CHEMICAL ENGINEERING JOURNAL
·
2026
·
IF 12.5
Yirui Sun,Jinyi Xu,Feiyang Chen,Juan Yang,Xiaoxian Hu,Lijin Huang,Lite Yang
Medium-entropy doping strategy is introduced to stabilize spinel LMO for electrochemical lithium extraction. • Medium-entropy regulation effectively suppresses Jahn–Teller distortion and stabilizes the spinel framework. • Optimized Li + migration pathways significantly enhance Li + diffusion kinetics and intercalation reversibility. • The ME-LMO electrode delivers high Li + adsorption capacity with low energy consumption. • Superior Li + selectivity is achieved in both binary systems and simulated salt lake brines. Selective lithium extraction from salt lake brines is critical for sustainable lithium supply under the global energy transition. LiMn 2 O 4 (LMO) is a promising electrode material for lithium extraction via capacitive deionization (CDI), yet its practical application is crippled by Jahn–Teller distortion and subsequent Mn dissolution. Herein, a multicomponent-doped LMO (ME-LMO, LiMn 1.98 Mg 0.005 Al 0.005 Co 0.005 Ni 0.005 O 4 ) was synthesized via a one-step solid-state sintering method using a medium-entropy configuration strategy to regulate lattice stability and Li + migration behavior. The synergistic interplay of multiple cations not only regulates local lattice strain and redistributes the Mn 3+ /Mn 4+ ratio to suppress the Jahn–Teller distortion and inhibit Mn leaching, but also induces lattice contraction and electronic modulation that collectively expedite Li + diffusion and enhance intercalation reversibility. Theoretical calculations further reveal that the multi-element doping configuration reconstructs the local Mn O electronic structure and provides more favorable thermodynamic conditions for Li + insertion. Benefiting from these synergistic effects, ME-LMO achieves a high Li + adsorption capacity of 24.23 mg g −1 , low energy consumption of 2.07 Wh mol −1 , and outstanding cycling stability with 86.6% retention after 100 cycles. More importantly, it exhibits extraordinary Li + selectivity, with separation factors of 78.98 (Li + /Na + ) and 91.19 (Li + /Mg 2+ ) in binary systems, and remarkably 994.28 (Li + /Na + ) and 289.62 (Li + /Mg 2+ ) in simulated brines. This work demonstrates the potential of a medium-entropy configuration strategy for stabilizing spinel frameworks and improving the performance of LMO-based electrodes for energy-efficient lithium extraction from complex brines. Download: Download high-res image (226KB) Download: Download full-size image
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高影响因子
COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS
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2022
·
IF 5.518
Ying Ji,Honglei Liu,Yujiao Guo,Junming Guo,Mingwu Xiang,Wei Bai,Xiaofang Liu,Hongli Bai
At high current density, low capacity and rapid capacity decay of spinel LiMn 2 O 4 cathode material during the cycle limit its application. Herein, element doping approach to restrain Jahn-teller effect combined with crystal plane regulation to mitigate Mn dissolution is employed to synthesize a series of truncated octahedron LiNi 0.02 Fe x Mn 1.98−x O 4 (x ≤ 0.12) which provide high exposure {111} surfaces as well as a small portion of {110} and {100} facets for offering Li + ion rapid diffusion channel. Many characterizations such as XRD , SEM and TEM show that Ni-Fe co-doped can effectively promote the development of crystal and the preferential growth of crystals planes. Electrochemical test results imply that at 1 C the difference between capacity and capacity retention ratio in terms of LiNi 0.02 Mn 1.98 O 4 (LNMO) and Ni-Fe co-doping samples are not obvious. With the increasing of current densities, Ni-Fe co-doping samples exceptional rate capability and cycle stability become apparent. The optimal LiNi 0.02 Fe 0.05 Mn 1.93 O 4 (LNFMO-5) and LNMO can keep 76.9% and 74.6% of their original capacity of 113.4 mAh·g ‐1 as well as 116.2 mAh·g ‐1 after 500 cycles at 1 C, respectively. At 10 C, the LNFMO-5 sample delivers the capacity of 89.3 mAh·g ‐1 and a higher capacity retention ratio of 72.9% after 2000 cycles, while the LNMO sample is only 63 mAh·g ‐1 and 67.2%. Even at 20 C, The LNFMO-5 sample still reaches a high specific capacity of 84.9 mAh·g ‐1 and a higher capacity retention ratio of 76.1% after 2000 cycles, which are much higher than the LNMO sample (63.0 mAh·g ‐1 ) and 57.4% capacity retention rate. CV and EIS analysis manifest that the LNFMO-5 has a higher D Li + and a lower E a than that of the LNMO. A unique Ni-Fe co-doped truncated octahedral LiMn 2 O 4 material with exceptional electrochemical property will be an attractive candidate for the preparation high-performance and long-cycle spinel LiMn 2 O 4 cathode materials.
