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  • Weitong DU, Xi HUANG, Zhuo CHEN, Hui LI
    Mining and Metallurgical Engineering. 2024, 44(4): 47-53.

    An overview of progress in the research on anode materials of lithium-ion batteries based on vanadium-based compounds (including vanadium oxide, vanadate, vanadate phosphate and oxide-free vanadium-based compounds) is presented. Furthermore, based on the analysis of relationship among modification method and structure of material and electrochemical performance, it is proposed that vanadium-based anode materials for lithium-ion batteries shall become the trend in the future research.

  • Zhen LEI, Ge CHEN, Chuan XU, Jiale SUN, Liu YANG, Huan TIAN, Yang LIU
    Mining and Metallurgical Engineering. 2024, 44(4): 81-83.

    Lithium sulfide was prepared by solid phase syntheses, with lithium metal as the lithium source, sulfur powder as the sulfur source, and lithium nitride as the additive. Thermodynamic analysis results show that lithium nitride can promote the reaction of lithium metal with sulfur powder to synthesize lithium sulfide; Li3N firstly reacts with sulfur powder to release N2, leading to holes formed on the molten lithium metal sheet and the contact area between lithium metal and sulfur powder further expanded. Thus a loose and porous skeleton structure is formed, which is conducive to subsequent crushing and can reduce the risk of secondary reactions in the following ball milling process. With Li∶S∶Li3N=2∶2∶0.4 (molar ratio), crude lithium sulfide can be obtained after 8 hours reaction at 100 ℃. It is then subjected to calcination, impurity removal and ball milling processes, and a kind of lithium sulfide products with purity greater than 99.95% and particle size less than 15 μm can be obtained, which can be used in EV. This method provides a new idea for industrial production of lithium sulfide products.

  • Lin JI, Binfeng FAN, Qingfu WANG, Weitao LI
    Mining and Metallurgical Engineering. 2024, 44(4): 72-74.

    The influence of polyether additives on performance of ultra-thin Li-ion battery copper foil with thickness of 5 μm was studied by electrochemistry, scanning electron microscopy, and X-ray diffractometer. The results show that addition of polyether additives into electrolyte can promote negative shift of Cu deposition potential, and polyether additives with suitable concentration can lead to finer grains of copper foil, which is conducive to improving the surface flatness of copper foil. When the mass concentration of polyether additives is 2.3 mg/L, the obtained copper foil has tensile strength of 620.43 MPa, elongation of 3.67%, glossiness of 161 GU, and surface roughness of 1.02 μm, presenting excellent overall performance. The electrolytic copper foil with high tensile strength has a preferred orientation of (111) plane.

  • Panyang ZHANG, Qingfu WANG, Moucui LI, Binfeng FAN, Xujun WANG, Shumiao JIN
    Mining and Metallurgical Engineering. 2024, 44(4): 84-89.

    A single-factor experiment was conducted to explore the influence of rotation speed and lateral swing speed of polishing brush, and polishing current on the performance of copper foil and pinholes. Based on that, the polishing process was also optimized by applying response surface methodology, and thus the performance and apparent quality of copper foil was also improved. The results show that by using on-line polishing, with the rotation speed of the polishing brush at 450 r/min, the lateral swing speed of 350 r/min, and the polishing current of 0.50 A, the smooth surface (S surface) of the generated copper foil is uniform, and the pinhole defects are significantly reduced.

  • Si DI, Xihong HE
    Mining and Metallurgical Engineering. 2024, 44(4): 109-114.

    In order to recover metal elements from the cathode materials of spent Li-ion batteries in an environmentally friendly and efficient way, three deep eutectic solvents (DES) were synthesized with choline chloride as hydrogen bond acceptor, malonic acid, succinic acid and adipate respectively as hydrogen bond donors. Then, Co and Li in the cathode materials of spent Li-ion batteries were leached by adopting these three DESs respectively. The effects of leaching time, liquid-solid ratio and reaction temperature on the leaching rates of Co and Li were explored, and the leaching residues were also characterized in terms of morphology and phase. The leaching mechanism was analyzed by FT-IR spectrum and UV-Vis absorption spectrum. It is shown that the leaching efficiency of metal elements can be enhanced by prolonging leaching time, increasing liquid-solid ratio and temperature. It is found that under the optimal conditions, including leaching time of 300 minutes, liquid-solid ratio of 100 mL/g, and temperature of 110 ℃, malonic acid-based DES, among those three kinds of DESs, can bring better leaching effect, with leaching rates of Co and Li all exceeding 99%. During the leaching of lithium cobalt oxide with those three DESs, Co exists in the form of bivalent in the leaching solution, and the coordination compound is in a tetrahedral structure.

  • Xuezhen XIE, Hui CHEN, Youming YE, Yuru WEN, Haohao MA, Jun ZENG
    Mining and Metallurgical Engineering. 2024, 44(4): 31-35.

