Ionics

https://doi.org/10.1007/s11581-022-04765-3

REVIEW

Recent advances in NASICON‑type oxide electrolytes for solid‑state

sodium‑ion rechargeable batteries
Kushal Singh1 · Anjan Chakraborty1 · Raghunayakula Thirupathi1 · Shobit Omar1,2

Received: 12 June 2022 / Revised: 25 August 2022 / Accepted: 18 September 2022

© The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature 2022

Abstract
Solid-state batteries have shown the potential to resolve the safety and durability issues associated with traditional liquid
electrolyte-based batteries. This article reviews the current developments of NASICON-type solid electrolytes for Na-ion
solid-state batteries. These ceramic-based oxides possess a 3D open-framework structure allowing for the fast diffusion of
large sodium ions. To date, the conductivity value as high as ~ 5 mS·cm−1 at 25 °C is reported for these materials, which needs
to be further improved. The requirement of high-temperature sintering (> 1200 °C), anisotropic thermal expansion, impurity
phase formation, and large interfacial impedance are other challenges of NASICON-type electrolytes. This article summa-
rizes various fundamental aspects governing the sodium-ion conduction in these oxides. Particular emphasis is given to the
strategies employed in recent investigations to improve the properties and alleviate the associated issues in designing stable
solid-state sodium-ion rechargeable batteries. This will also establish the groundwork for future research in these materials.

Keywords  Sodium ions · Inorganic solid electrolytes · Ionic conductivity · All-solid-state batteries · Interfaces

Introduction first commercialization by SONY Energytec in 1991 for the

The ever-increasing global energy demand has resulted in
not only a rapid depletion of already scarce fossil resources,
but also a severe environmental crisis [1, 2]. In recent years,
tremendous efforts have been made to evolve technologi-
cal solutions to effectively utilize renewable energy sources
such as solar, wind, and hydro. Since energy supply from
these sources can be intermittent, storage of excess energy
is critical for realizing a clean and sustainable future [3, 4].
Alternative energy storage solutions are also vital because of
the recent surge in our demand for electric vehicles, which
can mitigate our reliance on fossil fuels in automobile sec-
tor [5, 6]. Even though there exist multiple ways through
which energy can be stored, battery technology has shown
immense promise to play a massive role in the energy stor-
age sector over the next decade [1, 7–9]. Li-ion batteries
(LIBs) have dominated consumer electronics since their
* Shobit Omar
somar@iitk.ac.in
1
Materials Science and Engineering, Indian Institute
of Technology, Kanpur, Uttar Pradesh 208016, India
2
Sustainable Energy Engineering, Indian Institute
of Technology, Kanpur, Uttar Pradesh, 208016, India
handheld video recorder. They possess high specific energy
(~ 250 Wh/Kg), superior operating voltage (∼3.6 V), longer
cycle life (400–1200 cycles or 3–4 years), and a faster charg-
ing rate [10–17]. Although they are attractive, the short-
age of high-quality global lithium mineral reserves is a key
impediment to their broad usage in utility-scale storage
systems [18]. Besides inadequate availability, high Li cost
has driven the research to explore into other technologies.
Na-ion batteries (NIBs) could become a low-cost storage
alternative for future electric grids as intercalation chemistry
in both sodium and lithium is similar.
Even though research publications related to Li-ion bat-
teries are much more than Na-ion batteries (Fig. 1a), NIBs
have gained considerable scientific interest in recent years.
An exponential growth has been recorded in the research
associated with NIBs (Fig. 1b). Although larger and heavier
sodium exhibits slower diffusion, its widespread availability
and low cost make NIBs suitable for large-scale applications
[18–24].
One of the primary concerns for the practical applica-
tions of NIBs using non-aqueous liquid electrolytes arises
from battery safety regardless of the competitive ionic con-
ductivity (~ 10 mS·cm−1) [25]. The organic solvents utilised
in these electrolytes are flammable and thermally unstable,

