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Interfacial/bulk synergetic effects accelerating charge transferring for advanced lithium-ion capacitors

Chinese Chemical Letters 2024年第6期35卷 168-175页

作者： Chang Liu Zirui Song Xinglan Deng Shihong Xu Renji Zheng Wentao Deng Hongshuai Hou guoqiang zou Xiaobo Ji School of Chemistry and Chemical Engineering Hunan Institute of EngineeringXiangtan 411104China College of Chemistry and Chemical Engineering Central South UniversityChangsha 410083China Key Laboratory of Hunan Province for Clean and Efficient Utilization of Strategic Calcium-Containing Mineral Resources School of Minerals Processing and BioengineeringCentral South UniversityChangsha 410083China

The exploration of advanced materials through rational structure/phase design is the key to develop highperformance lithium-ion capacitors(LICs).However,high complexity of material preparation and difficulty in quantity production largely hinder the further development.Herein,Cu_(5)FeS_(4-x)/C(CFS@C)heterojunction with rich sulfur vacancies has successfully achieved from natural bornite,presenting low costeffective and bulk-production prospect.Density functional theory(DFT)calculations indicate that rich vacancies in bulk phase can decrease band gap of bornite and thus improve its intrinsic electron conductivity,as well as the heterojunction spontaneously evokes a built-in electric field between its interfacial region,largely reducing the migration barrier from 1.27 e V to 0.75 e V.Benefited from these merits,the CFS@C electrodes deliver outperformed lithium storage performance,e.g.,high reversible capacity(822.4m Ah/g at 0.1 A/g),excellent cycling stability(up to 820 cycles at 2 A/g and 540 cycles at 5 A/g with respective capacity retention of over or nearly 100%).With CFS@C as anode and porous carbon nanosheets(PCS)as cathode,the assembled CFS@C//PCS LIC full cells exhibit high energy/power density characteristics of 139.2 Wh/kg at 2500 W/kg.This work is expected to offer significant insights into structure modifications/devising toward natural minerals for advanced energy-storage systems.

关键词： Bulk/interfacial modification Heterostructure Sulfur vacancies Lithium ion capacitors Capacitors

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Lanthanum promoting bone formation by regulating osteogenesis,osteoclastogenesis and angiogenesis

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Journal of Rare Earths 2024年第3期42卷 621-628,I0007页

作者： Dandan zou Runlian Lin Yu Han Juan Jia guoqiang Zhou Haisong Zhang Kun Ge Hebei Key Laboratory of Chronic Kidney Diseases and Bone Metabolism Affiliated Hospital of Hebei UniversityBaoding071000China Key Laboratory of Medicinal Chemistry and Molecular Diagnosis of the Ministry of Education Key Laboratory of Chemical Biology of Hebei ProvinceCollege of Chemistry and Environmental ScienceHebei UniversityBaoding071002China

With lanthanum(La) in agriculture, medicine, and the chemical industry, La shows accumulation in the body, especially in the bone, because of its similar structure to calcium. Moreover, La has a direct role in bone formation regulating osteoblasts and osteoclasts. Nevertheless, bone formation is complex under the regulation of osteogenesis, osteoclastogenesis, and angiogenesis in the bone microenvironment. It is difficult to comprehensively understand the regulation of bone homeostasis from a single kind of cell.Herein, some bone microenvironment-related cells and mouse calvaria culture models were used to study the regulatory effect of La-based compound-lanthanum nitrate(La(NO_(3))_(3)) on bone formation.La(NO_(3))_(3) has good biological safety, and the osteogenic differentiation is significantly increased under La(NO_(3))_(3) treatment for bone marrow mesenchymal stem cells(BMMSC). In contrast, the differentiation,maturation, and bone erosion ability of osteoclasts are significantly decreased. Meanwhile, the angiogenesis ability of human umbilical vein endothelial cells(HUVEC) is significantly promoted when treated with La(NO_(3))_(3). Furthermore, bone metabolism and angiogenesis are improved under La(NO_(3))_(3) treatment in the calvaria ex vivo culture model and BMMSC-HUVEC co-culture system. These results suggest that La has the beneficial effect of promoting bone metabolism and improving bone formation in the bone microenvironment.