研究领域:
材料科学
·
电化学
·
储能技术
·
锂离子电池
·
正极材料
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DOI
高影响因子
Materials
·
2019
·Vol. 12
·期 24
·4123
·
IF 2.972
Chaoqi Shen,Hui Xu,Liu Liu,Heshan Hu,Siyuan Chen,Liwei Su,Lianbang Wang
Nano-sized spinel LiMn2O4/carbon nanotubes (LMO/CNTs) composite is facilely synthesized via a one-step dynamic hydrothermal approach. The characterizations and electrochemical measurements reveal that LiMn2O4particles with narrow size distribution are well dispersed with CNTs in the composite. The LMO/CNTs nanocomposite with 5 wt % CNTs displays a high specific discharge capacity of 114 mAh g−1at 1C rate, and the retention rate after 180 cycles at room temperature reaches 94.5% in the potential window of 3.3 to 4.3 V vs. Li/Li+. Furthermore, the electrochemical performance of the composite with 5 wt % CNTs at elevated temperature (55 °C) is also impressive, 90% discharging capacity could be maintained after 100 cycles at 1C. Such excellent electrochemical performance of the final product is attributed to the content of CNTs added in the hydrothermal process and small particle size inherited from pretreated MnO2precursor.Keywords:spinel lithium manganese oxide;carbon nanotubes;dynamic hydrothermal;nanocomposite
研究领域:
材料科学
·
电化学
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DOI
PubMed
高影响因子
JOM
·
2022
·Vol. 74
·期 12
·4672-4681
·
IF 2.597
Zhang Bao,Zhang Yingjie,Zhang Qi,Gao Yifeng,Zhu Bowen,Gong Rui,Wang Zhengwu,Bu JiaoJiao,Lian Zheng,Zhou Kai,Dong Peng,Zhang Yannan
Lithium ion spinel lithium manganate (LiMn 2 O 4 ) is a promising positive material due to its typical three-dimensional network as well as abundant manganese sources. However, the electrodes suffer from severe capacity degradation on account of the Jahn–Teller effect and spontaneous disproportionation reactions. In this work, we have fabricated Sm 3+ , Mo 6+ dual-doped LiMn 2 O 4 -positive materials using a facile solid phase strategy. Electrochemical test results show that the discharge capacity and capacity retention of the LMO-Sm&Mo material reaches 101.30 mAh g −1 and 88.08% after 200 cycles (85.69 mAh g −1 and 76.32% for LMO) at 1 C, which results from the synergistic enhancement of the double-cation (Sm 3+ , Mo 6+ ) doping strategy. Even at 10 C, LMO-Sm&Mo still exhibits a promising specific discharge capacity of 98.71 mAh g −1 . Moreover, ICP analysis indicates that the manganese dissolution of LMO-Sm&Mo in organic electrolyte is much lower than that of the undoped sample (LMO). Overall, the results indicate that the Sm 3+ , Mo 6+ co-doping is an effective strategy for enhancing the structural stability and electrochemical properties of spinel Mn-based positive electrodes.
