Journal of Cleaner Production
·
2026
·
IF 10.7
Wensen Liu,Hui Su,Xiaolin Peng,Zeng Wei,Lanxuan Wei,Zhaowu Zhu
Pyridinecarboxamide PA14 recovers Ni and Co from chloride media via a solvation mechanism without alkali addition. • Continuous countercurrent extraction (6 EX + 6 SC + 7 ST) achieves >99% recovery for both Ni and Co over 480 h. • Strip liquor contains 79 g/L Ni and 32 g/L Co, meeting battery-grade specs after D2EHPA purification. • PA14 exhibits outstanding stability over 800 h with no degradation, capacity loss, or metal poisoning. Efficient and alkali-free recovery of nickel (Ni) and cobalt (Co) from spent lithium-ion batteries remains a significant challenge in chloride-based hydrometallurgy, primarily due to the poor extractability of Ni 2+ and the severe emulsification issues encountered during practical operation. To address these limitations, this study introduces a novel pyridinecarboxamide-based (PA14) extraction system, featuring an elongated alkyl side chain that substantially enhances the oil solubility of extracted metal complexes and effectively eliminates emulsification. A continuous countercurrent extraction system comprising six extraction, six scrubbing, and seven stripping stages was developed and operated for over 480 h using real industrial leach liquor from spent NCM523 cathode materials. The system achieved over 99% recovery for both Ni and Co, yielding a strip liquor with 79 g/L Ni and 32 g/L Co, which, after di-(2-ethylhexyl) phosphoric acid (D2EHPA) purification, met battery-grade impurity specifications. Systematic parameter evaluation revealed that Fe(III) is co-extracted and migrates to the product stream, necessitating upstream removal or side-stream bleeding; feed acidity must be controlled below 0.1 mol/L to prevent protonation-induced emulsification; and elevated temperatures improve phase disengagement but reduce extraction efficiency, effects that are readily compensated by multistage configuration. Notably, the PA14 extractant demonstrated exceptional long-term stability over 800 h of continuous operation, with no detectable degradation, loss of extraction capacity, or metal poisoning. This work provides a complete, practical, and sustainable engineering solution for the clean recovery of valuable metals from spent NCM batteries, overcoming the bottlenecks of both extractability and process stability that have hindered prior chloride-based approaches. Download: Download high-res image (340KB) Download: Download full-size image
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DOI
高影响因子
Journal of Environmental Chemical Engineering
·
2025
·
IF 7.2
Xingwen Lu,Yue He,Zebiao Huang,Jiating Li,Zenghua Qi,Jianqiao Qin,Fei Wang
Addressing the escalating volume of retired lithium-ion batteries (LIBs) is crucial for protecting the environment and minimizing resource wastage. In this study, Li 2 CO 3 and NCM 111 carbonate precursor ((Ni 1/3 Co 1/3 Mn 1/3 )CO 3 ) were successfully generated from the retired ternary LIBs through a combined process of thermal reduction and carbonate precipitation. During the thermal reduction process, graphite interacted with the cathode material (LiNi 0.5 Co 0.2 Mn 0.3 O 2 ) from used LIBs, facilitating the conversion of Li from its LiO x polyhedral structure into Li 2 CO 3 . Simultaneously, the transition metals within LiNi 0.5 Co 0.2 Mn 0.3 O 2 were transformed into Ni (0) , Co (0) , and MnO. Under optimal conditions, a graphite/LiNi 0.5 Co 0.2 Mn 0.3 O 2 mass ratio of 0.15/1 was sintered at 750 °C for 120 min, resulting in the recovery of 98.7% Li as Li 2 CO 3 with a purity of 99.65% through water leaching and evaporation. After isolating Li as Li 2 CO 3 from spent NCM, the residue was dissolved and co-precipitated as NCM111 carbonate precursor ((Ni 1/3 Co 1/3 Mn 1/3 )CO 3 ) using ammonium complexing agents, with recovery ratios of 98.4%, 99.4%, and 99.7% for Ni, Co and Mn, respectively. The recovered precursors exhibited spherical morphology and rhodochrosite crystal structure. These results offer valuable insights into recycling valuable metals from used NCM batteries, thereby promoting the sustainability of the new energy industry.
