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Aging Behavior of Al- and Ga- Stabilized Li7la3zr2o12 Garnet-Type, Solid-State Electrolyte Based on Powder and Single Crystal X-Ray Diffraction

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Aging Behavior of Al- and Ga- Stabilized Li7la3zr2o12 Garnet-Type, Solid-State Electrolyte Based on Powder and Single Crystal X-Ray Diffraction crystals Article Aging Behavior of Al- and Ga- Stabilized Li7La3Zr2O12 Garnet-Type, Solid-State Electrolyte Based on Powder and Single Crystal X-ray Diffraction Günther J. Redhammer 1,* , Gerold Tippelt 1, Andreas Portenkirchner 1 and Daniel Rettenwander 2,3 1 Department of Chemistry & Physics of Materials, University of Salzburg, Jakob-Haringerstr. 2A, 5020 Salzburg, Austria; [email protected] (G.T.); [email protected] (A.P.) 2 Department of Material Science and Engineering, NTNU Norwegian University of Science and Technology, 7491 Trondheim, Norway; [email protected] 3 International Christian Doppler Laboratory for Solid-State Batteries, NTNU Norwegian University of Science and Technology, 7491 Trondheim, Norway * Correspondence: [email protected] Abstract: Li7La3Zr2O12 garnet (LLZO) belongs to the most promising solid electrolytes for the devel- opment of solid-state Li batteries. The stability of LLZO upon exposure to air is still a matter of discus- sion. Therefore, we performed a comprehensive study on the aging behavior of Al-stabilized LLZO (space group (SG) Ia3d) and Ga-stabilized LLZO (SG I43d) involving 98 powder and 51 single-crystal X-ray diffraction measurements. A Li+/H+ exchange starts immediately on exposure to air, whereby the exchange is more pronounced in samples with smaller particle/single-crystal diameter. A slight displacement of Li from interstitial Li2 (96h) toward the regular tetrahedral Li1 (24d) sites occurs in Al-stabilized LLZO. In addition, site occupancy at the 96h site decreases as Li+ is exchanged Citation: Redhammer, G.J.; Tippelt, by H+. More extensive hydration during a mild hydrothermal treatment of samples at 90 ◦C in- G.; Portenkirchner, A.; Rettenwander, D. Aging Behavior of Al- and Ga- duces a structural phase transition in Al-LLZO to SG I43d with a splitting of the 24d site into two 3+ + Stabilized Li7La3Zr2O12 Garnet-Type, independent tetrahedral sites (i.e., 12a and 12b), whereby Al solely occupies the 12a site. Li is Solid-State Electrolyte Based on preferably removed from the interstitial 48e site (equivalent to 96h). Analogous effects are observed Powder and Single Crystal X-ray in Ga-stabilized LLZO, which has SG I43d in the pristine state. Diffraction. Crystals 2021, 11, 721. https://doi.org/10.3390/cryst Keywords: LLZO solid-state electrolyte; prolonged aging; Li+-H+ cation exchange; structural phase 11070721 transition; single-crystal X-ray diffraction Academic Editor: Volodymyr Bon Received: 31 May 2021 1. Introduction Accepted: 18 June 2021 Published: 23 June 2021 Li7La3Zr2O12 garnet (LLZO) belongs to the most promising group of solid electrolytes in the development of solid-state Li batteries (SSLBs), due to their superior high Li-ion −1 Publisher’s Note: MDPI stays neutral conductivity of up to approximately 1 mS cm at room temperature combined with its with regard to jurisdictional claims in nonflammability, high chemical, and electrochemical stability, and its mechanical robust- published maps and institutional affil- ness [1,2]. iations. The high Li-ion conductivity is associated with its cubic Ia3d structure, which can be stabilized by substituting Li at the tetrahedral side with aliovalent cations such as Al3+ [3] and introducing Li-disorder. Endmember LLZO itself is tetragonal, has a space group I41/acd, and has distinctly lower Li-ion conductivity [4]. Hence, a large body of work has focused on stabilizing the cubic modification by replacing Li+ with e.g., Al3+, Ga3+, Fe3+ Copyright: © 2021 by the authors. Licensee MDPI, Basel, Switzerland. ([5–10] and references therein). This article is an open access article Although LLZO was originally assumed to be chemically stable during atmospheric distributed under the terms and exposure [11], it is now well established that it is sensitive to moisture, and sponta- + + conditions of the Creative Commons neous Li /H exchange takes place while the garnet framework retains its structural Attribution (CC BY) license (https:// stability [12–14]. Interestingly, its Li-ion conductivity decreases when exposed to humidity creativecommons.org/licenses/by/ and air [15]. Overall, the structural alterations and associated changes in properties in 4.0/). Li-oxide garnets are strongly related to their composition. For example, Galven et al. [16] Crystals 2021, 11, 721. https://doi.org/10.3390/cryst11070721 https://www.mdpi.com/journal/crystals Crystals 2021, 11, x FOR PEER REVIEW 2 of 24 Crystals 2021, 11, 721 2 of 23 Overall, the structural alterations and associated changes in properties in Li-oxide garnets demonstratedare strongly