Enhanced electrochemical performance of La- and Zn-co-doped LiMn2O4 spinel as the cathode material for lithium-ion batteries
Source abstract
Abstract
A series of compounds Li[La x Zn y Mn2−x−y ]O4 (x = y = 0.01–0.05) is synthesized by doping the pure spinel LiMn2O4 with lanthanum and zinc ions. These cathode materials are characterized by X-ray powder diffractometry, inductively coupled plasma optical emission spectrometry, scanning electron microscopy, transmission electron microscopy, cyclic voltammetry, galvanostatic charge–discharge studies, and electrochemical impedance spectroscopy (EIS). The particle sizes range from 42 to 140 nm. The results reveal that the pristine LiMn2O4 delivers a discharge capacity of 122.3 mAh g−1 at 0.1C while at 5C the reversible capacity reduces to 51 mAh g−1 that is about 41 % of the initial discharge capacity. Among all the doped samples, LiLa0.01Zn0.01Mn1.98O4 is the best composition that delivers a discharge capacity of 118 mAh g−1 with the low capacity fade of 0.18 mAh g−1 cycle−1 over the investigated 100 cycles. At a high current rate of 5C, 78 % of the initial discharge capacity in the first cycle is retained, while 95 % of the discharge capacity is recovered when the current density is reduced back to 0.1C. Our results demonstrate that the lanthanum and zinc co-doping has stabilized the structural integrity of the spinel host by suppressing the Jahn–Teller distortion and also provides short distances for Li+ diffusion as is clear from the EIS results.
Source: openaire · Quality: candidate unverified · Source record ↗
Research context
OpenAlex topics: Advancements in Battery Materials · Advanced Battery Materials and Technologies · Supercapacitor Materials and Fabrication
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (40)
Show source-provided references
1. Amine K, Tukamoto H, Yasuda H, Fujita H (1996) A new 3-volt spinel Li1+xMn1.5Ni0.5O4 for secondary lithium batteries. J Electrochem Soc 143:1607–161310.1149/1.1836686 ↗
2. Arumugam D, Kalaignan GP, Manisankar P (2008) Development of structural stability and the electrochemical performances of ‘La’ substituted spinel LiMn2O4 cathode materials for rechargeable lithium-ion batteries. Solid State Ionics 179:580–58610.1016/j.ssi.2008.04.010 ↗
3. Bellitto C, Bauer EM, Righini G, Green MA, Branford WR, Antonini A, Pasquali M (2004) The effect of doping LiMn2O4 spinel on its use as a cathode in Li-ion batteries: neutron diffraction and electrochemical studies. J Phys Chem Solids 65:29–3710.1016/j.jpcs.2003.09.003 ↗
4. Bonino F, Panero S, Satolli D, Scrosati B (2001) Synthesis and characterization of Li2MxMn4−xO8 (M = Co, Fe) as positive active materials for lithium ion cells. J Power Sources 97–98:389–39210.1016/S0378-7753(01)00630-9 ↗
5. Ein-Eli Y, Urian RC, Wen W, Mukerjee S (2005) Low temperature performance of copper/nickel modified LiMn2O4 spinels. Electrochim Acta 50:1931–193710.1016/j.electacta.2004.09.002 ↗
6. Goktepe H, Sahan H, Patat S, Ulgen A (2009) Enhanced cyclability of triple-metal-doped LiMn2O4 spinel as the cathode material for rechargeable lithium batteries. Ionics 15:233–23910.1007/s11581-008-0265-5 ↗
7. Gummow RJ, de Kock A, Thackeray MM (1994) Improved capacity retention in rechargeable 4 V lithium/lithium manganese oxide (spinel) cells. Solid State Ionics 69:59–6710.1016/0167-2738(94)90450-2 ↗
