Received: 21 February 2021 Revised: 14 April 2021 Accepted: 23 April 2021

DOI: 10.1002/inf2.12222

REVIEW ARTICLE

Progress and perspective of Li1 + xAlxTi2-x(PO4)3 ceramic

electrolyte in lithium batteries

Ke Yang1,2 | Likun Chen1,2 | Jiabin Ma1,2 | Yan-Bing He1 | Feiyu Kang1,2

1
Shenzhen All-Solid-State Lithium Battery
Electrolyte Engineering Research Center,
Abstract
Tsinghua Shenzhen International The replacement of liquid organic electrolytes with solid-state electrolytes
Graduate School, Institute of Materials
(SSEs) is a feasible way to solve the safety issues and improve the energy den-
Research (IMR), Shenzhen, China
2 sity of lithium batteries. Developing SSEs materials that can well match with
School of Materials Science and
Engineering, Tsinghua University, high-voltage cathodes and lithium metal anode is quite significant to develop
Beijing, China high-energy-density lithium batteries. Li1 + xAlxTi2-x(PO4)3 (LATP) SSE with

Correspondence
NASICON structure exhibits high ionic conductivity, low cost and superior air
Yan-Bing He, Shenzhen All-Solid-State stability, which enable it as one of the most hopeful candidates for all-solid-
Lithium Battery Electrolyte Engineering state batteries (ASSBs). However, the high interfacial impedance between
Research Center, Institute of Materials
Research (IMR), Tsinghua Shenzhen LATP and electrodes, and the severe interfacial side reactions with the lithium
International Graduate School, Shenzhen metal greatly limit its applications in ASSBs. This review introduces the crystal
518055, China.
structure and ion transport mechanisms of LATP and summarizes the key fac-
Email: [email protected]
tors affecting the ionic conductivity. The side reaction mechanisms of LATP
Feiyu Kang, Shenzhen All-Solid-State with Li metal and the promising strategies for optimizing interfacial compati-
Lithium Battery Electrolyte Engineering
bility are reviewed. We also summarize the applications of LATP including as
Research Center, Institute of Materials
Research (IMR), Tsinghua Shenzhen surface coatings of cathode particles, ion transport network additives and inor-
International Graduate School, Shenzhen ganic fillers of composite polymer electrolytes. At last, this review proposes the
518055, China; School of Materials Science
challenges and the future development directions of LATP in SSBs.
and Engineering, Tsinghua University,
Beijing, China.
Email: [email protected] KEYWORDS
crystal structure, interfaces, ionic conductivity, Li1 + xAlxTi2-x(PO4)3, lithium batteries
Funding information
Key-Area Research and Development
Program of Guangdong Province, Grant/
Award Number: 2020B090919001;
National Natural Science Foundation of
China, Grant/Award Number: U2001220;
Shenzhen All-Solid-State Lithium Battery
Electrolyte Engineering Research Center,
Grant/Award Number:
XMHT20200203006; Shenzhen Technical
Plan Project, Grant/Award Number:
JCYJ20180508152210821
JCYJ20170817161221958
JCYJ20180508152135822

This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided
the original work is properly cited.
© 2021 The Authors. InfoMat published by UESTC and John Wiley & Sons Australia, Ltd.

InfoMat. 2021;1–23. wileyonlinelibrary.com/journal/infomat 1

2 YANG ET AL.

1 | INTRODUCTION is mainly utilized in thin film batteries. The famous

garnet-type ICE Li7La3Zr2O12 exhibits room-temperature
The development of lithium-ion batteries (LIBs) not only ionic conductivity of 10
4 S/cm and good compatibility
provides a huge market for portable electronic devices, with Li metal anode, but the Li+/H+ exchange could
but also facilitates the actual commercialization of new form LiOH and Li2CO3 on the surface of LLZO, which
energy vehicles and electric ships. At the same time, LIBs greatly reduces its wettability with lithium metal and
alleviate the dependence on fossil fuels, reduce the pollu- results in large interfacial resistance.
tion to ecological environment and promote the use of Compared with other ICEs, the NASICON-type Li1
clean energy.1,2 However, the most commercial LIBs use + x xTi2-x(PO4)3 (LATP) ceramic electrolyte reveals high
Al
organic liquid electrolytes currently, which bring serious room-temperature ionic conductivity (10
4–10
3 S/cm),
safety problems due to their poor oxidation resistance, good chemical stability, high oxidation voltage (~6 V) and
high flammability and bad compatibility with lithium low prices of raw materials.16 In addition, the high stabil-
metal anode.3,4 Replacing the liquid electrolytes with ity against H2O/CO2 allows proceeding and preparation of
solid-state electrolytes (SSEs) is believed to thoroughly LATP materials in ambient air. However, side reactions
solve the safety issues.5 In addition, the SSEs have could occur when the LATP contacts with lithium metal,
attracted great interests due to their excellent mechanical in which the Ti4+ is reduced to Ti3+, forming an ionic/
strength and good electrochemical stability. Fortunately, electronic mixed conductive layer (MCL).17 This MCL is
the continuous attention and extensive research of SSEs responsible for continuous degradation of LATP/Li inter-
have significantly promoted the development of high- face and leads to battery failure ultimately. In addition,
energy-density solid-state batteries. the high impedance resistance originating from the solid–
As the core component of all-solid-state batteries solid contact between LATP SSE and electrodes limits the
(ASSBs), the SSEs can be mainly divided into three types: electrochemical performance of batteries greatly.18 Since
solid polymer electrolytes (SPEs), inorganic ceramic elec- it was discovered in 1976, there has been an increasing
trolytes (ICEs) and solid composite electrolytes (SCEs). interest in this NASICON-type SSE. Therefore, it is impor-
The SPEs usually consist of a poly(ethylene oxide) tant and timely to review the progress of LATP ceramic
(PEO),6 poly(vinylidene fluoride) (PVDF),7 polyacryloni- electrolyte and correlative solid-state batteries.
trile (PAN)8 and poly(vinylidene fluoride- In this review, we introduce the crystal structure and
hexafluoropropylene) copolymer (PVDF-HFP)9 as the Li+ transport mechanisms of LATP, and summarize the
matrix and some lithium salts such as Lithium key factors, including microstructure, secondary phases
bis(trifluoromethanesulfonyl) (LiTFSI), Lithium bis and sintering conditions, which show great effect on the
(fluorosulfonyl)imide (LiFSI) and Lithium perchlorate ionic conductivity. Furthermore, the research progress on
(LiClO4). The SPEs with light, flexible and scalable the interfacial reaction mechanisms and strategies to
nature properties are highly compatible with electrodes optimize interface compatibility are discussed. In addi-
and the manufacturing process of commercial LIBs. tion, the other applications of LATP as surface coatings
However, the low room-temperature ionic conductivity of cathode particles, ion transport network additives and
and unsatisfactory ability in suppressing lithium den- inorganic fillers of composite polymer electrolytes are
drites growth limit their applications in solid-state lith- exemplified. At last, the challenges and the development
ium metal batteries. By contrast, the ICEs are widely directions are outlined to promote the progress of LATP
studied due to their high room-temperature ionic con- SSE in future (Figure 1).
ductivity, large high-voltage oxidation resistance and
excellent mechanical robustness, but these ceramics pre-
sent rigid and brittle properties, which cause poor contact
with electrodes. Generally, the widely studied ICEs
include NASICON-type [Li1 + xAlxTi2-x(PO4)3, Li1
10
+ xAlxGe2-x(PO4)3], LISICON-type (Li1 + xZn1-xGeO4),11
Garnet-type (Li7La3Zr2O12),12 perovskite-type
(Li0.34La0.51TiO2.94), sulfide-based, LiPON,15 and so
13 14

on. These ICEs have their own advantages and draw-

backs when applied in ASSBs. For instance, sulfide-based
SSEs display high ionic conductivity, but they are limited
by high moisture sensitivity and poor electrochemical
window. LiPON electrolyte demonstrates room-
temperature ionic conductivity of only 10
6 S/cm, which FIGURE 1 Schematic of the structure in this review
YANG ET AL. 3

