SCIENCE CHINA Materials, Volume 64 , Issue 5 : 1071-1086(2021) https://doi.org/10.1007/s40843-020-1532-0

Carbon-emcoating architecture boosts lithium storage of Nb2O5

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  • ReceivedJul 2, 2020
  • AcceptedSep 30, 2020
  • PublishedDec 24, 2020



The authors thank Prof. Dr. Zhicheng Zhong and Dr. Ri He from Ningbo Institute of Materials Technology & Engineering, CAS for scientific discussions about phase conversion mechanism. The help from Prof. Dr. Qiuju Zhang in Ningbo Institute of Materials Technology & Engineering, CAS, in structure modelling of Nb2O5 is appreciated. The authors also thank Prof. Dr. Wei Cao from Ningbo University for scientific discussions about the emcoating structure interpretation. This research was supported by the National Key R&D Program of China (2016YFB0100100), the National Natural Science Foundation of China (51702335 and 21773279), Zhejiang Non-profit Technology Applied Research Program (LGG19B010001), Ningbo Municipal Natural Science Foundation (2018A610084), the CAS-EU S&T Cooperation Partner Program (174433KYSB20150013), and the Key Laboratory of Bio-based Polymeric Materials of Zhejiang Province. Cheng YJ acknowledges the funding from Marie Sklodowska-Curie Fellowship in EU. Peter G. Bruce is indebted to the Engineering and Physical Sciences Research Council (EPSRC), including the SUPERGEN Energy Storage Hub (EP/L019469/1), Enabling Next Generation Lithium Batteries (EP/M009521/1), Henry Royce Institute for Advanced Materials (EP/R00661X/1, EP/S019367/1, EP/R010145/1) and the Faraday Institution All-Solid-State Batteries with Li and Na Anodes (FIRG007, FIRG008) for financial support.

Interest statement

The authors declare no conflict of interest.

Contributions statement

Cheng YJ conceived the idea. Ji Q and Wang X designed the experiments and contributed to data analysis. Zuo X carried out the TEM and Raman tests. Xu Z operated the theoretical calculation and GITT measurements. Gao X designed and performed the DEMS test. The paper was written by Ji Q with support from Cheng YJ. All authors helped in the revision of the paper and contributed to the general discussion.

Author information

Qing Ji received his BE degree from Beijing University of Chemical Technology (2012). He is a PhD candidate at the University of Nottingham Ningbo China, jointly with Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences (CAS). His research interest focuses on negative electrodes for lithium-ion batteries.

Ya-Jun Cheng is currently a professor at Ningbo Institute of Materials Technology and Engineering, CAS. He received his BSc degree from Peking University, China, followed by a Master degree from the University of Siegen, Germany, and completed PhD at Max-Planck Institute for Polymer Research in Mainz, Germany. His research interests focus on polymer/inorganic nanohybrids for advanced battery applications.

Binjie Hu received her PhD degree at the University of Newcastle, UK. Then she worked as research fellow and teaching fellow at the University of Birmingham, UK (2000–2006) and University of Cambridge, UK (2007-2010), respectively. She is currently an associate professor of the University of Nottingham Ningbo China. Her research areas include micro/nano-materials engineering and green engineering.

Yonggao Xia received his PhD in energy and materials science from Saga University, Japan (2008). He is currently a professor at Ningbo Institute of Materials Technology and Engineering, CAS, heading the research group of Novel Organic Electrolyte and Corresponding Devices. His research focuses on advanced materials and technologies for lithium-ion batteries.

Supplementary data

Supplementary information

Supporting data are available in the online version of the paper.


