ENVIRONMENTAL TECHNOLOGY
·
2023
·
IF 2.8
Dong-yan Liu,Shi-neng Sun,Duan-yang Li
The recycling of cathode materials for spent NCM has always been a major concern for the energy industry. However, among the current processing methods, the general leaching efficiency of Li is between 85% and 93%, with much room for improvement. The recovery of Ni, Co and Mn requires a high cost of secondary purification. In this study, to recycle the NCM cathode material, a route of sulphated reduction roasting – selective Li water leaching – efficiency acid leaching of Ni, Co, Mn – extraction separation – crystallisation was adopted. The results showed that after roasting (a temperature of 800 °C, a reaction time of 90 min, a carbon content of 26%, and a sulphuric acid addition of nH2SO4:nLi = 0.85), Li water leaching efficiency was 98.6%, followed by acid leaching of Ni, Co and Mn at around 99%. Mn, Co were extracted with Di-(2-ethylhexyl) phosphoric acid and 2-Ethylhexyl phosphonic acid mono-2-ethylhexyl ester respectively to obtain Ni, Co, Mn solutions, which eventually were crystallized for manganese sulphate, cobalt sulphate, lithium carbonate and nickel sulphate products, with high purity of 99.40%, 98.95%, 99.10%, and 99.95%. The results of this study improved the leaching efficiency of Li and were closely linked to the actual industrial preparation of Ni, Co and Mn sulphates, providing a feasible and promising basis for spent NCM cathode materials industrial recovery.
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
WASTE MANAGEMENT
·
2026
·
IF 7.3
Yunfeng Liu,Lu Yao,Xuechun Yang,Zheng Jiao,Nianci Guan
Li was fully extracted; Ni, Co and Mn recoveries exceeded 97 %. • 0.30 M ascorbic acid enabled leaching without additional reducing agents or heating. • Pressurized CO 2 enhanced ascorbic-acid leaching beyond physical pressurization. • Product-layer diffusion best described the overall leaching kinetics. • Leachate-derived NCM811 retained 150 mAh/g after 200 cycles. The recovery of critical metals from spent Ni–Co–Mn (NCM) cathodes commonly requires concentrated acids, auxiliary reductants, or energy-intensive treatment. Here, pressurized CO 2 –ascorbic acid leaching was integrated with leachate-based NCM811 regeneration. Under the optimized condition, 0.30 mol/L ascorbic acid, 7 MPa CO 2 , a solid-to-liquid ratio of 20 g/L, and 25 °C, Li was completely extracted within 80 min, while the extraction efficiencies of Ni, Co, and Mn reached 98.3 %, 97.1 %, and 97.2 %, respectively, without a separately added reducing agent. Control experiments confirmed that the increase in metal extraction arose from the coupled action of pressurized CO 2 and ascorbic acid rather than from physical pressurization or CO 2 alone. Equilibrium analysis further indicated that ascorbic acid provided the principal acidity and reducing capacity, while the dissolved CO 2 /H 2 CO 3 /HCO 3 – equilibrium can maintain protons availability during lattice dissolution. Kinetic fitting showed that the leaching behavior was best described by the product-layer diffusion model. SEM–EDS, XRD, and XPS revealed particle fragmentation, progressive disruption of layered structural order, and changes in surface valence states. The Li/Ni/Co/Mn-rich leachate was further converted into regenerated NCM811, which delivered discharge capacity of 180 mAh/g initially, retained 150 mAh/g after 200 cycles, and maintained 55–60 mAh/g at 5C. This approach achieves high metal extraction at room temperature using a relatively low organic-acid concentration without separately added reducing agent, while returning the recovered metals to functional cathode production. Download: Download high-res image (220KB) Download: Download full-size image
✓ 已验证
DOI
高影响因子
Sustainable Energy & Fuels
·
2018
·Vol. 2
·期 7
·1481-1490
·
IF 0
Rong Zhou,Jianxing Huang,Shaobo Lai,Jiyang Li,Feng Wang,Zhiqiang Chen,Weiqing Lin,Chao Li,Jing Wang,Jinbao Zhao