研究领域:
材料科学
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环境工程
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化学工程
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能源技术
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可持续资源管理
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产品关联
DOI
高影响因子
Scientific Reports
·
2019
·Vol. 9
·期 1
·1-16
·
IF 4.011
An Fuqiang,Zhao Hongliang,Zhou Weinan,Ma Yonghong,Li Ping
Recently, high-energy density cells containing nickel-rich cathodes and silicon-based anodes have become a practical solution for increasing the driving range of electric vehicles. However, their long-term durability and storage performance is comparatively poor because of the unstable cathode-electrolyte-interphase (CEI) of the high-reactivity cathode and the continuous solid-electrolyte-interphase (SEI) growth. In this work, we study several electrolyte systems consisting of various additives, such as S-containing (1,3,2-dioxathiolane 2,2-dioxide (DTD), DTD + prop-1-ene-1,3-sultone (PES), methylene methanedisulfonate (MMDS)) and Si-containing (tris(trimethylsilyl) phosphate (TTSP) and tris(trimethylsilyl) borate (TMSB)) compounds, in comparison to the baseline electrolyte (BL = 1.0 M LiPF 6 + 3:5:2 w-w:w EC: EMC: DEC + 0.5 wt% lithium difluoro(oxalato)borate (LiDFOB) + 2 wt% lithium bis(fluorosulfonyl)imide (LiFSI) + 2 wt% fluoroethylene carbonate (FEC) + 1 wt% 1,3-propane sultone (PS)). Generally, electrolytes with Si-containing additives, particularly BL + 0.5% TTSP, show a lower impedance increase in the full cell, better beginning-of-life (BOL) performance, less reversible capacity loss through long-term cycles and better storage at elevated temperatures than do electrolytes with S-containing additives. On the contrary, electrolytes with S-containing additives exhibit the advantage of low SEI impedance but yield a worse performance in the full cell than do those with Si-containing additives. The difference between two types of additives is attributed to the distinct function of the electrodes, which is characterized by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and X-ray photoelectron spectroscopy (XPS), which was performed on full cells and half cells with fresh and harvested electrodes.
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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DOI
高影响因子
Energy Storage Materials
·
2024
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IF 18.9
Rongzheng Tian,Shan Yin,Zhenyu Wang,Kai Liu,Lianqi Zhang,Lingyun Zhu
Single-crystal LiNi x Co y Mn 1-x-y O 2 (SC-NCM) cathodes design is an effective solution for enhancing electrochemical performance of all-solid-state lithium battery (ASSLBs). For highly Ni-rich SC cathode (Ni>90 %), the accumulation of local stress caused by anisotropic lattice shrinkage at deeply charging state is more destructive, and even SC-NCM design can not prevent the structure damage and interfacial contact failure between cathode and solid electrolyte (SE). In this work, small-size single-crystal design and Al-doping strategy are firstly combined to synthesize LiNi 0.91 Co 0.04 Mn 0.04 Al 0.01 O 2 (S-SC-NCMA) cathode. Electrochemistry test, CP-SEM, GITT and in-situ EIS techniques are combined to reveal the interfacial evolution of cathode/SE. The kinetic limitation caused by local contact failure of cathode/SE and the formation of intergranular crack under high voltage are the main reason for capacity loss of ASSLBs. Small-size single-crystal design can reduce the volumetric strain effect and Al-doping strategy can further inhibit lattice shrinkage to improve contact. This work provides an effective cathode modification strategy for highly Ni-rich NCM (Ni>90 %) cathode to improve high-voltage performance of sulfide-based ASSLBs.
