Journal of Power Sources xxx (2018) xxx-xxx

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Journal of Power Sources

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Review article

Development of cold sintering process and its application in solid-state lithium

batteries
Yulong Liu, Qian Sun, Dawei Wang, Keegan Adair, Jianneng Liang, Xueliang Sun∗⁠

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Department of Mechanical and Materials Engineering, Western University, London, Ontario, N6A 5B9, Canada

ARTICLE INFO ABSTRACT

Keywords: Solid-state batteries (SSBs) are developed with the use of inflammable solid-state electrolytes to realize higher en-
Solid-state battery ergy density and improved safety. However, the densification temperature of solid electrolytes via conventional

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Solid-state electrolyte sintering methods is usually high, especially for oxide-type electrolytes. Advanced sintering techniques such as
Cold sintering process spark plasma sintering have been developed to decrease the heat-treatment temperature and time. Recently, a
Lithium ion battery
novel cold sintering process (CSP) has been developed, which offers an alternative route to the densification
Ionic conductivity
of many solid-state electrolyte materials below 300 °C. Generally, the CSP involves multi-stage non-equilibrium
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Electrochemical performance
processes such as dissolution-precipitation under external stress, viscous flow of saturated solutions and diffu-
sion of species. Herein, the CSP application in different solid electrolytes and electrodes are summarized. It is
expected that the CSP has great potential in preparing solid-state batteries with this new sintering technique.
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popular investigated oxide-type electrolytes due to its stability against

1. Introduction Li metal [6]. Additionally, NASICON-type (e.g., Li1⁠ .3Al0⁠ .3Ti1⁠ .7 (PO4⁠ )3⁠ ,
LATP) solid electrolytes have been widely investigated in previous re-
1.1. History and development of solid-state batteries searches due to the high conductivity and availability of raw materi-
als [7]. However, the oxide electrolytes usually need high temperature
Solid-state lithium ion batteries have been considered as one of the processing, which makes them difficult to couple with other electrode
most promising next-generation battery systems with improved energy materials because of side-reactions during co-sintering process. There-
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density and safety [1,2]. Among the reported classes of solid-state bat- fore, soft-electrolytes containing sulfide species have been widely devel-
teries, bulk-type inorganic solid-state lithium ion batteries show great oped. Over the past few years, different sulfide-based systems have been
promise for future EV (electric vehicle) applications. For solid-state elec- investigated sysmatically [8]. One type of promising sulfide-type elec-
trolytes and solid-state batteries, there has been impressive progress trolyte is Li2⁠ S–P2⁠ S5⁠ glass-ceramic discovered by Tatsusmisago, it shows
over past decades [3–5]. Herein, we will only give a brief introduction a high conductivity close to that of commercial liquid electrolytes due
to the development of solid-state electrolytes and batteries. to the precipitation of high conducive crystalline Li7⁠ P3⁠ S1⁠ 1 in the ma-
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Generally, oxide electrolytes show good ionic conductivity, chemi- trix [9]. Crystalline sulfides, such as the super ionic Li1⁠ 0GeP2⁠ S1⁠ 2 se-
cal stability, and wide electrochemical windows. So, they have received ries [10], thio-lithium ion super ionic conductors (thio-LISICON) [11],
great attentions during past decades. Garnet-type (e.g., Li7⁠ La3⁠ Zr2⁠ O1⁠ 2, and argyrodite (Li6⁠ PS5⁠ X, X = Cl, Br, I)-type sulfides were widely stud-
LLZO) solid electrolyte is one of the most ied by different groups after 2010 [12]. Detailed information on in-
organic lithium ion con
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∗ Corresponding author.
Email address: [email protected], [email protected] (X. Sun)

https://doi.org/10.1016/j.jpowsour.2018.05.015
Received 25 March 2018; Received in revised form 2 May 2018; Accepted 4 May 2018
Available online xxx
0378-7753/ © 2018.
Y. Liu et al. Journal of Power Sources xxx (2018) xxx-xxx

ductors can be found in the comprehensive reviews previously reported Unlike the rigid mechanical properties of oxide-based electrolytes,
[13–18]. the sulfide glass-type electrolytes are soft and have higher ionic con-
A monolithic all-solid-state oxide based battery of Li4⁠ Ti5⁠ O1⁠ 2/LATP/ ductivities. Therefore, the interfacial problems can be easily addressed
LiMn2⁠ O4⁠ was fabricated Brike and coworkers, which demonstrated a through high-pressure pressing at room temperature through room-tem-
limited capacity of 40 mAh g− ⁠ 1
due to the poor interfacial contact perature sintering mechanism. For example, Li3⁠ PO4⁠ -Li2⁠ S-SiS2⁠ glass elec-
[19]. To reduce the physical mismatch between LATP and electrodes, trolyte was pressed with spherical graphite and TiS2⁠ in a full battery.

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solid-state batteries were fabricated based on the NASICON electrolytes The overall resistance of fabricated cell was close to the resistance of
through deposition of thin film electrodes on the surface of LATP sheets pure solid electrolyte layer, which indicated that the interfacial contact
[20–23]. Compared to bulk-type solid-state batteries, the thin-film Li- resistance was negligible. Another example was the Li2⁠ S–P2⁠ S5⁠ glass-ce-