A novel strategy for selecting an additive based on understanding the influence of different functional groups on electrochemical characteristics is adopted. N,N-Diethylamino trimethylsilane (DEATMS) is tested as a bifunctional electrolyte additive to scavenge H2O and neutralize HF in the electrolyte and enhance the behaviour of graphite/LiNi0.5Co0.2Mn0.3O2 cells operating at a high voltage (4.5 V vs. Li/Li+) or elevated temperature (55 °C). With 2% DEATMS, no LiPF6 hydrolysis species is found after storage at 55 °C for 6 days, even with a moisture content of 2000 ppm in the electrolyte. In addition, the graphite/LiNi0.5Co0.2Mn0.3O2 cells containing DEATMS show cycling performances superior to those of the cells without DEATMS upon cycling for 100 cycles at a high voltage (85.5% vs. 72.0%) or high temperature (81.2% vs. 70.6%). The sacrificial oxidation of DEATMS on the cathode surface restricts direct contact between the electrolyte and cathode, improving the electrochemical performance. The ex situ surface analysis of the electrodes after cycling indicates that both the electrolyte decomposition and Mn dissolution are inhibited by the deposition of DEATMS oxidation products.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
JOURNAL OF ALLOYS AND COMPOUNDS
·
2018
·
IF 3.779
Yan Ding,Bangwei Deng,Hao Wang,Xiang Li,Tao Chen,Xinxiu Yan,Qi Wan,Meizhen Qu,Gongchang Peng
Reducing the lithium residues on the surface of LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM) cathode is one of the most main challenges in Li-ion battery research. To address this task, a surface coating of Prussian blue (PB) of metal-organic framework is applied to NCM cathode to solve this intractable problem via a simple dry-coating method. The transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) results show that the uniform smooth coating can provide a protective shell to block H 2 O and CO 2 absorption from the air, suppressing lithium residues formed on the surface. The color change experiment between PB and Li residuals illustrates PB can react directly with surface residual lithium species. As a result, the amount of residual lithium, such as LiOH and Li 2 CO 3 , is significantly reduced. The 0.5 wt% PB-modified NCM delivers a high discharge capacity retention of 81% after 500 cycles at 1 C discharge rate and exhibits a superior storage property after storing in air for 14 days. Furthermore, electrochemical impedance spectroscopy (EIS) confirms that the PB-NCM could hinder the impedance increase during cycling. These results clearly indicate that the PB coating layer contributes to the reduction of lithium residues and the creation of thinner cathode-electrolyte interface, improving structural stability and cycling performance of NCM.
研究领域:
材料科学
·
电化学
·
能源存储与转换
✓ 已验证
DOI
高影响因子
JOURNAL OF CHEMICAL AND ENGINEERING DATA
·
2026
·
IF 2.4
Fu Xinran,Guo Yu,Yu Gangqiang,Chen Biaohua,Dai Chengna
The increasing generation of spent lithium-ion batteries
(LIBs)
necessitates the development of sustainable recycling technologies
for critical metals. In this study, a novel aminosugar-based deep
eutectic solvent (DES) composed of glucosamine hydrochloride (GlcN·HCl)
and betaine hydrochloride (Betaine HCl) was developed for the simultaneous
recovery of cobalt (Co), lithium (Li), manganese (Mn), and nickel
(Ni) from spent nickel–cobalt-manganese (NCM) cathode materials.
Systematic screening identified this DES as highly efficient under
mild conditions. Under the optimized parameters (HBD/HBA ratio of
1:2, solid-to-liquid ratio of 0.01 g·g –1 , temperature
of 80 ° C, and leaching time of 80 min), leaching efficiencies
of 100% for Co, 98.98% for Li, 99.11% for Mn, and 100% for Ni were
achieved. Kinetic analysis based on the shrinking core model indicated
that the leaching process is controlled by surface chemical reactions,
with apparent activation energies of 53.43–62.94 kJ·mol –1 . Spectroscopic characterization and electronic structure
analysis revealed that extensive hydrogen bonding, strong polarity,
and favorable frontier molecular orbitals synergistically promote
metal–oxygen bond disruption and stabilize dissolved metal
species. This work highlights aminosugar-based DES as a green and
effective platform for NCM cathode recycling.
