Small
·
2024
·
IF 13
Zhiying Gao,Jingming Yao,Jitong Yan,Jun Sun,Congcong Du,Qiushi Dai,Yong Su,Jun Zhao,Jingzhao Chen,Xiaomei Li,Hui Li,Pan Zhang,Jun Ma,Hailong Qiu,Liqiang Zhang,Yongfu Tang,Jianyu Huang
Rechargeable aprotic lithium (Li)-oxygen battery (LOB) is a potential next-generation energy storage technology because of its high theoretical specific energy. However, the role of redox mediator on the oxide electrochemistry remains unclear. This is partly due to the intrinsic complexity of the battery chemistry and the lack of in-depth studies of oxygen electrodes at the atomic level by reliable techniques. Herein, cryo-transmission electron microscopy (cryo-TEM) is used to study how the redox mediator LiI affects the oxygen electrochemistry in LOBs. It is revealed that with or without LiI in the electrolyte, the discharge products are plate-like LiOH or toroidal Li 2 O 2 , respectively. The I 2 assists the decomposition of LiOH via the formation of LiIO 3 in the charge process. In addition, a LiI protective layer is formed on the Li anode surface by the shuttle of I 3 − , which inhibits the parasitic Li/electrolyte reaction and improves the cycle performance of the LOBs. The LOBs returned to 2e − oxygen reduction reaction (ORR) to produce Li 2 O 2 after the LiI in the electrolyte is consumed. This work provides new insight on the role of redox mediator on the complex electrochemistry in LOBs which may aid the design LOBs for practical applications.
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
JOURNAL OF MEMBRANE SCIENCE
·
2023
·
IF 9.5
Zhouyang Jiang,Wenhan Kong,Fenglin Zhao,Qingyue Han,Yangxi Liu,Suqing Wang,Haihui Wang
Highly purified LiOH is a common raw material of cathode active materials of lithium-ion batteries. Its demand is rapidly increasing with the fast development of the electric vehicles. The traditional enrichment process of LiOH relying on water evaporation requires a lot of energy. Here, we demonstrate the ability of NASICON-type Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 membrane electrodialysis to enrich the LiOH aqueous solution with a low concentration. This Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 membrane electrodialysis could extract 99.7% and 96.5% of Li + in 0.1, and 0.01 M LiOH feed solution, respectively, into 1 M LiOH receiving solution. And the transmembrane resistance between feed solution and receiving solution increased by 37.4, 389.5, and 964.6 Ω cm 2 , compared to the value for 1 M of LiOH feed solution as the feed solution concentration decreased to 0.1, 0.01 and 0.001 M, respectively. This quantitative assessment method for the resistance variation is crucial to the potential separation application of Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 membrane electrodialysis in salt-lake brine.
研究领域:
材料科学
·
能源工程
✓ 已验证
DOI
高影响因子
Advanced Energy Materials
·
2020
·Vol. 10
·期 38
·2001592
·
IF 25.245
Xiaodong Lin,Zongqiang Sun,Chun Tang,Yuhao Hong,Pan Xu,Xueyang Cui,Ruming Yuan,Zhiyou Zhou,Mingsen Zheng,Quanfeng Dong
The reduction of O 2 to solid Li 2 O 2 on discharge and the reverse oxidation of Li 2 O 2 to O 2 on recharge are the essential processes to determine the performance of Li-O 2 batteries. The discovery of effective catalysts with a favorable Li 2 O 2 formation/decomposition mechanism is vital for the development of high-performance Li-O 2 batteries. Here, a soluble catalyst of iodosylbenzene (PhIO) that can offer a highly reversible O 2 conversion is reported for the first time. Benefiting from its ability to capture and couple the LiO 2 intermediate, which is endowed by its polarized I 3+ O 2− bond where the I atom and O atom can serve as a Lewis acidic site and basic site (dual site) to interact with O 2 − and Li + , respectively, the formation and decomposition of Li 2 O 2 by a one-electron pathway can be effectively promoted, thus greatly improving the electrode surface passivation issue and the reaction kinetics. In addition, the side reactions caused by the traditional high-reactive LiO 2 intermediate can also be effectively suppressed by forming a series of low-reactive intermediates (LiO 2 3PhIO, (LiO 2 ) 2 4PhIO, and Li 2 O 2 4PhIO) instead. Consequently, the PhIO-catalyzed Li–O 2 batteries exhibit a low overpotential, a large capacity, and a good cyclability.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
International Journal of Electrochemical Science
·
2024
·
IF 1.3
Yanjie Xue,Jinsheng Zhao,Aifeng Li
Li-oxygen (Li-O 2 ) battery is a novel energy storage equipment. However, its poor reaction reversibility relating to the insoluble lithium peroxide (Li 2 O 2 ) generated during the discharge process, limits its application and development for large scale use. Therefore, the design and synthesis of effective catalysts which can efficiently catalyze the production and decomposition of Li 2 O 2 and exclude the generation of side-products has become the primary task to develop Li-O 2 batteries. Herein, a new type of electrocatalyst based on single-atom Ru and N, S-co-doped carbon materials (Ru/CNS/CNT) is introduced to reduce the overpotential of the battery reaction and accelerate the formation and decomposition of Li 2 O 2 . Galvanostatic charge-discharge tests were performed on the Li-oxygen (Li-O 2 ) battery with Ru/CNS/CNT as the cathode catalyst material. With a limited specific capacity of 1000 mA h g −1 , the battery can stably cycle for 79 cycles at a current density of 200 mA g −1 . Furthermore, the existence of the single atom of Ru was demonstrated according to the characterization of HAADF-STEM. The experimental results showed that composite material Ru/CNS/CNT can accelerate the formation and decomposition of lithium peroxide (Li 2 O 2 ), thereby greatly improving the cycling stability of the battery.