2 | CRYSTA L ST R U CTU R E AN D neutron diffraction (MD). There are three Li sites in LTP
L I + TRANSPORT M ECHANISMS crystal: M1 sites (Li1, 6b, sixfold oxygen coordination),
O F LA T P M2 sites (Li2, 18e, ten-fold oxygen coordination), and M3
sites (between M1 and M2, fourfold oxygen coordination;
The NASICON structure was discovered in Na+ conduc- Figure 2). The results show that Li+ preferentially
tor of NaM2(PO4)3 (M = Ge, Zr),10 which consists of PO4 occupies M1 sites in LTP, while Li+ tends to occupy M1
tetrahedra and MO6 octahedra. Two MO6 octahedra and and M3 sites in LATP. The increased Li+ helps to occupy
three PO4 tetrahedra connected by the top oxygen atoms M3 sites, which reduces electrostatic repulsion between
construct a three-dimensional Na+ transporting net- Li1 and Li3 ions. Redhammer et al22 demonstrated the
works. With the substitution of M sites and Na atoms by correlation between structure and ionic conductivity of
Ti and Li atoms, the material remains the primary LATP through single-crystal X-ray diffraction (XRD).
NASICON structure and converts into a Li+ conductor They found that the enhanced ionic conductivity is
LiTi2(PO4)3 (LTP). The pure LTP displays poor room- highly associated with additional Li+ at the M3 sites. In
temperature ionic conductivity because of the high grain addition, doping Al3+ can lower the Li─O bond strength
boundaries resistance. Specifically, structure modification and strengthen the Ti─O bond, which may promote the
through isovalent or aliovalent substitution of Ti has Li+ transport in LATP.23
been considered a practical solution to improve the ionic Li+ transport mechanisms in LATP ion conductors
conductivity of LTP crystal. For isovalent substitution, have been studied by experimental and theoretical
doping larger size ions can increase the size of Li+ trans- methods. Nuspl et al24 studied Li+ transport pathways in
port pathways and lower the activation energy. For LTP and LATP (x = 0.3) through MD method. The bar-
aliovalent substitution, the ionic conductivity is rier height of Li+ diffusion in LTP is 0.3 eV, which is
enhanced due to the increased Li+ concentration. Aono affected by electrostatic interactions around Li+. Interest-
et al19 applied several smaller cations to partially replace ingly, the bulk diffusion of LTP only changed slightly
Ti4+ in Li1.3M0.3Ti1.7(PO4)3 (M = Al3+, Cr3+, Ga3+, Fe3+, after Al replacement. Later, Lang et al25 investigated the
Sc3+, In3+, Y3+ and La3+). It was found that the impact of local structure of substitution variants on the
Li1.3Al0.3Ti1.7(PO4)3 sample shows the highest room- mobility of Li+ in LTP using minimum energy paths cal-
temperature ionic conductivity of 7  10
4 S cm
1, culations. It is found that there is a relationship between
which is attributed to the increased bulk density and the size of LiO6 octahedra and activation energy of Li+.
more Li+ for charge balance at the grain boundaries. Arbi Larger LiO6 octahedra size can lower energy barrier for
et al20 revealed that the partial replacement of Ti4+ with jump of Li+ (Figure 3A). They also found that the bulk
Al3+ and the increased Li+ concentration obviously transport of Li+ in LTP is only marginally changed with
decreased the c-axis length but slightly affected a-axis via Al substitution, which cannot explain the nearly three
a progressive contraction of AlO6 along the c-axis, which orders of magnitude increasement in ionic conductivity.
significantly promote the ionic conductivity. Thus, they proposed that the increased Li+ concentration
In addition, the Li distributions in LTP and LATP caused interstitial migration of Li ions in LATP. At pre-
crystal were also studied by Fourier map differences and sent, there are two main reasons to explain the high ionic
conductivity of LATP. First, the diffusion barrier at the
grain boundaries is significantly reduced. Second, the
increased Li+ concentration enhances Li+ mobility. Epp
et al28 revealed several transport pathways in
Li1.5Al0.5Ti1.5(PO4)3 by 7Li nuclear magnetic resonance
(NMR). The calculated activation energy between M1
and M3 sites of Li+ is 0.16 eV, which is consistent with
theoretical studies.25 Senyshyn et al26 studied Li+ diffu-
sion pathways in Li1.3Al0.3Ti1.7(PO4)3 via XRD and maxi-
mum entropy method reconstruction. The obtained
negative nuclear density maps revealed a zigzag shape of
Li+ transport pathway (M1-M3-M3-M1) with activation
energy of 0.33 eV (Figure 3B). In addition, Emery et al29
also investigated Li+ migration behaviors in
F I G U R E 2 Crystal structure of LiTi2(PO4)3 and M1, M2, and Li1.3Al0.3Ti1.7(PO4)3 using local structure and kinetics
M3 sites of Li atoms. Reproduced with permission: Copyright 2017, studies. They found that the Li+ motion occurs through
Elsevier Ltd21 the triangular oxygen planes formed between the Ti/AlO6
4 YANG ET AL.

F I G U R E 3 (A) Activation energies against the polyhedra volumes of LiO6 octahedra in LiX0.2Ti1.8(PO4)3. Reproduced with permission:
Copyright 2015, American Chemical Society.25 (B) Bond valence mismatch in Li1.3Al0.3Ti1.7(PO4)3 and maximum entropy method
reconstructed negative nuclear density maps. Reproduced with permission: Copyright 2016, American Chemical Society.26 (C) 2D slices of
the observed fourier map for Li1.4Al0.4Ti1.6(PO4)3 and Lithium pathways at 273 and 573 K. Reproduced with permission: Copyright 2020,
Elsevier Ltd27

octahedra and PO4 tetrahedra, and further induces the to suppress the growth of lithium dendrites. In this sec-
Ti/AlO6 stretching distortion. David et al27 confirmed tion, we will summarize the key factors affecting the
that the Li+ migration pathway only takes place between ionic conductivity from three aspects of microstructure,
M1 and M2 sites according to MD method (Figure 3C). secondary phases, and sintering conditions.
Although many researches have been done on the Li+
transport pathways in LATP, there are still controversial
viewpoints. Therefore, the development of advanced 3.1 | Microstructure
characterizations and simulation methods are necessary
for understanding Li+ diffusion behaviors and provide The microstructure of LATP plays key role on the crystalli-
theoretical supports for improving ionic conductivity zation and the ionic conductivity. LATP is obtained by par-
of LATP. tially replacing Ti4+ in LTP crystal with Al3+, thus the
content of Al3+ is the primary factor to determine the ionic
conductivity. Lang et al25 found that the extra Li+ can be
3 | K EY FA CTO RS FO R I ON I C easily trapped around Al3+ when the content of Al3+ is
CO NDUCTIVI T Y OF LATP low, which hinders the ions transport obviously. Arbi et
al30 proposed a core-shell model to demonstrate the impact
Ionic conductivity is an important parameter for SSEs. of Al content on ionic conductivity. The LATP presents
For the ideal SSEs, the room-temperature ionic conduc- composition heterogeneity when the Al content is low,
tivity as a key factor should be larger than 10
4 S cm
1 to which forms a Li-poor shell and Al-rich core structure,
achieve the excellent performance at room temperature. causing large grain boundaries resistance. With the Al con-
In addition, the certain mechanical strength is necessary tent increasing, the homogeneous composition in LATP
YANG ET AL. 5

F I G U R E 4 (A) Core-shell model used to explain observed electrical heterogeneity in NASICON samples. Reproduced with permission:
Copyright 2014, Elsevier Ltd.30 (B) Energy profile and the Li+ cooperative transport pathways in LATP-0.16 and LATP-0.50. Reproduced
with permission: Copyright 2020, The Royal Society of Chemistry.31 (C) Microstructure images of LATP-based samples with various amount
of LiTiOPO4. Reproduced with permission: Copyright 2016, Elsevier Ltd32

grains would decrease the grain boundaries resistance and boundaries is detrimental for ionic conductivity.33,34 There-
improve ionic conductivity (Figure 4A). Zhang et al31 dis- fore, the optimal Al content is believed to be around 0.3–
cussed the effect of the Al concentration on Li+ diffusion 0.5.35 Furthermore, some studies have adopted trivalent
behaviors in LATP using molecular dynamics method. By cations to ameliorate the microstructure of LATP.
comparing the ionic conductivity of Li1.16Al0.16Ti1.84(PO4)3, Dharmeth et al36 applied trivalent cations (R = Ga3+, Sc3+,
Li1.33Al0.33Ti1.67(PO4)3 and Li1.5Al0.5Ti1.5(PO4)3, it was Y3+) to substitute Al3+ in the Li1.3Al0.3-zRzTi1.7(PO4)3 and
observed that the Li1.5Al0.5Ti1.5(PO4)3 shows the highest studied the impact of concentration range (z = 0.01, 0.03,
ionic conductivity. They found that increasing the Al con- 0.05, 0.07) on the ionic conductivity of SSEs. Generally, the
centration in Li1.5Al0.5Ti1.5(PO4)3 could relieve the trapping ionic size of the dopant cations plays the decisive role on
effect on Li+ due to the delocalization of polarization inter- the ionic conductivity. When the ionic size difference
actions and the depopulation of oxygen atoms, resulting in between trivalent cations and Al3+ is small, the element
a smooth energy landscape and destabilization of Li+ substitution can take place inside lattice. For instance,
(Figure 4B). But when the Al content is high (x = 0.7), the since the ionic radius of Ga3+ has a small difference from
nonconductive phase AlPO4 formed around the grain Al3+, cation substitution can occur inside the lattice,
6 YANG ET AL.

