Progress in the modification of lithium-rich manganese-based layered cathode material

doi:10.12028/j.issn.2095-4239.2018.0010

Abstract

Abstract: Developing the high energy density cathode materials for lithium ion batteries is the key to satisfy the demands of rapid development of electric vehicles and hybrid electric vehicles. Compared with traditional cathodes including LiCoO₂ and LiFePO₄, layered Li-rich Mn-based cathode materials are expected to achieve the index requirement of 300 W·h·kg^-1 because their specific capacity could reach up to 250 mA·h·g^-1 and the average discharge voltage exceeds 3.5 V. However, Li-rich materials have a poor cycle performance and gradual voltage decay during cycling, which is due to the irreversible phase transition from layered to spinel. In recent years, researchers have carries out tremendous works to solve these issues. In this paper, according to modification technology, the current studies including lattice doping, surface coating, designs of microstructure and control of active crystal plane are reviewed.

Key words: Li-rich Mn-based cathode materials, lithium ion batteries, modification, voltage decay, cycle stability

CLC Number:

TM911

LI Yu, ZHAO Huichun, BAI Ying, WU Feng, WU Chuan. Progress in the modification of lithium-rich manganese-based layered cathode material[J]. Energy Storage Science and Technology, 2018, 7(3): 394-403.

References

[1] WANG J, HE X, PAILLARD E, et al. Lithium-and manganese-rich oxide cathode materials for high-energy lithium ion batteries[J]. Advanced Energy Materials, 2016, 6(21):1600906.
[2] LU Z H, MACNEIL D D, DAHN J R. Layered cathode materials LiNi_xLi_(1/3-2x/3)Mn_(2/3-x/3)O₂ for lithium-ion batteries[J]. Electrochemical and Solid State Letters, 2001, 4(11):A191-A194.
[3] ARMSTRONG A R, HOLZAPFEL M, NOVAK P, et al. Demonstrating oxygen loss and associated structural reorganization in the lithium battery cathode Li[Ni_0.2Li_0.2Mn_0.6]O₂[J]. Journal of American Chemical Society, 2006, 128(26):8694-8698.
[4] LU Z, CHEN Z, DAHN J R. Lack of cation clustering in Li[Ni_xLi_1/3-2x/3Mn_2/3-x/3]O₂ (0<x ≤ 1/2) and Li[Cr_xLi_(1-x)/3Mn_(2-2x)/3]O₂ (0< x < 1)[J]. Chemistry of Materials, 2003, 15:3214-3220.
[5] ROBERTSON A D. Mechanism of electrochemical activity in Li₂MnO₃[J]. Chemistry of Materials, 2003, 15(10):1984-1992.
[6] GU M, BELHAROUAK I, ZHENG J M, et al. Formation of the spinel phase in the layered composite cathode used in Li-ion batteries[J]. ACS Nano, 2013, 7(1):760-767.
[7] XU B, FELL C R, 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[J]. Energy & Environmental Science, 2011, 4(6):2223-2233.
[8] KNIGHT J C, NANDAKUMAR P, KAN W H, et al. Effect of Ru substitution on the first charge-discharge cycle of lithium-rich layered oxides[J]. Journal of Materials Chemistry A, 2015, 3(5):2006-2011.
[9] NAYAK P K, GRINBLAT J, LEVI M, et al. Al doping for mitigating the capacity fading and voltage decay of layered Li and Mn-rich cathodes for Li-ion batteries[J]. Advanced Energy Materials, 2016, 6(8):1502398.
[10] HE W, YUAN D, QIAN J, et al. Enhanced high-rate capability and cycling stability of Na-stabilized layered Li_1.2[Co_0.13Ni_0.13Mn_0.54]O₂ cathode material[J]. Journal of Materials Chemistry A, 2013, 1(37):11397-11403.
