Construction of nitrogen-doped carbon cladding LiMn₂O₄ film electrode with enhanced stability for electrochemically selective extraction of lithium ions

Abstract

Reducing the dissolution of Mn from LiMn₂O₄ (LMO) and enhancing the stability of film electrodes are critical and challenging for Li⁺ ions selective extraction via electrochemically switched ion exchange technology. In this work, we prepared a nitrogen-doped carbon cladding LMO (C-N@LMO) by polymerization of polypyrrole and high-temperature annealing in the N₂ gas to achieve the above purpose. The modified C-N@LMO film electrode exhibited lower Mn dissolution and better cyclic stability than the LMO film electrode. The dissolution ratio of Mn from the C-N@LMO film electrode decreased by 42% compared to the LMO film electrode after 10 cycles. The cladding layer not only acted as a protective layer but also functioned as a conductive shell, accelerating the migration rate of Li⁺ ions. The intercalation equilibrium time of the C-N@LMO film electrode reached within an hour during the extraction of Li⁺ ions, which was 33% less compared to the pure LMO film electrode. Meanwhile, the C-N@LMO film electrode retained evident selectivity toward Li⁺ ions, and the separation factor was 118.38 for Li⁺ toward Mg²⁺ in simulated brine. Therefore, the C-N@LMO film electrode would be a promising candidate for the recovery of Li⁺ ions from salt lakes.

Graphical abstract

Keywords

LiMn₂O₄ / lithium extraction / surface coating / cyclic stability / Mn dissolution

References

[1] Luo G, Li X, Chen L, Chao Y, Zhu W. Electrochemical lithium ion pumps for lithium recovery: a systematic review and influencing factors analysis. Desalination, 2023, 548(15): 116228

[2] Lukatskaya M R, Dunn B, Gogotsi Y. Multidimensional materials and device architectures for future hybrid energy storage. Nature Communications, 2016, 7(1): 12647

[3] Gao C, Liu H, Bi S, Li H, Ma C. Investigation the improvement of high voltage spinel LiNi_0.5Mn_1.5O₄ cathode material by anneal process for lithium ion batteries. Green Energy & Environment, 2021, 6(1): 114–123

[4] Zhang Q, Ma B, Wang C, Chen Y, Zhang W. Comprehensive utilization of complex rubidium ore resources: mineral dissociation and selective leaching of rubidium and potassium. International Journal of Minerals Metallurgy and Materials, 2023, 30(5): 857–867

[5] Shen K, He Q, Ru Q, Tang D, Oo T, Zaw M, Lwin N, Aung S, Tan S, Chen F. Flexible LATP composite membrane for lithium extraction from seawater via an electrochemical route. Journal of Membrane Science, 2023, 671: 121358

[6] Pramanik B, Nghiem L, Hai F. Extraction of strategically important elements from brines: constraints and opportunities. Water Research, 2022, 168: 115149

[7] Zhang Q, Li S, Sun S, Yin X, Yu J. Lithium selective adsorption on 1-D MnO₂ nanostructure ion-sieve. Advanced Powder Technology, 2009, 20(5): 432–437

[8] Jiang H, Yang Y, Yu J. Application of concentration-dependent HSDM to the lithium adsorption from brine in fixed bed columns. Separation and Purification Technology, 2020, 241: 116682

[9] Zhang Z, Du X, Wang Q, Gao F, Jin T, Hao X, Ma P, Li J, Guan G. A scalable three-dimensional porous λ-MnO₂/rGO/Ca-alginate composite electroactive film with potential-responsive ion-pumping effect for selective recovery of lithium ions. Separation and Purification Technology, 2021, 259: 118111

[10] Wang C, Zhai Y, Wang X, Zeng M. Preparation and characterization of lithium λ-MnO₂ ion-sieves. Frontiers of Chemical Science and Engineering, 2014, 8(4): 471–477

[11] Zhang L, Li L, Shi D, Li J, Peng X, Nie F. Selective extraction of lithium from alkaline brine using HBTA-TOPO synergistic extraction system. Separation and Purification Technology, 2017, 188: 167–173

[12] Grágeda M, González A, Grágeda M, Ushak S. Purification of brines by chemical precipitation and ion-exchange processes for obtaining battery-grade lithium compounds. International Journal of Energy Research, 2018, 42(7): 2386–2399

[13] Chen W, Li X, Chen L, Zhou G, Lu Q, Huang Y, Chao Y, Zhu W. Tailoring hydrophobic deep eutectic solvent for selective lithium recovery from the mother liquor of Li₂CO₃. Chemical Engineering Journal, 2021, 420(2): 127648

[14] Zhao Z, Liu G, Jia H, He L. Sandwiched liquid-membrane electrodialysis: lithium selective recovery from salt lake brines with high Mg/Li ratio. Journal of Membrane Science, 2020, 596: 117685

[15] Du X, Guan G, Li X, Jagadale A, Ma X, Wang Z, Hao X, Abudula A. A novel electroactive λ-MnO₂/PPy/PSS core–shell nanorod coated electrode for selective recovery of lithium ions at low concentration. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2016, 4(36): 13989–13996

