以废旧锰酸锂正极为原料制备Li0.25Na0.6MnO2钠离子电池正极材料的研究

doi:10.19799/j.cnki.2095-4239.2020.0080

储能科学与技术 ›› 2020, Vol. 9 ›› Issue (5): 1402-1409.doi: 10.19799/j.cnki.2095-4239.2020.0080

以废旧锰酸锂正极为原料制备Li_0.25Na_0.6MnO₂钠离子电池正极材料的研究

聂雪娇¹(), 郭晋芝², 王美怡¹, 谷振一², 赵欣欣¹, 杨旭¹, 梁皓杰², 吴兴隆^1,²()

^1.东北师范大学化学学院，吉林长春 130024
^2.东北师范大学紫外光发射材料与技术教育部重点实验室，吉林长春 130024

收稿日期:2020-02-23 修回日期:2020-03-04 出版日期:2020-09-05 发布日期:2020-09-08
通讯作者: 吴兴隆 E-mail:niexj320@nenu.edu.cn;xinglong@nenu.edu.cn
作者简介:聂雪娇（1995—），女，硕士研究生，研究方向为钠离子电池正极材料；E-mail：niexj320@nenu.edu.cn；
基金资助:
国家自然科学基金重大研究计划(91963118)

Using spent lithium manganate to prepare Li_0.25Na_0.6MnO₂as cathode material in sodium-ion batteries

Xuejiao NIE¹(), Jinzhi GUO², Meiyi WANG¹, Zhenyi GU², Xinxin ZHAO¹, Xu YANG¹, Haojie LIANG², Xinglong WU^1,²()

^1.Faculty of Chemistry, Northeast Normal University, Changchun 130024, Jilin, China
^2.Key Laboratory for UV Light-Emitting Materials and Technology of Ministry of Education, Northeast Normal University, Changchun 130024, Jilin, China

Received:2020-02-23 Revised:2020-03-04 Online:2020-09-05 Published:2020-09-08
Contact: Xinglong WU E-mail:niexj320@nenu.edu.cn;xinglong@nenu.edu.cn

摘要/Abstract

摘要：

随着锂离子电池(lithium-ion batteries,LIBs）在众多储能领域更大规模的广泛应用，废旧LIBs正在大量地产生，若不进行任何处理而随意丢弃，必将给人类赖以生存的生活环境造成极大的危害，而且也是一种资源浪费。本课题组对废旧LIBs中的锰酸锂正极进行回收和收集，并以此为主要原料，通过球磨和高温烧结相结合的过程，成功合成了钠离子电池（sodium-ion batteries,SIBs）正极材料Li_0.25Na_0.6MnO₂（LNMO），并对其的电化学性能、动力学特性和离子脱嵌导致的相变过程进行了研究。结果显示，LNMO表现出较高的比容量（131.5 mA·h/g）以及优异的倍率性能（容量保持率97.9%），该电极的表观离子扩散系数为10^-12 cm²/s数量级，表现出快的离子脱嵌能力和动力学过程，是它表现出优异倍率性能的主要原因之一。对废旧锰酸锂材料回收并应用于下一代低成本SIBs中，具有同时实现“废旧LIBs有效回收”和“解决SIBs原料来源”的重要意义。

关键词: 废旧锂离子电池, 锰酸锂正极, 回收与再利用, 钠离子电池, Li_0.25Na_0.6MnO₂

Abstract:

With the widespread application of lithium-ion batteries (LIBs) in many energy storage fields, spent LIBs are being produced in large quantities. Discarding LIBs without any treatment causes great harm to the natural environment on which human beings rely for survival and is a waste of resources. In this paper, we collect lithium manganate cathodes from spent LIBs as the main raw materials. Via a combination of ball milling and high temperature sintering, the sodium-ion battery (SIB) cathode material Li_0.25Na_0.6MnO₂ (LNMO) is successfully synthesized; its electrochemical performance, kinetic characteristics, and the phase transition process caused by ion de-insertion are then studied. The results show that LNMO has a high specific capacity (131.5 mA·h/g) and an excellent rate performance (97.9% capacity retention). The apparent ion diffusion coefficient of the electrode is on the order of 10^-12 cm²/s, showing a fast ion de-insertion ability and kinetic process, which is one of the main reasons for its excellent rate performance. Recycling spent lithium manganate materials and applying them to the next generation of low cost SIBs has the dual significance of simultaneously achieving the effective recycling of spent LIBs and finding a source of raw SIBs materials.