13
Vol.:(0123456789)
 Ionics
Fig. 1  (a) Number of research publications related to Na- and Li-ion batteries in recent years. (b) Percentage increase in research publications in
the area of Na- and Li-batteries since 2011. (Source: Scopus, Google scholar)
posing major safety concerns, especially when the batter-
ies are overcharged, internally shorted, or subjected to high
temperatures [26]. Several approaches have been studied to
modify the electrolyte and improve the safety and stabil-
ity of cells. Solid-state electrolytes (SEs) appear to be the
most attractive option because of their excellent thermal
and chemical stabilities [27–30]. Furthermore, SEs have a
broader electrochemical potential window (up to 8.8 V vs
Na/Na+ till now) than the liquid organic electrolytes (< 5 V
vs Na/Na+), allowing them to combine with high-voltage
cathodes and render high specific energy to the batteries
[30]. SEs also simplify the battery design by eliminating
the need for a separator to prevent physical contact between
the cathode and anode. Nonetheless, the solid-state NIBs
are still in the early stages of development, largely due to
the unavailability of solid electrolytes with high sodium-ion
conductivity and poor interfacial compatibility between the
electrodes and SE [27, 28, 31–37].
The cell chemistry of the solid-state NIBs differs from
that of the LIBs. Anode materials mainly comprise metallic
lithium for Li solid-state system, whereas metallic sodium
is used for Na solid-state system. Materials for the positive
electrode are primarily compounds containing the 3d tran-
sition metal cations, namely Co, Mn, Fe, or Ni, as redox-
active elements. For Li solid-state system, layered oxides
such as ­LiCoO2, ­Li[Ni1-x-yMnxCoy]O2, olivine-structured
­LiFePO4, spinel ­LiMn2O4, and NASICON-type ­Li3V2(PO4)3
with capacity values mostly in the range of 140–280 mAh/g
are used as cathode material [16, 38]. The direct analogues
of these materials, i.e., ­NaCoO2, ­NaFePO4, ­NaMn2O4, and
­Na3V2(PO4)3, are the preferred choice for Na solid-state bat-
teries with capacity values lying in the range of 100–250
mAh/g [21, 39, 40]. Several types of solid inorganic
13
electrolytes, i.e., NASICON, garnet, perovskite, LISICON,
LiPON, ­Li3N, sulfides, argyrodite, anti-perovskite, etc.,
are used for making solid-state LIBs [41]. However, for
Na solid-state systems, only NASICON, β//-alumina, and
sulfides are used as ceramic solid electrolytes [25].
Na-ion conducting SEs can be broadly classified into
three categories, viz. (1) polymer-based electrolytes, (2)
sulfide-based electrolytes, and (3) oxide-based electro-
lytes. It is noteworthy that the material to be employed
as an electrolyte should have a conductivity of at least
1 mS·cm −1 for any realistic design of solid-state NIBs.
Each type of the above-mentioned electrolytes has its
own sets of advantages and challenges [42–44]. Although
polymer-based electrolytes are more flexible and have
lower contact resistance between the electrode and elec-
trolyte, their room-temperature (RT) ionic conductivity
(~ ­10 −6–0.1 mS·cm −1) is inadequate [25, 45]. Sulfide-
based electrolytes managed to achieve moderate to high
ionic conductivity (~ 0.1–1 mS·cm−1) and form a favour-
able solid–solid interface with electrodes. However, their
poor stability under ambient air poses a major fabrica-
tion challenge [25, 46]. Oxide-based sodium β//-alumina
­( Na 2O-5Al 2O 3) was the first commercially used supe-
rionic conductor employed in Na-S and Zebra batter-
ies operating at ~ 250–300 °C [25, 30, 32, 46, 47]. The
requirement of high sintering temperature (> 1500 °C)
and the two-dimensional ionic conduction make this
ceramic unsuitable for large-scale storage applications
[25, 45, 46]. The oxides possessing the skeleton struc-
ture of NASICON (Na Super-Ionic Conductor) have
been demonstrated to achieve > 1 mS·cm −1 at RT [33].
The high conduction is attributed to the three-dimension-
ally connected interstitial sites, which can accommodate
Ionics
large-sized sodium ions and provide paths for fast 3D
ionic diffusion inside the structure. Furthermore, the
strong covalent framework imparts good thermal and
chemical stabilities to the structure [48–54]. Recognizing
the potential of NASICON-structured oxides, research-
ers all over the world have shown keen interest in devel-
oping them as SE for the solid-state NIBs operating at
RT. Nevertheless, the high ionic impedance offered by
the NASICON electrolyte and the interfacial reaction
between the electrode and electrolyte, which blocks the
large-scale transfer of ions across the interface and sig-
nificantly affect the cycling performance of solid-state
batteries (SSBs), remain the primary challenges.
The solid-state NIBs employing NASICON ceramic
electrolyte differ from Li-based SSBs. The melting point
of the metal anode plays a crucial role in cell reaction
kinetics. Since the Na metal possesses a lower melting
point ( TNa
m
 = 98 °C) than the Li metal ( TLi
m
 = 181 °C), it can
be converted into a molten state at a lower temperature,
resulting in enhanced kinetics [55]. Furthermore, molten
metal can spread homogeneously on the ceramic NASI-
CON electrolyte, suppressing the dendrite formation along
the grain boundaries [56]. Besides, sodium is relatively
softer than lithium, which makes handling and process-
ing less challenging. The solid electrolyte is also more
thermodynamically stable in direct contact with sodium
as Na is less reducing than Li. However, a large volume
change occurs in the electrode during charge–discharge
cycling of NIBs because of the bigger size of the sodium
ion, which may lead to poor cyclability. Thus, retaining a
stable electrode–electrolyte interface in Na-SSBs is more
challenging than in Li-SSBs.
A few review articles on NASICON-type materials
for SIBs have been previously published. Rajagopalan
et al. [57] reviewed the NASICON-structured electrode
and electrolyte materials, focusing mainly on the mecha-
nisms for ionic conduction inside the crystal lattice. Rao
et al. [58] looked into the synthesis and doping strategies
employed to enhance the Na-ion conductivity of NASI-
CON-based solid electrolytes. Similarly, Yang et al. [59]
presented the basic characteristics of NZSP and summa-
rized the approaches used to improve the grain and grain
boundary conductivities. However, in these studies, the
microstructure, thermal and mechanical properties crucial
for fabricating solid-state batteries were not discussed. The
current review article presents an overview of NASICON-
type oxides encompassing their chemistry, phase forma-
tion, microstructure, conduction mechanism, etc. It also
highlights the strategies utilized to improve sodium-ion
conductivity, the challenges associated with fabrication,
and the approaches used to overcome them. Other issues
are also discussed, which will aid in directing future
research on these materials for solid-state NIBs.
NASICON overview
Chemistry and crystal structure
In general, the chemical composition possessing the NASI-
CON structure can be represented as ­Na1+xZr2SixP3-xO12
(0 ≤ x ≤ 3) [60]. It consists of a rigid three-dimensional
network where each tetrahedron of either S ­ iO4 or P ­ O4 is
connected to four ­ZrO6 octahedra by corner shared oxy-
gen ions [61]. The pathways for the migration of Na ions
are formed by interconnecting channels that connect one
interstitial site to another through a structural bottleneck.
NASICON term can also be used to describe a fam-
ily of compounds with the general chemical formula of
­AMP3O12, where A denotes the sites occupied by cations
which can be monovalent (such as ­K+, ­Na+, ­Li+), divalent
(such as C ­ o2+, ­Ca2+, ­Mg2+, ­Cu2+, ­Ba2+), trivalent (such
as ­Y , ­A l 3+) or tetravalent (such as Z
3+
­ r 4+, ­G e 4+; ­H f 4+)
[25, 51]. On the other hand, M corresponds to the sites
occupied by cations that are divalent (such as M ­ n 2+,
­Cd , ­Ni , ­Co , ­Zn ), tetravalent (such as ­Zr , ­Si4+,
2+ 2+ 2+ 2+ 4+
­Ti4+), or pentavalent (such as S ­ b5+, ­Nb5+, ­V5+) [51, 60].
Due to this broad compositional space, NASICON-type
oxides can be used as a solid electrolyte in both Li and Na
SSBs. However, the Li-ion conductivity in NASICON-
type ­Li1.3Al0.3Ti1.7(PO4)3 solid electrolyte is much infe-
rior to that of N ­ a+ ionic conductivity in NASICON-type
­Na3Zr2Si2PO12 [62, 63]. This is attributed to the higher
mobility of N ­ a+ compared to L ­ i + inside the NASICON
structure, as both the ions possess similar conduction
pathways. The lower Lewis acidity of N ­ a+ compared to
+
­Li causes a weaker electrostatic attraction force between
­Na + and skeletal ­O 2− ions, enabling a facile transfer of
sodium ions [64]. On the other hand, the smaller ­Li+ ions
form a stronger bond with ­O2− resulting in lower Li-ion
conductivity.
When NASICON composition is represented as
­NaA /MP 3O 12, sodium is either completely or partially
filled in ­A / sites to preserve the bulk charge neutrality.
The occupancy of ­A/-sites governs the concentration of
the mobile Na-ions and their interactions with the immo-
bile skeleton atoms. These interactions or crystalline fields
can preferentially stabilize the sodium-ion at specific sites
resulting in a high activation energy barrier for migra-
tion within the crystal lattice. Although a wide range of
chemical compositions exists, not all of them crystallize
into the NASICON phase when synthesized. In a recent
work, Ouyang et al. [65] developed the phase stability
rules of NASICON-type materials with a broad compo-
sitional space. A high throughput DFT calculations were
performed on 3881 possible NASICON compounds with
the chemical formula of ­Na x M y M′ 2−y (AO 4 ) z (BO 4 ) 3−z .
13
 Ionics
While the Na content in the tested compositions ranged
from 0.0 to 4.0 (in steps of 0.5), the average M/M’ charge
state was increased from + 2 to + 5 (in steps of 0.5). A two-
dimensional descriptor was formulated, which can predict
NASICON compositions that are likely to be synthesized.
It was reported that ~ 83.4% of the total compositions eval-
uated in this study are unlikely to be synthesized with the
NASICON structure.
At room temperature, the crystal structure of
­Na1+xZr2P3-xSixO12 (0 ≤ x ≤ 3) remained monoclinic (C2/c)
in the range of 1.8 ≤ x ≤ 2.2, whereas the rhombohedral
phase ( R3c ) exists for all other values of x [51]. Several
monoclinic-rhombohedral phase transition studies demon-
strate that in the compositions with the above given x range,
the high-temperature stable rhombohedral phase loses sym-
metry upon cooling below 160 °C, resulting in the mono-
clinic distortion [66, 67]. Deng et al. [67] studied the phase
behavior of rhombohedral N ­ a1+xZr2SixP3-xO12 electrolytes by
constructing a phase diagram employing DFT calculations,
cluster expansion formalism and large-size Monte Carlo
simulations. It was revealed for the first time that the two
biphasic regions exist in the Na compositions of 0 < x < 3
and at temperatures below 650 K. This is in contrast to pre-
viously reported experimental results, which indicate that
a single phase exists in the whole compositional range and
temperature greater than 450 K. Moreover, four monophasic
regions are also found in the phase diagram [67]. However,
the phase separation in NZSP has experimentally not been
detected so far. The disagreement in the results is attributed
to the poor kinetic, which prevents the redistribution of Si
and P and inhibits the phase separation.
Figure 2a illustrates that the ­Na+ ions occupy two crystal-
lographically inequivalent interstitial sites in the rhombohe-
dral phase, namely Na(1) and Na(2), present at the Wycoff
positions of 6b and 18e, respectively. The Na(1) and Na(2)
Fig. 2  Schematic of NASICON-
type (a) rhombohedral ( R3c )
and (b) monoclinic (C2/c)
crystal structures
13
sites are six-fold coordinated with the neighboring oxygens
of ­SiO4/PO4 tetrahedra. There exists one Na(1) and three
Na(2) sites per formula unit. The low-symmetry monoclinic
phase possesses another different Na site, i.e., Na(3) along
with Na(1) and Na(2) sites (shown in Fig. 2b) [33, 68]. This
additional Na(3) sites are three-fold coordinated with the
adjacent ­ZrO6 octahedra [33, 69]. Thus, the monoclinic
phase consists of one Na(1), one Na(2) and two Na(3) sites
per formula unit.
Figure 3a shows the X-ray diffraction (XRD) profiles of
­Na3Zr2Si2PO12 (NZSP) collected at various temperatures
[70]. The monoclinic phase existing at RT in NZSP gradu-
ally transforms to the high-symmetry rhombohedral phase
on raising the temperature. It is worth noting that most of
the XRD peaks in both phases lie very close to each other
and therefore overlap. However, the distinction between the
two phases can be visualized from the small regions of the
XRD pattern, as shown in the enlarged view in Fig. 3b. With
increasing temperature, the diffraction peaks at 19.3° and
30.5°, which correspond to the monoclinic phase, gradually
fade away, indicating the transformation to the rhombohedral
phase.
Conduction pathways
Understanding the ionic transport mechanism is essential
for the rational design of NASICON-type ­NaA/MP3O12.
As stated earlier, ­Na+ ions occupy two crystallographically
distinct interstitial sites inside the rhombohedral structure.
In contrast, the monoclinic phase, which is formed by the
rotational distortion of the rhombohedral structure, has
three distinct locations for Na-ion migration inside the
stationary skeleton [33, 68]. During the rhombohedral to
monoclinic phase transition, the ­ZrO6 and (Si/P)O4 frame-
work remain unaffected and only the Na(2) sites of the
Ionics
Fig. 3  (a) XRD patterns of NZSP taken at various temperatures from RT to 200 °C. The enlarged view of the two regions in the XRD patterns is
also shown (b). (Reproduced with permission from ref. no. [70])
rhombohedral phase split into two positions, i.e., Na(2) and
Na(3) in the monoclinic phase [71]. It is noteworthy that
the Na-ion diffusion in both the structures occurs by pass-
ing through a bottleneck triangular area formed by the oxy-
gens of the neighbouring tetrahedral and octahedral units
(shown in Fig. 4). In rhombohedral structure, Na(1)-Na(2)-
Na(1) is the energetically preferred pathway for Na-ion dif-
fusion (Fig. 4a). Nonetheless, both the Na(1)-Na(2)-Na(1)
and Na(1)-Na(3)-Na(1) pathways are involved in ionic con-
duction inside the monoclinic phase (Fig. 4b). Thus, ­Na+
ion jumps from Na(1) to Na(2) or Na(3) (approximate gap
of 3 Å between sites depending on material composition),
resulting in 3D tunnelling of Na-ions through intercon-
nected interstitial sites [25, 33, 68, 73].
Fig. 4  Diffusion pathway in
NASICON-type (a) rhombohe-
dral and (b) monoclinic crystal
structures
In the rhombohedral structure (shown in Fig. 4a), each
Na(2) site is locally surrounded by two Na(1) sites, whereas
each Na(1) site is surrounded by six Na(2) sites [74]. Increas-
ing the distance between Na(1) and Na(2) increases the acti-
vation energy required for ionic conduction. However, if the
distance is considerably low, the activation energy rises as
well. As a result, the Na(1)-Na(2) distance should be optimal
for fast ion hopping, which can be attained by tuning the lattice
size [33]. Na ions avoid hopping between two Na(2) sites in the
rhombohedral symmetry as one oxygen ion resides between
the two Na(2) sites. Furthermore, the Na(1)-Na(1) and Na(2)-
Na(2) distances, which are reported to be 6.48 Å and 4.98 Å,
respectively, in ­Sc3+ substituted NZSP, are significantly greater
than the distance between Na(1) and Na(2) sites (3.46 Å) [74].
13
 Ionics
Fig. 5  Arrhenius plot for the ionic conductivity of rhombohedral and
monoclinic phase of pure N ­ a3Zr2Si2PO12 obtained through molecular
dynamics simulations. (Reproduced with permission from ref. no.
[72])
The sodium ions hop along the Na(1) → Na(2) → Na(1) chan-
nels and pass through the two bottleneck triangles, ­T1 and ­T2
in the rhombohedral structure, depicted in Fig. 4a.
The monoclinic unit-cell of NASICON contains four
Na(1) sites, four Na(2) sites, and eight Na(3) sites [60]. The
Na(2) sites are fully occupied, while Na(3) sites are nearly
half empty. Each Na(1) site in the local environment is sur-
rounded by two Na(2) sites and four Na(3) sites. However,
partially occupied Na(3) sites are strongly displaced towards
Na(1) sites [71]. A complete occupation of Na(2) sites tends
to resist the ionic movement. Bond valence analysis has been
performed in order to comprehend and predict sodium con-
duction through different possible conduction path inside
the monoclinic structure. By estimating the valence value
maxima (VUmax) of various possible pathways [75], it was
concluded that there exist two non-equivalent Na(1)-Na(3)
migration paths. Both of them exhibit much lower valence
values (VUmax is 0.984) compared to Na(1)-Na(2) pathway
(VUmax is 1.28). As a result, Na-ions diffuse easily along
with both the Na(1)-Na(3) paths without reaching a valence
sum higher than or equal to 1 at any stage. The valence bond
analysis also explains the exceptionally high ionic conductiv-
ity observed in the monoclinic NASICON structure [75, 76].