✓ 已验证
产品关联
DOI
高影响因子
Journal of Energy Chemistry
·
2025
·
IF 14.9
Lifan Wang,Pengfei Jiang,Ruixiang Li,Xindong Wang,Chun Zhan,Guicheng Liu
Composite cathodes integrating Ni-rich layered oxides and oxide solid electrolytes are essential for high-energy all-solid-state lithium-ion batteries (ASSLBs), yet interfacial degradation during high-temperature co-sintering (>600 °C) remains a critical challenge. While surface passivation strategies mitigate reactions below 400 °C, their effectiveness diminishes at elevated temperatures due to inability to counteract Li + concentration gradients. Here, we introduce in situ lithium compensators, i.e., LiOH/Li 2 CO 3 , into NCM-LATP composite cathodes to dynamically replenish Li + during co-sintering. These additives melt to form transient Li + -rich phases that back-diffuse Li + into NCM lattices, suppressing layered-to-rock salt transitions and stabilizing the interface. Quasi in situ XRD confirms retention of the layered structure at temperature up to 700 °C, while electrochemical tests demonstrate a reversible capacity of 222.2 mA h g −1 —comparable to NCM before co-sintering—and an impressive 65.3% capacity retention improvement over 100 cycles. In contrast, uncompensated cathodes exhibit severe degradation to 96.5 mA h g −1 due to Li depletion and resistive Li-Ti-O interphases. This strategy integrates sacrificial chemistry with scalable powder-mixing workflows, achieving a 93.4% reduction in interfacial impedance. By addressing Li + flux homogenization and structural stability, this work provides a practical pathway toward industrial-scale fabrication of high-performance ASSLBs.
✓ 已验证
产品关联
DOI
高影响因子
WASTE MANAGEMENT
·
2022
·
IF 8.816
Xihong He,Yunpeng Wen,Xinyao Wang,Yaru Cui,Linbo Li,Hongzhou Ma
Deep eutectic solvents (DESs) play an important role in efficient recovery of spent lithium-ion batteries (LIBs). In this study, we proposed an efficient and safe method by using a choline chloride-phenylphosphinic acid DES as a lixiviant for the leaching of LiNi x Co y Mn z O 2 (NCM) cathode active materials of spent LIBs. The leaching conditions were optimized based on the leaching time, liquid–solid ratio, and leaching temperature. Under optimal experimental conditions, the leaching efficiencies of Li, Co, Ni, and Mn reached 97.7 %, 97.0 %, 96.4 %, and 93.0 %, respectively. The kinetics of the leaching process were well-fitted using the logarithmic law equation. The apparent activation energies for Li, Co, Ni, and Mn have been reported to be 60.3 kJ/mol, 78.9 kJ/mol, 99.3 kJ/mol, and 82.1 kJ/mol, respectively. UV–visible spectroscopy and Fourier transform infrared analysis revealed that the coordination configurations of Ni and Co in the leaching solution were octahedral and tetrahedral, respectively. In addition, the P O bond in phenylphosphinic acid was involved in coordination during leaching. This finding may provide an effective and safe approach for leaching valuable metals from spent LIBs.