Key words: spent lithium ion batteries, lithium manganite cathode, recycling and reuse, sodium ion batteries, Li_0.25Na_0.6MnO₂

中图分类号:

O 646.21

聂雪娇, 郭晋芝, 王美怡, 谷振一, 赵欣欣, 杨旭, 梁皓杰, 吴兴隆. 以废旧锰酸锂正极为原料制备Li_0.25Na_0.6MnO₂钠离子电池正极材料的研究[J]. 储能科学与技术, 2020, 9(5): 1402-1409.

Xuejiao NIE, Jinzhi GUO, Meiyi WANG, Zhenyi GU, Xinxin ZHAO, Xu YANG, Haojie LIANG, Xinglong WU. Using spent lithium manganate to prepare Li_0.25Na_0.6MnO₂as cathode material in sodium-ion batteries[J]. Energy Storage Science and Technology, 2020, 9(5): 1402-1409.

图/表 8

图1

图2

表1

图3

图4

图5

表2

图6

参考文献 41

1	PANG W L, ZHANG X H, GUO J Z, et al. P2-type Na_2/3Mn_1-_xAl_xO₂ cathode material for sodium-ion batteries: Al-doped enhanced electrochemical properties and studies on the electrode kinetics[J]. Journal of Power Sources, 2017, 356: 80-88.
2	RAMASAMY H V, KALIYAPPAN K, THANGAVEL R, et al. Efficient method of designing stable layered cathode material for sodium ion batteries using aluminum doping[J]. Journal of Physical Chemistry Letters, 2017, 8(20): 5021-5030.
3	Springer Nature SharedIt.Recycle spent batteries[J]. Nature Energy, 2019, 4(4): 253-253.
4	HARPER G, SOMMERVILLE R, KENDRICK E, et al. Recycling lithium-ion batteries from electric vehicles[J]. Nature, 2019, 7781 (575): 75-86.
5	LI H, WANG Z, CHEN L, et al. Research on advanced materials for Li-ion batteries[J]. Advanced Materials, 2009, 21(45): 4593-4607.
6	YANG X, WANG Y Y, HOU B H, et al. Nano-SnO₂ decorated carbon cloth as flexible, self-supporting and additive-free anode for sodium/lithium-ion batteries[J]. Acta Metallurgica Sinica (English Letters), 2020, doi: 10.1007/s40195-020-01001-7. doi: 10.1007/s40195-020-01001-7
7	FAN B, CHEN X, ZHOU T, et al. A sustainable process for the recovery of valuable metals from spent lithium-ion batteries[J]. Waste Management and Research, 2016, 34(5): 474-481.
8	CHEN X, CAO L, KANG D, et al. Recovery of valuable metals from mixed types of spent lithium ion batteries. Part II: Selective extraction of lithium[J]. Waste Management, 2018, 80: 198-210.
9	LI T, ZHAO C, ZHA W, et al. A clean technique to fabricate the renewable and recyclable metal phosphate anode of the high-capacity lithium-ion battery[J]. Journal of Electroanalytical Chemistry, 2019, 855: doi: 10.1016/j.jelechem.2019.113625.
10	NATARAJAN S, ARAVINDAN V. Burgeoning prospects of spent lithium-ion batteries in multifarious applications[J]. Advanced Energy Materials, 2018, 8(33): doi: 10.1002/aenm.201802303.
11	HE L P, SUN S Y, SONG X F, et al. Recovery of cathode materials and Al from spent lithium-ion batteries by ultrasonic cleaning[J]. Waste Management, 2015, 46: 523-528.
12	CHEN X, CHEN Y, ZHOU T, et al. Hydrometallurgical recovery of metal values from sulfuric acid leaching liquor of spent lithium-ion batteries[J]. Waste Management, 2015, 38: 349-356.
13	MENG Q, ZHANG Y, DONG P. Use of electrochemical cathode-reduction method for leaching of cobalt from spent lithium-ion batteries[J]. Journal of Cleaner Production, 2018, 180: 64-70.
