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Eliminating H2O/HF and regulating interphase with bifunctional tolylene-2, 4-diisocyanate（TDI） additive for long life Li-ion battery

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Journal of Energy Chemistry 2024年第8期95卷 519-528页

作者： Xueyi Zeng Xiang Gao Peiqi Zhou Haijia Li Xin He Weizhen fan chaojun fan Tianxiang Yang Zhen Ma Xiaoyang Zhao Junmin Nan School of Chemistry South China Normal University Guangzhou Tinci Materials Technology Co.Ltd. School of Environmental Engineering and Chemistry Luoyang Institute of Science and Technology School of Geomatic and Environmental Engineering Henan Polytechnic Institute

Lithium-ion batteries（LIBs） featuring a Ni-rich cathode exhibit increased specific capacity,but the establishment of a stable interphase through the implementation of a functional electrolyte strategy remains challenging.Especially when the battery is operated under high temperature,the trace water present in the electrolyte will accelerate the hydrolysis of the electrolyte and the resulting HF will further erode the interphase.In order to enhance the long-term cycling performance of graphite/LiNi0.8Co0.1Mn0.1O2（NCM811） LIBs,herein,Tolylene-2,4-diisocyanate（TDI） additive containing lone-pair electrons is employed to formulate a novel bifunctional electrolyte aimed at eliminating H2O/HF generated at elevated temperature.After 1000 cycles at 25℃,the battery incorporating the TDI-containing electrolyte exhibits an impressive capacity retention of 94% at 1 C.In contrast,the battery utilizing the blank electrolyte has a lower capacity retention of only 78%.Furthermore,after undergoing 550 cycles at 1 C under45℃,the inclusion of TDI results in a notable enhancement of capacity,increasing it from 68% to 80%.This indicates TDI has a favorable influence on the cycling performance of LIBs,especially at elevated temperatures.The analysis of the film formation mechanism suggests that the lone pair of electrons of the isocyanate group in TDI play a crucial role in inhibiting the generation of H2O and HF,which leads to the formation of a thin and dense interphase.The existence of this interphase is thought to substantially enhance the cycling performance of the LIBs.This work not only improves the performance of graphite/NCM811 batteries at room temperature and high temperature by eliminating H2O/HF but also presents a novel strategy for advancing functional electrolyte development.

关键词： 4-diisocyanate Graphite/LiNi0.8Co0.1Mn0.1O2 battery H2O/HF eliminated additive Long-cycling performance Tolylene-2

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Elimination mechanism of coal and gas outburst based on geo‑dynamic system with stress–damage–seepage interactions

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International Journal of Coal Science & Technology 2023年第4期10卷 47-61页

作者： Lingjin Xu chaojun fan Mingkun Luo Sheng Li Jun Han Xiang Fu Bin Xiao College of Mining Liaoning Technical UniversityFuxin 123000China Energy Business Department Shanxi Lu’an Chemical GroupChangzhi 046200China Resource Department Liaoning Geology Engineering Vocational CollegeDandong 118000China

Coal and gas outburst is a complex dynamic disaster during coal underground mining.Revealing the disaster mechanism is of great signifcance for accurate prediction and prevention of coal and gas outburst.The geo-dynamic system of coal and gas outburst is proposed.The framework of geo-dynamic system is composed of gassy coal mass,geological dynamic environment and mining disturbance.Equations of stress–damage–seepage interaction for gassy coal mass is constructed to resolve the outburst elimination process by gas extraction with boreholes through layer in foor roadway.The results show the occurrence of outburst is divided into the evolution process of gestation,formation,development and termination of geo-dynamic system.The scale range of outburst occurrence is determined,which provides a spatial basis for the prevention and control of outburst.The formation criterion and instability criterion of coal and gas outburst are established.The formation criterion F1 is defned as the scale of the geo-dynamic system,and the instability criterion F2 is defned as the scale of the outburst geo-body.According to the geo-dynamic system,the elimination mechanism of coal and gas outburst—‘unloading+depressurization’is established,and the gas extraction by boreholes through layer in foor roadway for outburst elimination is given.For the research case,when the gas extraction is 120 days,the gas pressure of the coal seam is reduced to below 0.4 MPa,and the outburst danger is eliminated efectively.