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CoO2⁠ electrodes with LATP electrolyte showed an improved electro- ramic electrolyte, it was used in the fabrication of solid-state batteries
chemical performance of 120 mAh g− ⁠ 1 after annealing, which was at- with LiCoO2⁠ cathodes by Ohta and coworkers. A capacity of 102 mAh
tributed to the improved interface between LATP and LiCoO2⁠ electrode. g−⁠ 1
at room temperature was delivered, which was 73% of theoretical
Ohta and coworkers fabricated a solid battery based on LLZO elec- capacity of LiCoO2⁠ [36]. To increase the performance, a highly conduc-
trolyte, it showed a limited discharge capacity of 78 mAh g− ⁠ 1 due to tive Li2⁠ S–P2⁠ S5⁠ –GeS2⁠ (thio-LISICON) sulfide electrolyte was prepared by
the large interfacial resistance between LiCoO2⁠ /LLZO [24]. Later on, Kanno and coworkers, where the as-prepared In/thio-LISICON/LiCoO2⁠
the chemical information at interface between LLZO and LiCoO2⁠ after discharge capacity was only 80 mAh g− ⁠ 1 due to reduction of Ge species

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high temperature sintering was investigated by Park and coworkers, and [37]. In order to stabilize the interface and reduce the side reactions,
there was cross-diffusion of Co to LLZO and La/Zr to LiCoO2⁠ . In addi- argyrodite-type sulfide Li6⁠ PS5⁠ X(X = Cl, Br, F, I) electrolyte was recently
tion, a tetragonal LLZO phase was formed at the interface due to the developed and applied in solid-state batteries due to its high electro-
leaching of Al at high temperature, which further decreased the ionic chemical stability. Yubuchi and coworkers synthesized argyrodite sul-
conductivity at interface [25]. fide electrolytes using a solution method followed by the fabrication of
Furthermore, the moisture and carbon dioxide sensitivity of LLZO cells with a Li-In alloy anode and LiNi1⁠ /3Mn1⁠ /3Co1⁠ /3O2⁠ (NMC) layered
in the ambient environment has been proven to be problematic for cathode, showing a capacity of 140 mAh g− ⁠ 1 at room temperature [38].

bulk-type solid-state batteries with LLZO electrolyte, which may be un- Discovered in 2011, a superionic conducting Li1⁠ 0GeP2⁠ S1⁠ 2 demonstrated

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stable after assembly in air [26]. To reduce the influence of Li2⁠ CO3⁠ an extremely high ionic conductivity of 1 × 10− ⁠ 2 S cm−
⁠ 1 [10]. In 2016,

and in-homogenous contact at the electrode-electrolyte interface, dif- the same group fabricated batteries using this new superionic conduc-
ferent strategies such as co-sintering and the insertion of buffer lay- tor with higher chemical stability, which showed a stable cycling per-
ers were adopted for garnet-type electrolyte interfaces. As an example,
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formance for 1000 cycles [39]. Compared to oxide based solid-state bat-
Li3⁠ BO3⁠ (LBO) has been used as a sintering additive to reduce the heat- teries, sulfide based solid-batteries shows better electrochemical perfor-
ing temperature for the fabrication of LLZO/LCO cells at a lower tem- mance due to the low interfacial resistance.
perature of 700 °C [27]. With the addition of Li3⁠ BO3⁠ and Al2⁠ O3⁠ , co-sin- Bulk inorganic solid-state batteries have achieved remarkable
tering of Al-doped LLZO/LCO was successfully prepared due to simul- progress in recent years. Nevertheless, there are still several major chal-
taneous inter-diffusion of Al between garnet oxide and additives, which lenges that need to be addressed in order to realize their practical ap-
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delivered a charge-discharge capacities of 98 and 78 mAh g− ⁠ 1, respec-

plication. The problems that need to be overcome include the synthesis
tively [28].The formation of a stable and ionically conductive inter- of a robust solid electrolyte with high ionic conductivity, poor interfa-
face between solid electrolyte and electrode is critical to achieving func- cial compatibility and stability, and low-cost cell fabrication processes.
tional solid-state batteries. To alleviate the influence of Li2⁠ CO3⁠ , Li and Among the prominent interfacial problems, the severe side reactions be-
coworkers proposed that the incorporation of a small amount LiF into tween solid-state electrolyte and electrode during high-temperature sin-
the garnet LLZO electrolyte could effectively decrease the interface re- tering has largely impeded the progress of solid-state lithium ion bat-
sistance from 1260 Ω cm− ⁠ 2 to 345 Ω cm− ⁠ 2 [29]. As an alternative strat-
teries. Formation of an ion-blocking interface will increase the interface
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egy to form a stable interface, Han and coworkers utilized the Li2⁠ CO3⁠ resistance and slow down the transport of lithium ions. Therefore, the
layer on LLZO by forming a highly conductive Li2⁠ CO3⁠ -Li3⁠ BO3⁠ glass-ce- next section will address this issue with the development of advanced
ramic buffer layer to reduce the interface resistance between LLZO and sintering techniques.
LiCoO2⁠ . The full cell was capable of delivering a discharge capacity of
120 mAh g− ⁠ 1 at 100 °C and a long cycling life of over 100 cycle at room
1.2. Development of sintering techniques for solid-state batteries
temperature [31].
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To further reduce the solid-state diffusion length between electrode Solid electrolyte particles need to be bonded together by sintering
and electrolyte, 3D porous scaffold solid electrolytes were invented. before use in batteries. A sintering process usually involves two major
The electrode materials were filled into the pores using a wet chemical steps: densification and grain growth. Both steps require a thermody-
method followed by heat treatment, which resulted in lower sintering namic driving force, that is, the reduction of the total Gibbs free energy
temperatures and good electrolyte/electrode contact, as illustrated by of the system, rendering them thermodynamic favorable. Therefore, the
Kotobuki and coworkers [32,33]. Until now, the oxide-based solid-state process of sintering is intrinsically driven by the Gibbs free energy.
electrolytes have faced significant challenges in interfacial contact and During the sintering process, two popular mechanisms are often
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conductivity, and further efforts in both materials design and novel fab- mentioned in literature: solid-state sintering and liquid phase sinter-
rication processes are required to make further advancements. ing [40]. The latter is preferred during solid elec