14	YAO L, YAO H, XI G, et al. Recycling and synthesis of LiNi_1/3Co_1/3Mn_1/3O₂ from waste lithium ion batteries using d,l-malic acid[J]. RSC Advances, 2016, 6(22): 17947-17954.
15	MICHAUD X, SHI K, ZHITOMIRSKY I. Electrophoretic deposition of LiFePO₄ for Li-ion batteries[J]. Materials Letters, 2019, 241: 10-13.
16	CHEN B, BEN L, YU H, et al. Understanding surface structural stabilization of the high-temperature and high-voltage cycling performance of Al³⁺-modified LiMn₂O₄ cathode material[J]. ACS Applied Materials & Interfaces, 2018, 10(1): 550-559.
17	KITTA M, AKITA T, KOHYAMA M. Transmission electron microscopy investigation of the LiMn₂O₄/Na_xMnO₂ interface as a model study of a Na-ion battery electrode[J]. AIP Advances, 2016, 6(11): doi: 10.1063/1.4968605.
18	NIE X J, XI X T, YANG Y, et al. Recycled LiMn₂O₄ from the spent lithium ion batteries as cathode material for sodium ion batteries: Electrochemical properties, structural evolution and electrode kinetics[J]. Electrochimica Acta, 2019, 320: doi: 10.1016/j.electacta.2019.134626.
19	POTAPENKO A V, KIRILLOV S A. Enhancing high-rate electrochemical properties of LiMn₂O₄ in a LiMn₂O₄/LiNi_0.5Mn_1.5O₄ core/shell composite[J]. Electrochimica Acta, 2017, 258: 9-16.
20	YANG Y, GUO J Z, GU Z Y, et al. Effective recycling of the whole cathode in spent lithium ion batteries: From the widely used oxides to high-energy/stable phosphates[J]. ACS Sustainable Chemistry & Engineering, 2019, doi: 10.1021/acssuschemeng.9b00526. doi: 10.1021/acssuschemeng.9b00526
21	LIANG H J, HOU B H, LI W H, et al. Staging Na/K-ion de-/intercalation of graphite retrieved from spent Li-ion batteries: In operando X-ray diffraction studies and an advanced anode material for Na/K-ion batteries[J]. Energy & Environmental Science, 2019, 12(12): 3575-3584.
22	SUN Y, GUO S, ZHOU H. Adverse effects of interlayer-gliding in layered transition-metal oxides on electrochemical sodium-ion storage[J]. Energy & Environmental Science, 2019, 12(3): 825-840.
23	ORTIZ-VITORIANO N, DREWETT N E, GONZALO E, et al. High performance manganese-based layered oxide cathodes: Overcoming the challenges of sodium ion batteries[J]. Energy & Environmental Science, 2017, 10(5): 1051-1074.
24	LIU Q, HU Z, CHEN M, et al. Recent progress of layered transition metal oxide cathodes for sodium-ion batteries[J]. Small, 2019, doi: 10.1002/smll.201805381. doi: 10.1002/smll.201805381
25	GU Z Y, GUO J Z, SUN Z H, et al. Carbon-coating-increased working voltage and energy density towards an advanced Na₃V₂(PO₄)₂F₃@C cathode in sodium-ion batteries[J]. Science Bulletin, 2020, doi: 10.1016/j.scib.2020.01.018. doi: 10.1016/j.scib.2020.01.018
26	YOU Y, MANTHIRAM A. Progress in high-voltage cathode materials for rechargeable sodium-ion batteries[J]. Advanced Energy Materials, 2018, 8(2): doi: 10.1002/aenm.201701785.
27	WANG P F, YOU Y, YIN Y X, et al. Layered oxide cathodes for sodium-ion batteries: Phase transition, air stability, and performance[J]. Advanced Energy Materials, 2018, 8(8): doi: 10.1002/aenm.201701912.
28	郭晋芝, 万放, 吴兴隆, 等. 钠离子电池工作原理及关键电极材料研究进展[J]. 分子科学学报, 2016, 32(150): 265-279.
