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In Situ Curing Technology for Dual Ceramic Composed by

Organic–Inorganic Functional Polymer Gel Electrolyte for
Dendritic-Free and Robust Lithium–Metal Batteries
Sajid Hussain Siyal, Muhammad Sufyan Javed,* Ashique Hussain Jatoi, Jin-Le Lan,*
Yunhua Yu, Muhammad Saleem, and Xiaoping Yang

­otential applications in lithium–metal

p
Lithium–metal batteries (LiMBs) are promising energy storage devices due to the batteries (LiMBs) due to their high-energy
high capacity and minimum negative electrochemical potential. Nevertheless, densities and high-capacity with easy pro-
their concrete applications remain disturbed by unbalanced electrolyte–electrode cessability and lightweight.[1–5] Ceramic
based electrolytes for LiMBs are real rising
interfaces, limited electrochemical window, and high risk. Herein, a novel strategy power sources for portable electronic,
to obtain dual ceramic-based electrolytes that possesses a great potential in energy electrical, hybrid charged vehicles pen-
storages and higher level of energy densities in LiMBs. Dual-ceramic (lithium etrating to heavy scale energy storage/
aluminum titanium phosphate -lithium lanthanum titanium oxide (LATP-LLTO)) transportation systems owing to their
gel polymer electrolyte (DCGPE) film developed via the curable system aims to safe electrochemical and high mechanical
properties.[6–8] However, the applications
prepare flexible Li+ interpenetrating network film to integrate the two ceramic
of ceramic-based lithium–metal batteries
structures with polyethylene oxide (PEO) to yield the free-standing electrolytes film with large capacities and power densi-
for better battery safety and desired interfacial stability. The DCGPEs films present ties have been restricted due to interfacial
a satisfactory electrochemical performance, including good ionic conductivity, incompatibility and thermal runway which
large transference number, and wide electrochemical stability window at room further complicates the serious safety
temperature. Most importantly, the fundamental function of LATP and LLTO is issues.[9,10] Therefore, extensive research
has been devoted to overcome these
to support building a stable solid-electrolyte-interphase and limits the growth of issues, including the structural and inter-
dendrites. Thus, prepared dual ceramic-based electrolytes effectively render to facial design of ceramic electrolytes to face
inhibit lithium dendrite growth in a symmetrical cell Li//PEO + 10% LATP + 15% the key challenges of dendritic expansion
LLTO//Li test during charge/discharge at a current density of 2 and 0.25 mA cm−2 and limiting the side reactions among
above 2400 h without short-circuiting occurrence at room temperature. Besides, Li–metal anode and electrolytes.[11,12] It
is worth mentioning that the Li–metal is
the battery assembled of LiFePO4/PEO + 10% LATP + 20% LLTO/Li exhibits
a supreme anode candidate for LiMBs to
superior cyclic stability with high Coulombic efficiency. This study recommends get the high energy density due to the
that the binary network structures of Li-ion conductor help to design a prime large theoretical capacities (3860 mAh g−1)
solution of promising electrolyte for high-performance LiMBs applications. and the lowest negative potential (−3.040 V
vs the hydrogen electrode).[13] Neverthe-
less, there is much harm when combining
1. Introduction Li metal anode with conventional liquid electrolytes possesses
(lowest unoccupied molecular orbital) lower to Fermi level of
The development of in-organic ceramic-based electrolytes alkali metals anode,[14] such electrolytes can easily react with Li
has been widely gained significant attention because of their metal to form heterogeneous products and produce unstable

Dr. S. H. Siyal, Dr. J.-L. Lan, Prof. Y. Yu, Prof. X. Yang Dr. M. S. Javed
Department of Metallurgy and Materials Engineering Siyuan Laboratory
Dawood University of Engineering and Technology Guangzhou Key Laboratory of Vacuum Coating Technologies
Karachi, Sindh 74800, Pakistan and New Energy Materials
E-mail: lanjl@mail.buct.edu.cn Guangdong Provincial Engineering Technology Research Center
Dr. S. H. Siyal of Vacuum Coating Technologies and New Energy Materials
State Key Laboratory of Organic-Inorganic Composite Department of Physics
College of Materials Science and Engineering Jinan University
Beijing University of Chemical Technology Guangzhou 510632, P. R. China
Beijing 100029, P. R. China E-mail: safisabri@gmail.com
The ORCID identification number(s) for the author(s) of this article Dr. M. S. Javed
can be found under https://doi.org/10.1002/admi.202000830. Department of Physics
COMSATS University Islamabad
DOI: 10.1002/admi.202000830 Lahore Campus, Lahore 54000, Pakistan

