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Rational design of carbon skeleton interfaces for highly reversible sodium metal battery anodes

Journal of energy Chemistry 2024年第5期92卷 404-413页

作者： Fenqiang Luo Taiyu Lyu Jie Liu Peiwan Guo Junkai Chen Xiaoshan Feng Dechao Wang Zhifeng Zheng Key Laboratory of Advanced energy storage Technology Fujian Province UniversityFujian Provincial Industry Technologies Development Base for New EnergyCollaborative Innovation Platform for Advanced Electrochemical Energy Storage TechnologyNational User-Side Energy Storage Innovation Research and Development CenterTan Kah Kee Innovation Laboratory(IKKEM)College of EnergyXiamen UniversityXiamen 361102FujianChina College of Environmental Science and Engineering Fujian Normal UniversityFuzhou 350007FujianChina Department of Chemical Engineering Tsinghua UniversityBeijing 100084China

Sodium metal batteries(SMBs)have attracted increasing attention over time due to their abundance of sodium resources and low cost.However,the widespread application of SMBs as a viable technology remains a great challenge,such as uneven metallic deposition and dendrite formation during cycling.Carbon skeletons as sodiophilic hosts can alleviate the dendrite formation during the plating/stripping.For the carbon skeleton,how to rationalize the design sodiophilic interfaces between the sodium metal and carbon species remains key to developing desirable Na anodes.Herein,we fabricated four kinds of structural features for carbon skeletons using conventional calcination and flash Joule heating.The roles of conductivity,defects,oxygen content,and the distribution of graphite for the deposition of metallic sodium were discussed in detail.Based on interface engineering,the J1600 electrode,which has abundant Na-C species on its surface,showed the highest sodiophilic.There are uniform and rich F-Na species distributed in the inner solid electrolyte interface layer.This study investigated the different Na-deposition behavior in carbon hosts with distinct graphitic arrangements to pave the way for designing and optimizing advanced electrode materials.

关键词： Carbon skeleton Graphited structure Deposition mechanism Sodiummetal batteries

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The initial stages of Li_(2)O_(2) formation during oxygen reduction reaction in Li-O_(2) batteries:The significance of Li_(2)O_(2) in charge-transfer reactions within devices

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Journal of energy Chemistry 2024年第1期88卷 223-231,I0006页

作者： Daniela M.Josepetti Bianca P.Sousa Simone A.J.Rodrigues Renato G.Freitas Gustavo Doubek Advanced energy storage division LABCenter for Innovation on New EnergiesSchool of Chemical EngineeringUniversity of CampinasAv Albert Einstein 50013083-852CampinasSPBrazil Institute of Physics&Department of Chemistry Laboratory of Computational MaterialsFederal University of Mato Grosso78060-900CuiabáMTBrazil

Lithium-oxygen batteries are a promising technology because they can greatly surpass the energy density of lithium-ion batteries.However,this theoretical characteristic has not yet been converted into a real device with high cyclability.Problems with air contamination,metallic lithium reactivity,and complex discharge and charge reactions are the main issues for this technology.A fast and reversible oxygen reduction reaction(ORR)is crucial for good performance of secondary batteries',but the partial knowledge of its mechanisms,especially when devices are concerned,hinders further development.From this perspective,the present work uses operando Raman experiments and electrochemical impedance spectroscopy(EIS)to assess the first stages of the discharge processes in porous carbon electrodes,following their changes cycle by cycle at initial operation.A growth kinetic formation of the discharge product signal(Li_(2)O_(2))was observed with operando Raman,indicating a first-order reaction and enabling an analysis by a microkinetic model.The solution mechanism in the evaluated system was ascribed for an equivalent circuit with three time constants.While the time constant for the anode interface reveals to remain relatively constant after the first discharge,its surface seemed to be more non-uniform.The model indicated that the reaction occurs at the Li_(2)O_(2) surface,decreasing the associated resistance during the initial discharge phase.Furthermore,the growth of Li_(2)O_(2) forms a hetero-phase between Li_(2)O_(2)/electrolyte,while creating a more compact and homogeneous on the Li_(2)O_(2)/cathode surface.The methodology here described thus offers a way of directly probing changes in surface chemistry evolution during cycling from a device through EIS analysis.