研究领域:
材料科学
·
环境工程
·
化学工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF POWER SOURCES
·
2024
·
IF 8.1
Jincan Ren,Zhengbo Liu,Yu Tang,Zijia Yin,Tingting Yang,Zhiyong Huang,Wei Wang,Wenwen Cui,Chunxia Zhang,Zesheng Shen,Yingxia Liu,Yang Ren,Qi Liu
LiNi x Co y Mn 1-x-y O 2 (NCM, x ≥ 0.6) possessing a high nickel content is a favorable cathode candidate for next-generation lithium-ion batteries (LIBs) owing to its ultra-high energy density . However, its sluggish electrochemical kinetics at low temperatures and severe structure destruction at high temperatures limit its practical application. This study presents a facile surface modification strategy based on niobium (Nb) to achieve LiNbO 3 coating and Nb 5+ doping, which can address both problems under extreme temperatures (-30-50 °C). More specifically, the LiNbO 3 coating layer can decrease polarization and charge transfer resistance and enhance the structural stability of nickel-rich NCM (LiNi 0·83 Co 0·12 Mn 0·05 O 2 ); Nb 5+ dopants can widen the lithium-ion migration channels and thus improve the diffusion kinetics . The Nb-modified NCM (Nb-NCM) exhibits a high discharge specific capacity at subzero temperatures and excellent stability throughout the temperature range. To further evaluate the practical application potential of the Nb-NCM electrode, full cells are fabricated and tested using the Nb-NCM as a cathode and Li 4 Ti 5 O 12 (LTO) as an anode. Encouragingly, the full cell also shows excellent electrochemical performance between −30 and 50 °C. These findings provide a facile and scalable strategy to enhance the electrochemical performance of nickel-rich NCM across a broad temperature range.
✓ 已验证
DOI
高影响因子
Science Bulletin
·
2022
·
IF 20.577
Fangyuan Cheng,Xiaoyu Zhang,Peng Wei,Shixiong Sun,Yue Xu,Qing Li,Chun Fang,Jiantao Han,Yunhui Huang
The LiNi 0.8 Co 0.1 Mn 0.1 O 2 (Ni-rich NCM) cathode materials suffer from electrochemical performance degradation upon cycling due to detrimental cathode interface reactions and irreversible surface phase transition when operating at a high voltage (≥4.5 V). Herein, a traditional carbonate electrolyte with lithium difluoro(oxalato)borate (LiDFOB) and tris(trimethylsilyl)phosphate (TMSP) as dual additives that can preferentially oxidize and decompose to form a stable F, B and Si-rich cathode-electrolyte interphase (CEI) that effectively inhibits continual electrolyte decomposition, transition metal dissolves, surface phase transition and gas generation. In addition, TMSP also removes trace H 2 O/HF in the electrolyte to increase the electrolyte stability. Owing to the synergistic effect of LiDFOB and TMSP, the Li/LiNi 0.8 Co 0.1 Mn 0.1 O 2 half cells exhibit the capacity retention 76.3% after 500 cycles at a super high voltage of 4.7 V, the graphite/LiNi 0.8 Co 0.1 Mn 0.1 O 2 full cells exhibit high capacity retention of 82.8% after 500 cycles at 4.5 V, and Li/LiNi 0.8 Co 0.1 Mn 0.1 O 2 pouch cells exhibit high capacity retention 94% after 200 cycles at 4.5 V. This work is expected to provide an effective electrolyte optimizing strategy compatible with high energy density lithium-ion battery manufacturing systems.
研究领域:
电化学
·
材料科学
·
能源存储
·
锂离子电池
·
界面化学
✓ 已验证
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2021
·
IF 9.229
Xiaotang Shi,Tianle Zheng,Jianwei Xiong,Bingying Zhu,Ya-Jun Cheng,Yonggao Xia
Increasing the working voltage of lithium-ion batteries (LIBs) is an efficient way to increase energy density. However, high voltage triggers excessive electrolyte decomposition at the electrode–electrolyte interfaces, where the electrochemical performance such as cyclic stability and rate capability is seriously deteriorated. A new synergistic positive and passive approach is proposed in this work to construct a stable electrode–electrolyte interface at high voltage. As a positive approach, inorganic lithium sulfide salt (Li2S) is used as an electrolyte additive to build a stable cathode electrolyte interface (CEI) at the LiNi0.5Co0.2Mn0.3O2 (NCM523) cathode surface. In a passive way, acetonitrile (AN) is applied as a solvent additive to suppress oxidative decomposition of a carbonate electrolyte via preferential solvation with a lithium ion. Because of the synergistic interaction between the positive and passive approaches, the cyclic stabilities of NCM523/Li cells improved with a tiny amount of Li2S (0.01 mg mL–1) and AN (0.5 vol %). The capacity retention increased to 80.74% after 200 cycles compared to the cells with the blank electrolyte (67.98%) and AN-containing electrolyte (75.8%). What is more, the capacity retention of the NCM523/graphite full cell is increased from 65 to 81% with the addition of the same amount of Li2S and AN after 180 cycles. The mechanism is revealed on the basis of the theoretical calculations and various characterizations. The products derived from the preferential adsorption and oxidation of Li2S on the surface of NCM523 effectively increase the content of inorganic ingredients. However, the presence of AN prevents oxidation of the solvent. This study provides new principle guiding studies on a high-voltage lithium-ion battery with excellent electrochemical performance.