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solid electrolyte interphase (SEI) layer, which can lead in the of the amorphous domains in the matrix.[52,53] Electrolytes
formation of Li dendrites.[15,16] The uncontrolled Li dendrites films/membranes prepared by free radical photo polymeriza-
may trigger serious problems such as short circuits and internal tion (UV-curing) could be an interesting alternative to existing
explosions in batteries, which severely limit the efficiency of the polymer electrolyte.[54,55] This developed UV curing made
LiMBs.[17–19] Furthermore, it limits the Coulombic efficiencies the significant advancement in transitioning toward the new
due to their low conductivities at the elevated temperature and class of gel/solid state polymer electrolytes for their practical
confined stability window, which results in small ion mobility applications can be used to achieve good mechanical stability
and relatively large interfacial resistance[20–22] and electrochemical properties.[56,57] UV technology raised as
To resolve the aforementioned security problems and Li den- an effective and efficient technique in the fabrication of interpen-
drites, many strategies have been investigated regarding dual etrating films, polymer-ceramic networks reasonably free radical
organic-based electrolytes[23,24] and inorganic based electrolytes polymerization with excellent physical and chemical advantages
were prepared by complicated casting with a large number of as well as providing good optical and electrical advantages for
solvents.[25,26] These prepared solid-state polymer electrolytes electrolytes.[46,58,59] UV have high energy radiation which is a
mostly consist of single ceramic filler to solve the safety issues very efficient route with low processing costs used for surface
of LiMBs.[27,28] However, the brittle nature of inorganic types of modifications and mainly attributed to the salt-free preparation
ceramic electrolytes may hinder the practical applications of process.[60,61] As compared with previously surveyed polymeric
energy storage devices and cause structural failures.[29–32] There- electrolytes, UV processed electrolytes displayed significant elec-
fore, further modifications needed to incorporate with ceramic trochemical functionalities.[62,63] In addition, through the UV
fillers which can reduce the crystallization and enhance their photopolymerization of the films, the interface resistances were
ionic conductivity to improve their performances and having significantly reduced which can greatly improve the contact
some extraordinary advantages such as cost-efficient mass pro- between Li metal anode and electrolyte.[64,65] Therefore, the UV
duction. Inorganic fillers hold great promise for commercial regarded as smart and environmentally friendly, low energy con-
use in lithium–metal batteries.[33–35] However, the reaction- sumption with no emission of volatile combustible fumes.[66,67]
products such as free radicals and residual monomer formed UV curing could be conducted at ordinary temperature, pro-
by the introduction of the thermal initiation are easy to react cessed the reaction very quickly, and appropriate for the large-
with metal electrodes.[36–38] These reaction-products cover the scale fabrication which considered as a coeffective method for
surface of the Li metal, increasing the interfacial resistance and the preparation of gel electrolytes.[68–70] Up to this end, there is
seriously degrading the charge and discharge cycle stability and no clear investigation in previous literature which focused on
the safety of batteries.[39–41] the behavior of the dual ceramic (LATP + LLTO) film effective-
Recently, different strategies for the fabrication of membranes ness on the improvement of the interface layers which help to Li
or films of composite/solid/polymer electrolytes were fulfilled metal anode as well as suppress the Li dendrite growth.
by a simple casting method.[42,43] Traditional casting modes are In this work, we ideally proposed the high ion-conducting
still facing some deficiencies due to loss of solvents, complica- flexible dual ceramic-based CGPEs film growing by the highly
tion in fabrication, lengthy, and hazardous contaminations.[44,45] robust strategy of in situ UV-curing at elevated operating tem-
Therefore, an interesting alternative to existing polymer elec- perature. The specific preparation method is demonstrated
trolyte which is a new technique design concept consisting of in details in Scheme 1, by the formulation of dual ceramic gel
multitype structure of polymer ceramic electrolytes have real- polymer electrolytes (DCGPEs) structurally stable film composed
ized to combine the benefits considered to be a promising of monomer PEO, LATP, LLTO (1:2 V%), and photoinitiator
approach for LiMBs.[46–48] By improving the mechanical stability diphenyl ketone fully characterized. Stable LATP nanoparticles
and promising potential as a safer electrolyte will be possible were used as the major crystalline structure phase, while facile
using ultraviolet (UV)-curing.[49] Currently gel composite elec- Li+ conductor LLTO filler contents have high reactivity and func-
trolytes are prepared by curing (using novel UV polymerization) tionality to improve the interfacial properties to the battery safety.
to formulate the polyethylene oxide (PEO) monomer, liquid/ The DCGPEs film presented greatly improved electrochemical
salt type plasticizers, and inorganic fillers to further improve performance, thermal stability, and mechanical properties. The
their conductivity, mechanical and electrochemical properties.[50] symmetrical structure avoids the side reactions of LATP/LLTO
PEO can be used as lowering the degree of crystallinity and with Li metal, on the other hand, it makes a good interface
reducing the glass transition temperature to enhance the con- between electrolyte and electrode to obtain the improved inter-
ductivity and reduce the interface resistance. In addition, PEO facial properties. Therefore, a dendrite-free Li–metal battery with
supports in mechanical performances with good flexibility.[51] A low interface resistance and high Li-ion transference number
procedure for effective crosslinking of composite membrane of has been successfully fabricated to demonstrate its superior per-
PEO by UV irradiation commonly attributed to an enlargement formance by such type of dual structural architecture.

Dr. A. H. Jatoi
Department of Chemistry
Shaheed Benazir Bhutto University
2. Experimental Section
Shaheed Benazirabad, Lahore 67540, Pakistan
2.1. Chemicals
Dr. M. Saleem
Department of Physics
Khwaja Fareed University of Engineering and Information Technology Titanium butoxide (C16H36O4Ti 99.5%), citrate (C6H8O7 99%),
RYK 64200, Pakistan acetonitrile (ACN 99%), ammonia (NH3 99%), aluminum

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Scheme 1. Design of ceramic–ceramic dual composite gel polymer electrolytes film (DCGPE).

nitrate nonahydrate (Al(NO3)3·9H2O 99.0%), lithium nitrate followed by the solution preparation. Initially, the solution
(LiNO3 >99.9%), ammonium phosphate monobasic (H6NO4P contains titanium butoxide Ti(C4H9O)4 (3.4 g) added with
>99.99%), lanthanum nitrate (La(NO3)3·6H2O >99.99%), La(NO3)3·6H2O (23 g) and LiNO3 (0.24 g) stirred vigorously
polyethylene oxide (PEO 600 000 g mol−1), polyvinylpyr- at 300 rpm for 30 min. At the same time, PVP (1.5 g) was
rolidone (PVP, 130 000 g mol−1), N,N-dimethylformamide dissolved in DMF as solvent (18.452 g) with concentrated
(DMF >99%), propylene carbonate (PC >99.0%), and salt acetic acid (HAc 5.126 g) dripped slowly during stirring. After
(lithium bis(trifluoromethanesulfonyl)imide) were purchased continuous stirring of 1 h, the solution loaded into the syringe
from Aladdin and Shenzhen Co. Ltd. propel for the electrospinning process with adjustment
of high voltage of 18 kV was applied for the preparation of
nanowire. The LLTO nanowires of thin sheets were collected
2.2. Synthesis of LATP Particles from the aluminum foil for vacuum drying for 8–12 h at 80 °C
and annealed at 900 °C in the air for 2 h with heating rate
Synthesis of LATP nanoparticle carried out taking the stoi- 2 °C min−1. Subsequently, the sheets of nanowires cooled to
chiometric weight of Li1.3Al0.3Ti1.5P(O4). First, C16H36O4Ti was obtain the desired LLTO nanowires.
dispersed with C6H8O7 in 30 mL deionized (DI) water under
magnetically stirring for 30 min. Second, (LiNO3, as received
(AR) 99%), (Al(NO3)3·9H2O purity 99.0%), C6H8O7 (99.99%), 2.4. Preparation of DCGPEs Film
and 3 mol of H6NO4P (AR, 99%) dissolved in 25 mL of DI
water. The above solutions combined for further stirring for a UV curing was employed with an emission intensity of
period of 4 h at 80 °C with the addition of ethylene glycol uti- 365 nm wavelengths to prepare dual ceramic gel polymer elec-
lized as a pyrogenic solvent. After that the drying was initiated trolyte film as demonstrated schematically (Figure 1). DCGPE
to evaporate the solvents at 150 °C for 4 h in the alumina cru- film was followed these steps: LATP nanoparticles and LLTO
cible and then annealing was carried out at 800 °C for 6 h in nanowires (mentioned in Table 1) were dispersed in ace-
the air to obtain the LATP powders. tonitrile followed by ultrasonic dispersion for 2 h. PEO was
added under the constant magnetic stirring into the mixture
of LATP and LLTO at identical temperatures for 8 h to obtain
2.3. Preparation of LLTO Nanowires the homogenous solution. Then, the photoinitiator was added
to the solution further stirring of 2 h before the utilization of
Ion conductor LLTO nanowires were formulated by the UV light. The prepared solution was poured into a silicone
electrospinning process and subsequent heat treatment mold with a thickness of 10 mm using a plunger syringe and

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Figure 1. XRD patterns of a) LATP and LLTO and b) DCGPE films.