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Y. Liu et al. Journal of Power Sources xxx (2018) xxx-xxx

trolyte preparation because of the simplicity and effectiveness in re- was obtained with a maximum relative density of 99.8%. By using a
ducing the sintering temperature. The so-called liquid phase sintering novel wet-chemical method to prepare the nano-sized LLZO precursors,
is a process where liquid-phases emerge during the sintering process, the sintering temperature of LLZO electrolyte was further lowered down
which is beneficial for mass transport and particle compaction. The typ- to 1000 °C, and a relative density of 96.5% was achieved [49]. In a sep-
ical process of liquid phase sintering is divided into multiple stages. The arate study, Rosenberger conducted experiments on LATP (Li1⁠ .3Al0⁠ .3Ti1⁠ .7
initial stage is similar to solid-state sintering, wherein the particles are (PO4⁠ )3⁠ ) electrolyte with field-assisted sintering [50]. It was shown that

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bonded together with the help of a liquid-phase formed at high temper- the relative density could be drastically improved from 85% at 0 V to
ature. The second stage involves the crystallization of dissolved species 95.5% at 20 V, however, a high resistance was obtained when sintering
after the liquid-solution is over-saturated. The final stage is the mass at increased voltages. The reason behind the increased resistance is the

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transport process, which result in the exchange of atoms between differ- poor intergranular contact and high grain-boundary resistance between
ent particles and finally grain growth [41]. large-grains. Furthermore, with a modified sol-gel method, Hoffman and
Conventionally, the sintering of materials only involves the applica- coworkers succeeded in the densification of LATP electrolyte in the tem-
tion of heat upon a green body with 40–60% density, which can facil- perature range of 850–1000 °C [51]. For LATP with a pure phase com-
itate the mass transport/diffusion. Thus, some advanced sintering tech- position, a relative density of 98% was obtained, which can achieve a
niques are developed by utilizing other factors such as external pressure high conductivity of 10− ⁠ 3 S cm−
⁠ 1 at room temperature.
and/or electric field in combination with external heating to facilitate Flash-sintering is similar to field-assisted sintering, except the ap-
the mass transport. Caused by pressure or an applied electric field, the

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plied current is alternative current [52]. In flashing sintering, there is
mass transport in materials can be largely enhanced, and lower sinter- a possibility of lithium loss due to crystal structure breakdown, which
ing temperatures can be realized. Several advanced sintering techniques makes the technique unsuitable for densification of solid electrolytes.
that are widely reported in the densification of solid electrolytes include Stoldt and coworkers applied flash sintering on a LAGP (Li1⁠ .5Al0⁠ .5Ge1⁠ .5
hot pressing, field-assisted sintering, flash sintering, microwave sinter- (PO4⁠ )3⁠ ) electrolyte with a high frequency electric field. While no such
ing and spark plasma sintering. Here, we will briefly introduce the basic deterioration behavior was observed due to the use of high frequency,
principles of the advanced sintering techniques and list some examples the pellet demonstrated an ionic conductivity of 1.5 × 10− ⁠ 4 S cm−
⁠ 1 [53].
for further understanding [41,42].
This work demonstrated the ability of electric field sintering in condens-

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Hot pressing is a sintering technique based on the stress-intensity
ing conductive electrolytes with high frequency.
densification mechanism. The mass transfer/diffusion between parti-
Similar to the pressure effects that can enhance sintering, the ap-
cles is accelerated during the sintering process due to the pressure
plication of an external field such as electromagnetic radiation can im-
gradient created by the external force applied on particles, thereby
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prove the sintering process [41]. Microwaves can also be utilized as
decreasing the sintering temperature and time. By hot-press sinter-
the heat sources in the sintering process, especially for high dielec-
ing of the screen-printed electrodes on the as-sintered electrolyte pel-
tric ceramics such as solid electrolytes [54]. Perovskite-type (LLTO,
let, Kobayashi and coworkers fabricated a
La0⁠ .5Li0⁠ .5TiO3⁠ ) electrolytes are usually sintered at high temperature,
Li3⁠ V2⁠ (PO4⁠ )3⁠ /Li1⁠ .5Al0⁠ .5Ge1⁠ .5(PO4⁠ )3⁠ /Li3⁠ V2⁠ (PO4⁠ )3⁠ symmetric battery (LVP as
which leads to lithium loss. As an alternative, Nan and coworkers pre-
both cathode and anode). This process was able to avoid the elec-
pared LLTO by a microwave sintering method [55]. A dense LLTO ce-
trolyte/electrode element mutual-diffusion phenomenon, and no impu-
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ramic was obtained, and exhibited a different lattice structure and mi-
rity phases were observed in the sintered sample [21]. The as-obtained
crostructure in comparison with the conventional sintering method. Un-
battery delivered a discharge specific capacity of 104 mAh g− ⁠ 1 at 80 °C
fortunately, a lower ionic conductivity (7.2 × 10− ⁠ 7 S cm− ⁠ 1) was obtained
and 42 mAh g −
⁠ 1
at 25 °C, respectively. Furthermore, as reported by
due to the formation of more grain boundaries.
Sakamoto and coworkers, an ionic conductivity of 4.0 × 10− ⁠ 4 S cm− ⁠ 1 was
During spark plasma sintering (SPS), an electric current is pulsed
observed at room temperature for the hot-pressed Li7⁠ La3⁠ Zr2⁠ O1⁠ 2 (LLZO) through a conductive die, such as graphite, to apply thermal energy
pellet at 1000 °C with 40 MPa pressure [43]. To increase the ionic con- on powders through Joule heating [56]. Near theoretical sinter-den-
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ductivity of the electrolyte, this group introduced some doping ele- sities can be achieved with significantly shorter holding time for any
ments at different atomic sites to stabilize the cubic crystal structure powder compacts, regardless of the electrical conductivity of the pow-
of the LLZO pellet. An ionic conductivity of 8.7 × 10− ⁠ 4 S cm− ⁠ 1 at room
ders [56,57]. In the past years, tremendous efforts have been dedi-
temperature was obtained after hot-pressing for Ta doping LLZO [44]. cated to fabricating dense solid electrolytes and solid-state batteries
Apart from the oxide solid electrolytes, hot-press sintering was widely using spark plasma sintering. Different solid electrolytes, such as per-
used in sulfide electrolytes as well, especially for glass-ceramic sulfides ovskite LLTO, NASICON-type Y doped LiZr2⁠ (PO4)3⁠ , and garnet LLZO
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(Li2⁠ S-P2⁠ S5⁠ ) [45]. electrolyte were prepared using the spark plasma sintering technique
Field-assisted sintering is widely used for ceramics, especially for [58–61]. In addition, cathode materials including LiFePO4⁠ , Li2⁠ CoPO4⁠ F,
low or non-conductive materials. The working principle behind this and LiCoO2⁠ , were densified as well [62–64]. Aboulaich and cowork-
method is the passing of heat through a graphite die under high-cur- ers fabricated a Li3⁠ V2⁠ (PO4⁠ )3⁠ /Li1⁠ .5Al0⁠ .5Ge1⁠ .5 (PO4⁠ )3⁠ /LiFePO4⁠ solid-state
rent in short time [46]. [47] The application of field-assisted sinter- battery, which delivered a capacity of 80 mAh g− ⁠ 1 at 0.05 C rate [65].
ing was proven to be effective in the preparation of oxide solid-state Furthermore, Kobayashi and coworkers recently assembled a solid-state
electrolytes in previous reports. Zhang and coworker applied this tech- battery with LiCoO2⁠ electrode and a new Li2⁠ .2C0⁠ .8B0⁠ .2O3⁠ oxide-elec-
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nique in the synthesis of LLZO electrolyte for the first time [48]. They trolyte that was capable of deliver
showed that LLZO could be densified from 1100 to 1180 °C within
10 min, and a high conductivity of 5.7 × 10− ⁠ 4 S cm− ⁠ 1 at room

