Research Article

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Addressing the Interface Issues in All-Solid-State Bulk-Type Lithium

Ion Battery via an All-Composite Approach
Ru-Jun Chen, Yi-Bo Zhang, Ting Liu, Bing-Qing Xu, Yuan-Hua Lin, Ce-Wen Nan,* and Yang Shen*
School of Materials Science and Engineering, State Key Lab of New Ceramics and Fine Processing, Tsinghua University, Beijing
100084, China
*
S Supporting Information

ABSTRACT: All-solid-state bulk-type lithium ion batteries (LIBs) are considered

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ultimate solutions to the safety issues associated with conventional LIBs using
flammable liquid electrolyte. The development of bulk-type all-solid-state LIBs has
been hindered by the low loading of active cathode materials, hence low specific
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surface capacity, and by the high interface resistance, which results in low rate and
cyclic performance. In this contribution, we propose and demonstrate a synergistic
all-composite approach to fabricating flexible all-solid-state LIBs. PEO-based
composite cathode layers (filled with LiFePO4 particles) of ∼300 μm in thickness
and composite electrolyte layers (filled with Al-LLZTO particles) are stacked layer-
by-layer with lithium foils as negative layer and hot-pressed into a monolithic all-
solid-state LIB. The flexible LIB delivers a high specific discharge capacity of 155
mAh/g, which corresponds to an ultrahigh surface capacity of 10.8 mAh/cm2,
exhibits excellent capacity retention up to at least 10 cycles and could work properly
under harsh operating conditions such as bending or being sectioned into pieces.
The all-composite approach is favorable for improving both mesoscopic and microscopic interfaces inside the all-solid-state LIB
and may provide a new toolbox for design and fabrication of all-solid-state LIBs.
KEYWORDS: lithium ion battery, bulk-type all-solid-state battery, solid-state electrolyte, composite, Li7La3Zr2O12,, PEO

■ INTRODUCTION
The long-standing challenge for conventional lithium ion
battery (LIBs) has been the safety issues related to the
flammable organic liquid electrolyte, which limits the mass
application of conventional LIBs in electric vehicles (EVs) or
other energy storage applications.1−4 The ultimate solution to
the fire hazard of conventional lithium ion battery lies in the
implementation of all-solid-state LIBs, where the flammable
liquid electrolyte is completely replaced by solid-state electro-
lyte. In addition to their intrinsic safety and reliability, all-solid-
state LIBs also exhibit higher energy density and higher power
density.5,6 As a result of their highly integrated monolithic
structure, composite cathode with higher density allows for
higher loading of active cathode materials. Plus, the solid
electrolyte of high structural integrity may prevent the growth
of lithium dendrites, making it possible for the use of lithium
metal as the anode.7,8 These favorable features give rise to
much enhanced energy density of all-solid-state LIBs.
Among all the all-solid-state lithium batteries with different
structure designs, thin-film solid-state batteries have been
intensively studied and widely used in microelectronic
industries as power supply for ICs or RF devices, where
capacity retention instead of total capacity plays a more critical
role.9 These film batteries consist of three layers of thin films
serving as positive electrode, solid electrolyte and negative
electrode, respectively.10,11 Although thin-film solid-state
batteries deliver excellent capacity retention of over thousands
of cycles,9 their total capacity is rather low because of the small
thickness of the cathode layer which contains very small
amount of active cathode material. In current thin-film LIBs,
substrate and other inactive components occupy a large portion
of space inside the battery, resulting in very low surface capacity
(5 μAh/cm2 to 100 μAh/cm2).10 Increasing the thickness of the
electrodes in all-solid-state batteries is thought to be helpful for
decreasing the relative ratio of inactive cell components such as
current collectors, and thus increases the specific energy
density.12 This approach, however, could not be adopted due to
both technical and intrinsic scientific limitations. Current thin-
film-deposition techniques, such as RF-sputtering, pulsed laser
deposition or atomic layer deposition9,13−15 are expensive and
time-consuming, which makes it rather difficult and not cost-
effective, if not impossible, to expand the thin-film structure
into bulk-type LIBs by simply increasing the thickness of
cathode layer. More importantly, increasing the thickness of the
active cathode layers also substantially increase the distance for
lithium transportation during charge−discharge cycles, resulting
in much increased impedance. The cycling performance of the
solid LIBs is also significantly compromised by the cracks, both
inside the cathode layers and at the interface between electrode
and electrolyte layers, arising from the volumetric change of
Received: December 19, 2016
Accepted: February 28, 2017
Published: February 28, 2017