placed filled mold under UV curing (wavelength λ = 365 nm) (W1 − W0 )

Y (%) = × 100% (1)
for 1 min. The UV-cured film was first dried on a hotplate at W1
60 °C for 2–4 h and then continuously dried in a vacuum oven
at 50 °C for overnight to obtain the free-standing gel film, where W0 and W1 are the weight of the gel films before and
with the desired thickness of 160–200 µm. after absorbing the liquid electrolyte, respectively.
Electrochemical performances of gel electrolytes were measured
on the AutoLab PGSTAT-302N at ordinary temperatures. Ionic
2.5. Characterization of LATP Particle, LLTO, conductivities were assessed by AC-impedance (electrochemical
and UV-DCGPE Film impedance spectroscopy (EIS)) within the frequency scale adjusted
from 0.1–1000 Hz applied on the sandwiched cell of DCGPEs into
X-ray powder diffraction (XRD) (Max: 2500 with Cu Kα + PC, dual comparable stainless-steel discs. Ionic conductivities deter-
Rigaku Co. Japan) was employed to determine the structure mined by Equation (2).
and crystallization properties of UV cured electrolyte films
and crystalline structures of LATP/LLTO. The surface micro- L
σ= (2)
structure of the gel films and LATP/LLTO were examined (R b × S )
by scanning electron microscope (S-4700 Hitachi) equipped
energy dispersion spectroscopy (EDS) functions and infrared where σ is the ionic conductivities, Rb is the bulk resistance,
analysis by Fourier-transform infrared spectroscopy (FTIR) L is the thickness of gel film, and S is the area between elec-
(Nexus, 670-USA). Mechanical performance of the six-film sam- trode and electrolyte, respectively. Generally ionic conductivity
ples of 60 mm × 10 mm × 0.15 mm, length*width*thickness of polymer and ceramic electrolytes consist of PEO, LATP, and
of each film measured according to the american society for LLTO given in Table 2.
testing and materials D882 was done by a universal testing The electrochemical stability was recorded using sandwich cells
machine (Instron-1121, UK) with the tensile rate of 2 mm min−1 of Li/electrolyte films/stainless steel (SS) with the method of linear
and the gauge length of 25.4 mm. Thermogravimetric anal- sweep voltammetry (LSV) in the potential voltage ranging from
yses (TGA) of the samples were monitored under airflow over open-circuit voltage to 2.0 to 7.0 V at a scan rate of 0.1 mV s−1.
the temperature range from room temperature to 900 °C at a Lithium (Li) transference number was characterized by the
heating rate of 10 °C min−1. To determine the electrolyte uptake method of chronoamperometry (CA) with a polarization voltage
of the samples, the DCGPEs films were immersed in a liquid of 0.05 V, in the coin cell of Li/electrolyte films/Li. The lithium
electrolyte and the electrolyte uptake amount Y(%) was calcu- transference number was counted by Equation (3)
lated using Equation (1).
I ss ( ∆V − I oR o )
tLi + = (3)
I o ( ∆V − I ssRss )
Table 1. List the formulations for the preparation of dual ceramic gel
polymer electrolytes (DCPGE) films.
where ∆V, Io, and Iss denoted as polarization voltage, initial
Sample representation Sample name and steady-state currents, Ro and Rss were denoted as an initial
1. PEO + 10% LATP
Table 2. Ionic conductivities.
2. PEO + 10% LLTO
3. PEO + 10% LATP + 10% LLTO Sample/electrolyte Conductivity [S cm−1]
4. PEO + 10% LATP + 15% LLTO PEO 6.8 × 10−6
5. PEO + 10% LATP + 20% LLTO LATP 4.42 × 10−4
6. PEO + 10% LATP + 25% LLTO LLTO 2 × 10−5

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and steady-state of the bulk resistances, respectively. In addi- tions shown in Figure 1b, the difference in the distribution
tion, symmetric cells Li/electrolyte films used to measure the of LATP, and LLTO in matrix PEO observed in X-ray diffrac-
electrochemical stability between Li metal and electrolyte films tion patterns. There are obvious peaks or shape changes of
and the cycling performances of the plating/stripping of metal LATP and LLTO were evident in the dual ceramic gel polymer
Li. To observe the growth of Li dendrite on the Li–metal, the electrolyte films of PEO + 10 wt% LATP + 10 wt% LLTO and
Li/DCPGE/Li cells were disassembled in the glovebox after PEO + 10 wt% LATP + 15 wt% LLTO films. Polymer matrix sup-
cycling. The surface morphologies of the Li–metal were charac- presses its crystallization behavior due to the introduction of
terized by scanning electron microscope (SEM). The charge/dis- LATP and LLTO, for PEO + 10 wt% LATP + 20 wt% LLTO and
charge was tested using the battery test equipment named LAND PEO + 10 wt% LATP + 25 wt% LLTO films, it is demonstrated
(CT 2001A) to obtained the properties of the electrolyte films that LATP and LLTO particles present in the gel film and dis-
prepared the full cell according to Li/electrolyte films/LiFePO4 in sociate to design the complexes with PEO.
the potential range of 2.7−4.2 V with different current densities. As SEM morphology of LATP powders shown in Figure 2a,
it exists in the grain size range between 150 and 260 nm and
prepared the LATP at an annealing temperature of 800 °C.
3. Results and Discussion While, Figure 2b, LLTO SEM images obtained after annealing
at 900 °C for 2 h, the annealed the nanoparticles are uniformly
To confirm the conventional phase identification of dual dispersed, grain boundaries are obvious, and the average grain
ceramic gel polymer electrolyte (LATP + LLTO + PEO), LATP, size of LLTO is 160–220 nm. The average diameter of LATP and
LLTO, PEO, and other given samples with various concentra- LLTO are in Figure 2c,d.
tions were examined by powder diffraction (XRD) patterns dis- A remarkable crystallinity and phase purity within each LATP
plays in Figure 1a. The XRD pattern of the LATP is indexed well grain are also demonstrated by high-resolution transmission
with that of the standard sodium (Na) super ionic conductor electron microscopy (HRTEM). Figure 3 shows the HRTEM
(NASICON) LATP (powder diffraction file (PDF)# 35-0754), images of the LATP powder and LLTO nanowires, from which a
indicating that impurity-free LATP was produced under the clear 2D crystal sublattice and the interplanar distance of 0.352 and
conventional annealing temperature of 800 °C. The LLTO 0.243 nm can be readily assigned to the crystal planes. The SAED
holds cubic types of arrangements with a perovskite-based patterns of LATP particles show in Figure 3a depicted a cubic
structure; LLTO synthesized and calcined at high temperature garnet crystalline structure which is in keeping with the XRD pat-
900 °C shows sharp diffraction peaks and well-indexed to a tern. Figure 3b shows the selected area electron diffraction pattern
standard pattern of the perovskite-type Li0.33La0.557TiO3 (PDF# of the prepared LLTO nanowires and the light-dark stripes between
87-0935). These reflections of NASICON type and perovskite- the lattices at the (110) crystal plane observed under HRTEM.
type structures can be observed in the homologous selected The dual ceramic gel polymer electrolyte films were pre-
area electron diffraction (SAED) of LATP and LLTO. The XRD pared with LATP and LLTO by the UV curing and microstruc-
patterns of pure PEO, DCGPE films with different concentra- turally investigated by SEM. In Figure 4a, the microstructure of

Figure 2. SEM of a) LATP, b) LLTO, c) average particle size of LATP before calcined at 800 °C, and d) average particle size of LLTO calcined at 900 °C.

