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SCIENCE CHINA Materials, Volume 60, Issue 9: 839-848(2017) https://doi.org/10.1007/s40843-017-9083-9

A novel lithium-ion battery comprising Li-rich@Cr2O5 composite cathode and Li4Ti5O12 anode with controllable coulombic efficiency

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  • ReceivedJun 19, 2017
  • AcceptedJul 24, 2017
  • PublishedAug 30, 2017

Abstract

Through meticulous design, a Li-lacking Cr2O5 cathode is physically mixed with Li-rich Li1.2Ni0.13Co0.13Mn0.54O2 (LNCM) cathode to form composite cathodes LNCM@xCr2O5 (x = 0, 0.1, 0.2, 0.3, 0.35, 0.4, mass ratio) in order to make use of the excess lithium produced by the Li-rich component in the first charge-discharge process. The initial coulombic efficiency (ICE) of LNCM half-cell has been significantly increased from 75.5% (x = 0) to 108.9% (x = 0.35). A novel full-cell comprising LNCM@Cr2O5 composite cathode and Li4Ti5O12 anode has been developed. Such electrode accordance, i.e., LNCM@ Cr2O5//Li4Ti5O12 (“L-cell”), shows a particularly high ICE of 97.7%. The “L-cell” can transmit an outstanding reversible capacity up to 250 mA h g−1 and has 94% capacity retention during 50 cycles. It also has superior rate capacities as high as 122 and 94 mA h g−1 at 1.25 and 2.5 A g−1 current densities, which are even better in comparison of Li-rich//graphite full-cell (“G-cell”). The high performance of “L-cell” benefiting from the well-designed coulombic efficiency accordance mechanism displays a great potential for fast charge-discharge applications in future high-energy lithium ion batteries.


Funded by

National Natural Science Foundation of China(51577175)

NSAF(U1630106)


Acknowledgment

This work was supported by the National Natural Science Foundation of China (51577175), and NSAF (U1630106). We are also grateful to Elementec Ltd. in Suzhou for its technical support.


Interest statement

The authors declare that they have no conflict of interest.


Contributions statement

Ding X performed the main experiments; He X and Liao J participated in the characterization. Zou B, Li Y, Tang Z and Shao Y conceived and supervised the project; Ding X wrote the manuscript with support from Chen C, Zou B, Tang Z. All authors contributed to the general discussion.


Author information

Xiang Ding received his bachelor degree from Jilin University (JLU) in 2015. He is currently pursuing his master degree under the supervision of Prof. Chunhua Chen at the Institute for CAS Key Laboratory of Materials for Energy Conversions, University of Science and Technology of China (USTC). His research interests are the materials for rechargeable lithium ion batteries.


Chunhua Chen is a professor of the Department of Materials Science and Engineering at USTC. He graduated from USTC in 1986 and received his master degree at USTC in 1989. He obtained his PhD degree at Delft University of Technology (TUD), Netherlands, in 1998. Then he worked in Argonne National Laboratory (ANL), USA, until 2002. His research interest focuses on the materials and systems for secondary batteries. He has published more than 200 research papers with a current H-index of 46.


Supplement

Supplementary information

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


References

[1] Chu S, Majumdar A. Opportunities and challenges for a sustainable energy future. Nature, 2012, 488: 294-303 CrossRef PubMed ADS Google Scholar

[2] Yi TF, Han X, Yang SY, et al. Enhanced electrochemical performance of Li-rich low-Co Li1.2Mn0.56Ni0.16Co0.08−xAlxO2 (0≤x≤0.08) as cathode materials. Sci China Mater, 2016, 59: 618-628 CrossRef Google Scholar

[3] Dunn B, Kamath H, Tarascon JM. Electrical energy storage for the grid: a battery of choices. Science, 2011, 334: 928-935 CrossRef PubMed ADS Google Scholar

