Nature Communications
·
2024
·Vol. 15
·期 1
·1-14
·
IF 14.7
Ji Weijie,Luo Bi,Wang Qi,Yu Guihui,Zhang Zixun,Tian Yi,Zhao Zaowen,Zhao Ruirui,Wang Shubin,Wang Xiaowei,Zhang Bao,Zhang Jiafeng,Sang Zhiyuan,Liang Ji
Controllable engineering of thin lithium (Li) metal is essential for increasing the energy density of solid-state batteries and clarifying the interfacial evolution mechanisms of a lithium metal negative electrode. However, fabricating a thin lithium electrode faces significant challenges due to the fragility and high viscosity of Li metal. Herein, through facile treatment of Ta-doped Li 7 La 3 Zr 2 O 12 (LLZTO) with trifluoromethanesulfonic acid, its surface Li 2 CO 3 species is converted into a lithiophilic layer with LiCF 3 SO 3 and LiF components. It enables the thickness control of Li metal negative electrodes, ranging from 0.78 μm to 30 μm. Quasi-solid-state lithium-metal battery with an optimized 7.54 μm-thick lithium metal negative electrode, a commercial LiNi 0.83 Co 0.11 Mn 0.06 O 2 positive electrode, and a negative/positive electrode capacity ratio of 1.1 shows a 500 cycles lifespan with a final discharge specific capacity of 99 mAh g −1 at 2.35 mA cm −2 and 25 °C. Through multi-scale characterizations of the thin lithium negative electrode, we clarify the multi-dimensional compositional evolution and failure mechanisms of lithium-deficient and -rich regions (0.78 μm and 7.54 μm), on its surface, inside it, or at the Li/LLZTO interface.
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
JOURNAL OF SOLID STATE CHEMISTRY
·
2025
·
IF 3.5
Mingming Huang,Shoushuang Li,Rui Cui,Laura C.J. Pereira,Ambre Theron,Olivier Mentré,Xiedong Cheng,Feifan Li,Hui Shao,Minfeng Lü
Two transition metal selenites Li 2 Mn 2.5 (SeO 3 ) 4 and Li 2 Co 3 (SeO 3 ) 4 were synthesized using hydrothermal and solid-state reactions, respectively. Both compounds form similar three-dimensional (3D) frameworks featuring twisted one-dimensional (1D) chains, where transition metal polyhedra connect through shared corners or edges. However, Li 2 Co 3 (SeO 3 ) 4 and Li 2 Mn 2.5 (SeO 3 ) 4 exhibit distinct structural features. The former contains one type of [4 + 2] Li, two different CoO 6 octahedra, and two SeO 3 pyramids. The latter possesses one type of [5 + 1] Li, one Mn 3+ O 6 octahedron, one Mn 2+ O 5 square-pyramid, and two SeO 3 pyramids. Consequently, the lithium polyhedron undergoes unusually strong irregular distortions in the cobalt compound, but experiences strong distortions in the manganese compound. Magnetic measurements confirm that Li 2 Co 3 (SeO 3 ) 4 with a S = 3/2 uniform spin chain structure possess a long-range antiferromagnetic ordering and field-induced spin-flip transition at 2K, where the fitting via the Bonner–Fisher model with interchain mean-field corrections yields J intra /k B = -4.32(2) K, J inter /k B = −0.64(10) K, g = 2.34(3). Systematic distortion regularities in central metal cation polyhedra emerge from quantifying the ratio of SeO 3 groups to total cation polyhedra within lithium transition metal selenites.
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高影响因子
JOURNAL OF HAZARDOUS MATERIALS
·
2025
·
IF 11.3
Guanqing Hu,Qingguo Zhang,Yongde Yan,Yun Xue,Fuqiu Ma,Yuelin Wang,Xin Liu,Jinlong Song
With the rapid development of the global nuclear industry, substantial amounts of radioactive tributyl phosphate (TBP) have accumulated during the PUREX process. Prolonged accumulation poses significant environmental risks. Therefore, this study proposes an efficient molten salt oxidation (MSO) method for the treatment of gelled TBP. Comprehensive thermal analysis data indicate that the oxidation process of gelled TBP primarily consists of three stages. The composition of the waste salts after the MSO process was analyzed using X-ray diffraction spectroscopy. Fourier transform infrared spectroscopy revealed that the primary functional groups in gelled TBP were progressively degraded with increasing temperature. Scanning electron microscopy clearly illustrated the decomposition process of gelled TBP. X-ray photoelectron spectroscopy results identified the predominant forms of residual substances. The generated exhaust gas was analyzed using gas mass spectrometry and chromatography. Additionally, through DFT calculations of TBP, the possible reaction mechanism of TBP in the molten salts was deduced. In the molten state, carbonate can effectively absorb P 2 O 5 and eventually form stable NaPO 3 , which is the reason for the 94.90 % retention rate of phosphorus element. During the experimental process, the degradation rate of gelled TBP reached as high as 99.99 %. The MSO method proposed in this study shows great potential for the treatment of liquid organic waste.