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Figure 3. HRTEM images corresponding as the a) LATP particle [113] axis of zone annealed at 800 °C and b) LLTO nanowires [101] zone axis annealed
at 900 °C.

PEO + 10% LATP gel film displays dispersed mutually employing hydrogen bonds and useful for electrolyte consisting of organic,
a homogenized structure in the PEO matrix. Figure 4b shows the inorganic, and composites. Figure 6a shows that FTIR spectra
composite of LLTO nanowire in the PEO polymer matrix, due to of pure PEO, PEO + 10% LATP, PEO + 10% LLTO, PEO + 10%
the high density of the LLTO nanowires; these were settled during LATP + 10% LLTO, PEO + 10% LATP + 15% LLTO, PEO + 10%
the UV curing, resulting in proper distribution of the LLTO LATP + 20% LLTO, and PEO + 10% LATP + 25% LLTO gel elec-
along with the cross-section of the PEO and shaped into a proper trolyte films. PEO thin film showed strong IR bands around
network. The microstructure morphology of dual ceramic gel 2900 cm−1 was associated with stretching band of CH mode,
polymer electrolyte surfaces shows that the LATP and LLTO nano- 1450 cm−1 band with asymmetric bending, 1350 cm−1 band was
particles are homogeneously dispersed in the matrix (Figure 4d). connected with CH2, 1100 cm−1 characteristics absorption peaks
The results indicated that both fillers of different contents show associated with COC stretching, peaks of 960 cm−1 associ-
good compatibility in the polymer matrix that was support in ated with CH2CH2 and 840 cm−1 associated with CH2 were
the formation of interconnecting conductive ion network with observed. All these characteristics absorption peaks indicated
no porous structure. SEM image of PEO + 10% LATP + 20% that electrolyte films successfully composed by UV.
LLTO and PEO + 10% LATP + 25% LLTO enriched with LLTO For the PEO + 10% LATP + 15% LLTO electrolyte film,
contents along with LATP (Figure 4e,f). Figure S1a,b in the Sup- the typical sharp peaks belong to Ti-O-La-Al were observed,
porting Information shows the morphology of PEO + 20% LATP denoting that these electrolytes films successfully prepared.
and PEO + 20% LLTO, respectively. The microstructures of Figure 6b is the differential scanning calorimetry (DSC)
PEO + 20% LATP with light dots of LATP particles at the surface, results of dual electrolytes films including pure PEO,
while blurry dots of particles at the beneath the surface are shown PEO + LATP, and PEO + LLTO are presented. The endothermic
in Figure S1a in the Supporting Information. It indicates that peak was found at 55. 8 in the black curve, corresponding to
LATP nanoparticles are not well dispersed in the composite mem- the melting temperature of PEO, while endothermic peaks
brane. The particle sizes are uniform with maximum amount as of PEO + 10% LATP at 50.6, PEO + 10% LLTO at 51.3, and
fully enriched with 20 wt% of LATP loading. The microstructures PEO + 10% LATP + 15% LLTO exactly at 55.
of PEO + 20% LLTO is shown in Figure S1b in the Supporting
Information. The random distribution of LLTO particles with
large aspect ratios in the PEO matrix can be clearly observed. It 3.1. Electrochemical Performances of UV Crosslinked
should be pointed out that obvious aggregation of LLTO particles LATP + LLTO + PEO Dual Ceramic Gel Polymer Electrolyte Film
is observed in sample containing 20 wt% LLTO.
The energy dispersion spectra mappings of DCGPE, fur- Ion conductivities of DCGPE compared with single inorganic
ther confirmed by the existence of LATP and LLTO were dis- PEO + 10% LATP and PEO + 10% LLTO are related to the
persed mutually utilizing the homogenized structure in the creation of the fastest Li migration pathways in the vicinity
electrolyte membrane. As shown in Figure 5, the polymer of the particles. Ion conductivities of PEO + 10% LATP,
matrix EDS confirmed the existence of (O, Al, Ti, P, and La) PEO + 10% LLTO, and DCGPE films including PEO + 10%
elements in the gel film. This structural design can solve the LATP + 10% LLTO, PEO + 10% LATP + 15% LLTO, PEO + 10%
problem that LATP and LLTO are incompatible with the Li LATP + 20% LLTO, and PEO + 10% LATP + 25% LLTO were
metal negative electrode and the presence of both fillers is fabricated and placed in between two SS electrodes to assemble
beneficial to reduce the interface impedance. Also, the con- an SS/films/SS symmetric blocking cell to test different LATP
tent of both fillers substantially increases the interaction and LLTO contents in the gel film electrolytes. The AC imped-
among the polymer and the inorganic nanoparticles, making ance plot of the gel film electrolytes is shown in Figure 7a, the
their synergistic effects more obvious. corresponding ion conductivities were calculated according to
Infrared spectroscopic investigation reveals specific interac- Equation (1) at room temperature and the results are shown in
tion among polymer. This technique applied to study the mech- Table 3. As can be seen from the figure the bulk impedance
anism of interpolymer miscibility through the formation of of LATP is 4.10 Ω. The addition of 10 wt% of LLTO can reduce

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Figure 4. SEM images of the a) PEO + 10% LATP, b) PEO + 10% LLTO, c) PEO + 10% LATP + 10% LLTO, d) PEO + 10% LATP + 15% LLTO, e) PEO + 10%
LATP + 20% LLTO, and f) PEO + 10% LATP + 20% LLTO.

the bulk impedance of the DCGPE films electrolyte and as the is shown in Figure 7b, the results show that an appropriate
LLTO content increases the bulk impedance of the electrolyte amount of ceramic fillers in the UV cured gel electrolyte films
decreases. When the mass fraction of LLTO is 15 wt% with can reduce the interface impedance between the lithium elec-
constant LATP 10%, the ion conductivity of the corresponding trode and the electrolyte. Since the interface between the
electrolyte is the highest to be 9.87 × 10−3 S cm−1. Due to UV layers is spontaneously formed, there is a perfect transition
curing phenomena and the excellent dispersion of LATP and between the layers of the LATP-LLTO. The gel electrolyte of
LLTO in the PEO matrix greatly enhanced conductivity. PEO + 10% LATP + 15% LLTO film, the interface impedance
The Li//Li symmetrical battery was assembled with the gel (66 Ω) between the electrode and the lithium metal electrode
electrolyte films, the interface performance between the gel was significantly lower than that of PEO + 10% LATP (322 Ω)
electrolytes and the lithium metal electrode was studied by and PEO + 10% LLTO (195 Ω) indicating that the dual ceramic
the AC impedance method. The resulting interface impedance gel polymer electrolytes were in good contact with the lithium

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Figure 5. SEM-EDS mapping analysis of the PEO + 10 wt% LATP + 15 wt% LLTO.

