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Reinvestigations of the Li2O–Al2O3 system. Part I: LiAlO2 and Li3AlO3

Reinvestigations of the Li2O–Al2O3 system. Part I: LiAlO2 and Li3AlO3 30 Pol. J. Chem. Tech., Vol. 23, No. 3, 2021 Polish Journal of Chemical Technology, 23, 3, 30—36, 10.2478/pjct-2021-0027 Reinvestigations of the Li O–Al O system. Part I: LiAlO and Li AlO 2 2 3 2 3 3 Piotr Tabero , Artur Frąckowiak, Grażyna Dąbrowska West Pomeranian University of Technology Szczecin, Faculty of Chemical Technology and Engineering, Department of Inorganic and Analytical Chemistry, Piastow Avenue 42, 71-065 Szczecin, Poland Corresponding author: e-mail: ptab@zut.edu.pl Reinvestigations of the Li O–Al O system focused on the synthesis and properties of LiAlO and Li AlO phases 2 2 3 2 3 3 have been performed with the help of XRD and IR measuring techniques and Li CO , LiOH H O, Al O -sl., 2 3 2 2 3 α-Al O , Al(NO ) 9H O and boehmite as reactants. Results of investigations have shown the formation of α-, 2 3 3 3 2 β-, and γ- polymorphs of LiAlO . It was found that only the use of LiOH H O as a reactant yields to β-LiAlO 2 2 2 as a reaction product. On the other hand, it was proved that Li AlO does not form in the Li O–Al O system. 3 3 2 2 3 A new method for the synthesis of α-LiAlO was developed, consisting in grinding the mixture of Li CO and 2 2 3 Al(NO ) 9H O and heating the obtained paste at the temperature range of 400–600 C. The IR spectroscopy was 3 3 2 used to characterize obtained phases. Keywords: Li O–Al O system, LiAlO , Li AlO , XRD, IR. 2 2 3 2 3 3 INTRODUCTION perature 623 K. On the other hand, the cubic form of LiAlO described by Debray and Hardy is in fact the Compounds containing lithium have been the subject of teragonal γ-LiAlO . Table 1 presents the basic crystal- comprehensive research for many years due to many dif- lographic data of polymorphic modifi cations of LiAlO . ferent industrial applications, including the production of The tetragonal γ-LiAlO is considered to be the most 1–3 glass and heat-resistant ceramics , luminescent ionizing thermodynamically stable polymorphic modifi cation of 4, 5 6–9 radiation detectors , carbonate fuel cell components , 10 LiAlO and it is considered to be a potential material carbon dioxide absorbents and solid electrolytes used for 11, 12 for obtaining tritium for the purposes of nuclear fusion, the production of lithium-ion batteries . Lithium alu- substrates for epitaxial growth of II-V semiconductors minates are active catalysts for the hydrophosphinization 13 such as GaN, components for the production of liquid of alkynes, alkenes and carbodiimides . Lithium-based 9, 12, 15–17, 37–39 carbonate fuel cells or radiation dosimeters . ceramics have been identifi ed as the most important In recent years, however, attention has been paid to the material for obtaining tritium in Test Modules (TBMs) of 38–44 hexagonal form of α-LiAlO . It has been shown that the International Thermonuclear Experimental Reactor 14–18 at the operating temperature of the fuel cell equal to Project, ITER . 650 C, the alpha variety is more stable than the gamma The literature review has shown that 5 compounds variety . The α-LiAlO polymorph is also considered as are formed in the two-component system of Li O–Al O 2 2 3 a component for the production of electrode protective oxides: Li AlO , Li AlO , LiAl O , LiAlO and LiAl O . 5 4 3 3 2 3.5 2 5 8 40–42 19 layers in lithium batteries . A necessary condition for Hatch suggests that limited or continuous solid solutions the use of α-LiAlO , however, is to obtain a product may form between LiAl O and γ-Al O . So far, no phase 5 8 2 3 containing nanometric grain size. diagram of the Li O–Al O system has been developed 2 2 3 The literature review shows that the α-LiAlO formed in the entire concentration range of the components. at temperatures not exceeding 600 C is nanocrystalline, There are two versions of the phase diagram of the 20, 21 however, it is most often contaminated with substrates system in the range of LiAlO –Al O , which show 2 2 3 45, 46 or by-products of the synthesis reaction . The large that one LiAl O compound is formed. In none of these 5 8 broadening of the diffraction refl ections of the α-LiAlO works, there was any information about the formation 2 obtained in such conditions is related to the presence of the LiAl O compound, mentioned by M. Kriens 2 3.5 of crystallites with dimensions of the order of 7–15 nm and co-authors . There are three versions of the phase and a strong structure defect. SEM and TEM micro- diagram of the Li O–Al O system, developed based 2 2 3 23–25 scopic studies revealed the presence of dislocations and on thermodynamic data available in the literature . inclusions of spinel-like fragments or amorphous areas Despite numerous studies on the Li O-Al O system, 2 2 3 in the α-LiAlO samples tested . On the other hand, at there is still controversy about the number and type of temperatures above 650 C, a slowly progressing phase phases formed in it, methods of their preparation and 19–55 transition under these conditions begins, leading to the properties . Therefore, our work aimed to verify the 27, 40 tetragonal γ-LiAlO . literature data on the Li O–Al O system. The fi rst part 2 2 3 The conducted literature review showed that the au- of our investigations was focused on the LiAlO and thors of the studies disagreed as to the temperature of Li AlO phases. 3 3 phase transitions and the thermal stability of the LiAlO The LiAlO compound has four polymorphic modifi ca- 2 2 20, 47 o 26–46 26–29 30, 31 polymorphs. Lejus , found that at 900 C, α-LiAlO tions : hexagonal α , orthorhombic β , tetrago- undergoes a reversible transformation to the high- nal γ and the δ-LiAlO formed at pressures above 9 33 34 temperature γ polymorph however, the transformation GPa . High-pressure studies carried out by Lei et al. showed that the monoclinic form of β’-LiAlO obtained from γ to α is very slow. LiAlO melts at 1700 C, but 35 o by Cheng under the pressure of 1.8 GPa is in fact the at temperatures higher than 1300 C, it decomposes into orthorhombic modifi cation of β-LiAlO and it can be LiAl O and Li O, caused by the high volatility of lithium 5 8 2 obtained already at the pressure of 0.8 GPa and tem- oxide. According to Lehmann et al. slow irreversible Pol. J. Chem. Tech., Vol. 23, No. 3, 2021 31 transformation of α→γ-LiAlO occurs at temperatures The syntheses of Li AlO and LiAlO were carried 2 3 3 2 o 48 above 600 C. Hummel and co-workers claim that out using a conventional solid-state reaction method, 56–59 the α phase undergoes a rapid phase transition at the analogous to that presented in . temperature of 1200–1300 C, and the melting point of The substrates weighed in suitable proportions were LiAlO is equal to 1610 ± 15 C. homogenized in an agate mortar and calcinated in the 49 o Isupov et al. investigated the effect of the gaseous temperature range of 400–1200 C in 24 h stages. The samples were heated in the furnace FCF 3.5/1350 (Czylok, atmosphere on the type of LiAlO modifi cation produced Poland). Temperatures of calcination of samples were using gibbsite and Li CO mixture. They showed that 2 3 estimated basing on literature data concerning Li O- during synthesis at 800 C in air with typical partial water 19, 21, 23, 29, 47, 48, 55 Al O system . pressure of 1300 Pa forms α-LiAlO contaminated with 2 2 3 In the frames of this work new method of LiAlO small amounts of γ-LiAlO . Synthesis in helium with synthesis was developed. Lithium carbonate and alumi- water partial pressure not exceeding 4 Pa form both num nitrate(V) nonahydrate weighed in stochiometric modifi cations in similar amounts but in vacuum with proportions were ground in a mortar until the release water pressure of 0.1 Pa mostly γ-LiAlO is formed. 