研究领域:
核化学与化工
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环境科学
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计算化学
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产品关联
DOI
PubMed
高影响因子
JOURNAL OF POWER SOURCES
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2018
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IF 6.945
Shidong Song,Limei Yu,Yanli Ruan,Jian Sun,Butian Chen,Wu Xu,Ji-Guang Zhang
Irreversible parasitic reactions and the resulting accumulation of insulating side products are main barriers for practical application of rechargeable lithium–oxygen (Li O 2 ) batteries . Therefore, it is critical to develop multifunctional oxygen electrodes suitable for oxygen reduction reaction , oxygen evolution reaction , and decomposition of side reaction products. Here we report the application of ultrafine ruthenium on boron carbide (Ru/B 4 C) with highly efficient multifunctional activities as carbon-free oxygen electrodes for Li O 2 batteries. Li 2 CO 3 and LiOH can be completely decomposed by Ru/B 4 C at 4.0 V and 4.1 V, respectively, within the stability window of the electrolyte. A Li O 2 battery using the Ru/B 4 C oxygen electrode achieves low overpotentials for Li O 2 reactions, and excellent cycling performance under the capacities of 300 and 500 mAh g −1 Ru/B4C . In-situ gas chromatography analysis reveals that O 2 is the major gas product during charging. Only a negligible amount of CO 2 is observed in the first charging process. Therefore, Ru/B 4 C can be a very promising oxygen-electrode material for Li O 2 batteries and Li–air batteries operated in ambient air.
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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产品关联
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
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2025
·
IF 9
Jiayu Li,Lin Zhang,Haiyan Wang,Qun Cui
The post-Li 2 CO 3 precipitation liquor (the residual raffinate after Li 2 CO 3 precipitation with pH of 10–12), referred to as the mother liquor, still contains 20 ∼ 25 % of unrecovered Li + . Efficiently extracting lithium ions from the mother liquor has become one of the key challenges to enterprises. A titanium-based ion sieve precursor (LTO-Co/CTAB) was prepared via simultaneous doping of cobalt (II) acetate tetrahydrate ((CH 3 COO) 2 Co·4H 2 O) and cetyltrimethylammonium bromide (CTAB) by solid-phase synthesis method. After acid washing of LTO-Co/CTAB, the Co/CTAB co-doped titanium-based ion sieve (HTO-Co/CTAB) was characterized by XRD, SEM, XPS, etc. Adsorption isotherms and kinetics of Li + on HTO-Co/CTAB, along with its Li + /Na + and Li + /K + separation selectivity in the mother liquor were investigated. The results showed that the solid-phase Co doping coupled with CTAB-assisted dispersion enabled successful nano-scale refinement and functional modification of HTO-Co/CTAB. The formation of Co-O-Ti bonds, lattice distortions and its short diffusion paths of nanoparticles (100–200 nm) were all beneficial for the diffusion and enrichment of Li + within the channels of HTO-Co/CTAB. The adsorption behavior of Li + on HTO-Co/CTAB was well-described by Langmuir isotherm adsorption model ( R 2 = 0.996) and pseudo-second-order kinetic model ( R 2 = 0.996). An equilibrium uptake capacity of HTO-Co/CTAB for Li + in the mother liquor (initial concentration of Li + , Na + and K + was 1450, 33,800 and 6900 mg/L) could reach 39.78 mg/g, which was 39 % higher than that of HTO, and the equilibrium time was shortened to 5 h compared to HTO (20 h). The separation factors of Li + /Na + and Li + /K + for HTO-Co/CTAB were 677.45 and 284.43, respectively, and it had excellent stability.