Figure 6. a) FTIR spectra of pure PEO, PEO + 10% LATP, PEO + 10% LLTO, PEO + 10% LATP + 10% LLTO, PEO + 10% LATP + 15% LLTO, PEO + 10%
LATP + 20% LLTO, PEO + 10% LATP + 25% LLTO and b) DSC curves of all samples of electrolytes.

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Figure 7. a) Impedance-spectra of SS/DCGPE/SS cell, b) the AC impedance spectra of Li/Li cells, c) linear sweep voltammograms of Li/SS cells using
PEO + 10% LATP, PEO + 10% LLTO, PEO + 10% LATP + 10% LLTO, PEO + 10% LATP + 15% LLTO, PEO + 10% LATP + 20% LLTO, and PEO + 10%
LATP + 25% LLTO, and d) TGA graphs of electrolyte films.

electrode. Dramatically, when the addition amount of LLTO are beneficial to reduce impurities in the system and increase
exceeds 25% in the PEO matrix with LATP 10%, the interface the oxidation potential. The electrochemical working window
resistance of the corresponding electrolyte and Li-electrode is of PEO + 10% LATP + 20% LLTO and PEO + 10% LATP + 25%
decreased due to partial LLTO deposition. These results showed LLTO is reduced compared to PEO + 10% LATP + 15% LLTO,
that the effect of both inorganic fillers can reduce impedance which may be ascribed due to the agglomeration of LLTO
between the lithium anode and DCGPE film. affecting the complete curing of the electrolyte.
The electrochemical stability of the dual gel film electrolyte is To ensure the safety of the electrolyte material, the electrolyte
an important basic parameter of the battery systems. The oxida- material is required to have a wide temperature range and excel-
tion potential value of the electrolyte is generally tested by LSV is lent thermal stability. TGA to characterize the thermal stability of
to characterize the electrochemical stability window of the electro- electrolyte materials, rising from room temperature to 1000 °C
lytes. As shown in Figure 7c, PEO + 10% LATP and PEO + 10% in an air atmosphere at a heating rate of 10 °C min−1. The char-
LLTO oxidatively degrade at ≈4.0 and 4.6 V, while dual ceramic acterization results are shown in Figure 7d, the initial decom-
gel polymer electrolyte film of PEO + 10% LATP + 15% LLTO of position temperature of the LATP and LLTO based gel film
stability window can be as high as 5.43 V. This result indicates electrolytes with different mass fractions. The highest, the cor-
that the addition of LATP and LLTO nano­particles is beneficial to responding decomposition temperature is 420 °C. It can be seen
improve the stability window of the electrolytes. However, LATP that the gel electrolyte films have no obvious weight loss before
has a certain inhibitory effect on the decomposition of anions 420 °C, and the thermal decomposition temperature rises pro-
in lithium and LLTO has a certain trapping effect on impurities gressively with the enhancement of fillers. The thermal stability
such as water vapor in the liquid electrolyte. These functionalities of the gel film electrolyte is slightly improved, when the LATP
contents reach 20% and 25%. The thermal decomposition tem-
perature of the electrolytes reaches a maximum of about 357 °C.
Table 3. Ion conductivities of prepared UV dual ceramic gel electrolyte.
The improvement of the thermal stability of electrolytes by com-
Electrolyte film composition Ion conductivity [S cm−1] bine the addition of LATP and LLTO is mainly because fillers act
as physical crosslinking points in PEO-based electrolytes.
PEO + 10% LATP 2.54 × 10−4
The ion conductivities of the electrolytes are composed of
PEO + 10% LLTO 2.81 × 10−5 anionic and cationic behaviors, but it is a fact that the move-
PEO + 10% LATP + 10% LLTO 8.01 × 10−3 ments of ion migration of Li ions make sense. Therefore, we
PEO + 10% LATP + 15% LLTO 9.87 × 10−3 evaluated the lithium transference (tLi +) of dual ceramic gel
PEO + 10% LATP + 20% LLTO 6.96 × 10−3
polymer electrolyte gel films with the method of steady-state
polarization and the result is shown in Figure 8a–f. The trans-
PEO + 10% LATP + 25% LLTO 5.02 × 10−3
ference (tLi + ) of PEO + 10% LATP + 15% LLTO was 0.82, which

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Figure 8. The chronoamperometry profiles of a) Li/PEO + 10% LATP/Li, b) Li/PEO + 10% LLTO, c) Li/PEO + 10% LATP + 10% LLTO/Li, d) Li/PEO + 10%
LATP + 15% LLTO/Li, e) Li/PEO + 10% LATP + 20% LLTO/Li, and f) Li/PEO + 10% LATP + 25% LLTO/Li symmetrical cells under a polarization voltage
of 50 mV. The corresponding EISs before and after the polarization are shown in insets.

was higher than other gel electrolyte films. The improvement without the occurrence of transient voltage drop. In Figure 9c,
in Li-transference due to addition to the optimal amount of the symmetrical cell of Li/Li accompanied with gel electro-
LATP and LLTO added may be ascribed to the fact that it can lyte of PEO + 10% LATP + 10% LLTO exhibits a good inhibi-
limit the movement of (bis)(trifluoromethanesulfonyl)imide via tory effect on lithium dendrite growth. The cell with UV cured
chemical interaction and therefore promote the dissociation of PEO + 10% LATP + 15% LLTO shows a very extraordinary stable
Li+. Besides, the larger radius of pores resulting from the pres- voltage tends response during the 2400 h cycling (Figure 9d).
ence of La3+ is also favorable for the migration of Li+. In Figure 9e,f cell with PEO + 10% LATP + 20% LLTO and
The long-term stability and electrochemical compatibility PEO + 10% LATP + 25% LLTO electrolytes shows the stable pro-
of UV cured gel films investigated against the lithium metal file with the Li–metal electrode due to combining percentage of
electrode during Li plating/stripping cyclic process on a sym- LATP and LLTO. Besides, the cell with PEO + 10% LATP + 15%
metrical double lithium cell. Figure 9 shows time versus LLTO electrolyte gel film can effectively improve the interface
voltage profiles of cell with the prepared gel film including stability between the electrolyte and Li electrode. This can be
PEO + 10% LATP, PEO + 10% LLTO, PEO + 10% LATP + 10% ascribed to the formation of interface film by the reaction gel
LLTO, PEO + 10% LATP + 15% LLTO, PEO + 10% LATP + 20% electrolyte and electrode which indicating the SEI layer can
LLTO, and PEO + 10% LATP + 25% LLTO cycling with a current remain stable during cycling. Two factors play an important
density of 2 mA cm−2, as shown in Figure 9a. The cells using role in promoting identical stripping/plating of lithium. First,
PEO + 10% LATP gel electrolyte initially exhibited small fluctua- the dual ceramic gel polymer electrolyte completely avoids the
tions and stable polarization voltage after the 1300 h of cycling side reaction with Li metal and improves the interface stability
the larger overpotentials were seen, the symmetric cell for LLTO between the electrode and the electrolyte. Second, the calculated
gel film as shown in Figure 9b stably cycled from 500 to 2000 h amount of 15% LLTO with 10% LATP distributed in the PEO

