ACS Omega
·
2021
·
IF 3.512
Yaqing Zhang,Hongyan Xie,Huixin Jin,Xiaohui Li,Qiang Zhang,Yezhu Li,KaiFeng Li,Fenglan Luo,Wenlei Li,Chenzhe Li
In this study, LiMn2–xTixO4 cathode materials were synthesized by a simple one-step hydrothermal method, and the effects of Ti doping on the sample structure and electrochemical properties were examined. The results indicated that Ti doping did not affect the spinel structure of LiMn2O4, and no other hybrid phases were produced. Furthermore, appropriate doping with Ti improved the particle uniformity of the samples. The electrochemical performance results showed that LiMn1.97Ti0.03O4 exhibited much better cycling performance than the undoped sample. The discharge capacity of LiMn1.97Ti0.03O4 reached 136 mAh g–1 at 25 °C at 0.2C, and the specific capacity reached 106.2 mAh g–1 after 300 cycles, with a capacity retention rate of 78.09%. Additionally, the specific capacity of LiMn1.97Ti0.03O4 was 102.3 mAh g–1 after 100 cycles at 55 °C, with a capacity retention rate of 75.44%. The Ti-doped samples thus exhibited an impressive high-rate performance. The discharge capacity of LiMn2O4 was only 31.3 mAh g–1 at 10C, while the discharge-specific capacity of LiMn1.97Ti0.03O4 reached 73.4 mAh g–1. Furthermore, to assess the higher Li+ diffusion coefficient and lower internal resistance of the Ti-doped samples, cyclic voltammetry and impedance spectra data were obtained. Our results showed that Ti doping enhanced the crystal structure of LiMn2O4 and improved Li+ diffusion, resulting in significant improvements in the cycling and rate performance of Ti-doped samples.
研究领域:
材料科学
·
电化学
·
储能
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DOI
高影响因子
CERAMICS INTERNATIONAL
·
2025
·
IF 5.6
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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DOI
高影响因子
JOURNAL OF POWER SOURCES
·
2025
·
IF 7.9
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
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电化学
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能源存储
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无机化学
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固态化学
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锂离子电池
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产品关联
DOI
高影响因子
DESALINATION
·
2024
·
IF 8.3
Guiying Tian,Jian Gao,Shuxiao Yan,Hui Wang,Ruilin Li,Jun Xiang,Wei Du,Lei Zhang,Na Tang
with the unprecedented demand for raw lithium, the spinel LiMn 2 O 4 has been widely studied for electrochemical Li-recovery from salt-lake brines, but its industrialization is hindered by the poor cyclability induced by manganese dissolution and Jahn-Teller distortion within octahedral structure. In this work, Cr-doped and carbon-coated LiMn 2 O 4 (C-LMO-Cr) electrodes prepared via coprecipitation-calcination method are employed to improve cycling stability and lithium selectivity for electrochemical Li-recovery. The results confirm the C-LMO-Cr electrode exhibits super-high retention rate of 98.76 % and 95.70 % of the initial capacity (27 mg·g −1 ) after 300 and 500 cycles, respectively. The carbon buffering on the C-LMO-Cr surface effectively impedes the initial manganese dissolution with the enhanced charge transfer. Moreover, the structural evolution from Raman/XPS analysis and theoretical calculations confirms that the shrinking lattice of the carbon-buffering LMO-Cr enhances Li + selectivity and Li + migration. When assembled in a hybrid capacitive deionization (HCDI) device, the optimal C-LMO-Cr electrode displays high adsorption capacity of ∼21 mg·g −1 , moderate energy consumption of 13 Wh·mol −1 (Li + ) with a remarkable increase in Mg/Li ratio from 1.67 to 158 in the original brine from Jiezechaka. Therefore, these results demonstrate a promising potential of C-LMO-Cr electrodes for long-acting electrochemical lithium-recovery from original brines.
