Nano Energy
·
2023
·
IF 17.6
Zhendong Li,Wenjun Liang,Jiahe Chen,Libo Song,Tengpeng Xiong,Weiping Xie,Sudong Wu,Di Hu,Xiayin Yao,Zhe Peng
Confining lithium (Li) deposition in three-dimensional scaffold is commonly employed to suppress Li dendrite and enhance the cycling stability of next generation Li metal batteries (LMBs). However, the efficiency of this strategy is often degraded under lean-Li conditions, due to the serious precipitation of deposited Li on the top surface of the electronic conducting scaffold such as carbon or metal matrix. Here it is found that building an insulating interlayer on the scaffold but with a high Li + transfer dynamism, can be a promising strategy to address the above challenge. We successfully three-dimensionalize an insulating and robust nanodiamond (ND) network on carbon paper (CP) via chemical vapor deposition , which not only retards the electron transfer to avoid the top Li precipitation, but also exhibits impressive Li affinity and mobility to undergo an in-depth Li + transportation throughout the scaffold. Based on this advanced three-dimensionalized ND network, the Li anode performance in CP@ND significantly exceeds that in the traditional carbon fiber matrix, particularly under lean-Li conditions. Furthermore, the application of CP@ND leads to a sharply improved cyclability of all-solid-state LMBs, establishing a novel guideline of protecting Li anode in the electrolyte-mobility-limited environment.
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CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Honglin Yan,Yuan Ha,Tao Ye,Xiaoya Gao,Xiangting Yue,Zhimin Li
Ni-rich LiNi x Mn 1- x O 2 cathodes have been extensively probed to resolve the electrochemical performance degradation in the absence of Co 3+ compared to LiNi x Co y Mn 1- x - y O 2 cathodes for lithium-ion batteries. Herein, LiNi 0.6 Mn 0.4 O 2 (NM64) and a series of nonmagnetic Al 3+ ions substituted NM64 cathode materials are designed and prepared via a sol–gel route. It is found that the inferior electrochemical performance of NM64 derives from the magnetic frustration arising from Mn ions and the unstable Mn 3+ ions, which will lead to severe Li/Ni mixing, and weak structural and interfacial stabilities of the cathode. The superconducting quantum interference device (SQUID) analysis proves that the nonmagnetic Al 3+ ion can lower the Li/Ni disorder in NM64 cathode by relieving magnetic frustration. Moreover, the dQ/dV and XPS analyses confirm that both structural and interfacial stabilities are enhanced for NM64 cathode owing to Al 3+ substitution, contributing to fewer byproducts after a long cycle. Consequently, LiNi 0.582 Mn 0.388 Al 0.03 O 2 cathode delivers a high discharging capacity of 179 mAh g −1 at 1.0C with a capacity retention of 87.6% after 100 cycles. This study not only gives an in-depth understanding of the mechanism of electrochemical performance degradation for NM64 cathode, but also demonstrates an efficient solving approach through Al 3+ complementary substitution.
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JOURNAL OF MEMBRANE SCIENCE
·
2023
·
IF 9.5
Qin Dong,Tao Wang,Die Su,Ruiyi Gan,Minhua Shao,Cunpu Li,Qingfei Liu,Zidong Wei
The commercialization of Li–S batteries has been seriously hampered by the infamous “shuttle effect” of soluble lithium polysulfide intermediates (LiPSs, Li 2 S x , 4 ≤ x ≤ 8) and sluggish sulfur species conversion kinetics. In this work, vinyl ferrocene and styrene were copolymerized onto a polypropylene (PP) separator to prevent LiPS shuttling based on the electrostatic and orbital interactions between ferrocene and LiPSs, which increased the reactivity of LiPSs. Therefore, the “shuttle effect” can be successfully suppressed by a separator that combines thermodynamic anchoring and kinetic acceleration for LiPSs.