研究领域:
材料科学
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电化学
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储能技术
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锂离子电池
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高影响因子
Journal of Materials Chemistry A
·
2021
·Vol. 9
·期 31
·17039-17047
·
IF 12.732
Fuxin Wei,Shufen Wu,Jiliang Zhang,Hongyang Fan,Liuyang Wang,Vincent Wing-hei Lau,Sizhou Hou,Minmin Zhang,Jiafeng Zhang,Bo Liang,Ruirui Zhao
Developing all solid-state lithium ion batteries (ASSBs) is a promising way to solve safety issues surrounding liquid-based batteries, yet the interfacial issues make ASSBs insufficient in providing long-term cycling performance or acceptable rate capabilities. Herein, we propose a new kind of electrolyte configuration, comprising a 3D ceramic framework filled with plastic crystals on the surface, to effectively enhance the interfacial Li diffusion kinetics. The soft plastic crystals enable not only excellent contact with the rigid framework and cathodes, but also rapid molecular reorganization to accommodate the interfacial Li, achieving ultrafast Li diffusion globally via the 3D framework. As a result, the ASSBs with the proposed electrolyte (i.e. garnet-succinonitrile composites) show an extremely low interfacial resistance, providing an initial discharge capacity of 165.3 mA h g−1 and a 95% capacity retention after 100 cycles when using a LiNi0.5Co0.2Mn0.3O2 (NCM) cathode. Furthermore, these NCM-ASSBs using the designed electrolyte even exhibit better cycling performance within a higher voltage range (2.8–4.5 V) than conventional lithium ion batteries (LIBs) using conventional liquid electrolytes (LEs). A capacity retention rate of 92% for 3DLLZO-PCE is demonstrated, against the 85% for LE-LIBs after 50 cycles. We believe that this strategy provides useful guidance for constructing high-performance ASSBs, which is important in their further commercialization.
研究领域:
材料科学
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电化学
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电池技术
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固态电解质
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DOI
高影响因子
Advanced Energy Materials
·
2019
·Vol. 10
·期 4
·1903311
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IF 24.884
Jun Zhang,Chao Zheng,Lujie Li,Yang Xia,Hui Huang,Yongping Gan,Chu Liang,Xinping He,Xinyong Tao,Wenkui Zhang
High-performance rechargeable all-solid-state lithium metal batteries with high energy density and enhanced safety are attractive for applications like portable electronic devices and electric vehicles. Among the various solid electrolytes, argyrodite Li 6 PS 5 Cl with high ionic conductivity and easy processability is of great interest. However, the low interface compatibility between sulfide solid electrolytes and high capacity cathodes like nickel-rich layered oxides requires many thorny issues to be resolved, such as the space charge layer (SCL) and interfacial reactions. In this work, in situ electrochemical impedance spectroscopy and in situ Raman spectroscopy measurements are performed to monitor the detailed interface evolutions in a LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM)/Li 6 PS 5 Cl/Li cell. Combining with ex situ characterizations including scanning electron microscopy and X-ray photoelectron spectroscopy, the evolution of the SCL and the chemical bond vibration at NCM/Li 6 PS 5 Cl interface during the early cycles is elaborated. It is found that the Li + ion migration, which varies with the potential change, is a very significant cause of these interface behaviors. For the long-term cycling, the SCL, interfacial reactions, lithium dendrites, and chemo-mechanical failure have an integrated effect on interfaces, further deteriorating the interfacial structure and electrochemical performance. This research provides a new insight on intra and intercycle interfacial evolution of solid-state batteries.
