Citation: Zhang Zonghui, Ren Jinjun, Hu Lili. Structure Investigations on 100LiO_1/2-(100-x)PO_5/2-xTeO₂ Fast Ionic Conducting Glasses Using Solid-State Nuclear Magnetic Resonance Spectroscopy[J]. Acta Physico-Chimica Sinica, ;2020, 36(11): 200104. doi: 10.3866/PKU.WHXB202001048 shu

Structure Investigations on 100LiO_1/2-(100-x)PO_5/2-xTeO₂ Fast Ionic Conducting Glasses Using Solid-State Nuclear Magnetic Resonance Spectroscopy

Zhang Zonghui ^1,2 ,
Ren Jinjun ^1,2,, ,
Hu Lili ^1,2,,

1.
Key Laboratory of Materials for High Power Laser, Shanghai Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Shanghai 201800, P. R. China
2.
Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, P. R. China

Corresponding author: Ren Jinjun, renjinjunsiom@163.com Hu Lili, hulili@siom.ac.cn
Received Date: 19 January 2020
Revised Date: 18 February 2020
Accepted Date: 19 February 2020
Available Online: 9 March 2020
Fund Project: the National Natural Science Foundation of China 61675218The project was supported by the National Natural Science Foundation of China (61675218) and the 100 Talents Program of Chinese Academy of Sciences

