碳酸酯类电解液中Mg(NO3)2添加剂抑制锂枝晶生长的研究

doi:10.13208/j.electrochem.200711

摘要/Abstract

摘要：

在锂-硫化聚丙烯腈电池体系中,负极锂枝晶的形成和生长严重恶化了电池充放电性能,并给电池带来了安全隐患。而在更有利于稳定正极硫化聚丙烯腈材料的碳酸酯类电解液中,锂枝晶生长尤为严重。本文通过将硝酸镁添加到碳酸酯类电解液中,研究硝酸根和镁离子对锂金属表面改性的共同作用。实验数据发现,在硝酸根和镁离子共同作用下,锂枝晶生长被有效抑制。当硝酸镁浓度为100 mmol·L^-1时,锂铜半电池的库仑效率明显提高,并显著改善了锂-硫化聚丙烯腈电池的循环性能。300次循环后容量保持率为71%,远高于硝酸锂的61%和无添加剂的50%。

关键词: 硝酸镁, 锂枝晶, 电解液添加剂, 电化学性质

Abstract:

In the lithium-sulfurized polyacrylonitrile battery system, the formation and growth of lithium dendrites in the negative electrode seriously deteriorate the charge and discharge performance of the battery. If the growth of lithium dendrites pierces the separator and causes thermal runaway, it will also bring serious damage to the battery, causing potential safety risks. In the carbonate electrolyte that is more conducive to stabilizing the positive electrode sulfurized polyacrylonitrile material, the growth of lithium dendrites is particularly serious. In this paper, magnesium nitrate was added to the carbonate electrolyte to investigate the combined effect of nitrate and magnesium ions on the surface modification of lithium metal. Studies have found that during the cycle, magnesium ions were reduced on the surface of the lithium negative electrode to form a lithium-magnesium alloy layer, which reduced excessive side reactions between the electrolyte and the negative electrode. The reduction of magnesium ions into magnesium metal could guide the uniform deposition of lithium ions and reduce the formation of lithium dendrites; at the same time, nitrate could form an SEI film with high ionic conductivity rich in nitrogen oxides with lithium ions, which could make lithium ions at the interface that conducts quickly at the location, and under the combined action of the two, the formation and growth of lithium dendrites were inhibited, and the cycle performance of the battery was improved. The experimental data showed that under the combined action of nitrate and magnesium ions, the growth of lithium dendrites was effectively inhibited. When the concentration of magnesium nitrate was 100 mmol·L^-1, the coulombic efficiency of the lithium copper half-cell was significantly improved, and the cycle performance of lithium-sulfide polypropylene nitrile battery was also significantly enhanced. The capacity retention rate after 300 cycles was 71%, which was much higher than 61% of lithium nitrate and 50% without additives.

Key words: magnesium nitrate, lithium dendirte, electrolyte additive, electrochemical property

张彪, 帅毅, 王玉, 杨纳川, 陈康华. 碳酸酯类电解液中Mg(NO₃)₂添加剂抑制锂枝晶生长的研究[J]. 电化学（中英文）, 2021, 27(4): 423-428.

Biao Zhang, Yi Shuai, Yu Wang, Na-Chuan Yang, Kang-Hua Chen. Study on Inhibition of Lithium Dendrite Growth by Mg(NO₃)₂ Additive in Carbonate Electrolyte[J]. Journal of Electrochemistry, 2021, 27(4): 423-428.