resulting in the increases of structure parameters and The pristine LATP and different composite SSEs were
highest ionic conductivity (~10
3 S cm
1). In case of the sintered at 900 C for densification. The ionic conductivity
Sc3+ and Y3+, the large ionic size difference leads to the of pristine LATP with insulating AlPO4 was about
formation of nonconductive ScPO4 and YPO4 toward grain 1  10
4 S cm
1. When the composite contains 10 wt%
boundaries, blocking Li+ transport and deteriorating over- LiTiOPO4, the ionic conductivity of SSE reduces obvi-
all ionic conductivity. Except for replacing Al3+ with triva- ously due to large consumption of AlPO4, leading to the
lent cations, many studies have shown that replacing Ti4+ abnormal grains growth and cracks inside pellet.
in the LATP lattice can also improve ionic conductivity. Lu Whereas, a balance was obtained with the addition of
et al37 synthesized W-doped LATP via solid state reactions 5 wt% LiTiOPO4. On the one hand, a small amount
by adding WO3 to the raw materials. XRD examinations of AlPO4 can react with LiTiOPO4 to form LATP. On the
indicate that the W6+ is incorporated into the lattice owing other hand, most of AlPO4 help to ensure the compact-
to the substitution of W6+ for Ti4+, which promotes the ness of LATP and control the growth rate of grains with-
occupancy of M2 sites and creates more Li+ vacancies in out forming voids in the pellet. Besides AlPO4, LiTiPO5
LATP. The maximum ionic conductivity reaches and Li4P2O7 are also the secondary phases of LATP.42
5.49  10
4 S cm
1 at 5 wt% of WO3. Bai et al38 reported a Optimizing sintering conditions is effective to eliminate
Li1.4Al0.4Ti1.6(PO4)3/3 wt% GeO2 composite electrolyte, in these secondary phases, which will be summarized in the
which the Ti4+ is substituted by Ge4+ and the excess GeO2 next section.
at the grain boundaries may enhance Li+ diffusion
through grain boundaries.
In general, the microstructure of LATP such as grains 3.3 | Sintering conditions
and grain boundaries has an important effect on ionic
conductivity. The relationship between the content of Al Critically, the ionic conductivity of LATP SSE is governed
element and ionic conductivity has been clearly by grains and grain boundaries. Namely, the overall ionic
explained. A proper amount of Al element (x = 0.3–0.5) conductivity consists of bulk conductivity and grain
improves ionic conductivity significantly. In addition, cat- boundaries conductivity. Specifically, the bulk conductiv-
ions doping can also increase lattice parameters to ity for microstructure can be improved by optimizing Al
improve ionic conductivity. In terms of large grain content and doping cations. For grain boundaries con-
boundaries impedance of LATP, many studies have ductivity, the high temperature sintering process is pre-
shown that the metal oxide fillers can improve the Li+ requisite to achieve low grain boundaries resistance.
diffusion characteristics at the grain boundaries. How- Suitable sintering conditions determine the overall ionic
ever, advanced characterizations and simulation methods conductivity of LATP SSE. In this section, the sintering
to reveal the Li+ transport mechanisms at the grain conditions are systematically reviewed from three aspects
boundaries need to be further explored. such as sintering temperature, sintering techniques and
sintering aids.

3.2 | Secondary phases

3.3.1 | Sintering temperature
Another important factor affecting ionic conductivity of
LATP is the secondary phases. Specifically, the AlPO4 At present, LATP SSE has been successfully synthesized
formed in sintered LATP pellet due to Li+ loss is the by several routes, which can be generally divided into
main secondary phase, which seems like “double-edged solid-based and liquid-based approaches.43 Normally, in
sword” for ionic conductivity.39 The smaller unit cell of the solid-based methods, the solid chemical precursors
AlPO4 can densify LATP ceramic pellet, which is benefi- are mixed together and ball milled, followed by solid-
cial for ionic conductivity due to space charge effect state reactions through annealing and sintering treat-
when it is controlled in low content.40 Nevertheless, the ment. The solid-based methods include melt-
AlPO4 phase is nonconductive for Li+, so the increased quenching,44 mechanical activation,45 spark plasma
amount of AlPO4 will hinder Li+ transport through grain sintering (SPS),46 field-assisted sintering technique
boundaries and decrease the overall ionic conductivity.41 (FAST)47 and microwave-assisted sintering.48 For liquid-
Therefore, it is essential to balance the densification and based methods, the chemical precursors are usually dis-
ionic conductivity at the same time. Thomas et al32 inves- solved in solvents or aqueous solutions, followed by heat
tigated the influence of LiTiOPO4 fillers on the micro- treatment and sintering. Specially, the liquid-based
structure and ionic conductivity of LATP (Figure 4C). methods require lower heat treatment temperature
YANG ET AL. 7

compared with solid-based approaches to obtain the crys- obtained SSEs have larger grains and less grain bound-
tal structure. Common liquid-based methods consist of aries. However, lithium loss and secondary phases forma-
sol–gel method,49 co-precipitation50 and solution-based tion are inevitable during high temperature treatment.34
method.51 We mainly focus on pellet sintering tempera- In contrast, the liquid-based methods require lower
ture to illustrate the impact of sintering process on ionic sintering temperature, which is conductive to large-scale
conductivity clearly. production.53 The sol–gel method is a common route of
Paul et al52 investigated the influence of sintering liquid-based method specifically. Zhao et al54 discussed
temperature on the microstructure and ionic conductivity the impact of heat treatment and sintering temperature
of glass–ceramic Li1 + x + yAlxTi2
xSiyP3
yO12 (LATPS, on ionic conductivity. They found that the low heat treat-
x = 0.3, y = 0.2) using melt-quenching method. With the ment temperature (<600 C) would induce incomplete
sintering temperature increases from 700 to 900 C, the reactions between precursors. The optimal sintering pro-
grain bulk conductivity improves from 4.6  10
6 S cm
1 cess is pre-heating at 850 C for 5 h and then sintering at
to 1.09  10
3 S cm
1, while the grain boundaries con- 900 C for 3 h. The density of the obtained LATP ceramic
ductivity only changes slightly. Significantly, the grain reaches 95% and the room-temperature ionic conductiv-
boundaries ionic conductivity increases from 4  10
6 S ity is 6  10
4 S cm
1. In addition, the aqueous solution-
cm
1 to 3.63  10
4 S cm
1 with the sintering tempera- based method is widely adopted due to the reduction cost
ture increasing from 900 to 1000 C. The insulting TiO2 of solvents. Ma et al51 prepared Li1.3Al0.3Ti1.7(PO4)3 SSE
appeared at 900 C and AlPO4 emerged at 1000 C. There- via the solution method and found the pellet sintered at
fore, the obvious enhancement of grain boundaries ionic 800 C for 12 h exhibited the highest room-temperature
conductivity may be attributed to uniform distribution of ionic conductivity of 1.21  10
3 S cm
1. Except for the
AlPO4 at grain boundaries, which reduces blocking effect sintering temperature, the pH values of the precursor
of TiO2. As a result, the optimal sintering temperature of solutions are of great significance as well for the solution-
LATPS SSE was 900–1000 C. Solid-based methods usu- based method. Kou et al55 discussed the effect of pH on
ally require higher sintering temperature and longer the ionic conductivity and cycling stability of the battery.
holding time to achieve maximum densification, thus the They found that when the pH is adjusted to 6.0, the

TABLE 1 Synthetic routes, sintering temperatures, and ionic conductivity of LATP

Composition Synthetic routes Sintering temperature ( C) Ionic conductivity (S/cm) References

4
Li1.4Al0.4Ti1.6(PO4)3 Co-precipitation 900 1.83  10 50

Li1.5Al0.5Ti1.5(PO4)3 Co-precipitation 1050 1.5  10
4 56

Li1.3Al0.3Ti1.7(PO4)3 Sol–gel 750 1.68  10
8 57

Li1.3Al0.3Ti1.7(PO4)3 Sol–gel 900 1.2  10
4 58

Li1.3Al0.3Ti1.7(PO4)3 Sol–gel 900 1  10
3 49

4
Li1.4Al0.4Ti1.6(PO4)3 Sol–gel 950 5.9  10 59

Li1.3Al0.3Ti1.7(PO4)3 Sol–gel 1000 (3–4)10
4 60

Li1.3Al0.3Ti1.7(PO4)3 Sol–gel 1000 4.2  10
4 61

Li1.5Al0.5Ti1.5(PO4)3 Sol–gel 1000 4.5  10
4 62

4
Li1 + xAlxTi2-x(PO4)3 Sol–gel 1100 1.83  10 63

Li1.3Al0.3Ti1.7(PO4)3 Mechanical activation 900 6.2  10
5 64

Li1.4Al0.4Ti1.6(PO4)3 Mechanical activation 900 1.09  10
3 45

Li1.3Al0.3Ti1.7(PO4)3 Spray drying method 900 6.22  10
4 65

4
Li1.3Al0.3Ti1.7(PO4)3 Spray drying method 900 1.182  10 55

Li1.3Al0.3Ti1.7(PO4)3 Solution method 800 1.21  10
3 51

Li1.5Al0.5Ti1.5(PO4)3 Solution method 900 5  10
3 66

Li1 + xAlxTi2-x(PO4)3 Melt-quenching method 950 1.3  10
3 67

4
Li1.3Al0.3Ti1.7(PO4)3 Melt-quenching method 850 4  10 68

Li1.3Al0.3Ti1.7(PO4)3 Molten-flux method 800 7.02  10
4 69

Li1.3Al0.3Ti1.7(PO4)3 Modified pechini method 900 6  10
4 70

Abbreviation: LATP, Li1 + xAlxTi2-x(PO4)3.

8 YANG ET AL.

LATP SSE presents the highest ionic conductivity of The UHS features high heating (103–104 C min
1) and
1.182  10
3 S cm
1. The LiCoO2/LATP/Li full battery cooling rates, and high sintering temperature (3000 C),
retains capacity retention of 94.28% after 300 cycles. The which enable ultrafast sintering times of 10 s. The ultra-
ionic conductivity of LATP pellets via different synthetic fast heating rate at high temperature for only several sec-
methods and sintering temperature is highlighted as onds helps to reduce the segregation of impurities at grain
shown in Table 1. Compared with the solid-based boundaries. Some dense LLZO and LATP/LLZTO double-
methods, the liquid-based methods based on homoge- layer SSEs were successfully prepared using this method.
neous phase construction at the atomic/molecular level As a result, the Li/LLZO/Li symmetric cell demonstrates
can not only control the LATP powders with precise stoi- the critical current density (CCD) as high as 3.2 mA cm
2,
chiometric ratio, but also reduce the total preparation which greatly promote the development of preparation
cost by lowering the sintering temperature. In addition, process and improvement of the electrochemical perfor-
the liquid-based methods lead to higher ionic conductiv- mance of the inorganic solid electrolytes.
ity than that of solid-based methods.