研究领域:
材料科学
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电化学
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DOI
高影响因子
DESALINATION
·
2026
·
IF 9.9
Yu Qing,Yang Bao,Yuhao Pan
Cr/F co-doped LiMn 2 O 4 was compared with undoped, Cr-only and F-only spinel controls. • Co-doping raised 1C capacity to 124.6 mAh g −1 and HCDI Li + uptake to 35.07 mg g −1 . • The co-doped electrode kept 83% of its Li + uptake over 100 cycles with 1.4% Mn loss. • A reference-cell test traced most capacity fade to the carbon counter electrode. • Li + /Mg 2+ separation factor of 24.0 in untreated old brine with acid-free desorption. Spinel LiMn 2 O 4 (LMO) is a Li + -selective intercalation host for hybrid capacitive deionization (HCDI), but Jahn–Teller distortion and Mn dissolution limit its durability in Mg-rich brines. Here, Cr 3+ and F − were introduced at the nominal cationic and anionic sites of LMO to obtain LiCr 0.05 Mn 1.95 O 3.95 F 0.05 (CFLMO), and undoped, Cr-only (CrLMO) and F-only (FLMO) controls were prepared by the same route. XRD and FTIR showed that the average spinel framework was retained, and Cr 2p and F 1s XPS detected both added elements near the CFLMO surface. At 1C, CFLMO delivered a discharge capacity of 124.6 mAh g −1 (84% of the theoretical value), compared with 92.1 mAh g −1 for LMO. In HCDI tests with 32.74 mg L −1 Li + , CFLMO reached a salt adsorption capacity (SAC) of 35.07 mg g −1 at a charge efficiency of 0.89. After 100 adsorption–desorption cycles against an activated‑carbon (AC) counter electrode, CFLMO retained 83% of its initial SAC with a Mn dissolution ratio of 1.4%; replacing the AC electrode in an LMO||AC reference cell restored part of the lost adsorption response, identifying a counter-electrode contribution to cell-level capacity loss. In untreated Yiliping salt-lake old brine (Mg 2+ /Li + mass ratio 36.1), three CFLMO electrodes recovered 37.5 ± 1.5 mg g −1 Li + with a Li + /Mg 2+ separation factor of 24.0 ± 2.7, and desorption into pure water lowered the Mg 2+ /Li + mass ratio to 1.52 ± 0.18. The matched-control and real-brine results support Cr/F-modified LMO as a candidate for selective lithium recovery from Mg-rich salt-lake brines.
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高影响因子
JOURNAL OF POWER SOURCES
·
2025
·
IF 7.9
Yukun Pan,Yuhu Li,Lei Hu,Yudong Yang,Jiacheng Guo,Sijie Yang
To address the rapid capacity degradation of spinel LiMn 2 O 4 caused by Mn dissolution and Jahn-Teller distortion, this work develops a surface-engineered LiMn 2 O 4 material (LMO@NCM) through a urea-assisted homogeneous precipitation and gradient sintering strategy. The resultant gradient Ni-Co co-doped LiNi x Co y Mn 2-x-y O 4 coating synergistically combines bulk-phase doping and surface modification benefits. Systematic investigations reveal that LMO@NCM1 % delivers enhanced cycling stability with an initial discharge capacity of 119.74 mA h g −1 and 92.25 % capacity retention after 200 cycles at 1C (148 mA h g −1 ) under 25 °C, significantly outperforming pristine LMO (116.48 mA h g −1 , 84.47 % retention).Characterization results revealed that the Ni-Co gradient co-doping improved the electrode's interfacial kinetics, suppressed manganese dissolution, and mitigated side reactions between the electrolyte and the electrode, thereby significantly enhancing the battery's rate capability and cycling stability.
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高影响因子
Journal of Energy Storage
·
2024
·
IF 8.9
Wangqiong Xu,Xianrong Li,Baiyan Guo,Beituo Liu,Ruiming Yang,Shimei Guo,Zhe Li,Ruijuan Qi,Rong Huang
Critical barriers to the extensive applications of the spinel LiMn 2 O 4 cathodes include grievous capacity degradation and structural collapse. Bulk elemental doping combining surface modification, which is a common approach to address these challenges. Here, synchronous bulk Mo-doped and in-situ surface reconstructed layer coated LiMo 0.02 Mn 1.98 O 4 cathodes are prepared by tuning the annealing temperatures. Using the spherical aberration-corrected scanning transmission microscopy (Cs-STEM) technique, we demonstrate that part of Mo 6+ ions dopes into the octahedral Mn 16d sites to form LiMo 0.02 Mn 1.98 O 4 that strengthens bulk structural stability. The other part of Mo 6+ ions or the Mn atom occupying the Mn 16c sites of the spinel to form a surface reconstructed layer on the outermost surface that suppresses the side reaction and slows down the decomposition of the electrolyte. Specifically, the LiMo 0.02 Mn 1.98 O 4 cathode calcined at 750 °C with an appropriate surface reconstructed layer exhibits an outstanding capacity retention of 76.28 % after 1000 cycles at 10C at 25 °C. Our work provides a simple and novel way toward high electrochemical performance tuning for spinel LiMn 2 O 4 cathodes.