[1] Ohzuku T, Ueda A, Yamamoto N. Zero-strain insertion material of Li[Li1/3Ti5/3]O4 for rechargeable lithium cells. J Electrochem Soc, 1995, 1421431-1435 CrossRef ADS Google Scholar

[2] Poizot P, Laruelle S, Grugeon S, et al. Nano-sized transition-metal oxides as negative-electrode materials for lithium-ion batteries. Nature, 2000, 407496-499 CrossRef ADS Google Scholar

[3] Hu YS, Kienle L, Guo YG, et al. High lithium electroactivity of nanometer-sized rutile TiO2. Adv Mater, 2006, 181421-1426 CrossRef Google Scholar

[4] Zhao Y, Wang LP, Sougrati MT, et al. A review on design strategies for carbon based metal oxides and sulfides nanocomposites for high performance Li and Na ion battery anodes. Adv Energy Mater, 2017, 71601424 CrossRef Google Scholar

[5] Kim KT, Yu CY, Yoon CS, et al. Carbon-coated Li4Ti5O12 nanowires showing high rate capability as an anode material for rechargeable sodium batteries. Nano Energy, 2015, 12725-734 CrossRef Google Scholar

[6] Li N, Zhou G, Li F, et al. A self-standing and flexible electrode of Li4Ti5O12 nanosheets with a N-doped carbon coating for high rate lithium ion batteries. Adv Funct Mater, 2013, 235429-5435 CrossRef Google Scholar

[7] Zhu GN, Liu HJ, Zhuang JH, et al. Carbon-coated nano-sized Li4Ti5O12 nanoporous micro-sphere as anode material for high-rate lithium-ion batteries. Energy Environ Sci, 2011, 44016-4022 CrossRef Google Scholar

[8] Ko YN, Park SB, Jung KY, et al. One-pot facile synthesis of ant-cave-structured metal oxide–carbon microballs by continuous process for use as anode materials in Li-ion batteries. Nano Lett, 2013, 135462-5466 CrossRef ADS Google Scholar

[9] Li W, Wang F, Feng S, et al. Sol–gel design strategy for ultradispersed TiO2 nanoparticles on graphene for high-performance lithium ion batteries. J Am Chem Soc, 2013, 13518300-18303 CrossRef Google Scholar

[10] Liu Y, Zhang N, Jiao L, et al. Ultrasmall Sn nanoparticles embedded in carbon as high-performance anode for sodium-ion batteries. Adv Funct Mater, 2015, 25214-220 CrossRef Google Scholar

[11] Chen Z, Dahn JR. Reducing carbon in LiFePO4/C composite electrodes to maximize specific energy, volumetric energy, and tap density. J Electrochem Soc, 2002, 149A1184 CrossRef ADS Google Scholar

[12] Ko YN, Kang YC. Co9S8–carbon composite as anode materials with improved Na-storage performance. Carbon, 2015, 9485-90 CrossRef Google Scholar

[13] Lu Y, Zhang N, Zhao Q, et al. Micro-nanostructured CuO/C spheres as high-performance anode materials for Na-ion batteries. Nanoscale, 2015, 72770-2776 CrossRef ADS Google Scholar

[14] Zhang N, Han X, Liu Y, et al. 3D porous γ-Fe2O3@C nanocomposite as high-performance anode material of Na-ion batteries. Adv Energy Mater, 2015, 51401123 CrossRef Google Scholar

[15] Xiao Y, Wang X, Xia Y, et al. Green facile scalable synthesis of titania/carbon nanocomposites: new use of old dental resins. ACS Appl Mater Interfaces, 2014, 618461-18468 CrossRef Google Scholar

[16] Wang X, Meng JQ, Wang M, et al. Facile scalable synthesis of TiO2/carbon nanohybrids with ultrasmall TiO2 nanoparticles homogeneously embedded in carbon matrix. ACS Appl Mater Interfaces, 2015, 724247-24255 CrossRef Google Scholar

[17] Zheng L, Wang X, Xia Y, et al. Scalable in situ synthesis of Li4Ti5O12/carbon nanohybrid with supersmall Li4Ti5O12 nanoparticles homogeneously embedded in carbon matrix. ACS Appl Mater Interfaces, 2018, 102591-2602 CrossRef Google Scholar

[18] Ji Q, Gao X, Zhang Q, et al. Dental resin monomer enables unique NbO2/carbon lithium-ion battery negative electrode with exceptional performance. Adv Funct Mater, 2019, 291904961 CrossRef Google Scholar

