GRAPHENE-CAGED SILICON-LITHIUM-ION BATTERIES

 IN    SMARTPHONES
                                           
V.Jameer Vajith, EEE Third year
                   
     
                                                                                                        
 
  ABSTRACT : 
                  
  More efficient smartphone batteries can be made by just replacing the graphite anode of the
ordinary Li-ion battery with silicon.Nanostructuring has been shown to be fruitful in addressing
the problems of high capacity Silicon anodes like unavoidable partial fracture during
electrochemical cycling.However, issues with the high cost and poor Coulombic efficiencies of
nano structured Silicon still need to be resolved. Si micro particles are a low cost alternative but
the above problems occur,thus making stable cycling in a real battery impractical.Here, I
introduce a method to encapsulate Si micro particles ( 1-3µm )using conformally synthesized
case of multilayered graphene.Thegraphene cage acts as a mechanically strong and flexible
buffer during deep galvanostaticcycling,allowing the Si micro particles to expand and contract
within the cage while retaining electrical conductivity on both the particle and electrode
level.Furthermore,the chemically inert graphene cage forms a stable Solid Electrolyte Interphase
( SEI ) minimizing irreversible consumption of Lithium ions and rapidly increasing the
Coulombic efficiency in the early cycles.Therefore,stable cycling and ninety percent capacity
retention is possible in 100 cycles with graphene caged Si-Li-on batteries.
 
 
 
KEYWORDS :
                            
                            Silicon-Lithium-ion batteries, Graphene, Silicon anode
 
 
 
INTRODUCTION :
           
 When phones are getting smart,why not batteries ? The processor we are currently using is 100
times better than that of a decade ago.But batteries are only 10 times better. The present day
batteries take too much time to get charged but easily get discharged. This is due to the
incapability of Lithium-ion battery in the feature vs. run-time
battle.largerscreens,Higherresolutions,GPSradios,Number of apps consume charge rapidly and
the latest issue added to this is 4G phones. High-end 4G phones search for the next-generation
signals which are scarce.So, we are in the need of a high efficient battery with better charge and
discharge cycles.Presentday ,Li-ion batteries have been widely used in portable electronic
devices such as phones,laptops,etc. The energy density and performance of Li-ion batteries
largelydepend on the physical and chemical properties of anode materials.Typically both
electrodes in a Li-on battery are intercalation compounds, which as their name implies, store Li+
by inserting them into their crystal structure in a topotactic manner. The theoretical specific
capacity of graphite is 372 mAh ( by forming intercalation compound Li ). Graphite is the
commercial anode material widely used for li batteries because of its high Coulombic
efficiencies and better cycle performances.Therfore the anode used in the ordinary Li-ion
batteries is based on graphite carbon, which stores upto 1 Li+ for every 6 C atoms between its
graphite layers.
   Due to the capacity limit of graphite, energy density of Li-ion battery can’t satisfy the
requirements of modern day smartphones. Traditional intercalation type graphite materials show
Li storage capacity (372 mAh , Li) due to limited Li ion storage sites within a  hexagonal carbon
structure. To meet the increasing demand for batteries of high energy densities, much effort has
been made to explore new anode materials.
 
HIGH CAPACITY SILICON ANODES :
                                  
                                Silicon has been considered as one of the most promising anode material
alternates for next-generation Li-on batteries because of its high gravimetric capacity and
volumetric capacity ( 2400mAh).Importantly,it is also cheap and environmentally benign.  
Silicon is the second most abundant metal on earth. A crystalline silicon anode has a theoretical
specific capacity of 4200 mAh, more than 10 times that of graphite anode (372 mAh) . replacing
the graphite in a cell with silicon means that we can use less anode material and fill up that extra
space with more cathode material effectively increasing the overall energy that is contained
within the same volume.This is due to the fundamental difference in the way that silicon stores
Lithium.The layered graphite structure absorbs the Li ions through  a process called
intercalation. Silicon, on the other hand, can absorb more lithium ions , because the two
materials form an alloy with theoretical specific capacity much higher than that of graphite.Each
Si atom can bind upto 4.4 Li atoms in its fully lithiated state, Si , compared to the 1 Lithium
atom per 6 carbon atoms for the fully lithiatedlithiated state of graphite  .
 For years,scientists have been trying ot use silicon to produce a lithium-ion battery anode
capable of storing 10 times more energy  than the existing commercial graphite anodes and
making smaller and lighter batteries with superior performance.[1]
 
 SILICON-LITHIUM-ION BATTERIES :
 
 
                                                        Si-Li-on batteries are an extension of widely used Li-ion
batteries. The discharging potential is about 0.2 V with respect to Li/Li+ which is lower than
most of other alloy type and metal oxide anodes.Furthermore,it is safer and stabler than graphite
9 lithiated Si is more stable in typical electrolytes than lithiatedgraphite.Almost every LIB in
existence today consists of a graphite electrode , an electrolyte ( usually a lithium salt ) and a
metal oxide electrode (usually an oxide containing Li ).when you charge a LIB, the graphite
anode sucks up Li+,when you discharge a LIB, a chemical reaction causes the ions to flow out of
the graphite to the cathode, creating electricity.Nevertheless , these batteries suffer from sever
capacity fading resulting from their low intrinsic electrical conductivity and great volume
variation during lithiation or delithiationprocess.The problem is Si anode absorbs so many Li
ions leading to the structural change of anode.For example, if a particle of Si absorbs as much as
Li as thermodynamically possible.Its volume increases by about 300 % that compares to about
7% expansion observed in the intercalation of lithium into graphite. The volume variation can
result in the fracture and pulverization of Si particles which leads to the electrical isolation of Si
fragments from nearest neighbours and eventually a loss in electrical contact between the
electrode materials, then finally leading rapid capacity fading during further cycling [2]. For this
reason , Si-Li-on battery loses all its potential in just 10 charge-discharge cycles which is
typically short.
  
