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A bird’s-eye view of Li-stuffed garnet-type

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Li7La3Zr2O12 ceramic electrolytes for advanced

Cite this: Energy Environ. Sci.,
2019, 12, 2957 all-solid-state Li batteries
Alfred Junio Samson, Kyle Hofstetter, Sourav Bag and Venkataraman Thangadurai *
Batteries with a solid-state electrolyte and a Li anode (solid-state Li batteries, SSLBs) are being
considered to replace conventional organic liquid-based Li-ion batteries due to SSLBs’ promise of higher
energy density and improved safety. The crucial component in SSLBs is the solid-state electrolyte which
must fulfill requirements in Li-ion conductivity, electrochemical stability, and chemical stability towards
the cathode and Li anode. Recently, much attention has been given to a class of ceramics with a
garnet-type structure, specifically on compositions based on Li-stuffed Li7La3Zr2O12 (LLZO) because they
fulfill all the enumerated requirements for a solid-state electrolyte. In this review, we update the
progress and analyze the trends in the three main approaches to realize the technological application of
Received 16th June 2019, LLZO as an electrolyte in SSLBs: (i) crystal structure and lithium content control by doping to enhance
Accepted 12th August 2019 Li-ion conductivity of LLZO, (ii) microstructure and dimension control by material processing and thin-
DOI: 10.1039/c9ee01548e film fabrication to reduce electrolyte resistance, and (iii) LLZO–electrode interface tuning to reduce
interfacial resistance and improve battery performance. Finally, we offer our perspectives on research
rsc.li/ees paths toward the realization of practical batteries with LLZO solid electrolytes.
Broader context
Li-ion batteries (LIBs) have revolutionized the portable electronics market and are now poised to transform transportation and grid energy storage. However,
state-of-the-art LIBs are approaching their limits in energy density; their safety in electric vehicle application is also in question. Both safety and performance
issues mainly originate from the state-of-the-art liquid or gel organic electrolytes, which are flammable and unsuitable with lithium metal and high voltage
cathodes. Batteries with a Li anode and non-flammable solid electrolytes which promise better performance and improved safety can potentially replace the
current LIBs. Many candidate solid electrolytes including polymers and solid-state (inorganic) membranes have been explored over the years but most face the
challenge of either low conductivity or instability with Li. Garnet-type-structured Li-based oxides are known to be stable with Li and show a Li-ion conductivity
of B10 3 S cm 1 at room temperature, which is an order of magnitude lower than those of conventional liquid electrolytes. The discovery of Li-stable and
highly conducting garnet-type Li7La3Zr2O12 (LLZO) in 2007 stirred researchers’ interest to optimize LLZO’s material properties. Herein, we present trends to
understand how strategies involving composition tuning, synthesis and fabrication, and interface modifications have paved the way for LLZO to become a
commercially appealing solid electrolyte.
1. Introduction LiPF6 dissolved in organic solvents8 has undoubtedly enjoyed a

great deal of success as the electrolyte of choice for LIBs that
Li-ion batteries (LIBs) are found in most portable electronic power portable electronic devices in almost 30 years. The primary
devices. Nowadays, LIBs also power electric vehicles and store reason for the choice of organic carbonates as an electrolyte
energy from renewable solar and wind resources.1–4 Although is their wider electrochemical stability window9,10 than that of
LIB technology has advanced significantly in recent years, an aqueous electrolyte. Carbonate mixture-based organic Li-ion
enhanced energy and power densities combined with improved electrolytes9 make it possible to obtain a B4 V cell, although they
safety are still needed if LIBs are going to power the future tend to be oxidized at above 4.5 V vs. Li.9,11 The higher energy
transportation system and store energy for large-scale grid power densities of LIBs (150–265 W h kg 1, 400–770 W h l 1)12–14 make
sources.5–7 The state-of-the-art electrolyte system composed of them more attractive over other secondary batteries such as
lead-acid (30–35 W h kg 1, 70–80 W h l 1)12,13 or nickel-metal
Department of Chemistry, University of Calgary, 2500 University Dr, hydride (55–75 W h kg 1, 165–240 W h l 1)12,13 which are
NW Calgary AB, T2N 1N4, Canada. E-mail: [email protected] limited to about 2 V due to the instability of aqueous electrolytes.
This journal is © The Royal Society of Chemistry 2019 Energy Environ. Sci., 2019, 12, 2957--2975 | 2957
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Review Energy & Environmental Science
Despite their commercial success, state-of-the-art LIBs show inorganic electrolyte separator. Solid inorganic electrolytes will
several limitations in applications requiring higher energy not only overcome the limitations of liquid electrolytes but
density, reliability, and safety such as electric vehicles (EVs). also offer possibilities for developing new battery chemistries
First, the organic carbonate-based electrolytes, especially those (especially, Li–O2 and Li–S).6 Inorganic lithium-ion conductive
that contain linear carbonates (e.g., dimethyl/diethyl- and ethyl oxides and non-oxides form a class of solid-state electrolytes
methyl carbonates), are highly flammable.9,10 Their flammability that is of interest. Commonly studied examples of such solid-
leads to limits in the maximum operating temperature (130–150 1C) state electrolytes18,19 include Li-b-alumina, Li3N, NASICON
to prevent exothermic chemical reactions between the electrodes (sodium superionic conductor)-type Li1.3Al0.3Ti1.7(PO4)3, LISICON
and electrolyte.15 Secondly, the toxicity of current electrolytes’ (lithium superionic conductor)-type Li14ZnGe4O16, thio-LISICON
decomposition products10,16,17 presents a concern for the (Li3.4Si0.4P0.6S4), perovskite-type La(2/3) x&(1/3) 2xLi3xTiO3
environment and health. Finally, the conventional electrolytes (& = vacancy), sulfide glass/ceramic (Li2S–P2S5), LiPON
are not compatible with high capacity metallic Li anodes and (Li2.88PO3.73N0.14) and Li-stuffed garnet-type Li5La3M2O12
high voltage (Z5 V) cathodes.11,14 (M = Nb, Ta). These solid-state materials have merits and demerits
Finding an alternative to the liquid carbonate-based electro- when used as electrolytes in all-solid-state Li-ion batteries,19 and
lytes has been the subject of intensive research in the past several reviews18,20–22 have discussed their physical and chemical
several decades. One of the options is to use a solid-state, properties, advantages, and disadvantages.
Dr. Alfred Junio Samson is a Kyle Hofstetter completed his

research associate in Prof. MSc degree in Chemistry under
Thangadurai’s laboratory at the the guidance of Prof. Thangadurai
University of Calgary. He earned at the University of Calgary,
his double MSc in materials Canada. His research is focused on
science and engineering from the development of next-generation
Luleå University of Technology solid-state Li batteries.
in Sweden and Saarland Univer-
sity in Germany, and PhD in
energy conversion from Technical
University of Denmark. His current
research is on the development of
Alfred Junio Samson solid-state batteries using ceramic Kyle Hofstetter
electrolytes.
Sourav Bag obtained his MSc Dr. Venkataraman Thangadurai

