Coupling effect of the conductivities of Li ions and electrons by introducing LLTO@C fibers in the LiNi_0.8Co_0.15Al_0.05O₂ cathode

Abstract

To probe the coupling effect of the electron and Li ion conductivities in Ni-rich layered materials (LiNi_0.8Co_0.15Al_0.05O₂, NCA), lithium lanthanum titanate (LLTO) nanofiber and carbon-coated LLTO fiber (LLTO@C) materials were introduced to polyvinylidene difluoride in a cathode. The enhancement of the conductivity was indicated by the suppressed impedance and polarization. At 1 and 5 C, the cathodes with coupling conductive paths had a more stable cycling performance. The coupling mechanism was analyzed based on the chemical state and structure evolution of NCA after cycling for 200 cycles at 5 C. In the pristine cathode, the propagation of lattice damaged regions, which consist of high-density edge-dislocation walls, destroyed the bulk integrity of NCA. In addition, the formation of a rock-salt phase on the surface of NCA caused a capacity loss. In contrast, in the LLTO@C modified cathode, although the formation of dislocation-driven atomic lattice broken regions and cation mixing occurred, they were limited to a scale of several atoms, which retarded the generation of the rock-salt phase and resulted in a pre-eminent capacity retention. Only NiO phase “pitting” occurred. A mechanism based on the synergistic transport of Li ions and electrons was proposed.

Keywords

Ni-rich cathode / coupling mechanism / dislocation wall / coaxial structure / cation mixing

References

[1] Guo LF, Zhang SY, Xie J, Zhen D, Jin Y, Wan KY, Zhuang DG, Zheng WQ, Zhao XB. Controlled synthesis of nanosized Si by magnesiothermic reduction from diatomite as anode material for Li-ion batteries. Int. J. Miner. Metall. Mater., 2020, 27(4): 515.

[2] Li DB, Cao LY, Liu CD, Cao GQ, Hu JH, Chen JB, Shao GS. A designer fast Li-ion conductor Li_6.25PS_5.25Cl_0.75 and its contribution to the polyethylene oxide based electrolyte. Appl. Surf. Sci., 2019, 493, 1326.

[3] Goodenough JB. Electrochemical energy storage in a sustainable modern society. Energy Environ. Sci., 2014, 7(1): 14.

[4] Han Y, Liu SY, Cui L, Xu L, Xie J, Xia XK, Hao WK, Wang B, Li H, Gao J. Graphene-immobilized flower-like Ni₃S₂ nanoflakes as a stable binder-free anode material for sodium-ion batteries. Int. J. Miner. Metall. Mater., 2018, 25(1): 88.

[5] Y.M. Sun, N. Liu, and Y. Cui, Promises and challenges of nan-omaterials for lithium-based rechargeable batteries, Nat. Energy, 1(2016), No. 7, art. No. 16071.

[6] Cao GQ, Ren YY, Wu KK, Yao HH, Hu JH, Shao GS, Yuan GH. Life extension strategy and research progress of zirconium alloy cladding applied to light water reactors. Surf. Technol., 2019, 48(11): 69.

[7] G.Q. Cao, L. Yang, G.H. Yuan, J.H. Hu, G.S. Shao, and L. Yan, Chemical diversity of iron species and structure evolution during the oxidation of C14 laves phase Zr(Fe, Nb)₂ in subcritical environment, Corros. Sci., 162(2020), art. No. 108218.

[8] Iqbal A, Chen L, Chen Y, Gao YX, Chen F, Li DC. Lithium-ion full cell with high energy density using nickel-rich LiNi_0.8Co_0.1Mn_0.1O₂ cathode and SiO-C composite anode. Int. J. Miner. Metall. Mater., 2018, 25(12): 1473.

[9] Wang LP, Chen G, Shen QX, Li GM, Guan SY, Li B. Direct electrodeposition of ionic liquid-based template-free SnCo alloy nanowires as an anode for Li-ion batteries. Int. J. Miner. Metall. Mater., 2018, 25(9): 1027.