3.3.3 | Sintering aids

3.3.2 | Sintering techniques
Although the ionic conductivity of LATP SSE has made
The conventional sintering process requires high tempera- great progress due to the development of sintering tech-
ture to obtain dense LATP pellets, while the lithium loss niques, the complicated equip ment and high costs are
makes it difficult to obtain SSE with accurate stoichiomet- always required. Various sintering aids have been
ric ratio. Thus, the rapid sintering techniques are devel- adopted to fabricate high performance LATP pellets.
oped such as SPS, FAST and microwave-assisted sintering. Many studies have shown that adding sintering aids with
In principle, based on microscopic electric discharge, SPS the low melting point can coarsen and densify LATP pel-
can transform ceramic powders to dense pellets with resis- lets.76 These sintering aids maintain the liquid phase at
tive heating at high rate (>100 C min
1).71 For instance, high temperatures, which reduce the crystallization tem-
Xu et al72 prepared highly dense LATP SSE with nearly perature and enhance the densification of ceramics to a
100% densification at 650 C, which delivers an outstand- certain extent. Common sintering aids are mainly various
ing room-temperature ionic conductivity of 1.12  10
3 S lithium salts, such as Li2O, Li3PO4, Li3BO3, LiBO2,77 LiF
cm
1. Waetzig et al73 investigated the influence of and so on. Aono et al78 added Li2O as sintering aids to
sintering method on the ionic conductivity of LATP for the first time, which reduced the porosity of the
Li1.3Al0.3Ti1.7(PO4)3 pelletik. They found that SPS sintering ceramic effectively and the room-temperature ionic con-
process not only achieves higher density than the tradi- ductivity is 3  10
4 S cm
1. Davaasuren et al66 found
tional sintering method, but also reduces the content of that the Li2B4O7 sintering aids acting as ion-conducting
secondary phases obviously. FAST applies a certain volt- bridge between LATP grains can remarkably reduce the
age to the sample during sintering to enhance the density. grain boundaries resistance from 3500 to 1500 Ωcm. In
The applied voltage was considered to significantly influ- addition, Kwatek et al79 introduced Li2.9B0.9S0.1O3.1 glass
ence the density and ionic conductivity of pellets. Andrew as additive material to LATP. They found that the forma-
et al74 applied different voltage (0 V, 2 V, 10 V, 20 V) dur- tion of ionic conducting phosphates at grain boundaries
ing sintering to investigate the impact of voltage on densi- is the main reason for the increasement of ionic conduc-
fication and microstructure. When the voltage increases tivity. In general, the action mechanisms of sintering aids
from 0 to 20 V, the relative density of the sample is are mainly reflected in increasing density of LATP pellets
improved from 85 to 95.5%. Furthermore, microwave- and promoting Li+ transport at grain boundaries. Adding
assisted sintering is another rapid sintering method with a sintering aids provides an important idea for preparing
unique sintering mechanism. The interactions between high-density ceramic pellets, and the exploration of novel
microwaves and molecules cause the electromagnetic sintering aids can further improve the ionic conductivity
energy of the material to be dissipated, so that the mate- of LATP SSE.
rial absorbs the energy of the microwaves to achieve fast
volumetric sintering. For example, Hallopeau et al48 syn-
thesized LATP pellets at 890 C for only 10 min, and the 4 | INTERFACES BETWEEN LATP
obtained SSE delivers room-temperature ionic conductiv- SSE AND ELECTRODES
ity of 3.15  10
4 S cm
1. Recently, Wang et al75 reported
an ultrafast high-temperature sintering (UHS) process to To realize the excellent performance of SSBs, it is essen-
fabricate SSE by radiative heating under inert atmosphere. tial to not only develop SSEs with high room-temperature
YANG ET AL. 9

ionic conductivity, but also construct low impedance and Kim et al18 deposited 500 nm-thick LiCoO2 (LCO) thin film
high chemical stability electrode/electrolyte interface. on the surface of LATP pellet by sputtering and annealing
For LATP SSE, there are two major problems. First, the method at 500 C. The obtained LCO/LATP interface
high interfacial impedance resistance originating from remains stable without the formation of intermixture and
the poor contact between LATP SSE and electrodes limits secondary phase for 50 cycles. The sintering temperature is
the electrochemical performance of batteries severely. considered a crucial parameter for this technique. Later,
Second, the Ti4+ can easily be reduced to Ti3+ by lithium Kato et al80 studied the impact of sintering temperature on
metal, resulting in the failure of LATP. Therefore, the the LiNi1/3Co1/3Mn1/3O2 (NCM)/LATP interfacial proper-
two difficulties of high interface impedance and interfacial ties. The mutual diffusion region exists in both
side reactions must be solved simultaneously for con- NCM/LATP-700 and NCM/LATP-900, but the
structing ASSBs using LATP SSE. In this section, the latest NCM/LATP-900 has three orders of magnitude larger
research progress with regard to the interfaces between interfacial resistance than the NCM/LATP-700. The Co-
LATP SSE and electrodes and the development of interfa- rich region and MnCo2O4 impurity formed at the
cial optimization strategies are summarized in details. NCM/LATP interface at 900 C greatly retard Li+ transfer
across the interface. Hoshina et al81 also found that more
impurity phases could form at the LiNi0.5Mn1.5O4/LATP
4.1 | Interfaces between LATP SSE and interface with increasing heat treatment temperature.
cathodes Therefore, a suitable sintering temperature is necessary to
balance the interfacial resistance and the amount of impu-
The main problem of the LATP SSE/cathode interface is rity phases. Nevertheless, the low mass loading of cathode
the high impedance resistance originating from the “solid– active materials and the complicated process of this tech-
solid” contact, which leads to that Li+ cannot transport nique limit its practical applications.
quickly through the interface and limits the electrochemi- A buffer layer such as liquid electrolytes (LE),82 poly-
cal performance of batteries. High temperature annealing mer solid electrolytes,83 plastic-crystal electrolytes84 and
is an effective method to tackle this issue. For example, depositing cathode materials on LATP pellet techniques80

F I G U R E 5 (A) lithium ions and electrons fluxes with LE as both sides of the LATP. Reproduced with permission: Copyright 2018,
Elsevier Ltd.82 (B) Illustration of Li+ migration across the Li/LATP/LFP cell without and with PEO adhesion. Reproduced with permission:
Copyright 2019, Elsevier Ltd.83 (C) Solid-state battery with DPCE and the SEM images, energy-dispersive X-ray spectroscopy mapping of
DPCE. Reproduced with permission: Copyright 2019, American Chemical Society.85 (D) Cycling stability of all-solid-state Li-S battery at 0.1C
and 75 C. Reproduced with permission: Copyright 2020, Elsevier Ltd86
10 YANG ET AL.