30 31 33 of CO bubbles ceases. The semi-fi nished product thus The structure of the α-LiAlO , β-LiAlO , γ-LiAlO 2 2 2 obtained was in the form of a paste. Subsequently, the and δ-LiAlO2 is known. The crystal lattice of the hex- paste obtained was heated in an air atmosphere in the agonal layered α-LiAlO and the high-pressure tetragonal temperature range of 400–600 C, then, after taking it δ-LiAlO are deformed variants of the NaCl structure + 3+ out of the furnace, it was cooled to room temperature with ordered Li and Al ions in the octahedral sites. in desiccator, ground in a mortar and subjected to X- In the structure of γ-LiAlO LiO and AlO tetrahedra 2 4 4 ray investigations. connected by common corners form layers that con- The phase composition of samples was investigated by nect to adjacent layers by common edges. In turn, the using XRD method and identifi ed by powder diffraction β-LiAlO crystal lattice with a deformed wurtzite struc- patterns of obtained samples recorded with the aid of ture is built of LiO and AlO tetrahedrons connected 4 4 the diffractometer EMPYREAN II, (PANalytical, The via common corners . Nederlands) using the CuKa radiation with a graphite IR spectra of α-LiAlO , β-LiAlO and γ-LiAlO are 2 2 2 32, 47, 50–52 monochromator with the help of Highscore + software known . and PDF4+ICDD database. The powder diffraction La Ginestra and co-workers , as a result of heating patterns of selected phases were indexed using the RE- at 400 C for 500 hours of the mixture of γ-Al O and 2 3 FINEMENT program of DHN/PDS package. Li O obtained the Li AlO phase and presented the 2 2 3 3 The IR spectra were recorded on the SPECORD powder diffraction pattern of this compound. The authors M 80 spectrometer (Carl Zeiss, Jena, Germany). The did not manage to obtain single-phase Li AlO sample, 3 3 measurements were made within the wavenumber range but only a mixture containing about 40% of unreacted –1 of 4000–200 cm . The infrared spectra were made by reagents. According to the researchers, the Li AlO is 3 3 pelleting a sample with KBr in the weight ratio of 1:300. metastable and above 420 C it decomposes with the The mean crystallite size of selected samples was release of α-LiAlO and Li AlO . The authors of the 2 5 4 calculated using the Scherrer formula: study failed to obtain the Li AlO phase with the use of 3 3 Li CO , LiNO and Li O . The existence of the Li AlO 2 3 3 2 3 3 compound was also postulated by Kroger and Fingars and Fedorov and Shamari , but the compound was not where: β – the half-width of the refl ex (hkl) [rad], characterized by them. D – mean crystallite size in the direction perpendicular hkl to the plane (hkl) [Å], λ – wavelength of the X-ray radiation used, λ = 1.5406 [Å], EXPERIMENTAL k – Scherrer’s constant equal to k = 0.94, The following materials were used for the research: o θ – refl ection angle, related to the refl ection (hkl) [ ]. Li CO , a.p. (POCh, Poland), LiOH H O (Loba Che- 2 3 2 mie, Austria), Al O pure, sintered, denoted as Al O -sl 2 3 2 3 RESULTS AND DISCUSSION (POCh, Poland), boehmite-γ-AlOOH (POCH, Poland) and Al(NO ) 9H O a.p. (POCH. Poland). α-Al O was Transition modifi cations of alumina such as γ-, η-, 3 3 2 2 3 obtained by sintering Al O -sl at 1200 C for 4 hours. δ- and θ- Al O obtained in the temperature range 2 3 2 3 Table 1. Basic crystallographic data of α-LiAlO , β-LiAlO , γ-LiAlO and δ-LiAlO phases, where CS-crystal system: O – orthor- 2 2 2 2 hombic, T – tetragonal, H – hexagonal HP(GPa)-modifi cation obtain under high pressure equal to (GPa), SG (no.) – space group and its number; D – distorted structure, TW – this work 32 Pol. J. Chem. Tech., Vol. 23, No. 3, 2021 400–1000 C have a defective spinel structure based on by a very large number of crystallization water molecules 60, 61 a cubic close packed lattice of oxide ions . For this contained in the crystal lattice of aluminum nitrate(V) reason, the powder diffraction patterns of individual nanohydrate, which, released during intense grinding, modifi cations reported in the literature are similar to enables the aluminum nitrate(V) hydrolysis reaction lead- each other (similar d values). It is very diffi cult to ing to strong acidifi cation of the reaction medium and hkl clearly identify these transition alumina. In this work, initiates the decomposition of Li CO . The mechanism 2 3 when writing about this type of phases, we will use the of this process is currently being researched and the common symbol Al O -sl (spinel like). results will be presented in the next paper. The paste 2 3 In the fi rst stage of investigations synthesis of LiAlO obtained after the evolution of CO bubbles had ceased 2 2 was carried out using Li CO and α-Al O , Al O -sl and was then heated in a furnace under an air atmosphere 2 3 2 3 2 3 boehmite as aluminum precursors. Figures 1A and 1B in the temperature range of 400–600 C. Figure 2 shows show fragments of powder diffractograms of the reaction the diffractograms recorded after the successive stages mixtures prepared with the use of Al O -sl and Li CO of heating the obtained paste. 2 3 2 3 (Fig. 1A) or of α-Al O and Li CO (Fig. 1B) with the 2 3 2 3 compositions corresponding to the LiAlO phase, and samples recorded after successive heating stages in the temperature range of 450–1000 C. Figure 2. Powder diffraction patterns recorded during the synthesis of α-LiAlO with a new method using Figure 1. Fragments of the powder diffractograms of the reaction Li CO and Al(NO ) 9H O after the heating steps 2 3 3 3 2 mixture prepared with the use of Al O -sl and Li CO 2 3 2 3 at the following temperatures: a – 400 C x 30 min, (A) and with the use of α-Al O and Li CO (B) with o o 2 3 2 3 b – 400 C x d and c – 600 C x 30 min. * – means the composition corresponding to the LiAlO phase LiNO , ■ – means α-LiAlO 3 2 and samples recorded after successive heating stages in the temperature range of 450–1000 C Single-phase sample containing α-LiAlO was obtained after 30 minutes of heating at 600 C, while the synthesis During the heating stage at 450 C, almost all boehm- with Al O -sl and Li CO required heating the reactants 2 3 2 3 ite used in the synthesis decomposed to form Al O -sl, o o 2 3 at 700 C. Lithium nitrate(V) melts at 255 C, and boils and the further synthesis process was carried out in o and decomposes at 600 C. The presence of LiNO this sample with the use of in situ formed precursor. refl ections (PDF 04-010-5519) on the diffractogram of A single-phase sample containing α-LiAlO was obtained o the reaction mixture after the heating step at 400 C using boehmite and Al O -sl after the heating stage at 2 3 for 30 minutes shows that even molten LiNO slowly the temperature of 700 C. In both cases, the α-LiAlO reacts with the components of the reaction mixture. modifi cation appeared in reaction mixtures after a heat- The α-LiALO obtained at the temperature of 600 C ing stage at 500 C. Pure α-LiAlO obtained after sintering 2 x 30 min was characterized by strongly broadened dif- o o at 700 C was stable up to the temperature of 900 C, fraction refl ections, and the average size of crystallites at which the slow phase change leading to γ-LiAlO in this preparation determined by the Scherrer method began. However, a single-phase sample of γ-LiAlO was 2 was equal to 75Å. This value is consistent with the re- obtained only after the heating stage at 1000 °C. The sults of the research presented in , where the effect of reaction of LiAlO synthesis with the use of corundum 2 calcination time of the α-LiAlO sample at 600 C on was much slower. During it, the α-LiAlO modifi cation 2 the size of crystallites was analyzed. The reason for the appeared in the reaction mixture after a heating stage at signifi cant broadening of diffraction refl ections is, inter 550 C, but we failed to obtain a single-phase sample of alia, a high concentration of defects in the crystal lattice α-LiAlO . On the other hand small amounts of γ-LiAlO 2 2 of α-LiAlO obtained at low temperatures . It should were detected after the heating stage at 650 C while be mentioned, however, that regardless of the type of the pure γ-LiAlO was obtained after the heating stage metal precursors used in the synthesis of α-LiAlO , the at 950 C (Fig. 1A and 1B). refl exes of this phase were considerable broadened. In the frames of this work new method of LiAlO The crystallite size determined by the Scherrer method synthesis was developed using a mixture of aluminum during the synthesis of α-LiAlO with the use of Li CO 2 2 3 nitrate(V) and lithium carbonate as reactants. Grind- and boehmite increased gradually with the increase of . o ing of the Li CO and Al(NO ) 9H O solids initiates temperature from 101 Å (600 C x 24 h) through 389 Å 2 3 3 3 2 o o the reaction between them, as evidenced by CO gas (700 C x 24 h) to 406 Å (850 C x 24 h). bubbles intensively emitted during the grinding of the The literature review showed that the Li AlO phase 3 3 reagents in the mortar. The reaction is probably favored obtained by La Ginestra et al. is relatively poorly Pol. J. Chem. Tech., Vol. 23, No. 3, 2021 33 studied. Taking into account the comments of the au- contained a mixture of α- and β-LiAO , and the intensity thors of the work , an attempt was made to obtain the of refl ections characteristic of α-LiAO increased. The Li AlO phase by heating a mixture of LiOH H O and sample after the heating step at 700 C for 24 h con- 3 3 2 Al O -sl with a composition corresponding to the Li AlO tained γ-LiAlO as the main component, accompanied 2 3 3 3 2 phase in the temperature range of 400–500 C. The dif- by lower amounts of α- and β-LiAlO . fractograms recorded after the fi rst and second heating steps at 400 C for 72 h resembled that of the Li AlO 3 3 phase presented by Ginestera. However, X-ray phase analysis showed that the samples obtained at 400 C were not single-phase and contained a mixture of LiOH (PDF 00-032-0564), Li CO and β-LiAlO (PDF 00-033- 2 3 2 0785) (Fig. 3). Figure 4. Fragments of the powder diffraction patterns recor- ded after successive stages of heating the mixture of LiOH H O and Al O -sl