关键词： Lanthanum Bone microenvironment Osteogenic differentiation Angiogenesis Rare earths

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Ultra-Low-Dose Pre-Metallation Strategy Served for Commercial Metal-Ion Capacitors

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Nano-Micro Letters 2022年第3期14卷 276-291页

作者： Zirui Song Guiyu Zhang Xinglan Deng Kangyu zou Xuhuan Xiao Roya Momen Abouzar Massoudi Wentao Deng Jiugang Hu Hongshuai Hou guoqiang zou Xiaobo Ji College of Chemistry and Chemical Engineering Central South UniversityChangsha 410083People’s Republic of China Department of Semiconductors Materials and Energy Research Center P.O.Box 14155/4777TehranIran College of Material Science and Engineering Zhengzhou UniversityZhengzhou 450001People’s Republic of China

Sacrificial pre-metallation strategy could compensate for the irreversible consumption of metal ions and reduce the potential of anode,thereby elevating the cycle performance as well as open-circuit voltage for full metal ion capacitors(MICs).However,suffered from massive-dosage abuse,exorbitant decomposition potential,and side effects of decomposition residue,the wide application of sacrificial approach was restricted.Herein,assisted with density functional theory calculations,strongly coupled interface(M-O-C,M=Li/Na/K)and electron donating group have been put forward to regulate the band gap and highest occupied molecular orbital level of metal oxalate(M_(2)C_(2)O_(4)),reducing polarization phenomenon and Gibbs free energy required for decomposition,which eventually decrease the practical decomposition potential from 4.50 to 3.95 V.Remarkably,full sodium ion capacitors constituted of commercial materials(activated carbon//hard carbon)could deliver a prominent energy density of 118.2 Wh kg^(−1)as well as excellent cycle stability under an ultra-low dosage pre-sodiation reagent of 15-30 wt%(far less than currently 100 wt%).Noteworthily,decomposition mechanism of sacrificial compound and the relative influence on the system of MICs after pre-metallation were initially revealed by in situ differential electrochemical mass spectrometry,offering in-depth insights for comprehending the function of cathode additives.In addition,this breakthrough has been successfully utilized in high performance lithium/potassium ion capacitors with Li_(2)C_(2)O_(4)/K_(2)C_(2)O_(4) as pre-metallation reagent,which will convincingly promote the commercialization of MICs.

关键词： Coupled interface Pre-metallation Metal oxalate Decomposition potential

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Natural Stibnite for Lithium‑/Sodium‑Ion Batteries:Carbon Dots Evoked High Initial Coulombic Efficiency

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Nano-Micro Letters 2022年第8期14卷 208-228页

作者： Yinger Xiang Laiqiang Xu Li Yang Yu Ye Zhaofei Ge Jiae Wu Wentao Deng guoqiang zou Hongshuai Hou Xiaobo Ji College of Chemistry and Chemical Engineering Central South UniversityChangsha 410083People’s Republic of China College of Science Hunan University of Technology and BusinessChangsha 410205People’s Republic of China School of Material Science and Engineering Zhengzhou UniversityZhengzhou 450001People’s Republic of China

The application of Sb_(2)S_(3)with marvelous theoretical capacity for alkali metal-ion batteries is seriously limited by its poor electrical conductivity and low initial coulombic efficiency(ICE).In this work,natural stibnite modified by carbon dots(Sb_(2)S_(3)@xCDs)is elaborately designed with high ICE.Greatly,chemical processes of local oxidation–partial reduction–deep coupling for stibnite reduction of CDs are clearly demonstrated,confirmed with in situ high-temperature X-ray diffraction.More impressively,the ICE for lithium-ion batteries(LIBs)is enhanced to 85%,through the effect of oxygen-rich carbon matrix on C–S bonds which inhibit the conversion of sulfur to sulfite,well supported by X-ray photoelectron spectroscopy characterization of solid electrolyte interphase layers helped with density functional theory calculations.Not than less,it is found that Sb–O–C bonds existed in the interface effectively promote the electronic conductivity and expedite ion transmission by reducing the bandgap and restraining the slip of the dislocation.As a result,the optimal sample delivers a tremendous reversible capacity of 660 mAh g^(−1)in LIBs at a high current rate of 5 A g^(−1).This work provides a new methodology for enhancing the electrochemical energy storage performance of metal sulfides,especially for improving the ICE.