[10] Faenza NV, Pereira N, Halat DM, Vinckeviciute J, Bruce L, Radin MD, Mukherjee P, Badway F, Halajko A, Cosandey F, Grey CP, Van der Ven A, Amatucci GG. Phase evolution and degradation modes of R3-m Li_xNi_1−y−zCo_yAl_zO₂ electrodes cycled near complete delithiation. Chem. Mater., 2018, 30(21): 7545.

[11] P.Y. Hou, J.M. Yin, M. Ding, J.Z. Huang, and X.J. Xu, Surface/interfacial structure and chemistry of high-energy nickel-rich layered oxide cathodes: Advances and perspectives, Small, 13(2017), No. 45, art. No. 1701802.

[12] Bak SM, Nam KW, Chang WY, Yu XQ, Hu EY, Hwang S, Stach EA, Kim KB, Chung KY, Yang XQ. Correlating structural changes and gas evolution during the thermal decomposition of charged Li_xNi_0.8Co_0.15Al_0.05O₂ cathode materials. Chem. Mater., 2013, 25(3): 337.

[13] Cheng KL, Mu DB, Wu BR, Wang L, Jiang Y, Wang R. Electrochemical performance of a nickel-rich LiNi_0.6Co_0.2Mn_0.2O₂ cathode material for lithium-ion batteries under different cut-off voltages. Int. J. Miner. Metall. Mater., 2017, 24(3): 342.

[14] Kim UH, Jun DW, Park KJ, Zhang Q, Kaghazchi P, Aurbach D, Major DT, Goobes G, Dixit M, Leifer N, Wang CM, Yan P, Ahn D, Kim KH, Yoon CS, Sun YK. Pushing the limit of layered transition metal oxide cathodes for high-energy density rechargeable Li ion batteries. Energy Environ. Sci., 2018, 11(5): 1271.

[15] Lee KK, Yoon WS, Kim KB, Lee KY, Hong ST. Thermal behavior and the decomposition mechanism of electro-chemically delithiated Li_1−xNiO₂. J. Power Sources, 2001, 97–98, 321.

[16] Hwang S, Chang W, Kim SM, Su D, Kim DH, Lee JY, Chung KY, Stach EA. Investigation of changes in the surface structure of Li_xNi_0.8Co_0.15Al_0.05O₂ cathode materials induced by the initial charge. Chem. Mater., 2014, 26(2): 1084.

[17] Zhang HL, Omenya F, Whittingham MS, Wang CM, Zhou GW. Formation of an anti-core-shell structure in layered oxide cathodes for Li-ion batteries. ACS Energy Lett., 2017, 2(11): 2598.

[18] Lee SH, Lee S, Jin BS, Kim HS. Preparation and electrochemical performances of Ni-rich LiNi_0.91Co_0.06Mn_0.03O₂ cathode for high-energy LIBs. Int. J. Hydrogen Energy, 2019, 44(26): 13684.

[19] Abraham DP, Twesten RD, Balasubramanian M, Petrov I, McBreen J, Amine K. Surface changes on LiNi_0.8Co_0.2O₂ particles during testing of high-power lithium-ion cells. Electrochem. Commun., 2002, 4(8): 620.

[20] Zhao JK, Wang ZX, Wang JX, Guo HJ, Li XH, Gui WH, Chen N, Yan GH. Anchoring K⁺ in Li⁺ sites of LiNi_0.8Co_0.15Al_0.05O₂ cathode material to suppress its structural degradation during high-voltage cycling. Energy Technol., 2018, 6(12): 2358.

[21] Yang J, Xia YY. Suppressing the phase transition of the layered Ni-rich oxide cathode during high-voltage cycling by introducing low-content Li₂MnO₃. ACS Appl. Mater. Interfaces, 2016, 8(2): 1297.

[22] Fu CC, Li GS, Luo D, Li Q, Fan JM, Li LP. Nickel-rich layered microspheres cathodes: lithium/nickel disordering and electrochemical performance. ACS Appl. Mater. Interfaces, 2014, 6(18): 15822.