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Y. Liu et al. Journal of Power Sources xxx (2018) xxx-xxx

ing a discharge capacity of 118 mAh g− ⁠ 1 at 10 μA cm−

⁠ 2 [66,67]. during the sintering process, unlike the traditional cold sintering with
In this section, we illustrate that the sintering temperature and time high pressure.
of solid electrolyte/battery materials can be well-controlled through
a combination of applied pressure, temperature and electric field us-
2.2. Typical stages of the cold sintering process
ing different sintering techniques (Table 1). However, a temperature of
600–1000 °C is still high enough for side reactions to occur between
The CSP can be described at the macro- and micro-levels, as depicted

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electrode and electrolytes. In the following section, we introduce a novel
in Fig. 1 [75,76]. As shown in Fig. 1a, a liquid phase is introduced at
sintering process which can enable sintering of solid electrolyte/battery
the particle-particle interface and the particle ensembles are homoge-
materials at a temperature less than 300 °C.
nously wetted with an appropriate amount of solution (water or volatile

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solutes). The powders are then compacted under an external pressure,
2. Basics of the cold sintering process which is facilitated by the addition of liquid lubricant at the particle
interfaces. Furthermore, the sharp edges of the particles are dissolved
2.1. Background of the cold sintering process into the solution and then precipitate into pores or interstitial spaces be-
tween particles under an applied external pressure and heat. Finally, the
The term cold sintering was firstly introduced in 1978 by Gutamanas powders are sintered together after the complete removal of the solution
and coworkers [68]. It was named as cold sintering because the metal/ [76].

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ceramic powers were compacted at a high pressure (∼GPa) and relative From the microstructure observations collected in previous reports,
low temperature, such processes were widely observed in power metal- the CSP can also be described as in Fig. 1b, which involves the disso-
lurgy field. lution and rearrangement of atoms at the surface sites of crystals af-
In 1986, a hydrothermal assisted hot pressing concept was gener- ter wetting of the surface. This is followed by a dissolution-precipita-
ated by combining hydrothermal processing with isostatic pressing, and tion process, which is triggered by the breakdown of an equilibrium
a broad series of ceramics were prepared with more than 90% theoret- state of solid-liquid mixture phases. In this stage, ionic species and/or
ical density [69]. For instances, nanometric α-quartz was successfully atomic clusters diffuse through the liquid and precipitate on particles
densified at low temperature with sol-gel silica as precursors. The un- at sites away from the stressed contact areas. Finally, an amorphous

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derlying mechanism shows that water as an additive plays an impor- phase may form in the grain boundary regions after sintering, leading to
tant role in the densification process through forming the inter-particle suppressed grain boundary diffusion or mobility and thus limited grain
necks [70,71]. Very recently, researchers reported the densification of growth [75].
precursors of BaTiO3⁠ ceramic with a new process of reactive hydrother-
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During the CSP, three possible mechanisms are proposed to enable
mal process at low temperature [72]. enhanced particle compaction and mass transport, including liquid-en-
Inspired by these previous works, a new type of CSP for ceramics hanced creep, Marangoni flow at the liquid-liquid interphase and diffu-
was invented by Randel's group [73–75]. The new CSP can enhance siophoresis at the solid-liquid interface. It can be concluded that the CSP
the inter-diffusion between particles through adding a transient sol- process is an outcome of multiple mechanical-chemical coupling effects,
vent to the powder, which enables low temperatures (120 ºC-300 °C) which yields improved mass transport and is further beneficial for the
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and pressures (350–500 MPa) particle densification process [76].

