Citation: Li-Heng ZHANG, Hai-Tao GU, Ying LUO, Qing-Yu DONG, Yan-Bin SHEN, Jing-Ying XIE. Tris(trimethylsilyl)-Based Additives Enables Practical 5 V LiNi_0.5Mn_1.5O₄ Batteries[J]. Chinese Journal of Inorganic Chemistry, ;2022, 38(10): 2091-2102. doi: 10.11862/CJIC.2022.215 shu

Tris(trimethylsilyl)-Based Additives Enables Practical 5 V LiNi_0.5Mn_1.5O₄ Batteries

Li-Heng ZHANG ¹ ,
Hai-Tao GU ² ,
Ying LUO ² ,
Qing-Yu DONG ³ ,
Yan-Bin SHEN ^3,, ,
Jing-Ying XIE ^{1, 2,,}

1.
School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001, China
2.
State Key Laboratory of Space Power-Sources Technology, Shanghai Institute of Space Power-Sources, Shanghai 200245, China
3.
i-Lab, CAS Center for Excellence in Nanoscience, Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, Suzhou, Jiangsu 215123, China

Corresponding author: Yan-Bin SHEN, ybshen2017@sinano.ac.cn Jing-Ying XIE, jyxie@hit.edu.cn
Received Date: 9 July 2022
Revised Date: 29 August 2022

Figures(10)

