Silicon Alloy Based Anodes for Lithium Ion Batteries

T.Thilagan

Teacher Mentors : Mdm Jane Lim, Prof. Venkateshamy Reddy

Introduction Aim
Lithium-ion (Li-ion) batteries are widely used in applications such as electric cars, new age In this project, SiOx based composites was used as it has the advantages of a long life cycle and also the
elctronics and pacemakers.(1,2) However with the recent there is a growing demand for Li-ion ability of absorbing and retaining large quanities of Li, which gives it a higher specific capacity
batteries with with high charge density and long cycle life. However, the development of Li-ion (2043mAhg-1) than lithium-graphite. However, it has a low initial Columbic effieciency of only 47.8%.
batteries is limited due to the low theoractical capacity of commercialized carbon anode materials This project aims to improve the Columbic effiency of the composite while retaining the advantages of
(372mAhg-1). Silicon is a candidate as an alternative anode material due to its large theoratical SiOx compounds. Hence, a new nanosized SiO2- Graphite composite was prepared using high energy
specific capacity ( up to 4.2mole of Li per mole Silicon ) as well as good potential for Lithium mechanical milling (HEMM), followed by pyrolysis for 5 hours. SiO2 was chosen as the source of Si.
insertion and extraction (3). But however, Si undergoes rapid volume expansion during charge- Graphite was added in the milling process to improve cyclic performance and better electric contact. The
discharge cycles (approximately 4 times than the initial size), which pulverizes and breaksdown the SiO2 served as a matrix to strongly bind Si during the cyclic process Moreover, a contamination of Al2O3
anode material. appeared in the XRD pattern, which buffers volume changes (14-16). The composite electrodes displayed
Methods a reversible capacity of more than 900mAhg-1 for nearly 60 cycles.
Step 3 : Prepunder aration of Anode Slurry
Step 5 : Loading of cells into Cyclic
Step 1 : HEMM of SiOx-C Alloy • The ball-milling was Step 4 : Fabrication of Lithium Batteries
• 2mg of silicon-graphite Voltammeter
carried out in a Planetary
mixture was weighed using an
Mono Mill P-5 (Fritsch,
electronic balance.
Germany) at a rotation rate
• The Mixture was grinded is a
of 350 rpm. (Fig.1)
mortar and was added Super-P
Carbon and Polyvinylidene
• The milled powder
fluoride.
consisiting of SiO and Si
undewent pyrolysis at
• Two drops of N-Methyl-2-
800°C vacuum for 5 h.
pyrrolidone solvent was added
to the resulting mixture. The
• Pure graphite powder was Fig.4 Synthesised anode materials Fig.6 Fabricated cells
resulting suspension was later
added into to composite
transferred to a small vial
while it went through • The anode materials were dried in a baking oven for 3
container. Fig.7 Loading of fabricated cells into cyclic voltammeter
Fig.1 Planetary Mono Mill P-5 pyrolosis. Fig.3 Mixture placed in magnetic shaker
hours. (Fig.4) Once dried, they were transferred to the
argon filled glove box, where they were fabricated. • Fabricate cells are next run into electrodes
• It was then left for 24 hours of
Step 2 : X-Ray Diffraction (Fig.6) of Cyclic voltammeter (study of the
mixing by a magnetic mixing
working electrode potential against time).
machine.(Fig.3) to obtain a
• Firstly the plate cell was placed. In it, the anode material
homogeneously mixed slurry.
• The sample was was fixated. Following the addition of 2 drops of the • Two of the cells were loaded into the
characterized by X- liquid LiPF6. electrodes, which were run for 60 cycles
• The slurry mixture was brushed
ray diffraction (XRD, of charge and discharge.
and spread evenly, in a
Thermofisher- • Next the polymer porous separator was placed, followed
rectangular shape on copper
Scietific) to identify again by the addition of two drops of the liquid • Each cycle lasts for 12 hours. Hence, the
foils.
the physical phases electrolyte. Then, the Lithium metal was placed. The cell cyclic voltammetry does measure full
formed. (Fig.2) was then capped and then transferred to a presser, working capacity(electrode capacity) of
• Next, it was placed in a baking
which sealed the cell system completely. the cell synthesized. (Fig.7)
kiln at 70°C for 24 hours.
(Fig.4).The copper foil was
Fig.2 X-Ray Diffractor, Thermofisher Scientific recovered, and was conferred
to the next section.
Fig.4 Anode slurry baked in baking kiln C) Cyclic voltammograms

