Composites of tin oxide and different carbonaceous materials as negative electrodes in lithium-ion batteries
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Tin and tin oxide have been considered as suitable materials with a high theoretical capacity for lithium ion batteries. Their low cost, high safety, and other technical benefits placed them as promising replacements for graphite negative electrodes. The problem to overcome with tin oxide, as well as with other metallic materials, is high volume changes during alloying/dealloying, subsequent pulverization, delamination from current collectors following continuous degradation of the anode. To solve these issues, different approaches have been applied. A number of various architectures from nanostructures to core-shell, porous, anchored, and encapsulated have been studied to improve cycling performance. Much attention was paid to incorporate carbonaceous materials. Here, summarized results regarding utilization of the tin oxide-carbonaceous negative electrode material are presented.
KeywordsTin oxide Carbonaceous materials Lithium ion batteries
In 1991, Sony commercialized the first lithium-ion battery. Since that time during the next two decades, electronic devices have been rapidly developed. Nowadays, small portable electronic devices, that is, cellular phones, notebook computers, and cameras, are in common usage. This leads to increased demand for energy storage systems. Lithium-ion batteries can offer relatively high energy density, light design, long lifespan, and low environmental impact in comparison with other battery systems such as nickel-cadmium (NiCd), nickel-metal hydride (NiMH). A battery consists of negative (anode) and positive (cathode) electrodes separated with a solid or liquid electrolyte containing lithium ions. External connection of the electrodes causes a chemical reaction occurring at both electrodes and forces electron movement from the anode to cathode. At the same time, lithium ions migrate through the electrolyte. The obtained current flow can be utilized by the user. Thus, electrodes are key battery components to obtain high energy/high power densities and better cycling stability and Coulombic efficiency .
Examples of synthesis of nanosized-SnO2 material
SnCl4, NaOH, H2O
200 ∘C, 1h, autoclave
SnCl2 ⋅H2O, NaOH, H2O
800 ∘C in air, 8h, furnace
K2SnO3, C6H12O6, H2O
180 ∘C, 4h, autoclave
Vapor-Liquid-Solid (VLS) method
600 ∘C under O2 flow
PVP, SnCl4 ⋅5H2O, C2H5OH
Voltage of 20 kV
SnCl2 ⋅2H2O, C3H6O, H2O, NaOH
180 ∘C, 15h, autoclave
Carbon is known not to react with tin and does not form tin carbide . It is very crucial in terms of utilizing carbon as a buffer in preventing electric contact loss of the tin negative electrode with the current collector . The carbon phase, as a good electronic conductor, is known to improve electrical contact between the active material and the current collector . This review is focused on the modification of tin oxide-carbon negative electrode materials in lithium-ion batteries. I wanted to show the strategies used to improve battery performance by incorporation of tin oxide into the carbonaceous matrix as a negative electrode in energy storage and energy conversion applications.
SnO2 - based negative electrode materials modified with a carbonaceous matrix
The Li2O layer was supposed to act a stabilizing barrier against Sn agglomeration.
Read et al. showed the possibility to use hard carbons as a diluent to embed metal oxides into the carbon matrix . The tin oxide particles were trapped and separated by carbon. This method allowed to obtain a material with the specific capacity of 480 mAh g− 1 after the first cycle with capacity retention of 83% for the 40th cycle. The authors claimed that a significant part of the total capacity of the electrode material origins from the hard carbon part. The final conclusion was that to minimize capacity fade, one should perform additional studies in different configurations, i.e., variations in the SnO2 to carbon ratio, the origin of carbon precursor, the particle size of the tin oxide, and the heat treatment procedure .
Electrode materials consisting of carbon and tin-tin oxide parts showed capacity values of 435 mAh g− 1 for the 30th cycle at C/2 — rate with coulombic efficiency equal to 98% . The result evidences that modification of tin oxide nanoparticles improves electrochemical properties of the Sn/SnO2-based electrode in terms of cycling performances. However, the problem with high irreversible capacity loss for the first cycle (50%) may limit practical application of such electrode.
