1. R. Murugan, et al. Fast Lithium Ion Conduction in Garnet-Type Li 7La3Zr2O12. Angew.

Chem. Int. Ed. 2007, 46, 77787781.

Objective: Synthesis of Li7La3Zr2O12 or LLZO

Zr is fixed-valent and more stable against chemical reaction with elemental Li. Replacing Ti with Zr in
LLTO is unsuccessful due to formation of the pyrochlore phase La 2Zr2O7.

Li5La3M2O12 (M = Nb, Ta) possess garnet-related structure and high Li + ion conductivity and is predicted
to move in 3D network. This research area gave rise to further studies on conductivity optimization by
chemical substitutions and structural modifications. Among the garnet-related structures,
Li6BaLa2Ta2O12 exhibited the highest Li+ conductivity and stable but the total conductivity at room
temperature is not sufficiently high to develop an ideal ASS LIB

Advantages of Li7La3Zr2O12
Good thermal and chemical stability against reactions with electrode materials
Low cost
Environmental benignity
Ease of preparation and densification

Synthesis
LiOH heated at 200 C for 6 hrs added with 10% excess LiOH (i)
La2O3 heated at 900 C for 9 hrs (ii)
ZrO2 (no heating) (iii)

Powders (i), (ii) and (iii) are ball-milled with zirconia balls for 12 hrs in 2-propanol in air. (A)
(A) is heated at 900 C then ball-milled with zirconia balls for 12 hrs in 2-propanol in air. (B)
(B) is heated at 900 C then ball-milled with zirconia balls for 12 hrs in 2-propanol in air. (C)
(C) is pressed under isostatic pressure and annealed at 1230 C (at 1 C/min) for 36 hrs
(D)
(D) (sintered dense slab) cut into thinner pellets using diamond saw

Characterization
1. XRD to monitor phase formation
2. Electrical conductivity measurements using impedance and gain-phase analyzer in the
temperature range of 18-350 C; pellets are cut into 2 sizes (thin: 0.18 cm x 0.98 cm diam; thick:
1.02 cm x 0.92 cm diam); Li +-blocking Au electrodes (Au paste cured at 700 C for 1 hr); Prior to
impedance measurements, samples are equilibrated for 3-6 hrs at constant temperature.
3. TG and DTA - 20900208 C in air with a heating/cooling rate of 28 C/min and isothermally at
900 C.
4. Stability - LLZO pellet is reacted with a large excess of molten lithium for 48 hrs in a Mo crucible

Results:
 LLZO has a high total conductivity of 3 x 10 -4 S/cm at 25 C better than any garnet-like
structures previously reported
Total and bulk conductivity can be improved by low-temperature synthesis of fine-grain Li 7La3Zr2O12
with easily available reactants and by densification by a suitable sintering process
Arrhenius plots for bulk and total electrical conductivities show no appreciable shift in conductivity
for the both heating and cooling cycle. thermal stability without phase transformation within 25
350 C. Conductivity of the thin pellet is slightly higher than the thick pellet.
The charge transfer across the individual grain boundaries occurs with the same activation energy
as the transfer with the bulk of the grains. This can be attributed to the ease of sintering the
polycrystalline samples. O, Zr and La are rigidly bound in the framework of garnet-structure, their
mobility will be negligible at the operating temperatures, and hence, ionic motion is due to the
transport of Li+ ions.
Ionic nature of electrical conductivity was confirmed by emf measurements employing LLZO as
electrolyte and Li and Al (or LiAl) as electrodes. Al is alloyed first by chemical reaction with Li and
by coulometric titration of Li into Al from the opposite Li electrode. The resulting voltage was in the
same range with the theoretical value.
TG-TGA no significant change in mass and no detectable phase transition in both heating and
cooling over 20 900 C
LLZO is found to be stable in molten Li and chemically stable when exposed to moisture and air for
several weeks
2. C. A. Geiger, et al. Crystal chemistry and stability of LLZO garnet: a fast lithium
ion conductor. Inorg. Chem. 2011, 50, 10891097.

Objective: Study crystal, chemical and structural properties and stability relations of LLZO garnet
prepared via two sintering methods and investigate the reasons behind its high ion conductivity.

Motivation: The detailed crystal chemistry of Li-oxide garnets is not well understood, nor is the
relationship between crystal chemistry and conduction behavior. X-ray powder-based structure
determinations are plagued by the problem of poor scattering by Li, while neutron powder
diffraction measurements are more sensitive at detecting the Li atom, but the data sets are still
limited.