was also introduced to reduce impedance resistance, espe- volume changes of cathode materials. Thus SN was utilized
cially at high mass loading of cathode active materials. as a buffer layer to reduce impedance resistance.90 In addi-
Wang et al82 employed 2 μl LE (1 M LiPF6 in EC/DMC/ tion, in-situ polymerization is also an effective solution to
DEC) at the LiFePO4 (LFP)/LATP interface (Figure 5A). the interfacial issue. A small amount of liquid precursors
The trace amount of LE not only wet the interface, but also are added to keep cathode and SSE in good contact, and
infiltrate the pores of cathode, enabling a three-dimen- then the LE are converted into solid phases through in-situ
sional continuous Li+ flux with additional solid–liquid con- polymerization reactions. Liu et al91 constructed a cathodic
tact. As a result, the LFP/LATP/Li battery delivers specific gel polymer electrolyte (CGPE) between NASICON-type
capacity of 125 mAh g
1 at 1C and 98 mAh g
1 at 4C. LAGP SSE and LiMn2O4 cathode by in-situ polymerization.
Although building the solid–liquid hybrid electrolyte is The CGPE was prepared by polymerizing 1.5 wt% pen-
effective to reduce impedance resistance, the existence of taerythritol tetraacrylate (PETEA) in 1M LiTFSI in
liquid organic electrolyte may still bring safety risks. Yang adiponitrile LE, exhibiting ionic conductivity of 10
3 S
et al83 applied PEO adhesive as interfacial buffer layer to cm
1 at 25 C and high oxidation voltage of 4.8 V. Conse-
contact LATP SSE and LFP cathode in view of its Li+ con- quently, the LiMn2O4/LAGP/Li battery delivered capacity
ducting ability and great compatibility with Li metal anode. retention of 80.3% after 120 cycles at 0.1C. Moreover, the
Meanwhile, PEO adhesive was also employed as binder polymer buffer layers could also be employed in lithium-
inside the cathode components (Figure 5B). The interfacial sulfur (Li-S) batteries. There are two interfacial issues
resistance of Li/LATP/Li battery was reduced from 2478 to between LATP SSE and sulfur cathode, which are the large
242 Ω and the LFP/LATP/Li full cell showed capacity impedance resistance and the chemical instability with
retention of 97.3% at 0.3C after 100 cycles at 60 C. In order polysulfides during discharge process.92 Thus, these poly-
to enhance the mechanical strength of the PEO buffer mer electrolytes not only reduce the impedance resistance
layer, Jin et al87 constructed a LATP nanoparticle- effectively, but also prevent the side reactions of LATP with
reinforced polymer layer between LATP SSE and LFP cath- polysulfides. For instance, PEO polymer was applied as
ode. Unfortunately, PEO-based polymer electrolytes are buffer layer between LATP and sulfurized polyacrylonitrile
limited by their poor electrochemical window, which (SPAN) cathode materials.86 Subsequently, the all-solid-
reduced their compatibility with high-voltage cathodes state Li-S battery delivered ultrahigh discharge specific
severely. A recent study revealed that the terminal ─OH capacity of 1793 mAh g
1 at 75 C and cycled stable for
group is the chief culprit, which will be oxidized as the 120 cycles (Figure 5D).
voltage higher than 4.05 V.88 Therefore, the PEO electro- Apart from the poor contact and chemical instability
lyte cannot be used as the interface layer between high with polysulfides, the space charge layer existed at cath-
voltage cathode and LATP SSE. As shown in Figure 5C, ode/SSE interface is another factor for raising the inter-
Liang et al85 coated LATP SSE with PAN at cathode side nal resistance.93 The space charge layer is formed due to
and PEO at anode side to deliberately satisfy the disparate local charge carrier depletion or enrichment, which in
interface demands of high-voltage cathode and Li metal turn influenced the charge transport. Cheng et al94 rev-
anode. Wherein, the PAN layer achieves compact contact ealed the effect of space charge layer between LixV2O5
with LiNi0.6Co0.2Mn0.2O2 (NCM622) and the PEO layer cathode and Li1.5Al0.5Ge1.5(PO4)3 (LAGP) by tuning
prevents LATP from reduction. Compared with pure PEO LixV2O5 charge potential and estimating Li+ transport
interface design, this PAN-PEO double-layer polymer elec- behaviors across the interface using two-dimensional
trolyte (PDPE) structure exhibited excellent compatibility nuclear magnetic resonance (2D-NMR) exchange spec-
with electrodes. Besides, the anions can be immobilized by trum (Figure 6). The Li+ exchange activation energy was
LATP ceramic effectively, which increases the Li+ transfer- demonstrated to be 0.315 eV for the space-charge-free
ence number (tLi+) from 0.41 to 0.82. As a result, the interface, which is remarkably increased to 0.515 eV with
Li/PDPE/Li symmetric cell can steadily cycle over 1000 h a space charge layer, indicating that the space charge
at 0.2 mA cm
2. Moreover, the NCM622/PDPE/Li battery layer was responsible for the increased interfacial
delivers high capacity retention of 89% (135.6 mAh g
1) resistance.
after 120 cycles at 0.5C and 60 C. However, the poor room- In summary, the stable interface with low interfacial
temperature ionic conductivity of PEO interlayer hinders resistance between LATP SSE and cathode was realized
the operations at room temperature. Fortunately, Alarco by interface modifications. Unfortunately, it still remains
et al89 reported that a large variety of lithium salts can be a challenge to clearly understand the Li+ transport mech-
dissolved in succinonitrile (SN) in 2004, reaching high anisms between cathodes and SSEs due to the current
ionic conductivity of 3 mS cm
1 at 25 C. The plasticity of limited characterization methods. The interfacial behav-
SN is similar to the SPEs, suggesting it will accommodate iors are required to be further explored.
YANG ET AL. 11

F I G U R E 6 Activation energy of Li+ exchange and 6 Li 2D

exchange NMR spectrum with and without space-charge layer.
F I G U R E 7 (A) Cross-section image of LATGP/lithium
Copyright 2020, Elsevier Ltd94
interface. Reproduced with permission: Copyright 2013, American
Chemical Society.17 (B) Illustration of the chemomechanical failure
4.2 | Interfaces between LATP SSE and mechanism at the LATP/lithium interface. Reproduced with
Li metal anode permission: Copyright 2020, American Chemical Society.96
(C) Schematic illustration of multi-step thermal runaway reaction
4.2.1 | Interface failure mechanisms between LATP and metallic Li. Reproduced with permission:
between LATP and Li metal Copyright 2020, Elsevier Ltd97

As is well known, side reactions could occur when the

LATP SSE contacts with lithium metal, which is related thermal stability of oxide-based SSEs with metallic Li
to the reduction of Ti4+ to Ti3+ at 2.17 V95 to form an using the accelerating rate calorimeter (ARC) method.
ionic/electronic mixed conductive layer (MCL). Pascal et They proposed that thermal runaway behaviors may be
al17 investigated the chemical stability of LATP-type SSEs attributed to multi-step reaction mechanisms
against Li metal anode. The rapid reactions cause large (Figure 7C). First, interfaces are formed after SSEs con-
increase of interfacial impedance resistance. Figure 7A tact with metallic Li. As the temperature increases, the
exhibited the cross-sectional image of interface after the interfacial reactions are accelerated and the contact with
Li1.6Al0.5Ti0.95Ge0.5(PO4)3 (LATGP) sample contacts with melted Li gets more intimate. Then the increasing tem-
Li metal for 12 h. The image suggests that the reaction perature and heat generated by interfacial reactions pro-
moves from the lithium surface to the bulk of LATGP mote the thermal decomposition of SSEs, leading to
with thickness of 15 μm. In addition, the color of aged increased oxygen activity from SSEs. Finally, the Li-
LATGP turned dark, further indicating the severe reac- oxygen reactions at the elevated temperature induced
tions. Zhu et al96 studied the inherent failure mecha- thermal runaway. By comparing the heat generation rate
nisms of Li1.3Al0.3Ti1.7(PO4)3/Li interface. They found of four prevalent oxides SSEs, the thermal stability versus
that with the reduction of Ti4+ to Ti3+, electrons can Li was identified to follow the order of
inject into the LATP, forming the amorphous lithiated- LAGP<LATP<LLTO<LLZO. Therefore, the artificial
phase Li3Al0.3Ti1.7(PO4)3 and leading to at least 3 magni- protections are highly essential to stabilize the LATP/lith-
tude orders increase of electronic conductivity at the ium interface.
interface (Figure 7B). The constant degradation of
Li1.3Al0.3Ti1.7(PO4)3 and the sizable volumetric expansion
in the lithiated LATP break up the bulk electrolyte even- 4.2.2 | Interface modifications between
tually. It was reported that the reaction products include LATP and Li metal
Ti3P, TiAl, Li3P, Li2O, AlPO4 and Li3PO4.98 These prod-
ucts still conduct electrons, which cannot suppress inter- Various artificial buffer layers have been employed to
facial reactions. Moreover, Chen et al97 quantified the modify the LATP/lithium interface, including polymer
12 YANG ET AL.

electrolytes, liquid organic electrolytes and inorganic sur- the continuous side reactions and reduce the interfacial
face coatings. In the earlier studies, SPEs were applied as resistance simultaneously (Figure 8D). The Li-Li symmet-
buffer layers to ameliorate the interfacial stability by in- ric cell can remain stable for 300 h at 0.2 mA cm
2. As is
situ polymerization method99 and directly coating thin known, polymer electrolytes exhibit flexible and visco-
polymer electrolytes100 on the surface of Li metal. For elastic, which can inhabit side reactions effectively. How-
instance, Zhou et al100 synthesized a cross-linked ever, the poor mechanical strength and low ionic
poly(ethylene glycol) methyl ether acrylate (CPMEA) Li+ conductivity deteriorate the electrochemical performance
polymer conductor. They designed polymer/ceramic/ of batteries. On the one hand, lithium dendrites can pen-
polymer sandwich electrolyte (PCPSE) using the CPMEA etrate the polymer electrolytes easily, which cause inter-
as the buffer layer. In this PCPSE structure, the double- face failure. On the other hand, the widely used PEO-
layer electric field at the Li/polymer interface is reduced based polymer electrolyte can be reduced by lithium
because of the blocked TFSI
transport by LATP ceramic. metal,104 resulting in large impedance resistance and
As a result, the LFP/LATP/Li battery show high colum- uneven surface morphology. The commercial LiPON thin
bic efficiency of 99.8–100% over 640 cycles at 60 C. Liu SSE can also serve as stable buffer layer, while the low
et al99 introduced cross-linked PEGDA/Pyr13TFSI ionogel ionic conductivity cannot favor fast Li+ transport through
interlayer via in-situ polymerization reactions. The the interface.18 Similar to cathodic interfacial modifica-
formed robust and elastic buffer layer could prevent tion, liquid organic electrolytes were applied between

F I G U R E 8 (A) Architecture of LiFePO4/LATP/PPA-Li-1335C batteries. Reproduced with permission: Copyright 2017, The Royal
Society of Chemistry.69 (B) Illustration of LATP/Li interface with and without ALD Al2O3. Reproduced with permission: Copyright 2018,
American Chemical Society.101 (C) Illustration of the coating process to prepare LiF, MgF2, and B2O3 coated Li. Reproduced with
permission: Copyright 2020, Wiley-VCH.102 (D) Cross-sectional SEM images of the LATP/Li metal anode interfaces with the ionogel
interlayer. Reproduced with permission: Copyright 2020, American Chemical Society.99 (E, F) Schematic of the preparation of ultrathin ZnO
layer coated LATP pellet by magnetron sputtering and Long cycling performance of Li/ZnO@LATP@ZnO/Li symmetric cells at various
current densities. Reproduced with permission: Copyright 2019, Wiley-VCH103
YANG ET AL. 13

