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Tao et al. Energy Mater 2022;2:200036 https://dx.doi.org/10.20517/energymater.2022.46 Page 23 of 35

[179]
interfacial affinity in ASSLSBs . Furthermore, a graphite fluoride-lithium fluoride-Li composite as a
[155]
dendrite-free lithium anode for Li-ion batteries exhibits long-term stability in ambient air .
The introduction of various interface layers with high ionic conductivity between Li anodes and SSEs has
been demonstrated to be an effective method for wetting the interface and achieving intimate contact,
which may be the main strategy to reduce interfacial resistance .
[180]
Fabricating composite SSEs between sulfur cathodes and lithium anodes
An increasing number of investigations have focused on composite electrolytes, which are promising for
overcoming issues related to dendrite growth, the shuttle effect of sulfur and the large interfacial resistance
in practical ASSLSBs because they have the combined advantages of inorganic and organic electrolytes, such
as good interfacial contact, high ionic conductivity and excellent thermal stability. The inorganic portion
can afford continuous Li-ion transfer channels in an organic-based composite and the organic portion with
flexibility improves the interfacial contact to reduce the interfacial resistance .
[181]
Composite solid electrolytes composed of a PEO-based polymer and an inorganic Li-ion conductor possess
good ionic conductivity and interfacial stability and have been employed as electrolytes for ASSLSB cells
showing good cycle stability. Example composites include P(EO) Li(CF SO ) N-10 wt.%ϒ-LiAlO 2 [182] , PEO-
20
2 2
3
lithium bis(trifluoromethanesulfonyl)imide (PEO LiTFSI)/nanosilica/N-methyl-N-propylpiperidinium-
18
[183]
bis(trifluoromethanesulfonyl)imide (PP13TFSI) , polyacrylonitrile-LiClO /15 wt.% Li La 0.557 TiO
0.33
3
4
nanowire , 3D garnet-type Li La Zr Al O /PEO , Li Al Ge (PO ) /PEO-based gel-polymer ,
[185]
[186]
[184]
2
3
6.4
0.2
1.5
0.5
1.5
12
4 3
[187]
Li I SnP S /P(EO) /LiI , poly(vinylidene fluoride-hexafluoropropylene) (PVDF-HFP)/Li Al Ti (PO )
2 12
1.5
0.5
1.5
3
4 3
10+x x
(LATP) nanoparticles , well-aligned Li La 0.557 TiO nanowires/polymer electrolyte , inorganic Al O
[188]
[188]
3
3
0.33
2
[144]
fillers/lithium bis(fluorosulfonyl)imide-PEO/Li-ion conducting glass-ceramic , Li La Zr O /carbon
3
7
12
2
[189]
[189]
foam/PEO , Li La 0.557 TiO nanofibers/sulfonamide lithium-PEO , Li P S /PEO-LiClO 4 [190] , Li La Zr 1.4
7 3 11
3
3
0.33
6.4
Ta O /PEO/LiTFSI and PEO/LiTFSI/Li Al Ge (PO ) [192] .
[191]
4 3
0.6
12
0.4
1.6
1.4
This improved performance may be attributed to the synergistic effect of the inorganic and organic portions
of the composites. For example, the improvement of PEO LiTFSI conductivity caused by the addition of
18
nano-SiO is due to the surface interaction between ionic species and O/OH groups at the filler surface and
2
the addition of PP13TFSI results in the generation of a passivation film with lower resistance .
[183]
Li La TiO nanowire fillers with high ionic conductivity and large aspect ratio filled in a
3
0.557
0.33
[184]
polyacrylonitrile-LiClO electrolyte can form fast conductive networks and Li-ion diffusion pathways .
4
However, the agglomeration of one-dimensional ceramic fillers could be an issue in fabricating
homogeneous composite solid electrolytes for their practical application. In order to avoid the
agglomeration of fillers, 3D ceramic networks were soaked into Li salt-polymer solutions for fabricating the
+
composite solid electrolytes, which can afford continuous channels for Li transfer in the electrolytes and
structural reinforcement . Since LATP nanoparticles have a strong impact on the recrystallization kinetics
[185]
of the polymer-based matrix to promote local amorphous areas and enhance the stability of the long-term
structure and PVDF-HFP has large dielectric constant, good interfacial compatibility and high ionic
[186]
conductivity, they have been chosen to fabricate a novel composite gel polymer electrolyte . Introducing
+
the well-aligned inorganic Li -conductive nanowires into the solid polymer electrolytes can result in an
increase in ionic conductivity, because of a fast ion conduction pathway without crossing junctions on the
[189]
surface of the well-aligned nanowires . A composite electrolyte additive, the Li La Zr O nanoparticle-
7
3
12
2
decorated carbon foam, can be used as both the interfacial stabilizer and filler to improve ionic and
[144]
electronic conductivity of the electrolyte/electrode interface . PEO-LiClO , with good electrochemical
4
stability, can effectively prevent the reaction between the Li P S glass-ceramic electrolyte and lithium,
7 3 11