[23] Liu BS, Wang ZB, Yu FD, Xue Y, Wang GJ, Zhang Y, Zhou YX. Facile strategy of NCA cation mixing regulation and its effect on electrochemical performance. RSC Adv., 2016, 6(110): 108558.

[24] Hayashi T, Okada J, Toda E, Kuzuo R, Oshimura N, Kuwata N, Kawamura J. Degradation mechanism of LiNi_0.82Co_0.15Al_0.03O₂ positive electrodes of a lithium-ion battery by a long-term cycling test. J. Electrochem. Soc., 2014, 161(6): A1007.

[25] Sharifi-Asl S, Soto FA, Nie A, Yuan YF, Asayesh-Ardakani H, Foroozan T, Yurkiv V, Song B, Mashayek F, Klie RF, Amine Lu J, Balbuena PB, Shahbazian-Yassar R. Facet-dependent thermal instability in LiCoO₂. Nano Lett., 2017, 17(4): 2165.

[26] Zhang JF, Zhang JY, Ou X, Wang CH, Peng CL, Zhang B. Enhancing high-voltage performance of Ni-rich cathode by surface modification of self-assembled NASICON fast ionic conductor LiZr₂(PO₄)₃. ACS Appl. Mater. Interfaces, 2019, 11(17): 15507.

[27] Xu CL, Xiang W, Wu ZG, Li YC, Xu YD, Hua WB, Guo XD, Zhang XB, Zhong BH. A comparative study of crystalline and amorphous Li_0.5La_0.5TiO₃ as surface coating layers to enhance the electrochemical performance of LiNi_0.815Co0.15Al_0.035O₂ cathode. J. Alloys Compd., 2018, 740, 428.

[28] Ren YY, Yao HH, Hu JH, Cao GQ, Tian JJ, Pan JM. Evolution of “spinodal decomposition”-like structures during the oxidation of Zr(Fe,Nb)₂ under subcritical environment. Scripta Mater., 2020, 187, 107.

[29] Ito S, Fujiki S, Yamada T, Aihara Y, Park Y, Kim TY, Baek SW, Lee JM, Doo S, Machida N. A rocking chair type all-solid-state lithium ion battery adopting Li₂O-ZrO₂ coated LiNi_0.8Co_0.15Al_0.05O₂ and a sulfide based electrolyte. J. Power Sources, 2014, 248, 943.

[30] Duan JG, Wu C, Cao YB, Du K, Peng ZD, Hu GR. Enhanced electrochemical performance and thermal stability of LiNi_0.80Co_0.15Al_0.05O₂ via nano-sized LiMnPO₄ coating. Electrochim. Acta, 2016, 221, 14.

[31] Zhao EY, Chen MM, Hu ZB, Chen DF, Yang LM, Xiao XL. Improved cycle stability of high-capacity Ni-rich LiNi_0.8Mn_0.1Co_0.1O₂ at high cut-off voltage by Li₂SiO₃ coating. J. Power Sources, 2017, 343, 345.

[32] Jiang XD, Wei Y, Yu XH, Dong P, Zhang YJ, Zhang YN, Liu JX. CeVO₄-coated LiNi_0.6Co_0.2Mn_0.2O₂ as positive material: Towards the excellent electrochemical performance at normal and high temperature. J. Mater. Sci. Mater. Electron., 2018, 29(18): 15869.

[33] Huang YQ, Huang YH, Hu XL. Enhanced electrochemical performance of LiNi_0.8Co_0.15Al_0.05O₂ by nanoscale surface modification with Co₃O₄. Electrochim. Acta, 2017, 231, 294.

[34] Sun SM, Liu T, Niu QH, Sun XL, Song DP, Liu H, Zhou XX, Ohsaka T, Wu JF. Improvement of superior cycle performance of LiNi_0.8Co_0.15Al_0.05O₂ cathode for lithium-ion batteries by multiple compound modifications. J. Electroanal. Chem., 2019, 838, 178.