Bui et al. [61] studied the conduction mechanisms in
NZSP exhibiting the monoclinic structure using the density
functional theoretical calculations. Four elementary diffu-
sion steps are identified, of which three are inner-chain pro-
cesses, while the remaining one is an inter-chain process.
In the inner-chain diffusion, the sodium ions migrate inside
the chain. On the other hand, in the inter-chain diffusion,
the sodium ions also jump across the chains. Combining
13
these elementary diffusion steps, three preferable conduc-
tion pathways in the x, y and z directions are examined. It is
found that in all the pathways, sodium ions are required to
pass through the puckered hexagonal ring with sides hav-
ing alternate tetrahedral and octahedral edges. Furthermore,
the activation energy involved for sodium-ion diffusion in
x, y and z directions are 285 meV, 315 meV, and 260 meV,
respectively, indicating a high three-dimensional conductiv-
ity inside the NZSP lattice.
In a recent work, Zhang et al. [77] used ab initio molecu-
lar dynamics simulations and climbing image nudged elastic
model calculations and reported a much lower diffusion bar-
rier for the correlated migration compared to the single-ion
direct hopping mechanism in the monoclinic NZSP. The
obtained results suggest that instead of a direct hopping
mechanism, correlated diffusion is the preferred conduction
mechanism in NZSP. Furthermore, it is predicted that this
type of correlated conduction can be enhanced by increasing
the ­Na+ ion concentration.
Factors influencing the sodium‑ion conductivity
The magnitude of ionic conductivity in NASICON mate-
rial is primarily determined by the concentration of mobile
ions present in the local symmetrical structure, the number
of available hopping sites, and the energy barrier for diffu-
sion [45, 78]. Besides, the % bulk density of the specimen,
phase stability, and the vacancy distribution throughout the
structure are all important controlling parameters to improve
conductivity. Increasing the concentration of charge carriers
increases conductivity but only to a certain extent. At very
high Na content, the conductivity declines mainly because
there are insufficient vacant sites for allowing the migration
of sodium ions. Thus, the concentration of available vacan-
cies and occupied Na-sites should be optimal to accomplish
fast sodium-ion conduction within the lattice. Based on the
conductivity survey performed on a wide range of NASI-
CON compounds, Guin et al. [69] suggested that the maxi-
mum conductivity is attained in the compositions that have
Na content in the range of 3.2–3.5 per formula unit. The
maximum Na ions present in a single unit cell is 4. Similarly,
Zhang et al. [77] reported the highest conductivity in NZSP
at an optimum Na content of 3.3–3.55 per formula unit.
The sodium-ion conductivity is also dependent on the
crystalline phase present in the NASICON compounds at
RT. Since the rhombohedral phase is more symmetric than
the distorted monoclinic phase, it exhibits lower activa-
tion energy for sodium-ion diffusion. Ran et al. [72] per-
formed molecular dynamics simulations to study the ionic
conductivity in NZSP possessing pure rhombohedral and
monoclinic phases. The ionic conductivity of the rhombo-
hedral phase is predicted to be one order of magnitude supe-
rior to that of the monoclinic phase (as shown in Fig. 5).
Ionics
Furthermore, the activation energy for the rhombohedral
phase (0.23 eV) is found to be much lower compared to the
monoclinic phase (0.33 eV).
One of the strategies to improve the ionic conductivity is
to enlarge the area of the smallest oxygen triangle, T ­ 1, which
serves as a bottleneck for ionic conduction in NASICON
electrolytes [79]. The distance between the Na-ion and the
nearest oxygen ions is also critical [33]. In addition, the host
(M) and dopant ­(M/) cations in ­AMM/P3O12 composition
should have the ideal size to achieve high ionic conductiv-
ity [69]. The partial substitution with acceptor cations in
NASICON structure plays an important role as doping not
only modifies the bottleneck area (depending on the bond
length and ionic radius) but also boosts the concentration of
mobile Na-ion in the NASICON structure because of charge
imbalance [80–82].
The arrangement of S ­ i4+ and P­ 5+ in the NZSP composi-
tions also impacts the sodium-ion transportation inside the
NASICON crystal structure. Roy et al. [68, 83] illustrate this
effect by performing molecular dynamics simulations on the
pure NZSP compound. Three framework structures of NZSP
are considered with different Si/P ordering. The structure in
which ­Si4+ ions are uniformly distributed, well-constructed
percolation channels of sodium ions are seen. On the other
hand, islands of ­Na+-ions exist in the framework structure
with ­Si4+ rich planes. The low ionic conductivity observed
­ i4+ rich planes is ascribed to the modu-
in the structure with S
lation of the electrostatic potential energy landscape, which
originates because of the higher electrostatic repulsion of
­Na+ with P ­ 5+ compared to S ­ i4+. Thus, the distribution of
Si/P in NZSP could be one of the reasons for observing
conductivity variation in NZSP specimens when prepared
under different processing conditions.
The sintering temperature and the holding time are two
critical parameters that determine the % bulk density and
microstructure of any sintered specimen. In NASICON-type
oxides, sintering at elevated temperatures (> 1200 °C) results
in the formation of an electrically insulating secondary phase
of monoclinic-ZrO2 at the grain boundaries [84–87]. The
formation of zirconia is associated with the volatilization of
the Na and P elements from the bulk samples on subjecting
them to high sintering temperature. In several investigations,
excess amounts of P and Na are added during the powder
synthesis process to compensate for the cation volatilization
and consequently suppress the ­ZrO2 formation [81, 88, 89].
In addition, multiple materials processing approaches, such
as sol–gel powder synthesis [34, 90], the addition of sinter-
ing aids ­(Na3BO3 [91–93], ­Bi2O3 [94], ­Na2SiO3 [70], ­Na2O,
etc.), and various additives (Antimony tin oxide [95], Indium
tin oxide [96], etc.) to the starting mixture, and the use of
advanced sintering techniques [50, 88, 97], are adopted to
attain high densification without subjecting the specimens to
the elevated sintering temperatures. Other secondary phases
such as tetragonal ­Na3PO4 and ­Na2ZrSi2O7 are also com-
monly detected at grain boundaries.
The magnitude of ionic conductivity inside the grains and
across the grain boundaries differs within the polycrystal-
line ceramic electrolyte. Several conductivity studies have
revealed that the grain boundaries offer a significant por-
tion of the total resistivity in NASICON-type oxides at RT
[87]. The blocking nature of grain boundaries is attributed
to the formation of insulating secondary phases, generation
of micro-cracks, and poor grain to grain contact because of
the cuboidal shaped grains in the microstructure.
Powder synthesis and bulk sample fabrication
Powders of NASICON oxides are extensively synthesized
using two methods, i.e., sol–gel and solid-state reaction pro-
cesses [90, 95, 98–101]. However, in a few studies, other
processes such as hydrothermal [102, 103], co-precipitation
[104], mechanochemical synthesis [105], and combustion
synthesis [106] are also employed for the powder synthesis.
In the solid-state reaction method, the stoichiometric pro-
portions of required powder reactants are thoroughly mixed
and ground into fine particles using wet ball milling. The
powder mixtures are then calcined to attain the NASICON
phase. The as-calcined powder is pressed into bulk green
ceramics which are subjected to high-temperature sintering
(> 1200 °C) to achieve high densification. Even though the
solid-state reaction is a simple and low-cost method, the
high-temperature treatment is a primary concern as it may
cause the volatilization of high vapour pressure elements,
such as Na and P and formation of undesirable secondary
phases [89, 100, 107–111].
On the other hand, the sol–gel synthesis method offers the
possibility of low-temperature processing, better morphologi-
cal control, and superior chemical homogeneity within the
specimen [84, 105, 108]. However, the high cost incurred in
this method and the processing complexity are the main chal-
lenges, especially for large-scale production. In this process-
ing route, precursors of Zr and Si are initially hydrolyzed,
followed by the addition of P and Na salts. The colloidal
solution is then slowly heated to form a gel network which
is subsequently subjected to temperatures in the range of 700
to 1000 °C for the crystallization of a desirable NASICON
phase [112, 113]. Bulk samples are pressed using the nano-
sized powder and are sintered at relatively low temperatures
between 1000 to 1250 °C [113, 114]. The processing param-
eters such as calcination temperature, sintering temperature,
and pH of the sol are vital in stabilizing various phases in the
bulk specimen. The sintering temperature cannot be too high
since this could cause impurities such as Z ­ rO2 and N
­ a3PO4 to
develop in the microstructure. In most cases, excess P and Na
are added to compensate for the evaporation of these elements
during the synthesis process [81, 89].
13
 Ionics
Even though wet-chemistry approaches for synthesizing
nano-sized powders are advantageous for producing dense
specimens at low temperatures, these processes require
expensive precursors and challenging to scale up. As a
result, alternative materials processing techniques are desir-
able for lowering the sintering temperature while avoiding
the formation of impurity phases, which have an adverse
effect on sodium-ion conduction. These solutions should
also be cost-effective and adaptable to large-scale material
production.
In recent work by Naqash et al. [115], a novel method
based on solution-assisted solid-state reaction (SA-SSR)
is developed for the powder synthesis of NASICON
compounds. This process is gaining popularity as it is
convenient, utilizes low-cost raw materials (water or acid
soluble salts), and is simple to scale up for large-scale
production. Figure 6 shows the schematic depicting the
steps involved in the powder synthesis of NZSP. The stoi-
chiometric amounts of nitrates of Na and Zr are initially
dissolved in water. Si(OC2H5)4 (TEOS), which serves as
a Si source, is then added to the solution, followed by a
little amount of nitric acid for the hydrolysis of TEOS.
Subsequently, a stoichiometric amount of ­NH4H2PO4 is
added, and stirred for 30 min to generate a homogenous
precipitate. The precipitate-containing solution is then
slowly heated to 100 °C for the gentle removal of water.
The resulting solid product is subsequently calcined in a
Fig. 6  Schematic depicting the steps involved in the solution-assisted solid-state reaction method for the powder synthesis of NASICON-type
oxides. The process is described in ref. no. [115]
13
furnace at 800–1000 °C to produce the NASICON phase.
The SA-SSR yields powder with good chemical homoge-
neity, low Z­ rO2 secondary phase and ultrafine particles
of 0.1–0.2 μm.
The strategy of adding sintering aid in fabricating
dense bulk NASICON ceramics has also proven to be
effective. It is reported that several sintering aids such as
­Na3BO3 [91, 93], ­B i 2O3 [94], ­6 0Na 2O-10Nb2O5-30P2O5
[116] not only lower the sintering temperature but also
considerably improve the ionic conductivity. For exam-
ple, NZSP ceramic sample with 9.1 wt.% ­Na 3BO 3 sin-
tered at 700 °C exhibits three orders of magnitude supe-
rior conductivity (0.1 mS·cm−1) at RT than the specimen
without ­Na 3BO 3 [93]. Moreover, several advanced sin-
tering routes, such as microwave sintering [97], spark
plasma sintering [88], and cold sintering processes [50,
94, 117, 118] have been explored to achieve the required
densification at a relatively low sintering temperature
[50, 119]. Among these, the cold sintering process has
become increasingly attractive for the sintering of NASI-
CON electrolytes as it can achieve high densification
at a very low temperature (as low as 140 °C) [50]. This
recently developed technique utilizes various sintering
aids (also called transient liquid) such as water, ace-
tic acid, ­H NO 3, NaOH, KOH, etc. [119] Nevertheless,
this method requires further investigations to gain deep
insight into the actual sintering mechanism.
Ionics
Microstructure of sintered samples
The microstructure has a substantial influence on the final
properties of NASICON electrolytes. Good sintering, neg-
ligible porosity, and the absence of micro-cracks favor high
ionic conductivity [99, 120]. The microstructure of the
NZSP specimen sintered at 1200 °C reveals the presence
of several macropores and voids, which can be attributed
to the partial melting of the NASICON phase [121]. The
liquid phase flows between the solid particles leaving behind
macropores [106]. Increasing the sintering temperature and
holding time favour the grain growth and densification of
the sample, which improves the conductivity up to a certain
limit [88, 99, 122]. The excessive sintering temperature or
prolonged sintering duration results in Na/P deficient NZSP
and promotes the liquid phase formation and the unwanted
secondary phases ­(ZrO2, ­Na3PO4, etc.) near the grain bound-
aries [84, 122, 123]. As a result, there has always been a
trade-off between the dense microstructure and the presence
of impurity phases.
Secondary phases such as Z ­ rO2, ­ZrSiO4, and S
­ iO2 can
also be present in polycrystalline NASICON electrolytes,
which may be detrimental to the mechanical integrity of
SSBs [124]. Since ­ZrO2 is more thermodynamically stable,
­ZrO2 crystallization occurs near the grain boundary region
before the NASICON phase [125]. According to an effec-
tive percolation theory, a small amount of the ­ZrO2 impu-
rity phase in the grain boundary has a minimal influence on
ionic conductivity since it acts as porosity. However, a large
amount of Z ­ rO2 formation could lead to a different stoichi-
ometry caused by the Zr-deficiency in the NASICON phase
[115, 126]. As a result, an inhomogeneous distribution of
Na ions exists within the grains and grain boundaries, which
has a detrimental effect on the intergranular migration of Na
ions [81, 119, 127].
The grain boundaries in the NZSP specimen can be
altered by using suitable dopants, varying the dopant con-
centration, and controlling the reactivity with the host ele-
ment [58]. Partial substitution with rare-earth elements
(such as L­ a3+, ­Y3+, ­Ce4+, ­Gd3+, etc.) in NZSP could result
in smaller size grains (~ 2–4 μm), greater necking between
Fig. 7  SEM micrograph of (a)
­Na3.4Sc0.4Zr1.6(SiO4)2(PO4)
(Reproduced with permission
form ref. no. [33]) and (b)
­Na3.33Ce0.02Sc0.33Zr1.65Si2PO12
(Reproduced with permission
form ref. no. [98])
the particles, and uniform cuboidal-shaped grains [128].
Further, this approach can reduce the sintering temperature
and holding time and enhance the carrier concentration
[129]. Figure 7 shows the cuboidal-shaped grains typi-
cally observed in the microstructure of these NASICON
compositions.
An optimum amount of various additives (such as NaF,
Antimony tin oxide, Indium tin oxide, etc.) are added
in NZSP to achieve dense microstructure, better neck-
ing between the grains, and uniform grain size [95, 96,
130]. Suzuki et al. [93] found that adding N ­ a 3BO 3 into
the NZSP improves the microstructure by promoting neck
formation and grain growth, leading to high densifica-
tion. The fractured surface of the ceramic without NBO
is shown in a secondary electron (SE) image and a back-
scattered electron (BSE) image in Fig. 8a and b, respec-
tively. The porous microstructure with nano-sized grains
(100–300 nm) suggests little sintering occurring at 700 °C.
The BSE image revealed a sparse ceramic microstructure,
indicating that necks developed to some extent between
NASICON grains. If the presence of the Z ­ rO2 impurity
phase is ignored, the NBO-free ceramic body exhibits a
relative theoretical density of 61% (see Fig. 8b). On the
other hand, the ceramic body sintered with 9.1 wt% NBO
possesses a dense microstructure, as shown in Fig. 8c, d).
Despite the presence of tiny pores, the neck development
and the grain growth progressed significantly compared to
the NBO free sample. The distribution of ­ZrO2 and NBO
phases is shown in the BSE micrograph (Fig. 8d).
Several sophisticated sintering processes are employed
to fabricate the bulk samples of NZSP electrolyte with
dense and fine-grained microstructure. Leng et al. [50]
used a cold sintering technique and optimized the process-
ing parameters to fabricate bulk specimens of Mg-doped
NASICON electrolyte (­ Na3.256Mg0.128Zr1.872Si2PO12). Fig-
ure 9 compares the microstructure of a specimen cold-
sintered at 140 °C for 1 h under 780 MPa with a speci-
men dry-pressed at 780 MPa for 1 h. The cold sintered
specimen exhibits higher densification, better sintering
morphologies such as particle packing and neck forma-
tion than the dry pressed sample.
13
 Ionics