Synthesis:

Method 1 (solid-state sintering, flux-based (i.e., molten Li-borates)

ZrO2 heated to 1273 K (i)
La2O3 heated to 1273 K (ii)
Li2CO3 heated 573 L (iii)

Powders (i), (ii), (iii) are mixed in stoichiometric proportions to obtain Li 7La3Zr2O12 with 5 wt
% extra Li2CO3 pressed to pellets and sintered at 1073 K (A)
(A) is ground and seeded with fine-grain Li 7La3Zr2O12 that had been made from previous
sintering experiments (B)
(B) is welded into Pt(Pd) and/or Au-capsules (2 cm x 5mm diam) heated at different
rates (50 300 C/hr) and held at temperatures of 1173 -1373 K overnight in a box furnace
(C)

Method 2 (hydrothermal experiments at elevated pressures)

Refer to Awaka, J.; Kijima, N.; Hayakawa, H.; Akimoto, J. Solid State Chem. 2009, 182,
20462052.

Characterization:
1. Electron-probe microanalysis to investigate composition of single crystals and determine
presence of additional phases from backscattered electron maps (samples used are from
Method I)
2. EDS general composition and presence of all common elements (detected Al, La and Zr
except Li)
3. Wavelength dispersive spectroscopy (WDS) for Al, La and Zr (accelerating voltage of 20 kV
and a beam current of 40 nA, with a beam diameter of 1 m)

The following mineral and phase standards were used: corundum (Al), zircon (Zr), and LaPO 4 (La).
The PRZ method (modified ZAF) was used for data correction.

4. Laser-ablation ICP-MS
5. Al MAS and MQMAS NMR Spectroscopy
6. 7Li MAS and 6Li MAS NMR Spectroscopy
7. X-ray Single-Crystal-Structure Determination and Powder Diffraction
3. J. Wolfenstine, et al. Electron microscopy characterization of hot-pressed Al
substituted LLZO. J Mater Sci 2012, 47, 44284431.

Objective: Examine microstructure of dense cubic LLZO using electron microscopy

Synthesis:
Li2CO3 + ZrO2 + La(OH)3 + Al2O3 (0.24 mol Al) calcined at 1000 C for 4 hrs (A)
Note: powders are mixed in BN-coated alumina crucible
(A) hot-pressed at 1000 C to form pellets (B)
(B) heated in air at 1000 C for 4 hrs to burn off residual graphite (C)
(C) cut into rectangular pieces for microstructural analysis

Characterization
1. SEM
2. TEM
3. STEM
4. EDS
4. J. Wolfenstine, et al. High conductivity of dense tetragonal LLZO. J Power
Sources 2012, 208, 193-196.

Objective: Determine total conductivity and the microstructure of tetragonal LLZO hot-pressed
near to theoretical density.

Synthesis:
Li2CO3 + ZrO2 + La(OH)3 mixed in stoichiometric proportions and dissolved in ~1.4 M HNO 3
(A)
(A) dried in a microwave oven contained in a fume hood (B)
(B) lightly ground with mortar and pestle and pressed into pellet using die and press (C)
(C) pellet is placed on ZrO2 plate and heated in air at 650 C for 15 h and subsequently at
1000 C for 4 h (D)
(D) hot-pressed at 1050 C at 40 MPa for I hr under air cut into rectangular pieces
(E)

Characterization:
1. XRD for phase purity of LLZO
2. Bulk density physical measurements
3. AC electrical conductivity measurements
4. Impedance analysis
5. E. Rangasamy, et al. The role of Al and Li concentration on the formation of cubic
garnet solid electrolyte of nominal composition LLZO. Solid State Ionics 2012,
206, 28 - 32.

Note:
LLZO Al (moles) Calcination Temp. (C) Li (moles)
Cubic 0.19 0.40 > 1180 C 5.96
6.27 (1230 C)
Tetragonal 0.074 0.10 < 1180 C 7.5 (800 C)

Objective: Synthesize LLZO with precise addition of Al and Li and evaluate the structure using
XRD and composition by (ICP-MS)

Synthesis:
Li2CO3 + ZrO2 + La(OH)3 + Al2O3 mixed in stoichiometric proportions (with variations of Li
and Al concentrations) in an agate milling vial (A)
(A) is cold-pressed into pellets (B)
(B) is placed in a BN-coated alumina combustion boat and calcined at 1000 C for 4 hrs
(C)
(C) is loaded into graphite die and heated at 1000 C under 40 MPa for 1 hr under flowing
Ar (D)
(D) is cut into 2 mm x 22 mm diam pellet and heated in air at 1000 C for 4 hrs to burn
residual graphite.

