Energy Storage Materials
·
2022
·
IF 20.831
Yunrui Zhang,Wenbo Wang,Meiling Hou,Yantao Zhang,Yaying Dou,Zehua Yang,Xiaoyang Xu,Haining Liu,Shanlin Qiao
Li metal batteries have won the fame for the enlarged cell potential and higher theoretical specific capacity. Nevertheless, the commercial implementation is still confronted with inevitable Li dendritic growth and depressed Coulombic efficiency. The Li + transfer behavior is the vital factor to ameliorate the durability of solid electrolyte interphase (SEI). Herein, a self-exfoliated TpTG covalent organic framework (COF) was developed to construct an artificial SEI film. The versatile cationic-skeleton of TpTG could spontaneously drive the formation of nano-mesh with thickness of 3∼6 nm, and facilitate uniform dispersibility on the Li metal surface. Moreover, the 7 Li solid-state nuclear magnetic resonance spectra, Fourier-transform infrared spectra, and density functional theory calculations have identified the energetic lithiophilicity and TFSI – repulsion features. The Cl – coordinated TpTG endowed with abundant lithiophilic sites can reconfigure the charge distribution and expedite the uniform Li + migration adjacent to the electrode|electrolyte interface. The uniform Li + flux distribution redounds to reversible lithium stripping/plating and tames the dendrite formation especially at high-rate protocols. The overwhelming evidences of lower polarization, prolonged lifespan, and compact Li deposition, corroborate the practicability of self-exfoliated TpTG to achieve the goal of high-energy-density Li metal batteries.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
Crystals
·
2022
·Vol. 12
·期 9
·1290
·
IF 2.67
Wanbao Wu,Qing Li,Miaomiao Cao,Deping Li,Jingyu Lu,Mingyu Li,Jiaheng Zhang
The application of high voltage cathode electrode materials is an effective way to increase the energy density of batteries. However, the development and design of a stable electrolyte at high voltages needs to be further addressed. Herein, we developed a non-flammable dual-salt deep eutectic solvent (DES) as a safe electrolyte containing LiTFSI, LiDFOB, and succinonitrile in different molar ratios. This non-flammable DES provides high ionic conductivity (4.23 mS cm−1) at 25 °C, high Li+transference number (0.75), and wide electrochemical stability (>5.5 V). When using the designed DES electrolytes in high voltage LiCoO2||Li cells, superior electrochemical performance was achieved at cut-off voltages of 3.0–4.45 V and 3.0–4.6 V, even at a high current density of 2 C. This work offers an in-depth understanding of the critical role of dual-salts in DES and provides an approach to designing safe electrolytes for high voltage LiCoO2||Li cells.Keywords:non-flammable;high Li+transference number;deep eutectic solvent;high voltage LCO;lithium metal battery
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
Nanoscale Research Letters
·
2021
·Vol. 16
·期 1
·1-8
·
IF 4.703
Yang Mao,Jue Nan,Chen Yuanfu,Wang Yong
Uniform migration of lithium (Li) ions between the separator and the lithium anode is critical for achieving good quality Li deposition, which is of much significance for lithium metal battery operation, especially for Li–sulfur (Li–S) batteries. Commercial separators such as polypropylene or polyethylene can be prepared by wet or dry processes, but they can indeed cause plentiful porosities, resulting in the uneven Li ion stripping/plating and finally the formation of Li dendrites. Thence, we constructed an atomic interlamellar ion channel by introducing the layered montmorillonite on the surface of the separator to guide Li ion flux and achieved stable Li deposition. The atomic interlamellar ion channel with a spacing of 1.4 nm showed strong absorption capacity for electrolytes and reserved capacity for Li ions, thus promoting rapid transfer of Li ions and resulting in even Li ion deposition at the anode. When assembled with the proposed separator, the Coulombic efficiency of Li||Cu batteries was 98.2% after 200 cycles and stable plating/stripping even after 800 h was achieved for the Li||Li symmetric batteries. Importantly, the proposed separator allows 140% specific capacity increase after 190 cycles as employing the Li–S batteries.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2023
·
IF 6.2
Boyu Li,Huan Wang,Weitao Zhou,Fan Liu,Jianxin He,Gaohui Du,Qingmei Su