关键词： Coal and gas outburst Geo-dynamic system Stress–damage–seepage coupling Elimination mechanism Instability criterion Gas extraction

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Reasonable start time of carbon dioxide injection in enhanced coalbed methane recovery involving thermal-hydraulic-mechanical couplings

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Frontiers of Earth Science 2023年第3期17卷 832-843页

作者： chaojun fan Lei YANG Bin XIAO Lijun ZHOU Haiou WEN Hao SUN College of Mining Liaoning Technical UniversityFuxin 123000China College of Safety Science and Engineering Liaoning Technical UniversityHuludao 125105China

Injection of gas (CO_(2)) into coal seams is an effective method to benefit from both CO_(2) geological storage and coalbed methane recovery. Based on the dual pore structure of coal mass, and the Weibull distribution of fracture permeability, a menmal-hydraulic-mechanical (THM) coupling mathematical model is proposed involving the non-isothermal adsorption of binary gases, dynamic gas diffusion between matrix and fractures, multiphase seepage, coal deformation, heat conduction and heat convection. This mathematical model is applied to study the process of CO_(2)-enhanced coalbed methane recovery (CO_(2)-ECBM). Results show that the CH4 content of CO_(2)-ECBM in coal seam decreases significantly when compared with that of regular drainage, and decreases rapidly in the early stage but slowly in the later stage. Coal seam permeability evolution is triggered by changes in gas adsorption/desorption, temperature and effective stress. For regular drainage, the early permeability shows a decreasing trend dominated by the increase of effective stress, while the later permeability shows an increasing trend dominated by the CH4 desorption caused shrinkage of coal matrix. For CO_(2)-ECBM, the permeability in coal seam generally shows a downward trend due to both matrix swelling induced by gas adsorption and thermal expansion, particularly near injection well. There appears an increased and delayed peak production rate of CH4. The CH4 production rate of CO_(2)-ECBM is always higher than that of regular drainage. The CH4 cumulative production and CO_(2) cumulative storage linearly increase with time, and the CH4 cumulative production of CO_(2)-ECBM increased by 39.2% in the duration of 5000 d compared with regular drainage. Reasonable CO_(2) injection starting time can overcome the issue of early CO_(2) breakthrough and ineffective increase of CH4 production. In the studied case, the optimal injection starting time is 2500 d. Compared with the simultaneous CH4 extraction and CO_(2) injection, the CH4 cumulative production of

关键词： CO_(2)sequestration coalbed methane reasonable injection start time thermo-hydro-mechanical coupling model numerical simulation

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Highly reinforce the interface stability using 2-Phenyl-1H-imidazole-1-sulfonate electrolyte additive to enhance the high temperature performance of LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)/graphite batteries

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Journal of Energy Chemistry 2023年第5期80卷 10-22,I0001页

作者： Xin He Yiting Li Wenlian Wang Xueyi Zeng Huilin Hu Haijia Li Weizhen fan chaojun fan Jian Cai Zhen Ma Junmin Nan School of Chemistry South China Normal UniversityGuangzhou 510006GuangdongChina Guangzhou Tinci Materials Technology Co. Ltd.Guangzhou 510760GuangdongChina

This work develops 2-Phenyl-1H-imidazole-1-sulfonate(PHIS)as a multi-functional electrolyte additive for H2O/HF scavenging and film formation to improve the high temperature performance of LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)/graphite batteries.After 450 cycles at room temperature(25℃),the discharge capacity retentions of batteries with blank and PHIS-containing electrolyte are 56.03%and 94.92%respectively.After 230 cycles at high temperatures(45℃),their values are 75.30%and 88.38%respectively.The enhanced electrochemical performance of the batteries with PHIS-containing electrolyte is supported by the spectroscopic characterization and theoretical calculations.It is demonstrated that this PHIS electrolyte additive can facilitate the construction of the electrode interface films,remove the H2O/HF in the electrolyte,and improve the electrochemical performance of the batteries.This work not only develops a sulfonate-based electrolyte but also can stimulate new ideas of functional additives to improve the battery performance.