Table 1
Summary of sintering techniques for solid-state batteries.

Sintering technique Solid Electrolyte/Solid Battery Sintering parameter Performance Ref.

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Hot sintering LLZO 1000 °C/1 h, 4.0 × 10−

⁠ 4 S cm−
⁠ 1
[43]
40 MPa, 98%
Hot sintering Ta-LLZO 1000 °C/1 h, 8.7 × 10−
⁠ 4 S cm−
⁠ 1
[44]
40 MPa, 98%
Field assisted sintering Al-LLZO 1150 °C/3 min, 5.7 × 10−
⁠ 4 S cm−
⁠ 1
[47]
10 MPa, 99.8%
Field assisted sintering LATP 900 °C/3 h, ∼1 × 10−
⁠ 3 S cm−
⁠ 1
[51]
N/A, 95.5%
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Flash sintering LAGP 800 °C/1 h, 1.5 × 10−

⁠ 4 S cm−
⁠ 1
[53]
N/A, N/A
Microwave sintering LLTO 800 W/20 min 7.2 × 10−
⁠ 7 S cm−
⁠ 1
[55]
N/A, 97%
Spark plasma sintering NASICON 1200 °C/20 min, 1.4 × 10−
⁠ 4 S cm−
⁠ 1
[58]
(Y-doped LZP) 40 MPa, 90%
Spark plasma sintering LLZO 1000 °C/10 min, 1.3 × 10−
⁠ 4 S cm−
⁠ 1
[59]
50 MPa, N/A
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Hot sintering Li3⁠ V2⁠ (PO4)3⁠ /LAGP/Li3⁠ V2⁠ (PO4⁠ )3⁠ 840 °C/2 h, 104 mAh g− ⁠ 1 (80 °C)
[22]
49 MPa, N/A 42 mAh g−
⁠ 1 (25 °C)

Spark plasma sintering Li3⁠ V2⁠ (PO4⁠ )3⁠ /LAGP/LiFePO4⁠ 680 °C/2 min, 80 mAh g−⁠ 1
[64]
100 MPa, N/A
Spark plasma sintering LiCoO2⁠ /Li2⁠ .2C0⁠ .8B0⁠ .2O3⁠ /Li 450 °C/1 min, 118 mAh g−
⁠ 1
[65]
30 MPa, N/A

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Y. Liu et al. Journal of Power Sources xxx (2018) xxx-xxx

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Fig. 1. Principles and process of cold sintering; (a) the three stages of the cold sintering process, and (b) the mechanism of cold sintering at the micro-structure level [75,76].
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300 °C higher than that of the CSP. As illustrated in Fig. 2b, the require-
2.3. Factors affecting the cold sintering process ments of Gibbs free energy reduction in the CSP is less compared to
that in conventional sintering routes due to the smaller energy barrier,
As investigated by Clive's group, the CSP process is determined by which accounts for the lower sintering temperature of the CSP [76].
several physical/chemical factors such as the choice of starting materi- This low-temperature behavior originates from the unique processing
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als, solute and physical parameters [77–80]. The most important step is pathway and special dynamic environment. In contrast to traditional
establishing a proper solution system that can enable an environment sintering techniques, the CSP is performed in a multistep manner. In
for the chemical reactions to take place. Due to the nature of mater- each step, the free energy barrier is relatively lower and could be eas-
ial dissolution, three different situations were observed experimentally ily overcome with the assistance of various mechanical-chemical effects.
[73]. (1) In the case of the congruent dissolution of materials, espe- The Gibbs energy change of the CSP is greatly reduced due to the combi-
cially hygroscopic compounds, the CSP is relatively simple and proceeds nation of liquid-assisted particle sliding and hydrothermal-assisted sin-
through a direct method. (2) If the materials are incongruent dissolu- tering procedures. In addition, the traditional sintering methods need
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tion, for example, BaTiO3⁠ , a passivating surface appears on the surface to overcome a huge energy barrier between the initial particles and fi-
that prevents the precipitation process and further densification [81]. nal consolidation status. The CSP phenomenon is similar to some nat-
To solve this issue, a saturated solution at the required stoichiometric ural sintering examples such as the formation of rocks and generation of
ratios is introduced to enable particle rearrangement, growth, and there- pearl. In contrast, the production of poly-crystals by solid-state reaction
fore densification. (3) For materials with negligible dissolution, a similar is more difficult in industry.
strategy is adopted through intentionally creating an aqueous solution
that contains the corresponding chemical constituents [82]. 2.4. Proposed mechanism of the cold sintering process
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Compared to the conventional sintering processes, the CSP can oc-

cur within a relatively low temperature region, as shown in Fig. 2a The use of the CSP has been reported with a wide range of ceramic
[81]. Taking BaTiO3⁠ as an example, the CSP region lies in the range and polymeric materials [79]. However, an understanding of the under-
of 120–900 °C, while the temperature of conventional sintering or ad- lying mechanism of the CSP is still unclear. Based on the previous re-
vanced sintering techniques are 100– sults, a unique mechanism of the cold sintering process was proposed by
Clive's group, as shown in Fig. 3 [80].

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Y. Liu et al. Journal of Power Sources xxx (2018) xxx-xxx

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Fig. 2. The cold sintering process at low temperature; (a) The relative density of cold sintered materials in comparison with other sintering techniques, and (b) schematic diagram showing
the Gibbs free energy change during cold sintering [76]. [81].
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Fig. 3. Proposed mechanism of cold sintering process [80].