[4] Zeng L, Pan A, Liang S, et al. Novel synthesis of V2O5 hollow microspheres for lithium ion batteries. Sci China Mater, 2016, 59: 567-573 CrossRef Google Scholar

[5] Hao J, Liu H, Ji Y, et al. Synthesis and electrochemical performance of Sn-doped LiNi0.5Mn1.5O4 cathode material for high-voltage lithium-ion batteries. Sci China Mater, 2017, 60: 315-323 CrossRef Google Scholar

[6] Padhi AK. Phospho-olivines as positive-electrode materials for rechargeable lithium batteries. J Electrochem Soc, 1997, 144: 1188-1194 CrossRef Google Scholar

[7] Zou BK, Ma XH, Tang ZF, et al. High rate LiMn2O4/carbon nanotube composite prepared by a two-step hydrothermal process. J Power Sources, 2014, 268: 491-497 CrossRef ADS Google Scholar

[8] Wu N, Wu H, Yuan W, et al. Facile synthesis of one-dimensional LiNi0.8Co0.15Al0.05O2 microrods as advanced cathode materials for lithium ion batteries. J Mater Chem A, 2015, 3: 13648-13652 CrossRef Google Scholar

[9] Johnson CS, Kim JS, Lefief C, et al. The significance of the Li2MnO3 component in ‘composite’ xLi2MnO3·(1−x)LiMn0.5Ni0.5O2 electrodes. Electrochem Commun, 2004, 6: 1085-1091 CrossRef Google Scholar

[10] Johnson CS, Li N, Lefief C, et al. Synthesis, characterization and electrochemistry of lithium battery electrodes: xLi2MnO3·(1−x)LiMn0.333Ni0.333Co0.333O2(0 ≤x ≤ 0.7). Chem Mater, 2008, 20: 6095-6106 CrossRef Google Scholar

[11] Shi JL, Zhang JN, He M, et al. Mitigating voltage decay of Li-rich cathode material via increasing Ni content for lithium-ion batteries. ACS Appl Mater Interfaces, 2016, 8: 20138-20146 CrossRef Google Scholar

[12] Martha SK, Nanda J, Veith GM, et al. Electrochemical and rate performance study of high-voltage lithium-rich composition: Li1.2Mn0.525Ni0.175Co0.1O2. J Power Sources, 2012, 199: 220-226 CrossRef Google Scholar

[13] Wu Y, Vadivel Murugan A, Manthiram A. Surface modification of high capacity layered Li[Li0.2Mn0.54Ni0.13Co0.13]O2 cathodes by AlPO4. J Electrochem Soc, 2008, 155: A635 CrossRef Google Scholar

[14] Xu H, Deng S, Chen G. Improved electrochemical performance of Li1.2Mn0.54Ni0.13Co0.13O2 by Mg doping for lithium ion battery cathode material. J Mater Chem A, 2014, 2: 15015-15021 CrossRef Google Scholar

[15] Zhang X, Belharouak I, Li L, et al. Structural and electrochemical study of Al2O3 and TiO2 coated Li1.2Ni0.13Mn0.54Co0.13O2 cathode material using ALD. Adv Energ Mater, 2013, 3: 1299-1307 CrossRef Google Scholar

[16] Liu J, Reeja-Jayan B, Manthiram A. Conductive surface modification with aluminum of high capacity layered Li[Li0.2Mn0.54-Ni0.13Co0.13]O2 cathodes. J Phys Chem C, 2010, 114: 9528-9533 CrossRef Google Scholar

[17] Zheng F, Yang C, Xiong X, et al. Nanoscale surface modification of lithium-rich layered-oxide composite cathodes for suppressing voltage fade. Angew Chem Int Ed, 2015, 54: 13058-13062 CrossRef PubMed Google Scholar

[18] Lee E, Park JS, Wu T, et al. Role of Cr3+/Cr6+ redox in chromium-substituted Li2MnO3·LiNi1/2Mn1/2O2 layered composite cathodes: electrochemistry and voltage fade. J Mater Chem A, 2015, 3: 9915-9924 CrossRef Google Scholar