Fig. 8  SE and BSE images

of the (a) fractured surface
and (b) ion-milled surface of
NZSP, respectively. SE and
BSE images are also given for
the similar surfaces (c) and (d)
of NZSP with 9.1 wt.% NBO,
respectively. (Reproduced with
permission from ref. no. [93])

Fig. 9  SEM micrographs
of the fractured surfaces of
­Na3.256Mg0.128Zr1.872Si2PO12
specimens (a, c) dry-pressed at
25 °C and (b,d) cold sintered
at 140 °C, respectively. Both
specimens were pressed under
the pressure of 780 MPa for
1 h. (Reprinted with permission
from ref. no. [50])

Both the relative density and ionic conductivity of
NASICON electrolytes are improved in the final stage of
the sintering process due to the considerable grain growth.
However, micro-cracking inside the large grains and along
the grain boundaries can occur to relieve the residual
stresses formed due to the anisotropic thermal expansion
in the NASICON lattice [33, 130]. Ma et al. [33] have
studied the microstructure of Sc-NZSP and reported that
NASICON-type materials often produce micro-cracks near
grain boundaries while cooling the material after sintering.
Although such types of micro-cracks pose an insignificant
influence on the bulk density due to their small volume,
they are detrimental to the conductivity of the sample as
these cracks block the transport of Na ions [33].

13
Ionics
Recent progress
Goodenough and Hong [131] discovered ­Na + ion dif-
fusion in the NASICON skeleton structure present in
­Na 1+x Zr 2 Si x P 3-x O 12 system. Subsequently, this three-
dimensional rigid framework has gained tremendous atten-
tion from the scientific community and become a centre of
interest to explore various properties. This is also possible
because of the compositional flexibility and high tolerance
shown by the NASICON crystal structure for substituting
various cations. As the structure accepts both isovalent
and aliovalent cation substitution, a wide range of NASI-
CON compositions can be synthesised. The present sec-
tion describes the recent efforts undertaken to increase
the sodium-ion conductivity of NZSP by doping it with
various elements. Moreover, the strategies that have been
employed recently to address the concerns of high sinter-
ing temperature, anisotropic thermal expansion, mechani-
cal stability, and large interfacial resistance of NASICON
electrolytes are also discussed.
Ionic conductivity
Previously researchers have extensively tried synthesizing
single-phase NASICON electrolytes, albeit with little suc-
cess [84, 86–88]. The primary concern has always been to
suppress the formation of secondary phases. An optimal
processing route is crucial in obtaining phase pure solid
NASICON electrolytes with improved electrical properties
[132, 133]. The simple processing steps, such as type of
solvent media, milling time, milling speed, and calcination
temperature, effectively regulate the phase formation and
the chemical stoichiometry inside the material. Thus, all
parameters are essential and impact the ionic conductivity
of the solid electrolyte [99, 134]. The majority of research
on NZSP has been on the partial elemental substitution of
NASICON structure with heteroatoms such as Zn, Sc, Ce,
Zr, La, etc. [33, 34, 54, 66, 84, 108, 129, 135] The ionic
conductivity of several NZSP-related compositions, which
are recently reported and have shown high magnitude, are
given in Table  1. At room temperature, the total ionic
conductivity in most of these compounds is in the range
of ~ 2–4 mS.cm−1. However, in a few NASICON composi-
tions, the magnitude of > 5 mS.cm−1 is also recorded [141,
145, 146].
The sol–gel method has been widely employed for
the synthesis of NASICON [100, 101]. Zhou et al. [147]
compared the microstructure of NASICON electrolyte
prepared by both the colloidal and sol–gel methods. The
sintered pellets fabricated from the calcined sol–gel pow-
der possess a single-phase (homogenous) microstructure.
However, a silica-rich glassy phase exists along the grain
boundaries in the pellets prepared using the calcined
colloidal powders. In another study, Lalère et al. [148]
found a traceable quantity of Z ­ rO2 near the grain bound-
ary region in NZSP synthesized using the sol–gel method,
which emphasized the importance of optimal processing
steps. As a result, the NZSP specimens exhibit a reason-
able ionic conductivity of 1.5 mS·cm −1 only at 200 °C.
Porkodi et al. [149] used an alternative synthesis approach
based on molecular precursor for the preparation of NASI-
CON oxides. This method produces nano-sized precursors,
which may be responsible for phase purity, good densifica-
tion, and high ionic conductivity in the resultant materials.
Naqash et al. [115] developed a unique solution-assisted
solid-state reaction method for the powder synthesis of
NZSP. This method promotes cation homogeneity, sup-
press ­Z rO 2 formation, and produce large-sized grains.
Thus, a reasonably good ionic conductivity of 1 mS.cm−1
is found for the NZSP sample at RT. This simple and
cost-effective method has also been applied to fabricate
specimens of other NASICON compositions, for exam-
ple, ­Na3+xZr2Si2+xP1−xO12 [146] and ­Na3+xScxZr2-xSi2PO12
[33]. Figure 10 shows the total and bulk conductivities
measured for N ­ a 3+xZr 2Si 2+xP 1−xO 12 (where 0 ≤ x ≤ 0.6)
samples prepared using the solution-assisted solid-state
reaction method [146]. A significantly high sodium-ion
conductivity of 5.2 mS.cm −1 at RT is reported in the
­Na 3.4Zr 2Si 2.4P 0.6O 12 composition. In recent work, Liu
et al. [145] investigated N­ b5+ doping for the first time into
­Na3.4Zr2Si2.4P0.6O12 by synthesising the powders using the
SA-SSR method. A remarkably high ionic conductivity
of 5.51 mS.cm−1 is found for N ­ a3.3Zr1.9Nb0.1Si2.4P0.6O12
5+
composition. Adding ­N b reduces the Na content in
­Na3.4Zr2Si2.4P0.6O12, and an optimal composition for maxi-
mum conductivity is seen when the Na amount is 3.3 per
formula unit. This NASICON composition has a favour-
able ratio of sodium ion concentration to vacancy concen-
tration inside the crystal structure, allowing for efficient
transfer of sodium ions.
Several advanced sintering techniques have been
used for the fabrication of NZSP electrolyte with dense
and fine-grained microstructure. They have fascinat-
ing advantages of moderate sintering temperature,
shorter sintering time, and greater yields. Leng et  al.
[50, 94] employed a cold sintering technique to fabri-
cate bulk specimens of Mg-doped NASICON electrolyte
­( Na 3.256Mg 0.128Zr 1.872Si 2PO 12). A conductivity of 0.041
mS·cm −1 is reported for the specimen cold sintered at
140 °C and 780 MPa for 1 h. Annealing the same sample
at 800 °C for 6 h significantly enhanced the ionic conduc-
tivity to 0.5 mS·cm−1, which is five times superior to the
dry-pressed specimen conventionally sintered at 1000 °C
(0.1 mS·cm−1).
13
 Table 1  Compositions, fabrication methods, and ionic conductivity of recently reported NASICON-type electrolytes
Compositions Method/sintering conditions Ionic conduc- Salient features Crystal structure Electrochemical References
tivity at 25 °C window vs Na/

13
(mS·cm−1) Na + (V)

Na3.1Zr1.95Mg0.05Si2PO12
Na3.256Mg0.0625Zr1.872Si2PO12
Na3.1Mg0.05Zr1.95Si2PO12
Na3.4Mg0.1Zr1.9Si2.2P0.8O12
Na3.4Sc0.4Zr1.6Si2PO12
Na3.125Zr1.75Sc0.125Ge0.125Si2PO12
Na3.4Sc2Si0.4P2.6O12
Na3.2Hf1.9Ca0.1Si2PO12
Na3.1Zr1.9Ga0.1Si2PO12
Solid-state reaction method
Sintering: 1225 °C
Solid-state reaction method
Sintering: 1300 °C, 24 h
Solid-state reaction method
Sintering: 1260 °C, 16 h
Solid-state reaction method
Sintering: 1250 °C
Solution-assisted solid-state method
Sintering: 1265 °C, 5 h
Solid-state reaction method
Sintering: 1100 °C, 12 h
Solid-state reaction method
Sintering: 1300 °C, 10 h
Solid-state reaction method
Sintering: 1250 °C, 16 h
Solid-state reaction method Sintering: 1.06
1250 °C,16 h
1.33 • High grain boundary conductivity M 6 [136]
(~ 1 mS.cm−1 at RT)
• > 95% relative theoretical density
2.7 • Formation of less insulating sec- M + R - [85]
ondary phase of doped-Na3PO4 is
formed, which reduces the effective
grain boundary resistance
3.5 • Dense microstructure with well M 4.5 [137]
crystallized grains is formed
• Enlargement of bottleneck trian-
gular area on doping with alkaline
earth cations
3.6 • Stable cycling of symmetric cell M 6 [138]
with Na as electrodes at 1 mA.cm−2
current density
• Excellent dendrites suppression
capability
4.0 • Chemical homogeneity M + R 6 [33]
• Cost-effective for large-scale
production
4.64 • Sc doping improves the stability of R - [72]
the rhombohedral phase at RT
• Ge doping reduces the monoclinic
to rhombohedral phase transition
temperature
2.4 • Increase in charge carrier density on R - [139]
Si substitution
• Enhanced correlated migration in
Si-doped samples
• Enlargement of the oxygen bot-
tleneck triangle T1
1.07 • ­Ca2+ doping increase both the M 8.8 [30]
charge carrier concentration and
specimen density
• Mixed ionic electronic conducting
phase is constructed on the surface
of the electrolyte, which ensures fast
charge transfer between Na and SE
• Enlargement of bottleneck area M 5 [80]
• Negligible electronic conductivity
Ionics
 Table 1  (continued)
Compositions
Na3.2Zr1.9Ca0.1Si2PO12
Na3Zr1.8Zn0.2Si2PO11.8
Na3.4Zr1.9Zn0.1Si2.2P0.8O12
Na3.3Zr1.7La0.3Si2PO12
Na3.3Zr1.7La0.3Si2PO12
Na3.3Zr1.9La0.1Si2PO12
NZSP + 5 wt % Antimony tin oxide
(ATO)
13
Method/sintering conditions
Sol–gel method
Sintering: 1250 °C, 5 h
Solid-state reaction method
Sintering: 1225 °C, 4 h
Solid-state reaction method
Sintering: 1250 °C
Sol–gel method
Sintering: 1250 °C, 12 h
Sol–gel method
Sintering: 1200 °C, 24 h
Solid-state reaction method
Sintering: 1150 °C
Solid-state reaction method
Sintering: 1100 °C, 6 h
Ionics
Ionic conduc- Salient features Crystal structure Electrochemical References
tivity at 25 °C window vs Na/
(mS·cm−1) Na + (V)
1.67 • A robust solid-state battery is M 7 [90]
developed by integrating Na metal
with monolithic Ca-doped NZSP
electrolyte
• Very low interfacial resistance of
the symmetrical cells with stable
sodium stripping/plating cycles at
0.3 mA.cm−2 for 600 h
1.44 • Lower valence state of the dopant M - [140]
is beneficial in achieving high bulk
conductivity mainly because of the
less electrostatic interaction with
­Na+
• Excessive doping reduces the con-
ductivity because of cell distortion
5.27 • ­Zn2+ doping enlarged the size of the M + R 6 [141]
bottleneck triangle and also raised
the concentration of Na-ions
• Solid-state cell based on SE with
polydopamine coating at the cath-
ode side exhibits a high capacity at
a C/2-rate
1.34 • ­La3+ ions exist in the form of phos- M + R - [142]
phate impurities, i.e. ­Na3La(PO4)2
• Si/P ratio contributes significantly
towards the conductivity enhance-
ment
3.4 • ­La3+ doping in NZSP generates new - - [34]
phases of ­Na3La(PO4)2, ­La2O3, and
­LaPO4 resulting in the formation of
composite electrolyte
• The ionic liquid was used on the
cathode side of the SE in SSBs to
serve as a wetting agent and enable
fast charge transfer kinetics
1.1 • Doping with rare earth elements - - [143]
increases the content and mobility
of the Na- ions inside the lattice
1.43 • 5 wt.% ATO addition significantly M 4.6 [95]
enhanced the densification process
 Table 1  (continued)
Compositions Method/sintering conditions Ionic conduc- Salient features Crystal structure Electrochemical References
tivity at 25 °C window vs Na/