and PhD in Chemistry from the is a full professor of chemistry
Indian Institute of Technology at the University of Calgary,
(IIT) Kharagpur, India. After a Canada. He is a Fellow of the
short postdoctoral stint at IIT Royal Society of Chemistry,
Bombay, India, he joined Prof. United Kingdom. He received his
Thangadurai’s group as a PhD from the Indian Institute of
postdoctoral research associate Science, Bangalore, India, and
at the University of Calgary, did his PDF at the University of
Canada. His current research Kiel, Germany. He received a
interests include fundamental prestigious PDF fellowship from
understanding of solid state the Alexander von Humboldt
Sourav Bag materials for energy storage. Venkataraman Thangadurai Foundation, Bonn, Germany.
Dr Thangadurai received his
Habilitation degree from the University of Kiel. His current
research activities include discovery of novel solid electrolytes
and mixed conductors for all-solid-state batteries, solid oxide
cells, and electrochemical gas sensors. He has published over 175
scientific papers in international refereed journals. In 2016, he
received the Keith Laidler Award from the Canadian Society of
Chemistry for his outstanding contributions to physical chemistry.
2958 | Energy Environ. Sci., 2019, 12, 2957--2975 This journal is © The Royal Society of Chemistry 2019
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Energy & Environmental Science Review
Among the various solid-state electrolytes, the garnet-type struc- structure composition (c-LLZO) in 200728 and Awaka et al.
tured materials have attracted increasing23 attention since the synthesized the tetragonal-type composition (t-LLZO) in 2009.29
discovery of facile Li-ion conductivity (B10 6 S cm 1 at 25 1C) Research on LLZO has progressed significantly, and groups have
in the nominal composition Li5La3M2O12 (M = Ta or Nb) by been exploring battery designs with possible commercialization in
Thangadurai et al.24 Garnet-type structure-derived materials have mind.33,34 Here, we analyze the advances in some of the strategies
several desired physical and chemical properties for application employed by researchers to push LLZO from a scientific curiosity
as electrolytes in solid-state lithium batteries: (i) a high ionic in 2007 to a technologically relevant material for solid-state
conductivity of B 1 10 3 S cm 1 at B25 1C,19,23,25 (ii) excellent lithium batteries. We also report the approaches for Li-ion
chemical stability with elemental Li,19,26 and (iii) a wide electro- conductivity enhancement and LLZO/electrode interface engi-
chemical stability window as determined by electrochemical neering as well as the opportunities and limitations of LLZO for
experimental methods27 (up to 9 V vs. Li+/Li).19 Our group has beyond Li-ion batteries.
recently reviewed the chemical and electrochemical stability of the
family of Li-stuffed garnets.27 Furthermore, an overview of structure–
chemical composition–ionic conductivity relationships of the family 2. Garnet framework and Li+ mobility
of Li-stuffed garnets was also reported in the literature.19,23
Among the Li-stuffed garnet-type Li-ion electrolytes, 2.1 Crystal structure and Li-ion conduction mechanism
Li7La3Zr2O12 (LLZO)-based compositions are notable since they LLZO adopts two distinct crystal structures – tetragonal (t-LLZO)
can achieve higher conductivity levels (B 1 mS cm 1 at 25 1C) and cubic (c-LLZO). The first reported LLZO composition,
compared to other garnets with lower Li contents30 through synthesized by Murugan et al.28 using solid-state (ceramic)
appropriate synthesis conditions and doping strategies.25,31,32 synthesis and sintering at 1230 1C, was reported to adopt a
Fig. 1 shows the continuous increase in the number of articles cubic garnet-type structure (a = 12.9682(6) Å; Ia3% d space group).
published containing ‘‘Li7La3Zr2O12’’ in the title, abstract, Soon after, another group35 also synthesized LLZO confirming
or keywords since Murugan et al. synthesized the cubic-type the formation of a cubic structure but only after heat treatment
at 1180 1C. Fig. 2a shows the crystal structure of c-LLZO
(space group Ia3% d).36–38 Lattice constants typically range from
a = 12.95–12.97 Å based on studies of ‘‘un-doped’’ LLZO.28,35,39–41
The garnet structure is a framework of 8-fold coordinated LaO8
dodecahedra (24c) and 6-fold coordinated ZrO6 octahedra (16a).
The Li atoms randomly and partially occupy the interstices of the
framework structure within two kinds of sites, the tetrahedral 24d
sites and the octahedral 48g or off-centered 96h sites. The 96h
sites are displaced off the 48g sites.37,38 The displacement
(48g–96h) is due to Li+–Li+ repulsion across a shared site face.
Fig. 1 Number of articles published until 2018 since the first report on
The 24d tetrahedral cage faces are face-shared with four neigh-
cubic-type LLZO (c-LLZO) in 200728 and tetragonal-type LLZO (t-LLZO) in boring octahedral cages and form a three-dimensional network
2009.29 (Accessed May 6, 2019, Web of Science.) of conduction pathways (a segment is shown in Fig. 2b).38,42–44
Fig. 2 (a) Crystal structure of cubic Li7La3Zr2O12 and (b) Wyckoff positions of the Li ions. The centers of tetrahedral and octahedral sites are noted as 24d
and 48g sites, respectively, and the 96h sites are slightly displaced off the 48g sites. LiO6 and LiO4 connection and the two possible Li migration pathways
(A and B), adapted from ref. 44. Path B is the most likely mechanism of Li migration in LLZO.
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In theory, different Li-diffusion pathways are possible,30 but

calculations and Li nuclear magnetic resonance suggest a
mechanism wherein the 24d Li ions are immobile, and Li
migrates by hopping between the octahedral sites in garnets
with lithium contents 5 and below.23,44–46 Based on ab initio
calculations, Xu et al.47 have proposed two potential pathways
of Li-ion migration in the cubic garnets (route A and route B)
with lithium contents 45 per formula unit. In route A, the
Li-ion migrates via the interstice between neighboring octa-
hedral sites, bypassing their common tetrahedral neighbor as

shown in Fig. 2b. In route B, the Li-ion moves through the
shared triangular faces (‘‘neck’’) of the octahedral and tetra-
hedral sites. The Li-ion migration in route A is associated with
an activation energy of 0.8 eV and is preferred when Li+ content
is lower, such as Li5La3Nb2O12, while route B is associated with
an activation energy of 0.26 eV and is preferred in highly
Li-stuffed garnets such as Li7LaZr2O12.19 Such a low-energy barrier
explains why LLZO exhibits rather high ionic conductivity. Fig. 3 Arrhenius plot of the total lithium-ion conductivity of cubic
‘‘Li7La3Zr2O12’’ (c-‘‘LLZO’’, dashed lines) and tetragonal LLZO (t-LLZO, solid
In 2009, it was reported by Awaka et al.29 that LLZO also
lines). Cubic ‘‘LLZO’’ from the work of (a) Murugan et al.,28 (b) Ohta et al.,39
adopts a tetragonal structure with space group I41/acd (no. 142) (c) Huang et al.,40 (d) Kaeriyama et al. (1230 1C),35 and (e) Kaeriyama et al.
after sintering at a lower temperature of 980 1C. Percival et al.48 (1200 1C).35 Tetragonal LLZO from the work of (f) Zhao et al.,50 (g)
also reported a tetragonal structure for a garnet-type Li7La3Sn2O12 Wolfenstine et al.,51 (h) Inada et al.,52 (i) Il’ina et al. (sol–gel),53 (j) Il’ina et al.
if sintered below 750 1C. Later on, it was shown that the tetragonal (ceramic),53 (k) Rangasamy et al.,54 (l) Awaka et al.,29 and (m) Kokal et al.
(sol–gel).55 The compositions may or may not contain traces of aluminum,
LLZO phase is the stable structure at room temperature.49
a common unintentional dopant that originates from alumina crucibles
In general, it was suggested that partial substitution of LLZO by during the high temperature sintering step.59,60
dopants such as Al3+ from the crucible or intentional doping
stabilizes the cubic phase. Tetragonal t-LLZO is a slightly distorted
cubic garnet-type structure.29 The lattice parameters reported in disorder in the Li-ion sublattice of c-LLZO. t-LLZO has a lower
the literature are a = 13.07–13.12 and c = 12.67–12.72 Å.29,50–55 ionic conductivity than c-LLZO because the mechanism of
In the transition from the cubic to the tetragonal phase (tetragonal synchronous collective motion requires a higher activation
distortion), the 24d site in the cubic phase is transformed into fully energy.61
occupied 8a sites and unoccupied 16e sites while the 96h site in The low Li-ion conducting tetragonal phase can undergo a
the cubic phase is transformed into two 16f and 32g sites.29,37,56,57 phase transition to the high ionic conducting cubic phase at
The notable differences of t-LLZO from c-LLZO is the ordering higher temperature. However, the specific temperature for the
of the Li atoms and occupation of lithium sites.58 The tetragonal experimentally observed phase transition varies. Adams and
distortion dramatically affects lithium distribution and lowers Rao reported a tetragonal-to-cubic phase transition at 177 1C
the ionic conductivity by two orders of magnitude at room for LLZO based on in situ X-ray diffraction (XRD) results32 while
temperature as shown in Fig. 3.28,29,35,39,40,50–55,57,59,60 The Geiger et al., using XRD, reported the transition to occur
lower lithium-ion conductivity in t-LLZO (bulk conductivity B between 100 and 150 1C.59 Kokal et al.55 showed, using differential
1 10 6 S cm 1)29 vs. c-LLZO (bulk conductivity B 1 scanning calorimetry, that the phase transition temperature is
10 4 S cm 1)28 has been explained by Awaka et al.29 as suppressed much higher at approximately 700 1C. It is deemed necessary to
hopping between Li sites by the complete tetrahedral 8a–vacancy stabilize the cubic phase at room temperature to take advantage
ordering, and the decrease in equivalent Li positions in the of its high ionic conductivity.
tetragonal phase compared to the cubic garnet-related phase. A significant amount of work has focused on the inclusion
Recently, Meier et al.61 have explained the difference in the of dopants to stabilize the cubic phase and using various
mechanism of Li-ion conduction in tetragonal and cubic LLZO synthesis methods that usually require several calcination steps
by first-principles calculations. in the range 750–1230 1C and total synthesis times of over one
The study found that the motion of Li ions in t-LLZO is day.28,36,40,41,59,62–64 A study on the effect of sintering temperature
entirely collective or synchronous which can be interpreted as a on the structure and ionic conductivity of LLZO found that the
consequence of the ordering within the Li-ion sublattice and cubic structure forms in a temperature range of 1150–1230 1C,40
the lack of available vacancies. In c-LLZO, the mechanism is an and that below the sintering temperature of 1150 1C, a tetragonal
asynchronous type dominated by single-ion jumps and induced structure is formed. However, it was not mentioned whether care
collective motion (Fig. 2b).61 The chance of single-ion jumps was taken to avoid aluminum contamination during the prepara-
that can occur at much lower energetic cost than a fully tion. Some were able to retain the cubic phase LLZO at room
synchronous collective motion of several ions at the same time temperature without the addition of dopants such as Al, but also
(in t-LLZO) is increased due to a large number of vacancies and found that cubic dopant-free LLZO does not exhibit a significant
Table 1 Li7La3Zr2O12 (LLZO) and LLZO-derived compositions by element substitution and their corresponding selected physical properties. The typical synthesis method is the ceramic process, unless
indicated. Tetragonal and cubic LLZO: t-, and c-LLZO, respectively (RT – room temperature; NR – not reported; † – estimated from available conductivity)
Composition, method, maximum Relative Lattice parameter a (Å); Total conductivity Activation energy for total
annealing/firing T in air (1C) density (%) impurities, comments at RT (S cm 1) conductivity (eV)
‘‘No substitution’’
c-‘‘LLZO’’, 1230/36 h28 92 12.9682(6) 2.4 10 4 0.31
c-‘‘LLZO’’, 1180/36 h35 NR NR (cubic) 2.0 10 4 NR
c-‘‘LLZO’’, 1200/36 h39 89–92 12.97 2.4 10 4 0.34
c-‘‘LLZO’’, 1230/35 h40 96 12.955(6) 3.6 10 4 (30 1C) NR
c-‘‘LLZO’’, 1200/35 h40 95 12.954(9) 4 10 5 (30 1C) 0.46
c-‘‘LLZO’’, 1230/36 h41 NR NR (cubic) 1.8 10 4 NR
Energy & Environmental Science
t-LLZO, 1000/5 h29 60 a = 13.134(4); c = 12.663(8) 4.2 10 7 0.58†

