Hollow CuO nanoparticles in carbon microspheres prepared from cellulose-cuprammonium solution as anode materials for Li-ion batteries
Graphical abstract
Introduction
Cellulose, as the most abundant and chemical compatible material, has been widely used as an efficient matrix to combine with other materials [1], [2], [3]. Because of the porous structure, the cellulose matrix in the hybrid not only acts as substrate but also sufficiently stables the nanostructures within it. Carbon-based materials and metallic nanoparticles (NPs) are the most common materials embedded into cellulose [4], [5]. Various hybrid materials based on cellulose were fabricated [6], [7], [8], and have been used in the fields such as thermal conductive film [9], biosensor [10], catalyst [11], [12], transparent conductor [13], optical device [14] and electrodes [15]. Integrating cellulose hosted materials with different NPs may afford new designed materials with advanced set of functions and enlarge the application of cellulose.
Hollow materials are a bunch of materials which contain the hollow structure inside them. Proper holes give these materials large surface areas and considerable inner volume to adapt to the volume changes during electronic and catalytic processes [16], for cargo delivery [17], or to form channels enabling the free movement of substances within the materials [18]. Template method is the most common way to create well-shaped hollow materials. SiO2 [19], bubbles [20], water soluble salts [21] and carbon-based polymers [22] have been used as efficient templates to form hollow structural materials. However, these processes are all involved the steps to remove the templates, which complicate the method and induce uncertainties. Nowadays, non-template method gradually became a significant approach to fabricate hollow materials [23]. Oswald ripening [24] and Kirkendall effect [25] are the well-known mechanism for the formation of hollow NPs. However, the non-template method also faces the shortages especially for the cost of precursor and low-yields. To further develop the application of hollow materials, finding a new approach to make integrated hollow materials, lower the cost, and increase the yields is still a priority and challenge.
Copper oxides, like other transitional metal oxides [26], [27], [28], [29] have shown remarkable potential as an energy conversion media [30], [31], [32] for lithium-ion batteries (LIBs), due to their abundance, environmental friendliness, chemical stability and high theoretical lithium storage capacity (670 mA h/g) [33], [34]. However, traditional CuO anodes suffer from a large initial irreversible capacity loss, poor cycling stability, and undesirable rate performance [35], [36]. To overcome these problems, basic strategies have been applied to relieve the volume variation and to improve the electrical contact of the anodes. Most methods require multiple steps, and the growth of the particles needs to be carefully controlled, which would limit the mass production of the anodes. Therefore, a facile method to produce CuO-based LIB anodes is necessary to fulfil these drawbacks.
Herein, we describe a new approach to fabricate carbon microspheres embedded with hollow CuO NPs. In order to simplified the process of making precursor and lower the cost, the copper-enriched cuprammonium-cellulose solution was chosen, as it naturally contains a lot of copper compounds and favourable for preparing copper NPs/cellulose materials [37]. Chemical crosslinked cuprammonium-cellulose microspheres were prepared and used as precursors to fabricate the hollow CuO NPs embedded carbon microspheres. The spontaneous formation of the hollow structure is associated with Kirkendall effect. Cellulose and its derived carbon played the key role in the formation of hollow structure. The obtained microspheres had two-level structures including micro-sized spheres and nano-sized hollow particles. When using as anodes of LIBs, the combination of carbon and the hollow CuO NPs provided higher electrochemical properties than the bare CuO microspheres. Above all, this is a facile and reliable method to create multiply hollow NPs hybridized carbon based materials.
Section snippets
Materials
The cotton linter pulp was supplied by Hubei Chemical Fiber Co. Ltd. (Xiangyang, China). The degree of polymerization (DP) was determined to be 580. CuSO4, NH3·H2O, NaOH, H2SO4, 2,2,4-trimethylpentane, Span 85, epoxy chloropropane (ECH), and ethyl alcohol of analytical grade were purchased from Sinopharm Chemical Reagent (Shanghai, China) and used without further purification.
Preparation of Cu(OH)2@RC microspheres
Cotton linter pulp was dissolved in a cuprammonium hydroxide solution with a concentration of 6 wt% in accordance with
Preparation and composition of the microspheres
Scheme 1 illustrates the fabrication of Cu(OH)2@RC, Cu@C and CuO@C microspheres from cellulose-cuprammonium solutions. Cotton linter pulps were directly dissolved in the cuprammonium solution. The emulsion method was introduced to prepare Cu(OH)2@RC microspheres. 2,2,4-trimethylpentane is the oil phase and the Span 85 is the surfactant to stable the cellulose-cuprammonium micro drops. Due to the high gelation temperature of the cellulose-cuprammonium solution, chemical cross-linking was
Conclusions
In summary, we introduced cuprammonium cellulose as the precursor to prepare CuO@C microspheres. Hollow CuO NPs were successfully obtained by directly oxidizing Cu NPs without a template. The sizes of the obtained hollow CuO NPs were around 100–200 nm and located within the carbon matrix. The formation of the hollow structure was based an oxygen oxidizing assisted Kirkendall effect. Cellulose served not only as a scaffold for amorphous Cu(OH)2 but also as the carbon source for CuO@C
Acknowledgement
This work was financially supported by National Natural Science Foundation of China (51473128 and 51273151).
