# Electronic Supplementary Material (ESI) for Physical Chemistry Chemical Physics
# This journal is © The Owner Societies 2011
data_global
_journal_name_full Phys.Chem.Chem.Phys.(PCCP)
_journal_coden_Cambridge 1326
_journal_volume ?
_journal_page_first ?
_journal_year ?
_publ_contact_author_name
'Juergen Janek' # Name of author for correspondence
_publ_contact_author_address # Address of author for correspondence
;
Physikalisch-Chemisches Institut, Justus Liebig Universitat
Giessen, Heinrich-Buff-Ring 58,35392 Giessen, Germany
;
_publ_contact_author_email juergen.janek@phys.chemie.uni-giessen.de
_publ_contact_author_fax ?
_publ_contact_author_phone +49(0)641-9934501
_publ_contact_letter
;
Please consider this CIF for publication. I certify that this contibution is the
original work of those listed as authors; that it has not been published
before (in any language or medium) and is not being considered for publication
elsewhere; that all authors concur with and are aware of the submission; that
all workers involved in the study are listed as authors or given proper credit
in the acknowledgements; that I have obtained permission for and acknowledged
the source of any excerpts from other copyright works; and that to the best of
my knowledge the paper contains no statements which are libellous, unlawful or
in any way actionable. All coauthors have made significant scientific
contributions to the work reported, including the ideas and their execution,
and share responsibility and accountability for the results.
;
_publ_requested_coeditor_name ?
_publ_requested_category ? # Acta C: one of CI/CM/CO/FI/FM/FO
# Definition of non standard CIF items (Reliability indices used in FULLPROF)
loop_
_publ_manuscript_incl_extra_item
_publ_manuscript_incl_extra_info
_publ_manuscript_incl_extra_defn
# Name Explanation Standard?
# ------ ----------- ---------
'_pd_proc_ls_prof_cR_factor' 'Prof. R-factor CORRECTED for background' no
'_pd_proc_ls_prof_cwR_factor' 'wProf.R-factor CORRECTED for background' no
'_pd_proc_ls_prof_cwR_expected' 'wProf.Expected CORRECTED for background' no
'_pd_proc_ls_prof_chi2' 'Chi-square for all considered points' no
'_pd_proc_ls_prof_echi2' 'Chi-2 for points with Bragg contribution' no
#=============================================================================
# 3. TITLE AND AUTHOR LIST
_publ_section_title
;
Structure and dynamics of the fast lithium ion conductor "Li7La3Zr2O12"
;
_publ_section_title_footnote .
# The loop structure below should contain the names and addresses of all
# authors, in the required order of publication. Repeat as necessary.
loop_
_publ_author_name
_publ_author_address
_publ_author_footnote
H.Buschmann
;
Physikalisch-Chemisches Institut, Justus Liebig Universitat Giessen,
Heinrich-Buff-Ring 58, 35392 Giessen, Germany
;
;
?
;
J.Dolle
;
Physikalisch-Chemisches Institut, Justus Liebig Universitat Giessen,
Heinrich-Buff-Ring 58, 35392 Giessen, Germany
;
.
S.Berendts
;
Physikalisch-Chemisches Institut, Justus Liebig Universitat Giessen,
Heinrich-Buff-Ring 58, 35392 Giessen, Germany
;
.
A.Kuhn
;
Institut fur Physikalische Chemie und Elektrochemie, Leibniz Universitat
Hannover, Callinstrasse 3a, 30167 Hannover, Germany
;
.
P.Bottke
;
Institut fur Physikalische Chemie und Elektrochemie, Leibniz Universitat
Hannover, Callinstrasse 3a, 30167 Hannover, Germany
;
.
M.Wilkening
;
Institut fur Physikalische Chemie und Elektrochemie, Leibniz Universitat
Hannover, Callinstrasse 3a, 30167 Hannover, Germany
;
.
;
P.Heitjans
;
;
Institut fur Physikalische Chemie und Elektrochemie, Leibniz Universitat
Hannover, Callinstrasse 3a, 30167 Hannover, Germany
;
.
A.Senyshyn
;
Forschungsneutronenquelle Heinz Maier-Leibnitz (FRM II), Technische Universitat
Munchen, Lichtenbergstrasse 1, 85747 Garching b. Munchen, Germany
;
.