关键词： LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)/graphite battery High temperature performance H_(2)O/HF scavenger 2-Phenyl-1H-imidazole-1-sulfonate Electrolyte additive

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Coal and gas outburst prediction model based on principal component analysis and improved support vector machine

Geohazard Mechanics

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Geohazard Mechanics 2023年第4期1卷 319-324页

作者： chaojun fan Xinfeng Lai Haiou Wen Lei Yang College of Mining Liaoning Technical UniversityFuxin123000China

In order to predict the coal outburst risk quickly and accurately,a PCA-FA-SVM based coal and gas outburst risk prediction model was designed.Principal component analysis(PCA)was used to pre-process the original data samples,extract the principal components of the samples,use firefly algorithm(FA)to improve the support vector machine model,and compare and analyze the prediction results of PCA-FA-SVM model with BP model,FA-SVM model,FA-BP model and SVM model.Accuracy rate,recall rate,Macro-F1 and model prediction time were used as evaluation indexes.The results show that:Principal component analysis improves the prediction efficiency and accuracy of FA-SVM model.The accuracy rate of PCA-FA-SVM model predicting coal and gas outburst risk is 0.962,recall rate is 0.955,Macro-F1 is 0.957,and model prediction time is 0.312s.Compared with other models,The comprehensive performance of PCA-FA-SVM model is better.

关键词： Coal and gas outburst Risk prediction Principal component analysis(PCA) Firefly algorithm(FA) Support vector machine(SVM)

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1950-2022年中国煤与瓦斯突出事故的时空分布规律

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辽宁工程技术大学学报（自然科学版） 2024年第3期43卷 279-287页

作者：范超军张鑫鹏杨雷富向杨振华李胜辽宁工程技术大学矿业学院辽宁阜新123000 辽宁地质工程职业学院资源系辽宁丹东118302

为厘清煤与瓦斯突出事故的发生规律,从时间和空间2个维度,对1950-2022年中国煤与瓦斯突出事故进行统计分析并提出防突措施与建议。研究结果表明:1950-2022年中国煤与瓦斯突出事故的时间分布特征可划分为大幅上升时期(1950-1980年)、持... 详细信息

为厘清煤与瓦斯突出事故的发生规律,从时间和空间2个维度,对1950-2022年中国煤与瓦斯突出事故进行统计分析并提出防突措施与建议。研究结果表明:1950-2022年中国煤与瓦斯突出事故的时间分布特征可划分为大幅上升时期(1950-1980年)、持续好转时期(1981-2000年)和稳定下降时期(2001-2022年)。空间分布特征为范围广、较集中、南多北少、南重北轻。煤与瓦斯突出事故发生次数随时间逐渐减少,死亡人数与煤矿事故总死亡人数之比随时间波动上涨。煤与瓦斯突出矿井的空间分布总体呈南多北少的特点。研究结果为中国煤与瓦斯突出事故防治提供参考。

关键词：煤与瓦斯突出突出矿井突出事故灾害防治时空分布

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PMMA基凝胶聚合物电解质在石墨/LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)电池中的研究

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电池工业 2024年第3期28卷 150-156页

作者：程鹏飞范超君刘倩彤范伟贞史利涛广州天赐高新材料股份有限公司广东广州510760

凝胶聚合物电解质(GPE)是当前最具商业化应用前景之一的准固态电解质,可以缓解甚至解决锂离子电池存在的漏液、挥发、燃烧等潜在安全问题。本文通过高温原位固化技术制备了一种以甲基丙烯酸甲酯为单体、聚乙二醇二甲基丙烯酸酯为交联剂... 详细信息