Recently, it was shown that graphene might be an excellent substrate for tin oxide nanoparticles . Graphene is known to exhibit high electric conductivity and good mechanical flexibility and may diminish the volume changes of metal oxides . Moreover, graphene is able to accommodate large amounts of lithium ions . Chen et al.D mixed 3-nm SnO2 nanoparticles with graphene at a weight ratio close to 1:1. The synergic effect of SnO2/graphene was achieved, showing superior cycling performance with a very high rate performance equal to 574 mAh g− 1 at a current density of 10 A g− 1. Such results were obtainable due to the presence of ultra-small sizes of tin(IV) dioxide able to reversibly react with lithium ions to form an alloy, and were able to accommodate volume changes during the battery test. Additionally, the presence of the graphene phase was utilized as a material able to enhance electric conductivity and lithium diffusion. These phenomena were achieved due to reducing the size of SnO2 nanoparticles and a shortened diffusion length within the particles and the graphene network. The authors claimed that the increase of capacity was also attributed to formation of a polymeric gel-like film at low potentials due to electrolyte decomposition , as well as simple lithium ion insertion/extraction on the graphene surface . However, it seems that this polymeric gel-like film acted rather as a solid electrolyte interphase (SEI) which is known to affect performance of lithium ion cells in terms of its storage and cycling . The ideal SEI film is expected to be thin, permeable for lithium ions and blocking for electrons. In general, the SEI layer influences initial capacity loss, battery cycle life, rate capability, and safety . As a protective layer, SEI itself does not enhance nor diminish the capacity of the lithium ion cell. Carbon nanotubes (CNTs), similarly like graphene, exhibit high electrical conductivity. Their tubular structure and flexible matrix are widely used in lithium-ion battery applications [68, 69]. Particularly, filling the inner surface of nanotubes with tin oxide is an advantage . In such situations, the carbonaceous matrix acts as a buffer for large volume expansion of Sn during the lithium ion insertion/extraction process. The presence of CNTs improved the conductivity of the material due to the presence of electronic conductive channels, and although volume expansion was still observed, it did not lead to pulverization .
The practical specific capacity of a graphite electrode of 350 mAh g− 1 is not attractive anymore for next-generation lithium-ion batteries. All tin oxide-based materials shown in this paper exhibited capacities higher than 430 mAh g− 1, and all those materials included usage of the carbonaceous matrix. This shows that the low cost and environmental benignity make tin oxides able to replace graphite anodes. The presence of the carbon phase is crucial for improved cycling performance of negative electrodes. The results showed that the major problem with huge volume changes of the tin oxide electrode may be successfully overcome by utilization of the carbonaceous matrix as a stress-accommodating phase, coupled with reducing the size of tin oxide particles. One should take into account that although the size of tin oxide-based electrode material can be reduced, it still itself undergoes volume changes. This one issue can not be overcome. Carbon is necessary to keep electric contact between tin and the current collector during alloying and dealloying of Sn. Although the engineering requirements and expectations regarding the capacity level were met, there are still two main problems to be solved: (1) transferring material preparation from the laboratory scale into the industrial scale. It is obvious that materials which are complicated to produce from the industrial point of view might not be attractive to manufacture. (2) reversibility and cycle stability need to be improved. The capacity retention in all cases was much lower than 80%. It is very low taking into account that in most cases, the number of cycles did not exceed the value of 100. Nowadays, the end of battery life is the point at which 80% of the initial capacity is reached. Thus, in a practically applied battery, a much lower capacity fade is required. Hence, the application of high capacity and high cyclability tin oxide-carbonaceous-based materials manufactured by a cost-effective, industrial-scalable process is the key parameter for usage of such materials in next-generation lithium-ion batteries.
This work was supported by the Polish Ministry of Science and Higher Education (DS no. 032406).
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