[19] Wang X, Ma L, Ji Q, et al. MnO/metal/carbon nanohybrid lithium-ion battery anode with enhanced electrochemical performance: universal facile scalable synthesis and fundamental understanding. Adv Mater Interfaces, 2019, 61900335 CrossRef Google Scholar

[20] Yang Z, Shen J, Archer LA. An in situ method of creating metal oxide–carbon composites and their application as anode materials for lithium-ion batteries. J Mater Chem, 2011, 2111092 CrossRef Google Scholar

[21] Chen Y, Ma X, Cui X, et al. In situ synthesis of carbon incorporated TiO2 with long-term performance as anode for lithium-ion batteries. J Power Sources, 2016, 302233-239 CrossRef ADS Google Scholar

[22] Cao S, Feng X, Song Y, et al. In situ carbonized cellulose-based hybrid film as flexible paper anode for lithium-ion batteries. ACS Appl Mater Interfaces, 2016, 81073-1079 CrossRef Google Scholar

[23] He M, Castel E, Laumann A, et al. In situ gas analysis of Li4Ti5O12 based electrodes at elevated temperatures. J Electrochem Soc, 2015, 162A870-A876 CrossRef Google Scholar

[24] Gao X, Chen Y, Johnson L, et al. Promoting solution phase discharge in Li–O2 batteries containing weakly solvating electrolyte solutions. Nat Mater, 2016, 15882-888 CrossRef ADS Google Scholar

[25] Chen Y, Freunberger SA, Peng Z, et al. Li–O2 battery with a dimethylformamide electrolyte. J Am Chem Soc, 2012, 1347952-7957 CrossRef Google Scholar

[26] Ryu SK, Jin H, Gondy D, et al. Activation of carbon fibres by steam and carbon dioxide. Carbon, 1993, 31841-842 CrossRef Google Scholar

[27] Rodríguez-Reinoso F, Molina-Sabio M, González MT. The use of steam and CO2 as activating agents in the preparation of activated carbons. Carbon, 1995, 3315-23 CrossRef Google Scholar

[28] Xia K, Gao Q, Wu C, et al. Activation, characterization and hydrogen storage properties of the mesoporous carbon CMK-3. Carbon, 2007, 451989-1996 CrossRef Google Scholar

[29] Xia K, Gao Q, Jiang J, et al. Hierarchical porous carbons with controlled micropores and mesopores for supercapacitor electrode materials. Carbon, 2008, 461718-1726 CrossRef Google Scholar

[30] Xia K, Gao Q, Song S, et al. CO2 activation of ordered porous carbon CMK-1 for hydrogen storage. Int J Hydrogen Energy, 2008, 33116-123 CrossRef Google Scholar

[31] Sevilla M, Mokaya R. Energy storage applications of activated carbons: supercapacitors and hydrogen storage. Energy Environ Sci, 2014, 71250-1280 CrossRef Google Scholar

[32] Zhang Y, Park SJ. Incorporation of RuO2 into charcoal-derived carbon with controllable microporosity by CO2 activation for high-performance supercapacitor. Carbon, 2017, 122287-297 CrossRef Google Scholar

[33] Roh JS. Structural study of the activated carbon fiber using laser Raman spectroscopy. Carbon Lett, 2008, 9127-130 CrossRef Google Scholar

[34] Balachandran U, Eror NG. Raman spectrum of the high temperature form of Nb2O5. J Mater Sci Lett, 1982, 1374-376 CrossRef Google Scholar

[35] Schrader B, Bergmann G. Die Intensität des Ramanspektrums polykristalliner Substanzen. Z Anal Chem, 1967, 225230-247 CrossRef Google Scholar

[36] Zhu S, Li J, Ma L, et al. Three-dimensional network of N-doped carbon ultrathin nanosheets with closely packed mesopores: controllable synthesis and application in electrochemical energy storage. ACS Appl Mater Interfaces, 2016, 811720-11728 CrossRef Google Scholar

[37] Hubbard CR, Snyder RL. RIR-measurement and use in quantitative XRD. Powder Diffr, 2013, 374-77 CrossRef ADS Google Scholar