References (65)
- et al.
Advanced materials through assembly of nanocelluloses
Adv. Mater.
(2018) - et al.
Calcium carbonate mineralization in chiral mesomorphic order-retaining ethyl cellulose/poly(acrylic acid) composite films
Polymer
(2018) - et al.
Calcium phosphate mineralization in cellulose derivative/poly(acrylic acid) composites having a chiral nematic mesomorphic structure
Biomacromolecules
(2015) - et al.
Step-by-step self-assembly of 2D few-layer reduced graphene oxide into 3D architecture of bacterial cellulose for a robust, ultralight, and recyclable all-carbon absorbent
Carbon
(2018) - et al.
Recyclable biomass carbon@SiO2@MnO2 aerogel with hierarchical structures for fast and selective oil-water separation
Chem. Eng. J.
(2018) - et al.
Constructing flexible cellulose–Cu nanocomposite film through in situ coating with highly single-side conductive performance
J. Mater. Chem. C
(2014) - et al.
Green method for production of cellulose multifilament from cellulose carbamate on a pilot scale
ACS Sustain. Chem. Eng.
(2014) - et al.
Sustainable preparation of copper particles decorated carbon microspheres and studies on their bactericidal activity and catalytic properties
ACS Sustain. Chem. Eng.
(2015) - et al.
Highly flexible biodegradable cellulose nanofiber/ graphene heat-spreader films with improved mechanical properties and enhanced thermal conductivity
J. Mater. Chem. C
(2018) - et al.
Biotemplated synthesis of gold nanoparticle-bacteria cellulose nanofiber nanocomposites and their application in biosensing
Adv. Funct. Mater.
(2010)
Cellulose nanofibrils enable flower-like BiOCl for high-performance photocatalysis under visible-light irradiation
Appl. Surf. Sci.
Green processing of plant biomass into mesoporous carbon as catalyst support
Chem. Eng. J.
A deformable and highly robust ethyl cellulose transparent conductor with a scalable silver nanowires bundle micromesh
Adv. Mater.
Flexible latex photonic films with tunable structural colors templated by cellulose nanocrystals
J. Mater. Chem. C
Pyrolyzed bacterial cellulose: a versatile support for lithium ion battery anode materials
Small
Hollow multishelled heterostructured anatase/TiO2(B) with superior rate capability and cycling performance
Adv. Mater.
Recent advances in functional nanostructured materials for bone-related diseases
J. Mater. Chem. B
Tube-in-tube hollow fiber catalytic membrane microreactor for the hydrogenation of nitrobenzene
Chem. Eng. J.
One-step assembly of coordination complexes for versatile film and particle engineering
Science
Gas bubble templated synthesis of Mn3O4-embedded hollow carbon nanospheres in ethanol flame for elastic supercapacitor
J. Alloys Compd.
Salt-templated growth of monodisperse hollow nanostructures
J. Mater. Chem. A
The synthesis, characterization and electrochemical performance of hollow sandwich microtubules composed of ultrathin Co3O4 nanosheets and porous carbon using a bio-template
J. Mater. Chem. A
Template-free synthesis of hollow structured Co3O4 nanoparticles as high-performance anodes for lithium-ion batteries
ACS Nano
The theory of Ostwald ripening
J Statist. Phys.
Formation of hollow nanocrystals through the nanoscale Kirkendall effect
Science
Novel GaNb49O124 microspheres with intercalation pseudocapacitance for ultrastable lithium-ion storage
Ceram. Int.
New Anode Material for Lithium-Ion Batteries: aluminum Niobate (AlNb11O29)
ACS Appl. Mater. Interfaces
Nanosheet-based Nb12O29 hierarchical microspheres for enhanced lithium storage
Chem. Commun.
MoNb12O33 as a new anode material for high capacity, safe, rapid and durable Li+ storage: structural characteristics, electrochemical properties and working mechanisms
J. Mater. Chem. A
Properties of glycerol and ethylene glycol mixture based SiO2-CuO/C hybrid nanofluid for enhanced solar energy transport
Sol. Energy Mat. Sol. C.
Absorption mechanism and performance characterization of CuO nanostructured absorbers
Sol. Energy Mat. Sol. C.
Complementary optical absorption and enhanced solar thermal conversion of CuO-ATO nanofluids
Sol. Energy Mat. Sol. C.
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