that related instability to their of Licomposition.7La3Sn2O12 Forin aexample, humid atmosphere, Galven et al. leading [16] demonstrated to pro- tonatedthat garnets instability Li7− ofxH LixLa7La3Sn3Sn2O2O1212, isin associateda humid a withtmosphere, a change leading in space to groupprotonated symme- garnets try fromLi7−xH tetragonalxLa3Sn2O12 to, is cubic, associated while with for Li a5 −changexHxLa in3Nb space2O12 group, the symmetry symmetry changed from tetragonal from to tetragonalcubic, towhile a non-centrosymmetric for Li5−xHxLa3Nb2O12, the cubic symmetry space group changed (I2 1from3).For tetragonal tetragonal to a non LLZO,-centro- Larrazsymmetric et al. [17] cubicfound space a transformation group (퐼2 3). from For tetragonal tetragonal LLZO, to the cubicLarraz modification et al. [17] found at high a trans- ◦ 1 temperaturesformation (T fromc ~645 tetragonalC) only whento the itcubic is completely modification shielded at high from temperatures any humidity, (Tc and~645 that °C ) only ◦ the appearancewhen it is ofcompletely a lower temperature shielded from cubic any phase humidity, between and 100 that and the 200 appearanceC occurs inof thea lower presencetemperature of water cubic either ph inase the between immediate 100 environmentand 200 °C occurs or in in the the sample presence itself. of Thewater same either in workersthe alsoimmediate observed environment the formation or in of athe cubic sample form itself. of LLZO The duringsame workers prolonged also heating observed of the ◦ + + pureformation tetragonal of LLZO a cubic at aroundform of 350 LLZOC induring air and prolonged interpreted heating it to beof thepure result tetragonal of Li /H LLZO at exchangearound based 350 on°C thermalin air and analysis interpreted and Ramanit to be the spectroscopy result of Li [+17/H].+ exchange Later, Orera based et al. on [ 18thermal] + + furtheranalysis attributed and Raman this structural spectroscopy change [17] in pure. Later, tetragonal Orera et LLZOal. [18] to further Li /H attributedexchange this and struc- I d foundtural two change different in cubic pure phases. tetragonal Deep LLZO hydration to Li+ led/H+ toexchange a non-centrosymmetric and found two 4different3 phase cubic e wherephases. Li is mainly Deep hydration exchanged led at theto a generalnon-centrosymmetric 48 octahedral site퐼4̅3푑 and phase the twowhere distinct Li is mainly tetra- ex- hedral sites have very different occupancies. In this structure, the protons are described as changed at the general 48e octahedral site and the two distinct tetrahedral sites have very being located close to the O oxygen atom based on powder neutron diffraction. Annealing different occupancies.2 In this structure, the protons are described as being located close to above 300 ◦C resulted in a second, more ‘normal’ garnet structure, Ia3d, with lower Li the O2 oxygen atom based on powder neutron diffraction. Annealing above 300 °C re- contents at the general 96h position (with octahedral coordinated Li+). Table1 summarizes sulted in a second, more ‘normal’ garnet structure, 퐼푎3̅푑, with lower Li contents at the the crystallographic positions, their Wykoff numbers, and multiplicities within the two general 96h position (with octahedral coordinated Li+). Table 1 summarizes the crystallo- main garnet structure types. graphic positions, their Wykoff numbers, and multiplicities within the two main garnet structure types. Table 1. Comparison of crystallographic positions in garnets with typical Ia3d [19] and acentric I43d symmetry. Table 1. Comparison of crystallographic positions in garnets with typical 퐼푎3̅푑 [19] and acentric ̅ 퐼43푑 symmetrySpace. Group Symmetry ¯ Space Group Symmetry ¯ Coordination Ion in LLZO Ia3d I43d Coordination Ion in LLZO 푰풂ퟑ̅풅 푰ퟒ̅ퟑ풅 24c 24d 8 La3+ 24c 24d 8 La3+ 4+ 16a 16a 16c 16c 6 6 Zr Zr4+ 12a 12a 4 4 Li+,Li Al+,3+ Al, Ga3+, 3+Ga3+ 24d 24d + 12b 12b 4 4 Li Li+ 96h 96h 48e 48e 4 +4 +2 2 Li+Li+ 48e 48e O2−O2− 96h 96h − 48e 48e O2 O2− UhlenbruckUhlenbruck et al. et [20 al.] found[20] found that LLZOthat LLZO garnets garnets react react with with water water and carbonand carbon dioxide dioxide eveneven at low at concentrationslow concentrations of these of these reactants, reactants, e.g., e.g., when when LLZO LLZO is stored is stored in a glovein a glove box. box. TheyThey state state that athat fast-initial a fast-initial reaction reaction of LLZO of LLZO with with moisture moisture takes takes place, place, presumably presumably by by + ++ + Li /HLi /Hexchange, exchange, and and is accompanied is accompanied by the by formationthe formation of LiOH of LiOH and Liand2CO Li3.2CO An3. increase An increase in thein lattice the lattice parameters parameters is proposed is propo bysed Galven by Galven et al. et [21 al.] to [21] be to caused be caused by the by replacement the replacement of strongerof stronger Li–O Li bonds–O bonds by much by much weaker weaker O–H ... O–OH…O
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