Abstract
Layered structure LiNi0.8Co0.15Al0.05O2 (NCA) with high energy density is considered to be the most promising cathode material, but poor structural stability hinders its further development. Here, Na+/Br- co-doped NCA (Na&Br-NCA) was prepared via simple solid phase method. Electrochemical studies showed that cation Na+ doping stabilizes the crystal structure, increases the lattice spacing, and reduces the mixing of cations. Anion Br- doping increases the spacing between the plates and forms a weaker Li-Br bond, which is more conducive to the insertion and extraction of Li+. At 2C, Na&Br-NCA exhibited a reversible capacity of 184.1 mAh g−1 with retention of 91.5% after 100 cycle and a superior rate performance (160.2 mAh g−1 at 5C) compared to pure NCA that showed 180.1 mAh g−1 with retention of 77.7% and 148.6 mAh g−1 at 5C. The results show that Na+/Br- co-doping is beneficial to stabilize the layered structure, reduce polarization, and promote lithium-ion diffusion of Na&Br-NCA. It also provides inspiration for other cation/anion co-doped modified cathode materials.
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References
- 1.
Qiu ZP, Zhang YJ, Huang XS, Duan JG, Wang D, NaYaKa GP, Li X, Dong P (2018) Beneficial effect of incorporating Ni-rich oxide and layered over-lithiated oxide into high-energy-density cathode materials for lithium-ion batteries. J Power Sources 400:341–349
- 2.
Duan JG, Hu GR, Cao YB, Tan CP, Wu C, Du K, Peng ZD (2016) Enhanced electrochemical performance and storage property of LiNi0.815Co0.15Al0.035O2 via Al gradient doping. J Power Sources 326:322–330
- 3.
Chen YX, Li YJ, Li W, Cao GL, Tang SY, Su QY, Deng SY, Guo J (2018) High-voltage electrochemical performance of LiNi0.5Co0.2Mn0.3O2 cathode material via the synergetic modification of the Zr/Ti elements. Electrochim Acta 281:48–59
- 4.
Lee JH, Yoon CS, Hwang JY, Kim SJ, Maglia F, Lamp P, Myung ST, Sun YK (2016) High-energy-density lithium-ion battery using a carbon-nanotube-Si composite anode and a compositionally graded Li[Ni0.85Co0.05Mn0.10]O2 cathode. Energy Environ Sci 9:2152–2158
- 5.
Xia SB, Zhang YJ, Dong P (2014) Improve electrochemical performance of CeO2 surface modification LiNi0.8Co0.15Al0.05O2 cathode material. Eur Phys J Appl Phys 66:30403
- 6.
Huang B, Li XH, Wang ZX, Guo HJ, Xiong XH (2014) Synthesis of Mg-doped LiNi0.8Co0.15Al0.05O2 oxide and its electrochemical behavior in high-voltage lithium-ion batteries. Ceram Int 40:13223–13230
- 7.
Zhao EY, Hu ZB, Xie L, Chen XP, Xiao XL, Liu XF (2015) A study of the structure–activity relationship of the electrochemical performance and Li/Ni mixing of lithium-rich materials by neutron diffraction. RSC Adv 5:31238–31244
- 8.
Hwang S, Kim SM, Bak SM, Chung KY, Chang W (2015) Investigating the reversibility of structural modifications of LixNiyMnzCo1–y–zO2 cathode materials during initial charge/discharge, at multiple length scales. Chem Mater 27:6044–6052
- 9.
Cho Y, Lee YS, Park SA, Lee Y, Cho J (2010) LiNi0.8Co0.15Al0.05O2 cathode materials prepared by TiO2 nanoparticle coatings on LiNi0.8Co0.15Al0.05(OH)2 precursors. Electrochim Acta 56:333–339
- 10.
Ito S, Fujiki S, Yamada T, Yamada T, Aihara Y, Park Y, Kim TY, Baek SW, Machida N (2014) A rocking chair type all-solid-state lithium ion battery adopting Li2O–ZrO2 coated LiNi0.8Co0.15Al0.05O2 and a sulfide based electrolyte. J Power Sources 248:943–950
- 11.
Wu G, Zhou YK (2019) TiP2O7-coated LiNi0.8Co0.15Al0.05O2 cathode materials with improved thermal stability and superior cycle life. J Energy Chem 28:151–159
- 12.
Huang B, Li XH, Wang ZX, Guo HJ (2014) A facile process for coating amorphous FePO4 onto LiNi0.8Co0.15Al0.05O2 and the effects on its electrochemical properties. Mater Lett 131:210–213
- 13.
