Nature Communications
·
2024
·Vol. 15
·期 1
·1-11
·
IF 14.7
Huang Jiangfeng,Xue Liang,Huang Yin,Jiang Yanchen,Wu Ping,Fan Xiulin,Zhu Junwu
LiMn 2 O 4 (LMO) is an attractive positive electrode material for aqueous lithium-ion batteries (ALIBs), but its inferior cycle performance limits the practical application. The degradation mechanism of LMO in ALIBs is still unclear, resulting in inability to predictably improve its structural stability. The electrode/electrolyte interface is believed to play an important role in electrode degradation. However, the interactions of the water-containing electrode/electrolyte interface of LMO are underexplored. In this work, we demonstrate the insertion of H 3 O + into LMO during cycling in aqueous electrolyte and elucidate the paradoxical effects of H 3 O + . The crystal H 3 O + enhances the structural stability of LMO by forming a gradient Mn 4+ -rich protective shell, but an excess amount of crystal H 3 O + leads to poor Li + conductivity, resulting in rapid capacity fading. Combining electrochemical analyses, structural characterizations, and first-principles calculations, we reveal the intercalation of H 3 O + into LMO and its associated mechanism on the structural evolution of LMO. Furthermore, we regulate the crystal H 3 O + content in LMO by modifying the hydrogen bond networks of aqueous electrolyte to restrict H 2 O molecule activity. This approach utilizes an appropriate amount of crystal H 3 O + to enhance the structural stability of LMO while maintaining sufficient Li + diffusion.
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
Nano-Micro Letters
·
2022
·Vol. 14
·期 1
·1-12
·
IF 23.655
Jiang Yuxin,Chai Liyuan,Zhang Dehe,Ouyang Fangping,Zhou Xiangyuan,Alhassan Sikpaam I.,Liu Sailin,He Yingjie,Yan Lvji,Wang Haiying,Zhang Wenchao
AbstractSection
Highlights
First report of a lithium-ion battery cathode as a deionization electrode for desalination.
A novel approach to suppress manganese dissolution by exposing the (111) facet is proposed.
Excellent desalination performance by the LiMn 2 O 4 /C cathode. The material achieves an ultrahigh desalination capacity of 117.3 mg g −1 at 1.0 V and a longer cycle life (200 cycles without capacity decay) with minor manganese dissolution during the cycling test in 10 mM aqueous LiCl solution.
AbstractSection
Abstract
Battery materials as emerging capacitive deionization electrodes for desalination have better salt removal capacities than traditional carbon-based materials. LiMn 2 O 4 , a widely used cathode material, is difficult to utilize as a deionization electrode due to its structural instability upon cycling and Mn dissolution in aqueous-based electrolytes. Herein, a facile and low-cost ball-milling routine was proposed to prepare a LiMn 2 O 4 material with highly exposed (111) facets. The prepared electrode exhibited relatively low dissolution of Mn during cycling, which shows its long cycle stability. In the hybrid capacitive deionization system, the LiMn 2 O 4 /C electrode delivered a high desalination capacity of 117.3 mg g −1 without obvious capacity decay at a voltage of 1.0 V with a 20 mM initial salt concentration. In addition, the exposed (111) facets significantly alleviated Mn ion dissolution, which also enhanced the structural steadiness.
研究领域:
材料科学
·
环境工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
DALTON TRANSACTIONS
·
2025
·
IF 3.3
Wangqiong Xu,Qiling Li,Shubiao Xia,Zhe Li,Feixiang Cheng,Shimei Guo
Surface coating is an effective approach for realizing the commercialization of cathode materials. Nowadays, ionically conducting surface coatings are commonly used to improve the electrochemical stability of LiMn2O4. In this work, LiMn2O4 cathodes decorated with in situ formed Ag nanoparticles with high electronic and ionic conductivity are prepared via a simple calcination process. The detailed microstructural mechanism of the influence of Ag on the electrochemical performance enhancement of spinel LiMn2O4 is uncovered by spherical-aberration-corrected (Cs-corrected) scanning transmission electron microscopy (STEM). The results demonstrate that the Ag coating helps to promote the transport of Li+ and strengthen the cycling stability by alleviating the decomposition of the electrolyte and manganese dissolution. Accordingly, the capacity retention rate of the optimized 5 wt% Ag/LiMn2O4 sample reached 80% after 900 cycles with an initial discharge-specific capacity of 100 mA h g−1 at 5 C (1 C = 148 mA h g−1). This work indicates that Ag coating is a promising technology for producing high-energy density lithium-ion batteries.