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Y. Liu et al. Journal of Power Sources xxx (2018) xxx-xxx

The first step is the densification stage, that is, the compaction of several opportunities awaiting in the future for expanding and deepen-
loosely-packed powders with the assistance of a liquid phase. As indi- ing our comprehensive understanding of this process.
cated by the proposed mechanism, the step involves particle rearrange-
ment, sliding of powders under fluid mechanics, and grain boundary 3. The development of cold sintering processes for solid-state
creep. In addition, the edges of particles are dissolved with the help batteries
of pressure and temperature gradients during the compaction stage. At

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the same time, excess liquid escapes from the pellet-press due to the 3.1. Cold sintering of solid-state electrolytes
poor sealing. Afterwards, the liquid phase is saturated with the evapora-
tion of the solvent, and the precipitation process begins. Meanwhile, the For solid-state electrolytes, the transport of lithium ions is usually

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mass transport is enhanced under the influence of pressure and curva- slow at the highly-resistive grain boundaries. To minimize the effect
ture gradients at the grain-boundaries. Finally, the crystals begin to nu- of the grain boundary on the ionic conductivity of the electrolyte,
cleate at the grain boundaries and surface of the highly hydroscopic ma- high-temperature treatment is required to enhance the interconnectiv-
terials after the evaporation of the liquid. The importance of this process ity between grains. However, high-temperature sintering has two detri-
was highlighted by Sebastian et al. in the preparation of a dielectric mental side-effects, i.e., lithium loss and secondary phase formation. To
Al2⁠ O3⁠ -NaCl composite with a relative density of 96%, where such a high counteract the lithium loss, advanced sintering techniques such as spark
relative density is achieved due to the hydroscopic nature of NaCl [83]. plasma sintering have been developed. However, the temperature range
However, in many cases there is the formation of intermediate phases of spark plasma sintering still possess the chance of side-reactions and

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between grains, as observed experimentally [79]. requires a complicated manufacturing process, making it hard to scale
In a recent report by Guillon and co-workers on the CSP of ZnO with up.
a small amount of water, they argued that the solution-precipitation Usually, the densification of sulfide-type electrolytes was more at-
mechanism proposed by Randall group was not enough to activate the tainable due to its low modulus, even at room temperature. This process
densification process. Due to the diffusion of H+ ⁠ and OH− ⁠ ions into the
was exemplified by Tatsumisago et al., who proposed a room tempera-
ZnO crystal, a high defect concentration could be produced at the grain ture pressure-sintering mechanism for sulfide electrolytes [87]. They as-
boundaries with high potentials. Because of the formed defect sites, a cribed the room temperature sintering to the low bond energies between

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high diffusion path was created, which was beneficial for mass-trans- the cation and anion species of the sulfide materials, which resulted in
port and low-temperature sintering. In the case of zinc acetate as addi- small-scale plasticity, making them favorable for room temperature sin-
tive, larger crystal growth could be promoted along the preferred crys- tering. Following this discovery, cold pressing was widely adopted for
tallographic planes due to the change of ionic species concentration at the processing of sulfide-based solid electrolytes (Table 2). However, the
TE
surface of ZnO [84]. The water could also trigger the flash sintering oxide-type electrolytes still require a high-temperature treatment to fa-
process at low temperature by increasing the specimen conductivity, as cilitate the mass-transport between particles. Only after high tempera-
observed by Luo et al., which extended the idea of CSP to field of wa- ture sintering will the oxide solid electrolyte exhibit a high conductivity
ter-assisted flash sintering process [85]. because of the drastic reduction of grain-boundary resistance.
Recently, a new assumption was proposed by Chen et al. by com- Recently, LAGP (Li1⁠ .5Al0⁠ .5Ge1⁠ .5 (PO4⁠ )3⁠ ) solid electrolyte was prepared
paring the mechanical behavior of dry and cold-sintered NaCl. The with the CSP method for first time by Seth et al. [92] By adding ethanol
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dry-pressed NaCl showed lower relative density than the cold sintered or water as the solvent during the CSP process, LAGP pellet with a
NaCl at low applied pressure where dissolution-precipitation process density of 80% was achieved at 120 °C in 20 min. However, the pellet
dominated. In high applied pressure of 200–300 MPa region, mechani- showed a relatively low ionic conductivity at room temperature due to
cal deformation became prominent in densifying the NaCl powders. Due the formation of an amorphous phase at the grain boundaries. After an-
to the low hardness of the NaCl crystal, the particles could be easily re- nealing at 650 °C (the crystallization temperature of LAGP), the ionic
arranged and reshaped by mechanical force. Thus, the plastic deforma- conductivity of the LAGP pellet reached up to 5.4 × 10− ⁠ 5 S cm−⁠ 1 at room
RR

tion for NaCl CSP cannot be neglected, especially at high applied pres- temperature (as shown in Fig. 4a). From the EIS tests, it was seen that
sure [86]. the improvement in ionic conductivity was attributed to the re-crystal-
Although there have been some reports on the CSP of inorganic lization of amorphous surfaces in the CSP sintered LAGP. Nonetheless,
compounds, the process is still at a very early stage. The best way they did not offer the microstructure evidence to prove the re-crystal-
to gain further understanding of the mechanism of the CSP is to de- lization phenomenon at the grain boundary of LAGP.
velop more materials in this field. There are In addition to the traditional LAGP solid electrolyte, composite sys-
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tems such as LAGP/(PVDF-HFP) have been fabricated by the CSP

process at 120 °C with water as the solvent (as

Table 2
Summary of low-temperature sintering of solid electrolytes.

Solid Electrolyte Sintering parameter Young's moduli Performance Ref.