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Figure 9. Electrochemical performance of the Li plating/stripping within current density of 2 mA cm−2 cells of a) Li/PEO + 10% LATP/Li,
b) Li/PEO + 10% LLTO/Li, c) Li/PEO + 10% LATP + 10% LLTO/Li, d) Li/PEO + 10% LATP + 15% LLTO/Li, e) Li/PEO + 10% LATP + 20% LLTO/Li, and
f) Li/PEO + 10% LATP + 25% LLTO/Li.

matrix formed the layer. Both LATP and LLTO provide a fast film and its effects. The surface morphology of the PEO + 10%
channel and also facilitate the formation of a uniform flow to LATP shown in Figure 10a, the surface of the Li–metal after
the Li, promoting the uniform distribution of Li. Comparing the cycling of more than 2400 h Li metal indicates dendrites. The
time–voltage curves of the Li/PEO + 10% LATP + 15% LLTO/Li surface of lithium metal as observed in Figure 10b of PEO + 10%
cell with other, it can be found that cell using UV cured gel elec- LLTO cell cycled with a similar period of 2400 h received large
trolyte film did not have a short circuit during the whole cycling, dendrites on the surface. In Figure 10c, the surface of Li–metal
However, in the first few electrode activation cycles, the cor- shows discernable uniform, so it can be demonstrated that
responding polarization voltage is not as stable as PEO + 10% DCGPE film constructively suppresses the dendritic growths
LATP + 15% LLTO electrolyte. This result indicates that UV and ensure ultra-long-term stability of Li-stripping-plating,
cured PEO + 10% LATP + 15% LLTO electrolyte has better LATP and LLTO particles serve as the ideal skeleton for Li metal,
compatibility and stability with lithium metal. Figure S2a–c in helping to achieve no volume change during stripping/plating
the Supporting Information shows the symmetrical cell Li// and suppressed dendrite growth. The visual photographs in
PEO + 10% LATP + 15% LLTO//Li test during charge/discharge Figure 10d further verified its external position of the Li metal
at a current density of 0.25 mA cm−2 up to 2000 h without short- even after the long cycling of above 2400 h. The appearance of
circuiting occurrence at room temperature compared with Li// lithium metal after cycling as shown in a schematic image of
PEO + 10% LATP//Li and Li//PEO + 10% LLTO//Li. Figure 10d,iii of Li/PEO + 10% LATP + 15% LLTO/Li is quite
The SEM images were taken from bare Li–metal and after clear and looks new.
repeated stripping/plating at 2 mAh cm−2. The observation vali- Further, investigate the practicability of dual ceramic gel
dates the authenticity of dual ceramic gel polymer electrolyte polymer electrolyte (PEO + 10% LATP + 15% LLTO), PEO + 10%

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Figure 10. SEM microstructure images of a) PEO + 10% LATP, b) PEO + 10% LLTO, c) PEO + 10% LATP + 15% LLTO, and d) photographs of corre-
sponding SEM Li–metal anodes of the i) PEO + 10% LATP, ii) PEO + 10% LLTO, and iii) PEO + 10% LATP + 15% LLTO after more than 2400 h.

Figure 11. a) Cycling performance of LiFePO4/PEO + 10% LATP + 15% LLTO/Li cell at 0.1 C, b) rate performance of the DCGPEs cell, c) particular charge
and discharge profiles at different C-rates, and d) cycle stability of cell LiFePO4/PEO + 10% LATP + 15% LLTO/Li at 0.2 C.