凝胶聚合物电解质(GPE)是当前最具商业化应用前景之一的准固态电解质,可以缓解甚至解决锂离子电池存在的漏液、挥发、燃烧等潜在安全问题。本文通过高温原位固化技术制备了一种以甲基丙烯酸甲酯为单体、聚乙二醇二甲基丙烯酸酯为交联剂、双(氟磺酰)亚胺锂为导电盐、碳酸乙烯酯/碳酸甲乙酯混合溶剂为增塑剂的GPE。通过热重分析对聚甲基丙烯酸甲酯(PMMA)基GPE的热力学性质进行了表征,采用计时安培法和电子扫描显微镜研究了PMMA基GPE对Al集流体的稳定性。研究结果表明,PMMA基GPE在室温拥有较高的电导率,达到6.61 mS/cm,同时可以将碳酸酯电解液的挥发温度由100.3℃提高至138.1℃。PMMA基GPE在高电位下对Al箔显示出良好的稳定性,4.3 V vs.Li/Li+以下不会发生铝箔腐蚀,而且在商用石墨/LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)软包电池中展现出良好的循环稳定性和容量保持能力,循环1000次后容量保持率为93.4%。

关键词：凝胶聚合物电解质甲基丙烯酸甲酯双(氟磺酰)亚胺锂原位固化

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Coal and gas outburst dynamic system

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International Journal of Mining Science and Technology 2017年第1期27卷 49-55页

作者： fan chaojun Li Sheng Luo Mingkun Du Wenzhang Yang Zhenhua College of Mining Engineering Liaoning Technical UniversityFuxin 123000China State Key Laboratory for Geo Mechanics and Deep Underground Engineering China University of Mining&Technology Xuzhou 221116China State Key Laboratory of Coal Resources and Safe Mining China University of Mining&TechnologyXuzhou 221116China

Coal and gas outburst is an extremely complex dynamic disaster in coal mine production process which will damage casualties and equipment facilities, and disorder the ventilation system by suddenly ejecting a great amount of coal and gas into roadway or working face. This paper analyzed the interaction among the three essential elements of coal and gas outburst dynamic system. A stress-seepage-damage coupling model was established which can be used to simulate the evolution of the dynamical system, and then the size scale of coal and gas outburst dynamical system was investigated. Results show that the dynamical system is consisted of three essential elements, coal-gas medium(material basis), geology dynamic environment(internal motivation) and mining disturbance(external motivation). On the case of C13 coal seam in Panyi Mine, the dynamical system exists in the range of 8–12 m in front of advancing face. The size scale will be larger where there are large geologic structures. This research plays an important guiding role for developing measures of coal and gas outburst prediction and prevention.

关键词：煤与瓦斯突出预测通风系统动力系统地质构造生产过程设备设施人员伤亡相互作用

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Establishment of NaLuF_(4):15%Tb-based low dose X-PDT agent and its application on efficient antitumor therapy

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International Journal of Minerals,Metallurgy and Materials 2024年第3期31卷 599-610页

作者： Yi Tian Zhiguang Fu Xiaosheng Zhu Chunjing Zhan Jinwei Hu Li fan chaojun Song Qian Yang Yu Wang Mei Shi Department of Radiation Oncology Xijing HospitalThe Fourth Military Medical UniversityXi’an 710032China Department of Oncology Air Force Medical CenterPLAThe Fourth Military Medical UniversityBeijing 100142China Department of Tumor Radiotherapy Air Force Medical CenterPLAThe Fourth Military Medical UniversityBeijing 100142China Department of Gastroenterology Air Force Hospital of Southern Theater CommandGuangzhou 510062China Department of Pharmaceutical Chemistry and Analysis School of PharmacyThe Fourth Military Medical UniversityXi’an 710032China School of Life Sciences Northwestern Polytechnical UniversityXi’an 710072China Institue of Materia Medica School of PharmacyThe Fourth Military Medical UniversityXi’an 710032China