研究领域:
材料科学
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电化学
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高影响因子
Journal of Materials Chemistry A
·
2022
·Vol. 10
·期 38
·20545-20551
·
IF 14.511
Canfu Zhang,Binbin Chen,Ziyang Cai,Fenglin Zhang,Renzhi Huang,Mengdie Yan,Yingchun Liu,Huilin Pan
The state-of-the-art water-in-salt electrolytes exhibit a wider electrochemical window than conventional dilute aqueous electrolytes. However, the extended electrochemical stability window via increasing the salt concentration has reached a bottleneck. An alternative approach is to effectively suppress H2O activity using multi-functional components. Here, we design an isolated water-in-salt solvation structure in aqueous electrolytes with the “hydrotropic” ionic liquid 1-methyl-1-propylpiperidinium bis(fluorosulfonyl)imide (PP13FSI). The addition of PP13FSI suppresses H2O clusters via the hydrophobic PP13+ cations and lithium-philic FSI− anions, showing a greatly extended electrochemical stability window up to 4.9 V. A robust alkaline-based organic–inorganic hybrid solid electrolyte interface is achieved on a low-voltage Li4Ti5O12 anode, which further extends kinetics stability of aqueous electrolytes. Aqueous Li4Ti5O12‖LiMn2O4 full cells demonstrate stable cycling over 1000 cycles at 2C rate and a capacity retention of 70% with an average coulombic efficiency of 99.7%. This work provides new avenues to explore effective approaches for the development of next-generation highly stable aqueous lithium-ion batteries.
研究领域:
电化学
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材料科学
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能源存储
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DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2026
·
IF 9.1
Jiaru Wei,Beichen Sun,Wenbiao Ma,Fengfeng Gao,Xiaowei An,Xiao Du,Xiaogang Hao
Spinel LiMn 2 O 4 is a promising electrode for electrochemically switched ion exchange (ESIX) lithium extraction, but its sluggish solid-phase diffusion and severe Mn dissolution limit its application in high-Mg 2+ /Li + salt lake brines. Herein, we report a clear size effect that regulates Li + intercalation kinetics and Mg 2+ /Li + separation by comparing hydrothermally synthesized nano-sized N-LiMn 2 O 4 (20–100 nm) and commercial micron-sized LiMn 2 O 4 (∼10 μm). Nanosizing induces preferential exposure of thermodynamically stable (111) facets, effectively suppressing surface reconstruction and Mn dissolution. In-situ distribution of relaxation time (DRT) reveals that the rate-limiting step changes from pure solid-phase diffusion in micron LiMn 2 O 4 to surface-diffusion co-control in N-LiMn 2 O 4 , reducing solid-phase diffusion resistance by 75% and charge-transfer resistance by 78.6%. Benefiting from kinetic optimization, the N-LiMn 2 O 4 /C/PVDF electrode maintains a Li + /Mg 2+ separation factor > 100 even at an ultrahigh Mg 2+ /Li + ratio of 500, far exceeding the micron counterpart. After optimization (wet film thickness = 200 μm, adsorption potential = 1.0 V), the electrode retains >90% capacity after 10 cycles in 200 mg·L −1 LiCl solution. This work clarifies the size-dependent kinetic transition mechanism and provides a rational design strategy for high-selectivity electrodes toward efficient lithium extraction from high-Mg/Li brines.