研究领域:
材料科学
·
能源技术
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF POWER SOURCES
·
2015
·
IF 6.217
Honglai Zhang,Zhaohui Li,Shishun Yu,Qizhen Xiao,Gangtie Lei,Yanhuai Ding
Carbon-encapsulated LiMn 2 O 4 (LMO@C) spheres were prepared using polymer microgel reactor, in which Mn 2+ ions are hydrolyzed in situ to form Mn(OH) 2 , and followed by annealing at a high temperature. The LMO@C spheres are constructed with the spinel LiMn 2 O 4 nanospheres that embedded in a porous carbon matrix uniformly. Owing to possessing three-dimensional (3D) electron-conductive and 3D ion-conductive networks, the LMO@C spheres exhibit high rate capability. They can deliver the specific capacities of 142, 137, 126, 107, and 91 mAh g −1 at the rates of 0.1C, 1C, 5C, 10C, and 20C (1C = 148 mA g −1 ), respectively. Owing to carbon encapsulation, the LMO@C spheres can retain 80% of the initial capacity at 1C rate after 1000 cycles at 25 °C, displaying stable cycling performance. The results suggest that the LMO@C spheres are promising cathode materials for high-power lithium-ion batteries.
研究领域:
材料科学
·
能源存储
✓ 已验证
产品关联
DOI
高影响因子
Journal of Energy Storage
·
2024
·
IF 8.9
Yifei Chen,Meng Li,Qin Zhu,Wei Bai,Xiaofang Liu,Mingwu Xiang,Junming Guo,Jintao Liu
The Jahn-Teller effect and Mn dissolution always restrict the practical electrochemical properties of spinel LiMn 2 O 4 cathode material. Herein, a low-temperature solid-state combustion method is employed to synthesize various truncated octahedral LiZn 0.03 Al x Mn 1.97- x O 4 ( x ≤ 0.08) with submicron structure. The Zn/Al dual-doping is conducive to forming {110} and {100} planes, and is also beneficial to the crystal development of LiMn 2 O 4 . It is found that as the amount of Al doping increases, the average particle size gradually decreases from 188 nm to 113 nm. In addition, the Zn/Al co-doping integrated with small particles can improve the high-rate performance. The optimal LiZn 0.03 Al 0.03 Mn 1.94 O 4 exhibits submicron truncated octahedral morphology, high crystallinity , and good particles dispersibility . Benefiting from these structure merits, the LiZn 0.03 Al 0.03 Mn 1.94 O 4 delivers the first discharge capacity of 113.1 mAh⋅g −1 and low capacity fade of 9.9 % after 300 cycles at 1C. It also shows the high first discharge capacity of 86.6 mAh⋅g −1 at 10C and the high capacity retention of 72.1 % after 2000 cycles. Even at ultrahigh current density of 15C and 20C, the ultralong cycling lifespans over 2000 cycles are also achieved in LiZn 0.03 Al 0.03 Mn 1.94 O 4 cathode material. The excellent electrochemical properties are ascribed to its relatively high Li + diffusion coefficient (1.60 × 10 −11 cm 2 ⋅s −1 ) and low apparent activation energy (25.45 kJ⋅mol −1 ) during the de-intercalation process. The Zn/Al dual-doping and submicron truncated octahedron designs of the LiMn 2 O 4 provide a scientific reference to prepare high-performance cathode materials.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
International Journal of Electrochemical Science
·
2023
·
IF 1.5
Chengyi Zhu,Jianxiong Liu,Xiaohua Yu,Yingjie Zhang,Xiaodong Jiang,Peng Dong,Yannan Zhang
Spinel LiMn2O4 has attracted increasing interest as promising cathode material owing to its low cost, high safety, and environmental friendliness. But the further development of LiMn2O4 is restricted by fast capacity fading upon cycling, especially at high temperatures. Herein, the one-dimensional (1D) Li4Ti5O12 coated LiMn2O4 nanorods (LMO-LTO) are successfully prepared by combining sol-gel and solid-state calcination method and ultimately enhance the cathode utilization in high-temperature and long-cycling conditions. The as-prepared LMO-LTO cathode delivers a high initial discharge capacity of 128.5 mAh g -1 at 0.1 C rate and exhibits a promising discharge capacity over 74.5 mAh g -1 at 10 C rate. Even under an elevated temperature of 55 O C, it still maintains 74.8% of its initial capacity at 1 C rate. Furthermore, the electrochemical impedance spectra (EIS) measurement confirm that compared with the pure LiMn2O4 nanorod, lower the charge transfer resistance (Rct) and enhanced Li + diffusion coefficient are also strong evidences of the improved electrochemical performance of LiMn2O4 nanorods after Li4Ti5O12 coating.