关键词： Li-O_(2)battery Operando Raman analysis Equivalent circuit modeling Time-constant distribution

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Exploring battery material failure mechanisms through synchrotron X-ray characterization techniques

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Journal of energy Chemistry 2024年第7期94卷 128-135页

作者： Lingzhe Fang Xiaozhao Liu Tao Li Department of Chemistry and Biochemistry Northern Ilinois UniversityDeKalbIL 60115USA X-ray Science division and Joint Center forenergy storage Research Argonne National LaboratoryLemontIL6439UA

Rechargeable battery cycling performance and related safety have been persistent concerns.It is crucial to decipher the capacity fading induced by electrode material failure via a range of techniques.Among these,synchrotron-based X-ray techniques with high flux and brightness play a key role in understanding degradation mechanisms.In this comprehensive review,we summarize recent advancements in degra-dation modes and mechanisms that were revealed by synchrotron X-ray methodologies.Subsequently,an overview of X-ray absorption spectroscopy and X-ray scattering techniques is introduced for charac-terizing failure phenomena at local coordination atomic environment and long-range order crystal struc-ture scale,respectively.At last,we envision the future of exploring material failure mechanism.

关键词： Battery failure Synchrotron-based techniques X-ray scattering X-ray absorption spectroscopy

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Roadmap for rechargeable batteries:present and beyond

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Science China Chemistry 2024年第1期67卷 13-42页

作者： Sen Xin Xu Zhang Lin Wang Haijun Yu Xin Chang Yu-Ming Zhao Qinghai Meng Pan Xu Chen-Zi Zhao Jiahang Chen Huichao Lu Xirui Kong Jiulin Wang Kai Chen Gang Huang Xinbo Zhang Yu Su Yao Xiao Shu-Lei Chou Shilin Zhang Zaiping Guo Aobing Du Guanglei Cui Gaojing Yang Qing Zhao Liubing Dong Dong Zhou Feiyu Kang Hu Hong Chunyi Zhi Zhizhang Yuan Xianfeng Li Yifei Mo Yizhou Zhu Dongfang Yu Xincheng Lei Jianxiong Zhao Jiayi Wang Dong Su Yu-Guo Guo Qiang Zhang Jun Chen Li-Jun Wan CAS Key Laboratory of Molecular Nanostructure and Nanotechnology CAS Research/Education Center for Excellence in Molecular SciencesBeijing National Laboratory for Molecular Sciences(BNLMS)Institute of ChemistryChinese Academy of Sciences(CAS)Beijing 100190China University of Chinese Academy of Sciences.Beijing 100049 China Institute of Advanced Battery Materials and Devices Faculty of Materials and ManufacturingBeijing University of TechnologyBeijing 100124China Key Laboratory of Advanced Functional Materials Ministry of EducationBeijing University of TechnologyBeijing 100124China Beijing Key Laboratory of Green Chemical Reaction Engineering and Technology Department of Chemical EngineeringTsinghua UniversityBeijing 100084China State Key Laboratory of Chemistry and Utilization of Carbon-Based energy resources College of ChemistryXinjiang UniversityUrumqi 830046China Department of Chemical Engineering Shanghai Jiao Tong UniversityShanghai 200240China State Key Laboratory of Rare Earth Resource Utilization Changchun Institute of Applied ChemistryChangchun 130022China Institute for Carbon Neutralization College of Chemistry and Materials EngineeringWenzhou UniversityWenzhou 325035China School of Chemical Engineering and Advanced Materials The University of AdelaideAdelaide 5000Australia Qingdao Industrial energy storage Research Institute Qingdao Institute of Bioenergy and Bioprocess TechnologyChinese Academy of SciencesQingdao 266101China Frontiers Science Center for New Organic Matter Key Laboratory of Advanced Energy Materials Chemistry(Ministry of Education)College of ChemistryNankai UniversityTianjin 300071China College of Chemistry and Materials Science Jinan UniversityGuangzhou 511443China Tsinghua Shenzhen International Graduate School Tsinghua UniversityShenzhen 518055China Department of Materials Science and Engineering City University of Hong KongHong Kong 999077China division of energy storage Dalian National Laboratory for Clean Energy(DNL)Dalian Institute of Chem

