate, high hydrogen storage capacity and superior reversibility. The initial dehydrogenation temperature of the composite was 105 °C, which is 205 °C lower than that of the pristine LiBH 4 , and the hydrogen desorption capacity was 4.12 wt% at 450 °C within 2000 s. The composite maintained its hydrogen absorption capacity of 2.8 wt% with a narrow gap after 5 de/hydrogenation cycles at 400 °C and 5.0 MPa. The Li 3 BO 3 additive clearly enhanced the hydrogen storage properties of LiBH 4 and facilitated the decomposition and formation of [BH 4 ] − , thus accelerating de/rehydrogenation of LiBH 4 . At the same time, Li 3 BO 3 offered numerous porous channels that enhanced hydrogen circulation.
✓ 已验证
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2026
·
IF 6.7
Jinting Chen,Lei Wang,Ming Yao,Yue Pan,Zeyu Zhang,Yawei Li,Haixiang Huang,Bogu Liu,Jianguang Yuan,Bao Zhang,Ying Wu
To address the sluggish dehydrogenation kinetics and high operating temperatures of LiBH 4 , Ti 2 VC 2 MXene was incorporated with LiBH 4 to modify its dehydrogenation performance. With 40 wt% Ti 2 VC 2 MXene additive, the onset dehydrogenation temperature of LiBH 4 is reduced to 98.31 °C, while the peak hydrogen release occurs at 332.86 °C. Isothermal dehydrogenation measurements demonstrate that the composite rapidly desorbs 9.50 wt% H 2 within 40 min at 325 °C, 10.67 times faster than that of LiBH 4 . Furthermore, the addition of 40 wt% Ti 2 VC 2 MXene effectively lowers the activation energies for the dehydrogenation to 104.76 and 112.99 kJ mol⁻ 1 , respectively. Mechanism studies reveal that the enhanced dehydrogenation performance originates from the in-situ formation of catalytic active species, including Ti 0 , V 0 and Li 3 BO 3 , promoting the cleavage of ionic and covalent bonds in LiBH 4 . Simultaneously, the multiphase Ti/V/Li 3 BO 3 hetero-ensembles create abundant interfacial boundaries, serving as efficient pathways for hydrogen diffusion and accelerating the dehydrogenation kinetics.
✓ 已验证
产品关联
DOI
高影响因子
Journal of Materials Chemistry A
·
2026
·
IF 9.2
Yang Yang,Yuanqiang Duan,Wenhao Jiang,Xiangqian Du,Yushuang Jiang,Hongjian Tang,Lunbo Duan
Desirable media for thermochemical energy storage (TCES) should possess stable reversibility without performance degradation. Herein, we demonstrate the potential CO2-carrying capacity, heat storage density, and long-term cycling stability of Li3BO3, which exhibits a CO2 uptake above 0.2 gCO2·gsorbent−1 from 500 °C to 590 °C, reaching a maximum of ∼0.32 gCO2·gsorbent−1 at 560 °C under 100% CO2. The Li3BO3 + CO2 system displayed a heat release of ∼909 J·gsorbent−1 during discharging and a heat absorption of ∼1110 J·gsorbent−1 during charging, without noticeable degradation over 30 cycles at 560 °C. The final-cycle heat storage capacity of ∼1146 J·gsorbent−1 was obtained, substantially outperforming those of previously reported CO2 carriers, such as CaO, SrO, and Li4SiO4. The carbonation pathway of Li3BO3 was further elucidated by in situ X-ray diffraction measurements and pCO2-T phase diagrams. Within the 400–580 °C window at pCO2 = 1 bar, two pathways were observed: (1) direct carbonation via Li3BO3 + CO2 → Li4B2O5 + Li2CO3 and (2) stepwise carbonation via Li3BO3 + CO2 → Li4B2O5 + Li2CO3, followed by Li4B2O5 + CO2 → Li6B4O9 + Li2CO3, wherein Li4B2O5 was produced as a key intermediate in the 500–560 °C window. The beneficial effects of Li4B2O5 were further explored via kinetic modeling and first-principles calculations. Li4B2O5 exhibited a significantly slower carbonation rate and a higher ionic diffusion barrier than Li3BO3, providing rate regulation and structural buffering to the reversible reaction (4Li3BO3 + 3CO2 ⇌ 3Li2CO3 + Li6B4O9) in both the forward and backward directions, thus endowing the Li3BO3 + CO2 system with long-term cyclic stability. The fundamental insights reported herein could provide guidance for the design of high-performing CO2 carriers in broader industrial scenarios, such as TCES, flue gas CO2 capture, and sorption-enhanced techniques.
