Electrochemical Behaviors of LixMO (x=0.79, 0.30, 0.08; M=Ni/Co/Mn) Recycled from Spent Li-ion Batteries as Cathodic Catalyst for Lithium-Oxygen Battery

doi:10.6023/A22050206

Acta Chimica Sinica ›› 2022, Vol. 80 ›› Issue (9): 1269-1276.DOI: 10.6023/A22050206 Previous Articles Next Articles

Article

基于废旧锂电池回收制备Li_xMO (x=0.79, 0.30, 0.08; M=Ni/Co/Mn)材料作为锂-氧气电池正极催化剂的电化学性能研究

张爽^a, 杨成飞^b, 杨玉波^b, 冯宁宁^b^,^*(), 杨刚^a^,^b^,^*()

a 苏州大学材料与化学化工学部苏州 215006
b 常熟理工学院江苏省先进材料实验室常熟 215500

投稿日期:2022-05-04 发布日期:2022-08-09
通讯作者: 冯宁宁, 杨刚
基金资助:
国家自然科学基金(22109015); 江苏省高校自然科学基金重大项目(18KJA430001); 江苏省高等学校基础科学面上项目(21KJB150025)

Electrochemical Behaviors of Li_xMO (x=0.79, 0.30, 0.08; M=Ni/Co/Mn) Recycled from Spent Li-ion Batteries as Cathodic Catalyst for Lithium-Oxygen Battery

Shuang Zhang^a, Chengfei Yang^b, Yubo Yang^b, Ningning Feng^b(), Gang Yang^a^,^b()

a School of Materials Science and Engineering, Soochow University, Suzhou 215006
b Jiangsu Laboratory of Advanced Functional Materials, Changshu Institute of Technology, Changshu 215500

Received:2022-05-04 Published:2022-08-09
Contact: Ningning Feng, Gang Yang
Supported by:
National Natural Science Foundation of China(22109015); Natural Science Foundation of Jiangsu Educational Department of China(18KJA430001); Natural Science Foundation of the Higher Education Institutions of Jiangsu Province(21KJB150025)

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Abstract

Lithium-oxygen battery has been studied as a hot spot because of its high theoretical specific capacity. But its severe discharge/charge polarization and poor cycle stability greatly hinder its large-scale applications at current stage. The rational design of cathodic catalysts for the oxygen reduction/evolution reaction (ORR/OER) is thus essential to reduce overpotential and extend cycling stability. Three kinds of multi-metal oxides Li_xMO (x=0.79, 0.30, 0.08; M=Ni/Co/Mn) with different lithium contents, which were recycled from the cathodes of spent lithium-ion batteries in different charging states, were explored as cathodic catalysts for lithium-oxygen batteries, respectively. The lithium content and phase structure of these multi-metal oxides Li_xMO were determined by inductive coupled plasma emission spectrometer (ICP) and X-ray diffraction (XRD). Phase transformation from layer to NiO-like rock-salt was observed upon continuous deintercalation of Li⁺ in Li_xMO materials (0.79→0.30→0.08). The dependence of the electrochemical behaviors on the lithium content and lattice structure of the Li_xMO catalysts was also investigated systematically. Compared to that of Li_0.79MO and Li_0.08MO, lithium-oxygen batteries with Li_0.30MO catalyst have delivered a higher specific capacity of 14655.9 mAh•g^–1, a lower charge potential of 3.83 V, and a higher round-trip efficiency of 72.2% under the limited capacity of 800 mAh•g^–1 and current density of 100 mA•g^–1. Moreover, the charge terminal voltage of Li_0.30MO catalyst is stable lower than 4.3 V even after 140 cycles. Furthermore, the ex-situ scanning electron microscope (SEM) and X-ray photoelectron spectroscopy (XPS) techniques were used to elucidate the reaction mechanisms with different Li_xMO catalysts. The superior catalytic activity of Li_0.30MO cathode can be mainly attributed to the synergistic effect between its layered/NiO-like rock-salt complex structure and oxygen vacancy formed, which can promote the reversible formation and decomposition of discharge product and improve the cycling stability of lithium-oxygen battery. Hence, the result corroborates that recycling of spent cathodes from lithium-ion batteries can serve as novel strategy to design large-scale and effective catalysts for lithium-oxygen battery.

Key words: spent lithium-ion battery, lithium content, multi-metal oxide, cathodic catalyst, lithium-oxygen battery

Cite this article

Shuang Zhang, Chengfei Yang, Yubo Yang, Ningning Feng, Gang Yang. Electrochemical Behaviors of Li_xMO (x=0.79, 0.30, 0.08; M=Ni/Co/Mn) Recycled from Spent Li-ion Batteries as Cathodic Catalyst for Lithium-Oxygen Battery[J]. Acta Chimica Sinica, 2022, 80(9): 1269-1276.

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Fig. & Tab. 7

Sample	Li	Ni	Co	Mn
A	0.79	0.85	0.10	0.05
B	0.30	0.85	0.10	0.05
C	0.08	0.85	0.10	0.05

Table 1. ICP-OES data of the recycled LixMO with different lithium content

Figure 1. Different charging states of spent Li-ion batteries

Figure 2. (a) XRD patterns of recycled LixMO (x=0.79, 0.30, 0.08; M=Ni/Co/Mn) with different lithium content and (b) SEM images of Li0.79MO, (c) Li0.30MO and (d) Li0.08MO

Figure 3. XPS spectra of recycled LixMO (x=0.79, 0.30, 0.08; M=Ni/Co/Mn) with different lithium content (a) Li 1s, (b) Ni 2p and (c) O 1s

Figure 4. (a) CV curves and (b) initial discharge/charge curves of lithium-oxygen batteries with recycled LixMO (x=0.79, 0.30, 0.08; M=Ni/Co/Mn) cathodic catalysts, cycling curves of lithium-oxygen batteries with (c) Li0.79MO, (d) Li0.30MO and (e) Li0.08MO, and (f) comparison of cycle performance of lithium-oxygen batteries with recycled LixMO (x=0.79, 0.30, 0.08; M=Ni/Co/Mn) cathodic catalysts

Figure 5. (a) SEM images of pristine electrode, (b) electrode after discharged to 2.3 V, (c) electrode after charged in lithium-oxygen batteries with Li0.79MO, (d) SEM images of pristine electrode, (e) electrode after discharged to 2.3 V, (f) electrode after charged in lithium-oxygen batteries with Li0.30MO, (g) SEM images of pristine electrode, (h) electrode after discharged to 2.3 V and (i) electrode after charged in lithium-oxygen batteries with Li0.08MO

Figure 6. XPS spectra of electrodes after discharged to 2.3 V and charged in lithium-oxygen batteries with Li0.79MO [(a) Li 1s and (b) C 1s], XPS spectra of electrodes after discharged to 2.3 V and charged in lithium-oxygen batteries with Li0.30MO [(c) Li 1s and (d) C 1s] and XPS spectra of electrodes after discharged to 2.3 V and charged in lithium-oxygen batteries with Li0.08MO [(e) Li 1s and (f) C 1s]

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基于废旧锂电池回收制备Li_xMO (x=0.79, 0.30, 0.08; M=Ni/Co/Mn)材料作为锂-氧气电池正极催化剂的电化学性能研究

Electrochemical Behaviors of Li_xMO (x=0.79, 0.30, 0.08; M=Ni/Co/Mn) Recycled from Spent Li-ion Batteries as Cathodic Catalyst for Lithium-Oxygen Battery

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