[11] LI Q, LI G, FU C, et al. K⁺-doped Li_1.2Mn_0.54Co_0.13Ni_0.13O₂:A novel cathode material with an enhanced cycling stability for lithium-ion batteries[J]. ACS Applied Materials & Interfaces, 2014, 6(13):10330-10341.
[12] JIN X, XU Q, LIU H, et al. Excellent rate capability of Mg doped Li[Li_0.2Ni_0.13Co_0.13Mn _0.54]O₂ cathode material for lithium-ion battery[J]. Electrochimica Acta, 2014, 136:19-26.
[13] DENG Z, MANTHIRAM A. Influence of cationic substitutions on the oxygen loss and reversible capacity of lithium-rich layered oxide cathodes[J]. The Journal of Physical Chemistry C, 2011, 115(14):7097-7103.
[14] YU S H, YOON T, MUN J, et al. Continuous activation of Li₂MnO₃ component upon cycling in Li_1.167Ni_0.233Co_0.100Mn_0.467Mo_0.033O₂ cathode material for lithium ion batteries[J]. Journal of Materials Chemistry A, 2013, 1(8):2833-2839.
[15] LI N, AN R, SU Y, et al. The role of yttrium content in improving electrochemical performance of layered lithium-rich cathode materials for Li-ion batteries[J]. Journal of Materials Chemistry A, 2013, 1(34):9760.
[16] LI X, XIN H, LIU Y, et al. Effect of niobium doping on the microstructure and electrochemical properties of lithium-rich layered Li[Li_0.2Ni_0.2Mn_0.6]O₂ as cathode materials for lithium ion batteries[J]. RSC Advances, 2015, 5(56):45351-45358.
[17] SONG B, ZHOU C, WANG H, et al. Advances in sustain stable voltage of Cr-doped Li-rich layered cathodes for lithium ion batteries[J]. Journal of the Electrochemical Society, 2014, 161(10):A1723-A1730.
[18] ZHAO T, CHEN S, LI L, et al. Organic-acid-assisted fabrication of low-cost Li-rich cathode material Li[Li_1/6Fe_1/6Ni_1/6Mn_1/2]O₂ for lithium-ion battery[J]. Acs Applied Materials & Interfaces, 2014, 6(24):22305-22315.
[19] ZHAO J, WANG Z, GUO H, et al. Synthesis and electrochemical characterization of Zn-doped Li-rich layered Li[Li_0.2Mn_0.54Ni_0.13Co_0.13]O₂ cathode material[J]. Ceramics International, 2015, 41(9):11396-11401.
[20] CHEN H, HU Q, HUANG Z, et al. Synthesis and electrochemical study of Zr-doped Li[Li_0.2Mn_0.54Ni_0.13Co_0.13]O₂ as cathode material for Li-ion battery[J]. Ceramics International, 2016, 42(1):263-269.
[21] WANG Y, YANG Z, QIAN Y, et al. New insights into improving rate performance of lithium-rich cathode material[J]. Advanced Materials, 2015, 27(26):3915-3920.
[22] PAN L, XIA Y, QIU B, et al. Structure and electrochemistry of B doped Li(Li_0.2Ni_0.13Co_0.13Mn_0.54)_1-xB_xO₂ as cathode materials for lithium-ion batteries[J]. Journal of Power Sources, 2016, 327:273-280.
[23] LI L, SONG B H, CHANG Y L, et al. Retarded phase transition by fluorine doping in Li-rich layered Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ cathode material[J]. Journal of Power Sources, 2015, 283:162-170.
[24] AN J, SHI L, CHEN G, et al. Insights into the stable layered structure of a Li-rich cathode material for lithium-ion batteries[J]. Journal of Materials Chemistry A, 2017, 5(37):19738-19744.
[25] ZHANG H, QIAO Q, LI G, et al. PO₄^3- polyanion-doping for stabilizing Li-rich layered oxides as cathode materials for advanced lithium-ion batteries[J]. Journal of Materials Chemistry A, 2014, 2(20):7454-7460.
[26] ZHANG H, LI F, PAN G L, et al. The effect of polyanion-doping on the structure and electrochemical performance of Li-rich layered oxides as cathode for lithium-ion batteries[J]. Journal of the Electrochemical Society, 2015, 162(9):A1899-A1904.