(from single crystal sample)
t-LLZO, ceramic + vibration (auto-consolidation), 1150/15 h50 93 a = 13.122; c = 12.690 5.67 10 5 (30 1C) 0.35
t-LLZO, ceramic + hot pressing, 1050/1 h (Ar)51 98 a = 13.077(1); c = 12.715(4) 2.3 10 5 0.41
t-LLZO, 1200/24 h52 91 NR (tetragonal) 1 10 5 0.43
This journal is © The Royal Society of Chemistry 2019

t-LLZO, 1250/8 h53 73 NR (tetragonal) 1.28 10 6 0.46
t-LLZO, sol–gel (citrate–nitrate), 1100/1 h53 66 NR (tetragonal), La0.5Zr0.5O1.75 5.19 10 6 0.48
t-LLZO, ceramic + hot pressing, 1050/1 h (Ar)54 95 a = 13.0682; c = 12.70201, La2Zr2O7 5.77 10 6 0.40
t-LLZO, sol–gel (modified Pechini), 900/4 h55 NR a = 13.122(3); c = 12.672(3) 3.12 10 7 0.67
Li-Site substitution
Li6.4Al0.19La3Zr2O11.8, sol–gel, 1200/36 h62 NR 12.9720 1.4 10 4 0.34
1.2 wt% Al–Li7La3Zr2O12, sol–gel (Pechini), 1200/6 h71 B88 NR (cubic) 2.0 10 4 NR
Li6.24Al0.24La3Zr2O11.98, ceramic + hot pressing, 1000/1 h (Ar)76 98 NR (cubic), La2Zr2O7 4.0 10 4 0.26
Li6.28Al0.24La3Zr2O12, sol–gel, 1000/4 h84 NR NR (cubic) 4 10 4 0.41
‘‘Al-doped’’-LLZO, sol–gel, 1100/3 h85 NR 12.9713(2), LiAlO2, Li2ZrO3 3 10 4 0.27
Li6.42Al0.32La3Zr1.91O12.02, sol–gel, 1000/7 h86 88.2 12.97, Li2ZrO3 1.5 10 5 NR
Li6.25Ga0.25La3Zr2O12, 1100/24 h87 94.1 NR 1.46 10 3 0.25
Li6.10Ga0.30La3Zr2O12, 1100/24 h87 96.3 12.9746 1.12 10 3 0.25
Li6.55Ga0.15La3Zr2O12 (2 wt% Al2O3 added during sintering), 1075/12 h106 NR NR 2.06 10 3 0.246
Li6.25Fe0.25La3Zr2O12, 1230/6 h113 NR 12.97690(10) 1.38 10 3 0.28
Li6.6Ge0.10La3Zr2O12, sol–gel, 1150/6 h107 98 12.963 2.8 10 4 0.38
La-Site substitution
Li6.6La2.6Ce0.4Zr2O12, ceramic +hot pressing, 1050/ 1 h (Ar)54 96 13.020, La2Zr2O7, CeO2 1.44 10 5 0.48
1.7 wt% Sr (for La)–Li7La3Zr2O12 (Al-contaminated), 1200/24 h88 94 12.980 5 10 4 0.31
Li7.2La2.8Ca0.2Zr2O12 (Al-contaminated), 1200/10 h89 NR 12.96023(8), unidentified impurity 3.9 10 5 NR
Li7La2.8Nd0.2Zr2O12 (Al-contaminated), 1200/10 h89 NR 12.95672(6), LaAlO3 3.3 10 5 NR
Zr-Site substitution
Li6.4La3Zr1.6Ta0.6O12 (2.5 wt% Al contamination), 1140/16 h25 NR 12.923 B1 10 3 0.35
Li6.75La3Zr1.75Nb0.25O12, ceramic, 1200/36 h39 89–92 12.953 8.0 10 4 0.31
1.7 wt% Al + 0.1 wt% Si + Li7La3Zr2O12, 1230/36 h68 B95 Cubic 6.8 10 4 NR
Li6.75La3Zr1.75Ta0.25O12, co-precipitation, 1000/3–4 h72 96 12.96 8.7 10 4 0.22
Li6.6La3Zr1.6Sb0.4O12, 1100/24 h82 91 12.95955 7.7 10 4 (30 1C) 0.34
Li6.5La3Zr1.75Te0.25O12, 1100/15 h90 NR 12.9134 1.02 10 3 (30 1C) 0.38
Li7La3Zr1.7Ti0.3O12, 1180/20 h91 92.1 12.961(7) 4.16 10 4 (30 1C) 0.48
Li6.4La3Zr1.7W0.3O12, 1100/36 h92 NR 12.96507 7.89 10 4 (30 1C) 0.45
Li6.6La3Zr1.8Mo0.2O12, sol–gel, 1100/3 h93 92.8 12.963 5.09 10 4 (30 1C) 0.29
Li7.1La3Zr1.9Cr0.1O12, 1230/16 h94 NR 13.073 5.2 10 4 0.39
Li7.2La3Zr1.8Gd0.2O12, 1220/36 h95 93–95 12.961, La2Zr2O7 2.3 10 4 0.25
Li7.06La3Zr1.94Y0.06O12, 1200/6 h96 NR 12.9672 8.1 10 4 0.26
Li7.06La3Zr1.94Y0.06O12, 1100/12 h97 54 12.974(3), unidentified impurity B1 10 6 0.47
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Energy Environ. Sci., 2019, 12, 2957--2975 | 2961

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Activation energy for total

enhancement of ionic conductivity.46,65 Nowadays, doping with
ions with ionic radii66 that is close to the host ions is the
strategy of choice to promote the stabilization of the cubic
conductivity (eV)
LLZO phase at room temperature and to increase ionic
conductivity.31,39,58,64,67–78
0.254
0.327
2.2 Approaching the structural limit
0.47
0.31
0.33
0.30
0.27
0.29
0.32
0.30
0.32
0.31
0.26
NR
NR
NR
NR
Several studies53,54,59,76 have postulated that cation substitution
stabilizes the cubic phase by reducing the Li content or increasing
Total conductivity
the Li vacancy concentration while maintaining oxygen stoichio-

at RT (S cm 1)
metry. The exact amount of Li vacancy required to stabilize cubic

2.91 10 4
1.65 10 4
8.29 10 4
4.10 10 4
4.03 10 4
4.41 10 4
2.02 10 4
6.35 10 4
8.83 10 4
B1 10 6
3.4 10 4
1.9 10 5
3.7 10 4
4.1 10 4
1.8 10 3
3.6 10 4
5.5 10 4
LLZO has not been identified but it is believed to be between
0.125–0.5 mol of Li vacancy.54,76,79–81 LLZO with a higher amount
of Li vacancy concentration (0.4–0.5 mol) has been known to exhibit
a maximum in ionic conductivity at room temperature.25,30,52,79,82
Co-doping is also widely employed in the field, which has been
shown to not only stabilize the cubic structure but also improve the
12.995(2), unidentified impurity
Li transport. The site preference of possible dopants in LLZO was

recently calculated83 using density functional theory (DFT), and can
Lattice parameter a (Å);
serve as a starting point in the search for LLZO-based compositions

impurities, comments
with superior properties.

Many elements have been substituted in each of the
elemental components of LLZO in search of a technologically
12.9549(8)
12.9508(4)
12.970(2)
relevant solid Li-ion electrolyte. Substitutions that have been

13.0826
13.0721
12.9492
12.9897
12.9705
12.967
12.978
Cubic
Cubic
performed include Al, Fe, Ge, and Ga for Li; Sr, Y and Ce for La;
12.95
12.95
12.95
NR
and Nb, Ti, Ta, Sb, Mg, Sc, Zn, Ru, W, and Te for Zr. Table 1 lists
further details of sintering temperature and duration, relative
Between 55 and 82
densities, and activation energies for ionic conduction of un-doped

and doped LLZO.25,28,29,35,39–41,50–55,62,68,69,71,72,74,76,77,82,84–110 Fig. 4
compiles the effects of each dopant and its concentration on
density (%)
the Li-ion conductivity and lattice constant of the garnet at

Relative
93.23
96.32
room temperature for single component substitution (i.e., only

B75
96.6
93.8
90.7
96.7
96.4
95.1
NR
NR
54
98
98
93
90
Li, La or Zr, in Fig. 4a, b, and c, respectively). The Li content for

the composition that exhibits the maximum Li-ion conductivity
Li7La3Zr1.89Al0.15O12, sol–gel, 1150/1 h100 (x = 0.15 in Li7La3Zr2 0.75xAlxO12)
is shown in each elemental substitution.