13
(mS·cm−1) Na + (V)

Na3.2Zr2Si2.2P0.8O12 -0.5NaF
Na3Zr2Si2PO12
Na3Zr2Si2PO12
Na3Zr2Si2PO12
Na3Zr2Si2PO12
Na3.3Zr1.9Nb0.1Si2.4P0.6O12
Na3.4Zr2Si2.4P0.6O12
Na3.3Zr1.65Sc0.33Ce0.02Si2PO12
Solid-state reaction method
Sintering: 1150 °C, 24 h
Solid-state reaction method
Sintering: 1275 °C, 15 h
Solid-state reaction method with
excess sodium
Sintering:1100 °C, 12 h
Solution-assisted solid-state method
Sintering: 1250 °C, 5 h
Solid-state reaction method
Sintering: 1200 °C
Solution-assisted solid-state reaction
Sintering:1260 °C, 5 h
Solution-assisted solid-state reaction
Sintering:1260 °C, 5 h
Solid-state reaction method
Sintering: 1250 °C, 5 h
3.6 • NaF assisted grain boundary M + R 4.2 [130]
modification and improved the ionic
conductivity
1.2 • Na-air cell is fabricated using M - [144]
NASICON ceramic as a separator
• Cell exhibits an electrochemical
discharge of 600 mAh.g−1, 30% less
than the theoretical value
1.13 • Only excess Na is added rather than M - [99]
both Na and P
1.0 • The powder processing method is M - [115]
convenient, low cost and has the
potential for large-scale production
1.8 • The spark plasma sintering method M - [88]
was used to fabricate samples
• Highly dense samples were pre-
pared at a relatively low sintering
temperature of 1100 °C
• The formation of the m-ZrO2
impurity phase is suppressed by the
addition of excess Na and P
5.5 • The ionic conductivity initially M - [145]
increases and then decreases with
the addition of ­Nb5+
5 • High densification at relatively low M + R - [146]
temperature
• High ionic conductivity because
of the optimal ratio of the vacant
and occupied sodium sites in the
structure
2.44 • Absence of impurity phase and M - [98]
microcracks
• Enlarged bottleneck triangular area
Ionics
Ionics
Fig. 10  Total (σtotal) and bulk (σb) conductivity of N
­ a3+xZr2Si2+xP1−xO12
as a function of x measured at 25 °C. (Reproduced with permission from
ref. no. [146])
da Silva et  al. [119] examined the ionic conduc-
tivity in the bulk specimens of Sc-doped NZSP
­(Na3.4Sc0.4Zr1.6Si2PO12) prepared using different sintering
methods. It was demonstrated that using the rapid sintering
techniques, such as Field Assisted Sintering Technology
(FAST) and Spark Plasma Sintering (SPS), sample densi-
fication (~ 99% of theoretical density) can be achieved at
lower temperatures than using the conventional sintering
method, with little variation in electrical properties. On the
other hand, the cold sintering technique, which requires sin-
tering aids and high mechanical pressure, result in moderate
densification (86.8% of theoretical density) but at tempera-
tures as low as 250 °C [119]. On annealing the cold-sintered
specimen at higher temperatures, an increase in both the
density and conductivity is noticed. The microwave sin-
tering technique has also been employed to prepare dense
NZSP ceramics at low temperatures [97]. The microwave
sintered NZSP specimen fabricated at 850 °C for 30 min
possesses a high relative density of 96% with fine-sized
Fig. 11  (a) Schematic of the
melt pool present during the
sintering of NZSP with 5 wt.%
­Na2SiO3. The arrow indicates
the diffusion of Na and Si from
the melt pool to the NASICON
phase. (b) The effect of N
­ a2SiO3
addition on the total ionic con-
ductivity and density of NZSP is
also shown. (Reproduced with
permission from ref. no. [70])
grains and an ionic conductivity of 0.251 mS·cm−1 at RT.
The obtained conductivity value is comparable to that of
the sample formed by solid-state sintering performed at
1200 °C for 720 min.
Numerous attempts have been made over the years to
address the low sinterability issue of NZSP ceramics by
adding a variety of sintering aids. These additives facilitate
sintering at low temperatures, thereby preventing the vola-
tilization of Na and P and shortening the material processing
time. Noi et al. [92] investigated the liquid-phase sintering
of NZSP using N ­ a3BO3 (NBO) as a sintering aid for the
first time to reduce the NASICON sintering temperature
to 900 °C. The dense liquid phase sintered NZSP sample
containing 4.8 wt% NBO exhibits high conductivity of ~ 1
mS·cm−1 at RT with an activation energy of 28 kJ ­mol−1.
The direct bonding of NZSP grains and the segregation of
NBO in particulate form are the main reasons for achieving
high ionic conductivity in the liquid-phase sintered NZSP.
Utilising the liquid phase sintering approach, Oh et al. [70]
fabricated dense NZSP specimens by adding sodium meta-
silicate as a sintering aid. The N­ a2SiO3 melt pool facilitates
the densification process and, on solidification, forms a Si-
rich secondary phase enhancing the grain boundary conduc-
tivity of NZSP. As illustrated in Fig. 11a, the melt pool also
acts as a source for Na and Si, which diffuse inside the grains
and augment the grain conductivity. Adding 5 wt.% N ­ a2SiO3
significantly raises the relative density of NZSP from 81 to
93% after sintering at 1175 °C for 10 h and consequently
improves the room temperature total ionic conductivity from
0.64 to 1.45 mS.cm−1 (shown in Fig. 11b).
Chen et al. [96] studied the effect of adding indium-tin
oxide (ITO) on the microstructure and conductivity of NZSP.
An optimized ITO addition (3 wt.%) results in the maximum
of both the grain and grain boundary conductivities in NZSP.
The conductivity enhancement is a direct consequence of
the dense microstructure, uniform grain size, close contact
between grains, and the reduction in electrostatic repulsion
between the ­In3+ and ­Na+. It is suggested that the excess ITO
13
 Ionics
present in the grain boundary favours high grain boundary
conductivity. Antimony-tin oxide (ATO) has also been used
as an additive to reduce the sintering temperature of NZSP
and boost its conductivity [95]. The NZSP ceramic with an
optimized 5 wt.% ATO sintered at 1100 °C for 6 h exhibits
a high conductivity of 1.43 mS·cm−1 at RT and good elec-
trochemical stability up to 4.6 V (vs. Na/Na+). The dense
microstructure with uniform and fine-sized grains is respon-
sible for observing fast conduction in the grain boundaries of
these specimens. In recent work, Zhang et al. [34] modified
the grain boundaries by introducing ­La3+ in ­Na3Zr2Si2PO12,
resulting in the formation of several secondary phases such
as ­La2O3, ­LaPO4, etc. The ion transport along the grain
boundaries is suggested to be facilitated due to the space-
charge effect.
Several previous investigations have focused on enlarg-
ing the triangular bottleneck area through which the sodium
ions migrate inside the NASICON skeleton structure. This
smallest cross-section area of the sodium-ion passageway
imposes geometrical constraints and, thereby, determines
the activation energy involved for the sodium ion conduc-
tion inside the NASICON lattice. Park et al. [81] studied
the grain and grain boundary diffusion behaviour at low and
high temperatures for the bare and 10 at.% Na excess NZSP.
Based on both experimental and computational results, it is
shown that the grain boundary conductivity is the limiting
factor of the total conductivity in NZSP at lower tempera-
tures (< 100 °C). On the other hand, at higher temperatures
(> 100 °C), the total conductivity is dictated by the grain
conductivity. In addition, the DFT calculations analysis
reveals that incorporating 10 at.% excess Na expands the
triangular bottleneck area and improves the thermodynamic
stability of the material. This leads to a significant enhance-
ment in the ionic conductivity of NZSP (e.g., 120 mS·cm−1
at 300 °C) [81].
Song et al. [137] observed that the cell volume and unit
cell parameters of NZSP are increased by partially substitut-
ing ­Zr4+ with alkaline earth ions ­(Na3.1Zr1.95M0.05Si2PO12
(M = Ca, Mg, Sr, Ba). Such substitution leads to a sig-
nificant increase in the bottleneck area of NZSP, although
only a minor variation exists for different alkaline earth
ions. Superior ionic conductivity of 3.5 mS·cm−1 at 25 °C
is measured for Mg-doped NZSP, and it is ascribed to the
formation of the largest bottleneck area (~ 6.522 Å2) com-
pared to the bare NZSP composition (5.223 Å2). Similarly,
Ruan et al. [143] examined the enhancement in the ionic
conductivity of NZSP by partial doping with rare earth ele-
ments ­(La3+, ­Nd3+, and Y ­ 3+) for Z
­ r4+. The Na-ion conduc-
tivity inside the lattice is improved because of the rise in
sodium concentration to compensate for the charge imbal-
ance created by acceptor cation substitution. In addition,
the larger size of the doping element has a positive effect on
the bottleneck area, resulting in conductivity improvement.
13
The maximum grain and total ionic conductivity of 1.43
and 1.1 mS·cm−1, respectively, at 25 °C are reported for
the ­Na3.1Zr1.9La0.1Si2PO12 sample. Ortiz-Mosquera et al.
[150] studied ­Na1+xGe2(SiO4)x(PO4)3−x (0 ≤ x ≤ 0.8) based
glass–ceramics exhibiting NASICON structure and possess-
ing a lowest activation energy for x = 0.6 composition. The
superior ionic conduction is a consequence of the bottleneck
size expansion caused by the partial replacement of a larger
­Si4+ ion (0.26 Å) for ­P5+ (0.17 Å).
The valence state and the amount of the substituting ele-
ment are also crucial parameters influencing the conductiv-
ity of the doped-NZSP materials. Both of them govern the
electrostatic interactions between ­Na+ and the doping cation,
which dictate the mobility of the sodium ion within the lat-
tice. Chen et al. [140] studied the impact of the valence state
and the content of dopants ­(Nb5+, ­Ti4+, ­Y3+, and ­Zn2+) on
the crystal structure and conductivity of doped NZSP ceram-
ics. It is shown that the dopants with a low valence state (i.e.,
­Zn2+) are beneficial for bulk conductivity improvement pri-
marily because of the minimal coulombic repulsion between
the dopant ion and the Na-ion. The highest conductivity
of 1.44 mS·cm−1 is measured in ­Na3Zr1.8Zn0.2Si2PO11.8.
An optimal doping amount for achieving maximum con-
ductivity lies between 5 and 10 mol.%. Adding excessive
doping amount reduces the conductivity on account of sig-
nificant lattice distortion. Shen et al. [138] optimized the
­Na3.4Mg0.1Zr1.9Si2.2P0.8O12 composition by systematically
replacing the P ­ 5+ with ­Si4+ and ­Zr4+ with ­Mg2+. The bulk
specimen of this composition fabricated via solid-state reac-
tion route exhibits an ionic conductivity of 3.6 mS·cm−1 at
RT, which is 17 times superior to the pristine NZSP. The
excellent conductivity seen in this composition is due to
higher sodium-ion concentration and the larger space avail-
able for ­Na+ migration.
Using multiple computational studies, Zhang et al. [77]
predicted the correlated migration mechanism inside NZSP,
and showed that increasing sodium-ion concentration acti-
vates the correlated migrations due to ­Na+-Na+ electrostatic
repulsion. These excess sodium ions are forced to occupy
the high energy sites which lead to the reduction in energy
barrier for diffusion. Santhoshkumar et al. [139] employed
several structural characterization techniques to investigate
the structure-conductivity correlations in scandium-based
NASICON compounds, namely N ­ a3+xSc2SixP3-xO12 (x = 0.0,
0.2, 0.4, 0.8) prepared using the solid-state reaction method.
Maximum ionic conductivity of 2.4 mS·cm−1 at 30 °C is
reported for ­Na3.4Sc2Si0·4P2·6O12 NASICON material. This
is attributed to the simultaneous increase in carrier density
and the ratio of vacant Na sites over occupied Na sites on Si-
doping, larger area of the oxygen triangle T1, and enhanced
correlated migration associated with a higher Na-ion con-
centration. A new type of Ca-doped Hf-based NASICON
electrolyte ­(Na3.2Hf1.9Ca0.1Si2PO12) has also been examined
Ionics
[30]. This composition possesses an ionic conductivity
of ~ 1.07 mS·cm−1 at 25 °C and a stable electrochemical
window up to 8.8 V (vs Na/Na+). The excellent conductiv-
ity found in this electrolyte is ascribed to the larger amount
of mobile ­Na+ inside the lattice, higher densification due to
Ca-doping, and improvement in grain boundary conductivity
associated with the chemical composition changes near the
grain boundary region.
Stabilization of high-temperature rhombohedral phase
and lowering the rhombohedral-monoclinic phase transition
temperature in NZSP have been tried previously, employing
various strategies. The rhombohedral phase is more symmet-
ric than monoclinic and thus exhibits higher Na-ion mobil-
ity. The stability of this phase at a lower temperature may
augment the ionic conductivity of the NZSP-based com-
pounds. Park et al. [151] observed that the phase transition
temperature plays a vital role in improving the sodium ion
conductivity in NASICON. An enhanced volume fraction
of high-temperature stable rhombohedral phase is achieved