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Journal of Cleaner Production
·
2022
·
IF 11.072
Brian Makuza,Dawei Yu,Zhu Huang,Xueyi Guo,Qinghua Tian,Kun Zhang,Baichao Zhang,Pengfei Liu
The vast amount of Lithium-ion batteries (LIBs) reaching their end-of-life calls for effective recycling processes, given the low recycling efficiency in the industry. This paper proposes an innovative sequential carbothermic reduction-selective hydrochlorination process to attain metallization of Ni-Co alloy, selective chlorination of Li, Mn, and Cu, and the formation of Al 2 O 3 to address some of the recycling challenges. The proposed process paves the way for short-range effective separation of the high-value metals in the LIB black mass based on magnetism and water solubility differences. After hydrochlorination at 1000 °C for 30 min with the material bed measuring 9 mm in thickness, Li and Mn water recovery reached 97.28% and 98.13%, respectively. The Ni and Co recoveries into the magnetic fraction reached 93.03% and 91.37%, respectively. Up to 95.28% Al, including graphite, reported to the non-magnetic fraction. Prolonged hydrochlorination time increased the chlorination degree despite negatively affecting the Ni-Co alloy recovering efficiency. Conversely, an increase in the thickness of the material bed had a reverse effect. Step-wise precipitation of the water-soluble product produced high-purity Li 2 CO 3 (≥99.5%) and Mn 3 O 4 . Compellingly, graphite with morphology and characteristic diffraction peaks and Raman bands similar to commercial graphite was regenerated by NaOH dissolution of the non-magnetic fraction. These findings demonstrate that a black mass with a complex composition (Li, Ni, Mn, Co, and Al) could be comprehensively recycled using synergetic carbothermic reduction and hydrochlorination. Besides the high recovery rates, the proposed process minimizes recycling process steps and chemical usage, which is of utmost industrial significance.
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RSC Advances
·
2019
·Vol. 9
·期 29
·16288-16295
·
IF 3.049
Shu-ying Zhen,Hai-tao Wu,Yan Wang,Na Li,Hao-sen Chen,Wei-li Song,Zhen-hua Wang,Wang Sun,Ke-ning Sun
Herein, hollow porous CuO–CuCo2O4 dodecahedrons are synthesized by using a simple self-sacrificial metal–organic framework (MOF) template, which resulted in dodecahedron morphology with hierarchically porous architecture. When evaluated as a cathodic electrocatalyst in lithium–oxygen batteries, the CuO–CuCo2O4 composite exhibits a significantly enhanced electrochemical performance, delivering an initial capacity of 6844 mA h g−1 with a remarkably decreased discharge/charge overpotential to 1.15 V (vs. Li/Li+) at a current density of 100 mA g−1 and showing excellent cyclic stability up to 111 charge/discharge cycles under a cut-off capacity of 1000 mA h g−1 at 400 mA g−1. The outstanding electrochemical performance of CuO–CuCo2O4 composite can be owing to the intrinsic catalytic activity, unique porous structure and the presence of substantial electrocatalytic sites. The ex situ XRD and SEM are also carried out to reveal the charge/discharge behavior and demonstrate the excellent reversibility of the CuO–CuCo2O4 based electrode.
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ChemSusChem
·
2019
·Vol. 12
·期 14
·3377-3382
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IF 7.804
Rusheng Fu,Yongkang Wu,Chongzhao Fan,Zuxin Long,Guangjie Shao,Zhaoping Liu
Graphical Breaking the ICE : The SiO anode in Li-ion batteries has low initial coulombic efficiency (ICE) because of the irreversible formation of Li 2 O and lithium silicates. Sn-mixed SiO shows great promise to address these issues by reactivating Li 2 O, in the inverse reaction to that occurring at the metal oxide anodes. Sn is shown to form an outstanding conductive phase, which boosts the reaction kinetics and also reactivates Li 2 O. The application of SiO anodes in Li-ion batteries is greatly restricted by its low initial coulombic efficiency (ICE). Usually, a pre-lithiation procedure is necessary to improve the ICE, but the available technologies are associated with safety issues. Metal (M)-mixed SiO shows great promise to address these issues by reactivating Li 2 O through the reaction M+Li 2 O→MO x +Li + , which is the inverse reaction to that occurring at MO x anodes. Sn is found to be a good choice of metal for this concept. Nanoscale Sn-mixed SiO composites are prepared by mechanical milling. Sn forms an outstanding conductive phase, which boosts the reaction kinetics and also reactivates the Li 2 O byproduct. Sn/SiO (1:2 w/w) delivers a significant improvement in ICE from 66.5 % to 85.5 %. A higher ICE value of >90 % is obtained when the Sn content is ≥50 wt %. However, additional electrolyte decomposition occurs, which is catalyzed by Sn. In addition, coarsening of the nano-Sn material reduces the inverse conversion reactivity of Sn/Li 2 O and subsequently results in rapid capacity fading. The quantitative analysis indicates that, in contrast to transition metals, the alloying and dealloying nature of Sn gives a 50 % improvement in reversible capacity, attributed to Sn/Li 2 O. This work gives a general strategy to choose metals for increasing the ICE of SiO x and metal oxides.