[27] MA L, MAO L, ZHAO X, et al. Improving the structural stability of Li-rich layered cathode materials through constructing the antisite-defect nanolayer by polyanion doping on the surface[J]. ChemElectroChem, 2017, 4(12):3068-3074.
[28] LIM S N, SEO J Y, JUNG D S, et al. The crystal structure and electrochemical performance of Li_1.167Mn_0.548Ni_0.18Co_0.105O₂ composite cathodes doped and co-doped with Mg and F[J]. Journal of Electroanalytical Chemistry, 2015, 740:88-94.
[29] LIU Y, NING D, ZHENG L, et al. Improving the electrochemical performances of Li-rich Li_1.20Ni_0.13Co_0.13Mn_0.54O₂ through a cooperative doping of Na⁺ and PO₄^3- with Na₃PO₄[J]. Journal of Power Sources, 2018, 375:1-10.
[30] CHEN J, LI Z, XIANG H, et al. Bifunctional effects of carbon coating on high-capacity Li_1.2Ni_0.13Co_0.13Mn_0.54O₂ cathode for lithium-ion batteries[J]. Journal of Solid State Electrochemistry, 2015, 19(4):1027-1035.
[31] MA D, ZHANG P, LI Y, et al. Li_1.2Mn_0.54Ni_0.13Co_0.13O₂-encapsulated carbon nanofiber network cathodes with improved stability and rate capability for Li-ion batteries[J]. Scientific Reports, 2015, 5:11257.
[32] ZHANG J, LU Q, FANG J, et al. Polyimide encapsulated lithium-rich cathode material for high voltage lithium-ion battery[J]. Acs Applied Materials & Interfaces, 2014, 6(20):17965-17973.
[33] WU F, LIU J, LI L, et al. Surface modification of Li-rich cathode materials for lithium-ion batteries with a PEDOT:PSS conducting polymer[J]. ACS Applied Materials & Interfaces, 2016, 8(35):23095-23104.
[34] ZHANG X, BELHAROUAK I, LI L, et al. Structural and electrochemical study of Al₂O₃ and TiO₂ coated Li_1.2Ni_0.13Mn_0.54Co_0.13O₂ cathode material using ALD[J]. Advanced Energy Materials, 2013, 3(10):1299-1307.
[35] ZHENG J M, LI J, ZHANG Z R, et al. The effects of TiO₂ coating on the electrochemical performance of LiLi_0.2Mn_0.54Ni_0.13Co_0.13O₂ cathode material for lithium-ion battery[J]. Solid State Ionics, 2008, 179(27-32):1794-1799.
[36] WU Y, MANTHIRAM A. Effect of surface modifications on the layered solid solution cathodes (1-z)LiLi_1/3Mn_2/3O₂-(z)LiMn_0.5-yNi_0.5-yCo_2yO₂[J]. Solid State Ionics, 2009, 180(1):50-56.
[37] WU F, LI N, SU Y F, et al. Can surface modification be more effective to enhance the electrochemical performance of lithium rich materials?[J]. Journal of Materials Chemistry, 2012, 22(4):1489-1497.
[38] WANG Z, LIU E, GUO L, et al. Cycle performance improvement of Li-rich layered cathode material Li[Li_0.2Mn_0.54Ni_0.13Co_0.13]O₂ by ZrO₂ coating[J]. Surface and Coatings Technology, 2013, 235:570-576.
[39] SHI S, TU J, TANG Y, et al. Enhanced cycling stability of Li[Li_0.2Mn_0.54Ni_0.13Co_0.13]O₂by surface modification of MgO with melting impregnation method[J]. Electrochimica Acta, 2013, 88:671-679.
[40] YUAN W, ZHANG H, LIU Q, et al. Surface modification of Li(Li_0.17Ni_0.2Co_0.05Mn_0.58)O₂ with CeO₂ as cathode material for Li-ion batteries[J]. Electrochimica Acta, 2014, 135:199-207.
[41] LIU J, MANTHIRAM A. Functional surface modifications of a high capacity layered Li[Li_0.2Mn_0.54Ni_0.13Co_0.13]O₂ cathode[J]. Journal of Materials Chemistry, 2010, 20(19):3961-3967.
[42] SHI S J, TU J P, ZHANG Y J, et al. Effect of Sm₂O₃ modification on Li[Li_0.2Mn_0.56Ni_0.16Co_0.08]O₂ cathode material for lithium ion batteries[J]. Electrochimica Acta, 2013, 108:441-448.