at a lower temperature of 150 °C by partial substitution
of Ge in NZSP ­(Na3Zr2-δGeδSi2PO12, where δ = 0.1, 0.2).
The Ge-doped specimens exhibit an ionic conductivity of
14 mS·cm−1 at 150 °C, almost two times superior to that
of the bare NZSP sample. A more recent study suggested
that adding NaF into the precursor induces phase transition
inside the grains of NZSP from monoclinic to rhombohedral
phase and simultaneously modifies the grain boundaries by
forming a “binder-like” glassy phase [130]. This simple and
low-cost approach enhances the ionic conductivity of NZSP
from 0.45 to 1.7 mS·cm−1 (for ­Na3Zr2Si2PO12-0.7NaF).
Most of the earlier investigations rely upon doping with
a single element for the ­Zr4+ site to improve the sodium-
ion conductivity in NZSP. Recently, a few co-doping
approaches have also been adopted in NZSP, which take
advantage of the synergy between two different dopant cati-
ons to improve conductivity. Pal et al. [152] employed a
co-doping scheme using ­Sc3+ and ­Yb3+ as co-dopants for
­Zr4+ to enhance the sodium-ion conductivity of NZSP.
The ­Na3.33Zr1.67Sc0.29Yb0.04Si2PO12 composition consists
of both monoclinic and rhombohedral phases at RT. This
composition exhibits a conductivity of 1.62 mS·cm−1 at RT,
which is more than 2.5 times higher than that of NZSP (0.61
mS·cm−1). The rhombohedral phase stabilization, higher
mobile sodium content, presence of microstructure with thin
and micro-cracks free grain boundaries, and the suppres-
sion of m-ZrO2 impurity phase formation are the main rea-
sons for achieving high ionic conductivity in the co-doped
samples. In a similar work, Thirupathi et al. [98] found that
co-doping of 1  mol.% C ­ e4+ in N­ a3.33Zr1.67Sc0.33Si2PO12
improves the sodium conductivity from 0.96 of 2.44
mS.cm−1. The increase in bottleneck triangular passage
area caused by a slight C­ e4+ addition is the possible reason
for the observed high conductivity. In more recent work,
Ran et al. [72] have demonstrated the enhancement in the
grain and grain boundary conductivities through Ge and Sc
co-doping in NZSP. An exceptionally high conductivity of
4.64 mS·cm−1 is achieved at RT in the co-doped composi-
tion of N
­ a3.125Zr1.75Sc0.125Ge0.125Si2PO12. It is reported that
the ­Sc3+ doping stabilizes the rhombohedral phase at RT,
while adding ­Ge4+ lowers the temperature at which the phase
transform from monoclinic to rhombohedral.
In summary, multiple strategies have been tested to
enhance the sodium ion conductivity in NZSP electrolytes
at room temperature. Most of them are focused on enlarging
the oxygen triangle bottleneck area, improving the sinter-
ability, increasing the charge carrier concentration, modi-
fying the grain boundaries, suppressing the formation of
secondary phases, stabilizing the high-temperature rhom-
bohedral phase, etc. The processing approach to synthe-
size nano-sized powder with good chemical homogeneity
using the cost-effective solution-assisted solid-state reaction
method appears to be most promising. A few studies have
also reported achieving high conductivity of > 5 mS.cm−1
at RT in specimens of different NASICON compositions
fabricated using this method. However, more detailed work
is required to elucidate the correlations between the process-
ing parameters, chemistry, and conductivity in these oxides.
Thermal expansion and microcracks
The existence of microcracks within the microstructure has
a detrimental effect on the conductivity and mechanical
properties of the solid-state electrolyte. It is well reported
that the micron-sized cracks in the NZSP-type materials
are related to the anisotropy of the axial thermal expansion
[153, 154]. The microcracking of ceramics occurs during the
cooling cycle of the final sintering stage of the electrolyte
fabrication. The thermal expansion coefficient (CTE) is a
fundamental material property that can be accurately meas-
ured in all the crystallographical directions using the high-
temperature XRD technique. Oota et al. [155] employed this
technique to study the compositional dependence of crystal-
lographic thermal expansion in N ­ a1+xZr2SixP3-xO12 (x = 0,
0.5, 1.0, 1.5, 2.0, 2.5, 3.0). Figure 12 shows a large thermal
expansion anisotropy between the a and c lattice parameters
for this compositional series. As the x value increases, the
slope of the curve of the a-axis changes from negative to
zero. On the other hand, the CTE value of the c-axis for all
the compositions is positive. The coefficient value initially
declines with the rise in x value, and after reaching minima
at x = 2, it starts increasing. Nevertheless, the overall lat-
tice volume thermal expansion is positive for all the tested
compositions. Similarly, Kaus et al. [156] reported a strong
anisotropic thermal expansion behaviour in NASICON-type
­Na3.4Sc2(SiO4)0.4(PO4)2.6. This composition exhibits a sig-
nificant expansion of 2.1% along the crystallographic c-axis
13
 Ionics
Fig. 12  Unit-cell parameters (a
and c) and unit-cell volume of
­Nal+xZr2SixP3-xO12 as a function
of temperature. Errors bars indi-
cates one standard deviation.
(Reproduced with permission
from ref. no. [155])
in the temperature regime of 25 to 600 °C. However, no
significant expansion (less than 0.1%) is observed along the
crystallographic a-axis. The change observed in the lattice
constants is reversible, and on cooling from 600 °C to RT,
the original lattice parameters are obtained.
Alamo et al. [157] studied the thermal expansion proper-
ties of the compositions present in the ­Na1+xZr2P3-xSixO12
(0 ≤ x ≤ 1) series. The results revealed the compositional
dependency and the lowest CTE value observed for x = 0.33.
Using the acoustic emission method, Srikanth et al. [153]
examined the microcracking induced by anisotropic ther-
mal expansion in several low thermal expansion materials,
including ­NaZr2P3O12. A direct correlation between micro-
cracking and the anisotropic axial CTE is established in this
study by detecting the formation of microcracks via intense
acoustic emission.
Ma et  al. [33] observed that NASICON-type com-
pounds often produce micro-cracks near grain boundaries
while cooling the material after sintering. Microcrack-
ing is attributed to the anisotropy in the axial thermal
expansion [153, 158]. Even though these micro-cracks
have a negligible effect on the density of the material
due to their smaller size, they significantly reduce the
13
conductivity of the sample by blocking the transport of
Na ions. Guin et al. [159] investigated the solid-solutions
of ­Na3+xSc2SixP3−xO12 with 0.05 < x < 0.8 fabricated using
the solid-state reaction method. The samples with a rela-
tive density of more than 97% exhibit conductivity 3 to 4
times lower than the specimens having a density between
90 to 96%. This is ascribed to the excessive grain growth in
the highly dense samples. The microcracking is observed
in the middle of the large-sized grains (~ 100 µm). The
thermal expansion anisotropy induces large residual stress
in the material on cooling, resulting in microcracks. How-
ever, microcracking primarily occurs at grain boundaries
for ceramic specimens possessing large grains and high
thermal expansion anisotropy [160].
Multiple investigations reported that microcracking
arises along the grain boundaries when the grains exceed
a critical size in polycrystalline NASICON materials
[161]. These cracks are generated due to the dissimilari-
ties in contraction during the cooling cycle of the sin-
tering process. According to Cleveland and Bradt [160],
there exists a critical grain size (Gs) for the occurrence of
microcracking, which can be calculated using the follow-
ing relationship.
Ionics
Fig. 13  Intragranular microcrack present in the densely sintered spec-
imen of N ­ aZr3P3O12 containing 2 wt.% MgO. The specimen was sin-
tered at 1200℃. (Reproduced with permission from ref no. [106])
Fig. 14  Thermal expansion behaviour of the sintered specimen of
­Na1+xZr2SixP3-xO12 compounds: (a) x = 0, (b) x = 0 with 2 wt.% MgO,
(c) x = 1 (d) x = 2, (e) x = 2 with 2 wt.% MgO. (Reproduced with per-
mission from ref. no. [106])
14.4 × 𝛾f
Gs = 2 (1)
E × Δ𝛼max × ΔT 2
where 𝛾f is the fracture surface energy for grain boundary
microcracking, Δαmax is the maximum difference in CTE of
a and c crystal axes, ΔT is the temperature change to initiate
microcracking during cooling, and E is an elastic modulus.
Using this relationship, Bradt [162] reported the value of GS
ranging from 2 to 14 μm for the NZSP materials.
Dhas et al. [106] studied the effect of MgO addition on
the microstructure of NZSP synthesized using the con-
trolled combustion process. The 2 wt.% MgO addition
not only facilitates densification but also lowers the grain
boundary microcracking by suppressing grain growth in
NZSP. Nevertheless, the intergranular and intragranular
cracks exist but only in large grains (shown in Fig. 13).
The thermal expansion curves of a few ­Na1+xZr2SixP3-xO12
are compared in Fig. 14. The thermal expansion coefficient
varies from negative to positive value with an increase
in Na content. The negative CTE value observed in
­NaZr2P3O12 is ascribed to the microcracking induced in
the sintered specimen by the large thermal expansion ani-
sotropy. The densely sintered sample of 2 wt.% MgO con-
taining ­NaZr2P3O12 shows a near-zero thermal expansion
coefficient as it possesses fine-sized grains, which suppress
the formation of microcracks. However, MgO addition
reduces the positive CTE value of the N ­ a3Zr2Si2PO12 spec-
imen from 3.9 × ­10–6 to 2.1 × ­10–6 /K, most likely because
of the higher bulk density of the MgO added specimen.
Pal et al. [152] studied the Yb and Sc co-doped NZSP
samples fabricated using the conventional solid-state reaction
method. No evidence of microcracks in the microstructure
has been reported in the sintered specimens. The presence
of small-sized grains (∼1.5 μm) in the microstructure is sug-
gested to be the main reason as the refined grains reduce the
effect of thermal expansion by absorbing the stresses in the
grain boundaries and mitigating the formation of microcracks.
Ortiz-Mosquera et  al. [150] studied the microstruc-
ture of the fractured surface of ­Na1+xGe2(SiO4)x(PO4)3−x
(0 ≤ x ≤ 0.8) fabricated using a glass–ceramic route. The
average grain size increases with Si content from 75 nm for
x = 0 to 22 μm for x = 0.8. The micrograph of the sample
with high Si content (x = 0.8) shows the existence of micro-
cracks. These microcracks are formed during the crystalliza-
tion process when the tensile stresses are generated because
of the difference in the CTE values of the crystalline phase
and the parent glass matrix.
In conclusion, microcracking is a critical issue that
severely diminishes the ionic conductivity of NASICON-
type oxides. High thermal expansion anisotropy present in
these materials is responsible for the formation of micro-
cracks during the cooling cycle of the sintering process.
It is evident from the previous studies that the grain size,
chemical composition and additives play a crucial role in
suppressing microcracking along the grain boundaries. Vari-
ous dopants (such as M ­ g2+, ­Sc3+, etc.) have shown immense
potential in reducing microcracks by lowering grain growth
and promoting densification. Nevertheless, further research
is required to systematically study the role of dopants on the
thermal expansion coefficient, which controls the amount of
microcracking in NASICON materials.
Mechanical properties and electrode–electrolyte
interface
The degradation of the mechanical strength of a solid elec-
trolyte, especially under cyclic charging, is a critical factor
13
 Ionics
affecting the lifetime of solid-state batteries. During the
charge–discharge cycles, intercalation/de-intercalation of
ions inside the electrode structure induces an enormous
cyclic volume change in the electrode. This dynamic phe-
nomenon directly influences the chemical, electrical and
mechanical properties, which possibly leads to microcrack-
ing, formation of structural defects, dendrites formation,
etc., at the electrode/electrolyte interface and within the solid
electrolyte [30, 138]. Understanding the elastic property of a
SE is crucial as the electrolyte must accommodate internal
stresses by deforming elastically to maintain a stable elec-
trode/electrolyte interface.
Young modulus and shear modulus are the two most
important parameters to study the electrolyte resistance
against the deformation from external pressure. Young
modulus measures the stiffness of the solid material, and its
value depends on the bonding and the crystal structure of
the material. NASICON electrolytes exhibit Young’s modu-
lus in the range of 72–88 GPa. Min [163] summarized the