with the composition 2 2 3 corresponding to the formula LiAlO : a – 1st stage o o 500 C x 72 h, b – 2nd stage 650 C x 72 h and c – 3rd stage-700 C x 72 h, where * – α-LiAlO , ■ – β-LiAlO , ♦ – γ-LiAlO and ● – Li CO 2 2 2 3 The conducted research indicates that the use of LiOH Figure 3. Fragments of the powder diffraction patterns recor- H O as a lithium precursor promotes the formation of ded after successive stages of heating the mixture β-LiAlO . However, while striving to eliminate lithium of LiOH H O and Al O -sl with the composition 2 2 3 carbonate from the reaction mixture by increasing the corresponding to the formula Li AlO : a – 1st 3 3 o o reaction temperature, the content of the α-LiAlO is stage 400 C x 72 h, b – 2nd stage 400 C x 72 h 2 simultaneously increased, and above 650 C β-LiAlO and c – 3rd stage-500 C x 72 h, where * – LiOH, ● – β-LiAlO and ♦ – Li CO undergoes a phase transition to γ-LiAlO . Currently, 2 2 3 2 research is conducted to obtain a single-phase β-LiAlO However, individual reflections from the Li AlO 3 3 sample and the results will be published soon. diffractogram presented by Ginestera were shifted by The powder diffractograms of the β-LiAlO , γ-LiAlO 2 2 0.01–0.20 degrees towards higher 2Theta angles in re- and α-LiAlO phases were indexed using the Refi nement lation to the position on our diffractograms and data program. The calculated values of the unit cell param- contained in PDF cards of LiOH, Li CO and β-LiAlO . 2 3 2 eters are shown in Table 1. In the case of β-LiAO , the Therefore, the conducted research shows that the phase results of the powder diffractogram pattern indexing are with the formula Li AlO is not formed. According to p resented in Table 2. 3 3 the literature data, LiOH identifi ed in reaction mixtures may be formed as a result of the reaction of Li O with Table 2. The result of the indexing of X-ray powder diffraction water contained in the air. LiOH is also formed as pattern of β-LiAlO obtained in this work a result of dehydration of LiOH H O in the temperature range 90–200 C and then in the temperature range o 49 420–550 C it decomposes with the release of Li O . The presence of Li CO in the obtained samples can also 2 3 be explained because both LiOH H O and LiOH have the ability to bind large amounts of CO from the air to form Li CO . After another heating step at 500 °C for 2 3 72 h, the content of β-LiAlO in the sample increased signifi cantly. This fact prompted us to try to synthesize β-LiAlO using a stoichiometric mixture of LiOH H O 2 2 and Al O -sl. Figure 4 shows the diffractograms of the 2 3 sample with the composition LiAlO after subsequent stages of heating. The analysis of the XRD test results showed that the reaction mixture after the fi rst stage of heating at 500 C for 72 h contained β-LiAlO as the main component, accompanied by Li CO and α-LiAlO 2 3 2 in much smaller amounts. After the second stage of heating at 650 C for 24 hours, the obtained product 34 Pol. J. Chem. Tech., Vol. 23, No. 3, 2021 To know better properties of obtained phases IR spec- LITERATURE CITED tra of γ-LiAlO , β-LiAlO and α-LiAlO were recorded. 2 2 2 1. Rebouças, L.B., Souza, M.T., Raupp-Pereira1, F., & Analysis of the number and positions of absorption bands Novaes de Oliveira, A.P. (2019). Characterization of Li O- recorded in their IR spectra has shown good agreement -Al O -SiO glass-ceramics produced from a Brazilian spodu- 2 3 2 32, 47, 50–52 with literature data . mene concentrate. Cerâmica 65, 366–377. DOI: 10.1590/0366- 2. Ahmadi, Moghadam, H. & Hossein, Paydar, M. (2016). The Effect of Nano CuO as Sintering Aid on Phase Formation, Microstructure and Properties of Li O-Stabilized ″-Alumina Ceramics. J. Ceram. Sci. Tech., 07(04), 441–446. DOI: 10.4416/ JCST2016-00075. 3. Shackelford, J.F. & Doremus, R.H. (2008). Ceramic and glass materials. Structure, properties and processing. Springer Science+Business Media LLC New York. ISBN 978-0-387- 73361-6. 4. Dhabekar, B., Raja, E.A., Gundu Rao, T.K., Kher, R.K. & Bhat, B.C. (2009). Thermoluminescence, optically stimulated luminescence and ESR studies on LiAl O :Tb. Indian. J. Pure 5 8 Ap. Phy., 47, 426–428. 5. Mandowska, E., Mandowski, A., Bilski, P., Marczewska, B., Twardak, A. & Gieszczyk, W. (2015). Lithium aluminate – a new detector for dosimetry. Prz. Elektrotech. 91(9), 117–120 (in Polish). 6. Gao, J., Shi, S., Xiao, R. & Li, H. (2016). Synthesis and ionic transport mechanisms of α-LiAlO , Solid State Ionics, Figure 5. IR spectra of: a) γ-LiAlO , b) β-LiAlO , c) α-LiAlO 2 2 2 286, 122–134. DOI: 10.1016/j.ssi.2015.12.028. 7. Özkan, G. & Incirkuş Ergençoglu, V. (2016). Synthesis Figure 5 shows the IR spectra of γ-LiAlO (curve a), and characterization of solid electrolyte structure mate- β-LiAlO (curve b) and α-LiAlO (curve c). The litera- 2 2 rial (LiAlO ) using different kinds of lithium and aluminum ture survey has shown that crystal lattices of γ-LiAlO 2 compounds for molten carbonate fuel cells. Indian J. Chem. and β-LiAlO are built up of LiO and AlO tertahedra, Technol. 23, 227–231. 2 4 4 32, 47, 50–52 8. Kim, J.E., Patil, K.Y., Han, J., Yoon, S.P., Nam, S.W., when α-LiAlO of LiO and AlO octahedra . 2 6 6 Lim, T.H., Hong, S.A., Kim, H. & Lim, H.Ch. (2009). Using The presence of LiO and AlO tetrahedra in crystal lat- 4 4 aluminum and Li CO particles to reinforce the α-LiAlO 2 3 2 tices of γ-LiAlO (Fig. 5, curve a) and β-LiAlO (Fig. 5, 2 2 matrix for molten carbonate fuel cells. Internat. J. Hydrogen curve b) with Li-O and Al-O bonds shorter than in the Energy 34(22), 9227–9232. DOI: 10.1016/j.ijhydene.2009.08.069. case of LiO and AlO octahedra is responsible for the 9. Ducan, Y. (2021). Theoretical Investigation of the 6 6 CO Capture Properties of γ-LiAlO and α-Li AlO . Micro 2 2 5 4 shift of absorption bands in their spectra towards higher Nanosyst. 13, 32–41. DOI: 10.2174/187640291166619091318 wavenumbers in comparison with the position of IR bands in the spectrum of α-LiAlO . Moreover, good agreement 10. Ávalos-Rendón, T., Casa-Madrid, J. & Pfeiffer, H. (2009). of the number and positions of absorption bands in IR Thermochemical Capture of Carbon Dioxide on Lithium Alu- minates (LiAlO and Li AlO ): A New Option for the CO spectrum of β-LiAlO obtained in our laboratory with 2 5 4 2 Absorption. J. Phys. Chem. A, 113, 6919–6923. DOI: 10.1021/ data in paper corroborates that polymorph of LiAlO jp902501v. obtained by Chang crystallizes in an orthorhombic system. 11. Raja, M., Sanjeev, G., Kumar, T.P. & Stephan, A.M. (2015). Lithium aluminate-based ceramic membranes as separa- tors for lithium-ion batteries. Ceram. Int. 41, 3045–50. DOI: CONCLUSIONS 10.1016/j.ceramint.2014.10.142. Using applied procedures of syntheses, three phases 12. Fouad, O.A., Farghaly, F.I. & Bahgat, M. (2007). A novel have been obtained: α-LiAlO , β-LiAlO γ-LiAlO . approach for synthesis of nanocrystalline γ-LiAlO from spent 2 2, 2 2 lithium-ion batteries. J. Anal. Appl. Pyrolysis. 78, 65–69. DOI: A new method of LiAlO synthesis was developed 10.1016/j.jaap.2006.04.002. consisting in grinding in mortar mixture of lithium car- 13. Pollard, V.A., Young, A., McLellan, R., Kennedy, A.R., bonate and aluminum nitrate(V) nonahydrate until the Tuttle, T., Robert, E. & Mulvey, R.E. (2019). Lithium-Alu- release of CO bubbles ceases and subsequent heating of minate-Catalyzed Hydrophosphination Applications. Angew. Chem. Int. Ed. 58, 1229–12296. DOI: 10.1002/anie.201906807. obtained paste in the temperature range of 400–600 C. 14. Indris, S. & Heitjans, P. (2006). Local electronic structure As a result of the reaction of LiOH H O with Al O - 2 2 3 in a LiAlO single crystal studied with Li NMR spectroscopy sl, β-LiAlO was obtained, contaminated with a small and comparison with quantum chemical calculations. Phys. Rev. amount of α-LiAO . 2 B 74, 245120-1-5. DOI: 10.1103/PhysRevB.74.245120. It has been shown that the powder diffractogram of 15. Duan, Y., Sorescu, D.C., Jiang, W. & Senor, D.J. (2020) Theoretical study of the electronic, thermodynamic, and the Li AO phase is a set of diffraction refl ections that 3 3 thermo-conductive properties of γ-LiAlO with Li isotope can be attributed to the mixture of LiOH, Li CO and 2 3 substitutions fortritium production. J. Nucl. Mater. 530, 151963. β-LiAlO . DOI: 10.1016/j.nucmat.2019.151963. The results of XRD and IR investigations showed that 16. Rasneur, B. (1985). Tritium breeding material γ-LiAlO . β-LiAlO crystallizes in an orthorhombic system. Fusion Technol. 8, 1909–1914. DOI: 10.13182/FST85-A40040. 2 Pol. J. Chem. Tech., Vol. 23, No. 3, 2021 35 17. Liu, Y.Y., Billone, M.C., Fischer, A.K., Tam, S.W., Clem- Zeitschrift für Kristallographie – Crystalline Materials. 231(3), mer, R.G. & Hollenberg, G.W. (1985). Solid tritium breeder 189–193. DOI: 10.14279/depositonce-5480. materials Li O and LiAlO - a data-base review. Fusion Sci. 39. Ha, N.T.T., Van Giap, T. & Thanh, N.T. (2020). Synthesis 2 2 Technol. 