研究领域:
材料科学
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环境工程
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产品关联
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
HYDROMETALLURGY
·
2022
·
IF 4.217
Jiadong Liu,Tsz Yau Mak,Zhe Meng,Xuyang Wang,Yulin Cao,Zhouguang Lu,Dawson Wai-Shun Suen,Xiao-Ying Lu,Yuanyuan Tang
Rechargeable lithium-ion batteries (LIBs) have been widely used in consumer electronics and electric vehicles . In terms of environmental restrictions and circular economy , proper treatment of spent LIBs is of great significance for achieving sustainable development. In this study, organic p -toluene sulfonic acid (PTSA) was employed to recycle valuable Li and Co elements from the spent LIBs for production of battery raw materials (e.g. Li 2 CO 3 and Co 3 O 4 ). Operation parameters such as PTSA concentration, hydrogen peroxide (H 2 O 2 ) concentration, solid-to-liquid ratio, leaching temperature and leaching time, were systematically investigated. Under the optimal conditions (0.9 vol% H 2 O 2 , 1.5 mol L −1 PTSA, 30 g L −1 solid-to-liquid ratio, 80 °C, and 60 min), the leaching efficiencies of commercial LiCoO 2 could reach ∼100% and 99% for Li and Co, respectively, while the corresponding values were about 95% and 93% for the spent LiCoO 2 . In addition, the selective precipitation of Co-rich compounds in cooled leachate allowed an effective separation of Co from the mixture. The high recovery yield of Co 3 O 4 and Li 2 CO 3 demonstrated the great potential of the PTSA-assisted leaching strategy in hydrometallurgical recycling of the spent LIBs for practical applications. Overall, this proposed recovery process is simple, efficient, and environmentally friendly and is of vital importance for rational treatment of spent LIBs.
研究领域:
环境科学
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材料科学
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产品关联
DOI
高影响因子
International Journal of Precision Engineering and Manufacturing-Green Technology
·
2023
·Vol. 11
·期 2
·449-461
·
IF 4.2
Yang Xinlei,Yang Fan,Afzal Muhammad,Sun Wanli,Kim Jung-Sik
La/Pr co-doped ceria (LCP) is processed to fabricate low-temperature ceramic fuel cell based on industrial-grade rare-earth carbonate electrolyte that is reached above a maximum power density of 750 mW/cm 2 at 520 °C. The charge carriers are investigated through LCP fuel cell having symmetric NCAL (Ni 0.8 Co 0.15 Al 0.05 LiO 2-δ ) electrodes using proton conductor BCZY (BaCe 0.7 Zr 0.1 Y 0.2 O 3-δ ) as a blocking layer and are found protons that dominate during the cell operation. The results of associated characterizations for HCC (hydrogen concentration cell) and the OCC (oxygen concentration cell) reveal that LCP material is mixed conductor of both protons and oxygen ions simultaneously. Transmission electron microscopy (TEM), X-ray Photoelectron Spectroscopy (XPS) and Fourier-transform infrared spectroscopy (FTIR) analysis before and after the electrochemical testing of the cell are performed which show an amorphous layer of LiOH/Li 2 CO 3 mixture that is formed after the tests on the surface of LCP structure. Conceptually, it looks that LiOH/Li 2 CO 3 mixture in molten state in the interface region of two-phase material promotes the proton conduction through LCP electrolyte, with negligible oxygen ion conduction.
研究领域:
能源材料
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固态电化学
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燃料电池
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材料科学
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纳米技术
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无机化学
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DOI
高影响因子
Nature Communications
·
2024
·Vol. 15
·期 1
·1-9
·
IF 14.7
Zhang Nian,Ren Guoxi,Li Lili,Wang Zhi,Yu Pengfei,Li Xiaobao,Zhou Jing,Zhang Hui,Zhang Linjuan,Liu Zhi,Liu Xiaosong
Garnet-type Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 (LLZO) is considered a promising solid electrolyte, but the surface degradation in air hinders its application for all-solid-state battery. Recent studies have mainly focused on the final products of the LLZO surface reactions due to lacking of powerful in situ characterization methods. Here, we use ambient pressure X-ray spectroscopies to in situ investigate the dynamical evolution of LLZO surface in different gas environments. The newly developed ambient pressure mapping of resonant Auger spectroscopy clearly distinguishes the lithium containing species, including LiOH, Li 2 O, Li 2 CO 3 and lattice oxygen. The reaction of CO 2 with LLZO to form Li 2 CO 3 is found to be a thermodynamically favored self-limiting reaction. On the contrary, the reaction of H 2 O with LLZO lags behind that of CO 2 , but intensifies at high pressure. More interestingly, the results provide direct spectroscopic evidence for the existence of Li + /H + exchange and reveal the importance of the initial layer formed on clean electrolyte surface in determining their air stability. This work demonstrates that the newly developed in situ technologies pave a new way to investigate the oxygen evolution and surface degradation mechanism in energy materials.
