Solid Electrolyte Membranes Based on Li2O–Al2O3–GeO2–SiO2–P2O5 Glasses for All-Solid State Batteries
Abstract
:1. Introduction
2. Experimental
3. Results and Discussion
3.1. Characterization and Thermal Behavior of the Glasses
3.2. Crystallization Behavior
3.3. Transport Properties of Glasses
3.4. Short-Range Structure of the Glasses
4. Conclusions
Author Contributions
Funding
Institutional Review Board Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
- Zhang, F.; Huang, Q.A.; Tang, Z.; Li, A.; Shao, Q.; Zhang, L.; Li, X. A review of mechanics-related material damages in all-solid-state batteries: Mechanisms, performance impacts and mitigation strategies. Nano Energy 2020, 70, 104545. [Google Scholar] [CrossRef]
- Zhang, Z.; Shao, Y.; Lotsch, B.; Hu, Y.-S.; Li, H.; Janek, J.; Nazar, L.F.; Nan, C.-W.; Maier, J.; Armand, M.; et al. New horizons for inorganic solid state ion conductors. Energy Environ. Sci. 2018, 11, 1945–1976. [Google Scholar] [CrossRef] [Green Version]
- Sun, C.; Liu, J.; Gong, Y.; Wilkinson, D.P.; Zhang, J. Recent advances in all-solid-state rechargeable lithium batteries. Nano Energy 2017, 33, 363–386. [Google Scholar] [CrossRef] [Green Version]
- Liu, Q.; Jiang, L.; Zheng, P.; Sun, J.; Liu, C.; Chai, J.; Li, X.; Zheng, Y.; Liu, Z. Recent Advances in Stability Issues of Inorganic Solid Electrolytes and Composite Solid Electrolytes for All-Solid-State Batteries. Chem. Rec. 2022, 22, e202200116. [Google Scholar] [CrossRef]
- Wang, Y.; Richards, W.D.; Ong, S.P.; Mara, L.J.; Kim, J.C.; Mo, Y.; Ceder, G. Design principles for solid-state lithium superionic conductors. Nat. Mater. 2015, 14, 1026–1031. [Google Scholar] [CrossRef]
- Bates, J.B.; Dudney, N.J.; Neudecker, B.; Ueda, A.; Evans, C.D. Thin film lithium and lithium-ion batteries. Solid State Ion. 2000, 135, 33–45. [Google Scholar] [CrossRef] [Green Version]
- Pershina, S.V.; Il’ina, E.A.; Druzhinin, K.V.; Farlenkov, A.S. Effect of Li2O–Al2O3–GeO2–P2O5 glass crystallization on stability versus molten lithium. J. Non-Cryst. Solids 2020, 527, 119708. [Google Scholar] [CrossRef]
- Klym, H.; Ingram, A.; Shpotyuk, O.; Hotra, O.; Popov, A.I. Positron trapping defects in free-volume investigation of Ge–Ga–S–CsCl glasses. Radiat. Meas. 2016, 90, 117–121. [Google Scholar] [CrossRef]
- Kozlovskiy, A.; Shlimas, D.I.; Zdorovets, M.V.; Popova, E.; Elsts, E.; Popov, A.I. Investigation of the Efficiency of Shielding Gamma and Electron Radiation Using Glasses Based on TeO2-WO3-Bi2O3-MoO3-SiO to Protect Electronic Circuits from the Negative Effects of Ionizing Radiation. Materials 2022, 15, 6071. [Google Scholar] [CrossRef]
- Kun, H.; Yanhang, W.; Chengkui, Z.; Huifeng, Z.; Yonghua, L.; Jiang, C.; Bin, H.; Juanrong, M. Influence of Al2O3 additions on crystallization mechanism and conductivity of Li2O–GeO2–P2O5 glass–ceramics. Physica B 2011, 406, 3947–3950. [Google Scholar] [CrossRef]
- Pershina, S.V.; Antonov, B.D.; Farlenkov, A.S.; Vovkotrub, E.G. Glass-ceramics in Li1+xAlxGe2−x(PO4)3 system: The effect of Al2O3 addition on microstructure, structure and electrical properties. J. Alloys Compd. 2020, 835, 155281. [Google Scholar] [CrossRef]
