Atomic-scale tuned interface of nickel-rich cathode for enhanced electrochemical performance in lithium-ion batteries

doi:10.1016/j.jmst.2020.02.080

Abstract

Abstract:

The Ni-rich layered LiNi_0.6Mn_0.2Co_0.2O₂ (NMC622) is one promising cathode for lithium-ion batteries (LIBs), but suffers from poor cycling stability under high cutoff potentials. The performance degradation was reflected as capacity fading and voltage drop, having their roots in instable interface of NMC622. Aimed at improving interfacial stability, in this study, we deposited nanoscale ZrO₂ coatings conformally over NMC622 cathodes using atomic layer deposition (ALD). We found that, under a high cutoff voltage (4.5 V), the ALD ZrO₂ coatings evidently improved the performance of NMC622 cathode, showing better cyclability and higher sustainable capacity. In addition, the ALD coatings dramatically boosted the rate capability of NMC622. All these compelling performance results are ascribed to the atomic-scale tunable ZrO₂ coatings via ALD, which create stable interface and thereby inhibit unfavorable evolutions. In the study, we utilize a suite of characterization tools and various analyses to clarify the effects of ALD ZrO₂ coatings. This study will be helpful for improving the performance of nickel-rich cathodes via interfacial engineering using ALD.

Key words: Atomic layer deposition, Lithium ion battery, Surface coating

Yongqiang Liu, Xin Wang, Jiyu Cai, Xiaoxiao Han, Dongsheng Geng, Jianlin Li, Xiangbo Meng. Atomic-scale tuned interface of nickel-rich cathode for enhanced electrochemical performance in lithium-ion batteries[J]. J. Mater. Sci. Technol., 2020, 54: 77-86.

Figures/Tables 10

Fig. 1. (a) Simple schematic illustration of the ALD ZrO2 deposition steps; (b) Enlarged three consecutive cycles for in-situ QCM measurements of ALD ZrO2; SEM images of (c) bare NGS and ALD-coated NGS with (d) 100 and (e) 200 cycles of ZrO2 at 100 °C.

Fig. 2. The ALD-20 cathode observed by (a) SEM and (b-f) EDS showing the elemental mapping images of (b) Ni, (c) Mn, (d) Co, (e) Zr, and (f) O.

Fig. 3. (a) Synchrotron-based powder XRD patterns of the bare, ALD-20, and ALD-40 cathodes. (b) Comparison of the bare, ALD-20, and ALD-40 cathodes for the XRD peaks of (003), (006)/(102) and (108)/(110).

Table 1 Lattice parameters and relative intensities of the bare and ZrO2-coated samples calculated from XRD measurement.

Sample	a/b (?)	c (?)	I₀₀₃/I₁₀₄	(I₁₀₆ + I₁₀₂)/I₁₀₁
Bare	2.8965	14.3208	1.3799	0.6339
ALD-20	2.9036	14.3231	1.3803	0.5192
ALD-40	2.9102	14.3915	1.4399	0.5431

Fig. 4. (a) The cycling performances at 0.5 C rate and (b) rate capacity at various current densities of the bare and different cycles ZrO2 coated cathodes measured in a voltage range of 3.0-4.5 V. The charge/discharge capacities of (c, d) the bare and (e, f) ALD-20 cathodes, in which (c) and (e) are the as-measured capacities while (d) and (f) are the normalized capacities.

Fig. 5. The cycle performance of the bare and ALD-20 NMC622 electrodes at 3 C rate in the range of 3.0-4.5 V: (a, b) the charge-discharge profiles for (a) ALD-20 and (b) bare NMC622 cathodes; (c) cyclability.

Fig. 6. Nyquist plots of the bare and ALD-20 NMC622/Li half-cells at 4.5 V vs. Li/Li+ as a function of cycle number at 0.5 C for (a) the 1st cycle, (b) the 30th cycle, and (c) the 50th cycle. (d) The equivalent circuit employed for simulating EIS in (a)-(c). (e) Charge-transfer resistance (Rct) and (f) surface film resistance (Rs) as a function of charge-discharge cycle number.

Table 2 C1s, O1s, and F1s XPS spectral assignment of the bare and ALD-20 cathode surface after 50 cycles in the voltage range of 3.0-4.5 V. The binding energies (BE), chemical bond, and the corresponding components are given [[91], [92], [93], [94], [95], [96], [97], [98], [99], [100]].

			This work		Reported in references
			Bare	ALD-20
Peak	Chem. bond	Assignment	BE (eV)	BE (eV)	BE ± σ_max (eV)	Ref.
C1s	C—C	Carbon black	284.2		284.2	[91]
		Aliphatic chain	284.8	284.8	284.7	[92]
	C—O	C—O—C	285.8	285.8	285.8 ± 0.2	[93]
	C=O	Li₂CO₃		289	289	[94]
		Li₂CO₃	289.4		289.6 ± 0.3	[92]
	C—F	PVDF		290.6	290.7	[95]
O1s	C—O	C—OH	532.9		532.9	[92]
				533.6	533.7	[96]
	C=O	Li₂CO₃	531.4		531.6	[97]
		Li₂CO₃		532	532	[95]
	Co—O	CoO_x(OH)_y	528.6		529	[92]
F1s	C—F	PVDF	687.8	687.8	688	[98]
	O—P—F	Li_xPO_yF_z	685.6	685.6	685.6	[92]
	Li—F	LiF	685		685	[99]
		LiF		684.6	684.5	[92]
	Zr—F	ZrF₄		685.4	685.5 ± 0.1	[100]

Fig. 7. High-resolution XPS spectra of C1s, O1s, and F1s of (a, c, e) the bare and (b, d, f) ALD-20 cathodes.

Fig. 8. Schematic of failure mechanism of (a) bare and (b) ZrO2 modified NMC622.

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