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Structure of Lithium Peroxide † || ‡ ,‡ ‡ Maria K

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Structure of Lithium Peroxide † || ‡ ,‡ ‡ Maria K LETTER pubs.acs.org/JPCL Structure of Lithium Peroxide † || ‡ ,‡ ‡ Maria K. Y. Chan,† Eric L. Shirley, Naba§ K. Karan, Mahalingam Balasubramanian,* Yang Ren, Jeffrey P. Greeley, and Tim T. Fister*, † ‡ § Center for Nanoscale Materials, Advanced Photon Source, and Chemical Sciences and Engineering, Argonne National Laboratory, Argonne, Illinois 60439, United States Optical) Technology Division, National Institute of Standards and Technology, Gaithersburg, Maryland 20899, United States ABSTRACT: The reliable identification of lithium oxide species, especially lithium peroxide (Li2O2), is of vital importance to the study of Li-air batteries. ff Previous X-ray di raction studies of Li2O2 resulted in the proposal of two disparate structures by Feher and F€oppl. In this Letter, we assess these competing Li2O2 structures using a combination of the following X-ray and first-principles techniques: (i) high-energy X-ray diffraction (XRD), (ii) comparisons of the measured nonresonant inelastic X-ray scattering (NIXS) spectra with those computed from first principles using the Bethe-Salpeter equation (BSE), and (iii) comparison of thermochemistry data with the formation enthalpies obtained from density functional theory (DFT) calcula- tions using a hybrid functional. All three approaches result in the identification € ’ of Foppl s proposal as the more appropriate structure for Li2O2. The measured and computed spectra and data presented in this Letter are useful as bench- marks for future characterization of Li2O2. SECTION: Molecular Structure, Quantum Chemistry, General Theory or competition with the extremely high energy density of To distinguish between the two proposed Li2O2 structures, Ffossil fuels, electrochemical cells based on lithium-oxygen (or Cota et al.3 symmetrized both structures and used density “lithium-air”) reactions are often touted as the technological heir functional theory (DFT) calculations to determine their relative to lithium ion batteries. In Li-air cells, discharge reactions stabilities and structural changes after relaxations. They found € producing lithium oxide (Li2O), lithium peroxide (Li2O2), and the Foppl structure to be 0.53 eV per O2 lower in energy than the possibly lithium superoxide (LiO2) occur near the surface of the Feher structure, and they also determined that the latter structure cathode. These discharge products are difficult to characterize undergoes drastic structural relaxations in DFT, including the because the peroxide and superoxide phases are metastable under lengthening of OÀO bonds from 1.28 to 1.53 Å. Cota’s DFT- ambient conditions. Many traditional spectroscopies for lithium relaxed structure is also shown in Figure 1, showing the lengthen- and oxygen, such as X-ray photoelectron spectroscopy, X-ray ing of OÀO bonds. Cota’s work provided strong evidence of € ’ absorption, and electron energy loss, are hampered by the low Foppl s as the actual structure of Li2O2, and subsequent DFT core binding energies of lithium and oxygen and typically require studies4,5 used the F€oppl structure. We note, however, that the ex situ vacuum conditions. X-ray diffraction (XRD) may at times exchange-correlation functional used by Cota et al., the generalized be difficult because of the small scattering cross section of such gradient approximation (GGA) of Perdew, Burke, and Erzenhof low-Z compounds and limited crystallinity of discharge products (PBE),6 is known to have large errors in treating the oxygen 7 8 such as Li2O2,Li2O, and possibly LiO2. molecule and oxides. Therefore, direct experimental evidence In the 1950s, two disparate crystal structures were proposed and more accurate first-principles methods are needed to deter- 1,2 ff for Li2O2 from XRD studies. They have surprisingly di erent mine the structure more conclusively. lithium sublattices, as shown in Figure 1. Along the c-lattice direction, In this Letter, we seek to elucidate the structure of Li2O2 using Feher’s original structure consists of lithium and oxygen atoms a combination of X-ray and first-principles techniques. Using nominally sharing each plane, whereas F€oppl’s revised structure high-energy X-rays, we obtain the powder XRD pattern and positions the lithium sites between adjacent oxygen planes. compare the accuracy of the Feher and F€oppl structures using Whereas the two structures have similar nearest-neighbor LiÀO Rietveld refinement. Taking advantage of the coordination sensi- distances (1.91 Å in Feher’s vs 1.98 Å in F€oppl’s), the OÀO tivity of nonresonant inelastic X-ray scattering (NIXS), we also distances in the peroxide anions are drastically different (1.28 and measure the lithium and oxygen K-edges of Li2O2. These NIXS 1.55 Å, respectively). Moreover, whereas there is only one type of Li site in the Feher structure, the F€oppl structure contains Received: August 8, 2011 two