© 2017 American Chemical Society 9654 DOI: 10.1021/acsami.6b16304

ACS Appl. Mater. Interfaces 2017, 9, 9654−9661
ACS Applied Materials & Interfaces
active materials during cycling. For these reasons, all-solid-state
LIBs could not be fabricated by simply expanding the layer-by-
layer structure from thin-film to bulk-type.16
To address these issues, composite approaches have been
adopted by preparing composite electrodes consisted of active
materials and electronic and ionic conductor additives to
increase the thickness of cathode. For instances, bulk-type all-
solid-state LIBs with composite cathodes consisted of active
cathode materials, inorganic or polymer solid-state electrolyte
and other additives on top of Li7La3Zr2O12 (LLZO) pellets as
solid electrolyte have been assembled.17−20 Though the
thickness of the cathodes in these batteries increased from
several microns in thin-film batteries to tens of microns, these
batteries contain very thick ceramic electrolyte pellets. As a
result, their specific volumetric capacity and energy density are
still low. Bulk-type composite electrode prepared by a colloidal
crystal templating method and sol−gel infiltration process can
exhibit high capacity and energy density, but the preparation
processes are too complex and time-consuming.21,22 Delaizir et
al. have successfully fabricated a monolithic solid-state lithium
battery by spark plasma sintering method with a composite
cathode as thick as 400 μm and achieved a high surface capacity
of 2.2 mAh/cm2, demonstrating the potential of bulk-type
composite electrodes in the application of all-solid-state LIBs.16
However, because of the all-ceramic structure of the battery, the
sintering condition was hard to control and a large portion of
the active materials could not be fully utilized. We have also
prepared compact three-dimensional composite electrodes by
one-step sintering of active materials and 0.44LiBO2·0.56LiF
and all-solid-state batteries have been assembled using dry
polymer electrolyte as the electrolyte layer.23,24 High surface
energy density and improved cycling performance have been
achieved.
The other critical component for all-solid-state LIBs is the
electrolyte. Poly(ethylene oxide) (PEO)-based composite
electrolytes containing inorganic nanoparticles, such as SiO2
or Al2O3, have been intensively explored and are still
considered as the most promising composite electrolyte.25,26
In these PEO-based composite electrolyte, the inorganic
nanoparticles act as cross-linking centers to reduce the
crystallinity of the polymer, giving rise to increased chain
mobility hence higher ionic conductivity. Plus, the strong Lewis
acid−base interaction between electrolyte ion species and the
surface chemical groups of inorganic nanoparticles can enhance
the dissociation and stabilize the anions. It is worth noting that
most of the inorganic nanoparticles used in the composite
electrolyte so far are inert, meaning that they are themselves of
rather low ionic conductivity. Further enhancement of ionic
conductivity of these PEO-based composite electrolytes may lie
in the employment of nanoparticles with high intrinsic ionic
conductivity. For this reason, LLZO or (Li0.35La0.55TiO3)
LLTO ceramic particles may hold the promise of achieving
higher ionic conductivity in PEO-based composite electrolyte.
For instance, Hu et.al., recently demonstrated that the addition
of LLZO in PEO can effectively increase the conductivity of the
composite electrolyte and block the growth of dendrites.27
In this contribution, we took a synergistic all-composite
approach to fabricating highly flexible all-solid-state LIBs. PEO
-based composite cathode layers of ∼300 μm in thickness are
prepared via hot-pressing using LiFePO4 as active cathode
materials and indium tin oxides (ITO) as electronic conductor
additive. Composite electrolytes consisted of Al-doped LLZO
and PEO dry electrolyte are then cast from solution into layers
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of ∼70 μm in thickness. The cathode layer, electrolyte layer and
lithium foil are then stacked layer-by-layer and hot-pressed into
an all-solid-state LIB of monolithic structure. The all-solid-state
battery cell was cycled at a constant current density of 100 μA/
cm2 at 60 °C and delivered an average specific discharge
capacity of 155 mAh/g, which translates into a surface capacity
as high as 10.8 mAh/cm2. Excellent capacity retention is
obtained and no capacity fading can be observed up to at least
ten cycles. In addition to the excellent electrochemical
performance, the all-solid-state LIB fabricated via the all-
composite approach is highly flexible and ductile. It still works
properly after being subjected to harsh conditions such as
repeated bending or even cutting into smaller pieces during