图/表 6

图1

图2

图3

图4

表1

图5

参考文献 25

[1]	Tarascon J M, Armand M. Issues and challenges facing rechargeable lithium batteries[J]. Nature, 2001, 414(6861): 359-367. doi: 10.1038/35104644 URL
[2]	Armand M, Tarascon J M. Building better batteries[J]. Nature, 2008, 451(7179): 652-657. doi: 10.1038/451652a URL
[3]	Xu W, Wang J L, Ding F, Chen X L, Nasybutin E, Zhang Y H, Zhang J G. Lithium metal anodes for rechargeable batteries[J]. Energy Environ. Sci., 2014, 7(2): 513-537. doi: 10.1039/C3EE40795K URL
[4]	Goodenough J B, Kim Y. Challenges for rechargeable Li batteries[J]. Chem. Mater., 2010, 22(3): 587-603. doi: 10.1021/cm901452z URL
[5]	Dunn B, Kamath H, Tarascon J M. Electrical energy storage for the grid: A battery of choices[J]. Science, 2011, 334(6058): 928-935. doi: 10.1126/science.1212741 URL
[6]	Wang G L, Liu J C, Tang S, Li H Y, Cao D X. Cobalt oxide-graphene nanocomposite as anode materials for lithium-ion batteries[J]. J. Solid State Electrochem., 2011, 15(11-12): 2587-2592. doi: 10.1007/s10008-010-1254-y URL
[7]	Tikekar M D, Choudhury S, Tu Z Y, Archer L A. Design principles for electrolytes and interfaces for stable lithium-metal batteries[J]. Nat. Energy, 2016, 1: 16114. doi: 10.1038/nenergy.2016.114 URL
[8]	Zhang X Q(张学强), Cheng X B(程新兵), Zhang Q(张强). Advances in interfaces between Li metal anode and electrolyte[J]. Adv. Mater. Inter., 2018, 5(2): 1701097. doi: 10.1002/admi.201701097 URL
[9]	Zhou D, Liu R L, He Y B, Li F Y, Liu M, Li B H, Yang Q H, Cai Q, Kang F Y. SiO₂ hollow nanosphere-based composite solid electrolyte for lithium metal batteries to suppress lithium dendrite growth and enhance cycle life[J]. Adv. Energy Mater., 2016, 6(7): 1502214. doi: 10.1002/aenm.201502214 URL
[10]	Guo Y P, Li H Q, Zhai T Y. Reviving lithium-metal anodes for next-generation high-energy batteries[D]. Adv. Mater., 2017, 29(29): 1700007.
[11]	Wood K N, Kazyak E, Chadwick A F, Chen K H, Zhang J G, Thornton K, Dasgupta N P. Dendrites and pits: Untangling the complex behavior of lithium metal anodes through operando video microscopy[J]. ACS Cent. Sci., 2016, 2(11): 790-801. doi: 10.1021/acscentsci.6b00260 URL
[12]	Zhang S S. Problem, status, and possible solutions for lithium metal anode of rechargeable batteries[J]. ACS Appl. Energy Mater., 2018, 1(3): 910-920. doi: 10.1021/acsaem.8b00055 URL
[13]	Cheng X B, Zhang R, Zhao C Z, Zhang Q. Toward safe lithium metal anode in rechargeable batteries: a review[J]. Chem. Rev., 2017, 117(15): 10403-10473. doi: 10.1021/acs.chemrev.7b00115 URL
[14]	Zheng G Y, Lee S W, Liang Z, Lee H W, Yan K, Yao H B, Wang H T, Li W Y, Chu S, Cui Y. Interconnected hollow carbon nanospheres for stable lithium metal anodes[J]. Nat. Nanotechnol., 2014, 9(8): 618-623. doi: 10.1038/nnano.2014.152 URL
[15]	Chen L, Connell J G, Nie A M, Huang Z N, Zavadil K R, Klavetter K C, Yuan Y F, Sharifi-Asl S, Shahbazian-Yassar R, Libera J A, Mane A U, Elam J W. Lithium metal protected by atomic layer deposition metal oxide for high performance anodes[J]. Mater. Chem. A, 2017, 5(24): 12297-12309. doi: 10.1039/C7TA03116E URL
[16]	Zhu B, Jin Y, Hu X Z, Zheng Q H, Zhang S, Wang Q J, Zhu J. Poly(dimethylsiloxane) Thin film as a stable interfacial layer for high-performance lithium-metal battery anodes[J]. Adv. Mater., 2017, 29(2): 1603755. doi: 10.1002/adma.v29.2 URL
[17]	Song J, Lee H, Choo M J, Park J K, Kim H T. Ionomer liquid electrolyte hybrid ionic conductor for high cycling stability of lithium metal electrodes[J]. Sci. Rep., 2015, 5: 14458. doi: 10.1038/srep14458 URL
[18]	Liu Y Y, Lin D C, Yuen P Y, Liu K, Xie J, Dauskardt R H, Cui Y. An artificial solid electrolyte interphase with high li-ion conductivity, mechanical strength, and flexibility for stable lithium metal anodes[J]. Adv. Mater., 2017, 29(10): 1605531. doi: 10.1002/adma.v29.10 URL
[19]	Liu W, Li W, Zhuo D, Zheng G Y, Lu Z D, Liu K, Cui Y. Core-shell nanoparticle coating as an interfacial layer for dendrite free lithium metal anodes[J]. ACS Cent. Sci., 2017, 3(2): 135-140. doi: 10.1021/acscentsci.6b00389 URL
[20]	Ma Y L, Zhou Z Z, Li C J, Wang L, Wang Y, Cheng X Q, Zuo P J, Du C Y, Huo H, Gao Y Z, Yin G P. Enabling reliable lithium metal batteries by a bifunctional anionic electrolyte additive[J]. Energy Storage Mater., 2018, 11: 197-204.
[21]	Ouyang Y, Guo Y P, Li D, Wei Y Q, Zhai T Y, Li H Q. Single additive with dual functional-ions for stabilizing lithium anodes[J]. ACS Appl. Mater. Inter., 2019, 11(12): 11360-11368. doi: 10.1021/acsami.8b21420 URL
[22]	Yan C, Yao Y X, Chen X, Cheng X B, Zhang X Q, Huang J Q, Zhang Q. Solvation chemistry of lithium nitrate in carbonate electrolyte for high voltage lithium metal battery[J]. Angew. Chem. Int. Ed., 2018, 130(43): 14055-14059.
[23]	Guo J, Wen Z Y, Wu M F, Jin J, Liu Y. Vinylene carbonate-LiNO₃: A hybrid additive in carbonic ester electrolytes for SEI modification on Li metal anode[J]. Electrochem. Commun., 2015, 51: 59-63. doi: 10.1016/j.elecom.2014.12.008 URL
[24]	Yuan Y X, Wu F, Chen G H, Bai Y, Wu C. Porous LiF layer fabricated by a facile chemical method toward dendrite-free lithium metal anode[J]. J. Energy Chem., 2019, 37: 197-203. doi: 10.1016/j.jechem.2019.03.014 URL
[25]	Jing P C, Lu H M, Yang W W, Cao Y, Xu B B, Cai W, Deng Y. Polyaniline-coated VS₄@rGO nanocomposite as high-performance cathode material for magnesium batteries based on Mg²⁺/Li⁺ dual ion electrolytes[J]. Ionics, 2020, 26(2): 777-787. doi: 10.1007/s11581-019-03239-3 URL