8, 1970–1984. DOI: 10.13182/FST85-A24573. of lithium aluminate for application in radiation dosimetry. 18. Morley, N.B., Abdou, M.A., Anderson, M., Calderoni, Mater. Lett. 267, 127506. DOI: 10.1016/j.matlet.2020.127506. P., Kurtz, R.J., Nygren, R., Raffray, R., Sawan, M., Sharpe, 40. Jimenez-Becerril, J. & Garcia-Sosa, I. (2011). Synthesis P., Smolentsev, S., Willms, S. & Ying, A.Y. (2006). Over- of lithium aluminate by thermal decomposition of a lithium view of fusion nuclear technology in the US. Fusion Eng. dawsonite-type precursor. J. Ceram. Process. Res. 12, 52–56. Des. 81, 33–43. DOI: 10.1016/j.fusengdes.2005.06.359. 41. Heo, S.J., Batra, R., Ramprasad, R. & Singh, P. (2018). 19. Strickler, D.W. & Roy, R. (1961). Studies in the System Crystal morphology and phase transformation of LiAlO : Li O–Al O –Fe O –H O. J. Am. Ceram. Soc. 44, 5, 225–230. combined experimental and fi rst-principles Studies. J. Phys. 2 2 3 2 3 2 DOI: 10.1111/j.1151-2916.1961.tb15365.x. Chem. C 222, 28797–28804. DOI: 10.1021/acs.jpcc.8b09716. 20. Lejus, A.M. & R. Collongues, R. (1962). Sur la structure 42. Patil, K.Y., Yoon, S.P., Han, J., Lim, T.H., Nam, S.W. & les propriétés des aluminates de lithium. Chimie Minérale Oh, I.H. (2011). The effect of lithium addition on aluminum- 2005–2007. reinforced α-LiAlO matrices for molten carbonate fuel 21. Kriens, M., Adiwidjaja, G., Guse, W., Klaska, K.H., Lathe, cells. Int. J. Hydrog. Energy, 36, 6237–6247. DOI: 10.1016/j. C. & Saalfeld, H. (1996). The crystal structures of LiAl O and 5 8 ijhydene.2011.01.161. Li Al O . N. Jb. Miner. Mh. 8, 344–350. 2 4 7 43. Park, J.S., Meng, X., Elam, J.W., Hao, S., Wolverton, 22. Hatch, R.A. (1943). Phase equilibrium in the system: Ch., Kim, Ch. & Cabana, J. (2014). Ultrathin Lithium-Ion Li O–Al O –SiO . Am. Mineral. 28, 471–496. DOI: 10.1111/ 2 2 3 2 Conducting Coatings for Increased Interfacial Stability in High j.1151-2916.1985.tb15280.x. Voltage Lithium-Ion Batteries. Chem. Mater. 26, 3128–3134. 23. Cook, L.P. & Plante, E.R. (1992). Phase Diagram of the DOI: 10.1021/cm500512n. System Li O–Al O . Ceram. Trans. 27, 193–222. 2 2 3 44. Cheng, F., Xin, Y., Huang, Y., Chen, J., Zhou, H. & 24. Byker, H.J., Eliezer, I., Eliezer, N. & Howald, R.A. (1979). Zhang, X. (2013). Enhanced electrochemical performances Calculation of a Phase Diagram for LiO –AlO System. J. 0.5 1.5 of 5 V spinel LiMn Ni O cathode materials by coating 1.58 0.42 4 Phys. Chem. 83, 18, 2349–2355. DOI: 10.1021/j100481a009. with LiAlO . J. Power Sources. 239, 181–188. DOI: 10.1016/j. 25. Konar, B., Van Ende, M.A. & Junh, I.H. (2018). Critical jpowsour.2013.03.143. Evaluation and Thermodynamic Optimization of the Li O- 45. Cao, H., Xia, B., Zhang, Y., Xu, N. (2005). LiAlO 2- Al O and Li O–MgO–Al O Systems. Metall. Mat. Trans. B 2 3 2 2 3 -coated LiCoO as cathode material for lithium ion batteries. 49, 2917–2944. DOI: 10.1007/s11663-018-1349-x. Solid State Ionics. 176, 911–914. DOI: 10.1016/j.ssi.2004.12.001. 26. Marezio, M. & Remeika, J.P. (1966). High-pressure 46. Danek, V., Tarniowy, M. & Suski, L. (2004) Kinet- synthesis and crystal srtucture of α-LiAlO . J. Chem. Phys. 44, ics of the α → γ phase transformation in LiAlO under 3143-4. DOI: 10.1063/1.1727203. various atmospheres within the 1073–1173 K temperatures 27. Lehmann, H.A. & Hesselbrarth, H.Z. (1961). Uber range. J. Mater. Sci. 39, 2429–2435. DOI: 10.1023/B:JM eine neue Modifi kation des LiAlO . Anorg. Allg. Chem. 313, SC.0000020006.46296.04. 117–120. DOI: 10.1002/zaac.19613130110. 47. Lejus, A.M. (1964). Sur la formation a haute tempera- 28. Dronskowski, R. (1993). Reactivity and acidity of Li in ture de spinelles non stechiométriques et de phases derivées LiAlO phases. Inorg. Chem. 32, 1–9. DOI: 10.1021/ic00053a001. dans plusieurs systémes d’oxydes a base d’alumina et dans le 29. Poepplmeler, K.R., Chiang, C.K. & Kipp, D.O. (1988). systéme alumina-nitrure d’aluminum. Rev. Hautes Tempér. et Synthesis of High-Surface-Area α-LiAlO . Inorg. Chem. 27, Réfract., 1, 53–95. 4523–4524. DOI: 10.1021/ic00298a002. 48. Hummel, F.A., Sastry, B.S.R. & Wotring, D. (1958). 30. Thery, J. (1961). Structure and properties of alkaline Studies in Lithium Oxide Systems: II, Li O∙Al O –Al O . J. 2 2 3 2 3 aluminates. Bull. Soc. Chim. Fr. 973–5. Am. Ceram. Soc. 41, 3, 88–92. DOI: 10.1111/j.1151-916.1958. 31. Marezio, M. (1965). The Crystal Structure of LiGaO . tb15448.x. Acta Cryst. 18, 481–484. DOI: 10.1107/S0365110X65001068. 49. Isupov, V.P., Bulina, N.V. & Borodulina, I.A. (2017). 32. Marezio, M. (1965). The Crystal Structure and Anoma- Effect of Water Vapor Pressure on the Phase Composition of lous Dispersion of γ-LiAlO . Acta Cryst. 19, 396–400. DOI: Lithium Monoaluminates Formed in the Interaction of Alu- 10.1107/S0365110X65003511. minum Hydroxide and Lithium Carbonate. Zhurnal Prikladnoi 33. Li, X., Kobayashi, T., Zhang, F., Kimoto, K. & Sekine, Khimii, 90, 986−991. DOI: 10.1134/S1070427217080043. T. (2004). A new high-pressure phase of LiAlO . J. Solid State 50. Tarte, P. (1967). Infra-red spectra of inorganic aluminates Chem. 177, 1939–1943. DOI: 10.1016/j.jssc.2003.12.014. and characteristic vibrational frequencies of AlO tetrahedra 34. Lei, L., He, D., Zou, Y. & Zhang, W. (2008). Phase trans- 4 and AlO octahedra. Spectrochim. Acta 23A, 2127–2143. DOI: itions of LiAlO at high pressure and high temperature. J. Solid 6 10.1016/0584-8539(67)80100-4. State Chem. 181, 1810–1815. DOI: 10.1016/j.jssc.2008.04.006. 51. Braun, P.A. (1952). Superstructure in Spinels. Nature 35. Chang, C.H. & Margrave, J.L. (1968). Highpressure- 170, 1123. DOI: 10.1038/1701123a0. -high temperature synthesis. III. Direct synthesis of new high- 52. Datta, R.K. & Roy, R. (1963). Phase Transitions in -pressure forms of LiAlO and LiGaO and polymorphism in 2 2 LiAl O . J. Am. Ceram. Soc. 46, 8, 388–390. DOI: 10.1111/j.1151- LiMO compounds (M=B, Al, Ga). J. Amer. Chem. Soc. 90, 5 8 2916.1963.tb11757.x. 2020–2022. DOI: 10.1021/ja01010a018. 53. La Ginestra, A., Lo Jacono, M. & Porta, P. (1972). The 36. Debray, L. & Hardy, A.C.R. (1960). Contribution a Vetu- preparation, characterization, and thermal behaviour of some de structurale des aluminates de lithium. Hebd. Seances Acad. lithium aluminum oxides: Li AlO and Li AlO . J. Thermal Sci. 251, 725–726. 3 3 5 4 Anal. 4, 5–17. DOI: 10.1007/bf02100945. 37. Waltereit, P., Brandt, O., Trampert, A., Grahn, H.T., Men- 54. Kroger, C. & Fingas, E. (1935). Über die Systeme niger, J., Ramsteiner, M.,M. Reiche, M. & Ploog, K.H. (2000). Alkalioxyd–CaO–Al O –SiO –CO . IV. Die CO -Drucke des Nitride semiconductors free of electrostatic fi elds for effi cient 2 3 2 2 2 kieselsäurereicheren Teils des Systems Li O–SiO –CO und white light-emitting diodes. Nature 406, 865–868. DOI: 2 2 2 10.1038/35022529. der Einwirkung von Al O auf Li CO . Z anorg. Allg. Chem. 2 3 2 3 38. Wiedemann, D., Indris, S., Meyen, M. & Pedersen, B. 224, 289–304. DOI: 10.1002/zaac.19352240309. (2016) Single-crystal neutron diffraction on γ-LiAlO : Structure 55. Fedorov, T.F. & Shamari, F.I. (1960). Prim. Vak. V. Met., determination and estimation of lithium diffusion pathway. Akad. Nauk SSSR, Inst. Met. A.A. Baikova, 137–142. 36 Pol. J. Chem. Tech., Vol. 23, No. 3, 2021 56. Walczak, J., Kurzawa, M. & Tabero, P. (1987). V Mo O Am. Ceram. Soc. 81, 1995–2012. DOI: 10.1111/j.1151-2916.1998. 9 6 40 and phase equilibria in the system V Mo O –Fe O . Ther- 9 6 40 2 3 tb02581.x. mochim. Acta 118, 1–7. DOI: 10.1016/0040-6031(87)80065-5. 61. Krokodis, X., Raybaud, P., Gobichon, A.E., Rebours, 57. Tabero, P. (2010). Formation and properties of the new B., Euzen, P. & Toulhoat, H. (2001). Theoretical Study of the Al V W O and Fe Al V W O phases with the M-Nb O 8 10 16 85 8-x x 10 16 85 2 5 Dehydration Process of Boehmite to γ-Alumina. J. Phys. Chem. structure. J. Therm. Anal. Calorim. 101, 560–566. DOI: 10.1007/ B 105, 5121–5130. DOI: 10.1021/jp0038310. s10973-010-0848-z. 62. Kim, J., Kang, H., Hwang, K. & Yoon, S. (2019). Thermal 58. Tabero, P., Frackowiak, A., Filipek, E., Dąbrowska, G., Ho- monnay, Z. & Szilágyi, P.Á. (2018). Synthesis, thermal stability Decomposition Study on Li O for Li NiO Synthesis as a Sac- 2 2 2 2 and unknown properties of Fe Al VO solid solution. Ceram. 1-x x 4 rifi cing Positive Additive of Lithium-Ion Batteries. Molecules Int. 44, 17759–17766. DOI: 10.1016/j.ceramint.2018.06.243. 24, 4624–4632. DOI: 10.3390/molecules24244624. 59. Filipek, E., Dabrowska, G. & Piz, M. (2010). Synthesis and 63. Tovar, T.M. & Le, Van, M.D. (2017). Supported lithium characterization of new compound in the V-Fe-Sb-O system. J. hydroxide for carbon dioxide adsorption in water-saturated Alloys Compd. 490, 93–97. DOI: 10.1016/j.jallcom.2009.10.123. environments. Adsorption 23, 51–56. DOI: 10.1007/s10450- 60. Levin, I. & Brandon, D. (1998). Metastable Alumina Polymorphs: Crystal Structures and Transition Sequences. J. 016-9817-6. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Polish Journal of Chemical Technology de Gruyter