[35] He XS, Du CY, Shen B, Chen C, Xu X, Wang YJ, Zuo PJ, Ma YL, Cheng XQ, Yin GP. Electronically conductive Sb-doped SnO₂ nanoparticles coated LiNi_0.8Co_0.15Al_0.05O₂ cathode material with enhanced electrochemical properties for Li-ion batteries. Electrochim. Acta, 2017, 236, 273.

[36] Liu CD, Cao GQ, Wu ZH, Hu JH, Wang HY, Shao GS. Surficial structure retention mechanism for LiNi_0.8Co_0.15Al_0.05O₂ in a full gradient cathode. ACS Appl. Mater. Interfaces, 2019, 11(35): 31991.

[37] Fan FY, Woodford WH, Li Z, Baram N, Smith KC, Helal A, Mckinley GH, Carter WC, Chiang YM. Polysulfide flow batteries enabled by percolating nanoscale conductor networks. Nano Lett., 2014, 14(4): 2210.

[38] Y.K. Wang, R.F. Zhang, J. Chen, H. Wu, S.Y. Lu, K. Wang, H.L. Li, C.J. Harris, K. Xi, R.V. Kumar, and S.J. Ding, Enhancing catalytic activity of titanium oxide in lithium-sulfur batteries by band engineering, Adv. Energy Mater., 9(2019), No. 24, art. No. 1900953.

[39] Amin R, Ravnsbaek DB, Chiang YM. Characterization of electronic and ionic transport in Li_1−xNi_0.8Co_0.15Al_0.05O₂ (NCA). J. Electrochem. Soc., 2015, 162(7): A1163.

[40] H. Yuan, J.Q. Huang, H.J. Peng, M.M. Titirici, R. Xiang, R.J Chen, Q.B. Liu, and Q. Zhang, A review of functional binders in lithium-sulfur batteries, Adv. Energy Mater., 8(2018), No. 31, art. No. 1802107.

[41] He XN, Li SY, Cao GQ, Hu JH, Zhang JH, Qiao R, Pan JM, Shao GS. In situ atomic-scale engineering of the chemistry and structure of the grain boundaries region of Li_3xLa_2/3−xTiO₃. Scripta Mater., 2020, 185, 134.

[42] Yang T, Li Y, Chan CK. Enhanced lithium ion conductivity in lithium lanthanum titanate solid electrolyte nanowires prepared by electrospinning. J. Power Sources, 2015, 287, 164.

[43] Teo WE, Ramakrishna S. A review on electrospinning design and nanofibre assemblies. Nanotechnology, 2006, 17(14): R89.

[44] W. Liu, S.W. Lee, D.C. Lin, F.F. Shi, S. Wang, A.D Sendek, and Y. Cui, Enhancing ionic conductivity in composite polymer electrolytes with well-aligned ceramic nanowires, Nat. Energy, 2(2017), No. 5, art. No. 17035.

[45] Zheng NC, Li XF, Yan S, Wang Q, Qiao R, Hu JH, Fan JJ, Cao GQ, Shao GS. Nano-porous Hollow Li_0.5La_0.5TiO₃ spheres and electronic structure modulation for ultra-fast H₂S detection. J. Mater. Chem. A, 2020, 8(5): 2376.

[46] L. Fan, S.Y. Wei, S.Y. Li, Q. Li, and Y.Y. Lu, Recent progress of the solid-state electrolytes for high-energy metal-based batteries, Adv. Energy Mater., 8(2018), No. 11, art. No. 1702657.

[47] Wang Q, Zhang JH, He XN, Cao GQ, Hu JH, Pan JM, Shao GS. Synergistic effect of cation ordered structure and grain boundary engineering on long-term cycling of Li_0.35La_0.55TiO₃-based solid batteries. J. Eur. Ceram. Soc., 2019, 39(11): 3332.