Rechargeable batteries currently hold the largest share of the electrochemical energy storage market,and they play a major role in the sustainable energy transition and industrial decarbonization to respond to global climate change.Due to the increased popularity of consumer electronics and electric vehicles,lithium-ion batteries have quickly become the most successful rechargeable batteries in the past three decades,yet growing demands in diversified application scenarios call for new types of rechargeable batteries.Tremendous efforts are made to developing the next-generation post-Li-ion rechargeable batteries,which include,but are not limited to solid-state batteries,lithium–sulfur batteries,sodium-/potassium-ion batteries,organic batteries,magnesium-/zinc-ion batteries,aqueous batteries and flow batteries.Despite the great achievements,challenges persist in precise understandings about the electrochemical reaction and charge transfer process,and optimal design of key materials and interfaces in a battery.This roadmap tends to provide an overview about the current research progress,key challenges and future prospects of various types of rechargeable batteries.New computational methods for materials development,and characterization techniques will also be discussed as they play an important role in battery research.

关键词： energy storage rechargeable batteries battery materials electrochemistry

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Designing ABC-6 family small pore zeolites by epitaxial growth approach

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Chinese Chemical Letters 2024年第3期35卷 508-512页

作者： Xiaohui Cui Jia Lv Chao Ma Yujiao Wang Zhenghao Jia Daliang Zhang Peng Guo Zhongmin Liu Henan Institute of Advanced Technology Zhengzhou UniversityZhengzhou 450001China National Engineering Research Center of Lower-Carbon Catalysis Technology Dalian Institute of Chemical PhysicsChinese Academy of SciencesDalian 116023China Multi-scale Porous Materials Center Institute of Advanced Interdisciplinary Studies&School of Chemistry EngineeringChongqing UniversityChongqing 400044China University of Chinese Academy of Sciences Beijing 100049China division of energy Research resources Dalian Institute of Chemical PhysicsChinese Academy of SciencesDalian 116023China

Aluminosilicate small pore zeolites belonging to ABC-6 family play crucially important roles in the high methanol conversion with the high selectivity of light olefins,gas separation and storage,and selective catalytic reduction of NO_(x).In this work,we report a general method,called the epitaxial growth approach,for designing ABC-6 family small pore zeolites.It is mainly realized through the epitaxial growth on the nonporous SOD-type zeolite in the presence of inorganic cations(Na^(+)and K^(+))combined with a variety of organic structure directing agents(OSDAs).In this case,a series of ABC-6 family small pore zeolites such as ERI-,SWY-,LEV-,AFX-,and PTT-type zeolites have been successfully synthesized within a few hours.More importantly,the advanced focused ion beam(FIB)and the low-dose high-resolution transmission electron microscopy(HRTEM)imaging technique have been utilized for unraveling the zeolite heterojunction at the atomic level during the epitaxial growth process.It turns out(222)crystallographic planes of the SOD-type zeolite substrate provide unique pre-building units,which facilitate the growth of targeted ABC-6 family small pore zeolites along its c-axis.Moreover,the morphologies of ERI-type zeolite can also be tuned through the epitaxial growth approach,achieving a longer lifetime in the methanol conversion.

关键词： Zeolite structure Zeolite synthesis Structural characterizations Low-dose imaging Focused ion beam

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Reinforcing effects of polypropylene on energy absorption and fracturing of cement-based tailings backfill under impact loading

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International Journal of Minerals,Metallurgy and Materials 2024年第4期31卷 650-664页

作者： Jiajian Li Shuai Cao Erol Yilmaz School of Civil and resources Engineering University of Science and Technology BeijingBeijing 100083China State Key Laboratory of High-Efficient Mining and Safety of Metal Mines of Ministry of Education University of Science and Technology BeijingBeijing 100083China Department of Civil Engineering Geotechnical DivisionRecep Tayyip Erdogan UniversityFenerRize TR53100Turkey