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LATP, and PEO + 10% LLTO film to evaluate the dual inor- become one of the most promising electrolytes and paves a new
ganic fillers strategy in the working battery systems. The full way in the practical application of the Li–metal batteries.
cell was assembled CR2032 coin cell with LiFePO4 (LFP) used
as a cathode, a Li metal as an anode, and UV cured gel films
as electrolytes. The cycling performance at current rate of 0.1 C Supporting Information
is displayed in Figure 11a, It is shown that the lithium–metal
Supporting Information is available from the Wiley Online Library or
battery exhibits excellent cycling stability with the PEO + 10% from the author.
LATP + 15% LLTO after 100 cycles at 0.1 C. (capacity reten-
tion 85.1% after 100 cycles). However, the final discharge
capacity of the LiFePO4/PEO + 10% LATP + 15% LLTO/Li noted Acknowledgements
137.2 mAh g−1 at the same current rate and the initial Coulombic
efficiency could reach 99.5%. Furthermore, the dual inorganic The work was financially supported by the National Natural Sciences
Foundation of China (Nos. 51772016, 51272021, 51402010, and 51072013)
particles are beneficial in the improving of the rate performance
and the Fundamental Research Funds for Central Universities (XK-1802-2).
of the battery as observed in Figure 11b, the rated capacity of the M.S.J. would like to thank China Postdoctoral Science Foundation for
cell using PEO + 10% LATP + 15% LLTO gel electrolyte delivers funding under project 2018M633280.
reversible capacities 161.2, 152.1, 138, 125, and 96.8 mAh g−1,
respectively. When the current density is retuned to 0.1 C, the
actual capacities of the battery restored to about 96.8%. The
charge–discharge curves of LiFePO4/PEO + 10% LATP + 15% Conflict of Interest
LLTO/Li at 0.1, 0.2, 0.5, 1, and 2 C are shown in Figure 11c The authors declare no conflict of interest.
and the clear potential plateaus performances demonstrated a
reversible cycling process. Also, with the increment of the cur-
rent density, the discharge capacity of the cell decreased gradu-
ally, which is due to the polarization effect caused by the limited Keywords
Li+ diffusion rate at a high current rate. In Figure 11d, shows dual ceramic gel polymer electrolytes, LATP, Li-dendrites, lithium–metal
the charge and discharge voltage curves of a cell consisting of batteries, LLTO, PEO, PVP
LiFePO4/PEO + 10% LATP + 15% LLTO/Li at 0.2 C. The excel-
lent cycle and rate performance of the cell using PEO + 10% Received: May 11, 2020
LATP + 15% LLTO gel film are attributed to the better electro- Revised: July 22, 2020
Published online:
chemical interfacial stability between electrolyte, the cathode,
and anode. The suppression of Li dendrite growth is demon-
strating that the optimal amount of LLTO in dual ceramic gel
polymer electrolyte film shows a great potential application for
[1] B. Liu, J.-G. Zhang, W. Xu, Joule 2018, 2, 833.
high-performance Li–metal batteries.
[2] J. Lim, Y. Li, D. H. Alsem, H. So, S. C. Lee, P. Bai, D. A. Cogswell,
X. Liu, N. Jin, Y.-S. Yu, N. J. Salmon, D. A. Shapiro, M. Z. Bazant,
T. Tyliszczak, W. C. Chueh, Science 2016, 353, 566.
4. Conclusions [3] J.-M. Tarascon, M. Armand, Nature 2001, 414, 359.
[4] Y. Sun, N. Liu, Y. Cui, Nat. Energy 2016, 1, 16071.
In summary, we successfully developed DCGPE [5] F. Shi, A. Pei, A. Vailionis, J. Xie, B. Liu, J. Zhao, Y. Gong, Y. Cui,
PEO + LATP + LLTO film via the UV photopolymerization pro- Proc. Natl. Acad. Sci. U. S. A. 2017, 114, 12138.
cess. The designed DCGPE prepares to introduce optimized [6] R.-J. Chen, Y.-B. Zhang, T. Liu, B.-Q. Xu, Y.-H. Lin, C.-W. Nan,
LATP and LLTO particles in the polymer matrix PEO that play Y. Shen, ACS Appl. Mater. Interfaces 2017, 9, 9654.
[7] W. Wang, E. Yi, A. J. Fici, R. M. Laine, J. Kieffer, J. Phys. Chem. C
a role of template structure with a highly extendable and flexible
2017, 121, 2563.
thin film. We achieved dual ceramic-based electrolyte exhibited
[8] Z. Tu, Y. Kambe, Y. Lu, L. A. Archer, Adv. Energy Mater. 2014, 4, 1300654.
super ion conductivities. LATP and LLTO particles act as an active [9] R. Schmuch, R. Wagner, G. Hörpel, T. Placke, M. Winter,
filler to improve the interfacial stability and help to avoid the side Nat. Energy 2018, 3, 267.
reactions. 10 wt% LATP along with 15 wt% LLTO, the obtained [10] D. Lin, Y. Liu, Y. Cui, Nat. Nanotechnol. 2017, 12, 194.
electrolyte exhibited high ionic conductivity of 9.87 × 10−3 S cm−1 [11] Y. Liu, Y. Fang, Z. Zhao, C. Yuan, X.-W. Lou, Adv. Energy Mater. 2019,
at room temperature, its electrochemical stability up to 5.4 V 9, 1804004.
versus Li/Li+ and the Li-ion transference number 0.82. In [12] J. A. Lewis, J. Tippens, F. J. Q. Cortes, M. T. Mcdowell, Trends Chem.
addition, the PEO + 10% LATP + 15% LLTO and PEO + 10% 2019, 1, 845.
LATP + 20% LLTO showed an effective suppression of Li den- [13] W. Xu, J. Wang, F. Ding, X. Chen, E. Nasybulin, Y. Zhang,
J. G. Zhang, Energy Environ. Sci. 2014, 7, 513.
drite growth when used in a Li battery. Finally, the battery with
[14] M. H. Braga, N. S. Grundish, A. J. Murchison, J. B. Goodenough,
PEO + 10% LATP + 15% LLTO delivered high capacity retention
Energy Environ. Sci. 2017, 10, 331.
reaching 85.1% after 100 cycles at 0.1 C, and the Coulombic effi- [15] L. Li, S. Basu, Y. Wang, Z. Chen, P. Hundekar, B. Wang, J. Shi, Y. Shi,
ciency can reach nearly 99.5% per cycle. This work will provide S. Narayanan, N. Koratkar, Science 2018, 359, 1513.
a clever solution to construct ceramic-based electrolytes with [16] G. A. Umeda, E. Menke, M. Richard, K. L. Stamm, F. Wudl, B. Dunn,
rigidity and adverse effect for Li–metal batteries. We believe that J. Mater. Chem. 2011, 21, 1593.
dual structure inorganic–inorganic compound electrolyte will [17] M. Armand, J.-M. Tarascon, Nature 2008, 451, 652.

Adv. Mater. Interfaces 2020, 2000830 2000830 (13 of 14) © 2020 Wiley-VCH GmbH
www.advancedsciencenews.com
www.advmatinterfaces.de