[48] Hu JH, Wang P, Liu PP, Cao GQ, Wang Q, Wei M, Mao J, Liang CH, Shao GQ. In situ fabrication of nano porous NiO-capped Ni₃P film as anode for Li-ion battery with different lithiation path and significantly enhanced electrochemical performance. Electrochim. Acta, 2016, 220, 258.

[49] Noh HJ, Youn SG, Yoon CS, Sun YK. Comparison of the structural and electrochemical properties of layered Li[Ni_x-Co_yMn_z]O₂ (x = 1/3, 0.5, 0.6, 0.7, 0.8 and 0.85) cathode material for lithium-ion batteries. J. Power Sources, 2013, 233, 121.

[50] Croguennec L, Pouillerie C, Delmas C. Structural characterisation of new metastable NiO₂ phases. Solid State Ionics, 2000, 135(1–4): 259.

[51] Wang P, Hu JH, Cao GQ, Zhang SL, Zhang P, Liang CH, Wang Z, Shao GS. Suppression on allotropic transformation of Sn planar anode with enhanced electrochemical peformance. Appl. Surf. Sci., 2018, 435, 1150.

[52] Hu JH, Yang L, Cao GQ, Yun YF, Yuan GH, Yue Q, Shao GS. On the oxidation behavior of (Zr,Nb)₂Fe under simulated nuclear reactor conditions. Corros. Sci., 2016, 112, 718.

[53] Li W, Reimers JN, Dahn JR. In situ X-ray diffraction and electrochemical studies of Li_1−xNiO₂. Solid State Ionics, 1993, 67(1–2): 123.

[54] Cao SQ, Wang QJ, Hu JH, Fu ZY, Bai KF, Shao GS, Cao GQ. Dominant growth of higher manganese silicide film on Si substrate by introducing a Si oxide capping layer. J. Alloys Compd., 2018, 740, 541.

[55] Cho Y, Oh P, Cho J. A new type of protective surface layer for high-capacity Ni-based cathode materials: Nanoscaled surface pillaring layer. Nano Lett., 2013, 13(3): 1145.

[56] Peng ZJ, Yang GW, Li FQ, Zhu ZH, Liu ZY. Improving the cathode properties of Ni-rich LiNi_0.6Co_0.2Mn_0.2O₂ at high voltages under 5C by Li₂SiO₃ coating and Si⁴⁺ doping. J. Alloys Compd., 2018, 762, 827.

[57] Zheng SJ, Huang R, Makimura Y, Ukyo Y, Fisher CAJ, Hirayama T, Ikuhara Y. Microstructural changes in LiNi_0.8Co_0.15Al_0.05O₂ positive electrode material during the first cycle. J. Electrochem. Soc., 2011, 158(4): A357.

[58] Setiawan H, Murti Petrus HTB, Perdana I. Reaction kinetics modeling for lithium and cobalt recovery from spent lithium-ion batteries using acetic acid. Int. J. Miner. Metall. Mater., 2019, 26(1): 98.

[59] Cao GQ, Yun YF, Xu HJ, Yuan GH, Hu JH, Shao GS. A mechanism assessment for the anti-corrosion of zirconia coating under the condition of subcritical water corrosion. Corros. Sci., 2019, 152, 54.

[60] Xu B, Fell CR, Chi MF, Meng YS. 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(6): 2223.

[61] Q. Wang, X.F. Li, X.N. He, L.Y. Cao, G.Q. Cao, H.J. Xu, J.H. Hu, and G.S. Shao, Two-pronged approach to regulate Li etching for a stable anode, J. Power Sources, 455(2020), art. No. 227988.

[62] Qian DN, Xu B, Cho HM, Hatsukade T, Carroll KJ, Meng YS. Lithium lanthanum titanium oxides: A fast ionic conductive coating for lithium-ion battery cathodes. Chem. Mater., 2012, 24(14): 2744.

[63] Guan HY, Lian F, Ren Y, Wen Y, Pan XR, Sun JL. Comparative study of different membranes as separators for rechargeable lithium-ion batteries. Int. J. Miner. Metall. Mater., 2013, 20(6): 598.