Reinvestigations of the Li2O–Al2O3 system. Part I: LiAlO2 and Li3AlO3

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Abstract

30 Pol. J. Chem. Tech., Vol. 23, No. 3, 2021 Polish Journal of Chemical Technology, 23, 3, 30—36, 10.2478/pjct-2021-0027 Reinvestigations of the Li O–Al O system. Part I: LiAlO and Li AlO 2 2 3 2 3 3 Piotr Tabero , Artur Frąckowiak, Grażyna Dąbrowska West Pomeranian University of Technology Szczecin, Faculty of Chemical Technology and Engineering, Department of Inorganic and Analytical Chemistry, Piastow Avenue 42, 71-065 Szczecin, Poland Corresponding author: e-mail: ptab@zut.edu.pl Reinvestigations of the Li O–Al O system focused on the synthesis and properties of LiAlO and Li AlO phases 2 2 3 2 3 3 have been performed with the help of XRD and IR measuring techniques and Li CO , LiOH H O, Al O -sl., 2 3 2 2 3 α-Al O , Al(NO ) 9H O and boehmite as reactants. Results of investigations have shown the formation of α-, 2 3 3 3 2 β-, and γ- polymorphs of LiAlO . It was found that only the use of LiOH H O as a reactant yields to β-LiAlO 2 2 2 as a reaction product. On the other hand, it was proved that Li AlO does not form in the Li O–Al O system. 3 3 2 2 3 A new method for the synthesis of α-LiAlO was developed, consisting in grinding the mixture of Li CO and 2 2 3 Al(NO ) 9H O and heating the obtained paste at the temperature range of 400–600 C. The IR spectroscopy was 3 3 2 used to characterize obtained phases. Keywords: Li O–Al O system, LiAlO , Li AlO , XRD, IR. 2 2 3 2 3 3 INTRODUCTION perature 623 K. On the other hand, the cubic form of LiAlO described by Debray and Hardy is in fact the Compounds containing lithium have been the subject of teragonal γ-LiAlO . Table 1 presents the basic crystal- comprehensive research for many years due to many dif- lographic data of polymorphic modifi cations of LiAlO . ferent industrial applications, including the production of The tetragonal γ-LiAlO is considered to be the most 1–3 glass and heat-resistant ceramics , luminescent ionizing thermodynamically stable polymorphic modifi cation of 4, 5 6–9 radiation detectors , carbonate fuel cell components , 10 LiAlO and it is considered to be a potential material carbon dioxide absorbents and solid electrolytes used for 11, 12 for obtaining tritium for the purposes of nuclear fusion, the production of lithium-ion batteries . Lithium alu- substrates for epitaxial growth of II-V semiconductors minates are active catalysts for the hydrophosphinization 13 such as GaN, components for the production of liquid of alkynes, alkenes and carbodiimides . Lithium-based 9, 12, 15–17, 37–39 carbonate fuel cells or radiation dosimeters . ceramics have been identifi ed as the most important In recent years, however, attention has been paid to the material for obtaining tritium in Test Modules (TBMs) of 38–44 hexagonal form of α-LiAlO . It has been shown that the International Thermonuclear Experimental Reactor 14–18 at the operating temperature of the fuel cell equal to Project, ITER . 650 C, the alpha variety is more stable than the gamma The literature review has shown that 5 compounds variety . The α-LiAlO polymorph is also considered as are formed in the two-component system of Li O–Al O 2 2 3 a component for the production of electrode protective oxides: Li AlO , Li AlO , LiAl O , LiAlO and LiAl O . 5 4 3 3 2 3.5 2 5 8 40–42 19 layers in lithium batteries . A necessary condition for Hatch suggests that limited or continuous solid solutions the use of α-LiAlO , however, is to obtain a product may form between LiAl O and γ-Al O . So far, no phase 5 8 2 3 containing nanometric grain size. diagram of the Li O–Al O system has been developed 2 2 3 The literature review shows that the α-LiAlO formed in the entire concentration range of the components. at temperatures not exceeding 600 C is nanocrystalline, There are two versions of the phase diagram of the 20, 21 however, it is most often contaminated with substrates system in the range of LiAlO –Al O , which show 2 2 3 45, 46 or by-products of the synthesis reaction . The large that one LiAl O compound is formed. In none of these 5 8 broadening of the diffraction refl ections of the α-LiAlO works, there was any information about the formation 2 obtained in such conditions is related to the presence of the LiAl O compound, mentioned by M. Kriens 2 3.5 of crystallites with dimensions of the order of 7–15 nm and co-authors . There are three versions of the phase and a strong structure defect. SEM and TEM micro- diagram of the Li O–Al O system, developed based 2 2 3 23–25 scopic studies revealed the presence of dislocations and on thermodynamic data available in the literature . inclusions of spinel-like fragments or amorphous areas Despite numerous studies on the Li O-Al O system, 2 2 3 in the α-LiAlO samples tested . On the other hand, at there is still controversy about the number and type of temperatures above 650 C, a slowly progressing phase phases formed in it, methods of their preparation and 19–55 transition under these conditions begins, leading to the properties . Therefore, our work aimed to verify the 27, 40 tetragonal γ-LiAlO . literature data on the Li O–Al O system. The fi rst part 2 2 3 The conducted literature review showed that the au- of our investigations was focused on the LiAlO and thors of the studies disagreed as to the temperature of Li AlO phases. 3 3 phase transitions and the thermal stability of the LiAlO The LiAlO compound has four polymorphic modifi ca- 2 2 20, 47 o 26–46 26–29 30, 31 polymorphs. Lejus , found that at 900 C, α-LiAlO tions : hexagonal α , orthorhombic β , tetrago- undergoes a reversible transformation to the high- nal γ and the δ-LiAlO formed at pressures above 9 33 34 temperature γ polymorph however, the transformation GPa . High-pressure studies carried out by Lei et al. showed that the monoclinic form of β’-LiAlO obtained from γ to α is very slow. LiAlO melts at 1700 C, but 35 o by Cheng under the pressure of 1.8 GPa is in fact the at temperatures higher than 1300 C, it decomposes into orthorhombic modifi cation of β-LiAlO and it can be LiAl O and Li O, caused by the high volatility of lithium 5 8 2 obtained already at the pressure of 0.8 GPa and tem- oxide. According to Lehmann et al. slow irreversible Pol. J. Chem. Tech., Vol. 23, No. 3, 2021 31 transformation of α→γ-LiAlO occurs at temperatures The syntheses of Li AlO and LiAlO were carried 2 3 3 2 o 48 above 600 C. Hummel and co-workers claim that out using a conventional solid-state reaction method, 56–59 the α phase undergoes a rapid phase transition at the analogous to that presented in . temperature of 1200–1300 C, and the melting point of The substrates weighed in suitable proportions were LiAlO is equal to 1610 ± 15 C. homogenized in an agate mortar and calcinated in the 49 o Isupov et al. investigated the effect of the gaseous temperature range of 400–1200 C in 24 h stages. The samples were heated in the furnace FCF 3.5/1350 (Czylok, atmosphere on the type of LiAlO modifi cation produced Poland). Temperatures of calcination of samples were using gibbsite and Li CO mixture. They showed that 2 3 estimated basing on literature data concerning Li O- during synthesis at 800 C in air with typical partial water 19, 21, 23, 29, 47, 48, 55 Al O system . pressure of 1300 Pa forms α-LiAlO contaminated with 2 2 3 In the frames of this work new method of LiAlO small amounts of γ-LiAlO . Synthesis in helium with synthesis was developed. Lithium carbonate and alumi- water partial pressure not exceeding 4 Pa form both num nitrate(V) nonahydrate weighed in stochiometric modifi cations in similar amounts but in vacuum with proportions were ground in a mortar until the release water pressure of 0.1 Pa mostly γ-LiAlO is formed. 