✓ 已验证
产品关联
DOI
高影响因子
Journal of Materials Chemistry A
·
2019
·Vol. 7
·期 36
·20633-20639
·
IF 10.733
Huilin Xie,Chunli Li,Wang Hay Kan,Maxim Avdeev,Chenyou Zhu,Zhikun Zhao,Xiaorong Chu,Daobin Mu,Feng Wu
All solid-state batteries have received significant attention due to their excellent safety performance. As a key component, the garnet-type electrolyte is one of the best known electrolytes due to its air stability and good compatibility with metallic lithium. However, the total Li+ conductivity of this kind of electrolyte is usually lower than that of the bulk electrolyte primarily due to the grain boundary resistance. In this study, we focused on engineering the electrolyte Li6.4La3Zr1.4Ta0.6O12 (LLZTO) by introducing Li3BO3 (LBO) into it to form the electrolyte LLZTO/LBO with the aim to consolidate the grain boundary. Via characterization by both neutron and X-ray diffraction, the as-prepared LLZTO was indexed as a pure cubic phase, where Ta certainly substituted the Zr sites. LLZTO/LBO still maintained the cubic structure, and the B atoms did not occupy any cation sites in the unit cell. It was demonstrated that an amorphous phase of a boracic substance was trapped inside the cubic LLZTO phase. The amorphous boracic phase sutured the gaps among the LLZTO grains and then lowered the grain boundary resistance without introducing impurities, ultimately consolidating the solid-state electrolyte. Electrochemical impedance spectroscopy revealed that the total Li+ conductivity of LLZTO/LBO reached 5.47 × 10−4 S cm−1, much higher than those of the as-prepared Li7La3Zr2O12 (LLZO) and LLZTO. Using LLZTO/LBO as an electrolyte, the LiNi0.8Co0.1Mn0.1O2/LiFePO4 hybrid solid battery showed an excellent cycling performance with the reversible capacity of 147.8 mA h g−1 at 0.2C for 100 cycles and the capacity retention of 93.8%. These results suggest that the consolidation of the grain boundary with LBO is a promising way to achieve an improved electrolyte, LLZO, with higher total Li+ conductivity.
研究领域:
材料科学
·
电化学
·
储能技术
·
固态电池
✓ 已验证
DOI
高影响因子
ACS Applied Energy Materials
·
2022
·
IF 6.959
Zhenglong Li,Shun Wang,Mingxia Gao,Kaicheng Xian,Yi Shen,Yaxiong Yang,Panyu Gao,Wenping Sun,Yongfeng Liu,Hongge Pan
LiBH4 as a promising candidate material for solid-state hydrogen storage still suffers from high dehydrogenation temperature and poor reversibility. A catalyzed LiBH4-based system with in situ introduced Li3BO3 and V is synthesized by adding NH4VO3 into LiBH4 followed by a heat treatment and a hydrogenation process. The optimized LiBH4 system introduced with 0.06 molar fraction of Li3BO3 + V, which is denoted as LiBH4–0.06LiBOV, shows excellent hydrogen storage kinetics and high reversible stability. The system starts to release hydrogen at 220 °C, and a capacity of 5.8 wt % H2 is obtained at 350 °C within 90 min. Furthermore, full rehydrogenation can be achieved at 500 °C and 50 bar of H2 for 50 min, and a capacity retention as high as 87.5% is obtained after five cycles. In situ introduced Li3BO3 and V lower the activation energy of LiBH4 and inhibit the generation of Li2B12H12 during the hydrogenation of LiBH4, which contribute to the synergistic catalytic effects on hydrogen desorption and absorption. In addition, the restraining of the particle size growth during dehydrogenation/hydrogenation is critical to inhibiting the generation of Li2B12H12 and thus improves the hydrogenation property of LiBH4. The catalyzed LiBH4 system provides new insights on LiBH4 as a high-density hydrogen storage material.
研究领域:
材料科学
·
氢气储存
·
固态化学
·
能量存储
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）