Results
A) SEM Morphology
B) X-Ray Diffraction(XRD) Pattern of SiOx composite

Fig. 9 XRD Patterns of SiO2 milled for 5h

Fig. 8(a) and 8(b) SEM Images of milled SiOx composites before loading into cyclic voltammogram and after cyclic
• Fig.9 showed the XRD patterns of the composite during
votammagram respectively. different prepartion steps as well as the SiO and the C
• It was observed that the composite powder consisted of clusters with size dozens powder. As seen from the pattern above, when SiO2 and Fig 10 Cyclic Voltammograms in the potential window fro 0 to 1.5V of (a) the comparison of the 1st cycle among the prepared composite
of hundreds of nanometers. Graphite was milled for 5 hours, the peak of elemental Si, electrodes (a) while (b) is the compasrion of the 1st cycle among the composite elctrode, SiO elctrode and Si elcetrode at the scan rate of
0.05mVs-1: (c) corresponds to the 1st to 10th cycles at 0.05mVs-1 while (d) is th comparison among the 1st to the 20th cyles at thier respective
• Due to the addidtion of 15wt.% of graphite to the milled powder, the O was observed, implying the decomposition of SiO2 speeds.
agglomeration of the particles was alleviated and the partcile size was more occured in the HEMM process. The reactions are : • As seen the cyclic voltammogram of the composite electrode, was different from those of Si and
uniform which can be credited to the dispersion and lubrication provided by a) 2SiO = Si + SiO2 SiO electrodes. During the first reduction scanning process, as in Fig. 10(a), the composite
graphite. b) SiO2 + C = SiO2-C electrode experienced a weak and broad peak in the range of 0.6V to 0.9V (circled region) which
• The morphology of the agglomerates became flat in Fig.8(a), while in Fig 8.(b), it • As an impurity 0.6w.t% of Al2 O3 was also detected. This corresponds to the formation of a solid electrolyte interphase (SEI) film on the surface of the active
was evenly distributed. This difference is due to to decomposition of SiO2 and the might provide an effective matrix which could slow down particles (12), and a weak peak in the range of 0.45V-0.25V, which correspongs to the formation of
further recombinition of the SiO2-C alloys during the charge-discharge cycles. the Si expansion. Li12Si7(3). The sharp reduction peak from 0.2V to 0V, and for pure Si electrode there were two
• There was no Si-C phase observed in the XRD patterns sharp reduction peaks at about 0.1V and 0V.
• The capacity loss resulted from the formation of SEI could be negligible in the pure SI and SIO
D) Cyclic Performance electrode, due to the existence of the SIO layer which hindered decomposition of the
• Fig.11(a) showed the discharge-charge curves of the composite electrode electrolyte.(13)
and the pure SiO electrode in the voltage range of 0.02-1.25V at the current • Overall, the cylic volatammogram of the somposite elctrode was very similar to that of the pure Si
density of 0.1 mAcm-2. The first cycle with the discahrgin process, elctrode.
coressponding to the Li insertation into the elctrodes. From the figure there • In the subsequent cycles followed, as shown in Fig. 10(b), the oxidation peaks were almost the
is a little difference on the discharge platforms between the composite same as the first scan, while the reduction peaks were different. Particularly, a new reduction peak
elctrode and the SiO electrode, which coincident with the cyclic occured at about 0.2V which corresponds to Li insertation into Si.
voltammograms. For the SiO electode, the first discharge and charge • The current of the redox reactions increased with cycling, implying a possible activation process
capacity were 2228.7 and 1183.5mAhg-1, witha columbic effeciency of 53%. during the insertation/extraction process(8,18). While in the susequent 6th to 10th cycles (shown
For the composite elctrode, the first discharge amd charge capacity were in Fig.10(c), the redox overlapped together.
1450.3 and 956.4mAhg-1 respectively. The columbic effeciency for the • When the scanning rate from 0.08 and 1.0mVs-1 (Fig.10(d)), the positions of the redox peaks were
composite electrode was 66%, which was much higher than that of SiO almost the same as those occred at 0.95mVs-1, which demonstrated that the nano structures of the
electrode. composite electrode became steady after the initial cycles.
• Fig. 11(b) showed the cyclic performance of the composite electrode and
the pure SiO electrode. From the figure, the cycling performance was much
better than that of pure SiO electrode. For the SiO electrode the cycling
performance was very poor, as after 25 cyles, its reversible capcity was lost
more than 50%. While the electrode revelaed a rechargeable capacity above
Conclusion
900mAhg-1, for nearly 60 cyles its reversible capacity retention was more
than 95%.
A new type of nanosized SiO composite was prepared using high energy
• The reason for the improved cycling could be as because of
- the uniform distribution of the active particles in the inactive matrix and mechanical milling and pyrolysis. The composite powders consisted of Si, Si-O, C.
the reduced particle size by the HEMM, which increased the mechanical The formation of the inactive SiO2 and SiO–C alloy phases could accommodate the
stability of the composite electrode(8,10) large volume cle capacity of above 900 mAh g-1 for nearly 60 cycles, with a
- the formation of SiO2 and the SiO-C alloy phases, as well as the graphite
added which act as dispersing agents and buffering matrixes which help to
capacity retention ratio of more than 95%. Although the agglomeration of the
maintain the cycling of the electrodes(8,10). Moreover with Al2O3 impurity and composite during the HEMM process and the first efficiency remains to be
graphite introduction, there was limited vlume expansion, and better electric improved, the SiO-C composite could be a promising candidate as anode material
contact during cycling. for lithium ion batteries.
Fig.11(a) The discharge and charge curves of the composite elctrode and pure SiO electrode
while Fig11.(b) is the cyclic performance of the composite elctrode and the pure SiO electrode