Park BC, Kim HB, Bang HJ, Prakash J, Sun YK (2008) Improvement of electrochemical performance of LiNi0.8Co0.15Al0.05O2 cathode materials by AlF3 coating at various temperatures. Ind Eng Chem Res 47:3876–3882
- 14.
Xie HB, Du K, Hu GR, Peng ZD, Cao YB (2016) The role of sodium in LiNi0.8Co0.15Al0.05O2 cathode material and its electrochemical behaviors. J Phys Chem C 120:3235–3241
- 15.
Bai X, Wei AJ, He R, Li W, Li XH, Zhang LH, Liu ZF (2020) The structural and electrochemical performance of Mg-doped LiNi0.85Co0.10Al0.05O2 prepared by a solid state method. J Electroanal Chem 858:113771
- 16.
Yang J, Huang BX, Yin JY (2016) Structure integrity endowed by a Ti-containing surface layer towards ultrastable LiNi0.8Co0.15Al0.05O2 for all-solid-stateithium batteries. J Electrochem Soc 163:A1530–A1534
- 17.
Lee MJ, Noh M, Park MH, Jo M, Kim H, Nam H, Cho J (2015) The role of nanoscale-range vanadium treatment in LiNi0.8Co0.15Al0.05O2 cathode materials for Li-ion batteries at elevated temperatures. J Mater Chem A 3:13453–13460
- 18.
Li X, Xie ZW, Liu WJ, Wang H, Qu MZ (2015) Effects of fluorine doping on structure, surface chemistry,and electrochemical performance of LiNi0.8Co0.15Al0.05O2. Electrochim Acta 174:1122–1130
- 19.
Chen T, Li X, Wang H, Yan XY, Wang L, Deng BW, Ge WJ, Qu MZ (2018) The effect of gradient boracic polyanion-doping on structure, morphology, and cycling performance of Ni-rich LiNi0.8Co0.15Al0.05O2 cathode material. J Power Sources 374:1–11
- 20.
Liu Y, Ning D, Zheng LR, Zhang QH, Liu XF (2018) Improving the electrochemical performances of Li-rich Li1.20Ni0.13Co0.13Mn0.54O2 through a cooperative doping of Na+ and PO43− with Na3PO4. J Power Sources 375:1–10
- 21.
Qiu ZP, Liu Z, Fu XJ, Liu JM, Zeng QG (2019) Improving the cycling performance of LiNi0.8Co0.15Al0.05O2 cathode materials via zirconium and fluorine co-substitution. J Alloys Compd 806:136–145
- 22.
Qiu L, Xiang W, Tian W, Xu CL, Li YC, Guo XD (2019) Polyanion and cation co-doping stabilized Ni-rich Ni–Co–Al material as cathode with enhanced electrochemical performance for Li-ion battery. Nano Energy 63:103818
- 23.
Liu W, Li XF, Xiong DB, Hao YC, Li JW, Lu SG (2017) Significantly improving cycling performance of cathodes in lithium ion batteries: the effect of Al2O3 and LiAlO2 coatings on LiNi0.6Co0.2Mn0.2O2. Nano Energy 44:111–120
- 24.
Xiang W, Liu WY, Zhang J, Wang S, Zhang TT, Yin K (2018) Controlled synthesis of nickel-rich layered oxide cathodes with preferentially exposed {010} active facets for high rate and long cycling stable lithium-ion batteries. J Alloys Compd 775:72–80
- 25.
Wang YY, Sun YY, Liu S, Li GR, Gao XP (2018) Na-doped LiNi0.8Co0.15Al0.05O2 with excellent stability of both capacity and potential as cathode materials for li-ion batteries. ACS Appl Energy Mater 1:3881–3889
- 26.
He SY, Wei AJ, Li W, Bai X, Zhang LH, Liu ZF (2019) An in-depth analysis detailing the structural and electrochemical properties within Br modified LiNi0.815Co0.15Al0.035O2(NCA) cathode material. Electrochim Acta 318:362–373
- 27.
Lei YK, Li YH, Jiang HY, Lai CY (2019) Preparing enhanced electrochemical performances Fe2O3-coated LiNi1/3Co1/3Mn1/3O2 cathode materials by thermal decomposition of iron citrate. J Mater Sci 54:4202–4211
- 28.
Baboo JP, Park H, Song J, Kim S, Jo J, Pham DT, Mathew V, Xiu Z, Kim J (2016) Facile redox synthesis of layered lini1/3Co1/3Mn1/3O2 for rechargeable li-ion batteries. Electrochim Acta 224:243–250
- 29.