X-ray excited photodynamic therapy(X-PDT)is the bravo answer of photodynamic therapy(PDT)for deep-seated tumors,as it employs X-ray as the irradiation source to overcome the limitation of light penetration depth.However,high X-ray irradiation dose caused organ lesions and side effects became the major barrier to X-PDT application.To address this issue,this work employed a classic-al co-precipitation reaction to synthesize NaLuF_(4):15%Tb^(3+)(NLF)with an average particle size of(23.48±0.91)nm,which was then coupled with the photosensitizer merocyanine 540(MC540)to form the X-PDT system NLF-MC540 with high production of singlet oxygen.The system could induce antitumor efficacy to about 24%in relative low dose X-ray irradiation range(0.1-0.3 Gy).In vivo,when NLF-MC540 irradiated by 0.1 Gy X-ray,the tumor inhibition percentage reached 89.5%±5.7%.The therapeutic mechanism of low dose X-PDT was found.A significant increase of neutrophils in serum was found on the third day after X-PDT.By immunohistochemical staining of tumor sections,the Ly6G^(+),CD8^(+),and CD11c^(+)cells infiltrated in the tumor microenvironment were studied.Utilizing the bilat-eral tumor model,the NLF-MC540 with 0.1 Gy X-ray irradiation could inhibit both the primary tumor and the distant tumor growth.De-tected by enzyme linked immunosorbent assay(ELISA),two cytokines IFN-γand TNF-αin serum were upregulated 7 and 6 times than negative control,respectively.Detected by enzyme linked immune spot assay(ELISPOT),the number of immune cells attributable to the IFN-γand TNF-αlevels in the group of low dose X-PDT were 14 and 6 times greater than that in the negative control group,respectively.Thus,it conclude that low dose X-PDT system could successfully upregulate the levels of immune cells,stimulate the secretion of cy-tokines(especially IFN-γand TNF-α),activate antitumor immunity,and finally inhibit colon tumor growth.

关键词： X-ray excited photodynamic therapy singlet oxygen low dose X-Ray irradiation efficient antitumor therapy anti-tumor immunity

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Structure and deformation measurements of shallow overburden during top coal caving longwall mining

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International Journal of Mining Science and Technology 2017年第6期27卷 1081-1085页

作者： Li Sheng fan chaojun Luo Mingkun Yang Zhenhua Lan Tianwei Zhang Haifeng College of Mining Liaoning Technical University State and Local Joint Engineering Laboratory for Gas Drainage & Ground Control of Deep Mines Henan Polytechnic University State Key Laboratory of Coal Resources and Safe Mining China University of Mining & Technology Chengyi Coal Mine Inner Mongolia Yitai Coal Co.Ltd.

Mining induced pressures are strong and overburden failure areas are large in top coal caving longwall mining, which constrains high production and safety mining. By employing the combination of the full view borehole photography technique and the seismic CT scanner technique, the deformation and failure of overlying strata of fully mechanized caving face in shallow coal seam were studied and the failure development of overburden was determined. Results show that the full view borehole photography can reveal the characteristics of strata, and the seismic CT scanner can reflect the characteristics of strata between the boreholes. The combined measurement technique can effectively determine the height of fractured and caved zones. The top end of the caved zone in Yangwangou coal mine employing the top coal caving longwall mining was at the depth of 171 m and fractured zone was at the depth of 106-110 m. The results provide a theoretic foundation for controlling the overburden strata in the shallow buried top coal caving panel.

关键词： Top coal caving Shallow depth Overburden failure and deformation Full view borehole photography Seismic CT scanner

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