研究领域:
材料科学
·
电化学
·
能源存储
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Nanomaterials
·
2022
·Vol. 12
·期 4
·635
·
IF 5.719
Mi Zhang,Hui Ren,Qingzhong Cui,Hanjian Li,Yongjin Chen
In order to improve thermal conductivity, energy performance, and combustion performance of the aluminum-containing thermite, nanocarbon materials were added to thermite. Aluminum/molybdenum and trioxide/nanocarbon materials (Al/MoO3/NCM) were fabricated by electrostatic spinning technology. The Al and MoO3particles of the nAl/MoO3/NCM thermite are much smaller than nitrocellulose (NC); thus, the two components can be better attached to NC fibers. Results on thermal conductivity demonstrated that the addition of NCM can improve the thermal conductivity of Al/MoO3, and the addition of reduced graphene oxide (RGO) has a more significant impact on thermal conductivity. Energy performance analysis results indicated that the energy performance of Al/MoO3/NCM thermite spinning is the best when the value of combustion oxygen equivalent ratio (Φ) is 0.90–1.00. The combustion performance results show that the addition of NCM can significantly increase the combustion rate of thermites, and the addition of RGO improves its combustion rate the most, followed by carbon nanotubes (CNT) and nanoflake graphite (NFG) being the lowest. By changing the shape of the Al/MoO3/NCM charge and the internal composition of the charge, the sensitivity of the agent can be adjusted, and the matching performance and use performance of the electric igniter can be improved.Keywords:Al/MoO3/NCM;electrostatic spinning;thermal conductivity;energy performance;combustion performance
研究领域:
材料科学
·
能源工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ACS Applied Energy Materials
·
2022
·
IF 6.959
Bin Liang,Fangyuan Cheng,Xiaoyu Ge,Xuejun Tan,Chun Fang,Jiantao Han
The Ni-rich LiNixMnyCozO2 (x + y + z = 1, x > 0.5, Ni-rich NMC) materials are one of the most potential cathodes for high energy density lithium-ion batteries (LIBs) due to their high specific capacity and relatively low cost. However, performances of LIBs with the Ni-rich NCM cathode below 0 °C are restricted by low ion conductivity of the electrolyte and a slow ion diffusion rate at the electrode–electrolyte interphase. Here, γ-butyrolactone (GBL) with a low melting point and high ion conductivity is used to partially replace ethylene carbonate, which is conducive to lower the freezing point and increase the low-temperature ionic conductivity of the electrolyte, and the addition of GBL improves the dissolution of lithium difluoro(oxalato)borate (LiDFOB) in a traditional carbonate solvent. Instead of lithium hexafluorophosphate (LiPF6), LiDFOB can form a F-, B-, and O-rich interfacial phase at the Ni-rich NCM cathode, suppressing the fatal interface reaction and reducing the interface impedance. As a result, the electrolyte using GBL as the cosolvent and LiDFOB as the lithium salt can significantly improve the specific discharge capacity and cycling stability of LiNi0.8Co0.1Mn0.1O2/Li cells at 0 °C and −30 °C. At 0 °C, the LiNi0.8Co0.1Mn0.1O2/Li cells have a discharge specific capacity of 160 mA h g–1 and a capacity retention rate of 99% over 100 cycles. They deliver a decent capacity at −30 °C. This rational design of an electrolyte via optimizing the combination of a solvent and a lithium salt has been confirmed to be a low cost but rather an effective method to improve the low-temperature performances of LIBs.
研究领域:
材料科学
·
电化学
✓ 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）