研究领域:
材料科学
·
电化学
·
能源存储
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Daming Yang,Guiru Sun,Xinru Wang,Fengyang Li,Ze Gao,Pingli Zhang,Wei Lu,Ming Feng
The photo-assisted lithium-oxygen (Li-O 2 ) cell is widely concerned due to its low overpotential. However, rapid recombination rate of photogenerated electrons and holes remains a fundamental challenge for photo-assisted Li-O 2 cells. Herein, we design an optical and magnetic fields co-assisted Li-O 2 cell based on α-Fe 2 O 3 nanospindles. We employed PL spectrum and I-t curve confirm that under the magnetic field, the photogenerated electrons and holes are driven via the opposite Lorentz forces in photo-assisted Li-O 2 cells, which is beneficial to accelerating the formation and decomposition of Li 2 O 2 . The optical and magnetic fields co-assisted Li-O 2 cell based on α-Fe 2 O 3 nanospindles achieves an ultra-high discharge platform of 3.47 V and a low charge platform of 3.57 V, as well as a surprising energy efficiency of 97.2%. In addition, the optical and magnetic fields co-assisted Li-O 2 cell can stably cycle for over 25 cycles. This study offers a reference for improving the electrochemical kinetics of photo-assisted Li-O 2 cell by introducing magnetic field, which opens up a new avenue for the development of high-performance Li-O 2 cells.
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 Materials Chemistry A
·
2016
·Vol. 5
·期 2
·544-553
·
IF 8.262
Qin Zhao,Caixia Wu,Lina Cong,Yuhang Zhang,Guiru Sun,Haiming Xie,Liqun Sun,Jia Liu
Controlling the geometric morphology and distributive location of discharge products play an important role in the reversibility and efficiency of Li–O2 batteries. This work presents novel Co2CrO4 nanospheres (CCO) prepared via a facile method, which are applied as the electrocatalysts for Li–O2 batteries. The as-prepared CCO was characterized by XRD, XPS, SEM, TEM, BET, and TG measurements. The CCO exhibited a yolk–shell microstructure, which could facilitate fast Li+ and O2 diffusion as well as possessing enough space for the discharge product deposition. In comparison to the performance of the cell without catalyst, the overpotential of the cell with CCO was apparently reduced and the cyclability significantly enhanced. Based on the experimental results and DFT calculations, direct evidence of the CCO employment being linked to the Li2O2 morphology was provided. In addition, a catalytic mechanism was proposed. Furthermore, fundamental information about the key factors and steps involved in the Li2O2 formation and decomposition was revealed. We expect that this study gives insight into the development of electrocatalysts, the selection of O2 electrode materials, and the design of O2 electrodes for Li–O2 batteries, as well as advancing our understanding of the catalytic mechanism.
研究领域:
材料科学
·
电化学
·
能源存储与转换
✓ 已验证
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Yongyang Zhu,Liming Zeng,Daifeng Wu,Renheng Tang,Qing Zhou
The lack of cost-effective regeneration techniques for LiBH 4 limits its large-scale applications for supplying hydrogen via hydrolysis. Now, we report a facile method to regenerate LiBH 4 by ball milling its real hydrolytic byproduct (LiBO 2 · x H 2 O) with cheap Al based reducing agents, instead of traditional Mg. Effective strategies are developed to promote the formation of LiBH 4 by introducing Li 2 O to enable the dense Al 2 O 3 to convert into LiAlO 2 on Al surface and break up passivation layers, and by partially replacing Al with Al-RE alloy to improve grinding and contacting efficiency of raw materials and facilitate the conversion from initial H + in LiBO 2 ·2H 2 O to final H ¯ in LiBH 4 . A yield of 10.4 % can be obtained for a relatively short ball milling time (10 h) for the Al-Al 2 Ce-Li 2 O-LiBO 2 ·2H 2 O system. Another advantage of this method is that the utilization of H + source in LiBO 2 ·2H 2 O improves energy efficiency and reduces the cost. This work broadens the species of reducing agents for borohydride regeneration and enriches its regeneration methods.