H.Ehrenberg
;
Institution
City
State
Postcode
UK
;
.
A.Lotnyk
;
Faculty of Engineering, Institute for Material Science, Synthesis and Real
Structure, Christian Albrechts Universitaet zu Kiel, Kaiserstr.2, D-24143 Kiel,
Germany
;
.
V.Duppel
;
Max Planck Institute for Solid State Research, Heisenbergstr. 1, D-70569
Stuttgart, Germany
;
.
L.Kienle
;
Faculty of Engineering, Institute for Material Science, Synthesis and Real
Structure, Christian Albrechts Universitat zu Kiel, Kaiserstr.2, D-24143 Kiel,
Germany
;
.
J.Janek
;
Physikalisch-ChemischesInstitut, Justus Liebig Universitat
Giessen,Heinrich-Buff-Ring 58,35392 Giessen, Germany
;
.
#=============================================================================
# 4. TEXT
_publ_section_synopsis .
_publ_section_abstract
;
The redetermined structure of Garnet-type Lithium Lanthanum Zirconium
Oxide,Li~7~La~3~Zr~2~O~12~, has cubic (Ia\=3d)
symmetry at 4 K. This is of interest with respect
to electrochemical properties.
The structure exhibits strong disorder of the Li-cations.
;
_publ_section_comment
;
(type here to add)
;
_publ_section_exptl_prep
# Details of the preparation of the sample(s)
# should be given here.
;
LLZO was prepared by a high temperature route using LiOH (Chempur, 99 %,
anhydrous), gamma-Al~2~O~3~ (Merck, anhydrous),
ZrO~2~ (Chempur, 99,9 %) and La~2~O~3~ (Chempur 99,99 %, dried at
900\%C for 12h).
;
_publ_section_exptl_refinement
;
Refinement has been performed by the full profile Rietveld method. The powder
diffraction pattern was indexed in a cubic system which was supplemented by
weak reflections from lithium carbonate.
;
_publ_section_references
;
(type here to add)
;
_publ_section_figure_captions
;
;
#=============================================================================
#=============================================================================
# If more than one structure is reported, the remaining sections should be
# completed per structure. For each data set, replace the '?' in the
# data_? line below by a unique identifier.
data_Li7La3Zr2O12
_database_code_depnum_ccdc_archive 'CCDC 833727'
#TrackingRef 'LixLa3Zr2O12_300K_final3.cif'
_refine_ls_weighting_scheme sigma
#Added by publCIF
_refine_ls_extinction_method no
#Added by publCIF
_refine_ls_extinction_coef 0
#Added by publCIF
_refine_ls_weighting_details 1/[Y~i~+\s(Y~i~)]
#Added by publCIF
_refine_ls_shift/su_max 0
#Added by publCIF
_atom_sites_solution_secondary heavy
#Added by publCIF
_atom_sites_solution_primary heavy
#Added by publCIF
_refine_ls_matrix_type full
#Added by publCIF
_exptl_absorpt_correction_T_min ?
#Added by publCIF
_diffrn_ambient_pressure 100
#Added by publCIF
_pd_char_colour white
#Added by publCIF
_pd_char_particle_morphology 'particle size <40 mkm'
#Added by publCIF
_pd_prep_pressure 100
#Added by publCIF
_pd_prep_temperature 1130
#Added by publCIF
_pd_spec_size_thick 40
#Added by publCIF
_pd_spec_size_equat 13
#Added by publCIF
_pd_spec_size_axial 13
#Added by publCIF
_diffrn_radiation_source 'research reactor FRM-II'
#Added by publCIF
_refine_ls_number_constraints 0
#Added by publCIF
_computing_data_reduction powder
#Added by publCIF
_computing_cell_refinement Rietveld
#Added by publCIF
#=============================================================================
# 5. CHEMICAL DATA
_chemical_name_systematic
; ?
;
_chemical_name_common 'Lithium Lanthanum Zirconium Oxide'
_chemical_formula_moiety ?