30 31 33 of CO bubbles ceases. The semi-fi nished product thus The structure of the α-LiAlO , β-LiAlO , γ-LiAlO 2 2 2 obtained was in the form of a paste. Subsequently, the and δ-LiAlO2 is known. The crystal lattice of the hex- paste obtained was heated in an air atmosphere in the agonal layered α-LiAlO and the high-pressure tetragonal temperature range of 400–600 C, then, after taking it δ-LiAlO are deformed variants of the NaCl structure + 3+ out of the furnace, it was cooled to room temperature with ordered Li and Al ions in the octahedral sites. in desiccator, ground in a mortar and subjected to X- In the structure of γ-LiAlO LiO and AlO tetrahedra 2 4 4 ray investigations. connected by common corners form layers that con- The phase composition of samples was investigated by nect to adjacent layers by common edges. In turn, the using XRD method and identifi ed by powder diffraction β-LiAlO crystal lattice with a deformed wurtzite struc- patterns of obtained samples recorded with the aid of ture is built of LiO and AlO tetrahedrons connected 4 4 the diffractometer EMPYREAN II, (PANalytical, The via common corners . Nederlands) using the CuKa radiation with a graphite IR spectra of α-LiAlO , β-LiAlO and γ-LiAlO are 2 2 2 32, 47, 50–52 monochromator with the help of Highscore + software known . and PDF4+ICDD database. The powder diffraction La Ginestra and co-workers , as a result of heating patterns of selected phases were indexed using the RE- at 400 C for 500 hours of the mixture of γ-Al O and 2 3 FINEMENT program of DHN/PDS package. Li O obtained the Li AlO phase and presented the 2 2 3 3 The IR spectra were recorded on the SPECORD powder diffraction pattern of this compound. The authors M 80 spectrometer (Carl Zeiss, Jena, Germany). The did not manage to obtain single-phase Li AlO sample, 3 3 measurements were made within the wavenumber range but only a mixture containing about 40% of unreacted –1 of 4000–200 cm . The infrared spectra were made by reagents. According to the researchers, the Li AlO is 3 3 pelleting a sample with KBr in the weight ratio of 1:300. metastable and above 420 C it decomposes with the The mean crystallite size of selected samples was release of α-LiAlO and Li AlO . The authors of the 2 5 4 calculated using the Scherrer formula: study failed to obtain the Li AlO phase with the use of 3 3 Li CO , LiNO and Li O . The existence of the Li AlO 2 3 3 2 3 3 compound was also postulated by Kroger and Fingars and Fedorov and Shamari , but the compound was not where: β – the half-width of the refl ex (hkl) [rad], characterized by them. D – mean crystallite size in the direction perpendicular hkl to the plane (hkl) [Å], λ – wavelength of the X-ray radiation used, λ = 1.5406 [Å], EXPERIMENTAL k – Scherrer’s constant equal to k = 0.94, The following materials were used for the research: o θ – refl ection angle, related to the refl ection (hkl) [ ]. Li CO , a.p. (POCh, Poland), LiOH H O (Loba Che- 2 3 2 mie, Austria), Al O pure, sintered, denoted as Al O -sl 2 3 2 3 RESULTS AND DISCUSSION (POCh, Poland), boehmite-γ-AlOOH (POCH, Poland) and Al(NO ) 9H O a.p. (POCH. Poland). α-Al O was Transition modifi cations of alumina such as γ-, η-, 3 3 2 2 3 obtained by sintering Al O -sl at 1200 C for 4 hours. δ- and θ- Al O obtained in the temperature range 2 3 2 3 Table 1. Basic crystallographic data of α-LiAlO , β-LiAlO , γ-LiAlO and δ-LiAlO phases, where CS-crystal system: O – orthor- 2 2 2 2 hombic, T – tetragonal, H – hexagonal HP(GPa)-modifi cation obtain under high pressure equal to (GPa), SG (no.) – space group and its number; D – distorted structure, TW – this work 32 Pol. J. Chem. Tech., Vol. 23, No. 3, 2021 400–1000 C have a defective spinel structure based on by a very large number of crystallization water molecules 60, 61 a cubic close packed lattice of oxide ions . For this contained in the crystal lattice of aluminum nitrate(V) reason, the powder diffraction patterns of individual nanohydrate, which, released during intense grinding, modifi cations reported in the literature are similar to enables the aluminum nitrate(V) hydrolysis reaction lead- each other (similar d values). It is very diffi cult to ing to strong acidifi cation of the reaction medium and hkl clearly identify these transition alumina. In this work, initiates the decomposition of Li CO . The mechanism 2 3 when writing about this type of phases, we will use the of this process is currently being researched and the common symbol Al O -sl (spinel like). results will be presented in the next paper. The paste 2 3 In the fi rst stage of investigations synthesis of LiAlO obtained after the evolution of CO bubbles had ceased 2 2 was carried out using Li CO and α-Al O , Al O -sl and was then heated in a furnace under an air atmosphere 2 3 2 3 2 3 boehmite as aluminum precursors. Figures 1A and 1B in the temperature range of 400–600 C. Figure 2 shows show fragments of powder diffractograms of the reaction the diffractograms recorded after the successive stages mixtures prepared with the use of Al O -sl and Li CO of heating the obtained paste. 2 3 2 3 (Fig. 1A) or of α-Al O and Li CO (Fig. 1B) with the 2 3 2 3 compositions corresponding to the LiAlO phase, and samples recorded after successive heating stages in the temperature range of 450–1000 C. Figure 2. Powder diffraction patterns recorded during the synthesis of α-LiAlO with a new method using Figure 1. Fragments of the powder diffractograms of the reaction Li CO and Al(NO ) 9H O after the heating steps 2 3 3 3 2 mixture prepared with the use of Al O -sl and Li CO 2 3 2 3 at the following temperatures: a – 400 C x 30 min, (A) and with the use of α-Al O and Li CO (B) with o o 2 3 2 3 b – 400 C x d and c – 600 C x 30 min. * – means the composition corresponding to the LiAlO phase LiNO , ■ – means α-LiAlO 3 2 and samples recorded after successive heating stages in the temperature range of 450–1000 C Single-phase sample containing α-LiAlO was obtained after 30 minutes of heating at 600 C, while the synthesis During the heating stage at 450 C, almost all boehm- with Al O -sl and Li CO required heating the reactants 2 3 2 3 ite used in the synthesis decomposed to form Al O -sl, o o 2 3 at 700 C. Lithium nitrate(V) melts at 255 C, and boils and the further synthesis process was carried out in o and decomposes at 600 C. The presence of LiNO this sample with the use of in situ formed precursor. refl ections (PDF 04-010-5519) on the diffractogram of A single-phase sample containing α-LiAlO was obtained o the reaction mixture after the heating step at 400 C using boehmite and Al O -sl after the heating stage at 2 3 for 30 minutes shows that even molten LiNO slowly the temperature of 700 C. In both cases, the α-LiAlO reacts with the components of the reaction mixture. modifi cation appeared in reaction mixtures after a heat- The α-LiALO obtained at the temperature of 600 C ing stage at 500 C. Pure α-LiAlO obtained after sintering 2 x 30 min was characterized by strongly broadened dif- o o at 700 C was stable up to the temperature of 900 C, fraction refl ections, and the average size of crystallites at which the slow phase change leading to γ-LiAlO in this preparation determined by the Scherrer method began. However, a single-phase sample of γ-LiAlO was 2 was equal to 75Å. This value is consistent with the re- obtained only after the heating stage at 1000 °C. The sults of the research presented in , where the effect of reaction of LiAlO synthesis with the use of corundum 2 calcination time of the α-LiAlO sample at 600 C on was much slower. During it, the α-LiAlO modifi cation 2 the size of crystallites was analyzed. The reason for the appeared in the reaction mixture after a heating stage at signifi cant broadening of diffraction refl ections is, inter 550 C, but we failed to obtain a single-phase sample of alia, a high concentration of defects in the crystal lattice α-LiAlO . On the other hand small amounts of γ-LiAlO 2 2 of α-LiAlO obtained at low temperatures . It should were detected after the heating stage at 650 C while be mentioned, however, that regardless of the type of the pure γ-LiAlO was obtained after the heating stage metal precursors used in the synthesis of α-LiAlO , the at 950 C (Fig. 1A and 1B). refl exes of this phase were considerable broadened. In the frames of this work new method of LiAlO The crystallite size determined by the Scherrer method synthesis was developed using a mixture of aluminum during the synthesis of α-LiAlO with the use of Li CO 2 2 3 nitrate(V) and lithium carbonate as reactants. Grind- and boehmite increased gradually with the increase of . o ing of the Li CO and Al(NO ) 9H O solids initiates temperature from 101 Å (600 C x 24 h) through 389 Å 2 3 3 3 2 o o the reaction between them, as evidenced by CO gas (700 C x 24 h) to 406 Å (850 C x 24 h). bubbles intensively emitted during the grinding of the The literature review showed that the Li AlO phase 3 3 reagents in the mortar. The reaction is probably favored obtained by La Ginestra et al. is relatively poorly Pol. J. Chem. Tech., Vol. 23, No. 3, 2021 33 studied. Taking into account the comments of the au- contained a mixture of α- and β-LiAO , and the intensity thors of the work , an attempt was made to obtain the of refl ections characteristic of α-LiAO increased. The Li AlO phase by heating a mixture of LiOH H O and sample after the heating step at 700 C for 24 h con- 3 3 2 Al O -sl with a composition corresponding to the Li AlO tained γ-LiAlO as the main component, accompanied 2 3 3 3 2 phase in the temperature range of 400–500 C. The dif- by lower amounts of α- and β-LiAlO . fractograms recorded after the fi rst and second heating steps at 400 C for 72 h resembled that of the Li AlO 3 3 phase presented by Ginestera. However, X-ray phase analysis showed that the samples obtained at 400 C were not single-phase and contained a mixture of LiOH (PDF 00-032-0564), Li CO and β-LiAlO (PDF 00-033- 2 3 2 0785) (Fig. 3). Figure 4. Fragments of the powder diffraction patterns recor- ded after successive stages of heating the mixture of LiOH H O and Al O -sl with the composition 2 2 3 corresponding to the formula LiAlO : a – 1st stage