[38] Li Y, Zhang S, Yu Q, et al. The effects of activated carbon supports on the structure and properties of TiO2 nanoparticles prepared by a sol–gel method. Appl Surf Sci, 2007, 2539254-9258 CrossRef ADS Google Scholar

[39] Li Q, Liu B, Li Y, et al. Ethylene glycol-mediated synthesis of nanoporous anatase TiO2 rods and rutile TiO2 self-assembly chrysanthemums. J Alloys Compd, 2009, 471477-480 CrossRef Google Scholar

[40] Bailón-García E, Elmouwahidi A, Álvarez MA, et al. New carbon xerogel-TiO2 composites with high performance as visible-light photocatalysts for dye mineralization. Appl Catal B-Environ, 2017, 20129-40 CrossRef Google Scholar

[41] Du X, Wu Y, Kou Y, et al. Amorphous carbon inhibited TiO2 phase transition in aqueous solution and its application in photocatalytic degradation of organic dye. J Alloys Compd, 2019, 810151917 CrossRef Google Scholar

[42] Xiao Q, Zhang J, Xiao C, et al. Solar photocatalytic degradation of methylene blue in carbon-doped TiO2 nanoparticles suspension. Sol Energy, 2008, 82706-713 CrossRef ADS Google Scholar

[43] Ohno T, Tsubota T, Toyofuku M, et al. Photocatalytic activity of a TiO2 photocatalyst doped with C4+ and S4+ ions having a rutile phase under visible light. Catal Lett, 2004, 98255-258 CrossRef Google Scholar

[44] Yabuuchi N, Yoshii K, Myung ST, et al. Detailed studies of a high-capacity electrode material for rechargeable batteries, Li2MnO3−LiCo1/3Ni1/3Mn1/3O2. J Am Chem Soc, 2011, 1334404-4419 CrossRef Google Scholar

[45] Schäfer H, Gruehn R, Schulte F. Die Modifikationen des Niobpentoxids. Angew Chem, 1966, 7828-41 CrossRef Google Scholar

[46] Pilarek B, Pelczarska AJ, Szczygieł I. Characterization of niobium(V) oxide received from different sources. J Therm Anal Calorim, 2017, 13077-83 CrossRef Google Scholar

[47] Valencia-Balvín C, Pérez-Walton S, Dalpian GM, et al. First-principles equation of state and phase stability of niobium pentoxide. Comput Mater Sci, 2014, 81133-140 CrossRef Google Scholar

[48] Viet AL, Reddy MV, Jose R, et al. Nanostructured Nb2O5 polymorphs by electrospinning for rechargeable lithium batteries. J Phys Chem C, 2010, 114664-671 CrossRef Google Scholar

[49] Rahman MM, Rani RA, Sadek AZ, et al. A vein-like nanoporous network of Nb2O5 with a higher lithium intercalation discharge cut-off voltage. J Mater Chem A, 2013, 111019-11025 CrossRef Google Scholar

[50] Flandrois S, Simon B. Carbon materials for lithium-ion rechargeable batteries. Carbon, 1999, 37165-180 CrossRef Google Scholar

[51] Duan Y, Zhang B, Zheng J, et al. Excess Li-ion storage on reconstructed surfaces of nanocrystals to boost battery performance. Nano Lett, 2017, 176018-6026 CrossRef ADS Google Scholar

[52] Shin JY, Samuelis D, Maier J. Sustained lithium-storage performance of hierarchical, nanoporous anatase TiO2 at high rates: emphasis on interfacial storage phenomena. Adv Funct Mater, 2011, 213464-3472 CrossRef Google Scholar

[53] Kumagai N, Koishikawa Y, Komaba S, et al. Thermodynamics and kinetics of lithium intercalation into Nb2O5 electrodes for a 2 V rechargeable lithium battery. J Electrochem Soc, 1999, 1463203-3210 CrossRef ADS Google Scholar

