The rapid growth of the worldwide demand of lithium for batteries (LIBs) can possibly lead to a shortage of its reserves. Sodium batteries represent a promising alternative because they enable much higher energy densities than other battery systems, with the exception of LIBs, and are not limited by sodium availability. Herein, we present a novel, Na + ion intercalation material, Na 0.45 Ni 0.22 Co 0.11 Mn 0.66 O 2 (space group P6 3 /mmc) synthesized in air by a coprecipitation method followed by a thermal treatment and a water-rinsing step. This material performs a specific capacity of 135 mA h g −1 with a Coulombic efficiency exceeding 99.7%. Upon long-term cycling tests the material shows excellent capacity retention after more than 250 cycles. Such an overall performance, superior to that of presently known sodium-ion cathodes, represents a step further toward the realization of sustainable batteries for efficient stationary energy storage.

Brønsted acid sites (BAS) in dry aluminosilicate zeolites, also known as bridging O H −H groups, may form hydrogen bonds with other framework oxygen atoms, O, in addition to BAS that are free of such interactions. These are referred to as perturbed and unperturbed BAS, respectively. However, hydrogen bonding may occur only for specific geometric orientations between two framework oxygen atoms, allowing an O H −H•••O interaction. To evaluate the possibility for such hydrogen bonding, we introduce an alignment angle κ that describes the angle between the Si−O H −Al bisector and the O H −O direction of a potential hydrogen-bonding donor−acceptor pair. A total of 27 zeolite framework topologies were analyzed, and the relevance of this approach was subsequently demonstrated for H-ZSM-5 with two different Si/Al ratios. Here, it could be unequivocally shown by advanced solid-state NMR methods that the debated 1 H NMR signal at ∼6 ppm arises due to the formation of hydrogen-bonded BAS.

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Isolated acid sites were selectively generated by postsynthesis modification of a borosilicate zeolite beta. To this end, samples were prepared with pairs of adjacent boron sites balanced by Ca2+ ions, whereas isolated boron in the zeolite framework was balanced by NH4 + ions. To avoid undesired boron leaching, these ion exchange reactions were carried out in methanol solution rather than in water. Trigonal boron forms near the NH4 + ions by decomposing the latter into NH3 (and a proton), and selective extraction of the trigonal boron is achieved by water treatment, whereas the tetrahedral boron near Ca2+ ions remains in the zeolite framework. The vacancies were refilled with aluminum by treatment with an aqueous Al­(NO3)3 solution. Two Brønsted acid sites with 1H chemical shifts of 4.0 and 5.0 ppm exist in the dehydrated samples. 1H–27Al REAPDOR solid-state NMR measurements yield quantitative information on the local H–Al distances of isolated H–Al two-spin and H–Al–Al three-spin systems. The nearest H–Al distance is determined at 2.50 Å with an accuracy of 2% (or better) by fitting the oscillatory part of the REAPDOR curves, which was not observed before for zeolite acid sites. The second nearrest Al neighbors show a much larger distance of about 5 Å for the acid protons with a chemical shift of δ = 4 ppm. A second acid site at δ = 5 ppm has an approximately 50% occupation of a second Al neighbor at 3.73 Å, possibly within the same six-ring. This high resolution of dipolar interaction is not observed in a standard zeolite Al-beta prepared by direct synthesis. The method is suitable to identify well-defined local ordering in Al distributions of zeolites.