- Jiang, P.; Cao, J.; Wei, B.; Qian, G.; Wang, S.; Shi, Y.; Du, G.; Lu, X.; Ouyang, C.; Cao, F.; et al. LiF involved interphase layer enabling thousand cycles of LAGP-based solid-state Li metal batteries with 80% capacity retention. Energy Storage Mater. 2022, 48, 145–154. [Google Scholar] [CrossRef]
- Kuo, P.H.; Du, J. Crystallization behavior of Li1+xAlxGe2−x(PO4)3 glass-ceramics: Effect of composition and thermal treatment. J. Non-Cryst. Solids 2019, 525, 119680. [Google Scholar] [CrossRef]
- Cruz, A.M.; Fereira, E.B.; Rodrigues, A.C.M. Controlled crystallization and ionic conductivity of a nanostructured LiAlGePO4 glass–ceramic. J. Non-Cryst. Solids 2009, 355, 2295–2301. [Google Scholar] [CrossRef]
- Zhu, Y.; Zhang, Y.; Lu, L. Influence of crystallization temperature on ionic conductivity of lithium aluminum germanium phosphate glass-ceramic. J. Power Sourc. 2015, 290, 123–129. [Google Scholar] [CrossRef]
- Pershina, S.V. Structural, thermal and electrical properties of Li2O–Al2O3–GeO2–P2O5 glasses. J. Alloys Compd. 2021, 871, 159532. [Google Scholar] [CrossRef]
- Lucci, A.; Battezzati, L.; Antonione, C.; Riontino, G. Influence of preannealing on crystallization kinetics of some metallic glasses. J. Non-Cryst. Solids 1981, 44, 287–295. [Google Scholar] [CrossRef]
- Prasad, N.S.; Varma, K.B.R. Crystallization kinetics of the LiBO2–Nb2O5 glass using differential thermal analysis. J. Am. Ceram. Soc. 2005, 88, 357–361. [Google Scholar] [CrossRef]
- Kun, H.; Yanhang, W.; Chengkui, Z.; Yonghua, L.; Huifeng, Z.; Bin, H.; Jiang, C. Crystallization Kinetics of Lithium Aluminum Germanium Phosphate Glass by DSC Technique. J. Wuhan Univ. Technol.-Mater. Sci. Ed. 2012, 27, 63–66. [Google Scholar] [CrossRef]
- Das, A.; Dixit, A.; Goswami, M.; Mythili, R.; Hajra, R.N. Study on crystallization kinetics and phase evolution in Li2O–Al2O3–GeO2–P2O5 glass ceramics system. AIP Conf. Proc. 2018, 1942, 140022. [Google Scholar] [CrossRef]
- Das, A.; Goswami, M.; Krishnan, M. Crystallization kinetics of Li2O–Al2O3–GeO2–P2O5 glass–ceramics system. J. Therm. Anal. Calorim. 2018, 131, 2421–2431. [Google Scholar] [CrossRef]
- Das, A.; Goswami, M.; Krishnan, M. Study on electrical and structural properties in SiO2 substituted Li2O–Al2O3–GeO2–P2O5 glass-ceramic systems. Ceram. Int. 2018, 44, 13373–13380. [Google Scholar] [CrossRef]
- Kilic, G.; Ilik, E.; Mahmoud, K.A.; El-Agawany, F.I.; Alomairy, S.; Rammah, Y.S. The role of B2O3 on the structural, thermal, and radiation protection efficacy of vanadium phosphate glasses. Appl. Phys. A 2021, 127, 265. [Google Scholar] [CrossRef]
- Dubois, G.; Volksen, W.; Magbitang, T.; Miller, R.D.; Gage, D.M.; Dauskardt, R.H. Molecular Network Reinforcement of Sol–Gel Glasses. Adv. Mater. 2007, 19, 3989–3994. [Google Scholar] [CrossRef]