Modified phosphate glasses can be used in all-solid-state batteries as solid electrolytes and cathodes due to their high ionic conductivity. The properties of fast ionic conducting glasses are strongly related to the structure of the glass networks. However, most previous works have focused on improving the ionic conductivity of such glasses by composition adjustments, while structural studies are scant. Structural investigations are essential to understand the composition dependence of the glass structure, which is valuable for improving the ionic conductivity and developing new ionic conducting glasses. In this work, phosphate ionic conducting glasses with compositions of 100LiO_1/2-(100-x)PO_5/2-xTeO₂ (x = 0, 10, 20, 25, 30) were synthesized, and their structures were investigated using Raman and solid-state nuclear magnetic resonance (SSNMR) spectroscopy. When x = 0, Raman and ³¹P magic angle spinning (MAS) NMR spectra showed that most of the phosphorus species were Q_0Te⁽²⁾ species, while the concentration of Q_0Te⁽¹⁾ species was negligible. Q_m_Te⁽ⁿ⁾ represents the phosphorus species with n bridging oxygen atoms (the oxygen atoms in P—O—P and P—O—Te linkages are both considered to be bridging oxygen atoms), and m Te atoms are connected to this [PO₄] tetrahedron. When PO_5/2 is substituted with TeO₂, long P—O—P chains are broken into short chains, and Q_0Te⁽²⁾ species gradually transform into Q_1Te⁽²⁾ and Q_0Te⁽¹⁾ species. Two-dimensional (2D) refocused incredible natural abundance double quantum transfer experiment (INADEQUATE) spectra proved that no isolated phosphorus species existed in the glasses; Q_0Te⁽²⁾, Q_1Te⁽²⁾, and Q_0Te⁽¹⁾ species were connected with each other through P—O—P linkages. Three- and four-coordinated Te were observed in the static ¹²⁵Te wideband uniform-rate smooth truncation quadrupolar Carr-Purcell-Meiboom-Gill (WURST-QCPMG) spectra. When the concentration of TeO₂ was low, four-coordinated Te was dominant. However, with the increase in TeO₂, the proportion of three-coordinated Te gradually increased, while that of four-coordinated Te decreased. The experimental contents of P—O—P, P—O—Te, and Te—O—Te linkages in these glasses were calculated from the deconvolutions of ³¹P and ¹²⁵Te NMR spectra. Then, the experimental contents were compared with the theoretical contents calculated according to a random distribution model. It was found that the experimental contents of homonuclear P—O—P and Te—O—Te linkages were slightly higher than their corresponding theoretical values, while the experimental content of heteronuclear P—O—Te was slightly lower than the theoretical value. These results indicated a weak priority for homonuclear connectivities. In this glass system, Li⁺ ions preferred to stay around [PO₄] tetrahedrons rather than tellurium oxygen polyhedrons. However, a small number of Li⁺ ions still interacted with tellurium oxygen polyhedrons to form [TeO₃] units. During the substitution of PO_5/2 by TeO₂, the fractions of bridging oxygen atoms in these glasses were almost unchanged, resulting in a slight change in the glass transition temperature. This work provides a comprehensive description of glass networks, depending on their compositions, which could be valuable for improving the ionic conductivity and for designing new fast ionic conducting glasses through structural modifications.
- Phosphotellurite glass,
- Solid-state NMR,
- Fast ionic conductor,
- Glass structure,
- Raman spectrum
1. [1]
  He, D.; Kang, S.; Zhang, L.; Chen, L.; Ding, Y.; Yin, Q.; Hu, L. High Power Laser Sci. Eng. 2017, 5, e1. doi: 10.1017/hpl.2016.46 doi: 10.1017/hpl.2016.46