[16] Ma W, Du X, Liu M, Gao F, Ma X, Li Y, Guan G, Hao X. A conductive chlorine ion-imprinted polymer threaded in metal–organic frameworks for electrochemically selective separation of chloride ions. Chemical Engineering Journal, 2021, 412: 128576

[17] Wang Q, Du X, Gao F, Liu F, Liu M, Hao X, Tang K, Guan G, Abudula A. A novel H_1.6Mn_1.6O₄/reduced graphene oxide composite film for selective electrochemical capturing lithium ions with low concentration. Separation and Purification Technology, 2019, 226: 59–67

[18] Zhao M, Ji Z, Zhang Y, Guo Z, Zhao Y, Liu J, Yuan J. Study on lithium extraction from brines based on LiMn₂O₄/Li_1−xMn₂O₄ by electrochemical method. Electrochimica Acta, 2017, 252: 350–361

[19] Zhou G, Chen L, Chao Y, Li X, Luo G, Zhu W. Progress in electrochemical lithium ion pumping for lithium recovery. Journal of Energy Chemistry, 2021, 59: 431–445

[20] Trocoli R, Battistel A, Mantia F. Selectivity of a lithium-recovery process based on LiFePO₄. Chemistry—A European Communication, 2014, 20: 9888–9891

[21] Xu W, He L, Zhao Z. Lithium extraction from high Mg/Li brine via electrochemical intercalation/de-intercalation system using LiMn₂O₄ materials. Desalination, 2021, 503: 114935

[22] Jiang Y, Chai L, Zhang D, Ouyang F, Zhou X, Alhassan S, Liu S, He Y, Yan L, Wang H, Zhang W. Facet-controlled LiMn₂O₄/C as deionization electrode with enhanced stability and high desalination performance. Nano-Micro Letters, 2022, 14(1): 176

[23] Banerjee A, Ziv B, Shilina Y, Luski S, Aurbach D, Halalay I. Acid-scavenging separators: a novel route for improving Li-ion batteries’ durability. ACS Energy Letters, 2017, 2(10): 2388–2393

[24] Zeng J, Li M, Li X, Chen C, Xiong D, Dong L, Li D, Lushington A, Sun X. A novel coating onto LiMn₂O₄ cathode with increased lithium ion battery performance. Applied Surface Science, 2014, 317: 884–891

[25] Zhang S, Fang S, Chen J, Ni L, Deng W, Zou G, Hou H, Ji X. Engineering d-p orbital hybridization for high-stable lithium manganate cathode. Chemical Engineering Journal, 2023, 451(1): 138511

[26] Luo F, Wei C, Zhang C, Gao H, Niu J, Ma W, Peng Z, Bai Y, Zhang Z. Operando X-ray diffraction analysis of the degradation mechanisms of a spinel LiMn₂O₄ cathode in different voltage windows. Journal of Energy Chemistry, 2020, 44: 138–146

[27] Wu Y, Cao C, Zhang J, Wang L, Ma X, Xu X. Hierarchical LiMn₂O₄ hollow cubes with exposed {111} planes as high-power cathodes for lithium-ion batteries. ACS Applied Materials & Interfaces, 2016, 8(30): 19567–19572

[28] Xiao Y, Zhang X, Zhu Y, Wang P, Yin Y, Yang X, Shi J, Liu J, Li H, Guo X, Zhong B H, Guo Y G. Suppressing manganese dissolution via exposing stable {111} facets for high-performance lithium-ion oxide cathode. Advanced Science, 2019, 6(13): 1801908

[29] Li X, Liu J, Meng X, Tang Y, Banis M, Yang J, Hu Y, Li R, Cai M, Sun X. Significant impact on cathode performance of lithium-ion batteries by precisely controlled metal oxide nanocoatings via atomic layer deposition. Journal of Power Sources, 2014, 247: 57–69

[30] Thackeray M, Johnson C, Kim J, Lauzze K, Vaughey J, Dietz N, Abraham D, Hackney S, Zeltner W, Anderson M. ZrO₂- and Li₂ZrO₃-stabilized spinel and layered electrodes for lithium batteries. Electrochemistry Communications, 2003, 5(9): 752–758

[31] Ju B, Wang X, Wu C, Wei Q, Yang X, Shu H, Bai Y. Excellent cycling stability of spherical spinel LiMn₂O₄ by Y₂O₃ coating for lithium-ion batteries. Journal of Solid State Electrochemistry, 2013, 18(1): 115–123

[32] Liu H, Cheng C, Hu Z, Zhang K. Improving the elevated temperature performance of Li/LiMn₂O₄ cells by coating with ZnO. Journal of Materials Science, 2005, 40(21): 5767–5769

[33] Qiao Y, Zhou Z, Chen Z, Du S, Cheng Q, Zhai H, Fritz N, Du Q, Yang Y. Visualizing ion diffusion in battery systems by fluorescence microscopy: a case study on the dissolution of LiMn₂O₄. Nano Energy, 2018, 45: 68–74