研究领域:
材料科学
·
化学工程
·
氢气储存
✓ 已验证
产品关联
DOI
高影响因子
Batteries & Supercaps
·
2023
·Vol. 7
·期 4
·e202300479
·
IF 5.7
Xingyi Zhan,Yifan Zhang,Liwei Su,Lei Zhang,Zijin Tong,Hao Wu,Lianbang Wang,Yuanhao Wang,Xiaoxiang Wang
The slow reaction kinetics of Li−O is currently the most pressing technical obstacle to the development of lithium-oxygen batteries. The Li 2 O 2 ′s growth/decomposition pathways dominate the battery performance and can be optimized by exploring efficient cathode catalysts. Herein, we prepare regular, polycrystalline, oxygen vacancy (V O )-riched PrO x uniformly anchored on few-layered graphene (FLG) nanosheets to boost the Li−O reactions. XRD, TGA, XPS, SEM, TEM, SEAD, and electrochemical test techniques are used to study their chemical composition, microstructure, battery performance, and the effect of FLG on the formation of polycrystalline and V O . It is confirmed that FLG provides a large specific surface area and good electron transport. Moreover, it works as an anchoring substrate to transform PrO x from single crystal to polycrystalline, which is beneficial for exposing catalytic sites and V O and improving the battery performance. This unique composition and structure offer efficient active sites, accelerate electron transport, and regulate the Li 2 O 2 ′s nucleation to form nanofilms or nanosheets on the catalyst. With this cathode catalyst, the battery achieved an ultralow total overpotential of 0.618 V, with a discharge capacity of 11489 mAh g −1 in the ultimate-capacity mode and a superior cyclability of 85 cycles under the limited capacity of 500 mAh g −1 . Graphical Vo-riched PrOx is anchored on graphene nanosheets with large specific surface area and high conductivity. Therefore, the active site of oxygen defect in Vo-riched PrOx could be fully exposed to promotes the adsorption and desorption of intermediates, accelerates electron transport, and reduces the reaction energy barrier for excellent OER/ORR activities.
研究领域:
材料科学
·
电化学
·
能源存储
·
纳米催化
·
电池技术
✓ 已验证
DOI
高影响因子
ChemSusChem
·
2024
·Vol. 18
·期 4
·e202401486
·
IF 7.5
Shirui Li,Kuikui Xiao,Xi Liu,Jiangdong Sun,Dong Cai,Shuo Yang,Yinhang Zhang,Huagui Nie,Zhi Yang
Cathode prelithium agent is regarded as the most applicable approach to compensate the initial capacity loss in lithium ion batteries (LIBs). Li 2 NiO 2 (LNO) has attracted numerous attention due to its superior environmental stability and reliable synthesis approach. To promote the commercial application of LNO, the understanding of the degradation mechanism induced by air-exposure and finding reliable strategies to improve the air stability are necessary. Herein, by preserving the LNO in different environments (relative humidity of 70 % and 40 %), the surface chemistry evolution of LNO is subtly investigated, which shows Li 2 CO 3 and LiOH cover the surface of the LNO, which decline the Li + diffusion kinetics as well as the charge capacity. What′s more, the slurry turns gel when the LNO exposed to the environment of 70 % relative humidity for 2 days and 40 % relative humidity for 5 days. Facile approaches, including washing the deteriorative LNO with ethanol, reacting the alkali components with H 3 BO 3 , and coating the LNO with Al 2 O 3 are conducted to recover the disabled LNO, which retains 84.2 % of initial capacity. In addition, a coating approach is proposed for the fresh LNO to effectively improve the air stability. This work provides guideline to the commercial application of the LNO. Graphical This work investigates the chemical evolution of LNO under varying conditions of relative humidity and exposure time. Since LNO will fail after two days of exposure to the environment with 70 % relative humidity, strategies to recover the failed LNO and improve the fresh LNO are proposed.