LATP SSE and Li metal anode as well, whereas these LE effect on the energy density of batteries. Consequently,
could be consumed during cycling, leading to large polar- the LFP/LATP/Li battery shows excellent capacity reten-
ization. Many studies have shown that building artificial tion of 96.6% after 500 cycles at 0.2 mA cm
2.
solid electrolyte interfaces (SEIs) on the surface of Li Some MCLs such as SnNx106 and Cu3N107 were pro-
metal is a practical solution. Liu et al69 immersed a posed to modify the interface between garnet SSE and
polished lithium foil in the solution (0.4 wt% poly- Li. For instance, Shi et al106 sputtered an ultrathin SnNx
phosphoric acid (PAA) in dimethyl sulfoxide (DMSO) sol- layer (180 ~ 250 nm) on the surface of Li6.4La3Zr1.4Ta0.6O12
vent) for 2 min to form artificial Li3PO4 SEI layer (LLZTO) SSE. Interestingly, the SnNx layer could in-situ
(Figure 8A). The interfacial property was changed from react with Li metal at 300 C, forming LiySn alloy and Li3N
MCL to SEI by this method. Besides, the artificial Li3PO4 electrolyte. The Li3N electrolyte with high ionic conductiv-
SEI layer remains stable without breakage/repair mecha- ity ensures efficient and uniform transportation of Li+ at
nism, which reduces consumption of liquid organic elec- the interface. Meanwhile, the LiySn alloy guides homoge-
trolytes. Yang et al102 casted a few drops of reaction neous electronic distribution to suppress the lithium den-
solution containing LiBF4 and Mg(ClO4)2 in dimethoxy drites nucleation. Similarly, a significant Li3N/Cu MCL
ethane (DME) on lithium foil for 30 s (Figure 8C). The was formed by conversion reaction between Cu3N and
surface of Li foil turned dark obviously due to the forma- molten Li at 200 C.107 Such an MCL not only displays
tion of coating layer, which includes LiF, MgF2 and B2O3. excellent wettability with Li metal, but also homogenizes
Through adding 5 μl liquid electrolyte on each side of the electric field distribution inside the MCL. Unfortu-
LATP pellet, the assembled LFP/LATP/Li battery showed nately, these MCLs are only effective for those ceramic
capacity retention of 84.6% after 500 cycles. In addition, electrolytes, which are chemically stable with lithium
various inorganic surface coatings, exhibiting high metal.
mechanical strength, have been successfully applied to In summary, artificial layers are essential to stabilize
modify the interfacial properties through rational film the LATP/lithium interface. Meanwhile, the artificial
growth methods. For instance, atomic layer deposition layers should be ionic conductors and electronic insula-
(ALD) is a typical deposition method which can realize tors. The electronic conductivity is detrimental at the
uniform coverage and conformal depositions. Signifi- Li/LATP interface. The ideal buffer layers should meet
cantly, the thickness of the film can be precisely con- the requirements of high mechanical strength, excellent
trolled at the atomic scale. Liu et al101 demonstrated the compatibility with lithium and high ionic conductivity.
successful application of Al2O3 coating (Figure 8B) with The in situ polymerization and MS may be practical
thickness of 15 nm on the surface of LATP pellet through routes for interface engineering, which need further
this method. The Li/LATP/Li symmetric cell exhibited explorations.
stable cycling behavior for 600 h at 0.01 mA cm
2. Inter-
estingly, the Al2O3 coating can be transformed to Li-Al-O
conducting layer, which promotes Li+ transport effi- 5 | A P P L I C A TI O N S OF LA T P
ciently at the Li/LATP interface. For the film growth IN L I Bs
method, magnetron sputtering (MS) is another popular
technique due to its low cost, simplicity and low opera- Currently, the LATP SSE is widely used in different types
tion temperature. Hao et al103 constructed of LIBs, including liquid LIBs, ASSBs and Li-S batteries.
multifunctional ZnO thin layer on the surface of LATP We summarize the applications progress of LATP in
pellets via MS method (Figure 8E). The lithiophilic ZnO recent years, including the surface coatings for cathode
layer helps to form a stable SEI interface according to the materials to enhance the structural stability and con-
reaction of ZnO + 2Li ! Li2O + Zn, which increases the struct ion transport networks as inorganic fillers to pre-
compatibility between LATP and Li and significantly pare SCEs and gel polymer electrolytes (GPEs).
reduces the interfacial impedance from 80 554 to 353 Ω.
In addition, the dense layer prevented the Li dendrites
growth at the grain boundaries or voids of LATP. There- 5.1 | Surface coatings for cathode
fore, the Li-Li symmetric battery cycles above 2000 h at materials
0.05 mA cm
2 and 1000 h at 0.2 mA cm
2 (Figure 8F).
The LFP/LATP/Li full battery can stably cycle 200 times. Nowadays, to construct high-energy-density LIBs, nickel-
In addition, Cheng et al105 utilized boron nitride rich layered cathodes attract great attention in consider-
(BN) film as protection layer by chemical vapor deposi- ation of their high specific capacity. Nevertheless, the
tion (CVD). The thin BN film (5–10 nm) exhibits chemi- structural and chemical stability of these cathodes is
cally inert and mechanically robust, which has negligible degraded due to large amounts of nickel, which results in
14 YANG ET AL.

the formation of the Li/Ni cation mixing layer108 and diffusion path of Li+, which increases the rate perfor-
microcracks along grain boundaries.109 In addition, the mance of batteries remarkably. Choi et al111 also system-
side reactions could occur between cathode materials and atically investigated the impact of mass fraction of LATP
liquid organic electrolytes, which leads to poor cycle per- coating layer on the discharge capacities and Li+ diffu-
formance of batteries. The SSE coating layer for cathode sion coefficient of NCM622. They found that 0.5 wt%
materials can significantly increase the structural stability LATP-coated NCM622 shows the highest diffusion coeffi-
and suppress side reactions. As is known, the sulfide- cient and the battery exhibits the best electrochemical
based SSEs display high ionic conductivity, but they are performance. If the amount of applied coating is larger
limited by high moisture sensitivity and poor electro- than the optimal amount, the kinetics of Li+ intercala-
chemical window. Besides, the space charge layer with tion would be retarded (Figure 9B). Therefore, the coat-
cathodes hinders the highly efficient Li+ transport across ing amount is crucial as well. In addition, Wang et al115
the interface. The LLZO was reported to exhibit high discovered that the LiCoO2 could react with LATP coat-
room-temperature ionic conductivity of 10
4 S cm
1, but ing layer at 700 C to form exclusively spinel phases and
the LiOH and Li2CO3 impurities could be easily formed Li3PO4. The spinel oxides possess high-voltage-stable
on the surface of LLZO due to the reactions with H2O structures with much weaker oxidizing ability of lattice
and CO2 in air. Therefore, compared with LLZO and oxygen than layered structure. Besides, the new formed
sulfide-based electrolytes, the LATP SSE shows higher Li3PO4 and LATP are good Li+ conductors with excellent
stability in ambient air, better compatibility with cath- chemical stability at high voltages. Consequently, the
odes and higher oxidation voltage, which enable it more modified LiCoO2 showed excellent 4.6 V high-voltage
suitable as the surface coatings for cathode materials. cycle performance at both room temperature and 45 C.
Especially, LATP coating layer could form Li+ transport Expect for the fast diffusion of Li+ inside cathodes, the
networks inside cathodes, which are vital for high- rapid transport of electrons is also significant for the per-
loading electrodes. For instance, Deng et al110 prepared a formance of batteries. Yang et al116 designed an ionic and
LATP-modified LiNi0.5Mn1.5O4 (LNMO) cathode by sol– electronic conductive dual-layer coating using LATP
gel method. The starting materials of LATP and LNMO and graphene nanosheets on LFP cathode materials. The
powders were mixed in solution under heat stirring to composite electrode exhibits much lower fading rate at
form gel, which was then calcined at high temperature the high rate of 10C at 55 C. Table 2 lists the reported dif-
(Figure 9A). The results demonstrate that the higher crys- ferent LATP-coated cathode materials. It can be observed
talline LATP with thinner thickness layer enables shorter that the cathode materials show improved

