p-n heterogeneous Sb2S3/SnO2 quantum dot anchored reduced graphene oxide nanosheets for high-performance lithium-ion batteries.

Antimony sulfide (Sb2S3) has a high theoretical specific capacity due to its two reaction mechanisms of conversion and alloying during the Li+-(de)intercalation process, thus becoming a promising lithium-ion battery (LIB) anode material. However, its poor inherent conductivity and large volume expansion during repeated Li+-(de)intercalation processes greatly hinder the in-depth development of Sb2S3 based LIB anode materials. Herein, an Sb2S3/SnO2@rGO composite was prepared by using an interface engineering technique involving metal-containing ionic liquid precursors, in which Sb2S3/SnO2 quantum dots (QDs) as p-n heterojunctions are uniformly anchored on the surface of reduced graphene oxide (rGO). The p-n heterogeneous interface between Sb2S3 and SnO2 QDs induces an internal electric field, promoting the electronic/ion transport during electrochemical reactions, and the QD-sized Sb2S3/SnO2 heterostructure with a larger surface area provides more active sites for Li+-(de)intercalation reactions. In addition, the rGO matrix acts as a buffer to prevent the aggregation of active Sb2S3 and SnO2 QDs, alleviate the volume expansion, and enhance the conductivity of the composite during repeated cycles. These advantages endow the designed Sb2S3/SnO2@rGO electrode with excellent reaction kinetics and good long cycling stability. As an anode material of LIBs, it can still provide a reversible specific capacity of 474 mA h g-1 after 2000 cycles at a high current density of 3.0 A g-1, which is superior to those of most of the previously reported Sb2S3-based carbon materials. The p-n heterostructure construction strategy of nano-metal sulfide/metal oxides in this work can provide inspiration for the design and synthesis of other advanced energy storage materials.

Rational Engineering of p-n Heterogeneous ZnS/SnO2 Quantum Dots with Fast Ion Kinetics for Superior Li/Na-Ion Battery.

Constructing heterogeneous nanostructures is an efficient strategy to improve the electrical and ionic conductivity of metal chalcogenide-based anodes. Herein, ZnS/SnO2 quantum dots (QDs) as p-n heterojunctions that are uniformly anchored to reduced graphene oxides (ZnS-SnO2 @rGO) are designed and engineered. Combining the merits of fast electron transport via the internal electric field and a greatly shortened Li/Na ion diffusion pathway in the ZnS/SnO2 QDs (3-5 nm), along with the excellent electrical conductivity and good structural stability provided by the rGO matrix, the ZnS-SnO2 @rGO anode exhibits enhanced electronic and ionic conductivity, which can be proved by both experiments and theoretical calculations. Consequently, the ZnS-SnO2 @rGO anode shows a significantly improved rate performance that simple counterpart composite anodes cannot achieve. Specifically, high reversible specific capacities are achieved for both lithium-ion battery (551 mA h g-1 at 5.0 A g-1 , 670 mA h g-1 at 3.0 A g-1 after 1400 cycles) and sodium-ion battery (334 mA h g-1 at 5.0 A g-1 , 313 mA h g-1 at 1.0 A g-1 after 400 cycles). Thus, this strategy to build semiconductor metal sulfides/metal oxide heterostructures at the atomic scale may inspire the rational design of metal compounds for high-performance battery applications.

A Selective Oxidation Strategy towards the Yolk-Shell Structured ZnS@C Material for Ultra-Stable Li-Ion Storage.

