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Disordered carbon anodes for Na-ion batteries—quo vadis?

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Science China Chemistry 2021年第10期64卷 1679-1692页

作者： Fei Xie Zhen Xu Zhenyu Guo Yaxiang Lu Liquan Chen Maria-Magdalena Titirici Yong-Sheng Hu Key Laboratory for Renewable Energy Beijing Key Laboratory for New Energy Materials and DevicesBeijing National Laboratory for Condensed Matter PhysicsInstitute of PhysicsChinese Academy of SciencesBeijing 100190China Department of Chemical Engineering Imperial College LondonLondon SW72AZUK

Na-ion batteries(NIBs)are gradually attracting much attention as an alternative to lead-acid batteries and supplement to Li-ion batteries(LIBs)owing to the abundant na resources and excellent cost-effectiveness.Since the most commonly used graphite as an anode material in LIBs cannot be inherently used in NIBs,tremendous efforts have been made to advance the fundamental understanding and design of suitable anode materials for NIBs,including the improvement of na storage capacity and the study on na storage mechanisms.According to all these studies,disordered carbons are now the most promising anode candidates for NIBs.In this review,we discuss the current challenges and remaining problems to be solved in the area of disordered carbon anode materials for NIBs and provide future insights and research directions.

关键词： disordered carbon anode Na-ion batteries

Hard carbon derived from coconut shells,walnut shells,and corn silk biomass waste exhibiting high capacity for Na-ion batteries

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Journal of Energy Chemistry 2021年第7期30卷 207-218页

作者： Cristina Nita Biao Zhang Joseph Dentzer Camélia Matei Ghimbeu Universitéde Haute-Alsace Institut de Science des Matériaux de Mulhouse(IS2M)CNRS UMR 7361F-68100 MulhouseFrance Universitéde Strasbourg F-67081 StrasbourgFrance Center for Advanced Laser Technologies(CETAL) National Institute for LasersPlasma and Radiation PhysicsAtomistilor 409 bisRO-77125 MagureleRomania Department of Applied Physics The Hong Kong Polytechnic UniversityKowloonHong KongChina Réseau sur le Stockage Electrochimique de l’Energie(RS2E) CNRS FR345933 Rue Saint Leu80039 Amiens CedexFrance

In recent years,hard carbon materials have gained significant interest as anode materials for Na-ion batteries.Biomass waste is considered one of the most interesting,renewable,available,and cost-effective precursor to obtain hard carbon(HC);however,HC properties must be finely tuned to achieve performance comparable to those provided by Li-ion batteries.In this work,three biomass wastes(coconut shells,walnut shells,and corn silk) were evaluated as potential precursors for HC preparation involving a pyrolysis process and subsequent acid washing to remove the inorganic impurities.All obtained materials exhibited low and similar specific surface areas(ionalities.The walnut shell HC possessed a lower amount of inorganic impurities and oxygen-based functional groups compared to the coconut shell and corn silk HCs,leading to higher initial coulombic efficiency(iCE).The structural organization was higher in the case of the walnut shell HC,while the corn silk HC revealed a heterogeneous structure combining both highly disordered carbon and localized graphitized domains.All HCs delivered high initial reversible capacities between 293 and 315 mAh g^(-1) at 50 mA g^(-1) current rate,which remained rather stable during long-term cycling.The best capacity(293 mAh g^(-1) after 100 charge/discharge cycles) and highest capacity retention(93%) was achieved in walnut HCs in half-cells,which could be associated with its higher sp2 C content,better organized structure,and fewer impurities.An "adsorption-insertion" na storage mechanism is suggested based on several techniques.The walnut HCs exhibited an attractive energy density of 279 Wh/kg when tested in full cells.