discharging. We note that not only could the superior
mechanical performances of the all-solid-state LIBs be
attributed to the composite structure but the all-composite
approach also has significant implications on the electro-
chemical performance of the LIBs. The hot-pressing process
during battery assembly is in favor of forming dense and good
interfaces between the cathode and electrolyte layer, which
gives rise to decreased interface impedance. Plus, the soft
polymer matrix employed in the composite cathode layers
could tolerate the substantial volumetric change of the active
cathode materials during the charge−discharge cycles and
prevent the formation of cracks induced by the stress.
■ EXPERIMENTAL SECTION
Preparation of Composite Electrolyte. The Al-doped
Li6.75La3Zr1.75Ta0.25O12 (Al-LLZTO) powders were prepared by
conventional solid-state reaction as reported in our previous work.22
Stoichiometric amount of LiOH·H2O (Aladdin Reagent), La2O3
(Sinopharm Chemical Reagent), ZrO 2 (Sinopharm Chemical
Reagent), Ta2O5 (Aladdin Reagent), and Al2O3 (Sinopharm Chemical
Reagent) were thoroughly mixed in 2-propanol for 8 h. The mixed
slurries were dried and calcined at 900 °C for 6 h. The as-calcined
powders were ball-milled in 2-propanol for 13 h followed by drying
process. The composite solid electrolytes (CSEs) were prepared by
solution method. PEO (Alfa Aesar) with an average molecular weight
of 300 000, LiN(CF3S02)2 (LITFSI, Aladdin reagent) and Al-LLZTO
were weighted according to the stoichiometric ratio. The PEO-LITFSI
concentration ratio was fixed at n(O)/n(Li) = 12 and the weight
percentage of Al-LLZTO was varied from 40 wt % to 80 wt %
according to the total PEO + Al-LLZTO weight of the CSEs. The Al-
LLZTO was ultrasonicated in acetonitrile for 4 h followed by the
addition of predetermined amounts of PEO and LITFSI. This solution
was then stirred at room temperature for 24 h until a homogeneous
electrolyte slurry was obtained. The mixture was cast on Teflon plates
in an argon-filled glovebox and dried under vacuum at 60 °C to
evaporate the solvent and get the CSE films. For ionic conductivity
measurement, the electrolyte film was pressed between two stainless
steel blocking electrodes.
Fabrication of the All-Solid-State Battery. Thick composite
cathode layers were prepared with hot-pressing method. Battery-grade
LiFePO4 powder was used as the active material of composite
cathodes. In2O5Sn (ITO) instead of other cheaper materials was
chosen as the electron conducting additive to increase the compaction
density of the composite electrolyte, which is in favor of shorter
migration paths for lithium ion and gives rise to higher volume energy
density. The weight percentage of ITO was set to 10 wt % with respect
to the weight of LiFePO4. The PEO-LITFSI concentration ratio was
fixed at n(O)/n(Li) = 12 and the weight percentage of PEO was varied
from 30 wt % to 10 wt % according to the total PEO + LiFePO4 +
ITO weight in the composite cathodes. To ensure homogeneous
dispersion of LiFePO4 and ITO particles in the PEO matrix,
stoichiometric amount of PEO, LITFSI, LiFePO4, and ITO were
first dissolved and thoroughly mixed by stirring in acetonitrile for 12 h
to obtain a homogeneous cathode slurry. The slurry was then
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completely dried in vacuum oven at 60 °C. The dried precursor of the
composite cathode was then subjected to freeze ball-milling at liquid
nitrogen temperature for 40 min. For the hot-pressing process, 50 mg
of the resultant composite cathode powders were hot-pressed at 40 °C
under vacuum into composite cathode layers of ∼300 μm in thickness.
For the assembly of all-solid-state LIBs, Au was sputtered on one
side of the composite cathode layer as current collector. A composite
electrolyte layer of ∼70 μm in thickness was then screen printed on
the other side of the composite cathode layer. To control the
uniformity of the electrolyte, a steel plate with a hole was installed in
the screen printer and the composite cathode was placed under the
hole. After the electrolyte slurry flowed through the hole, a uniform
electrolyte layer was obtained. The composite electrolyte layer was
dried in vacuum oven at 60 °C. Finally, a lithium foil of ∼100 μm in
thickness was attached on top of the composite electrolyte layer as
anode layer in an argon-filled glovebox. The schematic illustration for
the all-solid-state battery is shown in Figure S1. The whole all-solid-
state lithium battery was sealed in a LIR 2032 cell before testing.
Characterization of the Electrolyte and Battery. The phase
composition of the Al-LLZTO was characterized with X-ray diffraction
(XRD, RigakuDmax 2500). The electrochemical impedance measure-
ment was carried out with an impedance analyzer (ZAHNER-elektrik