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JOURNAL OF POWER SOURCES
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2019
·
IF 7.467
Shili Wang,Shimou Chen,Weiqun Gao,Lili Liu,Suojiang Zhang
In this paper, we propose a new electrolyte additive 3-Isocyanatopropyltriethoxysilane (IPTS) to improve the cycle stability and rate performance of Ni-Rich (LiNi 0·6 Co 0·2 Mn 0·2 O 2 ) cathode half-cell. Density function theory calculations suggest that IPTS has higher HOMO energy than solvent, which can decompose preferentially. Moreover, we confirm the oxidative decomposition by the linear scanning cyclic voltammetry , which can achieve stable at a cutoff voltage of 2.5–4.5 Vs. (Li/Li + ). The cyclic voltammetry curves at different scan rates indicate that the migration rate of lithium ions is higher in the cells with 0.5% additive than in the base electrolyte. After 150 cycles, the capacity retention rates in the base electrolyte and in the additive-containing electrolyte are 55.4% and 73.1%, respectively. X-ray photoelectron spectroscopy, scanning electron microscopy and transmission electron microscopy show that the additive is involved in film formation, and the obtained CEI film is very uniform and dense, which play a key role in stabilizing the electrolyte under high voltage.
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AIP Advances
·
2019
·Vol. 9
·期 2
·
IF 1.579
Li Sheng,Lan Lifang,Lu Lu,Lu Yan,Li Shaofang,Li Jun,Pan Chunyang,Zhao Fenghua
To investigate the effect of Ce doping on structure and the electrochemical properties of spinel LiNi 0.5 Mn 1.5 O 4 , especially the cycling performance at high temperature, spinel cathode materials LiNi 0.5-0.5x Mn 1.5-0.5x Ce x O 4 (x = 0, 0.01, 0.02, 0.03) were prepared by the sol-gel method for use in lithium ion batteries. For this purpose a half-cell was assembled with a lithium metal anode and a full-cell was paired with graphite. The characterization and analysis of the prepared LiNi 0.5-0.5x Mn 1.5-0.5x Ce x O 4 (x = 0, 0.01, 0.02, 0.03) composites revealed that all of the samples had a disordered spinel octahedron structure, and that the purity of the phase increased after appropriate Ce doping. Compared to the pristine sample, the prepared LiNi 0.495 Mn 1.495 Ce 0.02 O 4 , (x = 0.02) had outstanding electrochemical performance with an initial capacity of 133.8 mAh/g, and 131.9 mAh/g at 1 C and 55 °C after 50 cycles, and maintained a capacity retention value of 98.6% at 1 C and 25 °C at the 100th cycle. The introduction of Ce as dopant improved the electrochemical performance of LiNi 0.5 Mn 1.5 O 4 as a result of the synergistic effects of stronger structural stability, higher lithium ion diffusion coefficient, and lower electrochemical polarization.
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ELECTROCHIMICA ACTA
·
2018
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IF 5.116
Yuebin Yang,Hui Xu,Shanxing Wang,Yuanfu Deng,Xianying Qin,Xusong Qin,Guohua Chen
Li-ion batteries have held a dominant position in the energy storage area for decades. However, due to the limitation of its chemistry , the energy density of Li-ion batteries is limited to ∼300 W h kg −1 . In recent years, more attention has been paid to the Li-S batteries that are environmentally friendly, cost-effective and high energy density (theoretical value of cathode: ∼2600 W h kg −1 ). In this study, carbonized polydopamine (C-PDA)-coated hollow carbon nanofibers (CNFs) with TiO 2 nanoparticles interspersed in the void space between the CNF skeleton and carbon coating layer were subtly designed. The C-PDA/TiO 2 /CNF composite (CTC) was integrated with the commercial separator as a polysulfide filter to achieve high-performance Li-S batteries. It is reveals that the CTC coating layer could effectively filter and reactivate the dissolved polysulfides to achieve a stabilized sulfur-based cathode. The Li-S battery assembled by this integrated separator and the regular cathode (sulfur/Ketjen black) with 72.7 wt% of sulfur achieved a high specific capacity and low decay rate (632.5 mAh g −1 at the first cycle and 0.06% per cycle) at 2.0C for 500 cycles. These good results indicate that the C-PDA/TiO 2 /CNF-modified separator could be a promising separator candidate for high performance Li-S batteries.