LiNi_0.5Mn_1.5O₄ cathode materials have been considered promising candidates for high energy density Li-ion batteries due to their high operation potential. However, to develop 5 V LiNi_0.5Mn_1.5O₄-based batteries, practical electrolytes with high electrochemical stability are yet to be realized. In this work, tris(trimethylsilyl)-based additives, including tris(trimethylsilyl)borate (TMSB) and tris(trimethylsilyl)phosphite (TMSPi), were selected as electrolyte additives for typical ethylene carbonate (EC)-LiPF₆ based electrolyte to develop practical LiNi_0.5Mn_1.5O₄-based batteries. Combining theoretical calculations, physicochemical characterization, and electrochemical measurements, we found that both TMSB and TMSPi can improve the Coulombic efficiency and cycling stability of 5 V LiNi_0.5Mn_1.5O₄-based cells. Specifically, TMSB can act as the stabilizer for PF₆^- due to its electron deficiency nature, thereby suppressing the increase of cell impedance. In addition, thanks to its high highest occupied molecule orbital (HOMO) energy level, TMSPi can be preferentially oxidized on the surface of charged LiNi_0.5Mn_1.5O₄ electrodes, resulting in a decent rate capacity and high discharge platform. In addition, TMSPi is conducive to the formation of robust solid electrolyte interphase (SEI) on graphite anode through the nucleophilic attack, resulting in enhanced cycle performance. As a result, Graphite||LiNi_0.5Mn_1.5O₄ pouch cells with TMSPi - containing electrolyte displayed capacity retention of 88.9% after 100 cycles at 1C, superior to that in the blank (60.5%) and TMSB - containing (77.4%) electrolytes.
- electrolyte additive,
- LiNi_0.5Mn_1.5O₄,
- tris(trimethylsilyl)borate,
- tris(trimethylsilyl)phosphite
1. [1]
  Choi J W, Aurbach D. Promise and Reality of Post-Lithium-Ion Batteries with High Energy Densities[J]. Nat. Rev. Mater., 2016,1(4)16013. doi: 10.1038/natrevmats.2016.13
2. [2]
  Clark J M, Nishimura S, Yamada A, Islam S. High-Voltage Pyrophosphate Cathode: Insights into Local Structure and Lithium - Diffusion Pathways[J]. Angew. Chem. Int. Ed., 2012,51(52):13149-13153. doi: 10.1002/anie.201205997
3. [3]
  Fergus J W. Recent Developments in Cathode Materials for Lithium Ion Batteries[J]. J. Power Sources, 2010,195(4):939-954. doi: 10.1016/j.jpowsour.2009.08.089
4. [4]
  ZHAO J H, XIE M X, ZHANG H Y, YI R W, HU C J, KANG T, ZHENG L, CUI R G, CHEN H W, SHEN Y B, CHEN L W. In Situ Modification Strategy for Development of Room - Temperature Solid - State Lithium Batteries with High Rate Capability. Acta Phys. -Chim. Sin., 2021, 37(12): 2104003
5. [5]
  GUO F, CHEN P, KANG T, WANG Y L, LIU C H, SHEN Y B, LU W, CHEN L W. Silicon - Loaded Lithium - Carbon Composite Microspheres as Lithium Secondary Battery Anodes[J]. Acta Phys.-Chim. Sin., 2019,35(12):1365-1371. doi: 10.3866/PKU.WHXB201903008
6. [6]
  Zhang L H, Min F Q, Luo Y, Dang G J, Gu H T, Dong Q Y, Zhang M H, Sheng L M, Shen Y B, Chen L W, Xie J Y. Practical 4.4 V Li||NCM811 Batteries Enabled by a Thermal Stable and HF Free Carbonate-Based Electrolyte[J]. Nano Energy, 2022,96107122. doi: 10.1016/j.nanoen.2022.107122
7. [7]
  Sun Z Y, Zhou H B, Luo X H, Che Y X, Li W S, Xu M Q. Design of a Novel Electrolyte Additive for High Voltage LiCoO₂ Cathode Lithium- Ion Batteries: Lithium 4 - Benzonitrile Trimethyl Borate[J]. J. Power Sources, 2021,503230033. doi: 10.1016/j.jpowsour.2021.230033