Polypropylene(PP)fiber-reinforced cement-based tailings backfill(FRCTB)is a green compound material with superior crack resistance and has good prospects for application in underground mining.However,FRCTB exhibits susceptibility to dynamic events,such as impact ground pressure and blast vibrations.This paper investigates the energy and crack distribution behavior of FRCTB under dynamic impact,considering the height/diameter(H/D)effect.Split Hopkinson pressure bar,industrial computed tomography scan,and scanning electron microscopy(SEM)experiments were carried out on six types of FRCTB.Laboratory outcomes confirmed fiber aggregation at the bottom of specimens.When H/D was less than 0.8,the proportion of PP fibers distributed along theθangle direction of80°-90°increased.For the total energy,all samples presented similar energy absorption,reflectance,and transmittance.However,a rise in H/D may cause a rise in the energy absorption rate of FRCTB during the peak phase.A positive correlation existed between the average strain rate and absorbed energy per unit volume.The increase in H/D resulted in a decreased crack volume fraction of FRCTB.When the H/D was greater than or equal to 0.7,the maximum crack volume fraction of FRCTB was observed close to the incidence plane.Radial cracks were present only in the FRCTB with an H/D ratio of 0.5.Samples with H/D ratios of 0.5 and 0.6 showed similar distributions of weakly and heavily damaged areas.PP fibers can limit the emergence and expansion of cracks by influencing their path.SEM observations revealed considerable differences in the bonding strengths between fibers and the FRCTB.Fibers that adhered particularly well to the substrate were attracted together with the hydration products adhering to surfaces.These results show that FRCTB is promising as a sustainable and green backfill for determining the design properties of mining with backfill.

关键词： cement-based tailings fiber-reinforced backfills fracture energy absorption impact loading

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The influence of compact and ordered carbon coating on solid-state behaviors of silicon during electrochemical processes

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Carbon energy 2020年第1期2卷 143-150页

作者： Shuo Zhou Chen Fang Xiangyun Song Gao Liu energy storage and distributed resources division Lawrence Berkeley National LaboratoryBerkeleyCalifornia

To address the issues of large volume change and low conductivity of silicon(Si)materials,carbon coatings have been widely employed as surface protection agent and conductive medium to encapsulate the Si materials,which can improve the electrochemical performance of Si-based electrodes.There has been a strong demand to gain a deeper understanding of the impact of efficient carbon coating over the lithiation and delithiation process of Si materials.Here,we report the first observation of the extended two-phase transformation of carbon-coated Si nanoparticles(Si/C)during electrochemical processes.The Si/C nanoparticles were prepared by sintering Si nanoparticles with polyvinylidene chloride precursor.The Si/C electrode underwent a two-phase transition during the first 20 cycles at 0.2 C,but started to engage in solid solution reaction when the ordered compact carbon coating began to crack.Under higher current density conditions,the electrode was also found to be involved in solid solution reaction,which,however,was due to the overwhelming demand of kinetic property rather than the breaking of the carbon coating.In comparison,the Si/C composites prepared with sucrose possessed more disordered and porous carbon structures,and presented solid solution reaction throughout the entire cycling process.

关键词： anode carbon coating electrochemical behavior lithium-ion batteries silicon

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Precisely quantifying bulk transition metal valence evolution in conventional battery electrode by inverse partial fluorescence yield

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Journal of energy Chemistry 2022年第6期31卷 363-368,I0010页

作者： Kehua Dai Weiwei Shao Beibei Zhao Wenjuan Zhang Yan Feng Wenfeng Mao Guo Ai Gao Liu Jing Mao Wanli Yang College of Chemistry Tianjin Normal UniversityTianjin 300387China Advanced Light Source Lawrence Berkeley National LaboratoryBerkeleyCA 94720United States College of Physics and Materials Science Tianjin Normal UniversityTianjin 300387China energy storage and distributed resources division Energy Technologies AreaLawrence Berkeley National LaboratoryBerkeleyCA 94720United States School of Materials Science and Engineering Zhengzhou UniversityZhengzhou 450001HenanChina

Precisely quantifying transition metal(TM) redox in bulk is a key to understand the fundamental of optimizing cathode materials in secondary batteries. At present, the commonly used methods to probe TM redox are hard X-ray absorption spectroscopy(hXAS) and soft X-ray absorption spectroscopy(sXAS).However, they are both facing challenges to precisely quantify the valence states of some transition metals such as Mn. In this paper, Mn-L iPFY(inverse partial fluorescence yield) spectra extracted from Mn-L m RIXS(mapping of resonant inelastic X-ray scattering) is adopted to quantify Mn valence states. Mn-L i PFY spectra has been considered as a bulk-sensitive, non-distorted probe of TM valence states.However, the exact precision of this method is still unclear in quantifying practical battery electrodes.Herein, a series of LiMn_(2)O_(4) electrodes with different charge and discharge states are prepared. Based on their electrochemical capacity(generally considered to be very precise), the precision of Mn iPFY in quantifying bulk Mn valence state is confirmed, and the error range is unraveled. Mn-L mRIXS iPFY thus is identified as one of the best methods to quantify the bulk Mn valence state comparing with hXAS and sXAS.