Yang J, Xia YY (2016) Enhancement on the cycling stability of the layered Ni-rich oxide cathode by in-situ fabricating nano-thickness cation-mixing layers. J Electrochem Soc 163:A2665–A2672
- 30.
Cho Y, Oh P, Cho J (2013) A new type of protective surface layer for high-capacity Ni-based cathode materials: nanoscaled surface pillaring layer. Nano Lett 13:1145–1152
- 31.
Xie ZC, Zhang YY, Yuan AB, Xu JQ (2019) Effects of lithium excess and SnO2 surface coating on the electrochemical performance of LiNi0.8Co0.15Al0.05O2 cathode material for Li-ion batteries. J Alloys Compd 787:429–439
- 32.
Hao ZD, Xu XL, Deng SX, Wang H, Liu JB, Yan H (2019) In situ growth of Co3O4 coating layer derived from MOFs on LiNi0.8Co0.15Al0.05O2 cathode materials. Ionics 25:2469–2476
- 33.
Zheng JC, Yang Z, He ZJ, Tong H, Yu WJ, Zhang JF (2018) In situ formed LiNi0.8Co0.15Al0.05O2@Li4SiO4 composite cathode material with high rate capability and long cycling stability for lithium-ion batteries. Nano Energy 53:613–621
- 34.
Xia S, Li F, Chen F (2017) Preparation of FePO4 by liquid-phase method and modification on the surface of LiNi0.8Co0.15Al0.05O2 cathode material. J Alloys Compd 731:428–436
- 35.
Chen Z, Cao K, Zhu H (2019) Improved electrochemical performance of surface coated LiNi0.8Co0.15Al0.05O2 with polypyrrole. Front Chem 6:648
- 36.
Liu PC, Xiao L, Chen YF, Chen H (2019) Highly enhanced electrochemical performances of LiNi0.815Co0.15Al0.035O2 by coating via conductively LiTiO2 for lithium-ion batteries. Ceram Int 45:18398–18405
- 37.
Deng H, Li SM, Liu H, Mei J, Liu H, Liu GB (2019) Facile synthesis and electrochemical properties of LiNi0.8Co0.15Al0.05O2 with enlarged exposed active planes for Li-ion batteries. Ionics 25:827–834
- 38.
Zhang JF, Zhang JY, Ou X, Wang CH, Zhang B (2019) Enhancing high-voltage performance of Ni-rich cathode by surface modification of self-assembled NASICON-fast ion conductor LiZr2(PO4)3. ACS Appl Mater Interfaces 11:15507–15516
- 39.
Yan XX, Chen L, Shah SA, Liang JJ, Liu ZF (2017) The effect of Co3O4&LiCoO2 cladding layer on the high rate and storage property of high nickel material LiNi0.8Co0.15Al0.05O2 by simple one-step wet coating method. Electrochim Acta 249:179–188
- 40.
Hou PY, Zhang HZ, Deng XL, Xu XJ, Zhang LQ (2017) Stabilizing the electrode/electrolyte interface of LiNi0.8Co0.15Al0.05O2 through tailoring aluminum distribution in microspheres as long-life, high-rate, and safe cathode for lithium-ion batteries. ACS Appl Mater Interfaces 9:29643–29653
- 41.
Liu WM, Guo HH, Qin ML, Hong TL (2018) Effect of voltage range and BiPO4 Coating on the electrochemical properties of LiNi0.8Co0.15Al0.05O2. ChemistrySelect 3:7660–7666
- 42.
Li YC, Zhao WM, Xiang W, Wu ZG, Yang ZG (2018) Promoting the electrochemical performance of LiNi0.8Co0.1Mn0.1O2 cathode via LaAlO3 coating. J Alloys Compd 766:546–555
Funding
This work received support from the Venture & Innovation Support Program for Chongqing Overseas Returnees (No.cx2019128), the Key Project of Science and Technology Research of Chongqing Education Commission of China (No.KJZDK201801103), the Chongqing Technology Innovation and Application Development project of Chongqing Science and Technology Commission (No.cstc2019jscx-msxmX0358), the Youth project of Science and Technology research program of Chongqing Education Commission of China (No.KJQN201901110), and the Basic and Frontier Research Project of Chongqing Science and Technology Commission (No. cstc2019jcyj-msxmX0165).
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Yang, B., Zhou, L., Hu, X. et al. Enhancing the electrochemical performances of LiNi0.8Co0.15Al0.05O2 cathode material by anion/cation co-doping. Ionics (2021). https://doi.org/10.1007/s11581-021-03947-9
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Keywords
- NCA
- Na+ /Br- co-doped
- Lithium-ion batteries