_chemical_formula_structural 'Li7 La3 Zr2 O12'
_chemical_formula_analytical 'Al0.196 Li6.060 La3 Zr2 O12'
_chemical_formula_iupac Al~0.196~Li~6.060~La~3~Zr~2~O~12~
_chemical_formula_sum 'Al0.196 La3 Li6.060 O12 Zr2'
_chemical_formula_weight 838.505
_chemical_melting_point ?
_chemical_compound_source ? # for minerals and
# natural products
loop_
_atom_type_symbol
_atom_type_scat_length_neutron
_atom_type_scat_source
Li -0.19000 V.F._Sears_Neutron_News_3_26_(1992)
Al 0.34490 V.F._Sears_Neutron_News_3_26_(1992)
La 0.82400 V.F._Sears_Neutron_News_3_26_(1992)
Zr 0.71600 V.F._Sears_Neutron_News_3_26_(1992)
O 0.58030 V.F._Sears_Neutron_News_3_26_(1992)
#=============================================================================
# 6. POWDER SPECIMEN AND CRYSTAL DATA
_symmetry_cell_setting Cubic
_symmetry_space_group_name_H-M 'I a -3 d'
_symmetry_space_group_name_Hall '-I 4bd 2c 3'
loop_
_symmetry_equiv_pos_site_id
_symmetry_equiv_pos_as_xyz
1 x,y,z
2 1/4-y,3/4+x,1/4+z
3 -x,1/2-y,z
4 1/4+y,1/4-x,3/4+z
5 1/4+x,1/4-z,3/4+y
6 x,-y,1/2-z
7 3/4+x,1/4+z,1/4-y
8 3/4+z,1/4+y,1/4-x
9 1/2-x,y,-z
10 1/4-z,3/4+y,1/4+x
11 z,x,y
12 y,z,x
13 -y,1/2-z,x
14 z,-x,1/2-y
15 1/2-y,z,-x
16 -z,1/2-x,y
17 1/2-z,x,-y
18 y,-z,1/2-x
19 3/4+y,1/4+x,1/4-z
20 1/4-y,1/4-x,1/4-z
21 1/4-x,3/4+z,1/4+y
22 1/4-x,1/4-z,1/4-y
23 1/4+z,1/4-y,3/4+x
24 1/4-z,1/4-y,1/4-x
25 -x,-y,-z
26 1/4+y,3/4-x,1/4-z
27 x,1/2+y,-z
28 1/4-y,1/4+x,3/4-z
29 1/4-x,1/4+z,3/4-y
30 -x,y,1/2+z
31 3/4-x,1/4-z,1/4+y
32 3/4-z,1/4-y,1/4+x
33 1/2+x,-y,z
34 1/4+z,3/4-y,1/4-x
35 -z,-x,-y
36 -y,-z,-x
37 y,1/2+z,-x
38 -z,x,1/2+y
39 1/2+y,-z,x
40 z,1/2+x,-y
41 1/2+z,-x,y
42 -y,z,1/2+x
43 3/4-y,1/4-x,1/4+z
44 1/4+y,1/4+x,1/4+z
45 1/4+x,3/4-z,1/4-y
46 1/4+x,1/4+z,1/4+y
47 1/4-z,1/4+y,3/4-x
48 1/4+z,1/4+y,1/4+x
49 1/2+x,1/2+y,1/2+z
50 3/4-y,5/4+x,3/4+z
51 1/2-x,1-y,1/2+z
52 3/4+y,3/4-x,5/4+z
53 3/4+x,3/4-z,5/4+y
54 1/2+x,1/2-y,1-z
55 5/4+x,3/4+z,3/4-y
56 5/4+z,3/4+y,3/4-x
57 1-x,1/2+y,1/2-z
58 3/4-z,5/4+y,3/4+x
59 1/2+z,1/2+x,1/2+y
60 1/2+y,1/2+z,1/2+x
61 1/2-y,1-z,1/2+x
62 1/2+z,1/2-x,1-y
63 1-y,1/2+z,1/2-x
64 1/2-z,1-x,1/2+y
65 1-z,1/2+x,1/2-y
66 1/2+y,1/2-z,1-x
67 5/4+y,3/4+x,3/4-z
68 3/4-y,3/4-x,3/4-z
69 3/4-x,5/4+z,3/4+y
70 3/4-x,3/4-z,3/4-y
71 3/4+z,3/4-y,5/4+x
72 3/4-z,3/4-y,3/4-x
73 1/2-x,1/2-y,1/2-z
74 3/4+y,5/4-x,3/4-z
75 1/2+x,1+y,1/2-z
76 3/4-y,3/4+x,5/4-z
77 3/4-x,3/4+z,5/4-y
78 1/2-x,1/2+y,1+z
79 5/4-x,3/4-z,3/4+y
80 5/4-z,3/4-y,3/4+x
81 1+x,1/2-y,1/2+z
82 3/4+z,5/4-y,3/4-x
83 1/2-z,1/2-x,1/2-y
84 1/2-y,1/2-z,1/2-x
85 1/2+y,1+z,1/2-x
86 1/2-z,1/2+x,1+y
87 1+y,1/2-z,1/2+x
88 1/2+z,1+x,1/2-y
89 1+z,1/2-x,1/2+y
90 1/2-y,1/2+z,1+x
91 5/4-y,3/4-x,3/4+z
92 3/4+y,3/4+x,3/4+z
93 3/4+x,5/4-z,3/4-y
94 3/4+x,3/4+z,3/4+y
95 3/4-z,3/4+y,5/4-x
96 3/4+z,3/4+y,3/4+x
_cell_length_a 12.9727(2)