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DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2023
·
IF 8.6
Zheng Zhang,Jinfeng Zhang,Zhihua Zhang,Xiao Du,Xiaogang Hao,Xiaowei An,Guoqing Guan,Jun Li,Zhong Liu
A novel physically blended polyvinylidene fluoride (PVDF) and polyacrylic acid (PAA) composite binder enhanced LiMn 2 O 4 /C (carbon black) film based electrode was successfully fabricated, and applied in an electrochemically switched ion exchange (ESIX) process for selective extraction of Li + from high Mg/Li ratio brine. The multifunctional composite binder system enabled the obtained LiMn 2 O 4 /C/PVDF- b -PAA film coated electrode to exhibit superior mechanical, hydrophilic and electrochemical properties compared with the LiMn 2 O 4 /C/PVDF film coated electrode. Based on the density functional theory (DFT) calculations, the ion exchange interaction between H + of –COOH groups in PAA and Li + facilitated the transport of Li + at the electrode interface, which enhanced lithium extraction performance of the film coated electrode. For treating the simulated brine (Mg/Li: ∼500), the intercalation capacity of Li + was about 15.1 mg g −1 , and the total extraction efficiency of lithium reached up to 62.8% after two electrochemical intercalation tests. Moreover, the film coated electrode displayed excellent selectivity towards Li + ions even in pre-treated actual brine (Mg/Li: ∼292.2). The Mg/Li mass ratio in the recovery solution could decrease to 0.46, and the calculated Li + /Mg 2+ separation coefficient reached as high as 631.08. In particular, the highly stable and scalable electroactive film could be prepared effectively, thus increasing its applicability. It is expected that such a LiMn 2 O 4 /C/PVDF- b -PAA film coated electrode could be a promising candidate for the selective extraction of Li + from high Mg/Li mass ratio brines.
研究领域:
材料科学
·
电化学工程
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DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2020
·
IF 7.632
Xiaoyu Zhao,Yaoxin Jiao,Peijie Xue,Minghui Feng,Yanfei Wang,Zuoliang Sha
Electrochemical extraction of lithium from solution is an urgently needed process because of the abundant reserves of lithium in seawater/brine and many disadvantages of the present technologies including high energy consumption, low separation efficiency, and being harmful to the environment. Competitive electrode materials used in electrochemical extraction require high cyclic stability in corrosive ion-rich seawater/brine. In this work, a three-dimensional (3D) nanostructured hybrid inorganic-gel framework electrode of polypyrrole/Al2O3 was introduced on the surface of LiMn2O4 for the first time. It was paired with activated carbon to construct an asymmetric lithium capacitor with advantages of cost effectiveness, good cycle stability in brine, high selectivity, and capacity. Furthermore, a flow control system was induced to make lithium extraction a continuous operation, which will be favored by the industry. The Li+ extraction energy consumption was 1.41 W h·mol–1 Li+ with a capacity of 1.85 mmol·g–1 in simulated brine. The capacity retention after 30 cycles was 91.66% at the 1 C rate. These promising results indicate that the PPy/Al2O3-modified LMO possesses high extraction efficiency and long-term stability in complex brine medium.
研究领域:
材料科学
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电化学
·
环境工程
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DOI
高影响因子
JOURNAL OF NANOBIOTECHNOLOGY
·
2024
·Vol. 22
·期 1
·1-20
·
IF 10.6
Hu Chuan,Huang Ruipeng,Xia Jiechao,Hu Xianjing,Xie Dingqi,jin Yang,Qi Weiming,Zhao Chengliang,Hu Zhijun
Background The incidence of osteochondral defects caused by trauma, arthritis or tumours is increasing annually, but progress has not been made in terms of treatment methods. Due to the heterogeneous structure and biological characteristics of cartilage and subchondral bone, the integration of osteochondral repair is still a challenge.Results In the present study, a novel bilayer hydrogel scaffold was designed based on anatomical characteristics to imitate superficial cartilage and subchondral bone. The scaffold showed favourable biocompatibility, and the addition of an antioxidant nanozyme (LiMn2O4) promoted reactive oxygen species (ROS) scavenging by upregulating antioxidant proteins. The cartilage layer effectively protects against chondrocyte degradation in the inflammatory microenvironment. Subchondral bionic hydrogel scaffolds promote osteogenic differentiation of rat bone marrow mesenchymal stem cells (BMSCs) by regulating the AMPK pathway in vitro. Finally, an in vivo rat preclinical osteochondral defect model confirmed that the bilayer hydrogel scaffold efficiently promoted cartilage and subchondral bone regeneration.Conclusion sIn general, our biomimetic hydrogel scaffold with the ability to regulate the inflammatory microenvironment can effectively repair osteochondral defects. This strategy provides a promising method for regenerating tissues with heterogeneous structures and biological characteristics.Graphical abstract
研究领域:
组织工程
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再生医学
·
生物材料
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骨科
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干细胞生物学
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生物医学工程
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产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）