8. [8]
  Li H H, Jin J, Wei J P, Zhou Z, Yan J. Fast Synthesis of Core-Shell LiCoPO₄/C Nanocomposite via Microwave Heating and Its Electrochemical Li Intercalation Performances[J]. Electrochem. Commun., 2009,11(1):95-98. doi: 10.1016/j.elecom.2008.10.025
9. [9]
  Hu M, Tian Y, Su L W, Wei J P, Zhou Z. Preparation and Ni-Doping Effect of Nanosized Truncated Octahedral LiCoMnO₄ as Cathode Materials for 5 V Li-Ion Batteries[J]. ACS Appl. Mater. Interfaces, 2013,5(22):12185-12189. doi: 10.1021/am404250k
10. [10]
  Hu M, Tian Y, Wei J P, Wang D G, Zhou Z. Porous Hollow LiCoMnO₄ Microspheres as Cathode Materials for 5 V Lithium Ion Batteries[J]. J. Power Sources, 2014,247:794-798. doi: 10.1016/j.jpowsour.2013.09.038
11. [11]
  Hu M, Pang X L, Zhou Z. Recent Progress in High-Voltage Lithium Ion Batteries[J]. J. Power Sources, 2013,237:229-242. doi: 10.1016/j.jpowsour.2013.03.024
12. [12]
  Zhou L, Zhao D, Lou X. LiNi_0.5Mn_1.5O₄ Hollow Structures as High- Performance Cathodes for Lithium-Ion Batteries[J]. Angew. Chem. Int. Ed., 2012,51(1):239-241. doi: 10.1002/anie.201106998
13. [13]
  Shin D W, Manthiram A. Surface-Segregated, High-Voltage Spinel LiMn_1.5Ni_0.42Ga_0.08O₄ Cathodes with Superior High - Temperature Cyclability for Lithium-Ion Batteries[J]. Electrochem. Commun., 2011,13(11):1213-1216. doi: 10.1016/j.elecom.2011.08.041
14. [14]
  Marom R, Amalraj S F, Leifer N, Jacob D, Aurbach D. A Review of Advanced and Practical Lithium Battery Materials[J]. J. Mater. Chem., 2011,21(27):9938-9954. doi: 10.1039/c0jm04225k
15. [15]
  Lee H, Han T, Cho K Y, Ryou M H, Lee Y M. Dopamine as a Novel Electrolyte Additive for High - Voltage Lithium - Ion Batteries[J]. ACS Appl. Mater. Interfaces, 2016,8(33):21366-21372. doi: 10.1021/acsami.6b06074
16. [16]
  Park O K, Cho Y, Lee S, Yoo H, Song H, Cho J. Who Will Drive Electric Vehicles, Olivine or Spinel?[J]. Energy Environ. Sci., 2011,4(5):1621-1633. doi: 10.1039/c0ee00559b
17. [17]
  Kraytsberg A, Ein-Eli Y. Higher, Stronger, Better… A Review of 5 Volt Cathode Materials for Advanced Lithium - Ion Batteries[J]. Adv. Energy Mater., 2012,2(8):922-939. doi: 10.1002/aenm.201200068
18. [18]
  Xia J, Sinha N N, Chen L P, Kim G Y, Xiong D J, Dahn J R. Study of Methylene Methanedisulfonate as an Additive for Li - Ion Cells[J]. J. Electrochem. Soc., 2013,161(1):84-88.
19. [19]
  Dumaz P, Rossignol C, Mantoux A, Sergent N, Bouchet R. Kinetics Analysis of the Electro - catalyzed Degradation of High Potential LiNi_0.5Mn_1.5O₄ Active Materials[J]. J. Power Sources, 2020,469228337. doi: 10.1016/j.jpowsour.2020.228337
20. [20]
  Zou Z Y, Xu H T, Zhang H R, Tang Y, Cui G L. Electrolyte Therapy for Improving the Performance of LiNi_0.5Mn_1.5O₄ Cathodes Assem- bled Lithium-Ion Batteries[J]. ACS Appl. Mater. Interfaces, 2020,12(19):21368-21385. doi: 10.1021/acsami.0c02516
21. [21]
  Liao X L, Huang Q H, Mai S W, Wang X S, Xu M Q, Xing L D, Liao Y H, Li W S. Self - Discharge Suppression of 4.9 V LiNi_0.5Mn_1.5O₄ Cathode by Using Tris(trimethylsilyl)borate as an Electrolyte Additive[J]. J. Power Sources, 2014,272:501-507. doi: 10.1016/j.jpowsour.2014.08.117
22. [22]
  Rong H B, Xu M Q, Xie B Y, Liao X L, Huang W Z, Xing L D, Li W S. Tris(trimethylsilyl)borate (TMSB) as a Cathode Surface Film Forming Additive for 5V Li/LiNi_0.5Mn_1.5O₄ Li-Ion Cells[J]. Electrochim. Acta, 2014,147:31-39. doi: 10.1016/j.electacta.2014.09.105