研究领域:
材料科学
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电化学
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固态离子学
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能源存储
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界面化学
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电池技术
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DOI
高影响因子
ACS Applied Nano Materials
·
2022
·
IF 6.14
Xiaofei Wang,Shuonan Wang,Zhangkuo Han,Hao Liu,Libing Liao
Solid polymer electrolytes (SPEs) are considered to be an important move to revive high-energy-density lithium-metal batteries due to their good flexibility and high safety. However, the low room-temperature ionic conductivity of SPEs has always been a stumbling block for their practical applications. Herein, a composite SPE has been fabricated by the cooperation of polyethylene oxide (PEO) and a type of natural nanoclay-halloysite nanotube (HNT) in a poly(vinylidene fluoride) (PVDF) matrix. It is expected that the sticky PEO can improve the interfacial stability of the SPE and lithium foil, while the special structure and surface charge properties of the HNTs changed the coordination environment of lithium ions and facilitated Li+ running on highways along the HNT outer surface. The optimized SPE composite showed an outstanding room-temperature ionic conductivity of 2.45 × 10–4 S cm–1 and high ion transference number of 0.67 at 25 °C. A LiFePO4/SPE-H5/Li full battery retained a discharge capacity of 142 mAh g–1 after 200 cycles at a rate of 0.2 C (25 °C). In addition, SPE-H5 can also be used in a 4.3 V high voltage NCM/SPE-H5/Li battery due to its excellent electrochemical stability window (more than 5 V). This work also reveals that lower-cost natural clay minerals are excellent nanoceramic fillers in realizing sustainable high-energy-density energy storage.
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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DOI
高影响因子
ACS Applied Materials & Interfaces
·
2022
·
IF 10.383
Xiaoying Fan,Peng Chen,Xu Yin,Ruo-Xuan Qi,Chao Yang,Ya-Jun Cheng,Kunkun Guo,Cuirong Liu,Yonggao Xia
Increasing working voltage is a promising way to increase the energy density of lithium-ion batteries. Cycling and rate performance deteriorated due to excessive electrolyte decomposition and uncontrolled formation of a cathode–electrolyte interface (CEI) layer at a high voltage. A new concept is proposed to construct a high-voltage-stable electrode–electrolyte interface. An elastomeric poly(dimethyl siloxane) (PDMS) binder is incorporated into the electrode to modify the LiNi0.5Co0.2Mn0.3O2 (NCM 523) particle surface via an in situ cross-linking reaction between hydroxy-terminated PDMS and methyl trimethoxy silane promoted by moisture at ambient conditions (MPDMS). Improved electrochemical performance is achieved with the MPDMS binder in terms of reversible capacity (201 vs 185 mAh·g–1 at 0.2C), capacity retention (80 vs 68%, after 300 cycles at 1C), and rate performance (55.6% increase at 5C), as demonstrated by the NCM 523||Li half-cell. The NCM 523||graphite full-cell also shows improved performance at 4.6 V (147 vs 128 mAh·g–1, 82 vs 76%, after 200 cycles at 1C). The mechanism studies indicate that MPDMS exerts multiple effects, including cathode surface passivation, solvation structure tuning, electrolyte uptake enhancement, and mechanical stress relief. This work provides an inspiring route to realize high-voltage application of lithium-ion battery technology.
