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Hard carbon is one of the most promising anode materials for sodium‐ion batteries, but the low Coulombic efficiency is still a key barrier. In this paper, a series of nanostructured hard carbon materials with controlled architectures is synthesized. Using a combination of in situ X‐ray diffraction mapping, ex situ nuclear magnetic resonance (NMR), electron paramagnetic resonance, electrochemical techniques, and simulations, an “adsorption–intercalation” mechanism is established for Na ion storage. During the initial stages of Na insertion, Na ions adsorb on the defect sites of hard carbon with a wide adsorption energy distribution, producing a sloping voltage profile. In the second stage, Na ions intercalate into graphitic layers with suitable spacing to form NaC x compounds similar to the Li ion intercalation process in graphite, producing a flat low voltage plateau. The cation intercalation with a flat voltage plateau should be enhanced and the sloping region should be avoided. Guided by this knowledge, nonporous hard carbon material has been developed which has achieved high reversible capacity and Coulombic efficiency to fulfill practical application.
Semiconductor quantum dots (QDs) are extremely interesting materials for the development of photovoltaic devices, but currently the present the drawback is that the most efficient devices have been prepared with toxic heavy metals of Cd or Pb. Solar cells based on "green" QDs totally free of Cd or Pbpresent a modest efficiency of 2.52%. Herein we achieve effective surface passivation of the ternary CuInS 2 (CIS) QDs that provides high photovoltaic quality core/shell CIS/ZnS (CIS-Z) QDs, leading to the development of high-efficiency green QD solar cells that surpass the performance of those based on the toxic cadmium and lead chalcogenides QDs. Using wide absorption range QDs, CIS-Zbased quantum dot sensitized solar cell (QDSC) configuration with high QD loading and with the benefit of the recombination reduction with type-I core/shell structure, we boost the power conversion efficiency of Cd-and Pb-free QDSC to a record of 7.04% (with certified efficiency of 6.66%) under AM 1.5G one sun irradiation. This efficiency is the best performance to date for QDSCs and also demonstrates that it is possible to obtain comparable or even better photovoltaic performance from green CIS QDs to the toxic cadmium and lead chalcogenides QDs.
The enhancement of power conversion efficiency (PCE) and the development of toxic Cd-, Pb-free quantum dots (QDs) are critical for the prosperity of QD-based solar cells. It is known that the properties (such as light harvesting range, band gap alignment, density of trap state defects, etc.) of QD light harvesters play a crucial effect on the photovoltaic performance of QD based solar cells. Herein, high quality ∼4 nm Cd-, Pb-free Zn-Cu-In-Se alloyed QDs with an absorption onset extending to ∼1000 nm were developed as effective light harvesters to construct quantum dot sensitized solar cells (QDSCs). Due to the small particle size, the developed QD sensitizer can be efficiently immobilized on TiO2 film electrode in less than 0.5 h. An average PCE of 11.66% and a certified PCE of 11.61% have been demonstrated in the QDSCs based on these Zn-Cu-In-Se QDs. The remarkably improved photovoltaic performance for Zn-Cu-In-Se QDSCs vs Cu-In-Se QDSCs (11.66% vs 9.54% in PCE) is mainly derived from the higher conduction band edge, which favors the photogenerated electron extraction and results in higher photocurrent, and the alloyed structure of Zn-Cu-In-Se QD light harvester, which benefits the suppression of charge recombination at photoanode/electrolyte interfaces and thus improves the photovoltage.
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