关键词： Biomass Pyrolysis Hard carbon Anode Na-ion batteries Energy storage

Enhancing the cycling stability of Na-ion batteries by bonding MoS2 on assembled carbon-based materials

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nano Materials Science 2019年第4期1卷 310-317页

作者： Pin Song Jun Di Lixing Kang Manzhang Xu Bijun Tang Jun Xiong Jiewu Cui Qingsheng Zeng Jiadong Zhou Yongmin He Qundong Fu Juan Peng Shasha Guo Bo Lin Jingyu Zhang Peng Meng Zheng Liu School of Materials Science&Engineering Nanyang Technological UniversitySingapore639798Singapore Institute for Energy Research Jiangsu University301 Xuefu RoadZhenjiang212013China School of Materials Science and Engineering Hefei University of TechnologyHefei230009China Stage Key Laboratory of High-efficiency Coal Utilization and Green Chemical Engineering School of Chemistry and Chemical EngineeringNingxia UniversityYinchuan750021China

Room temperature Na-ion batteries(SIBs) show great potential for use as renewable energy storage systems.However, the large-scale application of SIBs has been hindered by the lack of an ideal SIBs anode material. We synthesized MoS2 on carbonized graphene-chitosan(G-C) using the hydrothermal method. The strong interaction between the MoS2 and the G-C greatly improved the electron transport rate and maintained the structural stability of the electrode, which lead to both an excellent rate capability and long cycle stability. The G-C monolith was proven to enhance the electrical conductivity of the composites and served as a matrix for uniformly dispersing active MoS2 nanosheets(NSs), as well as being a buffer material to adapt to changes in volume during the cycle.Serving as an anode material for SIBs, the MoS2-G-C electrode showed good cycling stability(527.3mAh g-1 at100 m A g-1 after 200 cycles), excellent rate capability, and a long cycle life(439.1 m Ah g-1 at 1 A g-1 after 200 cycles).

关键词： Na-ion batteries Carbon-based materials MoS2 Long cycle life

Metal–organic framework derived hierarchical porous TiO_2 nanopills as a super stable anode for Na-ion batteries

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Journal of Energy Chemistry 2017年第4期26卷 667-672页

作者： Huan Li Zhiguo Zhang Xiao Huang Tongbin Lan Mingdeng Wei Tingli Ma Graduate School of Life Science and Systems Engineering Kyushu Institute of Technology State Key Laboratory of Photocatalysis on Energy and Environment Fuzhou University School of Petroleum and Chemical Engineering Dalian University of Technology

Hierarchical porous Tionanopills were synthesized using a titanium metal-organic framework MIL-125（Ti） as precursor. The as-synthesized Tionanopills owned a large specific surface area of 102 m/g and unique porous structure. Furthermore, the obtained Tionanopills were applied as anode materials for Na-ion batteries for the first time. The as-synthesized Tionanopills achieved a high discharge capacity of 196.4 m Ah/g at a current density of 0.1 A/g. A discharge capacity of 115.9 m Ah/g was obtained at a high current density of 0.5 A/g and the capacity retention was remained as high as 90% even after 3000 cycles. The excellent electrochemical performance can be attributed to its unique hierarchical porous feature.

关键词： Hierarchical porous structure TiO2 nanopills Metal–organic framework Na-ion batteries

Designing a P2-type cathode material with Li in both na and transition metal layers for Na-ion batteries

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Chinese Physics B 2022年第9期31卷 157-162页

作者：高健翔孙凯郭浩李正耀王建林马小柏白雪东陈东风 China Institute of Atomic Energy Beijing 102413China State Key Laboratory for Surface Physics Institute of PhysicsChinese Academy of SciencesBeijing 100190China

P2-type layered oxides have been considered as promising cathode materials for Na-ion batteries,but the capac-ity decay resulting from the na+/vacancy ordering and phase transformation limits their future large-scale applica-tions.Herein,the impact of Li-doping in different layers on the structure and electrochemical performance of P2-type na_(0.7)Ni_(0.35)Mn_(0.65)O_(2) is investigated.It can be found that Li ions successfully enter both the na and transition metal layers.The strategy of Li-doping can improve the cycling stability and rate capability of P2-type layered oxides,which promotes the development of high-performance Na-ion batteries.

