Full Length ArticleLaser in-situ synthesis of SnO2/N-doped graphene nanocomposite with enhanced lithium storage properties based on both alloying and insertion reactions
Introduction
SnO2-based materials have attracted great attention as promising anodes for the next-generation Li-ion batteries [1], [2]. With properties of natural abundance, less toxicity, higher electrode potential and an attractive specific capacity of 782 mAh g−1 (cycling between Sn and Li4.4Sn), SnO2-based materials have been considered as low costs and high safety replacements for graphitic materials [2], [3], [4]. However, SnO2 tends to pulverization after several reaction cycles, due to substantial volume expansion increases up to 260% [4], [5], [6], which causes continual consumption of electrolyte, excessive growth of unstable solid electrolyte interface (SEI) layer and capacity fading [7], [8], [9], [10]. To address these problems, conductive buffer materials have been used as host materials to cooperate with SnO2 [4], [11], [12]. Due to their high electrical conductivity and volume buffer properties, the stability of SnO2-based anodes has been significantly improved.
Using polymer binders, such as poly vinylidene fluoride (PVDF) [13], polyacrylic acid (PAA) [14], carboxymethyl cellulose (CMC) [15], [16] and etc. to cooperate with SnO2 are another feasible approach to resolve these issues. Polymer binders can combine active materials and conducting parts together to maintain the structural integrity, thus the active materials show enhanced cycling performance during lithiation and delithiation [14], [17]. But polymer binders can reduce battery performances in aspects of increasing the electronic resistance and occupying weight in active materials, which inevitably compromise the electrochemical performance of electrode [18], [19], [20]. Moreover, nanomaterials normally have a larger surface area, which make them difficult to mix well with polymer binders [21]. Recently, in-situ synthesis methods have been carried out to grow nanocomposite on charge collector foils, benefit from no addition of any polymer binders, the as-prepared sample presents improved electrochemical performances in lithium storage application [17], [21], [22], [23], [24]. For example, Ui et al. [18] used an electrophoretic deposition (EPD) method to prepare a nano-SnO2 and acetylene black co-deposited film, which exhibited a reversible capacity of 504 mAh g−1 after 50 cycles for lithium storage. Followed by freeze-drying mixtures of graphene oxide and tin sol with a heat treatment, Botas et al. [25] prepared a SnO2-based nanocomposite foam with a reversible capacity of 1010 mAh g−1 after 50 cycles. Shen et al. [26] reported a porous carbon-nanofiber membrane (Sn-SnO2-CNF@C) and showed an enhanced specific capacity of 712.2 mA h g−1 at a high current density of 800 mA g−1 after 200 cycles. Liang et al. [27] deposited SnO2/nitrogen-doped graphene nanocomposites on a fiberglass membrane by using a hydrothermal method, the as-prepared binder-free electrodes also exhibited excellent lithium storage capacity.
Inspired by researches mentioned above, an efficient and environmentally friendly method was carried out to fabricate SnO2/nitrogen-doped graphene nanocomposite (SnO2/N-Gr) electrode, which combined processes of coating reactive precursors to Cu foils and followed by laser irradiation to trigger in-situ conversion of precursors. When the obtained electrode used as anode for lithium storage, it revealed both of high reversible capacities and good rate performance. Mechanisms of performance enhancement were investigated and discussed in this paper.