Metal chalcogenides are attractive anode materials for lithium-ion batteries (LIBs) due to their high theoretical capacities. With the advantages of low cost and abundance reserves, ZnS is regarded as the prime candidate anode material for future generations, but its practical application is hindered by the large volume expansion during repeated cycling processes and inherent poor conductivity. Rational design of the microstructure with large pore volume and high specific surface area is of great significance to solve these problems. Here, a carbon-coated ZnS yolk-shell structure (YS-ZnS@C) has been prepared by selective partial oxidation of a core-shell structured ZnS@C precursor in air and subsequent acid etching. Studies show that the carbon wrapping and proper etching to bring cavities can not only improve the material's electrical conductivity, but can also effectively alleviate the volume expansion problem of ZnS during its cycles. As a LIB anode material, the YS-ZnS@C exhibits an obvious superiority in capacity and cycle life compared to ZnS@C. The YS-ZnS@C composite shows a discharge capacity of 910 mA h g-1 at the current density of 100 mA g-1 after 65 cycles, compared to only 604 mA h g-1 for ZnS@C after 65 cycles. Notably, at a large current density of 3000 mA g-1, a capacity of 206 mA h g-1 can still be maintained after 1000 cycles (over three times of the capacity for ZnS@C). It is expected that the synthetic strategy developed here is applicable to designing various high-performance metal chalcogenide-based anode materials for LIBs.

A facile precursor route towards the synthesis of Fe1-xS@NC-rGO composite anode materials for high-performance lithium-ion batteries.

Iron-based sulfides are considered promising anode materials for lithium-ion batteries (LIBs) due to their low cost and high theoretical specific capacities. However, low conductivity and dissolution of lithium polysulfides during the reaction hamper their practical applications. Herein, we firstly synthesized N-doped carbon-coated Fe1-xS (Fe1-xS@NC) sheets through vacuum pyrolysis of the precursor Fe1-xS(en)0.5 (en = ethylenediamine). Then Fe1-xS@NC-rGO composites (rGO = reduced graphene oxide) were prepared in which the Fe1-xS@NC sheets were anchored on the rGO. The performance of the composites as an anode material for LIBs has been investigated. It is found that coating N-doped C on Fe1-xS surfaces can improve the surface conductivity and electrochemical kinetics of Fe1-xS, which is beneficial for the conversion between lithium polysulfides and Fe1-xS. In addition, the coated N-doped C on the Fe1-xS sheets can serve as a barrier to direct contact between the electrolyte and the material, reducing the dissolution of polysulfides and preventing the loss of active ingredients. More importantly, the double protection of the N-doped C layer and the flexible rGO substrate minimizes the structural damage caused by the cyclic expansion of Fe1-xS@NC-rGO. As expected, Fe1-xS@NC-rGO exhibits good rate performance with a reversible capacity of 939.5 mA h g-1 after 1690 cycles at a current density of 1.0 A g-1, along with outstanding charge and discharge performance and excellent long-term cycling stability. This work shows that the introduction of NC coating and the rGO matrix into Fe1-xS would synergistically enhance the performance of Fe1-xS for LIBs and highlights the effectiveness of the synthetic strategy for double carbon-based materials-protected sulfides in developing superior LIB electrodes.

Preparation of ZnS@N-doped-carbon composites via a ZnS-amine precursor vacuum pyrolysis route.

ZnS/carbon nanocomposites have potential electrochemical applications due to their improved conductivity and more active sites through modification of the carbon materials. Herein, we report a facile method to synthesize the nanocomposites comprising ZnS nanoparticles and nitrogen-doped carbon (ZnS@NC). The inorganic-organic hybrid ZnS-amine material ZnS(ba) (ba = n-butylamine) is synthesized on a large scale by a reflux method, which effectively shortens the reaction time while maintaining the high yield compared with the solvothermal method. Then ZnS(ba) is used as precursor for obtaining ZnS@NC nanocomposites via a vacuum pyrolysis route, in which the content of carbon and nitrogen can be controlled by adjusting the pyrolysis temperature. Further, a series of ZnS-amine hybrid materials ZnS(ha), ZnS(en)0.5 and ZnS(pda)0.5 (ha = n-hexylamine; en = ethylenediamine; pda = 1,3-propanediamine) are synthesized and used as precursors for the preparation of ZnS@NC materials, indicating the universality of this method. Moreover, the as-synthesized ZnS@NC materials exhibit remarkable lithium storage performance with outstanding cycling stability, high-rate capability and remarkable pseudo-capacitance characteristics.