[34] Ren Q, Yuan Y, Wang S. Interfacial strategies for suppression of Mn dissolution in rechargeable battery cathode materials. ACS Applied Materials & Interfaces, 2022, 14(20): 23022–23032

[35] Peng K, Peng T. Carbon covering to improve the storage performance of LiMn₂O₄ electrode at 60 °C. Ceramics International, 2014, 40(9): 15345–15349

[36] Tomon C, Sarawutanukul S, Phattharasupakun N, Duangdangchote S, Chomkhuntod P, Joraleechanchai N, Bunyanidhi P, Sawangphruk M. Core–shell structure of LiMn₂O₄ cathode material reduces phase transition and Mn dissolution in Li-ion batteries. Communications Chemistry, 2022, 5(1): 1–12

[37] Jiang Q, Wang X, Tang Z. Improving the electrochemical performance of LiMn₂O₄ by amorphous carbon coating. Fullerenes, Nanotubes, and Carbon Nanostructures, 2014, 23(8): 676–679

[38] Ilango P, Prasanna K, Do S, Jo Y, Lee C. Eco-friendly nitrogen-containing carbon encapsulated LiMn₂O₄ cathodes to enhance the electrochemical properties in rechargeable Li-ion batteries. Scientific Reports, 2016, 6(1): 29826

[39] Luo W, Li F, Gaumet J, Magri P, Diliberto S, Zhou L, Mai L. Bottom-up confined synthesis of nanorod-in-nanotube structured Sb@N-C for durable lithium and sodium storage. Advanced Energy Materials, 2018, 8(19): 1703237

[40] Fang J, Wang J, Ji Z, Cui J, Guo Z, Liu J, Zhao Y, Yuan J. Establishment of PPy-derived carbon encapsulated LiMn₂O₄ film electrode and its performance for efficient Li⁺ electrosorption. Separation and Purification Technology, 2022, 280: 119726

[41] Li S, Zhang J, Yan Y, Yu L, Zhao J. Manganese valence state regulated beta-manganese dioxide porous nanoflowers as high-performance cathodes at large current densities for aqueous magnesium ions battery capacitor. Journal of Energy Storage, 2023, 59: 106456

[42] Kim J, Kim K, Cho W, Shin W, Kanno R, Choi W. A truncated manganese spinel cathode for excellent power and lifetime in lithium-ion batteries. Nano Letters, 2012, 12(12): 6358–6365

[43] Mu C, Lou S, Ali R, Xiong H, Liu S, Wang H, Huo W, Yin L, Jia R, Liu Y. . Carbon-decorated LiMn₂O₄ nanorods with enhanced performance for supercapacitors. Journal of Alloys and Compounds, 2019, 805: 624–630

[44] Dong W, Huang X, Jin Y, Xie M, Zhao W, Huang F. Building an artificial solid electrolyte interphase on spinel lithium manganate for high performance aqueous lithium-ion batteries. Dalton Transactions, 2020, 49(24): 8136–8142

[45] Selvamani V, Phattharasupakun N, Wutthiprom J, Sawangphruk M. High-performance spinel LiMn₂O₄@carbon core–shell cathode materials for Li-ion batteries. Sustainable Energy & Fuels, 2019, 3(8): 1988–1994

[46] Batool A, Kanwal F, Imran M, Jamil T, Siddiqi S A. Synthesis of polypyrrole/zinc oxide composites and study of their structural, thermal and electrical properties. Synthetic Metals, 2012, 161(23): 2753–2758

[47] Lai F, Zhang X, Wu Q, Zhang J, Li Q, Huang Y, Liao Z, Wan H. Effect of surface modification with spinel NiFe₂O₄ on enhanced cyclic stability of LiMn₂O₄ cathode material in lithium ion batteries. ACS Sustainable Chemistry & Engineering, 2018, 6(1): 570–578

[48] Lawagon C, Nisola G, Cuevas R, Kim H, Lee S, Chung W. Li_1–xNi_0.33Co_1/3Mn_1/3O₂/Ag for electrochemical lithium recovery from brine. Chemical Engineering Journal, 2018, 348: 1000–1011

[49] Zhang E, Liu W, Liang Q, Liu X, Zhao Z, Yang Y. Selective recovery of Li⁺ in acidic environment based on one novel electroactive Li⁺-imprinted graphene-based hybrid aerogel. Chemical Engineering Journal, 2020, 385: 123948

[50] Kim S, Joo H, Moon T, Kim S, Yoon J. Rapid and selective lithium recovery from desalination brine using an electrochemical system. Environmental Science: Processes & Impacts, 2019, 21(4): 667–676

Competing interests

The authors declare that they have no competing interests.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Grant Nos. U21A20303, 22078217 and U20A20141).

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-023-2343-7 and is accessible for authorized users.

RIGHTS & PERMISSIONS

2023 Higher Education Press