[43] HE H, ZAN L, ZHANG Y. Effects of amorphous V₂O₅ coating on the electrochemical properties of Li[Li_0.2Mn_0.54Ni_0.13Co_0.13]O₂ as cathode material for Li-ion batteries[J]. Journal of Alloys and Compounds, 2016, 680:95-104.
[44] HOU M, LIU J, GUO S, et al. Enhanced electrochemical performance of Li-rich layered cathode materials by surface modification with P₂O₅[J]. Electrochemistry Communications, 2014, 49:83-87.
[45] SUN S, YIN Y, WAN N, et al. AlF₃ surface-coated Li[Li_0.2Ni_0.17Co_0.07Mn_0.56]O₂ nanoparticles with superior electrochemical performance for lithium-ion batteries[J]. ChemSusChem, 2015, 8(15):2544-2550.
[46] LI L, CHANG Y, XIA H, et al. NH₄F surface modification of Li-rich layered cathode materials[J]. Solid State Ionics, 2014, 264:36-44.
[47] ZHAO T, LI L, CHEN R, et al. Design of surface protective layer of LiF/FeF₃ nanoparticles in Li-rich cathode for high-capacity Li-ion batteries[J]. Nano Energy, 2015, 15:164-176.
[48] LIU X, HUANG T, YU A. Surface phase transformation and CaF₂ coating for enhanced electrochemical performance of Li-rich Mn-based cathodes[J]. Electrochimica Acta, 2015, 163:82-92.
[49] CHONG S, CHEN Y, YAN W, et al. Suppressing capacity fading and voltage decay of Li-rich layered cathode material by a surface nano-protective layer of CoF₂ for lithium-ion batteries[J]. Journal of Power Sources, 2016, 332:230-239.
[50] LIU B, ZHANG Z, WAN J, et al. Improved electrochemical properties of YF₃-coated Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ as cathode for Li-ion batteries[J]. Ionics, 2017, 23(6):1365-1374.
[51] ZHENG J, GU M, XIAO J, et al. Functioning mechanism of AlF₃ coating on the Li-and Mn-rich cathode materials[J]. Chemistry of Materials, 2014, 26(22):6320-6327.
[52] WANG D, BELHAROUAK I, ZHOU G, et al. Nanoarchitecture multi-structural cathode materials for high capacity lithium batteries[J]. Advanced Functional Materials, 2013, 23(8):1070-1075.
[53] WU F, LI N, SU Y, et al. Spinel/layered heterostructured cathode material for high-capacity and high-rate Li-ion batteries[J]. Advanced Materials, 2013, 25(27):3722-3726.
[54] LUO D, LI G, FU C, et al. A new spinel-layered Li-rich microsphere as a high-rate cathode material for Li-ion batteries[J]. Advanced Energy Materials, 2014, 4(11):1400062.
[55] PEI Y, XU C Y, XIAO Y C, et al. Phase transition induced synthesis of layered/spinel heterostructure with enhanced electrochemical properties[J]. Advanced Functional Materials, 2017, 27(7):1604349.
[56] XU M, FEI L, LU W, et al. Engineering hetero-epitaxial nanostructures with aligned Li-ion channels in Li-rich layered oxides for high-performance cathode application[J]. Nano Energy, 2017, 35:271-280.
[57] OH P, MYEONG S, CHO W, et al. Superior long-term energy retention and volumetric energy density for Li-rich cathode materials[J]. Nano Letters, 2014, 14(10):5965-5972.
[58] ZHANG L, LI N, WU B, et al. Sphere-shaped hierarchical cathode with enhanced growth of nanocrystal planes for high-rate and cycling-stable Li-ion batteries[J]. Nano Letters, 2015, 15(1):656-661.
[59] LI Y, BAI Y, WU C, et al. Three-dimensional fusiform hierarchical micro/nano Li_1.2Ni_0.2Mn_0.6O₂ with a preferred orientation (110) plane as a high energy cathode material for lithium-ion batteries[J]. Journal of Materials Chemistry A, 2016, 4(16):5942-5951.