研究领域:
材料科学
·
电化学
·
能源存储
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产品关联
DOI
高影响因子
ELECTROCHIMICA ACTA
·
2025
·
IF 5.6
Xiaoping Fan,Kui Liu,Chunfeng Sun,Jiasheng Wang,Hongqiang Wang,Youguo Huang,Qingyu Li,Fenghua Zheng,Peng Xi
Although hydrometallurgy is the primary method for recycling spent lithium-ion batteries (LIBs), handling the waste liquid produced during the leaching process remains a challenge due to the additional procedures and costs involved. This study presents an efficient, closed-loop recycling process for spent LiMn 2 O 4 (LMO) batteries. The waste LMO powders were initially leached with H 3 PO 4 and citric acid (CA) to obtain the leachate containing Li + , Mn 2+ , PO 4 3− and citrate ions. The metal ions leached into the solution are complexed by CA, achieving complete leaching of LMO. The H 3 PO 4 and CA provide both PO 4 3− and carbon sources for subsequent product preparation, minimizing resource waste and secondary pollution. The molar ratio of Li:Mn:Fe:PO 4 3− in the leachate was adjusted to 1:0.75:0.25:1, and LiMn 0.75 Fe 0.25 PO 4 (LMFP) with excellent performance was regenerated by spray drying and calcination. The regenerated LMFP-650 exhibited a capacity retention rate of 89.7% after 500 cycles, significantly improving the structural stability and cycling performance of LMO. This green, closed-loop recycling process prevents secondary pollution and promotes the sustainable development of the battery industry.
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DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
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2017
·
IF 3.133
Zhongdong Peng,Ying Li,Ke Du,Yanbin Cao,Guorong Hu
In order to improve the electrochemical performance of LiMn 2 O 4 at elevated temperatures, a series of Li 1.2 Ni 0.2 Mn 0.6 O 2 -modified LiMn 2 O 4 samples have been synthesized by a facile sol-gel method. The structure and morphology of pristine and modified LiMn 2 O 4 are investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. The Li 1.2 Ni 0.2 Mn 0.6 O 2 coating layer is identified by transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS), which plays an important role in reducing the dissolution of manganese, thereby improving the cycle performance and rate capability of the material. The 2 wt% Li 1.2 Ni 0.2 Mn 0.6 O 2 -modified LiMn 2 O 4 sample exhibits a higher capacity retention of 95.88% than that of the pristine one (81.2%) after 200 cycles at 1C and 25 °C. Furthermore, a capacity retention of 89.74% is obtained for the 2 wt%-modified LiMn 2 O 4 sample after 200 cycles at 1C and 55 °C, compared to 66.34% for the pristine one. Surface modification with a Li-rich Li 1.2 Ni 0.2 Mn 0.6 O 2 material is a good way to improve the elevated temperature performance of LiMn 2 O 4 .
研究领域:
材料科学
·
电化学
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DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2026
·
IF 3.9
Fangbing Li,Tuan Wang,Jinxuan Chen,Jie Hu,Haijun Xia,Enhao Xu,Hong Wu,Yun Zhang,Kaipeng Wu
The continuous accumulation of spent LiFePO4 (S-LFP) and LiMn2O4 (S-LMO) cathodes demands efficient and sustainable recycling strategies, as conventional hydrometallurgical processes rely heavily on external redox agents, increasing the cost and environmental burden. This study proposes an innovative synergistic leaching process that enables the upcycling of mixed spent LFP and LMO into high-voltage LiFexMn1–xPO4 (LFMP) without any additional redox agents. We established a multireaction feedback system centered on self-redox in a sulfuric acid medium through the design of multiple sets of experiments for verification, achieving highly efficient leaching of Li (99.5%), Mn (99.2%), and Fe (99.6%) under optimized conditions (H2SO4–metal molar ratio of 2, liquid–solid ratio of 5, temperature of 30 °C, and time of 120 min). The leachate was subsequently converted to an Fe–Mn–P composite precursor and then upcycled into LFMP. The regenerated LiFe0.4Mn0.6PO4 cathode delivers a remarkable energy density of 557.67 Wh kg–1 at 0.2 C, significantly surpassing that of commercial LFP and LMO. Electrochemical analysis confirmed that the diffusion capability of Li+ within the Mn reaction region is critical for the unlocking of energy density for LFMP electrodes. Economic and environmental assessments further confirmed the superior profitability (2.24 $ kg–1) and reduced greenhouse gas emissions of this synergistic upcycling route, demonstrating its potential as a sustainable and economically viable strategy for recycling multisource spent cathodes into new-generation high-energy-density materials.
