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DESALINATION · 2024 · IF 8.3

MXene-bridged HMO/PSF adsorptive membrane for selective lithium recovery from shale gas wastewater with suppressed Mn leaching

Yuchun Ren,Dandan Zhao,Fei Zhou,Yuan Liu,Chen Fu,Yongsheng Fu,Tao Gong,Zhenglian Wu,Xinyu Yang,Zefeng Cai

Lithium recovery from shale gas wastewater (SGW) is essential for the growth of a sustainable economy. However, traditional powder adsorbents suffer significant loss and poor recyclability, limiting their practical utility. Here, we fabricate an HMO/MXene/PSF adsorptive membrane, in which 2D MXene serves as the hydrogen bond interacting agent between H 1.33 Mn 1.67 O 4 (HMO) and polysulfone (PSF). Notably, MXene incorporation effectively mitigates Mn leaching due to the hydrogen bond interaction. Efficient lithium recovery from Sichuan Basin SGW is achieved, with a lithium adsorption capacity of 21.18 mg/g. After ten consecutive cycles of adsorption and desorption, the HMO/MXene/PSF membrane shows remarkable cyclic stability, with a negligible decrease in lithium adsorption capacity of merely 0.16 %. Filtration studies reveal that the membrane with a surface area of 12.56 cm 2 can effectively filter 160 mL of SGW. The stability of the membrane due to hydrogen bond interactions and the selective adsorption mechanism are further confirmed through DFT calculations. This work presents a novel concept for constructing a mixed matrix membrane for lithium extraction from SGW and is expected to inspire further efforts in developing LIS-based adsorbents for lithium recovery.

研究领域: 材料科学 · 环境工程
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CERAMICS INTERNATIONAL · 2025 · IF 5.6

Zn2⁺ doping regulates the surface morphology and Mn dissolution of spinel LiMn2O4 significantly enhancing its electrochemical performance

Zhengqing Pei,Jiawei Wang,Haifeng Wang,Kexin Zheng,Qian Wang,Xinjie Zhou,Dehua Ma,Ju Lu,Haijiao Xie

The spinel-structured LiMn 2 O 4 cathode material exhibits low specific capacity and rapid capacity decay under high current densities , significantly limiting its commercial application prospects. This study uses a coprecipitation and calcination method to dope Zn into LiMn 2 O 4 , discovering that doping Zn elements causes LiMn 2 O 4 to preferentially grow along the (110) and (100) crystal planes. The (110) and (100) crystal planes provide more Li ion channels, contributing to the improvement of rate performance. In the custom-designed LiZn 0.04 Mn 1.96 O₄ (LZMO-0.04) cathode, the strategic addition of Zn occupying Mn sites makes electrons more delocalized, increasing the free electron gas and enhancing the material’s conductivity. The LZMO-0.04 sample exhibits a rich variety of polymorphic morphologies, a lower Mn³⁺ content, and a higher Li⁺ diffusion coefficient . These optimization effects, resulting from the synergistic action of multiple factors, enabled the LZMO-0.04 sample to achieve an initial discharge capacity of 127.73 mAh/g with a capacity retention rate of 83.06 % after 300 cycles at a rate of 0.5C. Even with an increase to a high rate of 5 C over 1200 cycles, the capacity retention rate remained stable at 81.89 %, exhibiting excellent high-rate cycle stability.

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CHEMICAL ENGINEERING JOURNAL · 2024 · IF 13.3

Overcoming polarization and dissolution of manganese-based electrodes to enhance stability in electrochemical lithium extraction

Yingjun Qiao,Yonggan Ran,Zhiqiang Qian,Bing Zhao,Chengpeng Li,Zhong Liu

The Mn dissolution issue in manganese-based materials (LMO) represents one of the most challenging barriers to further commercial development of electrochemical lithium extraction, which is an efficient and clean way of extracting Li from liquid resources. Here, by leveraging the advantages of composite materials, a novel combination of reduced graphene oxide (rGO) and sulfonated ionic polymers (Nafion) is introduced to relieve the issues of electrode polarization and manganese dissolution, critical factors limiting the durability of LMO electrodes. By modifying with rGO to enhance electronic conductivity and surface characteristics, and capturing dissolved Mn 2+ through Nafion, the modified electrode showed significant improvement in cycling stability and lithium adsorption capacity. Experimental results confirm that this synergistic approach effectively mitigates polarization effects and controls disproportionation reactions, thereby enhancing the stability of the lithium extraction process, revealing a notable increase in electrode capacity retention from 79.04 % to 94.64 % after 30 cycles. Additionally, through DFT calculations and XPS analysis, the effectiveness of the manganese capture strategy is validated. This work presents an effective new strategy to extend the lifespan of manganese-based electrodes and enhance their adsorption performance.