Electrolyte	R_int/ohm
Electrolyte	5 h	50 h
No additive	222.1	397.4
200 mmol·L^-1 LiNO₃	147.9	208.8
100 mmol·L^-1 Mg(NO₃)₂	90.9	102.1

碳酸酯类电解液中Mg(NO₃)₂添加剂抑制锂枝晶生长的研究

Study on Inhibition of Lithium Dendrite Growth by Mg(NO₃)₂ Additive in Carbonate Electrolyte

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 6

参考文献 25

相关文章 14

Metrics

[1]	李虎东, 贾维尚, 闫新秀, 阳耀月. 定量的复合金属锂作为三维泡沫锂电极用于锂电池的研究[J]. 电化学（中英文）, 2022, 28(8): 2202051-.
[2]	张运丰, 王佳颖, 李晓洁, 赵诗宇, 何阳, 霍士康, 王雅莹, 谭畅. 锂金属电池用三维半互穿网络聚合物电解质的制备[J]. 电化学（中英文）, 2021, 27(4): 413-422.
[3]	魏壮壮, 张楠祥, 吴锋, 陈人杰. 锂硫电池多功能涂层隔膜的研究进展与展望[J]. 电化学（中英文）, 2020, 26(5): 716-730.
[4]	郭文君，李紫琼，柯若昊，钮东方，徐衡，张新胜. 脉冲电沉积抑制锂枝晶生成的研究[J]. 电化学（中英文）, 2018, 24(3): 246-252.
[5]	张鼎，朱芹，王瑛，赵成龙，刘世斌，徐守冬. 二氟草酸硼酸钠作为钠离子电池非水电解液添加剂的电化学性能[J]. 电化学（中英文）, 2017, 23(4): 473-479.
[6]	陈丁琼, 杨阳, 李秋丽，赵金保. 锂离子电池硅基负极材料的最新研究进展[J]. 电化学（中英文）, 2016, 22(5): 489-498.
[7]	姚洋洋, 刘冬冬, 王莉, 何向明, 李建军, 张鼎. 二氟草酸硼酸钠作为电解液添加剂对石墨负极性能的影响[J]. 电化学（中英文）, 2015, 21(4): 387-392.
[8]	陈红;姜涛;王春忠;陈岗;魏英进;. 锂离子电池正极材料Li_3V_2(PO_4)_3的制备及性能研究[J]. 电化学（中英文）, 2010, 16(1): 25-29.
[9]	陆宝仪, 赖艳艳, 李红, . 功能化碳纳米管的电化学性质及在6-巯基嘌呤分析检测中的应用[J]. 电化学（中英文）, 2009, 15(1): 67-73.
[10]	李静, 孙岚, 庄惠芳, 王成林, 杜荣归, 林昌健, . 铁掺杂TiO_2纳米管阵列制备及其光电化学性质[J]. 电化学（中英文）, 2008, 14(2): 213-217.
[11]	李永舫. 导电聚合物的电化学制备和电化学性质研究——中国科学院有机固体重点实验室导电聚合物电化学研究工作简介(I)[J]. 电化学（中英文）, 2004, 10(4): 369-378.
[12]	杜洪彦,程琥,杨勇. PEO基纳米复合聚合物电解质电化学性质的研究[J]. 电化学（中英文）, 2004, 10(2): 215-221.
[13]	李红,巢晖,计亮年,蒋雄. 双核钌配合物中金属间相互作用的电化学研究[J]. 电化学（中英文）, 2001, 7(2): 167-172.
[14]	范楼珍, 李永舫, 郑大贵, 李玉良, 朱道本. 加成基团对富勒烯电化学性质的影响[J]. 电化学（中英文）, 1997, 3(4): 371-377.