elastic properties of sodium-ion solid-state conductors for
next-generation NIBs using existing data and first-principle
calculations. NASICON-type oxides exhibit the highest elas-
tic properties and low anisotropic behaviour among vari-
ous studied materials. According to the stability criterion
of Monroe and Newman [164], the shear modulus of the
SEs must be twice or greater than that of sodium metal (3.3
GPa) to prevent dendrite penetration inside the electrolyte
[165]. The shear modulus of NASICON ceramic electrolytes
is 44.3 GPa, which is much higher than that of Na-metal.
Fracture toughness is another crucial mechanical prop-
erty of SEs as it is a measure of the resistance to fracture
that could occur during the cell operation. It governs the
crack growth, a succession that leads to the short-circuiting
of SSBs [166]. Nano-indentation is a useful technique to
Fig. 15  Correlations between the ionic conductivity, mechanical
properties, and composition of ­Na1+xMnx/2Zr2−x/2(PO4)3 with x vary-
ing between 0.5 and 2. The elastic modulus and hardness are given
13
determine the fracture strength in brittle solids. The indenta-
tion has a considerable compressive hydrostatic component
which prevents crack propagation and avoids fracture. More
recently, this technique has been applied to battery materials
as well.
Kalnaus et al. [167] reported the correlations between
ionic conductivity and mechanical properties in
­Na1+xMnx/2Zr2−x/2(PO4)3 (x = 0.5, 1.0, 1.5, and 2). A reduc-
tion in both the elastic modulus and hardness is observed
with an increase in x value (as shown in Fig. 15a). This
decrease appears to be non-linear, with a significant drop
(almost resembling a step function) as the x value increases
from 1 to 1.5. It is of practical interest to note that Hill's
equation, as illustrated by the dashed lines in Fig. 15a, can
describe the link between elastic modulus and nanoinden-
tation hardness and composition. The reduction in hard-
ness is advantageous for material processing, as it implies
reduced resistance to local plastic strain. Figure 15b shows
the effect of Na content on fracture toughness and conduc-
tivity. The fracture toughness (KIC) initially decreases and
then increases with the rise in the sodium content, reaching a
maximum value of 0.89 M ­ Pam1/2 at x = 2. The observed non-
linear relationship is attributed to the formation of a glassy
phase at an intermediate Na concentration. The maximum
ionic conductivity (∼2.85 × ­10–2 mS·cm−1) present in this
compositional series coincides with the maximum fracture
toughness. When this material is utilised as a sodium-ion
conducting phase in composite electrodes, the combination
of high fracture toughness and low hardness in the opti-
mal composition of x = 1.5 promotes the creation of stable
interfaces.
Valle et al. [168] investigated the mechanical properties
of hot-pressed von Alpen-type NASICON electrolyte of
composition ­Na3.1Zr1.55Si2.3P0.7O11 for NIBs. The fracture
in (a) while the fracture toughness (KIC) and room temperature con-
ductivity are shown in (b). (Reproduced with permission from ref.
no [167].)
Ionics
toughness of specimens fabricated using spray-dried powder
ranges from 1.05 to 1.09 ­MPam½. Furthermore, the elastic
modulus in these samples is reported to be 97.65 GPa. The
obtained values are found to be dependent on the microstruc-
tural aspects, viz., grain size, the fraction and distribution of
glass phase at grain boundaries and ­ZrO2 content.
Nonemacher et  al. [166] studied the micromechani-
cal properties of Al/Y substituted NASICON with the
compositions of ­Na1+2xAlxYxZr2-2x(PO4)3 (NAYZPx) and
­Na3+2xAlxYxZr2-2x(SiO4)2(PO4) (NAYZSiPx). The NAYZPx
compositions crystallizes with rhombohedral symmetry,
while NAYZSiPx transforms from monoclinic to rhombo-
hedral phase depending on the doping level and temperature.
The NAYZPx exhibits elastic modulus and hardness val-
ues in the range of ~ 72–82 GPa and ~ 4.8–5.8 GPa, respec-
tively. On the other hand, the elastic modulus and hardness
in NAYZSiPx lie in the range of ~ 72–88 GPa and ~ 5.6–7.6
GPa, respectively. The fracture toughness values for both the
compositional series are in the range of 1.30–1.58 MPa ­m½.
Yde-Andersen et al. [127] measured the average fracture
strength of ­Na 2.94Zr 1.49P 0.8Si 2.2O 10.85 using the three-
point bending method. The specimens sintered at 1200 °C
exhibit an average fracture strength of 162 MPa. Accord-
ing to another study, the average flexural strength of fully
dense NASICON bars tested using the four-point flexural
method is 98 MPa, which is lower than that of β″-alumina
(250–300 MPa) [169].
The realization of solid-state NIBs is mostly hindered by
low ionic conductivity of SEs and large electrode–electro-
lyte interfacial resistance [46, 170]. In general, the effective
contact area between the electrode and the SE is insufficient
compared to the electrode and liquid electrolyte. Thus, a
good interfacial contact between the SE and electrode are
required to minimize resistance and develop a high-capacity
sodium-ion battery. Employing a metallic anode can signifi-
cantly raise the energy density of a battery cell. Although the
metallic anode can be stripped and plated reversibly, several
challenges exist when using a solid electrolyte. Uchida et al.
[171] have successfully improved the interfacial contact and
lowered the resistance to 14 Ω ­cm2 at room temperature by
applying a simple mechanical compression load of 30 MPa
on a Na/NASICON assembly. The activation energy asso-
ciated with the charge transfer at Na/NASICON interface,
estimated by plotting the interfacial resistance versus 1/T,
is found to be 0.6 eV which is far greater than that of Na/β′′-
alumina (0.28 eV). This higher activation energy magnitude
is attributed to the interphase layer formed by pressing the
Na metal on the NASICON surface at room temperature.
The outer layer of NASICON is postulated to react with
Na metal at room temperature, creating a ­Na+ conducting
interphase layer. This thin passivation layer also serves as
a barrier for further reaction of NASICON with Na metal.
Besides, the presence of this interlayer improves the wetting
of sodium metal on the NASICON electrolyte, resulting in
better electrolyte-anode interfacial contact.
The high resistivity of the electrode and SE interface is
also linked to chemical and electrochemical compatibility
problems at the interface. Experimental investigations have
been unsuccessful in ascertaining the exact mechanisms by
which the high resistance develops at the interface. This is
primarily because of the difficulty accessing a thin interface
of two solid materials where the reaction occurs. DFT calcu-
lations have been found to be an effective tool for conducting
systematic studies on the chemical and electrochemical com-
patibility at the SE and electrode interface. Using this com-
putation method, Zhu et al. [172, 173] studied the chemical
and electrochemical stabilities of SE and electrode interfaces
in solid-state Li-ion batteries. It was shown that most solid
electrolytes, including NASICON, are not thermodynami-
cally stable. Interfacial reactions can occur either during
heat processing or during the charge–discharge cycling of
a battery. The interface decomposition to form interphase
layers is thermodynamically favourable. However, the slug-
gish kinetics of decomposition and poor electronic conduc-
tivity of decomposition interphases are predicted to be the
reasons for observing good stability experimentally. It was
further suggested that the decomposition interphases with
high electronic insulation and good ionic conductivity could
be advantageous in obtaining high interface stability [173].
Applying artificial interfacial coating layers with such prop-
erties is proposed as an effective strategy for stabilizing the
interface.
In another computational investigation, Lacivita et al.
[174] performed the DFT calculations to study the electro-
chemical stability window of sodium-ion conducting solid-
state electrolytes, the kinetic voltage limits for Na extraction
and the chemical reactivity with various cathode materials
commonly used in NIBs. All NASICON materials with
­[PO4]3− exhibit excellent anodic stability, resisting oxida-
tion up to 5 V. However, they all tend to decompose at low
potential. Moreover, no NASICON composition is thermo-
dynamically stable in contact with Na metal, which reduces
the polyanion groups, i.e. ­[SiO4]4− and ­[PO4]3−. The pure
phosphate containing NASICONs are found less stable than
those having ­[SiO4]4−. Furthermore, some chemical reactiv-
ity is found only for Si-containing NASICON compositions
with partially de-sodiated electrodes.
In a recent experimental study, Goodenough and co-
workers [56] revealed that the insertion of a dry ­Na+ con-
ductive thin polymer film or the interlayer formed from an
in situ reaction with molten Na could dramatically reduce
the electrode/SE interfacial resistance. Superior wetting of
sodium metal on the NASICON electrolyte is responsible for
the improved interface as it prevents the formation of den-
drites near the anode and their rapid penetration inside the
SE along the grain boundaries during the charging process.
13
 Ionics
The schematic of the dendrite formation and penetration
inside the inorganic electrolyte when the Na metal wetting
is poor is depicted in Fig. 16. The poor physical contact will
result in non-uniform coating and the rapid short-circuit of
the cell. On the other hand, when the ceramic surface is
modified by the presence of an artificial interlayer and is
easily wetted by Na metal, the unwanted dendrite nuclea-
tion is suppressed owing to the uniform N ­ a+ flux across the
interface. It is important to note that in this case the grain
boundaries of the ceramic electrolyte are not directly in con-
tact with the sodium anode. A significant improvement in
the cycling performance and high efficiency of the solid-
state sodium battery can be achieved using both the above-
mentioned strategies. In more recent work, Tian et al. [30]
reported a stable electrochemical performance of solid-state
NIBs for 2400 h at RT with the current density as high as
2 mA.cm−2. In this work, a mixed ionic-electronic interface
of ­Na2O/NaxSn was in situ constructed on the surface of
­Na3.2Hf1.9Ca0.1Si2PO12. The interlayer provides close physi-
cal contact between the SE and electrode and homogenous
deposition/dissolution of sodium at the interface. The full
cell based on modified electrolyte and ­Na3V2(PO4)3 and Na
as electrodes exhibits a capacity of 103.1 mAh.g−1 at 0.5 C
even after 300 cycles.
Improving the wettability of sodium on NASICON-
based electrolytes by making composites of sodium with
some other material is another approach reported in the
literature to achieve stable operation in SSBs. Fu et al.
Fig. 16  Schematic of the
sodium metal/solid electrolyte
interface where the sodium
metal possesses (a) a poor
wetting ability and (b) a good
wetting ability on ceramic
pellet. An artificial interlayer is
formed when the ceramic pellet
is easily wetted by sodium metal
(Reproduced with permission
from ref. no. [56])
13
[175] demonstrate a reduction of the interfacial resistance
of Na|NASICON from 1658 to 101 Ω·cm 2 by lowering
the surface tension of Na metal on forming composites
with amorphous S ­ iO 2. A uniform distribution of S­ iO 2
particles within the composite improved the wettability
of sodium. The Nyquist plot collected on the symmetric
cell using Na metal or Na-SiO2 as electrodes is shown in
Fig. 17a. The reduction of interfacial resistance is clearly
visible for cell based on Na-SiO2 electrodes. Further, the
solid-state Na-SiO2|NASICON|Na-SiO2 symmetric cell
exhibits a stable Na stripping/plating and can withstand
current density up to 500 μA/cm 2 (Fig. 17b) and cycling
test for more than 135 h (Fig. 17d). On the other hand, the
Na|NASICON|Na symmetric cell rapidly degrades in less
than 10 h at 100 μA/cm2 (shown in Fig. 17c). The Na-SiO2
composites facilitate intimate physical contact with the
NASICON electrolyte, resulting in a dramatic reduction in
the interfacial contact and significant enhancement in the
electrochemical stability of solid–solid interface.
In a recent study, Lu et al. [90] reported a high-perfor-
mance monolithic solid-state NIB in which molten sodium
­ nO2 decorated porous NASI-
metal is infiltrated into the S
CON electrolyte. The SE consists of a dense layer sand-
wiched between two porous layers of thickness ~ 100 μm.
The sodiophilic nature of ­S nO 2 enables sodium melt
to easily wet the inorganic electrolyte. This interfacial
resistance is significantly reduced with a stable cycling
Ionics