2. [2]
  Hu, L.; Chen, S.; Tang, J.; Wang, B.; Meng, T.; Chen, W.; Wen, L.; Hu, J.; Li, S.; Xu, Y.; et al. High Power Laser Sci. Eng. 2014, 2, e1. doi: 10.1017/hpl.2014.4 doi: 10.1017/hpl.2014.4
3. [3]
  Campbell, J. H.; Suratwala, T. I. J. Non. Cryst. Solids 2000, 263, 318. doi: 10.1016/S0022-3093(99)00645-6 doi: 10.1016/S0022-3093(99)00645-6
4. [4]
  Kim, Y. P.; Lee, G. S.; Kim, J. W.; Kim, M. S.; Ahn, H. S.; Lim, J. Y.; Kim, H. W.; Son, Y. J.; Knowles, J. C.; Hyun, J. K. J. Tissue Eng. Regen. Med. 2015, 9 (3), 236. doi: 10.1002/term.1626 doi: 10.1002/term.1626
5. [5]
  Ahmed, I.; Lewis, M.; Olsen, I.; Knowles, J. C. Biomaterials 2004, 25 (3), 491. doi: 10.1016/S0142-9612(03)00546-5 doi: 10.1016/S0142-9612(03)00546-5
6. [6]
  Shah, R.; Sinanan, A. C. M.; Knowles, J. C.; Hunt, N. P.; Lewis, M. P. Biomaterials 2005, 26 (13), 1497. doi: 10.1016/j.biomaterials.2004.04.049 doi: 10.1016/j.biomaterials.2004.04.049
7. [7]
  Ahmed, I.; Collins, C. A.; Lewis, M. P.; Olsen, I.; Knowles, J. C. Biomaterials 2004, 25 (16), 3223. doi: 10.1016/j.biomaterials.2003.10.013 doi: 10.1016/j.biomaterials.2003.10.013
8. [8]
  Mangion, M.; Johari, G. P. Phys. Rev. B 1987, 36 (16), 8845. doi: 10.1103/PhysRevB.36.8845 doi: 10.1103/PhysRevB.36.8845
9. [9]
  Martin, S. W. J. Am. Ceram. Soc. 1991, 74 (8), 1767. doi: 10.1111/j.1151-2916.1991.tb07788.x doi: 10.1111/j.1151-2916.1991.tb07788.x
10. [10]
  Brow, R. K. J. Non. Cryst. Solids 2000, 263, 1. doi: 10.1016/S0022-3093(99)00620-1 doi: 10.1016/S0022-3093(99)00620-1
11. [11]
  Brow, R. K.; Click, C. A.; Alam, T. M. J. Non. Cryst. Solids 2000, 274 (1–3), 9. doi: 10.1016/S0022-3093(00)00178-2 doi: 10.1016/S0022-3093(00)00178-2
12. [12]
  Nakata, S.; Togashi, T.; Honma, T.; Komatsu, T. J. Non. Cryst. Solids 2016, 450, 109. doi: 10.1016/j.jnoncrysol.2016.08.005 doi: 10.1016/j.jnoncrysol.2016.08.005
13. [13]
  Rioux, M.; Ledemi, Y.; Viens, J.; Morency, S.; Ghaffari, S. A.; Messaddeq, Y. RSC Adv. 2015, 5 (50), 40236. doi: 10.1039/C5RA00681C doi: 10.1039/C5RA00681C
14. [14]
  Rioux, M.; Ledemi, Y.; Messaddeq, Y. J. Non. Cryst. Solids 2017, 459, 169. doi: 10.1016/j.jnoncrysol.2017.01.011 doi: 10.1016/j.jnoncrysol.2017.01.011
15. [15]
  Cho, K. I.; Lee, S. H.; Shin, D. W.; Sun, Y. K. Electrochim. Acta 2006, 52 (4), 1576. doi: 10.1016/j.electacta.2006.02.065 doi: 10.1016/j.electacta.2006.02.065
16. [16]
  de Oliveira, M.; Oliveira, J. S.; Kundu, S.; Machado, N. M. P.; Rodrigues, A. C. M.; Eckert, H. J. Non. Cryst. Solids 2018, 482, 14. doi: 10.1016/j.jnoncrysol.2017.11.052 doi: 10.1016/j.jnoncrysol.2017.11.052
17. [17]
  Larink, D.; Rinke, M. T.; Eckert, H. J. Phys. Chem. C 2015, 119 (31), 17539. doi: 10.1021/acs.jpcc.5b04074 doi: 10.1021/acs.jpcc.5b04074
18. [18]
  de Oliveira, M.; Amjad, R. J.; de Camargo, A. S. S.; Eckert, H. J. Phys. Chem. C 2018, 122 (41), 23698. doi: 10.1021/acs.jpcc.8b07827 doi: 10.1021/acs.jpcc.8b07827
19. [19]
  Blais-Roberge, M.; Santagneli, S. H.; Messaddeq, S. H.; Rioux, M.; Ledemi, Y.; Eckert, H.; Messaddeq, Y. J. Phys. Chem. C 2017, 121 (25), 13823. doi: 10.1021/acs.jpcc.7b03684 doi: 10.1021/acs.jpcc.7b03684
20. [20]
  Dongbei, L.; Shuai, X.; Zhiwu, Y. Chin. J. Magn. Reson. 2017, 34 (1), 115. doi: 10.11938/cjmr20170114 doi: 10.11938/cjmr20170114
21. [21]
  Lesage, A.; Bardet, M.; Emsley, L. J. Am. Chem. Soc. 1999, 121 (47), 10987. doi: 10.1021/ja992272b doi: 10.1021/ja992272b
22. [22]
  Guerry, P.; Smith, M. E.; Brown, S. P. J. Am. Chem. Soc. 2009, 131 (33), 11861. doi: 10.1021/ja902238s doi: 10.1021/ja902238s