关键词： Carbon dots Sb_(2)S_(3) Initial Coulombic efficiency Interfacial bond Anode

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Methods of improving the initial Coulombic efficiency and rate performance of both anode and cathode materials for sodium-ion batteries

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Chinese Chemical Letters 2022年第2期33卷 730-742页

作者： Nkongolo Tshamala Aristote Kangyu zou Andi Di Wentao Deng Baowei Wang Xinglan Deng Hongshuai Hou guoqiang zou Xiaobo Ji College of Chemistry and Chemical Engineering Central South UniversityChangsha 410083China Department of Materials and Environmental Chemistry Stockholm UniversityStockholm 10691Sweden

Sodium-ion batteries(SIBs) have gained more scientists’ interest, owing to some facts such as the natural abundance of Na, the similarities of physicochemical characteristics between Li and Na. The irreversible Na+ions consumption during the first cycle of charge/discharge process(due to the formation of the solid electrolyte interface(SEI) on the electrode surface and other irreversible reactions) is the factor that determines high performance SIBs and largely reduces the capacity of the full cell SIBs. Thus, the initial coulombic efficiency(ICE) of SIBs for both anode and cathode materials, is a key parameter for high performance SIBs, and the point is to increase the transport rate of the Na+ions. Therefore, developing SIBs with high ICE and rate performance becomes vital to boost the commercialization of SIBs. Here we provide a review on the methods to improve the ICE and the rate performance, by summarizing some methods of improving the ICE and rate performance of the anode and cathode materials for SIBs, and end by a conclusion with some perspectives and recommendations.

关键词： Initial coulombic efficiency Rate performance Sodium-ion batteries Anode materials Cathode materials

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Topological reorganization and functional alteration of distinct genomic components in gallbladder cancer

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Frontiers of Medicine 2024年第1期18卷 109-127页

作者： guoqiang Li Peng Pu Mengqiao Pan Xiaoling Weng Shimei Qiu Yiming Li Sk Jahir Abbas Lu zou Ke Liu Zheng Wang Ziyu Shao Lin Jiang Wenguang Wu Yun Liu Rong Shao Fatao Liu Yingbin Liu Department of Biliary-Pancreatic Surgery Renji HospitalSchool of MedicineShanghai Jiao Tong UniversityShanghai200127China State Key Laboratory of Oncogenes and Related Genes Shanghai Cancer InstituteShanghai200127China Shanghai Key Laboratory of Biliary Tract Disease Shanghai200082China Department of Health Science and Engineering University of Shanghai for Science and TechnologyShanghai200082China Shanghai Tenth People’s Hospital of Tongji University Shanghai200072China Department of General Surgery Xinhua HospitalSchool of MedicineShanghai Jiao Tong UniversityShanghai200082China Department of Pharmacology Shanghai Jiao Tong University School of MedicineShanghai200025China

Altered three-dimensional architecture of chromatin influences various genomic regulators and subsequent gene expression in human cancer.However,knowledge of the topological rearrangement of genomic hierarchical layers in cancer is largely limited.Here,by taking advantage of in situ Hi-C,RNA-sequencing,and chromatin immunoprecipitation sequencing(ChIP-seq),we investigated structural reorganization and functional changes in chromosomal compartments,topologically associated domains(TADs),and CCCTC binding factor(CTCF)-mediated loops in gallbladder cancer(GBC)tissues and cell lines.We observed that the chromosomal compartment A/B switch was correlated with CTCF binding levels and gene expression changes.Increased inter-TAD interactions with weaker TAD boundaries were identified in cancer cell lines relative to normal controls.Furthermore,the chromatin short loops and cancer unique loops associated with chromatin remodeling and epithelial–mesenchymal transition activation were enriched in cancer compared with their control counterparts.Cancer-specific enhancer–promoter loops,which contain multiple transcription factor binding motifs,acted as a central element to regulate aberrant gene expression.Depletion of individual enhancers in each loop anchor that connects with promoters led to the inhibition of their corresponding gene expressions.Collectively,our data offer the landscape of hierarchical layers of cancer genome and functional alterations that contribute to the development of GBC.