IM6) in the frequency range from 1 Hz to 8 MHz at a voltage
amplitude of 50 mV. The microstructure of the pellet was
characterized with scanning electron microscopy (SEM, JEOLJSM-
7001 F). The cells were galvanostatically cycled between 2.3 and 3.8 V
vs Li/Li+ at 100 μA/cm2 at 60 °C. The testing temperature was
controlled by an environmental chamber (Cincinnati Sub-Zero MCB-
1.2-AC). Constant current charging was used for investigation of the
rate capacity with charging current set to 100 μA/cm2 and discharging
current varied from 100 μA/cm2 to 300 μA/cm2.
■ RESULTS AND DISCUSSIONS
Enhanced Ionic Conductivity of the Composite Solid
Electrolyte. The Al-LLZTO powders used in this study are of
pure cubic phase as indicated by the X-ray diffraction (XRD)
patterns shown in Figure S2. SEM images of the Al-LLZTO
powders (Figure S3) reveal that the powders exhibit uniform
size distribution with an average diameter of <1 μm. The cross-
section SEM images of the composite solid electrolytes with
different concentration of Al-LLZTO are shown in Figure 1.
Homogeneous dispersion is achieved even in the composite
electrolyte loaded with 80 wt % of Al-LLZTO and no obvious
agglomeration could be observed. At a low loading of Al-
LLZTO, the composite electrolyte exhibits high viscosity, while
Figure 1. Cross-section SEM images of the composite solid
electrolytes with different concentration (a) 40, (b) 60, and (c) 80
wt % of Al-LLZTO.
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as the content of Al-LLZTO increases, the viscosity decreases
substantially.
Figure 2 shows the Arrhenius plots for the composite solid
electrolytes with different Al-LLZTO contents. It can be
Figure 2. Arrhenius plots for the composite solid electrolytes with
different Al-LLZTO contents.
observed that the addition of Al-LLZTO can significantly
increase the conductivity of the electrolyte in comparison with
other PEO-based polymer electrolytes containing ionic
insulating additives.26 The composite electrolyte loaded with
60 wt % Al-LLZTO shows a highest conductivity of 2.48 ×
10−4 S/cm at 30 °C, which is comparable to the best results in
polymer electrolyte.27,28 Same composite electrolyte also
exhibits a wide electrochemical stability window up to ∼6 V,
as shown in Figure S4. Higher loading of Al-LLZTO may
introduce pores in the composite electrolyte and deteriorate the
ionic conductivity. The activation energies (Ea) are calculated
using the equation σ = A exp(Ea/kT), where σ is the ionic
conductivity, A is the pre-exponential constant, k is the
Boltzmann constant, and Ea is the activation energy. For the
composite electrolytes with 40 and 60 wt % Al-LLZTO, an
obvious change of slope around 60 °C can be observed, which
can be explained by the recrystallization of PEO from the
amorphous state when it is cooled to the transition temperature
at around 60 °C.29 However, no apparent change of slope can
be observed in the electrolyte with 80 wt % Al-LLZTO. The
decreased content of PEO and the low crystallinity of the PEO
in the low temperature range may contribute to this
phenomenon. The conductivity at 30 °C and activation
energies of the composite electrolytes with different Al-
LLZTO contents are listed in Table 1. It can be observed
that the activation energies of these composites electrolytes
below 60 °C are much lower compared with the ceramic-free
PEO electrolyte, while the activation energies above 60 °C are
of no substantial difference. In addition, the activation energies
Table 1. Ionic Conductivity at 30°C and Activation Energies
of the Composite Electrolytes with Different Al-LLZTO
Contents
40 wt % 60 wt % 80 wt %
conductivity at 30 °C 1.04 × 10−4 2.48 × 10−4 2.70 × 10−5
(S/cm)
activation energy below 65.51 60.11 48.34
60 °C (kJ/mol)
activation energy above 38.79 39.08 48.34
60 °C (kJ/mol)
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in the low-temperature range decrease as the concentration of
ceramic increases. These two phenomena can be attributed to
the reduction of the content and crystallinity of PEO, which
means minor structural change is induced in PEO by increasing
temperature, leading to minor variation of ionic conductivity of
the electrolyte and hence a lower activation energy in low
temperature range. Taking both of the mechanical and
electrochemical properties into consideration, we chose the
composite electrolyte containing 60 wt % Al-LLZTO to
assemble our all-solid-state lithium batteries.
Morphology and Electrochemical Performance of the
Composite Cathode. Because both active cathode materials
and electronic conductors are added in PEO matrix, we denote
composite cathodes with the content of PEO. Cross-section
SEM images of the composite cathode pellets with different
contents of PEO are shown in Figure 3. The polymer here can