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APPLIED ORGANOMETALLIC CHEMISTRY
·
2019
·Vol. 33
·期 3
·e4778
·
IF 3.259
Jicheng Xu,Zhilong Pu,Xuechao Xu,Yuanyuan Wang,Dongya Yang,Tao Zhang,Fengxian Qiu
With the gradual exhaustion of land mineral resources, oceans and lakes have attracted world attention because they are abundant in inorganic mineral resources including lithium, potassium, rubidium and cesium. Lithium is becoming the key material in manufacturing of primary and secondary batteries used in various portable devices and hybrid/electric vehicles. Rubidium has been widely applied inglobal positioning satellites, magneto-optic modulators, solid-state lasers, phosphors, and glass manufacturing. In this work, a novel dual-functional magnetic ion imprinting polymer (Fe 3 O 4 @SiO 2 @IIPs) powder was prepared using 12-crown-4 (12C4) and 18-crown-6 (18C6) as functional monomer, and characterized by FT-IR, elemental analysis, XRD, TGA, SEM and TEM. The adsorption performance of Fe 3 O 4 @SiO 2 @IIPs for simultaneous adsorption of lithium and rubidium from simulative salt lakes was evaluated by batches of experiments at various pH values, contact time, and initial concentrations. Kinetic experiments show that the adsorption process followed the pseudo second order kinetic model. Langmuir adsorption isotherm model and Freundlich adsorption equilibrium data were fitted; the results show that Langmuir isotherm model is more suitable for the adsorption process. Additionally, Fe 3 O 4 @SiO 2 @IIPs exhibit specificity towards Li(I) and Rb(I) and low competitive behavior with Na(I), K(I) and Mg (II). Additionally, the selectivity properties, reusability and adsorption thermodynamic were also investigated. The obtained results show that the prepared Fe 3 O 4 @SiO 2 @IIPs material remains high adsorption capacities after five cycles, exhibits excellent abilities to simultaneously and selectively recover Li + and Rb + and have a promising application in the simultaneous adsorption of lithium and rubidium ions.
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Energy Storage Materials
·
2019
·
IF 0
Jing Tian,Xuejun Zhou,Qingping Wu,Chilin Li
Mg-based batteries modulated by Li-salt additive can bypass the sluggish Mg solid diffusion at cathode side by kinetically better Li intercalation. However for this dual-salt system the highly electroactive cathodes endowed with high intrinsic conductivity and multi-electron transfer are still lacking, especially under large-sized grains and their high loading. Here a rhodizonate organic salt pre-pillared by K-ions (K 2 C 6 O 6 ) is proposed as high-rate cathode for Li-salt mediated Mg batteries. Under a high loading of 70 wt%, well-crystallized K 2 C 6 O 6 composed of ultra-large micro-sized grains (up to 30 μm) shows a reversible capacity more than 300 mA h/g at 0.1 C (based on three electron transfer), and up to 200, 130 and 60 mA h/g at 2 C, 5 C and 10 C respectively. The high bulk electron/ion conductivity and low solubility are responsible for such a superior performance based on fast Li-K electrochemical exchange and highly reversible Li intercalation without the assistance of nano-sizing, as a consequence of optimization and stabilization of desired electron structure and open framework by K-ion pre-supporting (instead of Li/Na-pillaring) and Mg-ion trapping between C 6 O 6 2- layers. These large monoliths of K 2 C 6 O 6 do not undergo serious grain fracture after long-term cycling, and at that time the Mg anode still remains compact and dendrite-free.
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JOURNAL OF THE SCIENCE OF FOOD AND AGRICULTURE
·
2019
·Vol. 99
·期 10
·4772-4780
·
IF 2.422
Zhibing Huang,Lijuan Zhang,Heng Gao,Yanling Wang,Xiujiang Li,Xinyu Huang,Ting Huang
BACKGROUND Monascus , a filamentous fungus, produces many bioactive substances. However, in the process of fermentation, Monascus also produces the mycotoxin citrinin. Owing to the presence of citrinin, the safety of Monascus products has been questioned and their wide application limited. Using soybean isoflavones (SI) as exogenous additives, alterations in citrinin production by Monascus aurantiacus Li AS3.4384 (MALA) in different media used for liquid state fermentation were investigated. RESULTS Results showed that the citrinin concentration was 95.98% lower than that of the control group after 16-days fermentation when 20.0 g L −1 SI were added to rice powder and inorganic salt medium. Citrinin production was reduced by 97.24% after 12-days fermentation with 10.0 g L −1 SI in starch inorganic salt medium; 82.52% after 20-days fermentation with 20.0 g L −1 SI in starch peptone medium with high starch content; 45.07% after 14-days fermentation with 5.0 g L −1 SI in starch peptone medium with low starch content; and 82.21% after 14-days fermentation with 20.0 g L −1 SI in yeast extract sucrose medium. CONCLUSION The developed method of removing citrinin is simple, safe, and effective, and it can be applied to reduce the citrinin content of Monascus products. © 2019 Society of Chemical Industry
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