Ideal
solid electrolytes for lithium (Li) metal batteries should
conduct Li+ rapidly with low activation energy, exhibit
a high Li+ transference number, form a stable interface
with the Li anode, and be electrochemically stable. However, the lack
of solid electrolytes that meet all of these criteria has remained
a considerable bottleneck in the advancement of lithium metal batteries.
In this study, we present a design strategy combining all of those
requirements in a balanced manner to realize quasi-solid-state electrolyte-enabled
Li metal batteries (LMBs). We prepared Li+-coordinated
triptycene-based ionic porous organic polymers (Li+@iPOPs).
The Li+@iPOPs with imidazolates and phenoxides exhibited
a high conductivity of 4.38 mS cm–1 at room temperature,
a low activation energy of 0.627 eV, a high Li+ transference
number of 0.95, a stable electrochemical window of up to 4.4 V, excellent
compatibility with Li metal electrodes, and high stability during
Li deposition/stripping cycles. The high performance is attributed
to charge delocalization in the backbone, mimicking the concept of
lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), which facilitates
the diffusion of coordinated Li+ through the porous space
of the triptycene-based iPOPs. In addition, Li metal batteries assembled
using Li+@Trp-Im-O-POPs as quasi-solid-state electrolytes
and a LiFePO4 cathode showed an initial capacity of 114
mAh g–1 and 86.7% retention up to 200 cycles.