Figure 3. Cross-section SEM images of the composite cathode pellets
with (a) 30, (b) 20, (c) 15, and (d) 10 wt % of polymer.
serve not only as the ionic transport path in the composite
cathode but also as the buffer to tolerate the volumetric changes
of the active materials during cycling. When the polymer
content is 30 wt %, obvious polymer phase can be observed and
LiFePO4 particles are separated by the polymer and not capable
of connecting to each other closely, which was detrimental to
the electronic conductivity of the composite cathode. Because
of the high content of polymer, the composite cathode exhibits
high viscosity. As the polymer content decreases to 20 or 15 wt
%, polymer serves as binder to connect the active materials
particles together. The composite cathodes are still dense and
are of high structural integrity with very small amount of pores,
exhibiting moderate viscosity as well as good mechanical
property. When the content of the polymer further reduces to
10%, more pores can be observed. In addition, the composite
electrode pellet becomes brittle, resembling the mechanical
behavior of a ceramic electrolyte pellet.
To test the electronic conductivity of the composite
cathodes, Au is sputtered on both sides of the cathodes with
mask and the potentiostatic polarization method was used with
a voltage of 2 V at 60 °C. As shown in Figure 4, the electronic
current stabilizes after being polarized with a DC bias for 300 s.
The corresponding electronic conductivity for the composite
electrodes is determined and listed in Table 2. As the content of
PEO increases from 10 to 30 wt %, the corresponding
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Figure 4. DC potentiostatic polarization currents for composite
cathodes under the voltage of 2 V at 60 °C.
electronic conductivity substantially decreases from 1.53 × 10−4
to 7.66 × 10−7 S/cm. Two main reasons may contribute to the
decrease of the electronic conductivity. First, the polymer
serves as an obstacle for the transportation of electrons as the
polymer is of rather low intrinsic electronic conductivity.
Second, an increase of the content of polymer can separate the
LiFePO4 particles apart and electronic transport pathway
cannot be established.
Morphology and Electrochemical Performance of All-
Composite LIB. The hot-pressing process gives rise to dense
interfaces between the composite cathode layer and the
composite electrolyte layer, as shown in Figure 5. No pores
or voids could be observed in the interfacial regions. Because of
the relative high viscosity and ductility of both composite
cathode and composite electrolyte compared with pure ceramic
pellets, the excellent interface contact is of critical importance
for improved cyclic performance of the all-solid-state LIBs in
that the interface between the composite cathode and
composite electrolyte layers may keep its structural integrity
albeit the large volumetric change during the charge/discharge
cycling.
Figure 6 shows the electrochemical impedance spectra (EIS)
of the assembled cells by composite cathodes with different
contents of polymer at 60 °C. Two semicircles and one short
tail could be readily observed in the EIS plots. The resistance of
the battery is assumed to be a complex resistance, including
resistances from the composite electrolyte, the composite
cathode, the interface between composite electrolyte and
lithium anode, the interface between composite electrolyte
and composite cathode. The interfacial resistance can always be
a hard problem to deal with in all-solid-state lithium batteries
and many methods have been put forward to reduce the
interfacial resistance.30 In our work, the flexible of the
composite electrolyte has effectively decreased the interface
resistance in our batteries. The overall resistance of the cells
assembled with different cathodes is listed in Table 2. In
contrary with the electronic conductivity of the composite
cathodes, the ionic conductivity of corresponding batteries
increases as the content of the polymer increases. Three
reasons may result in this trend. First of all, as we can see from
the SEM images, as the content of polymer decreased, more
pores appeared in the composite cathodes, which is detrimental
to the ionic conductivity of the electrodes. Second, the viscosity
of the composite electrodes decreased as the concentration of
polymer decreased, which may give rise to a degraded interface
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Table 2. Electronic Conductivity of the Different Cathodes and the Overall Resistance of Corresponding Batteries Assembled
by the Cathodes at 60 °C
content of PEO (wt %) 30 20 15 10
electronic conductivity (S/cm) 7.66 × 10−7 6.69 × 10−6 1.48 × 10−5 1.53 × 10−4
battery resistance (Ω) 546 828 1300 2753