inequivalent Li sites with different nearest-neighbor LiÀO Accepted: September 12, 2011 distances of 1.98 and 2.15 Å. Published: September 12, 2011 r 2011 American Chemical Society 2483 dx.doi.org/10.1021/jz201072b | J. Phys. Chem. Lett. 2011, 2, 2483–2486 The Journal of Physical Chemistry Letters LETTER spectra are compared with those calculated for the two proposed basis of the Rietveld refinement, the sample contained ∼12.9% (by structures using a Bethe-Salpeter (BSE) treatment, which accu- weight) impurity phases (mainly LiOH and Li2CO3). Figure 2 rately accounts for electronÀcore hole interactions. Finally, we summarizes the Rietveld refinement with the experimental data compare thermochemical data to accurate formation energies for these two structural models for Li2O2. The space-group (P63/ calculated from DFT using a hybrid functional. All three app- mmc in both structures) and Wyckoff sites for Li and O in the roaches result in the identification of the F€oppl structure as the symmetrized structures obtained from the original Feher and € 3 structure of Li2O2. Apart from ascertaining its structure, we Foppl structures as reported by Cota et al. were used as input for believe that the various measured and computed spectra and data the Rietveld refinements. The cell parameters a and c and variable α ’ α of Li2O2 presented here will be useful for future characterization internal parameters (Li) (Feher s structure) and (O) (both efforts in Li-air battery research. structures) are allowed to vary. Because the DFT-relaxed Feher ff α We used a commercial powder Li2O2 sample and took steps to structure di ers from the unrelaxed structure only in a, c, and , minimize exposure to air. XRD was performed at the Advanced the refinement procedure does not discriminate between the Photon Source (APS) using 114.82 keV X-rays (λ = 0.10798 Å). unrelaxed and relaxed Feher structures. The refined structural Rietveld refinement was performed on the powder XRD pattern parameters and the goodness-of-fit parameters are given in fi of Li2O2 using the two proposed structures for Li2O2.Onthe Table 1. Comparing the residuals and the goodness-of- t parameters from Figure 2 and Table 1 for these two structures, we see that the F€oppl structure is a much better fit than the Feher structure. The best fit for the Feher structure shows an OÀO bond length (1.25 Å) closer to that in the unrelaxed (1.28 Å) than in the DFT- relaxed (1.53 Å) structure of ref 3. The residuals are also particularly pronounced for the Feher structure compared with the F€oppl structure at larger 2θ (2θ >4°) values. We note that the typical range of 2θ (<80°) for typical Cu Kα and Fe Kα X-ray sources (λ = 1.54 and 1.936 Å, respectively) corresponds to 2θ values of up to approximately 5.16 and 4.11° in the current study. For 2θ < ° € 4.11 , the ratio of residuals (Rp) between the Feher and Foppl structures is reduced from a factor of 3.4 to a factor of 2.0. At very large 2θ values (2θ >6°), there are also multiple peaks in the measured Figure 1. Feher’s1 (left), DFT-relaxed Feher’s according to Cota3 spectra that are found in the refinement for the F€oppl structure but € ’ 2 (middle), and Foppl s (right) proposed crystal structures for Li2O2.Red notinthatfortheFeher structure. Therefore, whereas it may still be (larger) spheres represent oxygen atoms and blue (smaller) spheres possible to confirm the F€oppl structure by diffraction using conven- represent lithium atoms. Blue (dashed) horizontal lines indicate Li planes. tional lab X-rays, the use of high-energy synchrotron X-ray source is We can see that Li atoms are roughly in-plane with the O atoms in the Feher ff structure while Li planes cut through the OÀObondsintheFoppl€ structure. particularly e ective in discerning between these two structures. We note that XRD patterns become broadened in samples with reduced crystallinity, such as the case when Li2O2 is processed by ball-milling,9 or when it forms as a discharge product in Li-air batteries.10 Because NIXS is sensitive to short-range order often present in the complicated (i.e., high surface area) morphology in these situations, NIXS should provide a valuable foundation for in situ characterization of Li2O2 in operating batteries. The NIXS spectra of the Li2O2 pellet were measured from the lower energy resolution inelastic X-ray scattering (LERIX) instrument at the APS, simultaneously at momentum transfers À q of 0.6À8Å 1. The measured Li and O K-edges are shown in Figure 3, a and b, respectively. As seen in Figure 3a, the lithium K-edge spectrum evolves substantially with q. These changes arise when 1/q is comparable to the size of the Li 1s orbital, and the matrix element can no longer be approximated by dipole s f p transitions. In contrast, the O K-edge is limited to dipole transitions but is also Figure 2. Measured powder XRD pattern of Li2O2 (black, lower), and the Rietveld refinement according to the F€oppl (blue, middle) and Feher quite sensitive to changes in its lithium coordination.
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