[6] Synthesis of uniform TiO 2@ carbon composite nanofibers as anode for lithium ion batteries with enhanced electrochemical performance [12] Y.Liu K.Hanai, J.Nang, N.Imanishi, Electrochem,Solid State Kett.7 (2005) A369
References
Z Yang, G Du, Q Meng, Z Guo, X Yu, Z Chen, T Guo, R Zen
[1]The Infuence of the Graphite Structure on the Electrochemical Characteristics for the Anode of Secondary Lithium
(7] High-performance lithium-ion anodes using a hierarchical bottom-up approach A. Magasinki1 , P. Dixon1 , B. Hertzberg1 , A. Kvit2 , J. Ayala3
Batteries
and G. Yushin1
[2]Confining sulfur in double‐shelled hollow carbon spheres for lithium–sulfur batteries
http://www.nano-tech.gatech.edu/nmat2725_Nature_Materials_YUSHIN_March14T. Tran, J. Feikert, X. Song, K. Kinoshita, J. Electrochem. Soc.
C Zhang, HB Wu, C Yuan, Z Guo, XWD Lou
142 (1995) 3297.
[3]Superior stability and high capacity of restacked molybdenum disulfide as anode material for lithium ion batteries
https://link.springer.com/article/10.1007/BF00243741
G Du, Z Guo, S Wang, R Zeng, Z Chen, H Liu
hen, H Liu
http://aip.scitation.org/doi/10.1063/1.1989431.pdf
http://aip.scitation.org/doi/10.1063/1.1989431.pdf
[4]Highly Reversible Lithium Storage in Spheroidal Carbon‐Coated Silicon Nanocomposites as Anodes for Lithium‐Ion
[9] TRecent Progress in Synthesis and Application of Low-Dimensional Silicon Based Anode Material for Lithium Ion Battery
Batteries
[10]JH. Kim, H.J. Sohn, H. Kim, G. Jeong, W. Choi, J. Power Sources 170 (2007) 456.
Z.P. Guo, J.Z. Wang, H.K. Liu, S.X. Dou, J. Power Sources 146 (2005) 448.
https://energy.gov/sites/prod/files/2016/06/f32/es262_kostecki_2016_o_web.pdf
http://onlinelibrary.wiley.com/doi/10.1002/anie.200601676/full
[11] Lithium Insertion in SiAg Powders Produced by Mechanical Alloying
[5]Single wall carbon nanotube paper as anode for lithium-ion battery
X.X. Yuan, Y.J. Chao, Z.F. Ma, X.Y. Deng, Electrochem. Commun. 9 (2007) 2591.
T. Moritaz, N. Takami, J. Electrochem. Soc. 153 (2) (2006) A425.
http://citeseerx.ist.psu.edu/viewdoc/download?doi=10.1.1.855.5436&rep=rep1&type=pdf