Hard carbon microspheres (HCS) exhibit a highly reversible capacity of 262 mAh g−1 for K‐ion batteries. They present a superior rate capability for K‐ions to Na‐ions, where at 2C, HCS/K cells deliver 190 mAh g−1 in contrast to 97 mAh g−1 from HCS/Na cells. It is determined that the K‐ion diffusion coefficient of HCS is higher than that of Na‐ions.
Hard carbon is the leading candidate anode for commercialization of Na-ion batteries. Hard carbon has a unique local atomic structure, which is composed of nanodomains of layered rumpled sheets that have short-range local order resembling graphene within each layer but complete disorder along the caxis between layers. A primary challenge holding back the development of Na-ion batteries is that a complete understanding of the structure-capacity correlations of Na-ion storage in hard carbon has remained elusive. This article presents two key discoveries: first that characteristics of hard carbon's structure can be modified systematically by heteroatom doping, and second, that these structural changes greatly affect Na-ion storage properties, which reveals the mechanisms for Na storage in hard carbon. Specifically, via P or S doping, the interlayer spacing is dilated, which extends the low-voltage plateau capacity, while increasing the defect concentrations with P or B doping leads to higher sloping sodiation capacity. Our combined experimental studies and first principles calculations reveal that it is the Na-ion-defect binding that corresponds to the sloping capacity, while the Na intercalation between graphenic layers causes the low-potential plateau capacity. The new understanding provides a new set of guiding principles to optimize hard carbon for Na-ion battery applications.
There exist tremendous needs for sustainable storage solutions for intermittent renewable energy sources, such as solar and wind energy. Thus, systems based on Earthabundant elements deserve much attention. Potassium-ion batteries represent a promising candidate thanks to the abundance of potassium resources. As for the choices of anodes, graphite exhibits encouraging potassium-ion storage properties; however, it suffers limited rate capability and poor cycling stability. Here, we systematically investigated and compared non-graphitic carbons as K-ion anodes with sodium carboxymethyl cellulose as the binder. Compared to hard This article is protected by copyright. All rights reserved.2 carbon and soft carbon, a composite hard-soft carbon with 20 wt% soft carbon distributed in the matrix phase of hard carbon micron-spheres exhibits highly amenable performance: high capacity, high rate capability, and very stable long-term cycling. In contrast, pure hard carbon suffers limited rate capability, while the capacity of pure soft carbon fades more rapidly.
Na-ion
batteries (NIBs) have attracted great attention for scalable
electrical energy storage considering the abundance and wide availability
of Na resources. However, it remains elusive whether carbon anodes
can achieve the similar scale of successes in Na-ion batteries as
in Li-ion batteries. Currently, much attention is focused on hard
carbon while soft carbon is generally considered a poor choice. In
this study, we discover that soft carbon can be a high-rate anode
in NIBs if the preparation conditions are carefully chosen. Furthermore,
we discover that the turbostratic lattice of soft carbon is electrochemically
expandable, where d-spacing rises from 3.6 to 4.2
Å. Such a scale of lattice expansion only due to the Na-ion insertion
was not known for carbon materials. It is further learned that portions
of such lattice expansion are highly reversible, resulting in excellent
cycling performance. Moreover, soft carbon delivers a good capacity
at potentials above 0.2 V, which enables an intrinsically dendrite-free
anode for NIBs.
The capacity of hard carbon anodes in Na-ion batteries rarely reaches values beyond 300 mAh/g. We report that doping PO x into local structures of hard carbon increases its reversible capacity from 283 to 359 mAh/g. We confirm that the doped PO x is redox inactive by X-ray adsorption near edge structure measurements, thus not contributing to the higher capacity. We observe two significant changes of hard carbon's local structures caused by doping. First, the (002) d-spacing inside the turbostratic nanodomains is increased, revealed by both laboratory and synchrotron X-ray diffraction. Second, doping turns turbostratic nanodomains more defective along ab planes, indicated by neutron total scattering and the associated pair distribution function studies. The local structural changes of hard carbon are correlated to the higher capacity, where both the plateau and slope regions in the potential profiles are enhanced. Our study demonstrates that Na-ion storage in hard carbon heavily depends on carbon local structures, where such structures, despite being disordered, can be tuned toward unusually high capacities.
We synthesized a new type of carbon-polynanocrystalline graphite-by chemical vapor deposition on a nanoporous graphenic carbon as an epitaxial template. This carbon is composed of nanodomains being highly graphitic along c-axis and very graphenic along ab plane directions, where the nanodomains are randomly packed to form micron-sized particles, thus forming a polynanocrystalline structure. The polynanocrystalline graphite is very unique, structurally different from low-dimensional nanocrystalline carbon materials, e.g., fullerenes, carbon nanotubes, and graphene, nanoporous carbon, amorphous carbon and graphite, where it has a relatively low specific surface area of 91 m/g as well as a low Archimedes density of 0.92 g/cm. The structure is essentially hollow to a certain extent with randomly arranged nanosized graphite building blocks. This novel structure with disorder at nanometric scales but strict order at atomic scales enables substantially superior long-term cycling life for K-ion storage as an anode, where it exhibits 50% capacity retention over 240 cycles, whereas for graphite, it is only 6% retention over 140 cycles.
To fill the gap between batteries and supercapacitors requires integration of the following features in a single system: energy density well above that of supercapacitors, cycle life much longer than Li-ion batteries, and low cost. Along this line, we report a novel nonaqueous potassium-ion hybrid capacitor (KIC) that employs an anode of KTiO (KTO) microscaffolds constructed by nanorods and a cathode of N-doped nanoporous graphenic carbon (NGC). KTiO microscaffolds are studied for potential applications as the anode material in potassium-ion storage for the first time. This material exhibits an excellent capacity retention of 85% after 1000 cycles. In addition, the NGC//KTO KIC delivers a high energy density of 58.2 Wh kg based on the active mass in both electrodes, high power density of 7200 W kg, and outstanding cycling stability over 5000 cycles. The usage of K ions as the anode charge carrier instead of Li ions and the amenable performance of this device suggest that hybrid capacitor devices may welcome a new era of beyond lithium.
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