研究领域: 电化学 · 材料科学 · 能源化学 · 环境工程 · 无机化学
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CHEMICAL ENGINEERING JOURNAL · 2025 · IF 13.2

In situ polyamide nanofiltration coatings for enhanced lithium extraction from high Mg/Li brines

Qiyue Fan,Jie Lin,Yue Sun,Xiangting Hu,Hang Yu,Zhenda Lu

Lithium manganese oxide (LMO) ion sieves are promising for lithium extraction due to their high adsorption capacity. However, their practical application is often limited by structural degradation from manganese leakage, reduced lithium uptake, and poor Li + /Mg 2+ selectivity, especially in brines with high Mg/Li ratios. To overcome these challenges, we in-situ synthesized polyamide (PA) nanofiltration membranes on the surface of LMO using two distinct amine monomers, polyethyleneimine (PEI) and piperazine (PIP), to create novel composite adsorbents LMO@PA(PEI) and LMO@PA(PIP). Both the coated materials demonstrated improved lithium uptake capacity and cyclic stability in adsorption-desorption cycles in simulated brine. More importantly, under a challenging Li/Mg ratio of 1:50 in binary ion solutions, the separation factors (α) of HMO@PA(PEI) and HMO@PA(PIP) were 2.23 and 4.55 times higher than that of uncoated HMO, showcasing excellent Li + /Mg 2+ selectivity. These findings highlight that polyamide nanofiltration layers successfully endow LMO with enhanced capacity, selectivity, and long-term stability, presenting a promising and scalable approach for direct lithium extraction from high‑magnesium salt lakes.

CAS / MDL: 1336-21-6
研究领域: 材料科学 · 分离技术 · 能源材料 · 环境工程 · 无机化学
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ADVANCED FUNCTIONAL MATERIALS · 2025 · IF 19

In situ Composite of Cationic Porous Organic Polymers and ɛ-MnO2 as Cathode Materials for Aqueous Zinc Ion Batterys

Shuaizhou Chen,Xuewu Gao,Renyao Huang,Sha Fang,Xingzheng Peng,Mengke Li,Yi Feng,Xiongwei Qu,Xiaojie Zhang

Manganese-based oxides are promising cathode materials for aqueous zinc ion batteries (AZIBs) due to their high energy density and low cost. However, the cycling stability is severely limited by the sluggish reaction kinetics as well as the manganese dissolution. In this work, two pyridinium ionic porous organic polymers (iPOPs) composite ɛ-MnO 2 cathode materials, CN-POP@MnO 2 and PN-POP@MnO 2 , are prepared by an in situ composite method. The stable skeleton of iPOPs effectively prevents the structural collapse of the cathode. Its ionic sites and rigid network framework work together to disrupt the coordination environment of hydrated zinc ions, accelerating reaction kinetics and reducing cathode polarization. Therefore, the resultant batteries based on CN-POP@MnO 2 and PN-POP@MnO 2 cathodes exhibit excellent electrochemical performance. Especially for PN-POP-based batteries, the specific capacity is maintained at ≈96 mAh g −1 after 1500 cycles at 1 C, and the capacity attenuation rate is 0.017% per cycle.

研究领域: 材料科学 · 电化学 · 储能
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JOURNAL OF POWER SOURCES · 2025 · IF 7.9

Si-Al co-doping synergistically enhances the high-rate capacity and long-cycle life of spinel LiMn2O4

Jiao Ma,Qin Zhu,Zhihui Qian,Wei Bai,Rui Liu,Long Shi,Yongsheng Yang,Yujiao Guo,Mingwu Xiang,Junming Guo

The drawbacks of Jahn-Teller (J-T) effect, capacity decay at high temperature and the dissolution of Mn generated at elevated current density limit the large-scale application of LiMn 2 O 4 batteries . Herein, a Si 4+ /Al 3+ co-doping strategy of LiMn 2 O 4 is carefully developed to stabilize the [MnO 6 ] framework, thereby inhibiting the J-T distortion and ultimately alleviating Mn dissolution. The incorporation of Si 4+ and Al 3+ in LiMn 2 O 4 promotes the formation of a single-crystal truncated octahedral structure, with preferential grain growth along the {111}, {100} and {110} crystal plane, which decreases Mn dissolution and enhances the Li + transfer pathways. Furthermore, the integration of Si 4+ /Al 3+ co-doping producing smaller particles can shorten the migration paths of electrons and ions. Consequently, the optimized LiSi 0.05 Al 0.09 Mn 1.86 O 4 displays a decent initial discharge specific capacity of 103.2 mAh·g −1 and an excellent capacity storage percentage of 79.7 % after 1000 cycles at 10 C. Meanwhile, the optimal sample also exhibits respectable first discharge capacities of 91.9 mAh·g −1 and 61.8 mAh·g −1 at ultra-high rates of 20 C and 40 C, along with superior capacity storage ratios of 70.9 % and 70.7 % after 1000 cycles. More importantly, the optimized sample shows remarkable first discharge specific capacity of 107.1 mAh·g −1 at 55 °C and 10 C and exciting capacity storage rate of 61.9 % after 500 cycles. This study serves as a guide for advancing high-performance, high-stability LiMn 2 O 4 cathode materials for use in lithium-ion batteries.

研究领域: 材料科学 · 电化学 · 能源存储 · 无机化学 · 固态化学 · 锂离子电池
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