    With manganese sulfate as raw material and hexadecyl trimethyl ammonium bromide as modifier, trimanganese tetroxide was synthesized by complex-precipitation method, with which lithium manganate cathode material was then synthesized by high-temperature solid-state reaction. The effects of modifier amount on the morphology and particle size of trimanganese tetroxide and the specific discharge capacity of lithium manganate cathode material were all discussed. Results show that serious particle agglomeration can occur in the trimanganese tetroxide synthesized without modifier. With 3.0 g/L hexadecyl trimethyl ammonium bromide as the modifier, the synthesized trimanganese tetroxide has uniform particle size, and is dispersed without any agglomeration. Spinel lithium manganate was synthesized with the self-made modified trimanganese tetroxide, and then compared with the spinel lithium manganate synthesized with three kinds of trimanganese tetroxide available on the market. The results show that the lithium manganate synthesized with the self-made modified trimanganese tetroxide can present better electrochemical performance, delivering an initial discharge capacity of 120.43 mAh/g, with a retention rate of 96.79% after 50 cycles at 1C.

  • Hongliang WANG, Yanbin CHEN, Riquan YU, Mengxuan ZHOU, Shutian GU, Li XI
    Mining and Metallurgical Engineering. 2024, 44(4): 132-135.

    Ball milling was adopted to assist leaching of valuable metals from the cathode powder of spent batteries in citric acid and hydrogen peroxide system. It is found that ball milling can exert mechanical energy on the reaction solution, leading to changes in its structure and physical and chemical properties. As a result, chemical reactions can occur, which not only increases reaction rate, but also shortens leaching time. It is shown that after 30 min leaching at 60 ℃, with citric acid concentration of 0.8 mol/L, H2O2 at a mass fraction of 20%, liquid-solid ratio of 6∶1, and rotation speed of 60 r/min for a ball mill, the leaching rates of lithium, nickel, cobalt and manganese can reach 99.6%, 99.5%, 99.3% and 98.5% respectively. It is concluded that this processing technique, being characterized by low cost and high efficiency, can provide a certain reference for recycling of spent batteries.

  • Luntao DING, Peng ZHAO, Chunxian ZHOU, Dezhi WANG, Zhuangzhi WU, Xuebao LI, Youyuan ZHOU
    Mining and Metallurgical Engineering. 2024, 44(4): 24-30.

    LiMn0.6Fe0.4PO4/C (LMFP) composite synthesized by a combined process of co-precipitation and solid-phase sintering not only has low impurity content, uniform phase distribution, but also exhibits excellent electrochemical performance. It is shown that such process can inhibit the formation of Mn2P2O7 phase and improve the lithium ion diffusion rate of LMFP, while removing NH4+ and H2O. The Li-ion batteries assembled with LiMn0.6Fe0.4PO4/C exhibit excellent electrochemical performance, showing initial specific discharge capacity of 145.5 mAh/g at 1C and 111.9 mAh/g at 5C. It is concluded that this process, being simple and cost-effective, is suitable for industrial production. Such study provides a feasible scheme in designing cathode materials for commercialized high-performance Li-ion batteries.

  • Bowen TAO, Bowei JU, Feiyue TU
    Mining and Metallurgical Engineering. 2024, 44(4): 75-80.

    An argyrodite-type sulfide solid electrolyte Li6PS5Cl (LPSC) was solid-phase synthesized by adopting high energy ball milling in combination with heat treatment. It is found that prolonging ball milling time is conducive to crushing, mixing, grain refinement and amorphization reaction process of raw material powder; increasing sintering temperature is beneficial to the formation of a single pure phase, but too high temperature for sintering can make electrolyte melted and decomposed, leading to destroyed crystal structure. It is found that after 10 hours of ball milling and 8 hours of sintering at 550 ℃, the synthesized sulfide solid electrolyte exhibits higher ionic conductivity, reaching 3.57×10-3S/cm.

  • Ying WANG, Zhijun HE, Yan CHEN, Xiaoying YU, Huimin LI, Jing ZHANG, Xiangyi YIN
    Mining and Metallurgical Engineering. 2024, 44(4): 212-216.

    The basic flow of Midrex and HYL/Energiron technologies for direct reduction in a shaft furnace and the direct reduced iron output by each processing technique in recent years are firstly introduced, and then the equipment, raw materials and process characteristics of those two technologies are analyzed based on comparison. Based on the expounding of technical R&D and investment of global steel companies in these two technologies, it is pointed out that the development of hydrogen-based direct reduction process in a shaft furnace is closely related to grade of pellet ore, heat adsorption during hydrogen-based reduction reaction process, technologies for large-scale green hydrogen production and production cost among others. It is important for sustainable development of Chinese iron and steel industry to adopt hydrogen-based direct reduction in a shaft furnace that conforms to the national conditions.