o o 500 C x 72 h, b – 2nd stage 650 C x 72 h and c – 3rd stage-700 C x 72 h, where * – α-LiAlO , ■ – β-LiAlO , ♦ – γ-LiAlO and ● – Li CO 2 2 2 3 The conducted research indicates that the use of LiOH Figure 3. Fragments of the powder diffraction patterns recor- H O as a lithium precursor promotes the formation of ded after successive stages of heating the mixture β-LiAlO . However, while striving to eliminate lithium of LiOH H O and Al O -sl with the composition 2 2 3 carbonate from the reaction mixture by increasing the corresponding to the formula Li AlO : a – 1st 3 3 o o reaction temperature, the content of the α-LiAlO is stage 400 C x 72 h, b – 2nd stage 400 C x 72 h 2 simultaneously increased, and above 650 C β-LiAlO and c – 3rd stage-500 C x 72 h, where * – LiOH, ● – β-LiAlO and ♦ – Li CO undergoes a phase transition to γ-LiAlO . Currently, 2 2 3 2 research is conducted to obtain a single-phase β-LiAlO However, individual reflections from the Li AlO 3 3 sample and the results will be published soon. diffractogram presented by Ginestera were shifted by The powder diffractograms of the β-LiAlO , γ-LiAlO 2 2 0.01–0.20 degrees towards higher 2Theta angles in re- and α-LiAlO phases were indexed using the Refi nement lation to the position on our diffractograms and data program. The calculated values of the unit cell param- contained in PDF cards of LiOH, Li CO and β-LiAlO . 2 3 2 eters are shown in Table 1. In the case of β-LiAO , the Therefore, the conducted research shows that the phase results of the powder diffractogram pattern indexing are with the formula Li AlO is not formed. According to p resented in Table 2. 3 3 the literature data, LiOH identifi ed in reaction mixtures may be formed as a result of the reaction of Li O with Table 2. The result of the indexing of X-ray powder diffraction water contained in the air. LiOH is also formed as pattern of β-LiAlO obtained in this work a result of dehydration of LiOH H O in the temperature range 90–200 C and then in the temperature range o 49 420–550 C it decomposes with the release of Li O . The presence of Li CO in the obtained samples can also 2 3 be explained because both LiOH H O and LiOH have the ability to bind large amounts of CO from the air to form Li CO . After another heating step at 500 °C for 2 3 72 h, the content of β-LiAlO in the sample increased signifi cantly. This fact prompted us to try to synthesize β-LiAlO using a stoichiometric mixture of LiOH H O 2 2 and Al O -sl. Figure 4 shows the diffractograms of the 2 3 sample with the composition LiAlO after subsequent stages of heating. The analysis of the XRD test results showed that the reaction mixture after the fi rst stage of heating at 500 C for 72 h contained β-LiAlO as the main component, accompanied by Li CO and α-LiAlO 2 3 2 in much smaller amounts. After the second stage of heating at 650 C for 24 hours, the obtained product 34 Pol. J. Chem. Tech., Vol. 23, No. 3, 2021 To know better properties of obtained phases IR spec- LITERATURE CITED tra of γ-LiAlO , β-LiAlO and α-LiAlO were recorded. 2 2 2 1. Rebouças, L.B., Souza, M.T., Raupp-Pereira1, F., & Analysis of the number and positions of absorption bands Novaes de Oliveira, A.P. (2019). Characterization of Li O- recorded in their IR spectra has shown good agreement -Al O -SiO glass-ceramics produced from a Brazilian spodu- 2 3 2 32, 47, 50–52 with literature data . mene concentrate. Cerâmica 65, 366–377. DOI: 10.1590/0366- 2. Ahmadi, Moghadam, H. & Hossein, Paydar, M. (2016). The Effect of Nano CuO as Sintering Aid on Phase Formation, Microstructure and Properties of Li O-Stabilized ″-Alumina Ceramics. J. Ceram. Sci. Tech., 07(04), 441–446. DOI: 10.4416/ JCST2016-00075. 3. Shackelford, J.F. & Doremus, R.H. (2008). Ceramic and glass materials. Structure, properties and processing. Springer Science+Business Media LLC New York. ISBN 978-0-387- 73361-6. 4. Dhabekar, B., Raja, E.A., Gundu Rao, T.K., Kher, R.K. & Bhat, B.C. (2009). Thermoluminescence, optically stimulated luminescence and ESR studies on LiAl O :Tb. Indian. J. Pure 5 8 Ap. Phy., 47, 426–428. 5. Mandowska, E., Mandowski, A., Bilski, P., Marczewska, B., Twardak, A. & Gieszczyk, W. (2015). Lithium aluminate – a new detector for dosimetry. Prz. Elektrotech. 91(9), 117–120 (in Polish). 6. Gao, J., Shi, S., Xiao, R. & Li, H. (2016). Synthesis and ionic transport mechanisms of α-LiAlO , Solid State Ionics, Figure 5. IR spectra of: a) γ-LiAlO , b) β-LiAlO , c) α-LiAlO 2 2 2 286, 122–134. DOI: 10.1016/j.ssi.2015.12.028. 7. Özkan, G. & Incirkuş Ergençoglu, V. (2016). Synthesis Figure 5 shows the IR spectra of γ-LiAlO (curve a), and characterization of solid electrolyte structure mate- β-LiAlO (curve b) and α-LiAlO (curve c). The litera- 2 2 rial (LiAlO ) using different kinds of lithium and aluminum ture survey has shown that crystal lattices of γ-LiAlO 2 compounds for molten carbonate fuel cells. Indian J. Chem. and β-LiAlO are built up of LiO and AlO tertahedra, Technol. 23, 227–231. 2 4 4 32, 47, 50–52 8. Kim, J.E., Patil, K.Y., Han, J., Yoon, S.P., Nam, S.W., when α-LiAlO of LiO and AlO octahedra . 2 6 6 Lim, T.H., Hong, S.A., Kim, H. & Lim, H.Ch. (2009). Using The presence of LiO and AlO tetrahedra in crystal lat- 4 4 aluminum and Li CO particles to reinforce the α-LiAlO 2 3 2 tices of γ-LiAlO (Fig. 5, curve a) and β-LiAlO (Fig. 5, 2 2 matrix for molten carbonate fuel cells. Internat. J. Hydrogen curve b) with Li-O and Al-O bonds shorter than in the Energy 34(22), 9227–9232. DOI: 10.1016/j.ijhydene.2009.08.069. case of LiO and AlO octahedra is responsible for the 9. Ducan, Y. (2021). Theoretical Investigation of the 6 6 CO Capture Properties of γ-LiAlO and α-Li AlO . Micro 2 2 5 4 shift of absorption bands in their spectra towards higher Nanosyst. 13, 32–41. DOI: 10.2174/187640291166619091318 wavenumbers in comparison with the position of IR bands in the spectrum of α-LiAlO . Moreover, good agreement 10. Ávalos-Rendón, T., Casa-Madrid, J. & Pfeiffer, H. (2009). of the number and positions of absorption bands in IR Thermochemical Capture of Carbon Dioxide on Lithium Alu- minates (LiAlO and Li AlO ): A New Option for the CO spectrum of β-LiAlO obtained in our laboratory with 2 5 4 2 Absorption. J. Phys. Chem. A, 113, 6919–6923. DOI: 10.1021/ data in paper corroborates that polymorph of LiAlO jp902501v. obtained by Chang crystallizes in an orthorhombic system. 11. Raja, M., Sanjeev, G., Kumar, T.P. & Stephan, A.M. (2015). Lithium aluminate-based ceramic membranes as separa- tors for lithium-ion batteries. Ceram. Int. 41, 3045–50. DOI: CONCLUSIONS 10.1016/j.ceramint.2014.10.142. Using applied procedures of syntheses, three phases 12. Fouad, O.A., Farghaly, F.I. & Bahgat, M. (2007). A novel have been obtained: α-LiAlO , β-LiAlO γ-LiAlO . approach for synthesis of nanocrystalline γ-LiAlO from spent 2 2, 2 2 lithium-ion batteries. J. Anal. Appl. Pyrolysis. 78, 65–69. DOI: A new method of LiAlO synthesis was developed 10.1016/j.jaap.2006.04.002. consisting in grinding in mortar mixture of lithium car- 13. Pollard, V.A., Young, A., McLellan, R., Kennedy, A.R., bonate and aluminum nitrate(V) nonahydrate until the Tuttle, T., Robert, E. & Mulvey, R.E. (2019). Lithium-Alu- release of CO bubbles ceases and subsequent heating of minate-Catalyzed Hydrophosphination Applications. Angew. Chem. Int. Ed. 58, 1229–12296. DOI: 10.1002/anie.201906807. obtained paste in the temperature range of 400–600 C. 14. Indris, S. & Heitjans, P. (2006). Local electronic structure As a result of the reaction of LiOH H O with Al O - 2 2 3 in a LiAlO single crystal studied with Li NMR spectroscopy sl, β-LiAlO was obtained, contaminated with a small and comparison with quantum chemical calculations. Phys. Rev. amount of α-LiAO . 2 B 74, 245120-1-5. DOI: 10.1103/PhysRevB.74.245120. It has been shown that the powder diffractogram of 15. Duan, Y., Sorescu, D.C., Jiang, W. & Senor, D.J. (2020) Theoretical study of the electronic, thermodynamic, and the Li AO phase is a set of diffraction refl ections that 3 3 thermo-conductive properties of γ-LiAlO with Li isotope can be attributed to the mixture of LiOH, Li CO and 2 3 substitutions fortritium production. J. Nucl. Mater. 530, 151963. β-LiAlO . DOI: 10.1016/j.nucmat.2019.151963. The results of XRD and IR investigations showed that 16. Rasneur, B. (1985). Tritium breeding material γ-LiAlO . β-LiAlO crystallizes in an orthorhombic system. Fusion Technol. 8, 1909–1914. DOI: 10.13182/FST85-A40040. 2 Pol. J. Chem. Tech., Vol. 23, No. 3, 2021 35 17. Liu, Y.Y., Billone, M.C., Fischer, A.K., Tam, S.W., Clem- Zeitschrift für Kristallographie – Crystalline Materials. 231(3), mer, R.G. & Hollenberg, G.W. (1985). Solid tritium breeder 189–193. DOI: 10.14279/depositonce-5480. materials Li O and LiAlO - a data-base review. Fusion Sci. 39. Ha, N.T.T., Van Giap, T. & Thanh, N.T. (2020). Synthesis 2 2 Technol. 8, 1970–1984. DOI: 10.13182/FST85-A24573. of lithium aluminate for application in radiation dosimetry. 