0.3 mol Al-doped Li7La3Zr2O12 + 68 mol% Li3BO3, sol–gel, 900/10 h101
Li6.8La2.95,Ca0.05Zr1.75,Nb0.25O12, 790/40 h (Li3BO3 and Al2O3 additives
Fig. 4 illustrates that regardless of the site that is substituted

and regardless of the corresponding substitution element
in constant or varying lithium contents, the highest Li-ion
conductivities are obtained at lattice parameters in the range
Li6.45Ca0.05La2.95Ta0.6Zr1.4O12, solution method, 1125/6 h104
Li6.15Ga0.2La3Zr1.75Ta0.25O12, co-precipitation, 1000/3–4 h72
Li6.15Al0.2La3Zr1.75Ta0.25O12, co-precipitation, 1000/3–4 h72
Li6.65Ga0.15La3Zr1.90Sc0.10O12, sol–gel, 1200/6 h (dry O2)77
12.91–12.98 Å (marked by dashed lines). Substitutions that

result in lattice parameters outside this range exhibit lower
total Li-ion conductivity (the highest conductivity outside
Li6.375Al0.075La3Zr1.8Mo0.2O12, sol–gel, 1040/3 h105
Li5.72La2.98Ba0.02Zr1.65W0.35Al0.2O12, 1160/10 h109
this range is from Mg-substituted LLZO, 2.9 10 4 S cm 1,

Li6.52La2.98Ba0.02Zr1.9Y0.1Al0.2O12, 1160/10 h109
Li6.775Al0.05La3Zr1.925Sb0.075O12, 1170/6 h102
a = 13.0826 Å). The existence of an optimum lattice parameter

Li6.66La2.94Sr0.06Zr1.6Sb0.4O12, 1100/12 h110
has already been recognized in a study in which Nb was

Li6.5Ga0.2La2.9Sr0.1Zr2O12, 1100/6 h108
substituted for Zr while alkali earth metals with a variety of

Li7.16La3Zr1.84Y0.16O12, 1100/12 h97
Composition, method, maximum
Li7La3ZrNb0.5Y0.5O12, 1230/15 h99

Li7La3Zr1.95Mg0.1O12, 1075/12 h98
Li7La3Zr1.96Sc0.05O12, 1075/12 h98
ionic sizes (Mg, Ca, Sr, and Ba) were substituted for La in LLZO.111
The optimum lattice content seems to be between 12.94 and 12.96 Å,
annealing/firing T in air (1C)
both in compositions with constant lithium content and varying

lithium content by substitution. The trend of high Li-ion conductivity
(continued)
during sintering69)
within an optimum lattice parameter in LLZO follows what is

observed in all the other compositions in the garnet family.
Zeier30 noted an optimum lattice parameter at around 12.90–
Co-Doping
12.95 Å for the garnet family, which could have been slightly
Table 1
expanded depending on what is defined as ‘‘high conductivity.’’

It may seem that a simple lattice expansion will lead to expansion
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Fig. 4 Effect of elemental substitution in (a) Li, (b) La, and (c) Zr-sites on the conductivity and lattice parameter of LLZO. ‘‘Un-doped’’ c-LLZO exhibits
conductivities of 10 5–10 4 S cm 1 and a lattice parameter range of 12.95–12.97 Å. Refer to Table 1 for the references in each substitution. Ionic radii are
based on those given in ref. 66.
of Li-ion interstices for hopping that ultimately leads to high ionic or low Li concentration. Both structure and Li concentration
conductivity. However, computational work has shown that an extremes will result in Li-ion conductivity drop as reflected in the
expanded lattice offers marginal improvement in conductivity.75 peak features in conductivity in several of the dopants in Fig. 4.
The mechanism for the existence of maximum Li-ion conduc- Another feature in Fig. 4 is the Li content per formula unit (pfu) of
tivity within a lattice parameter range in LLZO is not rigorously the composition with the highest conductivity in each dopant. The
discussed. A computational study112 pointed out two examples on highest conducting LLZO-based compositions have Li contents
how the internal structural parameters such as the size or volume between 6.1 and 6.8 pfu, which are below the theoretical limit of
of the octahedral and tetrahedral Li-sites and the triangular 7.5.114 Fig. 5 summarizes the highest conductivities of the single-
window or ‘‘neck’’ (Fig. 2b) change with a dopant. In Ta-doped site substitution together with multi-site substitutions found in the
LLZO, the lattice contracts but both the site size for lithium and literature.25,28,29,35,39–41,50–55,62,68,69,71,72,74,76,77,82,84–106 Fig. 5 clearly
the neck area increase as Li vacancies increase. The site size and shows the clustering of the highest conducting compositions at
neck area increases are due to stronger Ta-ion pull on the Li contents between 6.1 and 6.8 and lattice constants between
neighboring O ions compared to Zr, with the LaO8 distorted cubic 12.91 and 12.98 Å, pointing to a possibility that an optimized
units remaining rigid against the Ta–O bond contraction. For limit of LLZO composition has already been reached. The
Al-doped compounds, the lattice expands with increased Al con- optimized limit for the garnet family, in general, has also
tent filling the tetrahedral site. The site sizes do not significantly been already pointed out by Zeier.30 The highest conductivity
change with Al-doping, but the neck size expands. Even though that has been achieved so far is 2.06 10 3 S cm 1 at room
Al3+ occupies the tetrahedral sites and is thought to be a ‘‘block- temperature for Li6.55Ga0.15La3Zr2O12106 – about an order of
ing’’ to Li conduction, its inclusion might turn out to be beneficial magnitude higher than the first LLZO synthesized in 2007
because of the corresponding increase in the average neck size.112 (3 10 4 S cm 1 at room temperature).28
The favorable effect on Li-sites and neck size will only exist It remains to be seen if researchers can still optimize the
in a particular window of doping concentration. Outside this composition of doped-LLZO to achieve a room temperature
window, the dopant is either low to cause changes or high that conductivity of greater than 2 10 3 S cm 1. Jalem et al.,78
it may no longer be accommodated in the garnet framework. using molecular dynamics simulation, calculated that high
It can also be the case that the substitution causes either high Li-ion conducting Ga-doped LLZO can reach a bulk Li-ion
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Fig. 5 Lithium-ion conductivity vs. nominal lithium content per formula

unit (pfu) and lattice constant of LLZO-based garnets. The highest con-
ducting compositions are clustered at lithium contents between 6.1 and
Fig. 6 Target thickness range of LLZO with the current achievable Li-ion
6.8 and lattice constants between 12.91 and 12.98 Å.
conductivities that will match the resistance of state-of-the-art liquid
electrolytes.115
conductivity of 6.08 10 3 S cm 1 at room temperature for the