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
ELECTROCHIMICA ACTA
·
2024
·
IF 5.5
Wangqiong Xu,Beituo Liu,Shubiao Xia,Lijuan Chen,Ruijuan Qi,Qiling Li,Shimei Guo,Feixiang Cheng,Rong Huang,Zhe Li
Mo doping plays a striking role in the stability enhancement of LiMn 2 O 4 cathode materials. However, the underlying microscopic mechanism is still unclear. Here, we elucidate that the relationship between the atomic position of Mo doping in LiMn 2 O 4 and the stability enhancement of Mo-doped LiMn 2 O 4 by utilizing the spherical aberration-corrected scanning transmission electron microscopy (Cs-STEM). It exhibits that the part of Mo 6+ ions occupy empty Mn 16c site to form a surface reconstructed layer of rock-salt like phase on the outermost surface and other Mo 6+ ions dope into the Mn octahedral 16d sites to form LiMo x Mn 2-x O 4 in bulk, which is beneficial for inhibiting the parasitic side reactions. Concomitantly, this dual modification of bulk structure and surface can significantly enhance electrode reversibility and Li + diffusion. As a result, excellent long cycling stability of the as-designed optimal LiMo 0.01 Mn 1.99 O 4 after 1500 cycles with 61.61 % capacity retention at 10 C (1 C = 148 mAh g −1 ) is presented, with an initial discharge capacity of 88.30 mAh g −1 . Our research provides a clever approach for regulating the surface structure/bulk architecture in LiMn 2 O 4 cathode materials.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
Materials Today Physics
·
2022
·
IF 11.021
Chaosheng Zhang,Xiwei Lan,Qing Liu,Le Yu,Yaqian Li,Xianluo Hu
LiMn 2 O 4 -based lithium-ion batteries (LIBs) have attracted considerable attention due to their cost advantage, but industrial use has been hindered by severe capacity deterioration during cycling with LiPF 6 -based carbonate electrolytes, especially under high-temperature (55 °C) cycling conditions. Herein, a bifunctional, Janus-faced, inorganic-organic hybrid separator is demonstrated to ensure long-term cycling reversibility of LiMn 2 O 4 ||graphite LIBs. The monolithic all-nanomat separator is constructed by a bottom layer of poly ( m -phenylene isophthalamide) nanofibers by electrospinning and a top layer of interpenetrating hydroxyapatite/bacterial cellulose fibers . Benefiting from such a unique Janus configuration, the as-formed separator exhibits synergistic coupling in functions, simultaneously scavenging trace acid and mitigating the dissolution/deposition of Mn 2+ ions in batteries. Consequently, the cells with the Janus separator achieve enhanced capacity retention compared with traditional cells with the commercial polyolefin separator over 100 cycles at 55 °C. Furthermore, bulk structure and surface chemistry characterizations confirm that irreversible structural change in the LiMn 2 O 4 cathode could be avoided, and the amount of manganese on the graphite anode from the cycled cells with the Janus separator is suppressed. This work demonstrates that a composite Janus all-nanomat separator offers an unexpected route towards highly durable LiMn 2 O 4 -based LIBs.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
JOURNAL OF POWER SOURCES
·
2022
·
IF 9.794
Yang Tao,Qing Liu,Yujiao Guo,Mingwu Xiang,Xiaofang Liu,Wei Bai,Junming Guo,Shulei Chou
Electrochemical properties of spinel LiMn 2 O 4 cathode material have been always suffered from Mn dissolution and Jahn-Teller distortion. Herein, various Ni/B dual-doped LiNi 0.08 B x Mn 1.92- x O 4 ( x = 0–0.15) with a truncated octahedral morphology are synthesized via a facile solid-state combustion. The effects of Ni/B co-doping on the morphology, crystal structure, Mn dissolution, Li + diffusion coefficient and activation energy are investigated. Due to the relatively high Ni–O and B–O bond energy than that of Mn–O bond, the structure stability of the LiMn 2 O 4 is enhanced, whilst restraining the Jahn-Teller distortion. The LiNi 0.08 Mn 1.92 O 4 shows (111), (110) and (100) facets. In comparison, the B-doping endows the LiNi 0.08 B x Mn 1.92- x O 4 ( x ≥ 0.02) with (111) and (100) facets. This morphology evolution without (110) facets effectively inhibits the Mn dissolution. Owing to the synergistic merits of Ni/B dual-doping and unique truncated octahedron , the optimized LiNi 0.08 B 0.06 Mn 1.86 O 4 delivers an initial discharge capacity of 113.9 mAh∙g −1 at 1C and maintains a durable cycling life up to 2000 cycles at 5C. Even at 20C, a capacity retention of 86.3% is still obtained after 2000 cycles. Furthermore, a capacity retention of 70.6% can be retained after 500 cycles at 5C and 55 °C. The truncated octahedral LiNi 0.08 B x Mn 1.92- x O 4 with excellent electrochemical performance will be a good candidate for developing long-life lithium-ion batteries.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2025
·
IF 9.7
Ziyan Pu,Zengquan Zhu,Xiao-Jun Lv,Yueming Li
Conventional lithium-ion batteries (LIBs) are nearing their theoretical capacity limit, and there is an urgent need to develop energy storage devices with higher energy densities and cycling stabilities. In this work, a hybrid electrode design, which combines the traditional “rocking chair” mechanism and “anion intercalation” mechanism to improve energy density is reported. The hybrid electrode is composed of LiMn 2 O 4 and N,P-doped graphite (NPG) to use both anion and cation storage mechanisms. This design enhances the electrochemical potential windows and the energy density of the fabricated cell. Electrochemical results show that the fabricated cell not only shows a 44.1 % higher capacity than conventional LIBs. It displays a stable cycle life across a wide climate temperature range from − 20 to 25 °C, with a capacity retention rate of 86 % after 600 cycles at 100 mA g −1 . This study demonstrates the critical role of doping graphite with N and P to improve the electrochemical performance of graphite in deep charge/discharge, providing a valuable strategy for developing cathode materials in dual-ion batteries.