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25Li2⁠ S·75P2⁠ S5⁠ glass RT/260Mpa 18 GPa 3.0 × 10− ⁠ 4 S cm− ⁠ 1

[88]
70Li2⁠ S·30P2⁠ S5⁠ (Li7⁠ P3⁠ S1⁠ 1) glass RT/360Mpa 22 GPa 1 × 10−⁠ 3 S cm− ⁠ 1
[88]
90Li3⁠ BO3⁠ ·10Li2⁠ SO4⁠ RT/360Mpa 53 GPa 9.4 × 10− ⁠ 6 S cm− ⁠ 1
[89]
33Li3⁠ BO3⁠ ·33Li2⁠ SO4⁠ ·33Li2⁠ CO3⁠ RT/360Mpa 51 GPa 1 × 10− ⁠ 5 S cm− ⁠ 1
[90]
NASICON + LiTFSI salt 120 °C/450Mpa 139 GPa 5 × 10− ⁠ 5 S cm− ⁠ 1 [91]

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Y. Liu et al. Journal of Power Sources xxx (2018) xxx-xxx

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Fig. 4. Cold sintering of LAGP electrolyte; (a) EIS of LAGP before and after annealing, (b) EDS mapping of LAGP/PVDF-HFP composite, (c) conductivity of the composites, and (d) activa-
tion energy of composites [74]. [92].

shown in Fig. 4b–d) [74]. Due to the low ionic conductivity of the nano particles to prepare thin LLZO electrolytes. Due to the small grains
TE
PVDF-HFP polymer, the conductivity of the composite electrolyte was of LLZO, a highly dense and transparent LLZO thin film was achieved,
found to decrease with an increase of polymer content. However, after with a high ionic conductivity of 1.3 mS cm− ⁠ 1 [96]. Fu et al. reported a

soaking in a liquid electrolyte, the conductivity was increased due to the three-dimensional bilayer LLZO sheet where one side of the sheet was
formation of fast ion transportation pathways through liquid electrolyte. porous after the introduction of PMMA polymer as pore-forming agent
In the report, with 5–10 wt % liquid electrolyte, the room temperature [97]. This bilayer sheet was mechanically stable and capable of hosting
ionic conductivity could increase to 1.0 × 10− ⁠ 4 S cm−
⁠ 1 at room temper- active materials for solid-state batteries. Furthermore, the development
EC

ature (as shown in Fig. 4c) [74]. At the same time, the activation en- of sulfide-electrolytes sheets is critical to realizing high energy density
ergy for the ionic conductivity was drastically reduced compared to the solid-state batteries. Kanno et al. reported the thin film thio-LISICON
pellet without soaking in liquid electrolyte. The relative density of the electrolyte with tape-casting in 2003, however, the ionic conductivity of
LAGP/(PVDF-HFP) composite was found to be close to 86%, which was the sheet-like sulfide electrolyte was largely decreased due to the addi-
significantly higher than the dry-press pellet without the addition of sol- tion of binder [98]. The binder was left in the electrolyte after process-
vent (74% relative density). Through characterization of the composite ing, and blocked the transportation of lithium ions. Nevertheless, excel-
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with SEM-EDS mapping, the composite exhibited a uniform mixture of lent electrochemical performances have been obtained with high con-
LAGP and PVDF-HFP. The enhancement of the ionic conductivity can ductivity electrolytes in pouch-cell solid-state batteries. In 2017, Nam
be attributed to two factors; the increase in relative density by incorpo- et al. fabricated a pouch-cell solid state battery with the tape-casting
rating polymers, and the formation of an ionic conducting network with method that was capable of delivering a high energy density with im-
the addition of liquid electrolyte. More recently, Clive's group improved proved safety at high temperature [99].
the ionic conductivity of the LAGP electrolyte by adding Li-salt (Li-TFSI)
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into the pellet, resulting in a conductivity of 5 × 10− ⁠ 5 S cm−

⁠ 1 at room
3.2. Cold sintering of solid-state electrodes
temperature [91].
Tape-casting of solid-state electrolytes are widely used for solid Typically, the sintering temperature of solid electrolytes can reach as
state battery fabrication. In the past few years, there have been re- high as 700 °C - 1000 °C by conventional sintering processes [1]. Impu-
ports on tape-casting of LATP, LAGP, LLZO and sulfide-based elec-
rity phases were detected at the interface between solid electrolyte and
trolytes. The first group of LAT(G)P sheets were developed by Ohara
electrode after the high-temperature sintering process, which are capa-
Inc. Using a quenching-crystallization process, which is now commer-
ble of blocking the transportation of lithium ions during electrochemi-
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cially available now. However, the LAT(G)P sheets still have room
cal cycling [25]. Thus, the CSP of active materials and solid electrolyte
for improvement in terms of performance and thickness before it can
could be a promising route in solving this issue.
be adopted for large scale applications. The tuning of thickness can
In one report by Guo, V2⁠ O5⁠ , a cathode material candidate for
be achieved by reducing particle size, lowering sintering temperature
lithium-ion batteries, was sintered by a CSP at 120 °C [74,100]. In the
with sintering additives, and increasing the density by forming com-
TEM micrographs of the CSP, a small amount of amorphous phase
posites with epoxy resin [93–95]. Recently, a garnet-type LLZO sheet
was detected at the grain boundaries after the dissolution-precipita-
was prepared by Yi et al., where they used flame-made
tion process, which is a typical charac

8
Y. Liu et al. Journal of Power Sources xxx (2018) xxx-xxx

teristic for the CSP pellet. To increase the electronic conductivity of the with equilibrated dihedral angles occurred at the triple points, where
V2⁠ O5⁠ pellet, 1–2 vol % conductive polymer PEDOT:PSS was added dur- small amounts of amorphous or glassy phases were identified. Cyclic
ing sintering. It was found that the composite showed an increase in voltammetry of the CSP LiFePO4⁠ electrode exhibited a redox peak
electronic conductivity greater than two orders of magnitude compared around 3.45 V, indicating the lithiation/delithiation in LiFePO4⁠ active
to the pure V2⁠ O5⁠ [100]. Such a composite is possible for application as materials. In charge-discharge tests, 155 mAh g− ⁠ 1
was achieved at 0.1 C
an electrode in solid-state batteries. during initial discharge process. 340 mAh cm− ⁠ 3
was calculated because

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Additionally, the CSP technique was also applied to LiFePO4⁠ cath- of the significantly higher density of the electrode in terms of volumet-
ode materials. A dense pellet consisting of cathode material, active car- ric capacity. Unfortunately, the discharge capacity was still low at high
bon and PVDF was sintered at a low temperature of 240 °C, as shown current density.