[60] LI Y, WU C, BAI Y, et al. Hierarchical mesoporous lithium-rich Li[Li_0.2Ni_0.2Mn_0.6]O₂ cathode material synthesized via ice templating for lithium-ion battery[J]. ACS Applied Materials & Interfaces, 2016, 8(29):18832-18840.
[61] WEI G Z, LU X, KE F S, et al. Crystal habit-tuned nanoplate material of Li[Li_1/3-2x/3Ni_xMn_2/3-x/3]O₂ for high-rate performance lithium-ion batteries[J]. Advanced Materials, 2010, 22(39):4364-4367.
[62] CHEN L, SU Y, CHEN S, et al. Hierarchical Li_1.2Ni_0.2Mn_0.6O₂ nanoplates with exposed {010} planes as high-performance cathode material for lithium-ion batteries[J]. Advanced Materials, 2014, 26(39):6756-6760.
[63] LI J, XING L, ZHANG R, et al. Tris (trimethylsilyl) borate as an electrolyte additive for improving interfacial stability of high voltage layered lithium-rich oxide cathode/carbonate-based electrolyte[J]. Journal of Power Sources, 2015, 285:360-366.
[64] NAYAK P K, GRINBLAT J, LEVI M, et al. Understanding the effect of lithium bis (oxalato) borate (LiBOB) on the structural and electrochemical aging of Li and Mn rich high capacity Li_1.2Ni_0.16Mn_0.56Co_0.08O₂ cathodes[J]. Journal of the Electrochemical Society, 2015, 162(4):A596-A602.
[65] TAN S, ZHANG Z, LI Y, et al. Tris (hexafluoro-iso-propyl) phosphate as an SEI-forming additive on improving the electrochemical performance of the Li[Li_0.2Mn_0.56Ni_0.16Co_0.08]O₂ cathode material[J]. Journal of the Electrochemical Society, 2013, 160(2):A285-A292.
[66] HAN J G, LEE S J, LEE J, et al. Tunable and robust phosphite-derived surface film to protect lithium-rich cathodes in lithium-ion batteries[J]. ACS Applied Materials & Interfaces, 2015, 7(15):8319-8329.
[67] PHAM H Q, NAM K M, HWANG E H, et al. Performance enhancement of 4.8 V Li_1.2Mn_0.525Ni_0.175Co_0.1O₂ battery cathode using fluorinated linear carbonate as a high-voltage additive[J]. Journal of the Electrochemical Society, 2014, 161(14):A2002-A2011.
[68] ZHU Y, CASSELMAN M D, LI Y, et al. Perfluoroalkyl-substituted ethylene carbonates:Novel electrolyte additives for high-voltage lithium-ion batteries[J]. Journal of Power Sources, 2014, 246:184-191.
[69] PATRA J, DAHIYA P P, TSENG C J, et al. Electrochemical performance of 0.5Li₂MnO₃-0.5Li(Mn_0.375Ni_0.375Co_0.25)O₂ composite cathode in pyrrolidinium-based ionic liquid electrolytes[J]. Journal of Power Sources, 2015, 294:22-30.
[70] JI Y, ZHANG Z, GAO M, et al. Electrochemical behavior of suberonitrile as a high-potential electrolyte additive and co-solvent for Li[Li_0.2Mn_0.56Ni_0.16Co_0.08]O₂ cathode material[J]. Journal of the Electrochemical Society, 2015, 162(4):A774-A780.
[71] WU F, ZHU Q, LI L, et al. A diisocyanate/sulfone binary electrolyte based on lithium difluoro (oxalate) borate for lithium batteries[J]. Journal of Materials Chemistry A, 2013, 1(11):3659-3666.
[72] ZHANG T, LI J T, LIU J, et al. Suppressing the voltage-fading of layered lithium-rich cathode materials via an aqueous binder for Li-ion batteries[J]. Chemical Communications, 2016, 52(25):4683-4686.
[73] WU F, LI W, CHEN L, et al. Polyacrylonitrile-polyvinylidene fluoride as high-performance composite binder for layered Li-rich oxides[J]. Journal of Power Sources, 2017, 359:226-233.