23. [23]
  Guéguen A, Bolli C, Mendez M A, Berg E J. Elucidating the Reactivity of Tris(trimethylsilyl) phosphite and Tris(trimethylsilyl)phosphate Additives in Carbonate Electrolytes—A Comparative Online Electrochemical Mass Spectrometry Study[J]. ACS Appl. Mater. Interfaces, 2019,3(1):290-299.
24. [24]
  Liao X L, Zheng X W, Chen J W, Huang Z Y, Xu M Q, Xing L D, Liao Y H, Lu Q L, Li X F, Li W S. Tris(trimethylsilyl)phosphate as Electrolyte Additive for Self-Discharge Suppression of Layered Nickel Cobalt Manganese Oxide[J]. Electrochim. Acta, 2016,212:352-359. doi: 10.1016/j.electacta.2016.07.026
25. [25]
  Yan G C, Li X H, Wang Z X, Guo H J, Wang C. Tris(trimethylsilyl) phosphate: A Film-Forming Additive for High Voltage Cathode Material in Lithium-Ion Batteries[J]. J. Power Sources, 2014,248:1306-1311. doi: 10.1016/j.jpowsour.2013.10.037
26. [26]
  Rong H B, Xu M Q, Xing L D, Li W S. Enhanced Cyclability of LiNi_0.5Mn_1.5O₄ Cathode in Carbonate Based Electrolyte with Incorporation of Tris(trimethylsilyl)phosphate (TMSP)[J]. J. Power Sources, 2014,261:148-155. doi: 10.1016/j.jpowsour.2014.03.032
27. [27]
  Mai S W, Xu M Q, Liao X L, Hu J N, Lin H B, Xing L D, Liao Y H, Li X P, Li W S. Tris(trimethylsilyl)phosphite as Electrolyte Additive for High Voltage Layered Lithium Nickel Cobalt Manganese Oxide Cathode of Lithium Ion Battery[J]. Electrochim. Acta, 2014,147:565-571. doi: 10.1016/j.electacta.2014.09.157
28. [28]
  Wang Y T, Xing L D, Li W S, Bedrov D. Why Do Sulfone - Based Electrolytes Show Stability at High Voltages? Insight from Density Functional Theory[J]. J. Phys. Chem. Lett., 2013,4(22):3992-3999. doi: 10.1021/jz401726p
29. [29]
  Han Y K, Yoo J, Yim T. Why is Tris(trimethylsilyl)phosphite Effective as an Additive for High - Voltage Lithium - Ion Batteries?[J]. J. Mater. Chem. A, 2015,3(20):10900-10909. doi: 10.1039/C5TA01253H
30. [30]
  Song Y M, Kim C K, Kim K E, Hong S Y, Choi N S. Exploiting Chemically and Electrochemically Reactive Phosphite Derivatives for High-Voltage Spinel LiNi_0.5Mn_1.5O₄ Cathodes[J]. J. Power Sources, 2016,302:22-30. doi: 10.1016/j.jpowsour.2015.10.043
31. [31]
  Yoon T, Park S, Mun J, Ryu J H, Choi W, Kang Y S, Park J H, Oh S M. Failure Mechanisms of LiNi_0.5Mn_1.5O₄ Electrode at Elevated Temperature[J]. J. Power Sources, 2012,215:312-316. doi: 10.1016/j.jpowsour.2012.04.103
32. [32]
  Marchini F, Williams F J, Calvo E J. Electrochemical Impedance Spectroscopy Study of the LixMn₂O₄ Interface with Natural Brine[J]. J. Electroanal. Chem., 2018,819:428-434. doi: 10.1016/j.jelechem.2017.11.071
33. [33]
  Ma Y, Wang C D, Ma J, Xu G J, Chen Z, Du X F, Zhang S, Zhou X H, Cui G L, Chen L Q. Interfacial Chemistry of γ - Glutamic Acid Derived Block Polymer Binder Directing the Interfacial Compatibility of High Voltage LiNi_0.5Mn_1.5O₄ Electrode[J]. Sci. China Chem., 2021,64(1):92-100. doi: 10.1007/s11426-020-9879-8
34. [34]
  Wang K, Xing L D, Zhu Y M, Zheng X W, Cai D D, Li W S. A Comparative Study of Si-Containing Electrolyte Additives for Lithium Ion Battery: Which One is Better and Why is It Better[J]. J. Power Sources, 2017,342:677-684. doi: 10.1016/j.jpowsour.2016.12.112
35. [35]
  Yim T, Han Y K. Tris(trimethylsilyl) Phosphite as an Efficient Electrolyte Additive to Improve the Surface Stability of Graphite Anodes[J]. ACS Appl. Mater. Interfaces, 2017,9(38):32851-32858. doi: 10.1021/acsami.7b11309