研究领域:
材料科学
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电化学
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能源技术
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产品关联
DOI
PubMed
高影响因子
Materials Horizons
·
2025
·
IF 10.7
Pengcheng Li,Zhuo Peng,Zhihao Sun,Chengyu Li,Jianjun Ma,Jun Wang,Run Yu,Cairong Jiang,Xiang Gao,Wenge Yang,Dongliang Chao,Yongjin Chen
The extremely fast charging/discharging of nickel-rich LiNixCoyMn1-x-yO2 (NCM) cathodes has raised concerns about rapid capacity decay. The birth defects and fragile lattice result in the sluggish Li+ diffusion kinetics and unfavorable structural degradation. Moreover, lattice strain, mechanical failures, surface reconstruction, and interfacial side reactions accelerate the decay process. Here, a proof-of-principle study of lattice plainification (LP) strategy in high-nickel NCM cathode is reported. The introduction of Al and Zr in transition metal layers by wet chemistry and calcination method enables the simplification of the complex lattice structures to obtain an order phase and repair the various defects of NCM, thereby enhancing the lithium-ion transport. The modified LP-NCM exhibits a high initial discharge capacity of 157.3 mAh/g with capacity retention of 81% after 300 cycles at a 5 C rate, significantly outperforming the pristine counterpart (50.9%). The LP-NCM/Gr pouch cells presented impressive cycling performance, achieving 80% capacity retention over 1000 cycles at 1 C, which far surpasses the performance of pristine NCM. Our method eliminates the rocksalt and disordered phases, suppresses oxygen, lithium, and transition metal vacancies, as well as Li/Ni mixing. LP-NCM after cycles exhibits nanopores rather than cracks of pristine NCM. Our investigations reveal the lattice plainification design approach flattens and toughens up the crystal lattice, which contributes to robust structural stability and improves the structure degradation, mechanical failures, and gas release. Our findings underscore the importance of lattice engineering and demonstrate the potential of the lattice plainification strategy for designing high-performance cathodes.
研究领域:
材料科学
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电化学
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储能技术
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纳米技术
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晶体工程
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产品关联
DOI
PubMed
高影响因子
Materials Today Energy
·
2025
·
IF 8.6
Yilian Song,Haoran Li,Kang Dong,Youjun Xing,Minghui Zhang,Mingzhu Yang,Xiang Huang,Wei Liu,Yongcheng Jin
The pursuit of high-voltage nickel-based layered terminal oxide materials (NCM) has gained significant research momentum owing to their compelling combination of cost-effectiveness and high energy density. However, critical challenges persist in mitigating parasitic interfacial reactions, electrolyte oxidative decomposition, and structural degradation mechanisms under elevated operating voltages (>4.3 V vs. Li/Li + ). Here, we propose a synergistic dual-additive electrolyte strategy by adding tris(pentafluorophenyl)borane (TPFPB) and lithium difluoro(oxalato)borate (LiDFOB) to a conventional carbonate-based electrolyte, aiming to enhance the performance of high-voltage LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM622). Theoretical and experimental analyses show that LiDFOB reduces harmful side products (e.g., HF, PF 5 ) by inhibiting LiPF 6 decomposition, while TPFPB's rigid structure promotes a uniform and dense cathode electrolyte interface (CEI) film on the cathode. The two additives work synergistically to enabling the Li/NCM622 half-cells to maintain a capacity retention of up to 76.8 % after 500 cycles at 1C under 4.5 V high voltage, while the cell prepared with an electrolyte without any additives only retained 7.6 % capacity after cycling. The synergistic strategy employing TPFPB and LiDFOB to enhance the high-voltage cycling stability provides a promising practical feasibility of high-voltage batteries for industrial application.
研究领域:
电化学
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能源材料
·
锂离子电池
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表面与界面工程
·
电解液化学
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产品关联
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2024
·
IF 9.4
Yongrui Luo,Yinnan Qian,Minghui Cai,Pengtao Zhang,Jixiao Li,Zhaoyan Luo,Jiangtao Hu,Yongliang Li,Qianling Zhang,Xiangzhong Ren
Plastic-crystal-embedded elastomer electrolytes (PCEEs), produced through polymerization-induced phase separation (PIPS), are gaining popularity as solid polymer electrolytes (SPEs). However, it remains to be investigated whether all monomer molecules can achieve polymerization-induced phase separation and the corresponding differences in lithium metal battery performance. Herein, we prepared PCEEs with different functional groups ( OH, CN, F) through in situ polymerization. Research findings show that PCEE containing – CN or – F achieves the separation of the plastic crystalline phase and succinonitrile (SN) phase, whereas PCEE containing OH cannot due to hydrogen bonding with the SN phase. Notably, the PCEE synthesized with the F monomer (FBA-PCEE) exhibited exceptional interfacial stability with lithium metal anodes and lithium iron phosphate (LFP) cathodes, due to its unique coordination mechanism with lithium ions. The FBA-PCEE demonstrated a high ionic conductivity (2.02 × 10 −3 S cm −1 ) and lithium-ion migration number ( t Li + = 0.75). Moreover, lithium symmetric cells incorporating FBA-PCEE demonstrated stable cycling performance for more than 1000 h at a current density of 0.1 mA cm −2 , resulting in the development of a solid electrolyte interphase (SEI) rich in LiF, Li 3 N, and Li 2 CO 3 over time. Additionally, incorporating FBA-PCEE facilitated the stable cycling of LPF over 1000 cycles at 0.5C, maintaining a capacity retention of 77.38 % after 500 cycles. When coupled with high-voltage Nickel Cobalt Manganese Oxide (NCM-622) cathodes and lithium metal anodes, a discharge capacity of 119.70 mAh g −1 at 0.1C was sustained after 100 cycles, exhibiting a capacity retention of 78.95 %. This study elucidates the critical role of monomer design in achieving PIPS, offering valuable insights into developing high-performance polymer composite electrolytes for advanced lithium metal batteries.