Figure 5. SEM image of the interface between composite cathode

containing 15 wt % polymer and the composite electrolyte.

Figure 6. Electrochemical impedance spectra of the assembled cells by

composite cathodes with different contents of polymer at 60 °C.

contact with the electrolyte. In addition, at a fixed weight, the

composite cathodes with fewer polymer was thicker than those
with more polymer, which may be another reason for the
differences of the resistance.
The all-solid-state lithium batteries assembled by composite
cathodes with different contents of polymer electrolyte were
cycled at 60 °C and the performance of the batteries was shown
in Figure 7. For simplicity, we denote the all-solid-state LIBs as
“#X” where X indicates the content of polymer in the
composite cathodes. Figure 7a shows the first three
galvanostatic charge and discharge curves for the #15 battery
measured between 2.3 and 3.8 V vs Li/Li+ at a constant current
density of 100 μA/cm2, which was much higher than the
current density used in conventional cycling test of all-solid-
state lithium batteries.16,17,31,32 In the first cycle, the charge and
discharge plateaus are at ∼3.6 and ∼3.2 V, respectively, with a Figure 7. (a) First three galvanostatic charge and discharge curves for
polarization gap of 0.4 V. This polarization gap is higher than the #15 battery measured between 2.3 and 3.8 V vs Li/Li+ at a
that of the conventional liquid battery using LiFePO4 as active constant current density 100 μA/cm2, (b) the discharge performance
cathode material. The relative high polarization of the battery in first ten cycles of batteries assembled with different composite
may be attributed to the high resistance. As we can see from the cathodes, and (c) the rate discharge performance of the #15 battery.
EIS results, the impedance of #15 battery is about 1300 Ω,
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which is much higher than that of its liquid counterpart. The
all-solid-state LIB deliveres a high specific discharge capacity of
152 mAh/g in the first cycle, which is 89% of the theoretical
capacity of LiFePO4. This indicates that the composite cathode
with 15 wt % of polymer electrolyte exhibits good electronic
and ionic conductivity and the majority of the active materials
can be effectively utilized in our battery. More importantly,
because of the large thickness of composite cathode layer in the
all-solid-state LIB, an ultrahigh high per area loading of active
cathode materials is achieved, giving rise to a significantly
enhanced surface capacity of 10.6 mAh/cm2, which is an
enhancement of ∼380% over that obtained in previous all-solid-
state batteries.16 However, the charge and discharge curves for
other batteries showed very large polarization because of
relative low ionic or electronic conductivity and the capacity
performance was unsatisfactory. The discharge performance for
first ten cycles of batteries assembled with different composite
cathodes is shown in Figure 7b. It can be observed that the #30
battery shows almost no capacity during cycling. This may be
ascribed to the low electronic conductivity of the composite
cathode as shown in Table 2. As a result of the low electronic
conductivity, very few active cathode materials can be utilized in
this battery. As the content of polymer in composite cathode
decreases to 20 wt %, the electronic conductivity of the
composite cathode increases by 1 order of magnitude and the
discharge capacity of the #20 battery increases to ∼30 mAh/g
as more active materials in the cathode can be utilized. Further
decrease of polymer content to 15 wt % gives rise to a great
improved cyclic performance (capacity retention of ∼100%
after 10 cycles) and a high discharge capacity (∼150 mAh/g)
for the #15 battery. The average specific discharge capacity of
155 mAh/g corresponds to a surface capacity as high as 10.8
mAh/cm2 and an energy density of 334 Wh/L. The Coulombic
efficiency of the battery maintains at a high value of above 97%
in the first 10 cycles. However, drastic decrease in discharge
capacity to ∼7 mAh/g is observed for the #10 battery when the
polymer content further decreases to 10 wt %. The capacity
decline may mainly be caused by the increase of the resistance
of the battery and the absence of continuous transportation
path for lithium ion in the thick composite cathode. As a result,
only the active cathode materials in a thin layer close to the
cathode/electrolyte interface can be utilized during cycling. We
note that both the electronic and ionic conductivity have to be
optimized concomitantly in the composite cathode layer to