8. Hassoun J, Lee KS, Sun YK, Scrosati B (2011) An advanced lithium ion battery based on high performance electrode materials. J Am Chem Soc 133:3139–314310.1021/ja110522x ↗
9. He BL, Zhou WJ, Liang YY, Bao SJ, Li HL (2006) Synthesis and electrochemical properties of chemically substituted LiMn2O4 prepared by a solution-based gel method. J Colloid Interface Sci 300:633–63910.1016/j.jcis.2006.04.002 ↗
10. Helan M, Berchmans LJ (2010) Synthesis of LiSm0.01Mn1.99O4 by molten salt technique. J Rare Earth 28(2):255–25910.1016/S1002-0721(09)60091-0 ↗
11. Hwang BJ, Santhanam R, Liu DG, Tsai YW (2001) Effect of Al-substitution on the stability of LiMn2O4 spinel, synthesized by citric acid sol–gel method. J Power Sources 102:326–33110.1016/S0378-7753(01)00769-8 ↗
12. Hwang BJ, Santhanam R, Hu SG (2002) Synthesis and characterization of multidoped lithium manganese oxide spinel, Li1.02Co0.1Ni0.1Mn1.8O4, for rechargeable lithium batteries. J Power Sources 108:250–25510.1016/S0378-7753(02)00023-X ↗
13. Iqbal MJ, Ahmad Z (2008) Electrical and dielectric properties of lithium manganate nanomaterials doped with rare-earth elements. J Power Sources 179:763–76910.1016/j.jpowsour.2007.12.115 ↗
14. Jang DH, Shin YJ, Oh SM (1996) Dissolution of spinel oxides and capacity losses in 4 V Li/LixMn2O4 cells. J Electrochem Soc 143:2204–221110.1149/1.1836981 ↗
15. Kang K, Meng YS, Breger J, Grey CP, Cedar G (2006) Electrodes with high power and high capacity for rechargeable lithium batteries. Science 311:977–97910.1126/science.1122152 ↗
16. Kashiwagi T, Nakayama M, Watanabe K, Wakihara M, Kobayashi Y, Miyashiro H (2006) Relationship between the electrochemical behavior and Li arrangement in Li x M y Mn2−y O4 (M = Co, Cr) with spinel structure. J Phys Chem B 110:4998–500410.1021/jp056334y ↗
17. Lee JH, Hong JK, Jang DH, Sun YK, Oh (2000) Degradation mechanisms in doped spinels of LiM0.05Mn1.95O4 (M = Li, B, Al, Co, and Ni) for Li secondary batteries. J Power Sources 89:7–1410.1016/S0378-7753(00)00375-X ↗
18. Liu H, Li Song, Zhang K (2005) Er-doped LiMn2O4. Inorg Mater 41(6):646–64910.1007/s10789-005-0183-0 ↗
19. Liu H, Cao Q, Fu LJ, Li C, Wu YP, Wu HQ (2006) Doping effects of zinc on LiFePO4 cathode material for lithium ion batteries. Electrochem Commun 8:1553–155710.1016/j.elecom.2006.07.014 ↗
20. Locati C, Lafont U, Simonin L, Ooms F, Kelder EM (2007) Mg-doped LiNi0.5Mn1.5O4 spinel for cathode materials. J Power Sources 174:847–85110.1016/j.jpowsour.2007.06.196 ↗
21. Mandal S, Rojas RM, Amarilla JM, Calle P, Kosova NV, Anufrienko VF, Rojo JM (2002) High temperature co-doped LiMn2O4-based spinels. Structural, electrical, and electrochemical characterization. Chem Mater 14:1598–160510.1021/cm011219v ↗
22. Murugan AV, Kale BB, Kunde BL, Aarti VK (2006) Comparison of different soft chemical routes synthesis of nanocrystalline LiMn2O4 and their influence on its physicochemical properties. J Solid State Electrochem 10:104–10910.1007/s10008-005-0675-5 ↗
23. Ohzuku T, Ariyoshi K, Takeda S, Sakai Y (2001) Synthesis and characterization of 5 V insertion material of Li[Fe y Mn2−y ]O4 for lithium-ion batteries. Electrochim Acta 46:2327–233610.1016/S0013-4686(00)00725-8 ↗