23. [23]
  O'Dell, L. A.; Schurko, R. W. Chem. Phys. Lett. 2008, 464 (1–3), 97. doi: 10.1016/j.cplett.2008.08.095a doi: 10.1016/j.cplett.2008.08.095a
24. [24]
  Massiot, D.; Fayon, F.; Capron, M.; King, I.; Le Calvé, S.; Alonso, B.; Durand, J. O.; Bujoli, B.; Gan, Z.; Hoatson, G. Magn. Reson. Chem. 2002, 40 (1), 70. doi: 10.1002/mrc.984 doi: 10.1002/mrc.984
25. [25]
  Chowdari, B. V..; Kumari, P. P. Mater. Res. Bull. 1999, 34 (2), 327. doi: 10.1016/S0025-5408(99)00012-4 doi: 10.1016/S0025-5408(99)00012-4
26. [26]
  Himei, Y.; Osaka, A.; Nanba, T.; Miura, Y. J. Non. Cryst. Solids 1994, 177, 164. doi: 10.1016/0022-3093(94)90526-6 doi: 10.1016/0022-3093(94)90526-6
27. [27]
  Sekiya, T.; Mochida, N.; Ohtsuka, A.; Tonokawa, M. J. Non. Cryst. Solids 1992, 144, 128. doi: 10.1016/S0022-3093(05)80393-X doi: 10.1016/S0022-3093(05)80393-X
28. [28]
  Irannejad, M.; Jose, G.; Jha, A.; Steenson, P. Opt. Commun. 2012, 285 (10–11), 2646. doi: 10.1016/j.optcom.2012.01.073 doi: 10.1016/j.optcom.2012.01.073
29. [29]
  Murugan, G. S.; Suzuki, T.; Ohishi, Y. J. Appl. Phys. 2006, 100 (2), 023107. doi: 10.1063/1.2215218 doi: 10.1063/1.2215218
30. [30]
  Brow, R. K.; Tallant, D. R.; Hudgens, J. J.; Martin, S. W.; Irwin, A. D. J. Non. Cryst. Solids 1994, 177, 221. doi: 10.1016/0022-3093(94)90534-7 doi: 10.1016/0022-3093(94)90534-7
1. [1]
  Xinzhi Ding , Chong Liu , Jing Niu , Nan Chen , Shutao Xu , Yingxu Wei , Zhongmin Liu . Solid-state NMR study of the stability of MOR framework aluminum. Chinese Journal of Structural Chemistry, 2024, 43(4): 100247-100247. doi: 10.1016/j.cjsc.2024.100247
2. [2]
  Huixin Chen , Chen Zhao , Hongjun Yue , Guiming Zhong , Xiang Han , Liang Yin , Ding Chen . Unraveling the reaction mechanism of high reversible capacity CuP₂/C anode with native oxidation PO_x component for sodium-ion batteries. Chinese Chemical Letters, 2025, 36(1): 109650-. doi: 10.1016/j.cclet.2024.109650
3. [3]
  Yang Deng , Yitao Ouyang , Chao Han . Constriction-susceptible makes fast cycling of lithium metal in solid-state batteries: Silicon as an example. Chinese Journal of Structural Chemistry, 2024, 43(7): 100276-100276. doi: 10.1016/j.cjsc.2024.100276
4. [4]
  Dong Sui , Jiayi Liu . Constriction-susceptible lithium support for fast cycling of solid-state lithium metal battery. Chinese Chemical Letters, 2025, 36(2): 110417-. doi: 10.1016/j.cclet.2024.110417
5. [5]
  Biao Fang , Runwei Mo . PVDF-based solid-state battery. Chinese Journal of Structural Chemistry, 2024, 43(8): 100347-100347. doi: 10.1016/j.cjsc.2024.100347
6. [6]
  Qian Wang , Ting Gao , Xiwen Lu , Hangchao Wang , Minggui Xu , Longtao Ren , Zheng Chang , Wen Liu . Nanophase separated, grafted alternate copolymer styrene-maleic anhydride as an efficient room temperature solid state lithium ion conductor. Chinese Chemical Letters, 2024, 35(7): 108887-. doi: 10.1016/j.cclet.2023.108887
7. [7]
  Tianyi Hou , Yunhui Huang , Henghui Xu . Interfacial engineering for advanced solid-state Li-metal batteries. Chinese Journal of Structural Chemistry, 2024, 43(7): 100313-100313. doi: 10.1016/j.cjsc.2024.100313
8. [8]
  Peng Jia , Yunna Guo , Dongliang Chen , Xuedong Zhang , Jingming Yao , Jianguo Lu , Liqiang Zhang . In-situ imaging electrocatalysis in a solid-state Li-O₂ battery with CuSe nanosheets as air cathode. Chinese Chemical Letters, 2024, 35(5): 108624-. doi: 10.1016/j.cclet.2023.108624
9. [9]
  Qianqian Song , Yunting Zhang , Jianli Liang , Si Liu , Jian Zhu , Xingbin Yan . Boron nitride nanofibers enhanced composite PEO-based solid-state polymer electrolytes for lithium metal batteries. Chinese Chemical Letters, 2024, 35(6): 108797-. doi: 10.1016/j.cclet.2023.108797