关键词： na_(0.7)Ni_(0.35)Mn_(0.65)O_(2) Li-doping P2-type cathode Na-ion batteries

Fast and highly reversible na^(+)intercalation/extraction in Zn/Mg dual-doped P2-na_(0.67)MnO_(2)cathode material for high-performance Na-ion batteries

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nano Research 2021年第10期14卷 3531-3537页

作者： Xiaoqin Huang Deli Li Haijian Huang Xiao Jiang Zeheng Yang Weixin Zhang School of Chemistry and Chemical Engineering Hefei University of TechnologyHefei 230009China Anhui Key Laboratory of Controllable Chemical Reaction&Material Chemical Engineering Hefei 230009China

P2-type layered na_(0.67)MnO_(2)has been considered to be a promising candidate cathode material for sodium ion batteries.Nevertheless,the undesired phase transitions during operation and the large na^(+)radius induced sluggish ion diffusion remain the stumbling blocks to realize its high performance.Herein,we propose a Zn/Mg co-doping strategy,which is proved to have bifunctional effects.First,relative to the pristine P2-na_(0.67)MnO_(2)and the single-ion(Zn/Mg)doped samples,the Zn/Mg dual-doped P2-na_(0.67)MnO_(2)demonstrates a lower Mn^(3+)/Mn^(4+)ratio and a higher lattice O content,which facilitate the structural stability of the cathode material.More intriguingly,the Zn/Mg co-doping gives rise to enlarged interplanar spacing,which provides spacious ion diffusion channels for fast na^(+)intercalation/extraction.As a result,the Zn/Mg dual-doped sample exhibits a high na^(+)diffusion coefficient and a solid-solution reaction during charge/discharge,with a cell volume change determined to be only 0.55%.Taking advantages of the above favorable features,the Zn/Mg dual-doped P2-na_(0.67)MnO_(2)demonstrates a high rate performance with 67.2 mAh·g^(-1)delivered at 10 C and a decent cycling stability with a capacity retention of 93.8%achieved at 1 C after 100 cycles.This work introduces the Zn/Mg co-doping strategy to simultaneously improve the cycling stability and rate capability of P2-na_(0.67)MnO_(2),which may offer a promising avenue for further performance enhancement of the layered Na-ion batteries cathode materials.

关键词： Na-ion batteries cathode materials co-doping na-ion diffusion structural stability

naV3O8 nanosheets@Polypyrrole Core-Shell Composites with Good Electrochemical Performance as Cathode for Na-ion batteries

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NaV3O8 Nanosheets@Polypyrrole Core-Shell Composites with Goo...

High temperature X-ray diffraction study of the formation of na_(2)Ti_(3)O_(7) from a mixture of sodium carbonate and titanium oxide

2015年第十四届全国应用化学年会

作者： KANG Hongyan LIU Yongchang WANG Yijing JIAO Lifang Key Laboratory of Advanced Energy Materials Chemistry (MOE) Collaborative Innovation Center of Chemical Science and Engineering (Tianjin) Nankai University

Novel naVO nanosheets@polypyrrole core-shell composites have been successfully prepared for the first time via a chemical oxidative polymerization method. Based on the morphological and microstructural characterization, it was found that the polypyrrole(PPy) was uniformly wrapped on the surfaces of the naVO nanosheets. When used as cathode for Na-ion batteries, the as-synthesized naVO@10% PPy composite shows significantly improved cycling performance(with a discharge capacity of 99 m Ah g after 60 cycles at 80 m A g) and better rate capacity(with a discharge capacity of 63 m Ah g at a high current density of 640 m A g) than pristine naVO nanosheets. The greatly enhanced performance benefits from the unique core-shell structure, where the PPy coating not only prevents the pulverization and aggregation of the lamellar naVO nanosheets during cycling, which can improve the cycling stability, but also enhances the electrical conductivity of the composite, which can facilitate na+ ion diffusion.