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in Fig. 5 [101]. Instead of using water as the solvent, a LiOH solu- In a recent paper, the CSP was extended to tape-casted cathode ma-
tion was used to increase the solubility of LiFePO4⁠ . The density of the terials, as displayed in Fig. 6 [102]. The sintered electrode was com-
electrode was increased gradually with an increase of applied pres- posed of LiFePO4⁠ and carbon nano-fibers, with no additional binder.
sure, with a relative density of 85% being achieved at ∼750 MPa. Af- A high density of 2.42 g cm− ⁠ 3 was achieved, corresponding to a rel-

ter the CSP, the LiFePO4⁠ was found to remain in a pure phase with ative density of ∼70%, which was much higher than conventional
no visible impurities from XRD characterization. From the cross-sec- tape-casted LiFePO4⁠ electrodes (1.9 g cm−⁠ 3
). Shown in Fig. 6a, the CSP
tion SEM and TEM images, a densified microstructure with the for- LiFePO4⁠ electrode contains highly-conductive CNF fillers, which are

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mation of grains with triple points and low porosity was observed, beneficial for electron conduction. Similar to previous reports, some
as seen in Fig. 5a. Clean grain boundaries of LiFePO4⁠ amorphous phase was observed at the grain boundaries in re

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Fig. 5. Cold sintering of a LiFePO4⁠ pellet; (a) TEM images of LiFePO4⁠ , and (b) cycling performance of LiFePO4⁠ [101].
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Fig. 6. Cold sintering of LiFePO4⁠ /carbon nano-fiber (CNF) thin film, (a) TEM images of LiFePO4⁠ /CNF, (b) cycling performance of LiFePO4⁠ /CNF [102].

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Y. Liu et al. Journal of Power Sources xxx (2018) xxx-xxx

gions of electrode. In the electrochemical tests, the CSP LiFePO4⁠ elec- the densification of a broad range of inorganic and inorganic-organic
trode showed good performance from 0.1 C to 1 C with a volumetric ca- composites. Furthermore, it has been successfully applied in solid-state
pacity of 373 mAh cm− ⁠ 3
. A high volumetric capacity of 247 mAh cm− ⁠ 3 electrolytes and solid-state batteries with reasonable performance being
and energy capacity of 102 mAh g− ⁠ 1
was observed at a rate of 10 C. achieved.
CSP shows great promise in preparation of solid electrolytes and
4. Conclusion and perspective composite electrodes, and needs further exploration. Fundamentally,

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there are a few issues that need further study:
In this report, the recent progress in the use of CSP for solid-state
electrolytes and electrodes has been summarized. Based on the reported 1. The enhanced ionic conductivity not only arises from the improved

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examples, it can be concluded that the CSP is a promising route to ob- density by filling the voids between particles through the precipi-
taining high compact density electrolytes/electrodes. However, the elec- tation of dissolved species, but also depends on improved bonding
trochemical properties of the CSP electrolytes/electrodes are still far between grain boundaries. The following work needs to explore the
from real application. There is still a large space for improvement in chemical/physical properties of grain boundaries, such as chemistry,
terms of physical/chemical properties. In addition, detailed character- composition, structure and their relationship with improved conduc-
izations on the microstructure will facilitate the design of high perfor- tivity, in order to reveal the role of CSP on improving the ionic con-
mance electrolyte/electrodes. ductivity.
2. For some target materials, their solubility is low or negligible in liq-

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Solid electrolytes and electrodes have a long history of manufac-
turing via thermal sintering. The dense body is achieved through the uid solutions, and additives with high solubility and high ionic con-
use of high temperatures to promote mass transport during the sin- ductivity are required in order to improve the bonding at grains,
tering process. However, high-temperature sintering invokes the for- tune the space charge layer and enhance the ionic conductivity. In
mation of blocking layers due to side-reactions. Thus, the develop- addition, some types of additives may enhance the solubility of tar-
ment of new sintering routes at lower temperatures are necessary. get materials in liquid solutions, and need further exploration to
Here, a facile sintering technique, the cold sintering process (CSP), widen the application of CSP techniques in solid-state batteries.
is introduced. It enables the densification of electrolyte/electrode at 3. In composite cathodes, special protection is needed for cathode ma-

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a lower temperature (<300 °C) in a short period of time. The basic terials, as most materials may be not chemical stable with liquid
solution or are soluble during the CSP. Different surface protection
mechanism of the CSP is the dissolution of the sharp-edges of par-
techniques and types of coating materials need to be involved and
ticles by a solvent and subsequent filling of the voids between par-
studied.
ticles through evaporation of solvent and precipitation of dissolved
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4. Cold co-sintering processes between electrolytes and cathodes are
species. Such an innovative mechanism can render
necessary in realizing good physical contacts. The
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Fig. 7. Summary of Cold sintering process and its application in solid-state batteries.

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Y. Liu et al. Journal of Power Sources xxx (2018) xxx-xxx

mismatch between electrolyte and electrode will deteriorate the elec-

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