[54] Cai Y, Li X, Wang L, et al. Oleylamine-assisted hydrothermal synthesis of ultrasmall NbOx nanoparticles and their in situ conversion to NbOx@C with highly reversible lithium storage. J Mater Chem A, 2015, 31396-1399 CrossRef Google Scholar

[55] Lin J, Yuan Y, Su Q, et al. Facile synthesis of Nb2O5/carbon nanocomposites as advanced anode materials for lithium-ion batteries. Electrochim Acta, 2018, 29263-71 CrossRef Google Scholar

[56] Wu W, Huang J, Li J, et al. Inducing [001]-orientation in Nb2O5 capsule-nanostructure for promoted Li+ diffusion process. Electrochim Acta, 2019, 298449-458 CrossRef Google Scholar

[57] Park H, Lee D, Song T. High capacity monoclinic Nb2O5 and semiconducting NbO2 composite as high-power anode material for Li-Ion batteries. J Power Sources, 2019, 414377-382 CrossRef ADS Google Scholar

[58] Cao D, Yao Z, Liu J, et al. H-Nb2O5 wired by tetragonal tungsten bronze related domains as high-rate anode for Li-ion batteries. Energy Storage Mater, 2018, 11152-160 CrossRef Google Scholar

[59] Chao D, Zhu C, Yang P, et al. Array of nanosheets render ultrafast and high-capacity Na-ion storage by tunable pseudocapacitance. Nat Commun, 2016, 712122 CrossRef ADS Google Scholar

[60] Dahn JR, Jiang J, Moshurchak LM, et al. High-rate overcharge protection of LiFePO4-based Li-ion cells using the redox shuttle additive 2,5-ditertbutyl-1,4-dimethoxybenzene. J Electrochem Soc, 2005, 152A1283 CrossRef ADS Google Scholar

[61] Lindström H, Södergren S, Solbrand A, et al. Li+ ion insertion in TiO2 (anatase). 2. Voltammetry on nanoporous films. J Phys Chem B, 1997, 1017717-7722 CrossRef Google Scholar

[62] Augustyn V, Simon P, Dunn B. Pseudocapacitive oxide materials for high-rate electrochemical energy storage. Energy Environ Sci, 2014, 71597-1614 CrossRef Google Scholar

[63] Weppner W, Huggins RA. Determination of the kinetic parameters of mixed-conducting electrodes and application to the system Li3Sb. J Electrochem Soc, 1977, 1241569-1578 CrossRef ADS Google Scholar

[64] Inada R, Kumasaka R, Inabe S, et al. Li+ insertion/extraction properties for TiNb2O7 single particle characterized by a particle-current collector integrated microelectrode. J Electrochem Soc, 2019, 166A5157-A5162 CrossRef ADS Google Scholar

[65] Rui XH, Ding N, Liu J, et al. Analysis of the chemical diffusion coefficient of lithium ions in Li3V2(PO4)3 cathode material. Electrochim Acta, 2010, 552384-2390 CrossRef Google Scholar

[66] Lanz M, Novák P. DEMS study of gas evolution at thick graphite electrodes for lithium-ion batteries: the effect of γ-butyrolactone. J Power Sources, 2001, 102277-282 CrossRef Google Scholar

[67] Onuki M, Kinoshita S, Sakata Y, et al. Identification of the source of evolved gas in Li-ion batteries using 13C-labeled solvents. J Electrochem Soc, 2008, 155A794 CrossRef ADS Google Scholar

[68] He YB, Li B, Liu M, et al. Gassing in Li4Ti5O12-based batteries and its remedy. Sci Rep, 2012, 2913 CrossRef ADS Google Scholar

[69] Bernhard R, Meini S, Gasteiger HA. On-line electrochemical mass spectrometry investigations on the gassing behavior of Li4Ti5O12 electrodes and its origins. J Electrochem Soc, 2014, 161A497-A505 CrossRef Google Scholar

[70] Fell CR, Sun L, Hallac PB, et al. Investigation of the gas generation in lithium titanate anode based lithium ion batteries. J Electrochem Soc, 2015, 162A1916-A1920 CrossRef Google Scholar

  • Figure 1

    Schematic illustration of the Nb2O5/carbon nanohybrid structure evolution from embedding to emcoating.