研究领域:
材料科学
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电化学
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固态电池
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表面化学
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光谱学
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DOI
高影响因子
ACS Applied Materials & Interfaces
·
2022
·
IF 10.383
Zhichuan Shen,Jiawei Zhong,Shiyong Jiang,Wenhao Xie,Shiying Zhan,Kaiji Lin,Linyong Zeng,Hailing Hu,Guide Lin,Yuhan Lin,Shuhui Sun,Zhicong Shi
Because of their high ionic conductivity, utilizing gel polymer electrolytes (GPEs) is thought to be an effective way to accomplish high-energy-density batteries. Nevertheless, most GPEs have poor adaptability to Ni-rich cathodes to alleviate the problem of inevitable rapid capacity decay during cycling. Therefore, to match LiNi0.8Co0.1Mn0.1O2 (NCM811), we applied pentaerythritol tetraacrylate (PETEA) monomers to polymerize in situ in a polyacrylonitrile (PAN) membrane to obtain GPEs (PETEA-TCGG-PAN). The impedance variations and key groups during the in situ polymerization of PETEA-TCGG-PAN are investigated in detail. PETEA-TCGG-PAN with a high lithium-ion transference number (0.77) exhibits an electrochemical decomposition voltage of 5.15 V. Noticeably, the NCM811|PETEA-TCGG-PAN|Li battery can cycle at 2C for 120 cycles with a capacity retention rate of 89%. Even at 6C, the discharge specific capacity is able to reach 101.47 mAh g–1. The combination of LiF and Li2CO3 at the CEI interface is the reason for the improved rate performance. Moreover, when commercialized LFP is used as the cathode, the battery can also cycle stably for 150 cycles at 0.5C. PETEA and PAN can together foster the transportation of Li+ with the construction of a fast ion transport channel, making a contribution to stable charge–discharge of the above batteries. This study provides an innovative design philosophy for designing in situ GPEs in high-energy-density lithium metal batteries.
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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高分子化学
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产品关联
DOI
PubMed
高影响因子
Inorganic Chemistry Frontiers
·
2024
·
IF 6.1
Yongquan Zhang,Hongchang Gao,Jingshun Wang,Qingguo Chi,Tiandong Zhang,Changhai Zhang,Yu Feng,Yue Zhang,Dianxue Cao,Kai Zhu
All-solid-state lithium metal batteries (ASSLMBs) are considered the most competitive next-generation energy storage batteries due to their high energy density and high safety. Polyethylene oxide (PEO) is an ideal solid-state electrolyte due to its high chain flexibility, high dielectric constant, and strong dissociation ability towards lithium salts. However, the application of PEO is severely hindered by drawbacks such as low ion conductivity at room temperature and low electrochemical window. In this work, we constructed a Li1.25Al0.25Zr1.75(PO4)3 (LAZP)/PEO composite solid-state electrolyte (CSSE) with improved ion conductivity, enlarged electrochemical window, and stable charge–discharge cycle performance. The CSSE leads to an obvious LiF layer and Li2CO3 formation at the interface of lithium metal. Meanwhile, the addition of LAZP reduces the side reaction between PEO and the lithium metal significantly and suppresses the deterioration of ion conductivity. In addition, we modified LiFePO4 (M-LFP), the cathode sheet of the ASSLMBs, by adding an appropriate proportion of multi-walled carbon nanotubes (MWCNTs), PEO and lithium bis(trifluoromethane sulfonimide) (LiTFSI) to improve the ionic and electronic conductivity inside the cathode of the ASSLMBs. The Li/CSSE/M-LFP full cell exhibits a specific discharge capacity of 152 mA h g−1 at 60 °C and 2 C rate and a capacity retention rate of 93.5% after 200 cycles at 1 C. This work demonstrates an effective strategy for increasing the specific capacity, rate ability and long-cycle performance of ASSLMBs.
研究领域:
材料科学
·
电化学
·
能源存储
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DOI
高影响因子
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