F I G U R E 9 (A) Schematic illustration of Li1.3Al0.3Ti0.7(PO4)3 coating layer by sol–gel method. Reproduced with permission: Copyright
2015, Elsevier Ltd.110 (B) Chemical diffusion coefficients of Li+ from the GITT data of the pristine and LATP-coated samples. Reproduced
with permission: Copyright 2015, Elsevier Ltd.111 (C) Illustration of potential distribution with LATP-coated cathode. Reproduced with
permission: Copyright 2018, American Chemical Society.112 (D) Charge–discharge profiles and cycle performance between 3 and 4.2 V of
LATP-LiCoO2jPEO-LiTFSIjLi cell. Reproduced with permission: Copyright 2020, Wiley-VCH.113 (E) Charge–discharge profiles between
3 and 4.5 V of LATP-LiCoO2jPEO-LiTFSIjLi cell. Reproduced with permission: Copyright 2020, American Chemical Society114
YANG ET AL. 15

electrochemical performance with LATP coating layer at of solid-state batteries. When the LiCoO2 was well coated
different temperatures. with LATP thin layer, the phosphorus-oxygen tetrahedron
The last but not least, the LATP coating layer can would inhibit the release of oxygen radicals. As a result, the
achieve the feasibility of mitigated polarization at the LATP@LiCoO2/PEO/Li SSB show obviously better cycle sta-
cathodes/SPEs interface,112 which is beneficial to weaken bility at high cut-off voltage of 4.2 V, and the capacity reten-
the space charge layer and endow the battery with tion is as high as 88.6% after 50 cycles at 0.2C (Figure 9D).
improved cycle stability (Figure 9C). Furthermore, the Furthermore, Nie et al114 investigated the gassing behavior
LATP coating layer could enhance the compatibility of LiCoO2/PEO-LiTFSI/Li batteries by differential electro-
between PEO solid polymer electrolyte and high-voltage chemical mass spectrometry (DEMS) method. They revealed
cathode materials. Liu et al113 studied the failure mecha- that the surface catalytic effect of LiCoO2 is the root cause of
nisms of LiCoO2/PEO interfaces. It was concluded that the unexpected H2 gas release at 4.2 V. As shown in Figure 9E,
strong oxidizing property of LiCoO2 after delithiation could the catalytic effect could be mitigated and the stable working
accelerate the decomposition of PEO and derive the self-oxy- voltage could be extended to above 4.5 V using stable LATP
gen-release of LiCoO2. At the same time, the continuous coating layer. Therefore, the LATP coating layer can greatly
growth of cathode electrolyte interface (CEI) and the destruc- improve the interfacial stability between solid-state polymer
tion of the LiCoO2 surface lead to performance degradation electrolyte and cathode.

TABLE 2 Electrochemical performance of batteries with LATP-coated cathode materials

Cathode materials Coating layer Liquid electrolytes Electrochemical performance References

110
LiNi0.5Mn1.5O4 Li1.3Al0.3Ti0.7(PO4)3 1M LiPF6 in Capacity retention of 83% after
EC/DMC (1:1) 100 cycles at 2C and 55 C
117
Li1.2Ni0.2Mn0.6O4 Li1.3Al0.3Ti0.7(PO4)3 1M LiPF6 in 264.7 mAh/g at 0.1C, capacity retention
EC/DMC (1:1) of 94.3% at 0.2C after 80 cycles
LiNi0.5Mn1.5O4 Li1 + xAlxTi2-x(PO4)3 1 M LiPF6 in 82.24 mAh/g at 0.1C and
20 C 118

EC/DEC (3:7)
119
LiNi0.5Mn1.5O4 Li1.4Al0.4Ti0.6(PO4)3 1M LiPF6 in 102 mAh/g at 20C, capacity retention of
EC/DMC (1:1) 68.9% at 0.1C after 500 cycles
120
LiCoO2 Li1.4Al0.4Ti0.6(PO4)3 1M LiPF6 in Capacity retention of 93.1% at 0.2C after
EC/DMC (1:1) 50 cycles
59
LiMn2O4 Li1.4Al0.4Ti0.6(PO4)3 1M LiPF6 in Capacity retention of 96% at 0.2C after
EC/DMC (1:1) 100 cycles
111
LiNi0.6Co0.2Mn0.2O2 Li1.3Al0.3Ti0.7(PO4)3 1M LiPF6 in Capacity retention of 98% at 0.1C after
EC/DEC (3:7) 100 cycles
121
LiNi0.8Co0.1Mn0.1O2 Li1.3Al0.3Ti0.7(PO4)3 1M LiPF6 in Capacity retention of 84.5% at 2C after
EC/DMC/EMC 200 cycles
(1:1:1)
122
LiNi0.8Co0.15Al0.05O2 Li1.3Al0.3Ti0.7(PO4)3 1M LiPF6 in Capacity retention of 89.5% at 2C after
EC/DMC/DEC 150 cycles
(1:1:1)
116
LiFePO4 Li1.4Al0.4Ti0.6(PO4)3/ 1M LiPF6 in Capacity retention of 91.24% after
graphene EC/DEC (1:1) 150 cycles at 10C and 55 C
123
Mg-droped LiCoO2 Li1.3Al0.3Ti0.7(PO4)3 0.9M LiPF6 in Capacity retention of 85% at 1C after
EC/EMC/DEC 500 cycles
(3:5:2)
124
Li1.2Mn0.54Ni0.13Co0.13O2 Li1.4Al0.4Ti0.6(PO4)3/ 1M LiPF6 in Capacity retention of 79% at 0.2C after
polyaniline DC/DMC/EMC 200 cycles
(1:1:1)
125
LiFe1/3Mn1/3Co1/3PO4/C Li1.4Al0.4Ti0.6(PO4)3/ 1M LiPF6 in Capacity retention of 81.01% at 1C after
porous carbon EC/EMC (1:2) 100 cycles

Abbreviation: LATP, Li1 + xAlxTi2-x(PO4)3.

16 YANG ET AL.

5.2 | Inorganic fillers for composite chains through insertion of regular pattern to cause the
organic–inorganic electrolytes cross-linking of polymer. The addition of LATP particles
shows great enhancement in tensile strength and ionic
As the inorganic fillers used to prepare composite conductivity. Consequently, the as-prepared GPE displays
organic–inorganic electrolytes is another typical applica- excellent capability on suppressing Li dendrites growth
tion for the LATP SSE. The LATP embedded in GPEs and and Li-Li symmetric cell displays cycle stability over
SCEs can greatly decrease the contact area of LATP with 1100 h at 2 mA cm
2. GPEs always show high ionic con-
lithium metal, which greatly suppress the side reactions. ductivity, but there is large amount of LE, in which the
As is known, the commercial polyolefin-based separa- safety risks cannot be completely solved. Nowadays,
tors are widely employed in commercial LIBs due to their many researchers and scholars believe that the develop-
economical cost and superior mechanical strength. How- ment of SSEs in ASSBs is critical for commercial applica-
ever, there are many disadvantages, including low poros- tions in the future.
ity and poor wettability with LE.126 To counteract the For SPEs, the transportation of Li+ mainly depends
above-mentioned issues of separators, it is a significant on the chain segment movements in the amorphous
strategy to prepare highly porous polymer membranes region of the polymer, which requires the batteries oper-
that show better affinity toward LE and serve as the skel- ating at the temperature higher than the glass transition
etons of GPEs. The PAN, PVDF, and PVDF-HFP are pri- temperature (Tg). However, the mechanical strength
marily employed as the host polymer materials of GPEs. would be reduced at high temperature, which is unable
On account of the combination of polymer skeletons and to suppress the Li dendrites growth. By contrast, the ICEs
LE, GPEs exhibit high ionic conductivity (10
3 S cm
1) show high ionic conductivity, but present poor contact
and acceptable electrochemical stability, which are con- with electrodes. SCEs combine the advantages of both
sidered good alternatives for commercial separators. SPEs and ICEs such as high ionic conductivity, excellent
There is a strong relationship between the porosity and flexibility and compact contact with electrodes. There-
electrolyte uptake, in which the higher porosity usually fore, they are considered one of the most promising elec-
means higher electrolyte uptake. Many studies demon- trolytes for ASSBs.130 The inorganic fillers can be
strated that introduction of LATP inorganic fillers to categorized into passive fillers and active fillers based on
these GPEs can increase the porosity and ionic conductiv- whether they are Li+ conductors. Commonly, the passive
ity significantly. Liang et al127 fabricated LATP/PAN fillers include SiO2,131 Al2O3,132 metal organic frame-
composite fiber-based membrane by electrospinning dis- works133 and so on. The active fillers generally involve all
persions of LATP particles and PAN solutions. The the Li+ conductors, such as LLZO,134 LLTO135 and
results showed that the ionic conductivity increased from LATP.136 Both the passive fillers and active fillers can
6.4  10
4 S cm
1 to 3.4  10
3 S cm
1 with the LATP work as plasticizers to reduce the crystallization of poly-
content of 15 wt%. Interestingly, the presence of LATP mer matrix. Moreover, the active fillers also provide Li+
particles decreases the fiber diameters and increases the pathways, thus they are better choices as fillers in the
surface area of fibers, which is beneficial to entrap more polymer matrix.137 Currently, the LATP-based SCEs have
LE, leading to enhanced ionic conductivity. In addition, been extensively applied in ASSBs. Liu et al136 added
the high ionic conductivity of LATP may also partially 1 wt% LATP nanoparticles into the PEO polymer, and
contribute to the overall ionic conductivity, which needs the room-temperature ionic conductivity increases from
further research to quantification. Similarly, Jagdeep 5.36  10
6 S cm
1 to 1.15  10
5 S cm
1 due to the
et al128 studied the effect of LATP particles on the poros- inhibition of PEO crystallization. For the active fillers
ity of LATP/PAN composite membrane. When LATP reinforced SCEs, the Li+ pathways may involve the poly-
content is 30 wt%, the composite membrane exhibits the mer matrix, ceramic bulk phase and interface region
maximum electrolyte uptake of 600% and between SPEs and ICEs. Wang et al138 suggested that the
the corresponding GPE show the highest ionic conductiv- LATP in PEO could establish interfaces with low energy
ity of 1.7 mS cm
1. As a result, the LFP/PAN-LATP/Li barrier for Li+ transportation. The calculated ionic con-
cell displays capacity retention of 87% after 200 cycles. ductivity of the interfaces is 3–4 times higher than that of
Apart from PAN polymer, PEO was also applied as the the bulk of PEO/LiClO4 with 10 wt% LATP particles
matrix of composite gel electrolytes on account of its (Figure 10A). Therefore, reducing the particle sizes or
good liquid absorption. Siyal et al129 prepared a novel constructing continuous Li+ transport networks can form
GPE membrane consisting of PEO, benzophenone more Li+ conducting interfaces, resulting in higher ionic
(Bp) and LATP particles by ultraviolet (UV) technology. conductivity of SCEs. Li et al140 fabricated a 3D-fiber-
Under UV irradiation, the Bp photo-initiator can form network reinforced bicontinuous SCE by electrospinning
free radicals, which are grafted onto PEO molecular and solution-casting method. As shown in Figure 10C,
YANG ET AL. 17