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DOI
高影响因子
VACUUM
·
2026
·
IF 4.3
Wangqiong Xu,Baiyan Guo,Xianrong Li,Kun Xu,Zhe Li,Shimei Guo
Spinel LiMn 2 O 4 with excellent cycling performance and low cost has been regarded as the most promising cathode material for lithium-ion batteries. However, the manganese dissolution and electrolyte decomposition significantly compromise structural stability, thereby hindering large-scale practical implementation. Here, we propose a surface modification strategy to enhance the structural stability of the LiMn 2 O 4 cathode using Ag nanoparticles as coating materials, where the size of the Ag nanoparticles is controlled by adjusting the decomposition temperatures of AgNO 3 to 600, 700, 750, and 800 °C. Combining the detailed structural characterization and performance characterization, we find that surface coating with the largest-sized Ag nanoparticles with 10.02 nm contributes to stabilizing the interface between the cathode materials and electrolyte, reducing the decomposition of electrolyte, and improving ion diffusion kinetics. Consequently, the corresponding Ag/LiMn 2 O 4 heterostructure exhibits outstanding cycle performance, with an initial discharge capacity of 101.6 mAh g -1 and capacity retention of 84.45% after 1000 cycles at 5 C under 25 °C. Our work demonstrates an effective method to improve the structural stability of LiMn 2 O 4 .
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DOI
高影响因子
JOURNAL OF RARE EARTHS
·
2026
·
IF 9.6
Hebi Zhang,Wei Jia,Jianxun Bao,Min Wu,Yannan Zhang,Ziyi Zhu,Jianbei Qiu,Hao Wu,Yingjie Zhang
Spinel lithium manganate (LiMn 2 O 4 ) is a promising cathode material for lithium-ion batteries (LIBs) due to its non-toxicity, cost-effectiveness, and recyclability. However, its development is hindered by rapid capacity degradation and structural collapse caused by Jahn-Teller distortion and Mn-ions dissolution. In this work, a dual-functional LaNiO 3 coating on LiMn 2 O 4 particles was introduced to prevent direct contact with the F-containing electrolyte, meanwhile, apply compressive stress on the surface of LiMn 2 O 4 , suppressing surface MnO 6 octahedra distortion and preserving cubic symmetry during deep charge-discharge cycles. The strong La–O bonds can strengthen interface Mn–O bonds and increase the activation energy for Mn-ions disproportionation and acid erosion, thus reducing Mn-ions dissolution. Additionally, LaNiO 3 can serve as a conductive synapse to improve conductivity of LiMn 2 O 4 and optimize the Li + migration pathway at the electrode-electrolyte interface, reducing the migration potential barrier of Li + . Electrochemical tests show that the 1 wt% LaNiO 3 -coated LiMn 2 O 4 cathode achieves an initial discharge capacity of 130.37 mAh/g with a capacity retention of 92.27% after 600 cycles. This performance is significantly superior to that of the unmodified LiMn 2 O 4 , which only exhibits an initial capacity of 115.63 mAh/g and a retention of 79.55%. This work offers an effective strategy to enhance LiMn 2 O 4 stability and capacity and provides a theoretical basis for using perovskite materials in surface modification.
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DOI
高影响因子
IONICS
·
2022
·Vol. 29
·期 1
·43-50
·
IF 2.961
Zhang Bao,Zhang Yannan,Duan Jianguo,Li Xue,Zeng Xiaoyuan,Zhou Kai,Wang Zhengwu,Lian Zheng,Dong Peng,Zhang Yingjie
As one of the most potential positive materials for cobalt-free lithium ion batteries, the lithium manganate cathode materials are extremely attractive because of their low-cost and low toxicity compared to other cathode materials, but they still suffer from the serious capacity fading because of the transition metal dissolution (Mn). Herein, a layer of Gd 2 O 3 coating is coated on the surface of lithium manganate by a simple wet chemical method. The Gd 2 O 3 coating can reduce the side reactions as well as Mn dissolution by suppressing the direct contact between the electrolyte and the positive electrodes. Consequently, the modified spinel LiMn 2 O 4 @Gd 2 O 3 electrode has delivered significantly improved electrochemical performance. ICP measurements demonstrate that the amount of manganese dissolved in electrolyte is effectively decreased, which is approximately one-third of the pristine sample. Thus, the LiMn 2 O 4 @Gd 2 O 3 provides higher capacity retention at both low current density (1 C) and high current density (5 C). This work reveals that the Gd 2 O 3 coating is a straightforward but effective strategy of enhancing the structural stability and inhibition of Mn dissolution of spinel Mn-based positive electrodes.