Solid-state lithium (Li) metal batteries (LMBs) are promising owing to enhanced safety and high energy density . However, the issues of Li dendrite growth and large electrolyte-electrode interfacial resistance still hinder their practical applications in LMBs. Here, a Li anode-electrolyte structure integration has been developed using in-situ chemical reactions between the polyvinylidene fluoride/Li 3x La 2/3−x TiO 3 /N-methyl pyrrolidone (PVDF/LLTO/NMP) solution and the Li metal interphase. After gradually coating the PVDF/LLTO/NMP solution onto Li metal, NMP as catalyst, inducing PVDF reacted with Li spontaneously to form lithium fluorine (LiF), and the accompanying Ti 4+ ions (in LLTO) are reduced to Ti 3+ ions to form a LLTO ionic/electronic conductor (Li x LLTO). After NMP evaporation, an ionic/electronic conductor protective layer of LiF/Li x LLTO is created between the PVDF/LLTO electrolytes and Li metal. When applying the integrated solid-state Li batteries (ISSLBs), the protective layer can reduce interfacial resistance and the formation of Li dendrites by regulating the even Li deposition redistributing the Li-ion transport. As a result, the as-assembled LiNi 0.8 Co 0.1 Mn 0.1 O 2 /ISSLBs achieves an initial capacity of 181 mA h g −1 and retains 83% capacity after 200 cycles at 0.5 C. This design can be an effective strategy to tailor the properties of Li-metal anodes for achieving dendrite-free LMBs with high performance and high safety.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
CHEMISTRY-A EUROPEAN JOURNAL
·
2023
·Vol. 29
·期 71
·e202302569
·
IF 4.3
Huai Chen,Jun Ma,Fei Liu,Mengqin Yao
Graphical The lithium-rich layered oxides (LLOs, Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 ) were successfully prepared based on a dual modification strategy, by co doped with anions and cations and coated with lithium carbonate coating. It founds that modified LLOs possess excellent electrochemical performance. Lithium-rich layered oxides (LLOs, Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 ) are widely used as cathode materials for lithium-ion batteries due to its high specific capacity, high operating voltage and low cost. However, the LLOs are faced with rapid decay of charge/discharge capacity and voltage, as well as interface side reactions, which limit its electrochemical performance. Herein, the dual strategies of sulfite/sodium ion co-doping and lithium carbonate coating were used to improve it. It founds that modified LLOs achieve 88.74 % initial coulomb efficiency, 295.3 mAh g −1 first turn discharge capacity, in addition to 216.9 mAh g −1 at 1 C, and 87.23 % capacity retention after 100 cycles. Mechanism research indicated that the excellent electrochemical performance benefits from the doping of both Na + and SO 3 2− , and it could significantly reduce the migration energy barrier of Li + and promote Li + migration. Meanwhile, anion and cation are co-doped greatly reduces the band gap of LLOs and increase its electrical conductivity, and its binding effect on Li + is weakened, making it easier for Li + to shuttle through the material. In addition, the lithium carbonate coating significantly inhibits the occurrence of interfacial side reactions of LLOs. This work provides a theoretical basis and practical guidance for the further development of LLOs with higher electrochemical performance.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ADVANCED MATERIALS
·
2023
·Vol. 36
·期 7
·2308275
·
IF 29.4
Xia Hu,Jiahao Yu,Yao Wang,Weiqian Guo,Xiang Zhang,Michel Armand,Feiyu Kang,Guoxiu Wang,Dong Zhou,Baohua Li
Lithium garnets are considered as promising solid-state electrolytes for next-generation solid-state Li metal batteries (SSLBs). However, the Li intrusion driven by external stack pressure triggers premature of Li metal batteries. Herein, for the first time, an in situ constructed interfacial shield is reported to efficiently inhibit the pressure-induced Li intrusion in SSLBs. Theoretical modeling and experimental investigations reveal that high-hardness metallic Mo nanocrystals inside the shield effectively suppress Li dendrite growth without alloy hardening-derived interfacial contact deterioration. Meanwhile the electrically insulated Li 2 S as a shield component considerably promotes interfacial wettability and hinders Li dendrite penetration into the bulk of garnet electrolyte. Interfacial shield-protected Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO)-based cells exhibit significantly enhanced cyclability without short circuits under conventional pressures of ≈0.2 MPa and even at high pressure of up to 70 MPa; which is the highest endurable stack pressure reported for SSLBs using garnet electrolytes. These key findings are expected to promote the wide-pressure-range applications of SSLBs.