- Kaur, A.; Khanna, A.; González-Barriuso, M.; Gonza’lez, F. Thermal and light emission properties of rare earth (Eu3+, Dy3+ and Er3+), alkali (Li+, Na+ and K+) and Al3+-doped barium tellurite and boro-tellurite glasses. J. Mater. Sci. Mater. Electron. 2021, 32, 17266–17281. [Google Scholar] [CrossRef]
- Dimitrov, V.; Komatsu, T. Average single bond strength and optical basicity of Na2O–GeO2 glasess. J. Ceram. Soc. Jpn. 2009, 117, 1105–1111. [Google Scholar] [CrossRef] [Green Version]
- Bih, L.; Omari, M.E.; Réau, J.-M.; Haddad, M.; Boudlich, D.; Yacoubi, A.; Nadiri, A. Electronic and ionic conductivity of glasses inside the Li2O–MoO3–P2O5 system. Solid State Ion. 2000, 6, 71–85. [Google Scholar] [CrossRef]
- Ray, N.H. Composition–property relationships in inorganic oxide glasses. J. Non-Cryst. Solids 1974, 15, 423–434. [Google Scholar] [CrossRef]
- Pershina, S.V.; Antonov, B.D.; Leonidov, I.I. Effect of MoO3 on structural, thermal and transport properties of lithium phosphate glasses. J. Non-Cryst. Solids 2021, 569, 120944. [Google Scholar] [CrossRef]
- Fokin, V.M.; Cabral, A.A.; Reis, R.M.C.V.; Nascimento, M.L.F.; Zanotto, E.D. Critical assessment of DTA/DSC methods for the study of nucleation kinetics in glasses. J. Non-Cryst. Solids 2010, 356, 358–367. [Google Scholar] [CrossRef]
- Rodrigues, A.M.; Narváez-Semanate, J.L.; Cabral, A.A.; Rodrigues, A.C.M. Determination of Crystallization Kinetics Parameters of a Li1.5Al0.5Ge1.5(PO4)3 (LAGP) Glass by Differential Scanning Calorimetry. Mater. Res. 2013, 16, 811–816. [Google Scholar] [CrossRef] [Green Version]
- Rani, S.; Sanghi, S.; Agarwal, A.; Ahlawat, N. Effect of Bi2O3 on the dynamics of Li+ ions in Li2O·P2O5 glasses. J. Mater. Sci. 2009, 44, 5781–5787. [Google Scholar] [CrossRef]
- Jlassi, I.; Sdiri, N.; Elhouichet, H.; Ferid, M. Raman and impedance spectroscopy methods of P2O5–Li2O–Al2O3 glass system doped with MgO. J. Alloys Compd. 2015, 645, 125–130. [Google Scholar] [CrossRef]
- Mariappan, C.R.; Yada, C.; Rosciano, F.; Roling, B. Correlation between micro-structural properties and ionic conductivity of Li1.5Al0.5Ge1.5(PO4)3 ceramics. J. Power Sourc. 2011, 196, 6456–6464. [Google Scholar] [CrossRef]
- Metwalli, E.E.; Brow, R.K.; Stover, F.S. Cation Effects on Anion Distributions in Aluminophosphate Glasses. J. Am. Ceram. Soc. 2001, 84, 1025–1032. [Google Scholar] [CrossRef]
- Saout, G.L.; Simon, P.; Fayon, F.; Blin, A.; Vaills, Y. Raman and infrared study of (PbO)x(P2O5)1−x glasses. J. Raman Spectrosc. 2002, 33, 740–746. [Google Scholar] [CrossRef]
- Toloman, D.; Biris, A.R.; Maniu, D.; Bratu, I.; Giurgiu, L.M.; Biris, A.S.; Ardelean, I. Phosphate glassy network depolymerization induced by CaO doping. Part. Sci. Technol. 2010, 28, 226–235. [Google Scholar] [CrossRef]
- Hudgens, J.J.; Brow, R.K.; Tallant, D.R.; Martin, S.W. Raman spectroscopy study of the structure of lithium and sodium ultraphosphate glasses. J. Non-Cryst. Solids 1998, 223, 21–31. [Google Scholar] [CrossRef]
- Roiland, C.; Fayon, F.; Simon, P.; Massiot, D. Characterization of the disordered phosphate network in CaO–P2O5 glasses by 31P solid-state NMR and Raman spectroscopies. J. Non-Cryst. Solids 2011, 357, 1636–1646. [Google Scholar] [CrossRef]