	GUO J Z, WAN F, WU X L, et al. Sodium-ion batteries: Work mechanism and the research progress of key electrode materials[J]. International Journal of Molecular Sciences, 2016, 32(150): 265-279.
29	GUO J Z, YANG Y, LIU D S, et al. A practicable Li/Na-ion hybrid full battery assembled by a high-voltage cathode and commercial graphite anode: Superior energy storage performance and working mechanism[J]. Advanced Energy Materials, 2018, 8(10): doi: 10.1002/aenm.201702504.
30	ZHANG X H, PANG W L, WAN F, et al. P2-Na_2/3Ni_1/3Mn_5/9Al_1/9O₂ microparticles as superior cathode material for sodium-ion batteries: Enhanced properties and mechanisam via graphene connection[J]. ACS Applied Materials & Interfaces, 2016, 8(32): 20650-20659.
31	GUO S, LI Q, LIU P, et al. Environmentally stable interface of layered oxide cathodes for sodium-ion batteries[J]. Nature Communications, 2017, 8(1): 135-143.
32	GONZALO E, ORTIZ-VITORIANO N, DREWETT N E, et al. P2 manganese rich sodium layered oxides: Rational stoichiometries for enhanced performance[J]. Journal of Power Sources, 2018, 401:117-125.
33	DI LECCE D, CAMPANELLA D, HASSOUN J. Insight on the enhanced reversibility of a multimetal layered oxide for sodium-ion battery[J]. The Journal of Physical Chemistry C, 2018, 122(42): 23925-23933.
34	DENG J, LUO W B, LU X, et al. High energy density sodium-ion battery with industrially feasible and air-stable O3-type layered oxide cathode[J]. Advanced Energy Materials, 2018, 8(5): doi: 10.1002/aenm.201701610.
35	穆林沁, 戚兴国, 胡勇胜, 等. 新型O3-NaCu_1/9Ni_2/9Fe_1/3Mn_1/3O₂钠离子电池正极材料研究[J]. 储能科学与技术, 2016, 5(3): 324-328.
	MU L Q, QI X G, HU Y S, et al. Electrochemical properties of O3-NaCu_1/9Ni_2/9Fe_1/3Mn_1/3O₂as cathode material for sodium-ion batteries[J]. Energy Storage Science and Technology, 2016, 5(3): 324-328.
36	KHAN M A, HAN D, LEE G, et al. P2/O3 phase-integrated Na_0.7MnO₂ cathode materials for sodium-ion rechargeable batteries[J]. Journal of Alloys and Compounds, 2019, 771: 987-993.
37	HASHEM A M, ABDEL-GHANY A E, ABUZEID H M, et al. EDTA as chelating agent for sol-gel synthesis of spinel LiMn₂O₄ cathode material for lithium batteries[J]. Journal of Alloys and Compounds, 2018, 737: 758-766.
38	LI J Y, LV H Y, ZHANG X H, et al. P2-type Na_0.53MnO₂nanorods with superior rate capabilities as advanced cathode material for sodium ion batteries[J]. Chemical Engineering Journal, 2017, 316: 499-505.
39	PANG W L, GUO J Z, ZHANG X H, et al. P2-type Na_2/3Mn_1/2Co_1/3Cu_1/6O₂ as advanced cathode material for sodium-ion batteries: Electrochemical properties and electrode kinetics[J]. Journal of Alloys and Compounds, 2019, 790: 1092-1100.
40	YUE J L, ZHOU Y N, YU X Q, et al. O3-type layered transition metal oxide Na(NiCoFeTi)_1/4O₂ as a high rate and long cycle life cathode material for sodium ion batteries[J]. Journal of Materials Chemistry A, 2015, 3: 23261-23267.
41	YABUUCHI N, YANO M, KUZE S, et al. Electrochemical behavior and structural change of spinel-type Li[Li_xMn_2-_x]O₄ (x=0 and 0.2) in sodium cells[J]. Electrochimica Acta, 2012, 82: 296-301.