x = 0.02 member in Li7 3xGaxLa3Zr2O12. This value may well be materials includes scalable, low-cost synthesis and processing
the upper limit of Li-ion conductivity for garnets considering methods that can retain the bulk material properties at reduced
that the Ga-doped LLZO samples exhibit one of the highest film thickness (o5 mm). Conventional solid-state synthesis
total conductivities reported in the literature.77,78,106 The calcu- is often the method of choice in producing dense ceramics
lated bulk Li-ion conductivity of the parent LLZO with the for evaluating the optimal composition. However, solid-state
tetragonal phase in the same study is about 1 10 5 S cm 1 synthesis typically lacks the flexibility to tailor grain sizes down
at room temperature.78 to the nanoscale. The electrical conductivities in Table 1 are
To date, the highest achieved Li-ion conductivity is still an generally reported using thick pellets. High-temperature sintering
order of magnitude lower than those of the common electro- also promotes Li2O loss; thus, the samples need to be covered
lytes for LIBs such as LiPF6 in ethylene carbonate (EC)/dimethyl in the same powder to mitigate evaporation.116 The sacrificial
carbonate (DMC) (B10 2 S cm 1).115 Nevertheless, the ohmic powder cover contributes to wastage of material and may not be
resistance of the LLZO can still be comparable to or even lower cost-effective in large-scale applications.
than that of a liquid electrolyte, which requires a separator in The approaches to obtain highly conductive LLZO thin films
the range 12–40 mm, if the thickness of LLZO is decreased by are summarized in Fig. 7.28,29,117–133 The conductivities at
employing thin-film manufacturing techniques as discussed in different temperatures of representative cubic and tetragonal
the next section. LLZO synthesized by the solid-state method (‘‘bulk’’) are also
Fig. 6 shows the calculated required thickness range of LLZO- shown for comparison. Further details about the data in Fig. 7
based materials with conductivities of 10 4 and 10 3 S cm 1 are listed in Table 2.28,29,117–133 Up to now, it has been possible
to meet an estimated range of resistance comparable to to obtain dense LLZO with conductivities similar to bulk LLZO
12–40 mm thick LiPF6 in EC/DMC with a typical conductivity sample values at reduced thicknesses in the micrometer range
of 1 10 2 S cm 1 and an area of 1 cm2. The relation between via a combination of nanoparticle powder formation by flame
the resistance and conductivity of an electrolyte is given by spray pyrolysis and tape casting.132,133 In general, regardless
R = (1/s) (t/A), where R is the resistance, s is the conductivity, of the synthesis method or deposition technique, films with
t is the thickness, and A is the area of the electrolyte. From Fig. 6, thicknesses less than a micrometer exhibit lower ionic conduc-
for LLZO with a conductivity of 10 3 S cm 1, the thickness should tivities than ‘‘bulk’’ values of LLZO (Fig. 7). Thin-film processing
be 1.2–4 mm to match the estimated resistance range of a in garnets can be challenging as the higher surface area to volume
conventional liquid Li-ion electrolyte. ratio of thin films accelerates Li2O loss.118,132,133 Thin films are
generally annealed or fired at temperatures o900 1C resulting in
low relative densities and crystallinity.118,119,132,133 Amorphous
3. Materials processing: structure and impurity phases are typical in thin films of LLZO-
microstructure and ionic conductivity based solid electrolytes.
Currently, one of the promising fabrication strategies for
As optimal compositions of LLZO-based ceramics are being LLZO as an electrolyte with demonstrated battery performance
realized, the next phase of study on these Li-stuffed garnet is tape casting. Wachsman and Hu’s groups have shown the
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Fig. 7 Conductivities at different temperatures of thin-film LLZO fabricated by various techniques: sol–gel (a-SG,117 b-SG,118 c-SG,119 d-SG120), pulsed
laser deposition (a-PLD,121 b-PLD,121 c-PLD,122 d-PLD,123 e-PLD,124 f-PLD125), chemical vapor deposition (CVD),126 radio frequency magnetron sputtering
(a-RFMS,127 b-RFMS,128 c-RFMS,129 d-RFMS,129 e-RFMS130), aerosol deposition (AD),131 and flame spray + tape casting (a-FS-TC,132 b-FS-TC133). The
conductivities of ‘‘bulk’’ cubic c-LLZO28 and tetragonal t-LLZO29 are shown for comparison.
feasibility of a bilayer framework of porous (B70 mm) and dense anode in Li-based batteries.140 Despite LLZO’s stability with Li,
(B20 mm) LLZO-based solid electrolytes fabricated by tape casting many studies report high interfacial area-specific resistance
for Li–S battery applications.33 The porous layer acts as a mechan- (ASR). Several hundreds to a couple of kO cm2 between the
ical support and sulfur cathode host while the dense layer separates garnet and lithium are typical,39,41,141–148 with one study
the Li and the cathode. Stable cycling of Li at 0.5 mA cm 2 for reporting an interfacial ASR as high as B180 kO cm2.149 These
300 h without Li dendrite formation using a porous/dense/porous studies point to a low contact area between Li and the garnet
LLZO framework was reported.34 In this case, the porous layer due to either poor adhesion or the presence of surface impurities
served as a host for the lithium as well as a mechanical support. such as Li2CO3. The direction of research in recent years has
Another fabrication strategy that can avoid the densification geared towards developing strategies to reduce the interfacial
and crystallinity issue in the formation of thin films of LLZO is resistance at the Li metal and garnet interface.27,150,151
to incorporate the as-synthesized highly conducting Li-garnets Fig. 8 shows an overview of the current strategies pursued to
into a Li-ion conducting polymer matrix and cast the ceramic– reduce the Li/LLZO interface ASR.139,144–147,152–166 Among the
polymer composite into a thin film. Polymers such as poly- reported techniques, heating Li near or at its melting point
(ethylene oxide) (PEO) offer mechanical stability, low cost, (180.5 1C) on the garnet surface is seen as the most straightforward
excellent forming ability, and Li-ion conductivity with the addition approach. After heating, the interfacial resistance has been
of a lithium salt (e.g., LiClO4, LiCF3SO3, and LiAsF6).134,135 Tao reported to drop to 25–28 O cm2 at room temperature.159,160
et al.136 have adopted the approach by preparing a composite of Aside from the poor adhesion between Li and LLZO due to
nanoparticles of LLZO and PEO and demonstrated a solid-state differences in mechanical properties,140,167 the formation of a
Li-S with a moderate specific capacity of 900 mA h g 1 at 37 1C. Li2CO3 passivation layer145,168–170 also hinders adhesion of Li to
the surface of LLZO. The Sakamoto group has demonstrated that
wet (glycol-based diamond paste) polishing the garnet surface before
4. Engineering the garnet–electrode heating Li onto the surface can further reduce the interfacial
interface resistance to 2 O cm2.145 The polishing was performed to remove
the Li2CO3 layer that formed during synthesis. Li et al. attempted to
4.1 Lithium metal/garnet interface avoid the Li2CO3 formation by including 2 wt% LiF during synthesis,
LLZO and the garnet family, in general, have excellent chemical which prevents the diffusion of moisture and CO2 in the garnet.162
and electrochemical stability with elemental Li24,27,28,138,139 – The addition of LiF has resulted in an ASR of 345 O cm2 between Li
the material widely considered as the ultimate choice as an and the garnet, compared to 1260 O cm2 without LiF addition.
Table 2 LLZO-based thin films prepared by various techniques. PLD – pulsed laser deposition, RF – radio frequency, MOCVD – metal organic vapor deposition, LA-CVD – laser-assisted chemical
Review
vapor deposition. RT – room temperature, NR – not reported
Maximum annealing/firing T (1C), Phase, impurity, lattice Total conductivity at Activation energy for
Method Composition, thickness atmosphere, substrate parameter (if reported) RT (S cm 1) total conductivity (eV)
Sol–gel, spin coating117 ‘‘LLZO’’, 760 nm 400/4 min, air, MgO(100) ‘‘Nanocrystalline’’, La2Zr2O7 B1 10 6 (43 1C) 0.6
(in-plane)
118
Sol–gel, dip coating ‘‘0.3 mol% Al + LLZO’’, 50 nm 900 (duration NR) + Li2CO3 powder, Cubic (minor phase), 2.8 10 7 0.61
air, MgO La2Zr2O7 (major phase)
6
Sol–gel + lithium dodecylsulfate, ‘‘0.3 mol% Al + LLZO’’, 50 nm 900 (duration NR) + Li2CO3 powder, Cubic, LaAlO4, 2.4 10 0.52
dip coating118 air, MgO
6
Sol–gel, spin coating119 ‘‘0.3 mol% Al + LLZO’’, 300 nm 600/10 min, air, Si Amorphous, La2Zr2O7 1.67 10 0.18
Sol–gel, dip coating120 ‘‘0.2 mol% Y + LLZO’’, 50 nm 800/10 min, air, Aluchrom alloy Cubic, unidentified impurity 3.4 10 8 (45 1C) NR
5
PLD121 Li4.7Al0.65La3Zr2.04O11.9, 30.4 nm 700/10 min (pO2 = 3.3 Pa) Cubic(111), 13.019(2) out-of- 1 10 0.52
Gd3Ga5O12(111) plane, 13.022(1) in-plane
2966 | Energy Environ. Sci., 2019, 12, 2957--2975