关键词： 3D genome cancer TADs loop gene regulation

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Aerophilic Triphase Interface Tuned by Carbon Dots Driving Durable and Flexible Rechargeable Zn‑Air Batteries

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Nano-Micro Letters 2023年第2期15卷 238-258页

作者： Kuixing Ding Yu Ye Jiugang Hu Liming Zhao Wei Jin Jia Luo Shan Cai Baicheng Weng guoqiang zou Hongshuai Hou Xiaobo Ji College of Chemistry and Chemical Engineering Central South UniversityChangsha 410083People’s Republic of China College of Standardization China Jiliang UniversityHangzhou 310018People’s Republic of China School of Environmental Science and Engineering Suzhou University of Science and TechnologySuzhou 215009People’s Republic of China

Efficient bifunctional catalysts for oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)are vital for rechargeable Zn-air batteries(ZABs).Herein,an oxygen-respirable sponge-like Co@C–O–Cs catalyst with oxygen-rich active sites was designed and constructed for both ORR and OER by a facile carbon dot-assisted strategy.The aerophilic triphase interface of Co@C–O–Cs cathode efficiently boosts oxygen diffusion and transfer.The theoretical calculations and experimental studies revealed that the Co–C–COC active sites can redistribute the local charge density and lower the reaction energy barrier.The Co@C–O–Cs catalyst displays superior bifunctional catalytic activities with a half-wave potential of 0.82 V for ORR and an ultralow overpotential of 294 mV at 10 mA cm^(−2) for OER.Moreover,it can drive the liquid ZABs with high peak power density(106.4 mW cm^(−2)),specific capacity(720.7 mAh g^(−1)),outstanding long-term cycle stability(over 750 cycles at 10 mA cm^(−2)),and exhibits excellent feasibility in flexible all-solid-state ZABs.These findings provide new insights into the rational design of efficient bifunctional oxygen catalysts in rechargeable metal-air batteries.

关键词： Aerophilic triphase interface Oxygen-rich active sites O2 diffusion Bifunctional oxygen catalyst Flexible rechargeable Zn-air battery

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K_(x)C_(y) phase induced expanded interlayer in ultra-thin carbon toward full potassium-ion capacitors

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Carbon Energy 2022年第6期4卷 1151-1168页

作者： Xinglan Deng Ye Tian Kangyu zou Jun Chen Xuhuan Xiao Shusheng Tao Zirui Song Wentao Deng Hongshuai Hou guoqiang zou Xiaobo Ji College of Chemistry and Chemical Engineering Central South UniversityChangshaHunanChina College of Materials Science and Engineering Zhengzhou UniversityZhengzhouChina

Carbonaceous materials have been regarded as highly promising anode candidates for potassium storage with their cost-effectiveness and environmental benignity.However,low specific capacity and difficulty in large-scale synthesis largely hinder their further development.Herein,a thermal-induced potassium–carbon alloy phase(K_(x)C_(y))with the expanded interlayer spacing strategy is first put forward.Through in situ high-temperature X-ray diffraction,a K_(2)C_(2) phase is evoked by thermal energy during the in-situ carbonization process of carbon quantum dots intermediate derived from potassium-containing precursors,whereas no lithium or sodium–carbon alloy phase is observed from lithium/sodium-containing precursors.The asobtained ultra-thin carbon nanosheets achieve adjustable layer spacing,preparation in bulk,delivering reversible potassium storage of 403.4 mAh g^(−1) at 100 mA g^(−1) and 161.2 mAh g^(−1) even at 5.0 A g^(−1),which is one of the most impressive K-storage performances reported so far with great potential application.Furthermore,the assembled potassium-ion hybrid capacitor by combining the impressive CFMs-900 anode with the three-dimensional framework-activated carbon delivers a high energy-power density of 251.7 Wh kg^(−1) at 250Wkg^(−1) with long-term stability.This study opens a scalable avenue to realize the expanded interlayer spacing,which can be extended to other multicarboxyl potassium salts and can provide approach for the design of high-performance carbon anode materials for potassium storage.