Fig. 17  Electrochemical
performance of symmetric
cells fabricated using Na metal
or Na-SiO2 as electrodes and
­Na3.2Zr1.9Mg0.1Si2PO12 as SE.
(a) EIS spectra, (b) Na strip-
ping/plating at current densities
ranging from 10 to 500 μA/cm2,
and (c) cycling tests at current
density 100 μA/cm2 of both the
cells are compared. The cycling
performance of symmetric
cell with Na-SiO2 electrode at
current densities of 0.1 mA/cm2
and 0.2 mA/cm.2 is also shown
(d). All the measurements were
conducted at room temperature.
(Reproduced with permission
from ref. no. [175])

performance is observed at different current densities from
0.1 to 0.3 mA ­cm−2.
Unlike the Na metal anode, the battery cathode is com-
posite in nature and generally comprises electroactive
material, SE, binders, and an electronically conductive
agent, making sodium-ion exchange process between the
cathode and the electrolyte rather complicated. Layered
oxides [176, 177], tunnelled structured oxides [178, 179],
and polyanionic compounds [180–182] are some of the
most commonly used electroactive materials for cathode,
which are also similar to NASICON-based SEs in terms
of stiffness. As a result of the low wettability of these
materials, the interfacial contact between the cathode and
inorganic electrolyte is inadequate, resulting in a lack of
effective ion transport channels and high interface imped-
ance. Moreover, the volume change associated with the
electroactive particles during the charge/discharge process
further damages the interfacial contact. Thus, improving
the physical connection between the cathode and SE is a
significant challenge for developing all-solid-state sodium
batteries.
In comparison to cathode/SE chemical compatibility,
more emphasis has been placed on improving cathode/SE
interfacial interaction. Mechanically mixing the particles of
SE with active material during the electrode preparation pro-
cess is a typical approach employed to improve the cathode/
electrolyte interaction. Recently, wet infiltration has been
used to construct the composite electrode structure [183].
The intimate contact between the solid electrolyte and elec-
trode is achieved by infiltrating the precursor solution of
the electroactive material into the porous side of the dense-
porous bilayer NZSP electrolyte. An effective ion transfer is
attained with minimum stresses resulting from the volume
change of the electroactive material during the charge–dis-
charge cycling.
In addition, the introduction of various liquid solvents
(such as organic liquid electrolyte, ionic liquid, etc.) between
SE and electrode has also been reported for augmenting the

13
 Ionics
interfacial contact [34, 184]. Combining the benefits of inor-
ganic ceramic electrolyte and organic polymer electrolyte,
a ceramic-polymer composite approach has also been used
to fabricate SEs with improved ionic conductivity, good
mechanical property and high chemical/thermal stability
[185]. Using this approach, solid electrolyte can accommo-
date the cyclic volume changes occurring in the cathode
during the charge–discharge process. Plcharski et al. [186]
investigated the addition of NASICON powder to PEO-NaI
solid electrolytes and found that the conductivity of PEO-
based composite solid electrolytes containing NASICON
is greatly increased when compared to pristine PEO-NaI
composites. Zhang et al. [53] integrated the polyethylene
oxide/NASICON composites to be used as a SE in NIBs.
The composite electrolyte exhibits a conductivity of 2.4
mS.cm−1 at 80 °C and is stable up to 150 °C. The polymer
provides flexibility to the composite, and the ceramic phase
renders the high conductivity. The solid-state battery based
on composite electrolyte, N ­ a3V2(PO4)3 and Na as electrodes
showed an initial reversible capacity of 106.1 mA h ­g−1 and
excellent cycling performance over 120 cycles. In a recent
investigation, Yang et al. [141] used a thin coating of poly-
dopamine on the cathode side of NASICON electrolyte to
attain a highly reversible capacity in SSBs.
In summary, the interfacial modification for the intimate
physical contact between electrodes and SEs is imperative
to achieve low interfacial resistance and high cyclability in
SSBs. Enhancing the wetting of sodium metal on NASICON
electrolytes by introducing interfacial interlayers, forming
composites, and giving heat treatment for uniform spread-
ing of molten Na onto the SE are a few strategies employed
for Na anode/SE interface modification, resulting in high
efficiency in SSBs. The challenge of high resistance in the
cathode/SE interface is addressed by constructing composite
cathodes with nanoarchitecture, adding liquid electrolyte or
polymer at the interface, and forming composite electrolyte
of NASICON and polymer.
Challenges and perspectives
The NASICON-type oxides generally exhibit good thermal
stability and fast 3D ionic conduction. Most studies have
focused on enhancing the sodium-ion conduction in these
oxides, and now the maximum ionic conductivity of ~ 5
mS·cm−1 at RT is reported in the literature [141, 145]. Nev-
ertheless, the practical application of NASICON electrolytes
is often restricted by the poor interfacial contact between the
electrode/SE interface and the short circuit of the cell caused
by the penetration of dendrites when utilizing pure Na as
an anode. Low interfacial conductivity of less than ­10–2
mS·cm−1 results in poor rate performance and short cycle
life [25, 90, 99, 130]. Moreover, the poor wettability of Na
13
metal on the NASICON surface has a strong influence on the
formation and growth of dendrites [56, 187] Since Na metal
does not wet the inorganic oxide electrolyte surface and has
poor physical contact with SE, a non-uniform Na-ion flux
exists across the interface. The Na ions plate preferentially at
the grain boundaries of the ceramic electrolyte where local
­Na+ flux is significant under the electrical field. This causes
the nucleation of dendrites which grow along the grain
boundaries and penetrate the NASICON-type electrolytes.
The addition of interfacial wetting agents and inserting a
buffer layer have been explored in the literature to resolve
this issue. These efforts have reduced the interfacial resist-
ance to some extent [30, 56, 188]. Nevertheless, the volume
change associated with the solid electrode during the charg-
ing-discharging cycles needs to be accommodated by SE for
maintaining the close connection with the solid electrode.
Developing interlayers with multiple functionalities of high
conductivity, good sodium wettability, and adequate flex-
ibility, which can provide intimate physical contact between
the electrode and SE and reduce the interfacial resistance,
remains the work for the future.
Another challenge associated with the NASICON based
electrolyte is the high resistance offered by grain bound-
aries. For reducing the grain boundary resistance, a high
sintering temperature (≥ 1200 °C) is essential, which could
further lead to challenges in material processing (for exam-
ple, secondary phase formation, evaporation of Na and P,
microcracking, etc.). The complex and expensive techniques
for synthesizing phase pure NASICON electrolytes are not
favourable for large-scale production. As a result, a cost-
effective and simple synthetic approach must be developed
to realize the bulk production of high-performance solid
electrolytes. Although, a recently developed solution-
assisted solid-state reaction method seems to resolve this
issue, more work is required to understand the correlations
between the processing parameters, chemistry, and conduc-
tivity in these oxides.
Even though these materials have been studied over the
last 45 years, there is still ambiguity about the correlations
between the crystal structure and ionic conductivity. Few
studies reported that the rhombohedral phase is more favour-
able for the conduction of sodium ions as it possesses higher
symmetry than the monoclinic phase [33, 72, 130]. While
other investigations suggested that the monoclinic phase
has superior ionic conductivity owing to the larger unit-cell
size and the lower energy barrier for Na ion conduction,
which is caused by the high-energy excited Na-sites [85,
138, 141, 142]. Also, the maximum total ionic conductiv-
ity in ­Na1+xZr2SixP3-xO12 found in the x range of 1.8 and
2.2, where the monoclinic phase is stable. A deeper insight
into the Na conduction mechanism can assist in the rational
design of new and improved NASICON compositions as an
alternative to the β-alumina.
Ionics
Fig. 18  Summary of strategies employed to improve the performance of NASICON-type oxides for sodium-ion batteries
In summary, improving the rate capability and cyclability
of solid-state sodium-ion batteries based on NASICON elec-
trolyte requires high ionic conduction across the electrolyte
and a good electrode/SE interface. Figure 18 summarizes
the strategies that have been employed in the past to over-
come the challenges associated with NASICON solid elec-
trolytes. Since previous approaches have been to a certain
extent successful in augmenting the conductivity in these
oxides, future research should be primarily focused on find-
ing solutions to reduce the interfacial resistance between
the electrode and SE by maintaining close physical contact
during the charging-discharging process.
Conclusions
Na-ion conducting solid electrolytes are critical for realiz-
ing the development of sodium-ion batteries in all-solid-
state designs. Among various materials, NASICON-type
oxides have shown tremendous potential as they can pro-
vide large interconnected channels for a fast migration of
the large sodium ions. A significant number of experimen-
tal and theoretical studies have been published in the past,
focussing on understanding, and improving several aspects
of these oxides. This review discusses the basic character-
istics and highlights the various challenges associated with
NASICON-type electrolytes. It also summarizes several
recently explored strategies to overcome these issues and to
tailor the properties of these oxides. Further, the ionic trans-
port mechanism inside the structure and the effect of adding
various dopants and sintering aids on the conductivity and
microstructure have been comprehensively described. More-
over, this review provides a perspective and future research
opportunities on these oxides, which show immense promise
in rechargeable solid-state batteries.
Acknowledgements  The authors gratefully acknowledge the support
from the Department of Science and Technology, Government of India
(grant no. EMR/2016/005438) toward the funding of this research.
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