Section snippets
Synthesis of SnO2/N-doped graphene nanocomposite
Preparation procedures for the SnO2/N-doped graphene nanocomposite (SnO2/N-Gr) electrode were described as following: 500 mg tin (II) chloride dehydrate (SnCl2·2H2O, Aldrich, 98.0%) was dissolved in 10 ml ethanol (C2H5OH, Sinopharm, 99%), and followed by aging two weeks to obtain stannic oxide sol. Then, the sol was diluted with a suitable amount of ethanol and dispersed to 20 ml graphene oxide colloids (Aqueous dispersion, Aldrich, 2 mg ml−1). In order to introduce the nitrogen element, 1 g urea (NH2
Physicochemical properties
Fig. 2(a) shows X-ray diffraction (XRD) patterns of the SnO2/N-Gr and the SnO2/Gr. Diffraction peaks at 2 Theta values of 26.6°, 33.9° and 51.8° can be indexed to the (110), (101), and (211) plane of tetragonal SnO2 (JCPS 00-001-0657). Average crystal sizes are calculated according to the Scherer’s formula by using the full width at half maximum (FWHM) peak of the (110) orientation [28], around 7.6 nm for the SnO2/N-Gr and 7.8 nm for the SnO2/Gr. Samples present similar crystal sizes, indicating
Discussion
Doping is well established as a method to modify and improve properties of materials. However, doping at the nanoscale is challenging and the reasons for exceptional performance are not well understood [29], [32]. According to previous studies, the enhancement of electrochemical performances related to N-doping can be attributed to these aspects: (1) N-doping could enhance the conductivity of the SnO2 to improve the overall conductivity of electrode [42], [43]; (2) N-doping could provide
Conclusions
In conclusion, a SnO2/N-doped graphene nanocomposite (SnO2/N-Gr) electrode has been prepared by a laser in-situ synthesis method as anode for lithium storage. It is found that the SnO2/N-Gr shows a significantly improved lithium storage capacities and rate performance compared with the pristine sample (SnO2/Gr). In particular, a high reversible capacity of 830 mAh g−1 can be obtained after 300 cycles (at a current density of 300 mA g−1), and even the current density increased up to of 3 A g−1, the SnO
Acknowledgement
This work was supported by the Zhejiang Provincial Natural Science Foundation of China (No. LQ17E020003).
References (58)
- et al.
Carbon-coated SnO2/graphene nanosheets as highly reversible anode materials for lithium ion batteries
Carbon
(2012) - et al.
A SnO2/graphene composite as a high stability electrode for lithium ion batteries
Carbon
(2011) - et al.
The developments of SnO2/graphene nanocomposites as anode materials for high performance lithium ion batteries: a review
J. Power Sources
(2016) - et al.
Porous SnO2@C/graphene nanocomposite with 3D carbon conductive network as a superior anode material for lithium-ion batteries
Electrochim. Acta
(2014) - et al.
Enhanced cyclability of amorphous carbon-coated SnO2-graphene composite as anode for Li-ion batteries
Electrochim. Acta
(2014) - et al.
The influence of graphene/carbon mass ratio on microstructure and electrochemical behavior in the graphene-SnO2-carbon composite as anodes for Li-ion batteries
J. Alloys Compd.
(2015) - et al.
SnO2/graphene composite as highly reversible anode materials for lithium ion batteries
J. Power Sources
(2013) - et al.
Sn@SnOx/C nanocomposites prepared by oxygen plasma-assisted milling as cyclic durable anodes for lithium ion batteries
J. Power Sources
(2013) - et al.
The role of carbon incorporation in SnO2 nanoparticles for Li rechargeable batteries
J. Power Sources
(2012) - et al.
Electrospun PVdF-based fibrous polymer electrolytes for lithium ion polymer batteries
Electrochim. Acta
(2004)
Fabrication of binder-free graphene-SnO2 electrodes by laser introduced conversion of precursors for lithium secondary batteries
Appl. Surf. Sci.
Fabrication of binder-free SnO2 nanoparticle electrode for lithium secondary batteries by electrophoretic deposition method
Electrochim. Acta
Anodic nanoporous SnO2 grown on Cu foils as superior binder-free Na-ion battery anodes
J. Power Sources
Lithium ion batteries made of electrodes with 99 wt% active materials and 1 wt% carbon nanotubes without binder or metal foils
J. Power Sources
DIP-coating process to fabricate SnO2/C nanotube networks as binder-free anodes for lithium ion batteries
Mater. Lett.