6
PLD121 Li4.8Al0.71La3Zr1.96O11.9, 26.2 nm 700/10 min (pO2 = 3.3 Pa), Cubic(001), 13.023(1) out-of- 2.5 10 0.55
Gd3Ga5O12(001) plane, 13.042(2) in-plane
PLD122 Li4.79La3Zr1.92O10.79, 200 nm 600/(duration NR) (pO2 = 1.33 Pa), Mainly amorphous with tet- 1.6 10 6 0.35
MgO(100) ragonal + cubic thin layers, (extrapolated)
La2Zr2O7
PLD123 Li6.19Al0.28La3Zr1.75Ta0.25O12 d, 300 (duration NR) (pO2 = 1.3 Pa), Amorphous 2.39 10 8 0.613
300 nm Si3N4 (extrapolated)
124
PLD Li6.22Al0.26La3Zr2O12 (target com- 50 (pO2 = 1.33 Pa), MgO(100), Cubic, La2Zr2O7, Li2CO3 1.2 10 3 (325 1C) 1.39 (o300 1C), 0.67
position), 380 nm annealing at 600/24 h + LiOH (4300 1C)
7
PLD125 ‘‘LLZO’’, 1 mm RT/(duration NR) (pO2 = 40 Pa), Amorphous 3.35 10 0.36 (no Arrhenius in
SrTiO3(100) the paper)
7
PLD125 ‘‘LLZO’’, 1 mm 800/30 min (pO2 = 40 Pa), SrTiO3(100) Cubic 1.78 10 0.41 (no Arrhenius in
the paper)
6
LA-CVD126 ‘‘LLZO’’, 850 nm Flow = 40% O2 in Ar, Pt Tetragonal (a = 13.061(2), 4.2 10 0.5
c = 12.744(2)), Li2PtO3, La2O3
MOCVD137 Li7.7La2Zr2O12.1, B5 mm 900–950/, total pressure = 400 Pa, Cubic NR NR
Al2O3
MOCVD137 ‘‘LLZO’’, B5 mm 750–850/, total pressure = 400 Pa, Tetragonal NR NR
Al2O3
7
RF magnetron sputtering127 ‘‘LLZO’’, 561 nm 0.67 Pa, RF power = 40 W, stainless Amorphous 4 10 0.7
steel (SUS)
4
RF magnetron sputtering128 Li7.9Al0.2La3Zr1.6Ta0.4O12.9 (target Ar at 0.5 Pa, RF power = 1.2 W cm 2, Cubic 1.2 10 (in-plane) 0.47
composition, Al from contamina- substrate T = 700 1C, Aluchrom YHf
tion), B1.8 mm
RF magnetron co-sputtering129 Li6.58Ga0.14La3Zr2O12 (target com- Ar at 0.05 Pa, RF power = 2.5 W cm 2 Cubic (a = 12.954), Ga- 1.6 10 5 (30 1C) 0.66 & 0.38 (see
position, co-sputter from LLZO, LLZO, 5 W cm 2 Li2O, 3 W cm 2 containing secondary phases (in-plane) ref. 129 for relaxation
Li2O, and Ga2O3), 500 nm Ga2O3, annealing at 700/2 h in O2, function fitting)
MgO(100)
6
RF magnetron co-sputtering130 Li–La–Ti–Zr–O from co-sputtered 1.2 Pa (Ar : O2 = 1 : 1), 300 1C substrate Amorphous, unknown 2.83 10 NR
Li0.33La0.56TiO3 and LLZO, temperature, annealing at 300/2 h in impurity phase
611.5 nm O2, Tin-doped indium oxide/glass
8
Aerosol deposition131 1 wt% Al + LLZO, 20 mm LiFePO4 on stainless steel, air Cubic 1.0 10 (140 1C) 1.3
3
Flame spray pyrolysis, tape- Li6.25Ga0.25La3Zr2O12, 25 mm 1130/0.3 h, air Cubic + tetragonal 1.3 10 0.28
casting132
4
Flame spray pyrolysis, tape- Li6.25Al0.25La3Zr2O12 + 50 wt% 1090/1 h, air Cubic 2.0 10 0.35
casting133 excess lithium, o30 mm
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Energy & Environmental Science
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Fig. 8 ASR comparison before (‘‘unmodified’’) and after modification (‘‘modified’’) strategies to improve the lithium metal /LLZO interface contact.
Current techniques include atomic layer deposition (ALD),139,147 sputtering,152–154 wet processing,155,156 thermal evaporation,144,157 polishing,145,158
heating,159,160 and other strategies.146,161–166
Among all the techniques reported, atomic layer deposition garnet. Various attempts have been made in order to ensure
(ALD) of Al2O3 has shown to be the most successful by reducing good contact between the garnet and cathode materials. Ohta
the ASR from 1710 to 1 O cm2 at room temperature.139 et al. were able to apply LiCoO2 (LCO) onto Li6.75La3Zr1.75Nb0.25O12
Upon heating Li on the ALD treated garnet, the lithiated Al2O3 by pulsed laser deposition.172 The ASR at the cathode interface
appears to increase the contact area while impeding the for- under a 3.95 V vs. Li/Li+ charge state was determined to be
mation of Li2CO3 impurities.139 Although very effective, ALD’s 170 O cm2, comparable to that of a liquid organic electrolyte.
implementation in commercial applications may be hard due Annealing cathode powders to the garnets has also been
to its current high cost and operational complexity.171 Simple performed. For example, Liu and colleagues coated V2O5 onto
polishing, or other scalable methods may be more appealing a Li7La2.75Ca0.25Zr1.75Nb0.25O12 pellet and the assembly was
for mass-market applications. One example is the wet processing heated to 800 1C for 10 s.173 The room temperature ASR of
technique developed by the Thangadurai group,155 in which a the assembly was 71 O cm2 based on equivalent circuit fitting of
Zn(NO3)2 solution is uniformly distributed on the garnet surface the impedance spectra. Similar annealing techniques were
and thermally decomposed to form ZnO. Another example is the performed by Park et al. in which LCO was heated on the LLZO
insertion of a gel interlayer composed of poly(vinylidene fluoride- surface at 700 1C for 6 h.174 However, time-of-flight secondary
co-hexafluoropropylene) PVDF–HFP soaked in a liquid electrolyte ion mass spectrometry and X-ray diffraction measurements
between the garnet and lithium metal anode.156 Another confirmed that upon heating, LCO causes the cubic LLZO
intriguing and potentially scalable strategy, which addresses phase to degrade to the tetragonal phase.
the issue from the lithium metal side instead of the garnet side, In addition to conventional intercalation cathode materials,
is the formation of a lithium–graphite composite anode as interfaces with next-generation cathode materials have been
reported by Duan et al.166 The Li–C composite was prepared studied, specifically with sulfur.33,136,175–177 Fu et al. demon-
by adding commercially available graphite powder in molten Li strated that the cubic LLZO phase was retained after mixing
with continuous stirring on a hotplate at 250 1C. The composite with molten sulfur; however, computational and experimental
is cast onto the garnet surface and delivers an interfacial results indicated that a passivation layer composed of Li2S and
resistance as low as 11 O cm2. For comparison, the pure Li2SO4 formed at the sulfur|LLZO interface.175
Li–garnet interface shows a resistance of 381 O cm2.166 Currently, to demonstrate a working Li battery, researchers
typically add a ‘‘small amount’’ of conventional liquid electro-
4.2 Cathode/garnet interface lyte between the garnet and the cathode.139,152 While removing
The cathode|garnet interface is currently less studied than the liquid electrolytes from commercial batteries and transitioning
lithium|garnet interface. However, as success in decreasing to all-solid-state batteries is ideal, the high interfacial resistance
the resistance at the Li|garnet interface is being realized, few between the garnet and cathode material remains a persistent
groups are beginning to investigate the cathode interface with problem; hence, liquid electrolytes may still stay for a while in
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some future battery designs. This strategy of garnet–liquid hybrid LiCoO2 and LLZO by radio frequency (RF) magnetron
electrolyte makes sense since it carries the advantages of reducing sputtering.181 The cell with the thin layer showed an initial
the high interfacial resistance between the garnet and the cathode discharge capacity of 80 mA h g 1 at a current density of 1 mA cm 2
and blocking lithium dendrite formation. while the cell without the Nb layer showed an initial discharge
Only a few reports have looked closely at the performance of capacity of 50 mA h g 1.
batteries with hybrid LLZO and liquid electrolytes.178–180 The Table 3 summarizes the performance of Li batteries that
characteristic finding from the studies is that although the cells involve LLZO as an electrolyte or a separator.33,39,41,69,136,139,144,
152,156,159,161,163,166,172,173,175,178,181–206
with hybrid electrolytes show consistently higher capacities Capacities close to
than all-solid-state cells, the hybrid cells show poorer cyclability practical values are attainable with LLZO when appropriate
and lower capacities than conventional liquid batteries.178–180 configuration or interface modifications are employed. How-
Xu et al. postulated that the poor cycling of cells with hybrid ever, much work is still required to demonstrate cells that
electrolytes is due to the Li+/H+ exchange on the garnet surface can be cycled much more than 500 times (possibly 5000 times)
in contact with the liquid electrolyte and the formation of and are capable of working at higher current densities
a resistive solid–liquid electrolyte interphase.178 A superbase (40.5 mA cm 2) or C-rates (41C). Also, many cathode materi-
n-BuLi and 1 M LiPF6 ethylene carbonate (EC)/dimethyl carbonate als are yet to be paired with LLZO-containing electrolytes.
(DMC) liquid electrolyte were added to Li6.5La3Zr1.5Ta0.5O12 to Recent studies of LLZO that report battery performance either
prepare a stable hybrid electrolyte. A hybrid electrolyte-based modify the surface layer of LLZO or uses LLZO as a part of a
LiFePO4/Li cell retained its capacity after 400 cycles at current composite or a hybrid electrolyte to address issues regarding
densities of 100 and 200 mA cm 2 at room temperature, while physical contact and chemical or electrochemical stability
batteries with no n-BuLi showed a rapid decrease in capacity between LLZO and the electrode. For example, Han and
after 10 cycles.178 co-workers were able to demonstrate a working cell with a high
voltage Li2FeMn3O8 (LFMO) cathode, an Al2O3-treated LLZO
(via ALD) electrolyte, and a Li anode. The cell capacity was
5. LLZO-based solid-state Li batteries 103 mA h g 1 (73% of the theoretical value of LFMO) at 0.1C at
room temperature (RT).139 It is also important to note that a
The first example of a solid-state battery with a LLZO-based small amount of liquid electrolyte was added between the
electrolyte using a LiCoO2 cathode and a Li anode was carried garnet and the cathode. He et al. demonstrated a battery with
out by Kotobuki et al. in 2010.41 A very low specific capacity of sputter-coated, Sn thin film-garnet electrolytes.152 The cell with Sn
15 mA h cm 2 and poor cycle life were obtained, and a high thin film-modified garnet delivered excellent performance as evi-
resistance associated with the electrolyte–electrode interface was denced by a slightly higher discharge capacity of 151.7 mA h g 1
realized. To deal with the interfacial resistance, Ohta et al. used with a LiFePO4 cathode at RT compared to a cell with a conven-
the pulsed laser deposition (PLD) method to deposit LiCoO2 onto tional liquid electrolyte (B143 mA h g 1).152 A small amount of
the garnet electrolyte and found enhanced capacity (129 mA h g 1) liquid electrolyte was also added between the garnet and the
as well as good cyclability (98% retention after 100th cycle) at 25 1C cathode in this study.
at a rate of 0.1C.172 Although promising, PLD is rather expensive Other surface modification strategies also lead to enhanced
for mass production of batteries.171 battery performance compared to bare LLZO as the electrolyte.
Ohta and co-workers69 have also attempted to co-sinter For example, a cell with a LiFePO4 cathode and with LLZO
a Li6.8(La2.95,Ca0.05)(Zr1.75,Nb0.25)O12 (with Li3BO3 additive) coated with polymer gel interlayers (PVDF–HFP with liquid
electrolyte with LiCoO2 at 790 1C to obtain a better interfacial electrolyte) on both sides as the electrolyte shows a specific
contact. However, the charge and discharge capacities of the capacity of 140 mA h g 1 at 1C at room temperature with stable
battery with a Li anode were only 98 and 78 mA h g 1, performance over 70 charge–discharge cycles.156 In another
respectively, which correspond to about 72 and 58% of work, a toothpaste-like cathode LiNi0.5Co0.2Mn0.3O2 that contains
the theoretical capacity. Since the study found no chemical an ionic liquid as a wetting agent has been introduced and cast
reaction between LCO and the garnet, the low capacity was on a garnet electrolyte surface. This method delivered a high
attributed to the processing (e.g., powder preparation and specific capacity of 175 mA h g 1 at 0.1C and stable perfor-
co-sintering conditions) that was not optimized. The study, mance for 500 cycles.161
however, did not consider the electrochemical nature of the Another strategy employed currently is the formation of a
garnet–LCO interface. Park et al.174 looked into the electro- composite of LLZO with a polymer. The ‘‘softness’’ of polymers
chemical properties at the interface, and suggested that it in a composite polymer electrolyte provides lower interfacial
is crucial to avoid direct contact between LiCoO2 and LLZO resistance (or ASR) with the electrode material than the pure
since the cubic phase of LLZO transforms into tetragonal after ceramic electrolyte.207 Garnet particles in PEO, PVDF–HFP, and
reacting with LiCoO2.174 It was found that surface modification polyethylene carbonate matrices have been successfully employed as
between LCO and LLZO (e.g., addition of Li3BO3) can hinder solid electrolytic membranes in ASLBs in recent studies.188,192,193,208
chemical cross-contamination.174 Kato and co-workers further A capacity of 120 mA h g 1 was obtained for LiFePO4 at 25 1C
explored the idea of adding an interlayer to separate LLZO and with 0.5C rate using a PVDF–HFP–Li7La3Zr2O12 composite
LiCoO2 by introducing a thin layer (10 nm) of Nb between electrolyte.194 Another report on poly(propylene carbonate)-based
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Table 3 Lithium metal batteries with LLZO as the electrolyte or part of the electrolyte or separator. RT – room temperature (exact temperature not
mentioned in the study). PEO – poly(ethylene oxide), EC – ethylene carbonate, DEC – diethyl carbonate, PVDF–HFP – poly(vinylidene fluoride-co-
hexafluoropropylene), LiTFSI – lithium bis(trifluoromethanesulfonyl)imide, DOL – dioxolane, DME – 1,2-dimethoxyethane
C-rate or current Capacity Number T