24. Park SH, Park KS, Sun YK, Nahm KS (2000) Characterization of a new spinel, Li1.02Al0.25Mn1.75O3.97S0.03, operating at potentials between 4.3 and 2.4 V. J Electrochem Soc 147:2116–212110.1149/1.1393494 ↗
25. Pistoia G, Antonini A, Rosati R, Zane D (1996) Storage characteristics of cathodes for Li-ion batteries. Electrochim Acta 41:2683–268910.1016/0013-4686(96)00122-3 ↗
26. Rojas RM, Amarilla JM, Pascual L, Rojo JM, Kovacheva D, Petrov K (2006) Combustion synthesis of nanocrystalline LiNi Y Co1−2Y Mn1+Y O4 spinels for 5 V cathode materials: characterization and electrochemical properties. J Power Sources 160:529–53510.1016/j.jpowsour.2006.01.012 ↗
27. Smith MJ, Gray FM (2010) Batteries, from cradle to grave. J Chem Educ 87(2):162–16710.1021/ed800053u ↗
28. Song D, Ikuta H, Uchida T, Wakihara M (1999) The spinel phases LiAlyMn2−yO4 (y = 0, 1/12, 1/9, 1/6, 1/3) and Li(Al, M)1/6Mn11/6O4 (M = Cr, Co) as the cathode for rechargeable lithium batteries. Solid State Ionics 117:151–15610.1016/S0167-2738(98)00258-6 ↗
29. Sun YK, Yoon CS, Kim CK, Youn SG, Lee YS, Yoshio M, Oh IH (2001) Degradation mechanism of spinel LiAl0.2Mn1.8O4 cathode materials on high temperature cycling. J Mater Chem 11:2519–252210.1039/b103709a ↗
30. Thackeray MM (1997) Manganese oxides for lithium batteries. Prog Solid State Chem 25:1–7110.1016/S0079-6786(97)81003-5 ↗
31. Thackeray MM, David WIF, Bruce PG, Goodenough JB (1983) Lithium insertion into manganese spinels. Mater Res Bull 18:461–47210.1016/0025-5408(83)90138-1 ↗
32. Thirunakaran R, Sivashanmugam A, Gopukumar S, Dunnill CW, Gregory DH (2008) Studies on chromium/aluminium-doped manganese spinel as cathode materials for lithium-ion batteries—a novel chelated sol–gel synthesis. J Mater Process Technol 208:520–53110.1016/j.jmatprotec.2008.01.017 ↗
33. Thirunakaran R, Sivashanmugam A, Gopukumar S, Rajalakshmi R (2009) Cerium and zinc: dual-doped LiMn2O4 spinels as cathode material for use in lithium rechargeable batteries. J Power Sources 187:565–57410.1016/j.jpowsour.2008.10.134 ↗
34. Thirunakaran R, Ravikumar R, Vanitha S, Gopukumar S, Sivashanmugam A (2011) Glutamic acid-assisted sol–gel synthesis of multi-doped spinel lithium manganate as cathode materials for lithium rechargeable batteries. Electrochim Acta 58:348–35810.1016/j.electacta.2011.09.054 ↗
35. Xia Y, Yoshio M (1977) Capacity fading on cycling of 4 V Li/LiMn2O4 cells. J Electrochem Soc 144:2593–260010.1149/1.1837870 ↗
36. Xia Y, Kumada N, Yoshio M (2000) Enhancing the elevated temperature performance of Li/LiMn2O4 cells by reducing LiMn2O4 surface area. J Power Sources 90:135–13810.1016/S0378-7753(00)00395-5 ↗
37. Yamada A (1996) Lattice Instability in Li(LixMn2−x)O4. J Solid State Chem 122:160–16510.1006/jssc.1996.0097 ↗
38. Yang MC, Xu B, Cheng JH, Pan CJ, Hwang BJ, Meng YS (2011) Electronic, structural, and electrochemical properties of LiNixCuyMn2−x−yO4 (0 < x < 0.5, 0 < y < 0.5) high-voltage spinel materials. Chem Mater 23:2832–284110.1021/cm200042z ↗
39. Yanwen T, Xiaoxue K, Liying L, Chaqing XU, Tao QU (2008) Research on cathode material of Li-ion battery by yttrium doping. J Rare Earth 26(2):279–28310.1016/S1002-0721(08)60081-2 ↗
40. Yi TF, Shu J, Zhu YR, Zhu RS (2009) Advanced electrochemical performance of LiMn1.4Cr0.2Ni0.4O4 as 5 V cathode material by citric-acid-assisted method. J Phys Chem Solids 70:153–15810.1016/j.jpcs.2008.09.021 ↗