_cell_length_b 12.9727(2)
_cell_length_c 12.9727(2)
_cell_angle_alpha 90.00000
_cell_angle_beta 90.00000
_cell_angle_gamma 90.00000
_cell_volume 2183.19(5)
_cell_formula_units_Z 8
_cell_measurement_temperature 300
_cell_special_details
; ?
;
_exptl_crystal_density_diffrn 5.102
_exptl_crystal_density_meas ?
_exptl_crystal_density_method 'not measured'
_exptl_crystal_F_000 230
# The next three fields give the specimen dimensions in mm. The equatorial
# plane contains the incident and diffracted beam.
# The next five fields are character fields that describe the specimen.
_pd_spec_mounting
# This field should be
# used to give details of the
# container.
'thin-wall cylinder vanadium container'
_pd_spec_mount_mode transmission # options are 'reflection'
# or 'transmission'
_pd_spec_shape cylinder # options are 'cylinder'
# 'flat_sheet' or 'irregular'
# The next four fields are normally only needed for transmission experiments.
_exptl_absorpt_coefficient_mu 0.0544
_exptl_absorpt_correction_type cylinder
_exptl_absorpt_process_details none
#=============================================================================
# 7. EXPERIMENTAL DATA
_exptl_special_details
; ?
;
# The following item is used to identify the equipment used to record
# the powder pattern when the diffractogram was measured at a laboratory
# other than the authors' home institution, e.g. when neutron or synchrotron
# radiation is used.
_pd_instr_location
; ?
;
_pd_calibration_special_details
# description of the method used
# to calibrate the instrument
; ?
;
_diffrn_ambient_temperature 300
_diffrn_source 'nuclear reactor'
_diffrn_radiation_type 'Constant Wavelength Neutron Diffraction'
_diffrn_radiation_wavelength 1.54820
_diffrn_source_type SPODI
_diffrn_radiation_monochromator Ge551
_diffrn_measurement_device_type 'high-resolution neutron powder'
_diffrn_measurement_method transmission
_diffrn_detector_area_resol_mean ? # Not in version 2.0.1
_diffrn_detector multidetector
_diffrn_detector_type SPODI # make or model of detector
_pd_meas_scan_method step # options are 'step', 'cont',
# 'tof', 'fixed' or
# 'disp' (= dispersive)
_pd_meas_special_details
; ?
;
# The following four items give details of the measured (not processed)
# powder pattern. Angles are in degrees.
_pd_meas_number_of_points 2958
_pd_meas_2theta_range_min 4.00
_pd_meas_2theta_range_max 151.9
_pd_meas_2theta_range_inc 0.05
#=============================================================================
# 8. REFINEMENT DATA
_refine_special_details
; ?
;
# Use the next field to give any special details about the fitting of the
# powder pattern.
_pd_proc_ls_special_details
; ?
;
# The next three items are given as text.
_pd_proc_ls_profile_function pseudo-Voight
_pd_proc_ls_background_function ?