测试结果	Li（0.25）	Na（0.6）	Mn（1）
理论值	0.25	0.6	1
实验值	0.23	0.57	0.95

峰	斜率	D/10^-12 cm²·s^-1
a	0.01445	2.3228
a'	0.00602	0.4031
b	0.01214	1.6395
b'	0.00786	0.6873
平均值	—	1.2632

[1]	徐雄文, 聂阳, 涂健, 许峥, 谢健, 赵新兵. 普鲁士蓝正极软包钠离子电池的滥用性能[J]. 储能科学与技术, 2022, 11(7): 2030-2039.
[2]	张平, 康利斌, 王明菊, 赵广, 罗振华, 唐堃, 陆雅翔, 胡勇胜. 钠离子电池储能技术及经济性分析[J]. 储能科学与技术, 2022, 11(6): 1892-1901.
[3]	张浩然, 车海英, 郭凯强, 申展, 张云龙, 陈航达, 周煌, 廖建平, 刘海梅, 马紫峰. Sn掺杂NaNi_1/3Fe_1/3Mn_1/3-_x Sn _x O₂ 正极材料制备及其电化学性能[J]. 储能科学与技术, 2022, 11(6): 1874-1882.
[4]	赵易飞, 杨振东, 李凤, 谢召军, 周震. 氮掺杂碳包覆Na₃V₂ （PO₄ ） ₂F₃ 钠离子电池正极材料的制备与性能[J]. 储能科学与技术, 2022, 11(6): 1883-1891.
[5]	孙畅, 邓泽荣, 江宁波, 张露露, FANG Hui, 杨学林. 钠离子电池正极材料氟磷酸钒钠研究进展[J]. 储能科学与技术, 2022, 11(4): 1184-1200.
[6]	胡海燕, 侴术雷, 肖遥. 基于分子轨道杂化的高电压钠离子电池层状氧化物正极材料[J]. 储能科学与技术, 2022, 11(4): 1093-1102.
[7]	刘倩楠, 胡伟平, 轷喆. 钠离子电池磷基负极材料研究进展[J]. 储能科学与技术, 2022, 11(4): 1201-1210.
[8]	赵志强, 刘恒均, 徐熙祥, 潘圆圆, 李庆浩, 李洪森, 胡涵, 李强. 储能科学中的磁性表征技术[J]. 储能科学与技术, 2022, 11(3): 818-833.
[9]	冯一峰, 沈佳妮, 车海英, 马紫峰, 贺益君, 谈文, 杨庆亨. 钠离子电池健康状态预测[J]. 储能科学与技术, 2021, 10(4): 1407-1415.
[10]	刘当玲, 王诗敏, 高智慧, 徐露富, 夏书标, 郭洪. 三维NZSPO/PAN-［PEO-NaTFST］复合钠离子电池固体电解质[J]. 储能科学与技术, 2021, 10(3): 931-937.
[11]	周琳, 杨佯, 胡勇胜. 合金电极失效机制：体积膨胀？电解液分解？[J]. 储能科学与技术, 2021, 10(3): 813-820.
[12]	李林林, 王昱杰, 门一飞, 杨伟, 邹汉波, 陈胜洲. 湿法冶金回收技术中无机酸作为浸出剂的研究进展[J]. 储能科学与技术, 2021, 10(1): 68-76.
[13]	李林林, 曹林娟, 麦永雄, 门一飞, 杨伟, 陈胜洲. 废旧锂离子电池有机酸湿法冶金回收技术研究进展[J]. 储能科学与技术, 2020, 9(6): 1641-1650.
[14]	易红明, 吕志强, 张华民, 宋明明, 郑　琼, 李先锋. 钠离子电池钒基聚阴离子型正极材料的发展现状与应用挑战[J]. 储能科学与技术, 2020, 9(5): 1350-1369.
[15]	马梦莹, 潘慧霖, 胡勇胜. 非水系钠离子电池的电解质研究进展[J]. 储能科学与技术, 2020, 9(5): 1234-1250.

以废旧锰酸锂正极为原料制备Li_0.25Na_0.6MnO₂钠离子电池正极材料的研究

Using spent lithium manganate to prepare Li_0.25Na_0.6MnO₂as cathode material in sodium-ion batteries

RichHTML

PDF