  • Figure 2

    Structure evolution of the Nb2O5/C nanohybrid from pristine Nb2O5 embedded with carbon (a) to emcoated with dense carbon (EDC, activated at 800°C for 2 h) (b), and to emcoated with porous carbon (EPC, activated at 900°C for 1 h) (c) induced by the CO2 activation. Image details: SEM (a-1, b-1, and c-1), TEM (a-2, b-2, and c-2), HRTEM (a-3, b-3, c-3, and c-4), and SAED (a-4, b-4, and c-5). Insets in a-1, b-1, and c-1: low magnification SEM images of the Nb2O5/C nanohybrids.

  • Figure 3

    Simulation model of the nanoparticulate powder for inner and outer surface area distribution estimation. Grey cube: bulk shape of the Nb2O5 nanoparticulate agglomerate. Black sphere: inside part of the Nb2O5 particles. Blue sphere: outside part of the Nb2O5 particles. Red sphere: Nb2O5 particles on the edge of cube.

  • Figure 4

    Structure characterizations of the Nb2O5/C nanohybrids with carbon embedding (pristine), EDC, and EPC. Thermogravimetric profiles (a) and Raman spectroscopy (b) of the pristine, embedded, and emcoated Nb2O5; N2 adsorption/desorption isotherms (inset: corresponding Barrett-Joyner-Halenda (BJH) pore size distribution curves) of the pristine embedded Nb2O5 (c), EDC structured Nb2O5/C (d), EPC structured Nb2O5/C (e) and coral Nb2O5 (f).

  • Figure 5

    XRD patterns of the pristine carbon embedded Nb2O5/C and carbon emcoated (both EDC and EPC) Nb2O5/C nanohybrids (a, b). XPS survey (c) and high-resolution O 1s (d), C 1s (e) and Nb 3d (f) of the EPC structured Nb2O5/C nanohybrid.

  • Figure 6

    Electrochemical performance of the pristine carbon embedding Nb2O5/C and carbon emcoating Nb2O5/C (1 C=200 mA g−1): charge/discharge profiles (a) and CV curves (b) of the EPC structured Nb2O5/C; cycling (c) and rate (d) performances of the pristine carbon embedding Nb2O5/C and carbon emcoating Nb2O5/C with the voltage range of 0.01–3.0 V; cycling (e), rate (f), and long cycling performance at 200 mA g−1 (g) with the cut-off voltage from 1.0 to 3.0 V.

  • Figure 7

    Kinetics analyses of the lithium ion storage mechanism of the EPC structured Nb2O5/C. Details: CV profiles at various scan rates (a); relationship between the peak current and scan rate in logarithmic format (b); capacitive contribution at a scan rate of 0.2 mV s−1 (c); contribution ratio of the capacitive and diffusion-controlled capacities at various scan rates (d). GITT analyses of the EPC structured Nb2O5. Details: GITT profiles of the discharge/charge process (e); single step of the GITT curves (f); linear fit of E versus τ1/2 for a typical titration (g); apparent lithium diffusion coefficient (DLi) of the EPC structured Nb2O5/C calculated from the GITT profiles (h). Additionally, the EIS results (Fig. S8) confirm the improved diffusion behavior from the unique carbon structure as well.

  • Figure 8

    DEMS patterns with initial discharge/charge cycle of the EPC structured Nb2O5/C (a) and commercial LTO electrode (b).

  • Table 1   Relationship between heat-treatment temperature and crystallographic phase of Nb2O5 [45]

    Temperature (°C)

    Crystallographic phase







  • Table 2   Electrochemical performance of the reported Nb2O5-based negative electrodes


    Potential range (V)

    Gravimetriccapacity(mA h g−1)

    Current density (mA g−1)




    225 (500th)





    298 (100th)





    385 (100th)



    Nb2O5 capsule


    421 (100th)



    Vein-like Nb2O5


    201 (50th)





    168 (500th)





    123 (900th)





    140 (200th)





    387 (200th)


    This work


    184 (500th)



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