- Galliano, P.G.; Porto Lopez, J.M.; Varetti, E.L.; Sobrados, I.; Sanz, J. Analysis by nuclear magnetic resonance and Raman spectroscopies of the structure of bioactive alkaline-earth selicophosphate glasses. Mater. Res. Bul. 1994, 29, 1297–1306. [Google Scholar] [CrossRef]
- Szumera, M. The structural role of manganese ions in soil active silicate–phosphate glasses. Spectrochim. Acta Part A Mol. Biomol. Spectrosc. 2014, 129, 601–608. [Google Scholar] [CrossRef]
- Sułowska, J.; Wacławska, I.; Olejniczak, Z. Structural studies of copper-containing multicomponent glasses from the SiO2–P2O5–K2O–CaO–MgO system. Vib. Spectrosc. 2013, 65, 44–49. [Google Scholar] [CrossRef]
- Tatsumisago, M.; Kowada, Y.; Minami, T. Raman spectra of rapidly quenched glasses and melts containing large amounts of Li2O. J. Non-Cryst. Solids 1992, 150, 207–211. [Google Scholar] [CrossRef]
- Belova, E.V.; Kolyagin, Y.A.; Uspenskaya, I.A. Structure and glass transition temperature of sodium-silicate glasses doped with iron. J. Non-Cryst. Solids 2015, 423–424, 50–57. [Google Scholar] [CrossRef]
- Scott, J.F. Raman Spectra of GeO2. Phys. Rev. B 1970, 1, 3488–3493. [Google Scholar] [CrossRef]
- Mernagh, T.P.; Liu, L.-G. Temperature dependence of Raman spectra of the quartz and rutile-types of GeO2. Phys. Chem. Miner. 1997, 24, 7–16. [Google Scholar] [CrossRef]
- Sahar, M.R.; Hussein, A.W.M.A.; Hussin, R. Structural characteristic of Na2O–P2O5–GeO2 glass systems. J. Non-Cryst. Solids 2007, 353, 1134–1140. [Google Scholar] [CrossRef] [Green Version]
- Osaka, A.; Takahashi, K.; Ikeda, M. Infrared study of trivalent cations B and Fe in amorphous and crystalline phosphates. J. Mater. Sci. Lett. 1984, 3, 36–38. [Google Scholar] [CrossRef]
- Moreau, F.; Durán, A.; Munoz, F. Structure and properties of high Li2O-containing aluminophosphate glasses. J. Eur. Ceram. Soc. 2009, 29, 1895–1902. [Google Scholar] [CrossRef]
- Pershina, S.V.; Raskovalov, A.A.; Antonov, B.D.; Yaroslavtseva, T.V.; Reznitskikh, O.G.; Baklanova, Y.V.; Pletneva, E.D. Extremal Li-ion conductivity behavior in the Li2O–Al2O3–P2O5 glass system. J. Non-Cryst. Solids 2015, 430, 64–72. [Google Scholar] [CrossRef]
- Kamitsos, E.I.; Yiannopoulos, Y.D.; Karakassides, M.A.; Chryssikos, G.D.; Jain, H. Raman and Infrared Structural Investigation of xRb2O(1−x)GeO2 Glasses. J. Phys. Chem. 1996, 100, 11755–11765. [Google Scholar] [CrossRef]
- Kumar, S.; Murugavel, S.; Rao, K.J. Absence of Germanate Anomaly in Ternary Lithium Germanophosphate Glasses: Modification Behavior of Mixed Glass System of Strong and Fragile Formers. J. Phys. Chem. B 2001, 105, 5862–5873. [Google Scholar] [CrossRef]
- Gandhi, Y.; Rao, M.V.R.; Rao, C.S.; Kityk, I.V.; Veeraiah, N. Role of Al2O3 in upconversion and NIR emission in Tm3+ and Er3+ codoped calcium fluoro phosphorous silicate glass system. J. Lumin. 2011, 131, 1443–1452. [Google Scholar] [CrossRef]
