High-entropy
materials, with complex compositions and unique cocktail
characteristics, have recently drawn significant attention. Additionally,
a family of sodium super ion conductors (NASICONs)-structured phosphates
in energy storage areas shows a comprehensive application for traditional
alkaline ion batteries and, in particular, solid-state electrolytes.
However, there is no precedent in fabricating this kind of NASICON-type
high-entropy phase. Here, we report the successful fabrication of
two well-crystallized high-entropy phosphates, namely, Na3(Ti0.2V0.2Mn0.2Cr0.2Zr0.2)2(PO4)3 (HE-N3M2P3) and Na(Ti0.2V0.2Mn0.2Cr0.2Zr0.2)2PO4O
x
(HE-NMP). The prepared materials
in which the transition metals (TMs) of Ti, V, Mn, Cr, and Zr occupy
the same 12c Wykoff position can form a structure analogous to R3̅c Na3V2(PO4)3 that is carefully determined by X-ray diffraction,
neutron diffraction, and transmission electron microscopy. Further,
their performance for sodium ion batteries and sodium-based solid-state
electrolytes was evaluated. The HE-N3M2P3 might exhibit a promising electrochemical performance for
sodium storage in terms of its structure resembling that of Na3V2(PO4)3. Meanwhile, the
HE-NMP shows considerable electrochemical activity with numerous broad
redox ranges during extraction and insertion of Na+, related
to the coexistence of several TM elements. The evaluated temperature-dependent
ionic conductivity for HE-NMP solid electrolyte varies from 10–6 to 10–5 S cm–1 from room temperature to 398.15 K, offering high potential for energy
storage applications as a new high-entropy system.
Fe–N–C
catalysts exhibit promising activity toward
the catalytic oxygen reduction reaction (ORR). However, applicability
of such catalysts is limited by serious oxidative corrosion via the
Fenton reaction. In this feature work, we prepared manganese–nitrogen
species by pyrolyzing a bimetal CdMn and P-phenylenediamine organic
complex (CdMn–PPD) under different atmospheres for the first
time. The experimental results suggest that the carbonized atmosphere
deeply affects the graphitization degree, pore structure of carbon,
and the formation of Mn–N active sites. Of the three prepared
catalysts, Mn@NPC–NH3 exhibited the greatest Mn–N
and pyridinic N content and delivered excellent ORR activity (E
onset: 0.95 V, E
1/2: 0.83 V). Even more impressive, the Fenton reaction was substantially
restrained by this catalyst. Overall, the Mn@NPC–NH3 offers superior stability to that of Fe–N–C catalysts,
providing new insight for further explorations of excellent non-noble
metal ORR catalysts.
Highly efficient
and durable flexible solid-state supercapacitors
(FSSSCs) are emerging as low-cost devices for portable and wearable
electronics due to the elimination of leakage of toxic/corrosive liquid
electrolytes and their capability to withstand elevated mechanical
stresses. Nevertheless, the spread of FSSSCs requires the development
of durable and highly conductive solid-state electrolytes, whose electrochemical
characteristics must be competitive with those of traditional liquid
electrolytes. Here, we propose an innovative composite solid-state
electrolyte prepared by incorporating metallic two-dimensional group-5
transition metal dichalcogenides, namely, liquid-phase exfoliated
functionalized niobium disulfide (f-NbS2) nanoflakes, into
a sulfonated poly(ether ether ketone) (SPEEK) polymeric matrix. The
terminal sulfonate groups in f-NbS2 nanoflakes interact
with the sulfonic acid groups of SPEEK by forming a robust hydrogen
bonding network. Consequently, the composite solid-state electrolyte
is mechanically/dimensionally stable even at a degree of sulfonation
of SPEEK as high as 70.2%. At this degree of sulfonation, the mechanical
strength is 38.3 MPa, and thanks to an efficient proton transport
through the Grotthuss mechanism, the proton conductivity is as high
as 94.4 mS cm–1 at room temperature. To elucidate
the importance of the interaction between the electrode materials
(including active materials and binders) and the solid-state electrolyte,
solid-state supercapacitors were produced using SPEEK and poly(vinylidene
fluoride) as proton conducting and nonconducting binders, respectively.
The use of our solid-state electrolyte in combination with proton-conducting
SPEEK binder and carbonaceous electrode materials (mixture of activated
carbon, single/few-layer graphene, and carbon black) results in a
solid-state supercapacitor with a specific capacitance of 116 F g–1 at 0.02 A g–1, optimal rate capability
(76 F g–1 at 10 A g–1), and electrochemical
stability during galvanostatic charge/discharge cycling and folding/bending
stresses.
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