achieve high discharge capacity and improved cyclic perform-
ance of the all-solid-state LIB. In #15 battery with optimized
content in the composite cathode layer, the interpenetrating
networks for ionic and electronic transportation are established
throughout the composite cathode layers. Moreover, the
polymer electrolyte in composite cathode serves as a binder
to compensate the volumetric change of the active materials
during cycling, therefore, good capacity retention is obtained
and no cycling-induced degradation can be observed in our
batteries. Figure 7c shows the rate discharge performance of the
#15 battery. Though the discharge capacity of the battery
decreases with the increasing of the current density, it still
retains relatively high at 150 (141 mAh/g) and 200 μA/cm2
(92 mAh/g). When the current density increases to 300 μA/
cm2, the discharge capacity substantially decreases to 31.4
mAh/g, which may be attributed to the low electronic
conductivity of the composite cathode. Further improvement
of rate performance of the all-solid-state LIBs may be achieved
by using additives of higher intrinsic electronic conductivity in
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the composite cathode layer to raise the overall electronic
conductivity.
In addition to the ultrahigh surface discharge capacity and
improved cyclic performances, the all-solid-state LIBs also
exhibit superior flexibility as well as good mechanical
properties. As shown in Figure 8, the all-solid-state LIB is
Figure 8. Demonstration of the superior flexibility and safety of the all-
solid-state LIBs (a and b) fabricated by all-composite approach. The
LIB is still working properly under harsh operating conditions such as
bending (c and d) or even being sectioned into pieces (e and f).
capable of powering a green LED light in its original form.
Thanks to its all-composite structure, the LIB is still working
properly under bending conditions. To demonstrate the
superior safety of the all-solid-state LIB under harsh operating
conditions, we section the as-assembled LIB into smaller pieces.
The sectioned LIB is still in a proper working order and powers
the green LED light.
■
CONCLUSIONS
Flexible bulk-type all-solid-state lithium-ion batteries with high
surface capacity and energy density are assembled via an all-
composite approach. PEO-based composite cathode layers
(filled with LiFePO4 particles) and composite electrolyte layers
(filled with Al-LLZTO particles) are stacked layer-by-layer with
lithium foils as negative layer and hot-pressed into an all-solid-
state monolithic LIB. The polymer-based composite approach
for the assembly of the all-solid-state LIBs combined with the
hot-pressing process leads to dense and good mesoscopic
interfaces between cathode and electrolyte layers as well as
microscopic interfaces between LiFePO4 (or Al-LLZTO) and
PEO inside the composite cathode (or electrolyte) layer.
Cycled at a constant density of 100 μA/cm2 at 60 °C, the LIB
delivered an average specific discharge capacity of 155 mAh/g,
corresponding to an ultrahigh surface discharge capacity of 10.8
mAh/cm2. Great capacity retention is also achieved up to 10
cycles and no capacity fading can be observed. Thanks to the
all-composite structure, the all-solid-state LIB exhibits superior
flexibility and safety under harsh operating conditions such as
bending or even being sectioned into pieces. The all-composite
approach implemented in this contribution is facile and may be
used as a new design paradigm for flexible bulk-type all-solid-
state LIBs.
DOI: 10.1021/acsami.6b16304
ACS Appl. Mater. Interfaces 2017, 9, 9654−9661
ACS Applied Materials & Interfaces
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsami.6b16304.
Illustration of structure of the all-solid-state battery,
microstructural images and XRD patterns of the LLZTO
powders, and the electrochemical stability of the
composite electrolyte (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
*E-mail: cwnan@mail.tsinghua.edu.cn.
*E-mail: shyang_mse@tsinghua.edu.cn.
ORCID
Yang Shen: 0000-0002-1421-0629
Author Contributions
The manuscript was written through contributions of all
authors. All authors have given approval to the final version of
the manuscript.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was supported by the NSF of China (Grant Nos.
51532002, 51572141, and 51625202) and Research fund of
Science and Technology in Shenzhen
(JSGG20150331155519130).
■
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9661 DOI: 10.1021/acsami.6b16304

ACS Appl. Mater. Interfaces 2017, 9, 9654−9661