关键词： naV3O8 nanosheets Polypyrrole Core-shell Na-ion batteries

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Journal of Energy Chemistry 2022年第2期31卷 210-218页

作者： Caroline Piffet Bénédicte Vertruyen Frédéric Hatert Rudi Cloots Frédéric Boschini Abdelfattah Mahmoud GREENMAT CESAM Research UnitChemistry DepartmentUniversity of Liège4000 LiègeBelgium Laboratory of Mineralogy Geology Research UnitUniversity of Liège4000 LiègeBelgium

na2Ti3O7 has attracted much attention in the field of anode materials for Na-ion batteries thanks to its non-toxicity and very low working potential of 0.3 V vs na0/na+.Building a clearer picture of its formation from cheap na_(2)CO_(3) and TiO_(2) starting materials is therefore of obvious interest.Here,we report new insights from an in-situ high temperature X-ray diffraction study conducted from room temperature to 800°C,complemented by ex-situ characterizations.We were thereby able to position the previously reported na_(4)Ti_(5)O_(12) and na_(2)Ti_(6)O_(13) intermediate phases in a reaction scheme involving three successive steps and temperature ranges.Shifts and/or broadening of a subset of the na_(2)Ti_(6)O_(13) reflections suggested a combination of intra-layer disorder with the well-established ordering of successive layers.This in-situ study was carried out on reproducible mixtures of na_(2)CO_(3) and TiO_(2) in 1:3 molar ratio prepared by spraydrying of mixed aqueous suspensions.Single-phase na_(2)Ti_(3)O_(7) was obtained after only 8 h at 800°C in air,instead of a minimum of 20 h for a conventional solid-state route using the same precursors.Microstructure analysis revealed~15 mm diameter granules made up from rectangular rods of a fewmm length presenting electrochemical properties in line with expectations.In the absence of grinding or formation of intimate composites with conductive carbon,the specific capacity of 137 m Ah/g at C/5 decreased at higher rates.

关键词： Formation mechanism High temperature XRD na_(2)Ti_(3)O_(7) Spray-drying synthesis Na-ion batteries

New insights into carbon-based and MXene anodes for na and K-ion storage: A review

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Journal of Energy Chemistry 2021年第11期30卷 660-691,I0016页

作者： Zhensheng Hong Hajar Maleki Tim Ludwig Yichao Zhen Michael Wilhelm Damin Lee Kwang-Ho Kim Sanjay Mathur Fujian Provincial Key Laboratory of Quantum Manipulation and New Energy Materials College of Physics and EnergyFujian Normal UniversityFuzhou 350117FujianChina Institute of Inorganic Chemistry University of CologneGreinstr.650939 CologneGermany Fujian Provincial Collaborative Innovation Center for Advanced High-Field Superconducting Materials and Engineering Fuzhou 350117FujianChina Global Frontiers of Hybrid Interfacial Materials Pusan National UniversitySouth Korea

Na-ion batteries and K-ion batteries are promising alternatives to vastly used lithium-ion batteries mainly due to the larger natural abundance of sodium and potassium resources. Carbon-based and MXene materials have received increasing attention due to their unique layered structure to accommodate the larger sodium and potassium ions. It’s proposed that ionic size disparity (K^(+): 1.38 Å;na^(+): 0.97 Å;Li^(+): 0.76 Å) leads to sluggish intercalation and extraction kinetics in larger alkali metal ions (AMIs). Nevertheless, the electrochemical inactivity of sodium intercalation in graphite suggests that different chemical properties of AMs and their interactions with carbon host and electrolytes is crucial for interfacial instability and irreversible capacity loss. Structural modifications by expanding interlayer spacing and defect engineering enable reduced diffusion barriers and enhanced insertion of sodium or potassium, but it blurs the electrochemical performance between battery and capacitor. This review provides insight into 2D carbon materials and their architectures for na and K-ion batteries through an in-depth analysis of structure–property interdependence and different electrochemical mechanisms supported by both experimental and theoretical data to discuss the promises and challenges of post-lithium batteries. Finally, the perspectives and potential directions regarding material design concepts for 2D carbon-based nanomaterials and MXene phases for metal-ion storage are proposed.

关键词： Na-ion batteries K-ion batteries Anode Carbon materials Structure design