Rapid induction hot pressing technique developed at

MSU results in test membranes of ~98% theoretical
density to enable fundamental studies.
Credit: G.L. Kohuth/MSU.

DOE: XRD for Li = 7.0 mol vs. Al = 0, 0.093, 0.130, 0.167, 0.204, 0.241, 0.278, 0.315,
0.352, 0.389 mol; XRD for Al = 0.24 vs. Li = 5.63, 6.24, 7.32

Characterization
1. XRD performed for (C) samples
2. AC-DC (room-temperature) electrical conductivity measurements
3. Impedance analysis
4. SEM
5. TEM
6. STEM
7. EDS

Notes: At least 0.204 mols Al is required to stabilize cLLZO, below this yields tLLZO. Above
0.389 mols Al, LaAlO3 forms. 5.63 6.24 mols Li produces single phase cLLZO. Above 6.24
mols, tLLZO forms
6. J. Wolfenstine, et al. Synthesis and high Li-ion conductivity of Ga-stabilized cubic
LLZO. Mater Chem Phys 2012, 134, 571-575.

Objective: To study the effect of Ga in LLZO.

Note: A Li6.25La3Zr2Ga0.25O12 composition was selected for study to mimic the Al-substituted
LLZO that yields stabilized cubic structure using such stoichiometric proportions

Synthesis:

Li2CO3 + (ZrO2)2CO3 x H2O + La(OH)3 + GaCl3 (in stoich proportions) mixed and dissolved in ~
1.4 M HNO3(aq) evaporated to dryness in microwave oven inside a fume hood (A)
(A) lightly ground with mortar and pestle and pressed into a pellet using die and press
(B)
(B) placed in a ZrO2 plate and heated in air at 650 C for 15 hrs and subsequently at 1000
C for 4 hrs under air (C)
(C) hot-pressed at 1000 C for 4 hrs under air cut into rectangular pieces (D)

Characterization
1. XRD - for (D) samples
2. SEM
3. EDS
4. AC and DC room-temperature electrical conductivity measurements to determine ionic
conductivity
5. Impedance analysis analyze ionic conduction contributions from bulk and grain
boundaries

Notes: Ga stabilizes the cubic phase of LLZO at room temperature per XRD results. Total ionic
conductivity falls within the range of Al-substituted LLZO.
7. K. Tadanaga, et al. Low temperature synthesis of highly ion conductive LLZO-
LiBO3 composites. Electrochem Commun 2013, 33, 51-54.

Notes: High-temperature synthesis causes Li loss and to prevent this is to cover the samples with
mother powders.

Motivation: Addition of -Al2O3 to LLZO or by sol-gel process lower the sintering temperature but
the densification has never been achieved.

To lower sintering temperature, additives must be of low melting points and make liquid phases
below sintering temperature effective. The liquid phase promotes the densification and coarsening
at low temp.

Objective: Synthesize LLZO-Li3BO3.

Synthesis: Al-doped LLZO by sol-gel

LiNO3 + La(NO3)3x6H2O dissolved in ethanol (A)

Zr(O-n-C3H7)4 + Al(O-sec-C4H9) + Ethyacetoacetate (B)
(A) + (B) stirred at room temperature for 1 hr to obtain a gel mixture (C)

Note: Mole ratio of precursors is

LiNO3:La(NO3)36H2O:Zr(O-n-C3H7)4:Al(O-sec-C4H9)3:EAcAc:ethanol = 7.7:3:2:0.3:1.6:50

(C) dried at 80 C for 12 hrs then 150 C for 5 hrs (D)

(D) ground then calcined at 600 C for 5 hrs (E)
(E) ball milled with zirconia balls for 12 hrs (F)
(F) + Li3BO3 with Li3BO3/LLZO = 0.68 in agate mortar, then pressed into pellets at 200 MPa (G)
(G) heated at 700 C for 5 hrs, then sintered at 900 C for 36 hrs in an alumina crucible (H)

Characterization
1. XRD
2. SEM
3. AC impedance analysis
4. Porosity computed from calculated density of pellets
5. Galvanostatic cycling reversibility of dissolution and deposition
8. K. Tadanaga, et al. Low temperature synthesis of highly ion conductive LLZO-
LiBO3 composites. Electrochem Commun 2013, 33, 51-54.