36. [36]
  Zaghib K, Mauger A, Groult H, Goodenough J B, Julien C M. Advanced Electrodes for High Power Li - Ion Batteries[J]. Materials, 2013,6(3):1028-1049. doi: 10.3390/ma6031028
37. [37]
  Qi X, Tao L, Hahn H, Schultz C, Gallus D R, Cao X, Nowak , Röser S, Li J, Laskovic I C, Rad B R, Winter M. Lifetime Limit of Tris(trimethylsilyl)phosphite as Electrolyte Additive for High Voltage Lithium Ion Batteries[J]. RSC Adv., 2016,6(44):38342-38349. doi: 10.1039/C6RA06555D
1. [1]
  Aoyu Huang , Jun Xu , Yu Huang , Gui Chu , Mao Wang , Lili Wang , Yongqi Sun , Zhen Jiang , Xiaobo Zhu . Tailoring Electrode-Electrolyte Interfaces via a Simple Slurry Additive for Stable High-Voltage Lithium-Ion Batteries. Acta Physico-Chimica Sinica, 2025, 41(4): 100037-. doi: 10.3866/PKU.WHXB202408007
2. [2]
  Guihuang Fang , Wei Chen , Hongwei Yang , Haisheng Fang , Chuang Yu , Maoxiang Wu . Improved performance of LiMn_0.8Fe_0.2PO₄ by addition of fluoroethylene carbonate electrolyte additive. Chinese Chemical Letters, 2024, 35(6): 108799-. doi: 10.1016/j.cclet.2023.108799
3. [3]
  Kunyao Peng , Xianbin Wang , Xingbin Yan . Converting LiNO₃ additive to single nitrogenous component Li₂N₂O₂ SEI layer on Li metal anode in carbonate-based electrolyte. Chinese Chemical Letters, 2024, 35(9): 109274-. doi: 10.1016/j.cclet.2023.109274
4. [4]
  Jiahe LIU , Gan TANG , Kai CHEN , Mingda ZHANG . Effect of low-temperature electrolyte additives on low-temperature performance of lithium cobaltate batteries. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 719-728. doi: 10.11862/CJIC.20250023
5. [5]
  Mei-Chen Liu , Qing-Song Liu , Yi-Zhou Quan , Jia-Ling Yu , Gang Wu , Xiu-Li Wang , Yu-Zhong Wang . Phosphorus-silicon-integrated electrolyte additive boosts cycling performance and safety of high-voltage lithium-ion batteries. Chinese Chemical Letters, 2024, 35(8): 109123-. doi: 10.1016/j.cclet.2023.109123
6. [6]
  Hengyi ZHU , Liyun JU , Haoyue ZHANG , Jiaxin DU , Yutong XIE , Li SONG , Yachao JIN , Mingdao ZHANG . Efficient regeneration of waste LiNi_0.5Co_0.2Mn_0.3O₂ cathode toward high-performance Li-ion battery. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 625-638. doi: 10.11862/CJIC.20240358
7. [7]
  Xi Tang , Chunlei Zhu , Yulu Yang , Shihan Qi , Mengqiu Cai , Abdullah N. Alodhayb , Jianmin Ma . Additive regulating Li⁺ solvation structure to construct dual LiF−rich electrode electrolyte interphases for sustaining 4.6 V Li||LiCoO₂ batteries. Chinese Chemical Letters, 2024, 35(12): 110014-. doi: 10.1016/j.cclet.2024.110014
8. [8]
  Mingjiao Lu , Zhixing Wang , Gui Luo , Huajun Guo , Xinhai Li , Guochun Yan , Qihou Li , Xianglin Li , Ding Wang , Jiexi Wang . Boosting the performance of LiNi_0.90Co_0.06Mn_0.04O₂ electrode by uniform Li₃PO₄ coating via atomic layer deposition. Chinese Chemical Letters, 2024, 35(5): 108638-. doi: 10.1016/j.cclet.2023.108638
9. [9]
  Tao Long , Peng Chen , Bin Feng , Caili Yang , Kairong Wang , Yulei Wang , Can Chen , Yaping Wang , Ruotong Li , Meng Wu , Minhuan Lan , Wei Kong Pang , Jian-Fang Wu , Yuan-Li Ding . Reinforced concrete-like Na_3.5V_1.5Mn_0.5(PO₄)₃@graphene hybrids with hierarchical porosity as durable and high-rate sodium-ion battery cathode. Chinese Chemical Letters, 2024, 35(4): 109267-. doi: 10.1016/j.cclet.2023.109267
