Single-ion conductive polymer electrolytes can improve
the safety
of lithium ion batteries (LIBs) by increasing the lithium transference
number (t
Li
+) and avoiding
the growth of lithium dendrites. Meanwhile, the self-assembled ordered
structure of liquid crystal polymer networks (LCNs) can provide specific
channels for the ordered transport of Li ions. Herein, single-ion
conductive nematic and cholesteric LCN electrolyte membranes (denoted
as NLCN-Li and CLCN-Li) were successfully prepared. NLCN-Li was then
coated on commercial Celgard 2325 while CLCN-Li was coated on poly(vinylidene
fluoride-hexafluoropropylene) film, coupled with plasticizer, to make
NLCN-Li/Cel and CLCN-Li/Pv quasi-solid-state electrolyte membranes,
respectively. Their electrochemical properties were evaluated, and
it was found that they possessed benign thermal stability and electrolyte/electrode
compatibility, high t
Li
+ up
to 0.98 and high electrochemical stability window up to 5.2 V. A small
amount (0.5M) of extra Li salt added to the plasticizer could improve
the ion conductivity from 1.79 × 10–5 to 5.04
× 10–4 S cm–1, while the t
Li
+ remained 0.85. The assembled
LFP|Li batteries also exhibited excellent cycling and rate performances.
The orderliness of the LCN layer played an important role in the distribution
and movement of Li ions, thereby affecting the Li deposition and growth
of Li dendrites. As the first report of nematic and cholesteric LCN
single-ion conductors, this work sheds light on the design and fabrication
of ordered quasi-solid-state electrolytes for high-performance and
safe LIBs.