Controllable synthesis of carbon-coated Sn-SnO2-carbon-nanofiber membrane as advanced binder-free anode for lithium-ion batteries
Electrochim. Acta
Nitrogen-doped carbon-coated SnxOy (x = 1 and y = 0 and 2) nanoparticles for rechargeable Li-ion batteries
Electrochim. Acta
High energy lithium ion battery electrode materials: enhanced charge storage via both alloying and insertion processes
Electrochim. Acta
Transition metal oxides for high performance sodium ion battery anodes
Nano Energy
The influence of graphene/carbon mass ratio on microstructure and electrochemical behavior in the graphene–SnO2–carbon composite as anodes for Li-ion batteries
J. Alloys Compd.
Facile strategy to produce N-doped carbon aerogels derived from seaweed for lithium-ion battery anode
J. Alloys Compd.
Mechanism of lithium storage in low temperature carbon
Carbon
A facile route to carbon-coated SnO2 nanoparticles combined with a new binder for enhanced cyclability of Li-ion rechargeable batteries
Electrochim. Acta
Designed constitution of NiO/Ni nanostructured electrode for high performance lithium ion battery
Electrochim. Acta
Formation of uniform N-doped carbon-coated SnO2 submicroboxes with enhanced lithium storage properties
Adv. Energy Mater.
Graphene enhanced carbon-coated tin dioxide nanoparticles for lithium-ion secondary batteries
J. Mater. Chem. A
Enhanced cyclic performance and lithium storage capacity of SnO2/graphene nanoporous electrodes with three-dimensionally delaminated flexible structure
Nano Lett.
Toward efficient binders for Li-ion battery Si-based anodes: polyacrylic acid
ACS Appl. Mater. Interfaces
Effect of carboxymethyl cellulose on aqueous processing of natural graphite negative electrodes and their electrochemical performance for lithium batteries
J. Electrochem. Soc.
Cited by (21)
Sandwich-like N-doped carbon coated SnNb<inf>2</inf>O<inf>6</inf> nanosheets for high-rate and long-life lithium storage
2024, Journal of Alloys and CompoundsUsed dye adsorbent derived N-doped magnetic carbon foam with enhanced electromagnetic wave absorption performance
2021, Journal of Alloys and CompoundsSelf-templating synthesis of carbon-encapsulated SnO<inf>2</inf> hollow spheres: A promising anode material for lithium-ion batteries
2020, Journal of Alloys and CompoundsCitation Excerpt :However, the large volume expansion of up to 359% after lithiation with Sn to form Sn5Li22 leads to a severe pulverization of the electrode [12], thus resulting in a loss of electric contact between the current collector and electrode. In addition, the large volume expansion may allow exposure to fresh surfaces of the electrode, thus causing continual consumption of electrolyte and formation of an unstable solid electrolyte interface (SEI) layer [11,13]. As a result, these materials inevitably undergo rapid capacity decay or poor cycling stability during discharge/charge cycles.
Solvothermal synthesis of graphene encapsulated selenium/carboxylated carbon nanotubes electrode for lithium–selenium battery
2019, Journal of Alloys and CompoundsCitation Excerpt :With the consumption of fossil fuels and the increasing environmental pollution, people urgently need to find a new type of clean, sustainable and environmentally friendly energy to replace the traditional energy sources [1,2]. Over the past 20 years, lithium-ion batteries (LIBs) have received a lot of attention, which has been widely used in people's daily lives [3–11]. However, commercial LIBs are not yet able to meet the high energy density and volumetric energy density requirements of hybrid electric vehicles.
Fabrication of SnO<inf>2</inf>/pyrolytic carbon nanosphere via methods of precursor atomization and combustion as a high reversibility anode for sodium storage
2019, Journal of Solid State ChemistryCitation Excerpt :Sodium is a natural abundant element and gives natural advantages in costs, so Na-ion batteries are considered as substitutes to Li-ion batteries, especially in the area of large-scale stationary energy storage [7]. Na-ion batteries present few fundamental difference with Li-ion batteries, however the commonly used graphitic materials always show poor electrochemical performance in sodium storage [9–11]. Because Na+ has a large ionic radii of 0.102 nm, which is about 55% larger than that of Li+, crystal lattices of graphitic materials are too small to accommodate Na+ [3,12,13].