10. [10]
  Jindong Hao , Yufen Lv , Shuyue Tian , Chao Ma , Wenxiu Cui , Huilan Yue , Wei Wei , Dong Yi . Additive-free synthesis of β-keto phosphorodithioates via geminal hydro-phosphorodithiolation of sulfoxonium ylides with P₄S₁₀ and alcohols. Chinese Chemical Letters, 2024, 35(9): 109513-. doi: 10.1016/j.cclet.2024.109513
11. [11]
  Jianbao Mei , Bei Li , Shu Zhang , Dongdong Xiao , Pu Hu , Geng Zhang . Enhanced Performance of Ternary NASICON-Type Na_3.5-xMn_0.5V_1.5-xZr_x(PO₄)₃/C Cathodes for Sodium-Ion Batteries. Acta Physico-Chimica Sinica, 2024, 40(12): 2407023-. doi: 10.3866/PKU.WHXB202407023
12. [12]
  Ziling Jiang , Shaoqing Chen , Chaochao Wei , Ziqi Zhang , Zhongkai Wu , Qiyue Luo , Liang Ming , Long Zhang , Chuang Yu . Enabling superior electrochemical performance of NCA cathode in Li_5.5PS_4.5Cl_1.5-based solid-state batteries with a dual-electrolyte layer. Chinese Chemical Letters, 2024, 35(4): 108561-. doi: 10.1016/j.cclet.2023.108561
13. [13]
  Jingzhuo Tian , Chaohong Guan , Haobin Hu , Enzhou Liu , Dongyuan Yang . 废塑料促进S型NiCr₂O₄/孪晶Cd_0.5Zn_0.5S同质异质结光催化产氢. Acta Physico-Chimica Sinica, 2025, 41(6): 100068-. doi: 10.1016/j.actphy.2025.100068
14. [14]
  Jing Guo . New electrolyte concept: Compact ion-pair aggregate electrolyte. Chinese Chemical Letters, 2025, 36(4): 110512-. doi: 10.1016/j.cclet.2024.110512
15. [15]
  Xiaodan Wang , Yingnan Liu , Zhibin Liu , Zhongjian Li , Tao Zhang , Yi Cheng , Lecheng Lei , Bin Yang , Yang Hou . Highly efficient electrosynthesis of H₂O₂ in acidic electrolyte on metal-free heteroatoms co-doped carbon nanosheets and simultaneously promoting Fenton process. Chinese Chemical Letters, 2024, 35(7): 108926-. doi: 10.1016/j.cclet.2023.108926
16. [16]
  Kezhen Qi , Shu-yuan Liu , Ruchun Li . Selective dissolution for stabilizing solid electrolyte interphase. Chinese Chemical Letters, 2024, 35(5): 109460-. doi: 10.1016/j.cclet.2023.109460
17. [17]
  Qin ZHU , Jiao MA , Zhihui QIAN , Yuxu LUO , Yujiao GUO , Mingwu XIANG , Xiaofang LIU , Ping NING , Junming GUO . Morphological evolution and electrochemical properties of cathode material LiAl_0.08Mn_1.92O₄ single crystal particles. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1549-1562. doi: 10.11862/CJIC.20240022
18. [18]
  Ting Hu , Yuxuan Guo , Yixuan Meng , Ze Zhang , Ji Yu , Jianxin Cai , Zhenyu Yang . Uniform lithium deposition induced by copper phthalocyanine additive for durable lithium anode in lithium-sulfur batteries. Chinese Chemical Letters, 2024, 35(5): 108603-. doi: 10.1016/j.cclet.2023.108603
19. [19]
  Rongjun Zhao , Tai Wu , Yong Hua , Yude Wang . Improving performance of perovskite solar cells enabled by defects passivation and carrier transport dynamics regulation via organic additive. Chinese Chemical Letters, 2025, 36(2): 109587-. doi: 10.1016/j.cclet.2024.109587
20. [20]
  Gregorio F. Ortiz . Some facets of the Mg/Na₃VCr_0.5Fe_0.5(PO₄)₃ battery. Chinese Chemical Letters, 2024, 35(10): 109391-. doi: 10.1016/j.cclet.2023.109391

Get Citation

PDF

XML

Metrics

PDF Downloads(42)
Abstract views(1424)
HTML views(424)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Tris(trimethylsilyl)-Based Additives Enables Practical 5 V LiNi0.5Mn1.5O4 Batteries

Metrics

通讯作者: 陈斌, bchen63@163.com

Tris(trimethylsilyl)-Based Additives Enables Practical 5 V LiNi_0.5Mn_1.5O₄ Batteries