_pd_proc_ls_pref_orient_corr no
# The following profile R-factors are NOT CORRECTED for background
# The sum is extended to all non-excluded points.
# These are the current CIF standard
_pd_proc_ls_prof_R_factor 2.22
_pd_proc_ls_prof_wR_factor 2.79
_pd_proc_ls_prof_wR_expected 0.94
# The following profile R-factors are CORRECTED for background
# The sum is extended to all non-excluded points.
# These items are not in the current CIF standard, but are defined above
_pd_proc_ls_prof_cR_factor 10.97
_pd_proc_ls_prof_cwR_factor 8.91
_pd_proc_ls_prof_cwR_expected 3.00
# The following items are not in the CIF standard, but are defined above
_pd_proc_ls_prof_chi2 8.8095
_pd_proc_ls_prof_echi2 8.8095
# Items related to LS refinement
_refine_ls_R_I_factor 3.42
_refine_ls_number_reflns 207
_refine_ls_number_parameters 84
_refine_ls_number_restraints 0
# The following four items apply to angular dispersive measurements.
# 2theta minimum, maximum and increment (in degrees) are for the
# intensities used in the refinement.
_pd_proc_2theta_range_min 4.07080
_pd_proc_2theta_range_max 151.97080
_pd_proc_2theta_range_inc 0.05
_pd_proc_wavelength 1.548200
_pd_block_diffractogram_id ? # The id used for the block containing
# the powder pattern profile (section 11)
# Give appropriate details in the next two text fields.
_pd_proc_info_excluded_regions '0.00-14.00, 41.30-42.50, 151.92-180.00'
_pd_proc_info_data_reduction ?
# The following items are used to identify the programs used.
_computing_data_collection \q2/\q
_computing_structure_solution known
_computing_structure_refinement FULLPROF
_computing_molecular_graphics Diamond
_computing_publication_material pubCIF
#=============================================================================
# 9. ATOMIC COORDINATES AND DISPLACEMENT PARAMETERS
loop_
_atom_site_label
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_occupancy
_atom_site_adp_type # Not in version 2.0.1
_atom_site_type_symbol
Li1 -0.12500 0.00000 0.25000 0.054(5) 0.54 Uiso Li
Al1 -0.12500 0.00000 0.25000 0.054(5) 0.06530 Uiso Al
Li2 0.1004(8) 0.6853(8) 0.5769(8) 0.031(3) 0.37 Uiso Li
La1 0.00000 0.25000 0.12500 0.0106(6) 1.00000 Uani La
Zr1 0.00000 0.00000 0.00000 0.0095(3) 1.00000 Uani Zr
O1 -0.03161(8) 0.05454(9) 0.14940(8) 0.0148(6) 1.00000 Uani O
loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_12
_atom_site_aniso_U_13
_atom_site_aniso_U_23
_atom_site_aniso_type_symbol
La1 0.0095(4) 0.0095(4) 0.0128(9) 0.0035(6) 0.00000 0.00000 La
Zr1 0.0095(3) 0.0095(3) 0.0095(3) 0.0005(5) 0.0005(5) 0.0005(5) Zr
O1 0.0170(6) 0.0179(6) 0.0094(5) 0.0018(5) -0.0006(4) -0.0026(5) O
# Note: if the displacement parameters were refined anisotropically
# the U matrices should be given as for single-crystal studies.
#=============================================================================
# 10. DISTANCES AND ANGLES / MOLECULAR GEOMETRY
_geom_special_details ?
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_site_symmetry_1
_geom_bond_site_symmetry_2
_geom_bond_distance
_geom_bond_publ_flag
Zr1 O1 .-3. 1 2.104(1) no
La1 O1 .32 1 2.516(1) no
La1 O1 .32 1 2.588(1) no
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_2
_geom_angle_site_symmetry_3
_geom_angle
_geom_angle_publ_flag
O1 Zr1 O1 1 .-3. 1 180.00(4) no
#=============================================================================
# The following lines are used to test the character set of files sent by
# network email or other means. They are not part of the CIF data set.
# abcdefghijklmnopqrstuvwxyzABCDEFGHIJKLMNOPQRSTUVWXYZ0123456789
# !@#$%^&*()_+{}:"~<>?|\-=[];'`,./