关键词： expanded interlayer K_(x)C_(y)phase potassium-ion capacitors themal-induced ultra-thin carbon

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High-yield red phosphorus sponge mediated robust lithium-sulfur battery

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Nano Research 2023年第6期16卷 8329-8337页

作者： Zheng Luo Shusheng Tao Ye Tian Hanyu Tu Laiqiang Xu Wentao Deng guoqiang zou Hongshuai Hou Xiaobo Ji State Key Laboratory of Powder Metallurgy College of Chemistry and Chemical EngineeringCentral South UniversityChangsha 410083China

Although lithium-sulfur(Li-S)batteries with high specific energy exhibit great potential for next-generation energy-storage systems,their practical applications are limited by the growth of Li dendrites and lithium polysulfides(LiPSs)shuttling.Herein,a highly porous red phosphorus sponge(HPPS)with well distributed pore structure was efficiently prepared via a facile and largescale hydrothermal process for polysulfides adsorption and dendrite suppression.As experimental demonstrated,the porous red phosphorus modified separator with increased active site greatly promotes the chemisorption of LiPSs to efficiently immobilize the active sulfur within the cathode section,while Li metal anode activated by Li_(3)P interlayer with abundant ionically conductive channels significantly eliminates the barrier for uniform Li^(+)permeation across the interlayer,contributing to the enhanced stability for both S cathode and Li anode.Mediated by the HPPS,long-term stability of 1,200 h with minor voltage hysteresis is achieved in symmetric cells with Li_(3)P@Li electrode while Li-S half-cell based on HPPS modified separator delivers an outperformed reversibility of 783.0 mAh·g^(−1)after 300 cycles as well as high-rate performance of 694.5 mAh·g^(−1)at 3 C,which further boosts the HPPS tuned full cells in practical S loading(3 mg·cm^(−2))and thin Li3P@Li electrode(100μm)with a capacity retention of 71.8%after 200 cycles at 0.5 C.This work provides a cost-effective and metal free mediator for simultaneously alleviating the fundamental issues of both S cathode and Li anode towards high energy density and long cycle life Li-S full batteries.

关键词： lithium-sulfur battery red phosphorus sponge separator chemical adsorption Li dendrite

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N,S-Doped Carbon Dots as Additive for Suppression of Zinc Dendrites in Alkaline Electrolyte

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中国化学:英文版 2023年第14期41卷 1697-1704页

作者： Shan Cai Ge Chang Jiugang Hu Jiae Wu Yuqing Luo guoqiang zou Hongshuai Hou Xiaobo Ji College of Chemistry and Chemical Engineering Central South UniversityChangshaHunan410083 China

The severe dendrite growth on zinc anode in alkaline electrolyte brings great challenge to the development of zinc-based batteries.It is a simple and effective strategy to inhibit zinc dendrite formation by introducing additives into the electrolyte.In this study,N,S-doped carbon dots(TU-CQDs)were synthesized and used as additives to regulate zinc deposition in a typical KOH electrolyte.The experimental and three-dimensional transient nucleation model disclosed that the special functional groups of carbon dots can change the electrode surface state and the coordination behaviors of zinc species in the electrolyte.Therefore,TU-CQDs can not only inhibit the hydrogen evolution reaction,but also achieve uniform zinc deposition.The in-situ synchrotron radiation X-ray imaging elucidated that TU-CQDs can effectively inhibit the dendrite growth and improve the reversibility of zinc plating/stripping process.This work provides a feasible route for regulating the reversibility of zinc metal anode in alkaline electrolyte.

关键词： Zinc anode Carbon dots Alkaline electrolyte Dendrite-free Electrode interfacesI Electrolyte additives

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