研究领域:
材料科学
·
电化学
·
锂离子电池
·
表面化学
·
能源存储
✓ 已验证
DOI
高影响因子
EES Catalysis
·
2023
·Vol. 1
·期 3
·312-321
·
IF 0
Yiqiao Wang,Siyuan Pan,Huan Li,Dewang Li,Yong Guo,Sijia Chi,Chuannan Geng,Shichao Wu,Quan-Hong Yang
Despite lithium–air batteries having unprecedented theoretical energy supremacy, rambling Li2O2 growth typically impedes O2 diffusion and electron transfer, causing low capacity, poor charging kinetics and short cycle life. Herein, we propose synergistic catalysis in the cathode by engineering the crystal facet of Fe2O3 nanoplates and introducing a visible light-excited photochemical effect. The growth of Li2O2 is regulated with a uniform distribution, mitigating local product aggregation and thus reducing the barriers of O2 diffusion and electron transfer. The improved reaction kinetics lead to ∼420% capacity improvement, low charge potential, superior rate performance, and long-term stability (300 cycles) in actual air. We reveal a mechanism that photoelectrons around each catalyst node and the resultant homogeneous internal electric field increase charge transfer, decrease soluble intermediates, and enable high electrochemical reversibility of amorphous Li2O2 with an ordered process. This study provides inspiring insights for future research into controlling product ordering in Li–air batteries.
研究领域:
电化学
·
纳米材料科学
·
能源化学
·
催化化学
·
电池技术
✓ 已验证
DOI
Energy Storage Materials
·
2022
·
IF 20.831
Yiqiao Wang,Siyuan Pan,Yong Guo,Shichao Wu,Quan-Hong Yang
Li-O 2 batteries require catalysts to solve the problem of sluggish oxygen-related reaction kinetics. However, the solid catalysts and redox mediators are intrinsically deficient due to poor solid contacts and shuttle problems, respectively. Here, we report lithium phthalimide-N-oxyl (LiPINO) as a phase transfer catalyst (PTC) for promoting Li 2 O 2 formation and its reversible decomposition through the solution-phase reactions. The interaction between LiPINO and oxygen species in the electrolyte enables the high dissolution and stability of oxygen species, the fast charge transfer at liquid-solid interfaces and superior kinetics, and the suppressed side reactions. The efficient bidirectional catalytic activity and high stability of LiPINO capacitate batteries with a highly improved discharge capacity (11400 mAh g −1 ), a largely lowered charge potential (3.14 V) and an extended cycle life (more than 200 cycles) both in O 2 and air. Our understanding of the phase-transfer catalysis towards the Li-O 2 electrochemistry and the discovery of the PTC with superior activity and stability provide deep insights into the design of the most reliable catalysts for Li-O 2 batteries.
研究领域:
电化学
·
能源材料
·
物理化学
·
电池技术
·
催化化学
✓ 已验证
DOI
高影响因子
INTERNATIONAL JOURNAL OF ENERGY RESEARCH
·
2021
·Vol. 45
·期 11
·16538-16550
·
IF 5.164
Sanchao Liu,Huihui He,Dongyun Zhang,Chengkang Chang
Summary To improve the electrochemical performances of high voltage LiCoMnO 4 spinel cathode material at 5.3 V, Cr doped LiCoMn 1-x Cr x O 4 ( x = 0, 0.025, 0.050, 0.075) materials were synthesized by a one-step solid-state at 750°C. Rietveld refinement results showed that the phase purity of spinel is promoted with the increase in Cr concentration, which can be explained by the strong Cr O bond that reduces oxygen deficiency and eliminates Li 2 MnO 3 impurity phase during the synthesis process. Such change in phase purity further causes the improvement in specific capacity, and the 5.0%Cr doped sample displays the best result with a value of 123.0 mAh/g at 0.1°C and 93.3 mAh/g at 10°C. For a comparison, the pristine sample only releases a capacity of 112.6 mAh/g at 0.1°C and 54.8 mAh/g at 10°C. Improved capacity retention, from 83.1% to 90.1% after 100 cycles at 1°C, is also observed due to the suppressed volume change during the redox process after the incorporation of Cr cations in the lattice. Promoted rate performance, attributed from the improved Li ion diffusion coefficient, is also confirmed in the experiment. The improvement of those electrochemical properties could be explained by high-phase purity and superior structural stability benefited from Cr-doping. Novelty statement LiCoMn 1-x Cr x O 4 ( x = 0, 0.025, 0.050, 0.075) materials were synthesized by a one-step solid-state at 750°C, Chromium had been confirmed to reduce oxygen loss during LiCoMnO 4 synthesis due to high oxygen affinity of Cr, which improves phase purity. As a result, the specific capacity was increased. Cr-doping enhances the structural stability so that capacity retention was promoted due to higher bond energy of Cr O than Mn O; rate performance was also enhanced due to the improved diffusion coefficient.
研究领域:
材料科学
·
电化学
·
储能
·
固态化学
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）