[19] He Z, Wang Z, Chen H, et al. Electrochemical performance of zirconium doped lithium rich layered Li1.2Mn0.54Ni0.13Co0.13O2 oxide with porous hollow structure. J Power Sources, 2015, 299: 334-341 CrossRef ADS Google Scholar

[20] Qiao QQ, Qin L, Li GR, et al. Sn-stabilized Li-rich layered Li(Li0.17Ni0.25Mn0.58)O2 oxide as a cathode for advanced lithium-ion batteries. J Mater Chem A, 2015, 3: 17627-17634 CrossRef Google Scholar

[21] Sun S, Wan N, Wu Q, et al. Surface-modified Li[Li0.2Ni0.17Co0.07-Mn0.56]O2 nanoparticles with MgF2 as cathode for Li-ion battery. Solid State Ion, 2015, 278: 85-90 CrossRef Google Scholar

[22] Yu H, Zhou H. High-energy cathode materials (Li2MnO3‒LiMO2) for lithium-ion batteries. J Phys Chem Lett, 2013, 4: 1268-1280 CrossRef PubMed Google Scholar

[23] Gao J, Kim J, Manthiram A. High capacity Li[Li0.2Mn0.54Ni0.13-Co0.13]O2‒V2O5 composite cathodes with low irreversible capacity loss for lithium ion batteries. Electrochem Commun, 2009, 11: 84-86 CrossRef Google Scholar

[24] Wu F, Wang Z, Su Y, et al. Li[Li0.2Mn0.54Ni0.13Co0.13]O2‒MoO3 composite cathodes with low irreversible capacity loss for lithium ion batteries. J Power Sources, 2014, 247: 20-25 CrossRef ADS Google Scholar

[25] Liu JL, Wang J, Xia YY. A new rechargeable lithium-ion battery with a xLi2MnO3·(1−x)LiMn0.4Ni0.4Co0.2O2 cathode and a hard carbon anode. Electrochim Acta, 2011, 56: 7392-7396 CrossRef Google Scholar

[26] Wang T, Chen Z, Zhao R, et al. A new high energy lithium ion batteries consisting of 0.5Li2MnO3·0.5LiMn0.33Ni0.33Co0.33O2 and soft carbon components. Electrochim Acta, 2016, 194: 1-9 CrossRef Google Scholar

[27] Pham HQ, Hwang EH, Kwon YG, et al. Understanding the interfacial phenomena of a 4.7 V and 55°C Li-ion battery with Li-rich layered oxide cathode and graphite anode and its correlation to high-energy cycling performance. J Power Sources, 2016, 323: 220-230 CrossRef ADS Google Scholar

[28] Zou B, Hu Q, Qu D, et al. A high energy density full lithium-ion cell based on specially matched coulombic efficiency. J Mater Chem A, 2016, 4: 4117-4124 CrossRef Google Scholar

[29] Elia GA, Wang J, Bresser D, et al. A new, high energy Sn–C/Li[Li0.2Ni0.4/3Co0.4/3Mn1.6/3]O2 lithium-ion battery. ACS Appl Mater Interfaces, 2014, 6: 12956-12961 CrossRef Google Scholar

[30] Li M, Hou X, Sha Y, et al. Facile spray-drying/pyrolysis synthesis of core–shell structure graphite/silicon-porous carbon composite as a superior anode for Li-ion batteries. J Power Sources, 2014, 248: 721-728 CrossRef ADS Google Scholar

[31] Ren JG, Wu QH, Hong G, et al. Silicon-graphene composite anodes for high-energy lithium batteries. Energ Tech, 2013, 1: 77-84 CrossRef Google Scholar

[32] Leroy S, Blanchard F, Dedryvère R, et al. Surface film formation on a graphite electrode in Li-ion batteries: AFM and XPS study. Surf Interface Anal, 2005, 37: 773-781 CrossRef Google Scholar