研究领域:
材料科学
·
电化学
·
电池技术
·
高分子化学
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产品关联
DOI
PubMed
高影响因子
ELECTROCHIMICA ACTA
·
2025
·
IF 5.6
Minghui Kong,Wenlong Wang,Jiaqiang Li,Qiang Yang,Runru Liu,Qi Liu,Daobin Mu,Li Li,Renjie Chen,Shuo Yang,Bin Wang,Feng Wu
This research explores the structural and interfacial regulation mechanisms of multi-element synergistic electrolytes for high voltage LiNi x Co y Mn 1-x-y O 2 (NCM) lithium ion batteries through a combined simulation-experiment approach. Theoretical calculations revealed that difluoroxalate borate ion (DFOB − ) exhibit a pronounced negative electrostatic potential distribution, with a binding energy to Li + (-110.26 kJ/mol) higher than conventional carbonate solvents (e.g., DMC, FEC), thus dominating the formation of anion-enriched solvation sheaths and significantly reducing Li + desolvation energy barriers (<30 kJ/mol). Raman spectroscopy and molecular dynamics simulations confirmed that LiDFOB introduction facilitates the transition of solvation structures from solvent-separated ion pairs (SSIPs) to contact ion pairs (CIPs) and aggregates (AGGs), with CIPs/AGGs proportion increasing from 29 % to 39 %, effectively suppressing LiPF 6 hydrolysis and mitigating electrode structural damage caused by solvent co-intercalation. Electrochemical tests demonstrated that the optimized 0.5 PB modified electrolyte(0.5 M lithium hexafluorophosphate+0.5 M lithium difluoro(oxalato)borate dissolved in a mixed solvent of dimethyl carbonate: fluoroethylene carbonate: propyl p-toluene sulfonate in a ratio of 3:1:1) enabled NCM811||Li half-cells to achieve 88 % capacity retention after 100 cycles at 4.5 V high voltage (versus 58 % for control group), along with stable lithium metal anode cycling for 500 h at 1 mA·cm −2 . Interface analysis revealed that DFOB⁻ and PPTs preferentially undergo redox reactions to form inorganic-rich cathode electrolyte interphase (CEI) films containing borides (LiₓBOyFz) and sulfonates (ROSO₂Li). On the anode side, synergistic effects of DFOB⁻, Propyl p-toluene sulfonate (PPTs) and FEC generate LiF/sulfur/boride-enriched composite solid electrolyte interface (SEI) layers, effectively suppressing transition metal dissolution and graphite structural degradation. This work provides a novel paradigm of "anion coordination-solvation structure-interface functionalization" for high-voltage lithium-ion batteries."
研究领域:
电化学
·
能源材料
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锂离子电池
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电池界面工程
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计算材料科学
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产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）