Year Electrolyte Cathode density (mA h g 1) of cycles (1C)
2010 Li7La3Zr2O1241 LiCoO2 2 mA cm 2 0.015 3 RT
2011 Li6.75La3(Zr1.75, Nb0.25)O1239 LiCoO2 3.5 mA cm 2 125 25 25
2012 Li6.75La3Zr1.75Nb0.25O12172 LiCoO2 3.5 mA cm 2 129 100 25
2014 Li6.8(La2.95,Ca0.05)(Zr1.75,Nb0.25)O1269 LiCoO2 1 mA g 1 (0.01C) 78 — 25
2014 Li7La3Zr2O12 with Nb interlayer181 LiCoO2 1 mA cm 2 80 25 RT
2014 Li7La3Zr2O12182 LiFePO4 35 mA cm 2 0.012 (mA h cm 2) 65 140

2016 Li7La2.75Ca0.25Zr1.75Nb0.25O12 with ALD deposited-Al2O3139 Li2FeMn3O8 0.1C 103 50 22
2016 Li7La3Zr2O12174 LiCoO2 0.2C 35 10 50
2016 Li7La3Zr2O12183 Amorphous TiS4 0.01 mA cm 2 500 15 25
2016 Li6.25Al0.25La3Zr2O12184 Li4Ti5O12 2–8 A kg 1 15 25 95
(anode material)
2016 Li6.4La3Zr1.4Ta0.6O12–PEO composite185 LiFePO4 0.1C 141.5 200 60
2017 Li7La2.75Ca0.25Zr1.75Nb0.25O12 bilayer33 S 200 mA cm 2 645 32 22
2017 Li6.85La2.9Ca0.1Zr1.75Nb0.25O12 with Ge layer144 LiFePO4 1C 140 100 RT
2017 Li7La2.75Ca0.25Zr1.75Nb0.25O12 with PVDF–HFP interlayer156 LiFePO4 50 mA cm 2 140 70 RT
2017 Li7La2.75Ca0.25Zr1.75Nb0.25O12173 V2O5 50 mA g 1 150 28 100
2017 Li7La3Zr2O12 + LiTFSI in DME/DOL175 S 200 mA g 1 1000 100 RT
2017 Li7La3Zr1.5Ta0.5O12 with 1 MLiPF6 in EC : DEC (1 : 1) + n-BuLi178 LiFePO4 100 mA cm 2 176.7 400 RT
2017 Li6.5La3Zr0.5Ta1.5O12 with PEO–LiTFSI layer186 LiFePO4 0.5 mA cm 2 141 300 80
2017 Li6.4La3Zr1.4Ta0.6O12 fillers in PEO/LiClO4 matrix187 LiFePO4 1C 140 500 60
2017 Al/Nb codoped-Li7La3Zr2O12 fillers in PEO/LiClO4 matrix136 S (in LLZO@carbon) 0.05 mA cm 2 900 90 37
2017 Li7La2.75Ca0.25Zr1.75Nb0.25O12 with ultrathin Al coating and LiFePO4 0.1 mA cm 2 132 100 20
1 MLiPF6 in EC : DEC (1 : 1)163
2017 Li6.4La3Zr1.4Ta0.6O12–PEO composite wet by ionic liquid188 LiFePO4 0.1C 133.2 150 25
2017 Li6.20Ga0.30La2.95Rb0.05Zr2O12189 LiFePO4 0.05C 152 20 60
2017 Li6.75La3Zr1.75Ta0.25O12–PVDF composite190 LiCoO2 0.4C 150 120 RT
2017 Li6.4La3Zr1.4Ta0.6O12191 Air (active carbon) 20 mA cm 2 1000 (of carbon) 50 80
2018 Li6.375La3Zr1.375Nb0.625O12 with Sn thin film152 LiFePO4 0.1C 151.7 100 RT
2018 Li6.5La3Zr1.5Ta0.5O12 (react with carbon at 700 1C)159 LiFePO4 100 mA cm 2 143 50 65
2018 Li6.5La3Zr1.5Ta0.5O12 (react with carbon at 700 1C)159 S 200 mA cm 2 800 60 65
2018 Li5.9Al0.2La3Zr1.75W0.25O12 with graphite layer161 LiNi0.5Co0.2Mn0.3O2 0.1C 175 500 RT
2018 Li6.25Al0.25La3Zr2O12–poly(ethylene carbonate)–polyvinylidene LiFePO4 1C 121.4 100 55
fluoride composite192
2018 Li6.4La3Zr1.4Ta0.6O12–PEO composite193 LiFePO4 0.2C 139.1 100 55
2018 Li7La3Zr2O12–PVDF–HFP composite194 LiFePO4 0.5C 110 180 25
2018 Li6.4La3Zr1.4Ta0.6O12195 LiFePO4 (Si anode) 8 mA cm 2 120 100 RT
2018 Li6.25La3Zr2Al0.25O12 with LiBr196 LiCoO2 0.02C 111.6 70 20
2018 Li7La3Zr2O12197 LiCoO2 210 mA cm 2 119.3 45 RT
2018 Li6.75La3Zr1.75Ta0.25O12198 LiNi0.5Co0.2Mn0.3O2 10 mA cm 2 76.6 5 80
2018 Li6.4La3Zr1.4Ta0.6O12–MgO composite199 S 0.1C 800 20 RT
2018 Li6.4La3Zr1.4Ta0.6O12200 S 390 mA cm 2 560 40 25
2019 Li6.5La3Zr0.5Ta1.5O12 with PEO–LiTFSI layer201 LiFePO4 0.2C 135 200 90
2019 Li7La2.75Ca0.25Zr1.75Nb0.25O12 with Ag layer202 LiMn2O4 0.2C 108 100 23
2019 Li6.4La3Zr1.4Ta0.6O12 rapid acid treated surface203 LiFePO4 0.1C 142.7 150 30
2019 Li6.4La3Zr1.4Ta0.6O12 rapid acid treated surface203 LiCoO2 0.1C 116 100 30
2019 Li6.5La3Zr1.5Nb0.5O12–PEO composite204 LiFePO4 0.05C 98.1 30 40
2019 Li7La3Zr2O12205 LiCoO2 50 mA cm 2 110 100 50
2019 Li7La3Zr2O12 nanofiber–PVDF–HFP composite206 LiFePO4 0.2C 119 120 RT
2019 Li6.5La3Zr1.5Ta0.5O12 (Li-graphite anode)166 LiFePO4 0.5C 158 100 RT
composite electrolytes shows an excellent capacity retention of Li-ion reduction through electron gain, and Li metal formation by
86.1% after 200 cycles for a Si anode.203 electron transfer due to electronic conduction in the garnet.
Besides interfacial resistance, a common problem with A recent study209 in which the researchers were able to visualize,
LLZO electrolytes is the formation of Li dendrite despite LLZO’s in real-time, the lithium dendrite growth in LLZO has suggested
high mechanical strength.27 Typically, Li/LLZO/Li cells short that the electronic conductivity of LLZO (10 8–10 7 S cm 1) is
circuit due to dendrite formation at current densities less than mostly responsible for the dendrite formation. Thus, future
0.9 mA cm 2.27,209 Further details on studies about dendrite studies should consider looking at the electronic conductivity of
formation and dendrite mitigating strategies can be found in the the garnet to suppress Li dendrite formation.
recent review article.27 Dendrite formation is thought to originate Beyond Li-ion batteries such as Li–S and Li–O2 are also investi-
from several mechanisms180 including high localized current gated with the garnet-type solid electrolytes.33,136,175,191,199,200
concentrations created by surface flaws, roughness, and/or wet- A promising study for solid-state Li–S batteries with garnet electro-
ting incompatibility, isolated Li-metal agglomerate formation by lytes so far has been the fabrication of bilayer electrolytes. A high S
View Article Online
loading of 7.5 mg cm 2 was achieved with this structure and a high or thick counterparts. The lower conductivity is due to the reduced
specific capacity of 645 mA h g 1 was obtained.33 The composite crystallinity of thin-film LLZO, which is caused by the inherent
route is another option for solid-state Li–S batteries. For example, a higher rate of Li2O loss in nano-size grains of LLZO during
composite of nanoparticles of LLZO and PEO–LiClO4 was success- thin-film processing. Tape casting and incorporation of the LLZO
fully employed as an electrolyte in a solid-state Li–S battery with a into a matrix that can be cast (e.g., a polymer) were found to be the
specific capacity of 900 mA h g 1 at 37 1C.136 promising routes for commercial applications.
Battery technologies that use LLZO and involve air and
moisture during operation may seem tricky because of the Lithium batteries with LLZO
reactivity of garnets with H2O and CO2.27,150 A rechargeable The chemical and electrochemical stability of the LLZO electro-
Li–O2 battery using a Li6.4La3Zr1.4Ta0.6O12 (LLZTO) electrolyte, lyte with lithium metal allows for a much higher energy density
a Li anode, and a composite cathode consisting of LLZTO, lithium battery compared to state-of-the-art liquid electrolyte-based
bis(trifluoromethanesulfonyl)imide (LITFSI), and active carbon Li-ion batteries. Numerous configurations of batteries with LLZO
was reported.191 The cell was operational at 80 1C for 50 cyles and Li have been studied over the last decade. Early trials of solid-
with a cutoff discharge capacity of 1000 mA h g 1 at a current state batteries revealed cathode capacities that are significantly lower