10. [10]
  Chaochao Wei , Ru Wang , Zhongkai Wu , Qiyue Luo , Ziling Jiang , Liang Ming , Jie Yang , Liping Wang , Chuang Yu . Revealing the size effect of FeS₂ on solid-state battery performances at different operating temperatures. Chinese Chemical Letters, 2024, 35(6): 108717-. doi: 10.1016/j.cclet.2023.108717
11. [11]
  Caixia Li , Yi Qiu , Yufeng Zhao , Wuliang Feng . Self assembled electron blocking and lithiophilic interface towards dendrite-free solid-state lithium battery. Chinese Chemical Letters, 2024, 35(4): 108846-. doi: 10.1016/j.cclet.2023.108846
12. [12]
  Ting WANG , Peipei ZHANG , Shuqin LIU , Ruihong WANG , Jianjun ZHANG . A Bi-CP-based solid-state thin-film sensor: Preparation and luminescence sensing for bioamine vapors. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1615-1621. doi: 10.11862/CJIC.20240134
13. [13]
  Ying Li , Yanjun Xu , Xingqi Han , Di Han , Xuesong Wu , Xinlong Wang , Zhongmin Su . A new metal–organic rotaxane framework for enhanced ion conductivity of solid-state electrolyte in lithium-metal batteries. Chinese Chemical Letters, 2024, 35(9): 109189-. doi: 10.1016/j.cclet.2023.109189
14. [14]
  Linhui Liu , Wuwan Xiong , Mingli Fu , Junliang Wu , Zhenguo Li , Daiqi Ye , Peirong Chen . Efficient NO_x abatement by passive adsorption over a Pd-SAPO-34 catalyst prepared by solid-state ion exchange. Chinese Chemical Letters, 2024, 35(4): 108870-. doi: 10.1016/j.cclet.2023.108870
15. [15]
  Shuai Li , Liuting Zhang , Fuying Wu , Yiqun Jiang , Xuebin Yu . Efficient catalysis of FeNiCu-based multi-site alloys on magnesium-hydride for solid-state hydrogen storage. Chinese Chemical Letters, 2025, 36(1): 109566-. doi: 10.1016/j.cclet.2024.109566
16. [16]
  Xin Li , Ling Zhang , Yunyan Fan , Shaojing Lin , Yong Lin , Yongsheng Ying , Meijiao Hu , Haiying Gao , Xianri Xu , Zhongbiao Xia , Xinchuan Lin , Junjie Lu , Xiang Han . Carbon interconnected microsized Si film toward high energy room temperature solid-state lithium-ion batteries. Chinese Chemical Letters, 2025, 36(2): 109776-. doi: 10.1016/j.cclet.2024.109776
17. [17]
  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
18. [18]
  Mengxiang Zhu , Tao Ding , Yunzhang Li , Yuanjie Peng , Ruiping Liu , Quan Zou , Leilei Yang , Shenglei Sun , Pin Zhou , Guosheng Shi , Dongting Yue . Graphene controlled solid-state growth of oxygen vacancies riched V₂O₅ catalyst to highly activate Fenton-like reaction. Chinese Chemical Letters, 2024, 35(12): 109833-. doi: 10.1016/j.cclet.2024.109833
19. [19]
  Ce Liang , Qiuhui Sun , Adel Al-Salihy , Mengxin Chen , Ping Xu . Recent advances in crystal phase induced surface-enhanced Raman scattering. Chinese Chemical Letters, 2024, 35(9): 109306-. doi: 10.1016/j.cclet.2023.109306
20. [20]
  Zizhuo Liang , Fuming Du , Ning Zhao , Xiangxin Guo . Revealing the reason for the unsuccessful fabrication of Li3Zr2Si2PO12 by solid state reaction. Chinese Journal of Structural Chemistry, 2023, 42(11): 100108-100108. doi: 10.1016/j.cjsc.2023.100108

Get Citation

PDF

XML

Metrics

PDF Downloads(12)
Abstract views(934)
HTML views(169)

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

Structure Investigations on 100LiO1/2-(100-x)PO5/2-xTeO2 Fast Ionic Conducting Glasses Using Solid-State Nuclear Magnetic Resonance Spectroscopy

Metrics

通讯作者: 陈斌, bchen63@163.com

Structure Investigations on 100LiO_1/2-(100-x)PO_5/2-xTeO₂ Fast Ionic Conducting Glasses Using Solid-State Nuclear Magnetic Resonance Spectroscopy