F I G U R E 1 0 (A) Calculated ionic conductivity of interfaces in LATP/PEO/LiClO4 composite electrolyte. Reproduced with permission:
Copyright 2018, American Chemical Society.138 (B) Illustration of epoxy-reinforced thin ceramic film. Reproduced with permission:
Copyright 2020, Wiley-VCH.139 (C) Schematic illustration of LATP/PAN/PEO composite electrolyte. Reproduced with permission: Copyright
2018, American Chemical Society.140 (D) LATP/PEO solid electrolyte prepared by ice-templating process. Reproduced with permission:
Copyright 2017, American Chemical Society141

the LATP/PAN composite fiber-based membrane was obtain SCEs with aligned ceramic fillers. For instance,
fabricated by electrospinning method, then the PEO- Liu et al142 constructed a 3D Li+ conductive networks by
LiTFSI acetonitrile solution was cast onto the fiber-based distributing the poly(ethylene glycol) diacrylate (PEGDA)
membrane, followed by a drying process to obtain a free- coated LATP particles orderly in poly(dimethylsiloxane)
standing composite electrolyte. The LATP/PAN fibers (PDMS) using an external AC electric field. The ionic
and PEO chains form the bicontinuous Li+ transport conductivity of aligned SCE is three times higher than
channels. With incorporation of LATP/PAN fibers, the Tg that of the random one. Zhai et al141 also reported a verti-
of PEO polymer decreases from
34.2 to
37.5 C, cally aligned LATP nanoparticles in the PEO matrix by
resulting in four times ionic conductivity higher than that ice-templating-based method (Figure 10D). With the ver-
of PEO-LiTFSI at 60 C. However, the LATP particles can- tically aligned nanowires structure, both the PEO and
not directly contact with each other in this kind of SCE. PEO/polyethylene glycol (PEG) polymer show higher
Afterward, Kim et al139 prepared an epoxy-reinforced room-temperature ionic conductivity.
thin ceramic film (ERTCF), which consists of continuous In general, the particle sizes, morphology and
Li+ channels constructed by over 86 vol% LATP ceramic arrangement of LATP ceramic fillers have great impact
powders and small amounts of epoxy polymer. The prep- on the ionic conductivity of SCEs. The continuous and
aration method is as follows: the LATP powders were dis- aligned Li+ pathways could promote the migration of Li+
solved in mixture of ethanol and silane using fish oil as significantly. At present, the room-temperature ionic con-
dissolvent, then the polyvinyl butyl alcohol as binders, ductivity of LATP-based SCEs could reach above 10
4 S
and the butyl benzyl phthalate as plasticizers were added cm
1, which cannot meet the requirements of practical
to the slurry. After slurry casting with doctor blade, the applications. Thus, the ionic conductivity needs to be fur-
composite powder film was hot-pressed and sintered to ther improved via structure design of inorganic fillers
form continuous Li+ pathways. Finally, the epoxy poly- and composition optimization of polymer matrix. Unfor-
mer was penetrated to the pores of LATP framework tunately, the inherent Li+ transport mechanisms of SCEs
(Figure 10B). The as-prepared ERTCF exhibited thickness with different material systems are unclear, which is vital
of 230 μm and ionic conductivity over 10
4 S cm
1 at for the structure design. Some advanced characterizations
25 C. If the epoxy polymer was replaced by Li+ conduc- and in-situ techniques should be further developed to
tive polymer, the ionic conductivity can be further deeply understand the Li+ transport behaviors. Besides,
increased. In addition, if the ceramic fillers distribute lin- few reports focus on the interactions between LATP inor-
early, the transportation of Li+ would become more effi- ganic fillers and polymer matrix, which should be
cient. Therefore, various methods were developed to attached importance in the future research.
18 YANG ET AL.

6 | SUMMARY A ND PERSPECTIVE thickness can be prepared to ameliorate the interfacial

instability.
The high ionic conductivity, excellent chemical stability, In terms of the applications in LIBs, although the
high oxidation voltage and low cost of NASICON-type poor flexibility of inorganic ceramic electrolyte LATP
Li1 + xAlxTi2-x(PO4)3 SSE make it one of the most promis- cannot be used in wearable electronics, it plays a key
ing candidates for ASSBs. Since its discovery in 1976, role when utilized as the surface coatings for cathode
great efforts have been made in LATP SSE and LATP- materials and as inorganic fillers for SCEs. Many
based batteries. Firstly, this review introduced the crystal reports have shown that the LATP coating layer for
structure and Li+ transport mechanisms of LATP. The cathode materials can increase the structural stability
high ionic conductivity compared with LTP can mainly and suppress side reactions with electrolytes effectively.
be attributed to the significantly reduced diffusion barrier In particular, the LATP coating layer could form Li+
at the grain boundaries and enhancement of Li+ mobility transport networks inside cathodes, which is of vital for
induced by increased Li+ concentration. Although many high-loading electrodes. For SCEs, the ionic conductiv-
studies have been done on the Li+ transport pathways ity is greatly influenced by the particle sizes, morphol-
and mechanisms in LATP, there are still controversial ogy and arrangement of LATP ceramic fillers. It is
results. It is highly necessary to apply advanced charac- significant to construct continuous and aligned Li+
terizations and simulation methods to further reveal the pathways in SCEs. Currently, the room-temperature
Li+ diffusion behaviors. Moreover, several key factors, ionic conductivity of LATP-based SCEs could reach
including microstructure, secondary phases and sintering above 10
4 S cm
1, which needs to be further improved
conditions were systematically discussed to demonstrate via structure design of inorganic fillers and composition
how to improve the ionic conductivity of LATP SSE. At optimization of polymer matrix. Last but not least, the
present, the highest room-temperature ionic conductivity basic interactions and Li+ transport mechanisms with
of LATP can reach 10
3 S cm
1, which can basically different materials systems of SCEs should be attached
meet the requirements for practical applications. importance in the future research.
Since the poor interface properties between LATP
SSE and electrodes, the large impedance resistance and ACKNOWLEDGMENTS
space charge layer against cathode materials greatly hin- This work was supported by Key-Area Research and Devel-
der the highly efficient Li+ transport across the interface, opment Program of Guangdong Province (2020B090919
which deteriorate the cycle stability of batteries. In addi- 001), the National Natural Science Foundation of China
tion, the chemical instability of LATP with lithium metal (U2001220), Shenzhen Technical Plan Project (Nos. JCYJ2
limits its practical applications in ASSBs severely. Varie- 0180508152210821, JCYJ20170817161221958, and JCYJ20
ties of buffer layers were successfully applied to tackle 180508152135822), and the Shenzhen All-Solid-State Lith-
these interfacial issues, such as LE, SPEs, and inorganic ium Battery Electrolyte Engineering Research Center
coatings. Specifically, for cathodic interfacial modifica- (XMHT20200203006).
tions, the ideal buffer layers should exhibit high ionic
conductivity, flexibility and great compatibility with high CONFLICT OF INTEREST
voltage cathode materials. However, the current charac- The authors declare there is no conflict of interest.
terizations make it difficult for us to deeply understand
the Li+ transport mechanisms between cathodes and ORCID
SSEs, thus the interfacial behaviors are required to be fur- Yan-Bing He https://orcid.org/0000-0001-5787-5498
ther explored. For the side reactions at anodic side, the
interface failure mechanisms have been explained RE FER EN CES
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YANG ET AL. 23

AUTHOR BIOGRAPHIES
focus on lithium ion power batteries and materials,
solid-state electrolytes, and lithium metal anodes.
Ke Yang is currently a postgraduate
student at Tsinghua Shenzhen Inter- Feiyu Kang is a full professor of
national Graduate School, Tsinghua School of Materials Science and Engi-
University. He obtained his B.S. neering and Tsinghua University Inter-
degree from China University of national Graduate School, Tsinghua
Petroleum in 2019. His research University. He received his Ph.D.
mainly focuses on the novel compos- degree from Hong Kong University of
ite electrolytes for solid-state high-energy-density lith- Science and Technology. His research
ium ion batteries. area is focusing on nanocarbon materials, lithium ion
batteries, supercapacitors, high safety secondary batte-
Yan-Bing He is currently an associate ries and materials.
professor of Tsinghua Shenzhen Inter-
national Graduate School, Tsinghua
University. He received his Ph.D.
degree from Tianjin University in How to cite this article: Yang K, Chen L, Ma J,
2010. He worked as a postdoctoral fel- He Y-B, Kang F. Progress and perspective of Li1
low at Graduate School at Shenzhen,
+ xAlxTi2-x(PO4)3 ceramic electrolyte in lithium
Tsinghua University from 2010 to 2012 and a visiting batteries. InfoMat. 2021;1–23. https://doi.org/10.
scholar at Hong Kong University of Science and Tech- 1002/inf2.12222
nology from 2012 to 2013. His research interests mainly