[33] Xu B, Fell CR, Chi M, et al. Identifying surface structural changes in layered Li-excess nickel manganese oxides in high voltage lithium ion batteries: a joint experimental and theoretical study. Energ Environ Sci, 2011, 4: 2223-2233 CrossRef Google Scholar

[34] 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, 133: 4404-4419 CrossRef PubMed Google Scholar

[35] Feng XY, Ding N, Wang L, et al. Synthesis and reversible lithium storage of Cr2O5 as a new high energy density cathode material for rechargeable lithium batteries. J Power Sources, 2013, 222: 184-187 CrossRef Google Scholar

[36] Beltrop K, Meister P, Klein S, et al. Does size really matter? New insights into the intercalation behavior of anions into a graphite-based positive electrode for dual-ion batteries. Electrochim Acta, 2016, 209: 44-55 CrossRef Google Scholar

[37] Rothermel S, Meister P, Schmuelling G, et al. Dual-graphite cells based on the reversible intercalation of bis(trifluoromethanesulfonyl)imide anions from an ionic liquid electrolyte. Energ Environ Sci, 2014, 7: 3412-3423 CrossRef Google Scholar

[38] Balabajew M, Reinhardt H, Bock N, et al. In-situ Raman study of the intercalation of bis(trifluoromethylsulfonyl)imid ions into graphite inside a dual-ion cell. Electrochim Acta, 2016, 211: 679-688 CrossRef Google Scholar

[39] Choi NS, Han JG, Ha SY, et al. Recent advances in the electrolytes for interfacial stability of high-voltage cathodes in lithium-ion batteries. RSC Adv, 2015, 5: 2732-2748 CrossRef Google Scholar

  • Figure 1

    Schematic diagram of the “L-cell” coulombic efficiency accordance mechanism.

  • Figure 2

    XRD patterns of (a) the synthesized powders Li-rich layer-structured LNCM and Cr2O5 cathodes and (b) Li4Ti5O12 and graphite anodes, respectively.

  • Figure 3

    SEM images of (a) LNCM, (b) Cr2O5, (c) LTO and (d) graphite.

  • Figure 4

    The electrochemical properties of several cathode materials: (a) the selected charge-discharge curves of LNCM at 0.1 and 0.5 C; (b) the selected charge-discharge curves of Cr2O5 at 0.1 and 0.5 C; (c) the cycling performances of LNCM and Cr2O5 at 0.5 C; (d) the first charge-discharge curves of LNCM@Cr2O5 composites with different x values.

  • Figure 5

    (a) The 1st charge-discharge curve of LTO at 0.1 C (1.0‒3.0 V, 1 C = 175 mA h g−1); (b) the cycling performance of LTO at 0.1 C; (c) the rate performance of LTO at different charge rates (1 C discharge); (d) the selected cycle curves of graphite at 0.1 C (0‒2V, 1 C = 372 mA h g−1); (e) the cycling performance of graphite at 0.1 C; (f) the rate performance of graphite at different charge rates (1 C discharge).

  • Figure 6

    (a) The selected charge and discharge curves of “G-cell” at a current density of 0.025 A g−1 (1.8‒4.6 V); (b) the selected charge and discharge curves of “L-cell” at a current density of 0.025 A g−1 (0.5‒2.96 V); (c) the cycling performances of “G-cell” and “L-cell” at a current density of 0.025 A g−1; (d) the rate performances of “G-cell” and “L-cell” at different discharge rates (0.25 A g−1 charge).

  • Figure 7

    EIS of the LNCM//LTO full-cell and “L-cell” (a) after 3 cycles and (b) after 50 cycles at discharged state of 2.3 V.

  • Figure 8

    Ex-situ XRD of first cycled, A1: Li-rich cathode in half cell; A2: Cr2O5 cathode in half cell; A3: LNCM@0.35Cr2O5 composite cathode in half cell; A4: LNCM@0.35Cr2O5 composite cathode in “L-cell”.

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