density of 20 mA cm 2. The proposed reaction route for discharge than the values obtained in practice from commercial Li-ion
is the formation of Li2O2 by reduction of O2 in the cathode batteries. Researchers then realized that interfacial issues between
followed by the reaction of Li2O2 with CO2 in air to form Li2CO3. LLZO and both electrodes (Li anode and cathodes) must be
During charging, Li2CO3 is electrochemically decomposed, at least addressed to make solid-state Li batteries commercially appealing.
partially, accompanied by the release of CO2. Chemical stability of Studies initially focused on reducing the resistance at the Li–LLZO
garnets under aqueous LiCl and LiOH was also studied to develop interface. A significant reduction of Li|LLZO interfacial ASR to
Li metal aqueous batteries.60,210,211 Further experimental and 1 O cm2 can be realized by the ALD technique. However, it remains
theoretical studies are needed in the area of application of to be seen whether adopting the technique can be cost-effective in
LLZO as an electrolyte or a separator in Li–air batteries. the future. Various simple techniques such as polishing, heating,
and wet processing were proposed to lower the Li|garnet interfacial
resistance. Research on reducing the interfacial resistance at the
6. Summary and outlook Li-cathode|LLZO interface has only started to gain interest in the last
few years. To date, the simplest method to address the interface
The attractive properties of Li-stuffed garnets make them one of
issue has been to add a small amount of liquid electrolyte between
the most promising options for all-solid-state Li batteries.
the garnet and cathode. This hybrid solid–liquid electrolyte may be a
Improvements in transport properties, synthesis and fabrica-
viable option for commercial batteries, but further understanding of
tion methods, and batteries based on garnet-type Li7La3Zr2O12
the underlying interface mechanisms is needed. In general, capa-
(LLZO) have been made since 2007. This review highlighted the
cities close to practical values are attainable with LLZO incorporated
key findings and challenges from more than a decade of work
into full cells when appropriate configuration or interface modifica-
in each of the three areas that are critical in realizing LLZO as a
tions are employed. However, the number of cycles is less than 500
membrane in solid-state batteries.
and at rather low C-rates (o1C).
Transport properties
Through an understanding of the crystal structure and the Conflicts of interest
ensuing optimization of the garnet framework by elemental
substitution, researchers have been able to increase the Li-ion There are no conflicts to declare.
conductivity of LLZO by an order of magnitude within a few
years. However, examination of the conductivities of LLZO-based Acknowledgements
compositions studied so far has revealed that researchers may
have already reached the optimum for crystal structure and Li+ One of us, V. T., thanks the Natural Sciences and Engineering
concentration for this family of Li-stuffed garnets. Still, the Research Council of Canada (NSERC) and the University of
improvement in Li-ion conductivity has already reached a point Calgary for providing the infrastructure for energy storage and
where the required thicknesses of the solid electrolyte are within conversion materials research. We thank Dr Suresh Mulmi for
the reach of commercially viable techniques of battery fabrication. his help on crystal structure illustration.
Synthesis and fabrication methods

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Energy &

A bird’s-eye view of Li-stuﬀed garnet-type

Li7La3Zr2O12 ceramic electrolytes for advanced

1. Introduction LiPF6 dissolved in organic solvents8 has undoubtedly enjoyed a

Review Energy & Environmental Science

Dr. Alfred Junio Samson is a Kyle Hofstetter completed his

Sourav Bag obtained his MSc Dr. Venkataraman Thangadurai

Energy & Environmental Science Review

Review Energy & Environmental Science

In theory, diﬀerent Li-diﬀusion pathways are possible,30 but

hedral sites, bypassing their common tetrahedral neighbor as

t-LLZO, 1000/5 h29 60 a = 13.134(4); c = 12.663(8) 4.2 10 7 0.58†

This journal is © The Royal Society of Chemistry 2019

Energy Environ. Sci., 2019, 12, 2957--2975 | 2961

Review Energy & Environmental Science

Activation energy for total

the Li vacancy concentration while maintaining oxygen stoichio-

metry. The exact amount of Li vacancy required to stabilize cubic

Li transport. The site preference of possible dopants in LLZO was

serve as a starting point in the search for LLZO-based compositions

with superior properties.

relevant solid Li-ion electrolyte. Substitutions that have been

densities, and activation energies for ionic conduction of un-doped

the Li-ion conductivity and lattice constant of the garnet at

room temperature for single component substitution (i.e., only

Li, La or Zr, in Fig. 4a, b, and c, respectively). The Li content for

is shown in each elemental substitution.

Li6.8La2.95,Ca0.05Zr1.75,Nb0.25O12, 790/40 h (Li3BO3 and Al2O3 additives

Fig. 4 illustrates that regardless of the site that is substituted

Li6.65Ga0.15La3Zr1.90Sc0.10O12, sol–gel, 1200/6 h (dry O2)77

12.91–12.98 Å (marked by dashed lines). Substitutions that

Li5.72La2.98Ba0.02Zr1.65W0.35Al0.2O12, 1160/10 h109

this range is from Mg-substituted LLZO, 2.9 10 4 S cm 1,

a = 13.0826 Å). The existence of an optimum lattice parameter

has already been recognized in a study in which Nb was

substituted for Zr while alkali earth metals with a variety of

Li7La3ZrNb0.5Y0.5O12, 1230/15 h99

both in compositions with constant lithium content and varying

within an optimum lattice parameter in LLZO follows what is

expanded depending on what is defined as ‘‘high conductivity.’’

Energy & Environmental Science Review

Review Energy & Environmental Science

Fig. 5 Lithium-ion conductivity vs. nominal lithium content per formula

conductivity of 6.08 10 3 S cm 1 at room temperature for the

Energy & Environmental Science Review

vapor deposition. RT – room temperature, NR – not reported

2966 | Energy Environ. Sci., 2019, 12, 2957--2975

This journal is © The Royal Society of Chemistry 2019

Energy & Environmental Science Review

Review Energy & Environmental Science

Energy & Environmental Science Review

C-rate or current Capacity Number T

2014 Li7La3Zr2O12182 LiFePO4 35 mA cm 2 0.012 (mA h cm 2) 65 140

Review Energy & Environmental Science

Synthesis and fabrication methods

Energy & Environmental Science Review

ChemSusChem, 2015, 8, 2154–2175. 38 R. Wagner, G. J. Redhammer, D. Rettenwander, A. Senyshyn,

Review Energy & Environmental Science