Glass Code | x Value | Method | Li2O, mol% | Al2O3, mol% | GeO2, mol% | SiO2, mol% | P2O5, mol% | (Li+Al)/ (Ge+Si+P) | O/P | ρ ± 0.04, g cm−3 |
---|---|---|---|---|---|---|---|---|---|---|
0Si | 0.0 | nominal | 18.75 | 6.25 | 37.50 | – | 37.50 | 0.33 | 4.1 | 2.98 |
AES | 18.0 | 7.0 | 38.1 | – | 36.9 | |||||
0.1Si | 0.1 | nominal | 19.51 | 6.09 | 36.59 | 2.44 | 35.37 | 0.34 | 4.2 | 3.03 |
AES | 18.9 | 6.9 | 37.0 | 2.5 | 34.7 | |||||
0.2Si | 0.2 | nominal | 20.24 | 5.95 | 35.71 | 4.76 | 33.34 | 0.35 | 4.3 | 3.01 |
AES | 20.1 | 6.0 | 36.2 | 4.6 | 33.1 | |||||
0.3Si | 0.3 | nominal | 20.93 | 5.81 | 34.88 | 6.98 | 31.40 | 0.36 | 4.5 | 3.05 |
AES | 20.8 | 5.9 | 35.3 | 7.1 | 30.9 | |||||
0.4Si | 0.4 | nominal | 21.59 | 5.68 | 34.09 | 9.09 | 29.55 | 0.36 | 4.6 | 2.96 |
AES | 20.9 | 5.6 | 34.3 | 9.0 | 30.2 | |||||
0.5Si | 0.5 | nominal | 22.22 | 5.56 | 33.33 | 11.11 | 27.78 | 0.38 | 4.7 | 2.87 |
AES | 22.0 | 5.6 | 33.0 | 11.1 | 28.3 |
x | α, °C min−1 | Tg, °C | Tc, °C | Tp, °C | ∆T, °C |
---|---|---|---|---|---|
0 | 3 | 519.7 | 613 | 616.9 | 93.3 |
5 | 523 | 623 | 625.4 | 100 | |
10 | 523.4 | 634.5 | 636.0 | 111.1 | |
0.1 | 3 | 505 | 616.9 | 619.6 | 111.9 |
5 | 510 | 626.1 | 629.9 | 116.1 | |
10 | 513.3 | 642.9 | 646.6 | 129.6 | |
15 | 527.6 | 652.9 | 657.8 | 125.3 | |
25 | 523.4 | 665.2 | 672.8 | 141.8 | |
0.2 | 3 | 495.6 | 626 | 632.1 | 130.4 |
5 | 498.4 | 638.1 | 645.3 | 139.7 | |
10 | 498 | 658.5 | 667.9 | 160.5 | |
0.3 | 3 | 472 | 640.5 | 646 | 168.5 |
5 | 485.1 | 659.7 | 667.1 | 174.6 | |
10 | 488 | 676.9 | 701.9 | 188.9 | |
0.4 | 3 | 458.7 | 617.8 | 631.9 | 159.1 |
5 | 475.7 | 634.8 | 655 | 159.1 | |
10 | 474.9 | 641.2 | 692.5 | 166.3 | |
0.5 | 3 | 440 | 580 | 631.2 | 140 |
5 | 462 | 598.5 | 653.7 | 136.5 | |
10 | 460 | 623 | 683.8 | 163 |
Band Position, cm−1 | Band Assignments | References |
---|---|---|
1255 | νs (P–O–P) | [39] |
νs (P=O) | [36,37,38] | |
1115 | νs (PO2)− | [36,37,38,39] |
νas (P–O–P) | [39,40] | |
νas (Si–O−) | [40,41,42] | |
775 | νas (P–O–P) | [38,39,40] |
νs (P–O–P) | [37,42] | |
νs (Si–O–Si) | [42,43] | |
575 | νs (O–Si–O) | [42,44] |
νs (O–P–O) | [42] | |
νs (Ge–O–P) | [11] | |
460–490 | νs (O–P–O) | [41,42] |
νs (Ge–O–Ge) | [11,45,46] | |
340 | δ (O–P–O) | [37] |
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Pershina, S.V.; Kuznetsova, T.A.; Vovkotrub, E.G.; Belyakov, S.A.; Kuznetsova, E.S. Solid Electrolyte Membranes Based on Li2O–Al2O3–GeO2–SiO2–P2O5 Glasses for All-Solid State Batteries. Membranes 2022, 12, 1245. https://doi.org/10.3390/membranes12121245
Pershina SV, Kuznetsova TA, Vovkotrub EG, Belyakov SA, Kuznetsova ES. Solid Electrolyte Membranes Based on Li2O–Al2O3–GeO2–SiO2–P2O5 Glasses for All-Solid State Batteries. Membranes. 2022; 12(12):1245. https://doi.org/10.3390/membranes12121245
Chicago/Turabian StylePershina, Svetlana V., Tamara A. Kuznetsova, Emma G. Vovkotrub, Semyon A. Belyakov, and Elena S. Kuznetsova. 2022. "Solid Electrolyte Membranes Based on Li2O–Al2O3–GeO2–SiO2–P2O5 Glasses for All-Solid State Batteries" Membranes 12, no. 12: 1245. https://doi.org/10.3390/membranes12121245