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Improved electrochemical performance of P2-type Na0.67Lix(Mn0.5Fe0.25Co0.25)1−xO2 cathode materials from Li ion substitution of the transition metal ions

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Abstract

In this work, we report the preparation and the enhanced electrochemical performance of P2-type Na0.67Lix(Mn0.5Fe0.25Co0.25)1−xO2 layered cathode materials with different Li substitutions via a nanomilling-assisted solid-state method. The experimental results show that the introduced lithium ions can greatly improve the performance of the material after entering the transition metal layer. Among these synthesized samples, the Na0.67Li0.03(Mn0.5Fe0.25Co0.25)0.97O2 electrode exhibits an exceptionally high specific capacity of 190.6 mAh g−1 at 0.1 C rate and a capacity retention of 89.5% after 30 cycles. Obviously, the specific capacity retention is improved by 15.3% compared with the pristine Na0.67(Mn0.5Fe0.25Co0.25)O2 without Li incorporation (the specific capacity retention is only 74.2% after 30 cycles). Simultaneously, the sample also shows a large increase in rate performance compared to the pristine material. All of the enhancement can be explained by the fact that the introduced Li ions suppress the phase transition during the charge–discharge process and avoid the volume expansion of the electrode, which significantly reduce the occurrence of micro-cracks within the electrode. The reduced polarization, the decreased internal resistance of the prepared electrodes and the increased sodium ion diffusion coefficient, as confirmed from the CV and EIS measurements, can be regarded as the three major reasons for the enhanced electrochemical performance of the Li ion-substituted materials.

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References

  1. Larcher D, Tarascon JM (2015) Towards greener and more sustainable batteries for electrical energy storage. Nat Chem 7:19–29. https://doi.org/10.1038/nchem.2085

    Article  Google Scholar 

  2. Ong SP, Chevrier VL, Hautier G et al (2011) Voltage, stability and diffusion barrier differences between sodium-ion and lithium-ion intercalation materials. Energy Environ Sci 4:3680–3688. https://doi.org/10.1039/c1ee01782a

    Article  Google Scholar 

  3. Raju V, Rains J, Gates C et al (2014) Superior cathode of sodium-ion batteries: orthorhombic V2O5 nanoparticles generated in nanoporous carbon by ambient hydrolysis deposition. Nano Lett 14:4119–4124. https://doi.org/10.1021/nl501692p

    Article  Google Scholar 

  4. Palomares V, Serras P, Villaluenga I, Hueso KB, Carretero González J, Rojo T (2012) Na-ion batteries, recent advances and present challenges to become low cost energy storage systems. Energy Environ Sci 5:5884–5901. https://doi.org/10.1039/c2ee02781j

    Article  Google Scholar 

  5. Zhao J, Xu J, Lee DH, Dimov N, Meng YS, Okada S (2014) Electrochemical and thermal properties of P2-type Na2/3Fe1/3Mn2/3O2 for Na-ion batteries. J Power Sour 264:235–239. https://doi.org/10.1016/j.jpowsour.2014.04.048

    Article  Google Scholar 

  6. Li ZY, Gao R, Sun L, Hu Z, Liu X (2015) Designing an advanced P2-Na0.67Mn0.65Ni0.2Co0.15O2 layered cathode material for Na-ion batteries. J Mater Chem A 3:16272–16278. https://doi.org/10.1039/c5ta02450a

    Article  Google Scholar 

  7. Sathiya M, Hemalatha K, Ramesha K, Tarascon JM, Prakash AS (2012) Synthesis, structure, and electrochemical properties of the layered sodium insertion cathode material: NaNi1/3Mn1/3Co1/3O2. Chem Mater 24:1846–1853. https://doi.org/10.1021/cm300466b

    Article  Google Scholar 

  8. Yabuuchi N, Kajiyama M, Iwatate J et al (2012) P2-type Nax[Fe1/2Mn1/2]O2 made from earth-abundant elements for rechargeable Na batteries. Nat Mater 11:512–517. https://doi.org/10.1038/nmat3309