18. Morley, N.B., Abdou, M.A., Anderson, M., Calderoni, Mater. Lett. 267, 127506. DOI: 10.1016/j.matlet.2020.127506. P., Kurtz, R.J., Nygren, R., Raffray, R., Sawan, M., Sharpe, 40. Jimenez-Becerril, J. & Garcia-Sosa, I. (2011). Synthesis P., Smolentsev, S., Willms, S. & Ying, A.Y. (2006). Over- of lithium aluminate by thermal decomposition of a lithium view of fusion nuclear technology in the US. Fusion Eng. dawsonite-type precursor. J. Ceram. Process. Res. 12, 52–56. Des. 81, 33–43. DOI: 10.1016/j.fusengdes.2005.06.359. 41. Heo, S.J., Batra, R., Ramprasad, R. & Singh, P. (2018). 19. Strickler, D.W. & Roy, R. (1961). Studies in the System Crystal morphology and phase transformation of LiAlO : Li O–Al O –Fe O –H O. J. Am. Ceram. Soc. 44, 5, 225–230. combined experimental and fi rst-principles Studies. J. Phys. 2 2 3 2 3 2 DOI: 10.1111/j.1151-2916.1961.tb15365.x. Chem. C 222, 28797–28804. DOI: 10.1021/acs.jpcc.8b09716. 20. Lejus, A.M. & R. Collongues, R. (1962). Sur la structure 42. Patil, K.Y., Yoon, S.P., Han, J., Lim, T.H., Nam, S.W. & les propriétés des aluminates de lithium. Chimie Minérale Oh, I.H. (2011). The effect of lithium addition on aluminum- 2005–2007. reinforced α-LiAlO matrices for molten carbonate fuel 21. Kriens, M., Adiwidjaja, G., Guse, W., Klaska, K.H., Lathe, cells. Int. J. Hydrog. Energy, 36, 6237–6247. DOI: 10.1016/j. C. & Saalfeld, H. (1996). The crystal structures of LiAl O and 5 8 ijhydene.2011.01.161. Li Al O . N. Jb. Miner. Mh. 8, 344–350. 2 4 7 43. Park, J.S., Meng, X., Elam, J.W., Hao, S., Wolverton, 22. Hatch, R.A. (1943). Phase equilibrium in the system: Ch., Kim, Ch. & Cabana, J. (2014). Ultrathin Lithium-Ion Li O–Al O –SiO . Am. Mineral. 28, 471–496. DOI: 10.1111/ 2 2 3 2 Conducting Coatings for Increased Interfacial Stability in High j.1151-2916.1985.tb15280.x. Voltage Lithium-Ion Batteries. Chem. Mater. 26, 3128–3134. 23. Cook, L.P. & Plante, E.R. (1992). Phase Diagram of the DOI: 10.1021/cm500512n. System Li O–Al O . Ceram. Trans. 27, 193–222. 2 2 3 44. Cheng, F., Xin, Y., Huang, Y., Chen, J., Zhou, H. & 24. Byker, H.J., Eliezer, I., Eliezer, N. & Howald, R.A. (1979). Zhang, X. (2013). Enhanced electrochemical performances Calculation of a Phase Diagram for LiO –AlO System. J. 0.5 1.5 of 5 V spinel LiMn Ni O cathode materials by coating 1.58 0.42 4 Phys. Chem. 83, 18, 2349–2355. DOI: 10.1021/j100481a009. with LiAlO . J. Power Sources. 239, 181–188. DOI: 10.1016/j. 25. Konar, B., Van Ende, M.A. & Junh, I.H. (2018). Critical jpowsour.2013.03.143. Evaluation and Thermodynamic Optimization of the Li O- 45. Cao, H., Xia, B., Zhang, Y., Xu, N. (2005). LiAlO 2- Al O and Li O–MgO–Al O Systems. Metall. Mat. Trans. B 2 3 2 2 3 -coated LiCoO as cathode material for lithium ion batteries. 49, 2917–2944. DOI: 10.1007/s11663-018-1349-x. Solid State Ionics. 176, 911–914. DOI: 10.1016/j.ssi.2004.12.001. 26. Marezio, M. & Remeika, J.P. (1966). High-pressure 46. Danek, V., Tarniowy, M. & Suski, L. (2004) Kinet- synthesis and crystal srtucture of α-LiAlO . J. Chem. Phys. 44, ics of the α → γ phase transformation in LiAlO under 3143-4. DOI: 10.1063/1.1727203. various atmospheres within the 1073–1173 K temperatures 27. Lehmann, H.A. & Hesselbrarth, H.Z. (1961). Uber range. J. Mater. Sci. 39, 2429–2435. DOI: 10.1023/B:JM eine neue Modifi kation des LiAlO . Anorg. Allg. Chem. 313, SC.0000020006.46296.04. 117–120. DOI: 10.1002/zaac.19613130110. 47. Lejus, A.M. (1964). Sur la formation a haute tempera- 28. Dronskowski, R. (1993). Reactivity and acidity of Li in ture de spinelles non stechiométriques et de phases derivées LiAlO phases. Inorg. Chem. 32, 1–9. DOI: 10.1021/ic00053a001. dans plusieurs systémes d’oxydes a base d’alumina et dans le 29. Poepplmeler, K.R., Chiang, C.K. & Kipp, D.O. (1988). systéme alumina-nitrure d’aluminum. Rev. Hautes Tempér. et Synthesis of High-Surface-Area α-LiAlO . Inorg. Chem. 27, Réfract., 1, 53–95. 4523–4524. DOI: 10.1021/ic00298a002. 48. Hummel, F.A., Sastry, B.S.R. & Wotring, D. (1958). 30. Thery, J. (1961). Structure and properties of alkaline Studies in Lithium Oxide Systems: II, Li O∙Al O –Al O . J. 2 2 3 2 3 aluminates. Bull. Soc. Chim. Fr. 973–5. Am. Ceram. Soc. 41, 3, 88–92. DOI: 10.1111/j.1151-916.1958. 31. Marezio, M. (1965). The Crystal Structure of LiGaO . tb15448.x. Acta Cryst. 18, 481–484. DOI: 10.1107/S0365110X65001068. 49. Isupov, V.P., Bulina, N.V. & Borodulina, I.A. (2017). 32. Marezio, M. (1965). The Crystal Structure and Anoma- Effect of Water Vapor Pressure on the Phase Composition of lous Dispersion of γ-LiAlO . Acta Cryst. 19, 396–400. DOI: Lithium Monoaluminates Formed in the Interaction of Alu- 10.1107/S0365110X65003511. minum Hydroxide and Lithium Carbonate. Zhurnal Prikladnoi 33. Li, X., Kobayashi, T., Zhang, F., Kimoto, K. & Sekine, Khimii, 90, 986−991. DOI: 10.1134/S1070427217080043. T. (2004). A new high-pressure phase of LiAlO . J. Solid State 50. Tarte, P. (1967). Infra-red spectra of inorganic aluminates Chem. 177, 1939–1943. DOI: 10.1016/j.jssc.2003.12.014. and characteristic vibrational frequencies of AlO tetrahedra 34. Lei, L., He, D., Zou, Y. & Zhang, W. (2008). Phase trans- 4 and AlO octahedra. Spectrochim. Acta 23A, 2127–2143. DOI: itions of LiAlO at high pressure and high temperature. J. Solid 6 10.1016/0584-8539(67)80100-4. State Chem. 181, 1810–1815. DOI: 10.1016/j.jssc.2008.04.006. 51. Braun, P.A. (1952). Superstructure in Spinels. Nature 35. Chang, C.H. & Margrave, J.L. (1968). Highpressure- 170, 1123. DOI: 10.1038/1701123a0. -high temperature synthesis. III. Direct synthesis of new high- 52. Datta, R.K. & Roy, R. (1963). Phase Transitions in -pressure forms of LiAlO and LiGaO and polymorphism in 2 2 LiAl O . J. Am. Ceram. Soc. 46, 8, 388–390. DOI: 10.1111/j.1151- LiMO compounds (M=B, Al, Ga). J. Amer. Chem. Soc. 90, 5 8 2916.1963.tb11757.x. 2020–2022. DOI: 10.1021/ja01010a018. 53. La Ginestra, A., Lo Jacono, M. & Porta, P. (1972). The 36. Debray, L. & Hardy, A.C.R. (1960). Contribution a Vetu- preparation, characterization, and thermal behaviour of some de structurale des aluminates de lithium. Hebd. Seances Acad. lithium aluminum oxides: Li AlO and Li AlO . J. Thermal Sci. 251, 725–726. 3 3 5 4 Anal. 4, 5–17. DOI: 10.1007/bf02100945. 37. Waltereit, P., Brandt, O., Trampert, A., Grahn, H.T., Men- 54. Kroger, C. & Fingas, E. (1935). Über die Systeme niger, J., Ramsteiner, M.,M. Reiche, M. & Ploog, K.H. (2000). Alkalioxyd–CaO–Al O –SiO –CO . IV. Die CO -Drucke des Nitride semiconductors free of electrostatic fi elds for effi cient 2 3 2 2 2 kieselsäurereicheren Teils des Systems Li O–SiO –CO und white light-emitting diodes. Nature 406, 865–868. DOI: 2 2 2 10.1038/35022529. der Einwirkung von Al O auf Li CO . Z anorg. Allg. Chem. 2 3 2 3 38. Wiedemann, D., Indris, S., Meyen, M. & Pedersen, B. 224, 289–304. DOI: 10.1002/zaac.19352240309. (2016) Single-crystal neutron diffraction on γ-LiAlO : Structure 55. Fedorov, T.F. & Shamari, F.I. (1960). Prim. Vak. V. Met., determination and estimation of lithium diffusion pathway. Akad. Nauk SSSR, Inst. Met. A.A. Baikova, 137–142. 36 Pol. J. Chem. Tech., Vol. 23, No. 3, 2021 56. Walczak, J., Kurzawa, M. & Tabero, P. (1987). V Mo O Am. Ceram. Soc. 81, 1995–2012. DOI: 10.1111/j.1151-2916.1998. 9 6 40 and phase equilibria in the system V Mo O –Fe O . Ther- 9 6 40 2 3 tb02581.x. mochim. Acta 118, 1–7. DOI: 10.1016/0040-6031(87)80065-5. 61. Krokodis, X., Raybaud, P., Gobichon, A.E., Rebours, 57. Tabero, P. (2010). Formation and properties of the new B., Euzen, P. & Toulhoat, H. (2001). Theoretical Study of the Al V W O and Fe Al V W O phases with the M-Nb O 8 10 16 85 8-x x 10 16 85 2 5 Dehydration Process of Boehmite to γ-Alumina. J. Phys. Chem. structure. J. Therm. Anal. Calorim. 101, 560–566. DOI: 10.1007/ B 105, 5121–5130. DOI: 10.1021/jp0038310. s10973-010-0848-z. 62. Kim, J., Kang, H., Hwang, K. & Yoon, S. (2019). Thermal 58. Tabero, P., Frackowiak, A., Filipek, E., Dąbrowska, G., Ho- monnay, Z. & Szilágyi, P.Á. (2018). Synthesis, thermal stability Decomposition Study on Li O for Li NiO Synthesis as a Sac- 2 2 2 2 and unknown properties of Fe Al VO solid solution. Ceram. 1-x x 4 rifi cing Positive Additive of Lithium-Ion Batteries. Molecules Int. 44, 17759–17766. DOI: 10.1016/j.ceramint.2018.06.243. 24, 4624–4632. DOI: 10.3390/molecules24244624. 59. Filipek, E., Dabrowska, G. & Piz, M. (2010). Synthesis and 63. Tovar, T.M. & Le, Van, M.D. (2017). Supported lithium characterization of new compound in the V-Fe-Sb-O system. J. hydroxide for carbon dioxide adsorption in water-saturated Alloys Compd. 490, 93–97. DOI: 10.1016/j.jallcom.2009.10.123. environments. Adsorption 23, 51–56. DOI: 10.1007/s10450- 60. Levin, I. & Brandon, D. (1998). Metastable Alumina Polymorphs: Crystal Structures and Transition Sequences. J. 016-9817-6.

Journal

Polish Journal of Chemical Technology – de Gruyter

Published: Sep 1, 2021

Keywords: Li 2 O–Al 2 O 3 system; LiAlO 2; Li 3 AlO 3; XRD; IR

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