Notes: High-temperature synthesis causes Li loss and to prevent this is to cover the samples with
mother powders.
9. S. Afyon, et al. A shortcut to garnet-type fast Li-ion conductors for all-solid state
batteries. J Mater Chem A 2015, 3, 18636-18648.

Modified sol-gel synthesis

SOL-GEL SYNTHESIS
SOL-GEL METHOD

The sol-gel method is generally considered superior to the solid state method for the powder synthesis. In
the solid state reaction, the mixing of precursors is at best at the particle level whereas atomic-level mixing
can be achieved in the sol-gel method theoretically. [1] Powders prepared through solid state reaction are
usually in the micron range. Using sol-gel method, nanoparticles of controllable sizes and morphology can
be obtained. The enhanced sinterability of sol-gel powders due to chemical homogeneity and small particle
size greatly reduces the energy barriers of densification thus lowers firing temperatures. Finally, novel
forms of ceramic products such as fibers and film can be fabricated using the sol-gel method.

There are several different kinds of sol-gel processes. [1, 2] The Pechini method used in this thesis falls
into the category of polymerized complex method. [3] First, the metal ions are added into citric acid (CA)
solution to form metal chelate complexes. Ethylene glycol (EG) is then added while the whole solution is
heated under constant stirring. The viscosity of the solution increases due to polyesterification and
evaporation of solvents. Finally, a highly viscous gel of continuous polymer network with metal ions
uniformly distributed and immobilized is formed. The metal oxides powder is obtained by breaking down the
polymers at high temperature (usually above 300 C).

The Pechini method is very suitable for the preparation of multi-component metal oxides because the CA
has strong affinity to most metal ions and form stable metal chelates almost indiscriminately. In this
dissertation, a modified version of the Pechini method, the EDTA/citrate complexing method, [4] was
adopted. The chelation of Ethylene-diamine-tetra-acetic acid (EDTA) and metal ions is more tolerant to pH,
temperature and metal ion concentration. The CA was used primarily as an esterification agent instead.
This modified Pechini method has been successfully applied to a variety of complex metal oxides but not to
the lithium garnet compounds yet. [5, 6, 7]

Powder synthesis via sol-gel method

Two garnet compounds were synthesized using the EDTA-citrate complexing process (ECCP),
Li7.2La3Zr1.8Sc0.2O12 (LLZS0.2) and Li7La3Zr2O12. The general procedure is shown in figure below. To prepare
the metal nitrate solution, LiOH, La 2O3 and Sc2O3 were dissolved in diluted nitric acid completely; ZrO(NO 3)2
powder was dissolved in mixture of H 2O2 and H2O at 100C. All solutions were then mixed well and added
into EDTA/ammonia solution. This step was conducted very slowly and carefully so no precipitates formed.
Subsequently, the whole solution was heated at 80 C for 30 minutes under constant stirring before citric
acid/H2O solution was added. The pH value was adjusted into neutral or slight basic range by adding
ammonia water. Finally, the solution was heated to 100 C until a clear gel was formed, which was then
heated at 350 C on hot plate to obtain a black resin. The resin was calcined in open air in a furnace at 500
C to burn off organic substances and obtain white fluffy powder. After grinding, the powder was heated to
800 C to form the garnet phase.
References:

1. Hench, L.L. and J.K. West, The Sol-Gel Process. Chemical Reviews, 1990. 90(1): p. 33-72.
2. Kakihana, M., ''Sol-Gel'' preparation of high temperature superconducting oxides. Journal of Sol-Gel
Science and Technology, 1996. 6(1): p. 7-55.
3. Pechini, M.P., U.S. Patent, Editor. 1967.
4. Zhou, W., Z.P. Shao, and W.Q. Jin, Synthesis of nanocrystalline conducting composite oxides based on
a non-ion selective combined complexing process for functional applications. Journal of Alloys and
Compounds, 2006. 426(1-2): p. 368-374.
5. Gu, H.X., et al., Anode-supported ScSZ-electrolyte SOFC with whole cell materials from combined
EDTA-citrate complexing synthesis process. Journal of Power Sources, 2007. 172(2): p. 704-712.
6. Patra, H., et al., Effect of process parameters on combined EDTA-citrate synthesis of
Ba0.5Sr0.5Co0.8Fe0.2O3 (-) (delta) perovskite. Powder Technology, 2011. 209(1-3): p. 98-104.
7. Ran, R., et al., Well-crystallized mesoporous samaria-doped ceria from EDTA-citrate complexing
process with in situ created NiO as recyclable template. Journal of Alloys and Compounds, 2010.
491(1-2): p. 271-277.
Source: (Dissertation)