研究领域:
材料科学
·
储能
·
电化学
·
固态电池
✓ 已验证
DOI
高影响因子
APPLIED CLAY SCIENCE
·
2024
·
IF 5.3
Fengyuan Wang,Min Yang,Yuchun Yang,Yanling Tian
With the escalating market demand for lithium, the development and efficient utilization of lithium resources have become crucial. This study introduced a method for leaching lithium from raw clay-type lithium ores using a composite sulfuric acid oxalic acid system. The experimental results revealed that the optimal conditions for the leaching process included roasting temperature of 600 °C, sulfuric acid concentration of 0.8 mol/L, liquid-solid ratio of 5 mL/g, leaching temperature of 90 °C, leaching duration of 90 min, and oxalic acid dosage of 2 g. Under these conditions, the leaching efficiency of lithium reached 93.45 %. The structural changes during the lithium leaching process and leaching mechanism were analyzed by XRD, SEM, TOF-SIMS. It was found that the minerals after mixed-acid leaching showed a loose morphology, a decrease in the average particle size, and a significant increase in the specific surface area as well as the pore volume, leading to improved lithium leaching efficiency. Furthermore, the mechanism underlying the mixed-acid leaching of lithium from clay-type lithium ores was explored. According to this mechanism, sulfuric acid first dissociated H + , which disrupted the mineral structure, allowing further destruction by oxalic acid. During this process, Li + was continuously replaced by H + and reacted with C 2 O 4 2− dissociated from oxalic acid to form water-soluble Li 2 C 2 O 4 .
研究领域:
化学工程
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
HYDROMETALLURGY
·
2020
·
IF 3.338
Lei Xu,Chen Chen,Ming-Lai Fu
The eventual fading and scrapping of lithium (Li)-ion batteries will result in the formation of a huge urban mine of spent batteries. Hydrometallurgy and further extraction/separation are effective ways in which to recover the valuable metal ions from such batteries. Herein, extraction and recovery of spent lithium cobalt oxide (LiCoO 2 ) battery leach liquors using Cyphos IL-101 is proposed. Based on the optimization of extraction conditions, continuous circulating extraction, and thermodynamic analysis, Cyphos IL-101 effectively extracted cobalt (Co) ions with excellent stability and high extraction capacity (35.25 g/L). The separation factor of Co and Li (β Co/Li ) was 102.11 in 0.5 M HCl at 60 °C under the optimal operation condition. Moreover, an increase in temperature increased Co extraction in the spent Li-ion battery leach liquors. The extractants before and after use were characterized using ultraviolet-visible (UV–Vis) absorption spectra , Fourier transform infrared (FTIR) spectra, and nuclear magnetic resonance (NMR) spectra. The extraction mechanism of cobalt ions by Cyphos IL-101 was suggested as that cobalt transferred to the organic phase from the aqueous phase in the form of [CoCl 4 ] 2− . 90.5% of Co and 86.2% of Li were recovered by precipitation after extraction separation in the forms of cobalt oxalate and lithium carbonate with the purity 87.4% and 74.2%. This suggested method might provide a promising strategy for recycling spent lithium cobalt oxide batteries.
研究领域:
环境科学
·
冶金学
·
材料科学
✓ 已验证
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2024
·
IF 8.1
Ronghao Liu,Jun Li,Xiaoxia Liu,Xiaolu Yin,Yanzhao Yang
The escalating disposal of lithium-ion batteries (LIBs) poses significant environmental challenges but also offers substantial opportunities for resource recovery. In this work, we introduce a recycling strategy using a green, cost-effective ternary deep eutectic solvent (DES) composed of guanidine hydrochloride, ethylene glycol, and maleic acid. The DES can achieve >99.5 % leach efficiency of lithium (Li) and cobalt (Co) at 100 °C, 9h, and L/S=50. The kinetic study found that the chemical reaction rate at the interface was the key to controlling the leaching process. The study of leaching mechanisms found that the acidity and coordination ability of DES were the main driving forces of leaching. Co loaded in the DES phase can almost precipitate out by using oxalic acid, achieving the separation of Li and Co. After reusing three times, the maximum load of Li in the DES phase reached 4.1 mg/g. These outstanding performances, along with the avoidance of the use of hazardous chemicals and the reduction of high costs, confirmed that the DES possesses a promising prospect for sustainable, large-scale application in efficiently leaching valuable metals from LiCoO 2 .