关键词： Cathode materials Valence state of transition metals Lithium-ion batteries Mapping of resonant inelastic X-ray scattering Inverse partial fluorescence yield

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Improving ionic conductivity of von-Alpen-type NASICON ceramic electrolytes via magnesium doping

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Journal of Advanced Ceramics 2023年第5期12卷 1058-1066页

作者： Il-Seop Jang Wooseok Go Bo-Ye Song Hayoung Park Yun Chan Kang Jinyoung Chun Emerging Materials R&D division Korea Institute of Ceramic Engineering and Technology(KICET)Jinju 52851Republic of Korea Department of Materials Science and Engineering Korea UniversitySeoul 02841Republic of Korea energy storage and Distribution resources division Lawrence Berkeley National LaboratoryBerkeley 94720USA

NASICON (sodium (Na) superionic conductor) compounds have attracted considerable attention as promising solid electrolyte materials for advanced Na-based batteries. In this study, we investigated the improvement in ionic conductivities of von-Alpen-type NASICON (vA-NASICON) ceramic electrolytes by introducing a magnesium ion (Mg^(2+)) as a heterogeneous element. The optimal Mg-doped vA-NASICON exhibited a high ionic conductivity of 3.64×10^(−3) S·cm^(−1), which was almost 80% higher than that of un-doped vA-NASICON. The changes in physicochemical properties of the vA-NASICONs through the Mg introduction were systematically analyzed, and their effects on the ionic conductivities of the vA-NASICON were studied in detail. When the optimal ratio of Mg^(2+) was used in a synthetic process, the relative density (96.6%) and grain boundary ionic conductivity (σgb) were maximized, which improved the total ionic conductivity (σt) of the vA-NASICON. However, when Mg^(2+) was introduced in excess, the ionic conductivity decreased because of the formation of an undesired sodium magnesium phosphate (NaxMgyPO_(4)) secondary phase. The results of this study are expected to be effectively applied in the development of advanced sodium-based solid electrolytes with high ionic conductivities.

关键词： NASICON solid electrolyte von-Alpen-type magnesium(Mg)doping ionic conductivity

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N-doped interconnected carbon aerogels as an efficient SeS2 host for long life Na-SeS2 batteries

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Nano Research 2020年第4期13卷 967-974页

作者： Yurui Deng Lunlun Gong Hoda Ahmed Yuelei Pan Xudong Cheng Siyu Zhu Heping Zhang State Key Laboratory of Fire Science University of Science and Technology of ChinaHefei 230026China energy storage and distributed resources division Lawrence Berkeley National LaboratoryBerkeleyCA 94720USA

Selenium sulfide(SeS2)cathodes have attracted much concern as an optimized choice comparing to sulfur and selenium for lithium and sodium storage.However,it also suffers from poor cycling stability due to the dissolution of reaction intermediate products.In this study,N-doped Interconnected carbon aerogels was applied as an efficient SeS2 host by infiltrating selenium sulfide into its microporous structure(denoted as SeS2@NCAs),which could effectively accommodate the volume change of SeS2 during cycling and alleviate the dissolution of reaction intermediate products.Therefore,as for Na storage,the SeS2@NCAs cathode delivers a superior long-term cycling performance of 536 mA·h·g^-1 at a current density of 0.5 A·g^-1 after 1,000 cycles with only 0.04%capacity decline per cycle and a high rate performance(524 mA·h·g^-1 at 2 A·g^-1 and 745 mA·h·g^-1 at 0.1 A·g^-1 retained),indicating the remarkable cycling stability of SeS2@NCAs cathodes.

关键词： sodium-SeS2 batteries N-doped interconnected carbon aerogels superior long-term cycling performance

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