[18] J. Kasemchainan, S. Zekoll, D. Spencer Jolly, Z. Ning, G. O. Hartley, [44] E. Kamio, T. Yasui, Y. Iida, J. P. Gong, H. Matsuyama, Adv. Mater.
J. Marrow, P. G. Bruce, Nat. Mater. 2019, 18, 1105. 2017, 29, 1704118.
[19] D. Li, L. Chen, T. Wang, L.-Z. Fan, Appl. Mater. Interfaces 2018, 10, [45] Q. Cheng, A. Li, N. Li, S. Li, A. Zangiabadi, T.-D. Li, W. Huang,
7069. A. C. Li, T. Jin, Q. Song, W. Xu, N. Ni, H. Zhai, M. Dontigny,
[20] H. Koshikawa, S. Matsuda, K. Kamiya, M. Miyayama, Y. Kubo, K. Zaghib, X. Chuan, D. Su, K. Yan, Y. Yang, Joule 2019, 6, 1510.
K. Uosaki, K. Hashimoto, S. Nakanishi, J. Power Sources 2018, 376, [46] C. Gerbaldi, J. R. Nair, G. Meligrana, R. Bongiovanni, S. Bodoardo,
147. N. Penazzi, Electrochim. Acta 2010, 55, 1460.
[21] L. Wang, Z. Zhou, X. Yan, F. Hou, L. Wen, W. Luo, J. Liang, [47] S. H. Siyal, M. Li, H. Li, J.-L. Lan, Y. Yu, X. Yang, Appl. Surf. Sci. 2019,
S. X. Dou, Energy Storage Mater. 2018, 14, 22. 494, 1119.
[22] J. Zheng, J. A. Lochala, A. Kwok, Z. D. Deng, J. Xiao, Adv. Sci. 2017, [48] A. Chamaani, M. Safa, N. Chawla, B.-E. Zahab, ACS Appl. Mater.
4, 1700032. Interfaces 2017, 9, 33819.
[23] Y. Xu, W. J. Lin, M. Gliege, R. Gunckel, Z. Zhao, H. Yu, L. L. Dai, [49] M. W. Logan, S. Langevin, B. Tan, A. W. Freeman, C. Hoffman,
J. Phys. Chem. B 2018, 122, 12077. D. B. Trigg, K. Gerasopoulos, J. Mater. Chem. A 2020, 8, 8485.
[24] X. Li, K. Qian, Y.-B. He, C. Liu, D. An, Y. Li, D. Zhou, Z. Lin, B. Li, [50] C. Gerbaldi, J. R. Nair, G. Meligrana, R. Bongiovanni, S. Bodoardo,
Q.-H. Yang, F. Kang, J. Mater. Chem. A 2017, 5, 18888. N. Penazzi, J. Appl. Electrochem. 2009, 39, 2199.
[25] D. Saikia, H.-Y. Wu, Y.-C. Pan, C.-C. Liao, C.-F. Chen, G. T. K. Fey, [51] M. Doytcheva, D. Dotcheva, R. Stamenova, C. Tsvetanov,
H.-M. Kao, Electrochim. Acta 2009, 54, 7156. Macromol. Mater. Eng. 2001, 286, 30.
[26] Y.-C. Jung, M.-S. Park, C.-H. Doh, D.-W. Kim, Electrochim. Acta 2016, [52] Y. Liu, J. Y. Lee, L. Hong, J. Power Sources 2004, 129, 303.
218, 271. [53] D. C. Forbes, N. A. Peppas, Polymer 2013, 54, 4486.
[27] J. Zheng, Y. Y. Hu, ACS Appl. Mater. Interfaces 2018, 10, 4113. [54] S. A. Langevin, B. Tan, A. W. Freeman, J. C. Gagnon, C. M. Hoffman,
[28] Y. Liu, J. Liu, Q. Sun, D. Wang, K. R. Adair, J. Liang, C. Zhang, M. W. Logan, J. P. Maranchi, K. Gerasopoulos, Chem. Commun.
L. Zhang, S. Lu, H. Huang, X. Song, X. Sun, ACS Appl. Mater. Inter- 2019, 55, 13085.
faces 2019, 11, 27890. [55] I. L. Johansson, D. Brandell, J. Mindemark, Batteries & Supercaps
[29] C. Galven, J.-L. Fourquet, M.-P. Crosnier-Lopez, F. Le Berre, Chemin- 2020, 3, 1.
form 2011, 42, 1892. [56] Z. Qiu, C. Liu, J. Xin, Q. Wang, J. Wu, W. Wang, J. Zhou, Y. Liu,
[30] A. M. Christie, S. J. Lilley, E. Staunton, Y. G. Andreev, P. G. Bruce, B. Guo, S. Shi, ACS Sustainable Chem. Eng. 2019, 7, 9875.
Nature 2005, 433, 50. [57] J. Jiang, H. Pan, W. Lin, W. Tu, H. Zhang, Mater. Chem. Phys. 2019,
[31] J. Zhang, J. Zhao, L. Yue, Q. Wang, J. Chai, Z. Liu, X. Zhou, H. Li, 236, 12178.
Y. Guo, G. Cui, L. Chen, Adv. Energy Mater. 2015, 24, 1501082. [58] A. Zhakeyev, P. Wang, L. Zhang, W. Shu, H. Wang, J. Xuan, Adv. Sci.
[32] Q. Zhou, J. Ma, S. Dong, X. Li, G. Cui, Adv. Mater. 2019, 50, 2017, 4, 1700187.
1902029. [59] Y. Cui, J. Chai, H. Du, Y. Duan, G. Xie, Z. Liu, G. Cu, ACS Appl. Mater.
[33] L. Yue, J. Ma, J. Zhang, J. Zhao, S. Dong, Z. Liu, G. Cui, L. Chen, Interfaces 2017, 9, 8737.
Energy Storage Mater. 2016, 5, 139. [60] A. Chiappone, J. R. Nair, C. Gerbaldi, R. Bongiovanni, E. Zeno,
[34] J. Zhang, J. Zhao, L. Yue, Q. Wang, J. Chai, Z. Liu, X. Zhou, Electrochim. Acta 2015, 153, 97.
H. Li, Y. Guo, G. Cui, L. Chen, Adv. Energy Mater. 2015, 5, [61] R. Kang, S. H. Oh, D. Y. Kim, ACS Appl. Mater. Interfaces 2014, 6, 6227.
1501082. [62] J. Amici, S. Romanin, M. Alidoost, D. Versaci, C. Francia,
[35] X. Wang, Y. Zhang, X. Zhang, T. Liu, Y.-H. Lin, L. Li, Y. Shen, F. Smeacetto, S. Bodoardo, J. Electroanal. Chem. 2019, 837, 103.
C.-W. Nan, ACS Appl. Mater. Interfaces 2018, 10, 24791. [63] Q. Lu, J. Yang, W. Lu, J. Wang, Y. Nuli, Electrochim. Acta 2015, 152, 489.
[36] J. B. Goodenough, K.-S. Park, J. Am. Chem. Soc. 2013, 135, 1167. [64] Y. Zhi, X. Sun, N. Li, S. Yuan, Z. Wang, L. Jin, J. Hang, L. Shi,
[37] C. Sun, X. Huang, J. Jin, Y. Lu, Q. Wang, J. Yang, Z. Wen, J. Power J. Alloys Compd. 2018, 737, 756.
Sources 2018, 377, 36. [65] J. Jeong, G. C. Marques, X. Feng, D. Boll, S. A. Singaraju,
[38] Y. Cui, X. Liang, J. Chai, Z. Cui, Q. Wang, W. He, X. Liu, Z. Liu, J. Aghassi-Hagmann, H. Hahn, B. Breitung, Adv. Mater. Interfaces
G. Cui, J. Feng, Adv. Sci. 2017, 4, 1700174. 2019, 6, 1901074.
[39] K. M. Diederichsen, E. J. Mcshane, B. D. Mccloskey, ACS Energy [66] Y. Yang, S. Jeong, L. Hu, H. Wu, S. W. Lee, Y. Cui, Proc. Natl. Acad.
Lett. 2017, 2, 2563. Sci. USA 2011, 108, 13013.
[40] C. Wang, Y. Yang, X. Liu, H. Zhong, H. Xu, Z. Xu, H. Shao, F. Ding, [67] W. Fan, X. Zhang, C. Li, S. Zhao, J. Wang, ACS Appl. Energy Mater.
ACS Appl. Mater. Interfaces 2017, 9, 13694. 2019, 2, 4513.
[41] X.-X. Zeng, Y.-X. Yin, N.-W. Li, W.-C. Du, Y.-G. Guo, L.-J. Wan, J. Am. [68] Z. Wei, Z. Zhang, S. Chen, Z. Wang, X. Yao, Y. Deng, X. Xu, Energy
Chem. Soc. 2016, 138, 15825. Storage Mater. 2019, 22, 337.
[42] P. Hovington, M. Lagacé, A. Guerfi, P. Bouchard, A. Mauger, [69] Z. Qiu, C. Liu, J. Xin, Q. Wang, J. Wu, W. Wang, J. Zhou, Y. Liu,
C. M. Julien, M. Armand, K. Zaghib, Nano Lett. 2015, 15, 2671. B. Guo, S. Shi, ACS Sustainable Chem. Eng. 2019, 7, 9875.
[43] W. Zhou, S. Wang, Y. Li, S. Xin, A. Manthiram, J. B. Goodenough, [70] M.-K. Song, J.-Y. Cho, B. W. Cho, H.-W. Rhee, J. Power Sources 2002,
J. Am. Chem. Soc. 2016, 138, 9385. 110, 209.

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