研究领域:
材料科学
·
能源存储技术
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Frontiers in Chemistry
·
2019
·
IF 3.782
Hai Yun,Zhang Ziwei,Liu Hao,Liao Libing,Fan Peng,Wu Yuanyuan,Lv Guocheng,Mei Lefu
Although the electrochemical properties of porous LiMn2O4 microspheres are usually improved compared to those of irregular LiMn2O4 particles, the effects of the different synthesis conditions on the preparation of the porous LiMn2O4 microspheres are rarely discussed in detail. In the present work, porous LiMn2O4 microspheres were successfully synthesized by using molten LiOH and porous Mn2O3 spheres as a template. Multiple factors were considered in the preparation process, including reagent concentration, pH, adding mode, heating time, etc. The morphology of the MnCO3 template was crucial for the preparation of porous LiMn2O4 microspheres and it was mainly affected by the concentration of reactants and the pH value of the solution during the precipitation process. During the lithiation of Mn2O3 microspheres, the heating temperature and the ratio between Mn2O3 and lithium salt were the most significant variables in terms of control over the morphology and purity of the LiMn2O4 microspheres. Furthermore, we demonstrated that the porous LiMn2O4 microspheres presented better rate capability and cyclability compared to commercial LiMn2O4 powder as cathode materials for lithium-ion batteries (LIBs). This study not only highlights the shape-controllable synthesis of LiMn2O4 microspheres as promising cathode materials, but also provides some useful guidance for the synthesis of porous LiMn2O4 microspheres and other LIB' electrode materials.
研究领域:
材料科学
·
能源存储技术
·
电化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2021
·
IF 7.312
Jia-Wei Fang,Jing Wang,Zhi-Yong Ji,Jia-Li Cui,Zhi-Yuan Guo,Jie Liu,Ying-Ying Zhao,Jun-Sheng Yuan
Improving the cycle stability and Li + electrosorption rate of the LiMn 2 O 4 (LMO) film electrode in the selective Li + electrosorption process is still a considerable challenge. In this work, a novel polypyrrole (PPy) - derived carbon encapsulated material LiMn 2 O 4 @Carbon/Nitrogen-4 (LMO@CN-4) was prepared by the three-dimensional in-situ polymerization and high-temperature annealing of PPy on the LMO surface. The LMO@CN-4 film electrode showed a faster Li + electrosorption rate, higher lithium-ion selectivity, and higher stability than the LMO film electrode. The maximum capacity of the LMO@CN-4 film electrode for Li + could reach 34.57 mg/g within 40 min in 0.05 mol/L LiCl solution. Even in the simulated concentrated seawater with a low Li + concentration (0.17 g/L), it could quickly reach adsorption equilibrium and maintain the high selectivity of Li + . The adsorption capacity was about 37.14 mg/g and the separation coefficient of α (Li + /Mg 2+ ), α (Li + /Na + ), and α (Li + /Ca 2+ ) was about 228.25, 2110.64, and 1381.89. The carbon encapsulation served as a conductive layer to enhance charge and ion transport. It also provided a buffer layer to prevent the volume collapse of the crystal and the dissolution of Mn. Therefore, the charge and discharge capacity of the LMO@CN-4 film electrode could be maintained at about 80% after 50 cycles at the 1C (148 mAh/g) rate, which was 20% higher than that of the bare LMO. What’s more, the high cycle stability and Li + electrosorption rate of the modified film electrode also suggested its potential for lithium electrosorption from concentration seawater.
研究领域:
材料科学
·
电化学工程
✓ 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）