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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

Abstract


Acknowledgment

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.


References

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  • 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

    500–600

    Hexagonal

    600–800

    Orthorhombic

    900

    Monoclinic

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

    Electrode

    Potential range (V)

    Gravimetriccapacity(mA h g−1)

    Current density (mA g−1)

    Ref.

    NbO2/C

    0.01–3.0

    225 (500th)

    200

    [18]

    NbOx@C

    0.01–3.0

    298 (100th)

    100

    [54]

    Nb2O5/C

    0.01–3.0

    385 (100th)

    100

    [55]

    Nb2O5 capsule

    0–3

    421 (100th)

    100

    [56]

    Vein-like Nb2O5

    1.0–3.0

    201 (50th)

    200

    [49]

    Nb2O5/CNTS

    1.0–3.0

    168 (500th)

    100

    [56]

    Nb2O5/NbO2

    1.0–3.0

    123 (900th)

    200

    [57]

    Nb2O5

    1.2–3.0

    140 (200th)

    100

    [58]

    Nb2O5/C

    0.01–3.0

    387 (200th)

    40

    This work

    1.0–3.0

    184 (500th)

    200

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