研究领域:
环境科学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
WASTE MANAGEMENT
·
2018
·
IF 4.723
Xiangping Chen,Chunxiu Guo,Hongrui Ma,Jiazhu Li,Tao Zhou,Ling Cao,Duozhi Kang
It is significant to recover metal values from spent lithium ion batteries (LIBs) for the alleviation or prevention of potential risks towards environmental pollution and public health, as well as for the conservation of valuable metals. Herein a hydrometallurgical process was proposed to explore the possibility for the leaching of different metals from waste cathodic materials (LiCoO 2 ) of spent LIBs using organics as reductant in sulfuric acid medium. According to the leaching results, about 98% Co and 96% Li can be leached under the optimal experimental conditions of reaction temperature - 95 °C, reaction time - 120 min, reductive agent dosage - 0.4 g/g, slurry density - 25 g/L, concentration of sulfuric acid-3 mol/L in H 2 SO 4 + glucose leaching system. Similar results (96% Co and 100% Li) can be obtained in H 2 SO 4 + sucrose leaching system under optimized leaching conditions. Despite a complete leaching of Li (∼100%), only 54% Co can be dissolved in the H 2 SO 4 + cellulose leaching system under optimized leaching conditions. Finally, different characterization methods, including UV–Vis, FT-IR, SEM and XRD, were employed for the tentative exploration of reductive leaching reactions using organic as reductant in sulfuric acid medium. All the leaching and characterization results confirm that both glucose and sucrose are effective reductants during leaching, while cellulose should be further degraded to organics with low molecular weights to achieve a satisfactory leaching performance.
研究领域:
环境科学
·
冶金学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ACS Sustainable Chemistry & Engineering
·
2022
·
IF 9.224
Shujie Tang,Mei Zhang,Min Guo
A new type of deep-eutectic solvents (DESs), consisting of ethylene glycol (EG) and sulfosalicylic acid dihydrate (SAD), were designed for efficient leaching valuable metals from cathode active materials (LiCoO2 and Li14.8Ni1.7Co8.5MnO30.5) of spent lithium-ion batteries (LIBs) for the first time. The as-prepared DESs possessed strong coordination ability and low viscosity, which were suitable for metal extraction. The influences of experiment parameters on extraction of Co and Li were systematically investigated, and the leaching mechanism and kinetics were elucidated in detail. Under the optimal conditions, the leaching efficiencies of Co and Li from pure LiCoO2 reached 93.5% and 98.3%, while those of Co, Ni, Mn, and Li achieved 94.8%, 99.1%, 100%, and 100% from the spent Li14.8Ni1.7Co8.5MnO30.5, respectively. Results revealed that the Li+ ions located in the interlayer of layered LiCoO2 were replaced by H+ ions and entered into solution, while Co3+ ions in the skeleton structure were reduced and coordinated by EG and sulfosalicylic acid (SA) to form four soluble Co2+–SA complexes, realizing synergistic and efficient leaching of Li and Co from the LIB cathode active material. Moreover, Co and Li leaching kinetics conformed to the shrinking core model, in which the interfacial chemical reaction was the limiting step, and the apparent activation energies were separately about 77.38 and 79.54 kJ/mol.
研究领域:
材料科学
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF ELECTROANALYTICAL CHEMISTRY
·
2021
·
IF 4.464
Xianli Huang,Dongmei Zhuang,Zhihui Chen,Hao Gong,Tao Wang,Jianping He,Xiaogang Zhang
It is so far an efficient way for depressing dendrite growth to adjust the electrolyte composition . Therefore, we study the electrochemical behavior of lithium metal electrodeposited in a LiPF 6 -propylene carbonate (PC) electrolyte by adding two kinds of crown ether . The effect of crown ether concentration on the Coulombic efficiency of lithium electrodes has be evaluated, and the electrodeposition behavior of lithium metal on negative electrode has be analyzed by cyclic voltammetric curve, electrodeposition curve and lithium metal deposition morphology. The results show that a certain amount of crown ether (15-crown-5 and 12-crown-4) can preferentially coordinate with lithium ion in the electrolyte and form complex compounds, which reduce the lithium ions concentration in the “hot spot” and level the lithium electrode greatly by inhibiting the preferential growth of lithium dendrite . A uniform and dense nano-columnar lithium layer could be obtained at the current density of 2.0 mA cm −2 when the deposition amount is 1.0 mAh cm −2 , and the concentration of 15-crown-5 and 12-crown-4 ether are 0.3 M and 0.2 M, respectively. Gaussian calculation results show that the lithium-crown complex has a relatively lower lowest unoccupied molecular orbit (LUMO), where electrons could be injected during the charging process, leading to decreased Coulumbic efficiency.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）