    Article  Google Scholar 

  9. Vassilaras P, Toumar AJ, Ceder G (2014) Electrochemical properties of NaNi1/3Co1/3Fe1/3O2 as a cathode material for Na-ion batteries. Electrochem Commun 38:79–81. https://doi.org/10.1016/j.elecom.2013.11.015

    Article  Google Scholar 

  10. Li X, Wu D, Zhou YN, Liu L, Yang XQ, Ceder G (2014) O3-type Na(Mn0.25Fe0.25Co0.25Ni0.25)O2: a quaternary layered cathode compound for rechargeable Na ion batteries. Electrochem Commun 49:51–54. https://doi.org/10.1016/j.elecom.2014.10.003

    Article  Google Scholar 

  11. Yoshida H, Yabuuchi N, Komaba S (2013) NaFe0.5Co0.5O2 as high energy and power positive electrode for Na-ion batteries. Electrochem Commun 34:60–63. https://doi.org/10.1016/j.elecom.2013.05.012

    Article  Google Scholar 

  12. Yuan D, Hu X, Qian J et al (2014) P2-type Na0.67Mn0.65Fe0.2Ni0.15O2 Cathode Material with High-capacity for Sodium-ion Battery. Electrochim Acta 116:300–305. https://doi.org/10.1016/j.electacta.2013.10.211

    Article  Google Scholar 

  13. Hasa I, Buchholz D, Passerini S, Scrosati B, Hassoun J (2014) High performance Na0.5[Ni0.23Fe0.13Mn0.63]O2 cathode for sodium-ion batteries. Adv Energy Mater. https://doi.org/10.1002/aenm.201400083

  14. Xu S, Wang Y, Ben L, et al. (2015) Fe—based tunnel—type Na0.61[Mn0.27Fe0.34Ti0.39]O2 designed by a new strategy as a cathode material for sodium—ion batteries. Adv Energy Mater 5:1501156. https://doi.org/10.1002/aenm.201501156

  15. Liu L, Li X, Bo SH et al (2015) High-performance P2-type Na2/3(Mn1/2Fe1/4Co1/4)O2 cathode material with superior rate capability for Na-Ion batteries. Adv Energy Mater 5:1500944. https://doi.org/10.1002/aenm.201500944

    Article  Google Scholar 

  16. Komaba S, Yabuuchi N, Nakayama T, Ogata A, Ishikawa T, Nakai I (2012) Study on the reversible electrode reaction of Na1–xNi0.5Mn0.5O2 for a rechargeable sodium-ion battery. Inorg Chem 51:6211–6220. https://doi.org/10.1021/ic300357d

    Article  Google Scholar 

  17. Ma X, Chen H, Ceder G (2011) Electrochemical properties of monoclinic NaMnO2. J Electrochem Soc 158:A1307–A1312. https://doi.org/10.1149/2.035112jes

    Article  Google Scholar 

  18. Liu Y, Fang X, Zhang A et al (2016) Layered P2-Na2/3[Ni1/3Mn2/3]O2, as high-voltage cathode for sodium-ion batteries: the capacity decay mechanism and Al2O3, surface modification. Nano Energy 27:27–34. https://doi.org/10.1016/j.nanoen.2016.06.026

    Article  Google Scholar 

  19. Oh SM, Myung ST, Hwang JY, Scrosati B, Amine K, Sun YK (2014) High capacity O3-type Na[Li0.05(Ni0.25Fe0.25Mn0.5)0.95]O2 cathode for sodium ion batteries. Chem Mater 26:6165–6171. https://doi.org/10.1021/cm502481b

    Article  Google Scholar 

  20. Xu J, Lee DH, Clément RJ et al (2014) Identifying the critical role of Li substitution in P2–Nax[LiyNizMn1–y–z]O2 (0 < x, y, z < 1) intercalation cathode materials for high-energy Na-ion batteries. Chem Mater 26:1260–1269. https://doi.org/10.1021/cm403855t