研究领域:
材料科学
·
能源存储技术
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产品关联
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2023
·
IF 8.6
Ao Zhou,Zhihong Liu,Zhiyong Liu
With the imminent peak in the retirement of rechargeable lithium-ion batteries worldwide, the development of efficient methods for recycling valuable elements from LIBs has attracted considerable attention. In this work, a novel method of NH 4 HSO 4 reduction roasting-selective ammonia leaching was proposed to thoroughly separate Li and Mn from the spent LiMn 2 O 4 cathode materials . Using the TG-DSC-FTIR, XRD, SEM-EDS and ICP methods, the detailed mechanism of reduction roasting process was revealed, showing that the Mn 4+ and Mn 3+ in the spinel structure of LiMn 2 O 4 were reduced by the NH 4 + from the molten ammonium salt, and transformed into water-soluble MnSO 4 and Li 2 Mn 2 (SO 4 ) 3 . According to the water-leaching performance of the roasting products, the sulfation conversion rate of Mn reaches 98.1 %, while Li is almost completely transformed under the optimal roasting conditions (475 ℃, 60 min). Using the NH 3 ·H 2 O-air leaching-system, complete separation of Li and Mn can be achieved. It was shown that the introduction of air into the ammonia solution at a rate of 0.2 L/min under the optimal leaching condition leads to Mn precipitation in the form of nanoscale Mn 3 O 4 particles with a precipitation rate of over 99.99 %, while Li still remains completely leached. Based on the in situ detection of the oxidation reduction potential and pH during the selective leaching, the key mechanism of efficient Mn precipitation was revealed. that is, the increasing potential accelerates the oxidation of Mn(OH) 2 , and the rapid consumption of Mn(OH) 2 promotes the hydrolysis of Mn 2+ , thereby achieving a significant improvement in the separation efficiency of Li and Mn.
研究领域:
材料科学
·
环境工程
·
化学工程
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产品关联
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2026
·
IF 9.1
Zipeng Qiao,Guoxing Ren,Yiming Zhao,Biaofeng Gao,Dongfu Liu,Wenhua Xu,Sizhe Li,Jialiang Zhang,Songwen Xiao
To address high chemical reagent consumption and poor selective lithium extraction in recycling mixed cathode materials from spent LiMn 2 O 4 (LMO) and LiFePO 4 (LFP) batteries, this study proposes a synergistic hydrometallurgical process without external oxidants/reductants, inspired by the Li-ion intercalation/deintercalation mechanism in lithium-ion batteries (LIBs). The process achieves efficient and selective Li leaching via the coupled redox reaction between LMO and LFP in an acidic system. Single-factor experiments determined the optimal leaching conditions: 0.8 mol/L HCl, LMO: LFP mass ratio of 1.6:1, liquid-to-solid ratio of 12 mL/g, 90 °C, and 6 h. Under these conditions, Li leaching efficiency reached 99.19 ± 0.93%, while Fe and Mn leaching efficiencies were only 0.41 ± 1.25% and 25.07 ± 0.84%, respectively. Kinetic analysis shows Li leaching is controlled by solid product layer diffusion, with an apparent activation energy of 6.94 kJ/mol. Thermodynamic and characterization analyses confirm that in the acidic environment, LMO reduction and LFP oxidation occur simultaneously; Mn and Fe precipitate into the slag phase as MnO 2 , Mn 3 (PO 4 ) 2 , and FePO 4 , facilitating efficient Li release. Subsequent pH adjustment of the leachate enabled the preparation of Li 2 CO 3 and Mn 3 O 4 , as well as LMO regeneration. Life cycle assessment indicates this self-driven redox process for preferential Li recovery from mixed spent LIBs has advantages of low energy consumption, minimal reagent usage, high profitability, and significant environmental benefits. It provides an efficient solution for synergistic treatment and closed-loop recycling of mixed spent LIBs, aligning with green chemistry and circular economy principles.
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DOI
高影响因子
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