    Article  Google Scholar 

  21. Zheng S, Zhong G, McDonald MJ et al (2016) Exploring the working mechanism of Li+ in O3-type NaLi0.1Ni0.35Mn0.55O2 cathode materials for rechargeable Na-ion batteries. J Mater Chem A 4:9054–9062. https://doi.org/10.1039/c6ta02230h

    Article  Google Scholar 

  22. Shannon RD (1976) Revised effective ionic radii and systematic studies of interatomie distances in halides and chaleogenides. Acta Crystallogr Sect A 32:751–767. https://doi.org/10.1107/s0567739476001551

    Article  Google Scholar 

  23. Li X, Ge W, Wang H et al (2017) Enhancing cycle stability and storage property of LiNi0.8Co0.15Al0.05O2 by using fast cooling method. Electrochim Acta 227:225–234. https://doi.org/10.1016/j.electacta.2016.12.138

    Article  Google Scholar 

  24. Thorne JS, Dunlap RA, Obrovac MN (2012) Structure and electrochemistry of NaxFexMn1−xO2 (1.0 ≤ x≤0.5) for Na-Ion battery positive electrodes. J Electrochem Soc 160:A361–A367. https://doi.org/10.1149/2.058302jes

    Article  Google Scholar 

  25. Shenouda AY, Liu HK (2008) Electrochemical behaviour of tin borophosphate negative electrodes for energy storage systems. J Power Sour 185:1386–1391. https://doi.org/10.1016/j.jpowsour.2008.08.042

    Article  Google Scholar 

  26. Shenouda AY, Murali KR (2008) Electrochemical properties of doped lithium titanate compounds and their performance in lithium rechargeable batteries. J Power Sour 176:332–339. https://doi.org/10.1016/j.jpowsour.2007.10.061

    Article  Google Scholar 

  27. Li B, Han C, He YB et al (2012) Facile synthesis of Li4Ti5O12/C composite with super rate performance. Energy Environ Sci 5:9595–9602. https://doi.org/10.1039/c2ee22591c

    Article  Google Scholar 

  28. Zhu YR, Yin LC, Yi TF, Liu H, Xie Y, Zhu RS (2013) Electrochemical performance and lithium-ion intercalation kinetics of submicron-sized Li4Ti5O12, anode material. J Alloy Compd 547:107–112. https://doi.org/10.1016/j.jallcom.2012.08.113

    Article  Google Scholar 

  29. Aragón MJ, Lavela P, Ortiz G, Alcántara R, Tirado JL (2017) Nanometric P2-Na2/3Fe1/3Mn2/3O2 with controlled morphology as cathode for sodium-ion batteries. J Alloy Compd 724:465–473. https://doi.org/10.1016/j.jallcom.2017.07.044

    Article  Google Scholar 

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Funding

The research was supported by Science and Technology Commission of Shanghai Municipality (14520503100, 13PJ1407400 and 201310-JD-B2-009) and National Natural Science Foundation of China (21306113) and Shanghai Municipal Education Commission (15ZZ095).

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Authors and Affiliations

  1. School of Materials Science and Engineering, Shanghai Institute of Technology, 100 Haiquan Road, Shanghai, 200235, People’s Republic of China

    Tingjian Lv, Li Guan, Peng Xiao, Dongyun Zhang & Chengkang Chang

  2. Shanghai Innovation Institute for Materials, Shanghai University, Shanghai, People’s Republic of China

    Chengkang Chang

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  1. Tingjian Lv
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  2. Li Guan
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  3. Peng Xiao
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  4. Dongyun Zhang
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Correspondence to Dongyun Zhang or Chengkang Chang.

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Lv, T., Guan, L., Xiao, P. et al. Improved electrochemical performance of P2-type Na0.67Lix(Mn0.5Fe0.25Co0.25)1−xO2 cathode materials from Li ion substitution of the transition metal ions. J Mater Sci 54, 5584–5594 (2019). https://doi.org/10.1007/s10853-018-03194-w

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