The second major issue is with the formation of Solid Electrolyte Interphase ( SEI ) layer
between the silicon and the liquid electrolyte. SEI layer is essential for the stability of the
battery.The electrolyte reacts vigorously with the anode during the initial formation change.A
thin passivative SEI layer builds up moderating the charge rate and restricting current. This
interphase prevents further decompostion of the electrolyte after the second charge.The SEI layer
is formed during battery discharging due to electrolyte decomposition on the surface of anode at
low potential.But in Si-Li-on batteries, during delithiation, since the Si particle shrinks,the SEI
layer breaks down into separate pieces and fresh Si  surface is exposed to the electrolyte. In later
cycles , new SEI layer continues to be formed on the newly exposed Si surfaces [3]. The SEI is
an electronic insulator but also a Li-on conductor, so the growth of the SEI layer eventually
terminated at a certain thickness. The thick SEI layer is harmful for the cycle life because it can
cause a rise of the electrode impedance / polarization and decrease of the electrode’s
electrochemical reactivity.As discussed above, a large volume change and unstable formation of
SEI filling are the main issues for the failures of Si anodes.
 
OVERCOMING THE DISADVANTAGES BY ‘CAGING’ GRAPHENE :
 
 
                                                          The solution for this serious problem is very simple.Just
encase each Si particle in a custom fit cage of graphene , the ‘wonder material’.
 Graphene is an allotrope of carbon in the form of a 2-dimensional atomic scale and honey-comb
lattice.It is only one atom thick.Even invisible to our naked eyes.Graphene has many
extraordinary properties.It is about 100 times stronger than the strongest steel , with thickness of
incredible 3.35Å.Its specific surface area is 2630 /g,similar to activated carbon ( Surface area of
1g of activated carbon equals the SA of a tennis court ). It is the lightest material of all ( 1 weighs
around only 0.77mg). This material has ultra high electrical conductivity and thermal
conductivity. This is the hardest material known ( harder than diamond ). It is the world’s
thinnest material which is million times thinner than paper. It is chemically
inert.Graphenesurprisingly , is different from the laws of nature. Nature has prevented the
formation of 2D crystal because it eventually gives rise to 3D crystal. But,graphene is the first
2D crystal that was isolated. The naturally opposing characters ductility and brittleness comes
together in graphenebecause it is more flexible than rubber and at the same time, it has a tensile
stiffness of 150,000,000 psi. The world’s best material graphene adds onto
another speciality.i.e.It is super cheap.Graphene is nothing but the top layer of graphite ( the stuff
used in pencils ). But the method to isolate 2D crystal was unknown till 2004when two scientists
isolated it.A material with such properties finds applications in almost every fields.

DISCUSSION AND METHODS :

 
 
                                                                 Scientists of Stanford university have made a battery
breakthrough that could boost the performance of Si-Li-on batteries. The researchers managed to
remove two long-standing barriers to these improvements by putting Si particles in
graphenecages.The carbon cages would allow the Si to expand and even break apart but keep the
pieces apart together so that they can continue to function.Thegraphene barriers would also block
the destructive chemical reactions with the electrolyte from occurring.Cui’s team first attempted
a similar using expensive nanoparticles and different coatings but they were not able to achieve a
high level of efficiency.Because nanoparticles are impractical for commercial uses and other
coating reduced the efficiency of Silicon.[4].This method makes use of much larger Si particles
that are 1-3 microns, or millionths of a meter in diameter, which are cheap and widely
available.These particles are the waste created by silicon ingots to make semiconductor
chips.They are like bits of sawdust of all shapes and sizes.Particles this big have never performed
well in battery anodes,so this is a very exciting achievement and a practical solution for the
problem. Getting a form fitting coat of grapheme on each Si particle is a bit of process.It can be
summarized in three steps[5].The first step is to coat the Si microparticles with Ni of thickness 2-
5 µm.Th second step is layers of grapheme are grown on top of this.Happily the nickel acts as a
catalyst to promote graphenegrowth.Thirdstepis to etch the nicel away with hydrofluoric acid ,
leaving enough of void within the cage for the silicon particle to expand.Graphene is the first
coating or the only coating that maintains high efficieny and the reactions can be carried out at
relatively low temperatures.
RESULTS :

The above method produces a very good result.The Si-Li-on battery produces double or triple
amount of energy capacity than the ordinary Li-on battery.The specific energy is 1550 Wh/kg
which is very much higher than 100-265 wh/kg of LIBs.It produces 10 times more energy.Si
anode can hold a charge of 4000 milliamphours per gram which is muc higher than 372
mAh/g.Si-Li-on battery increases energy density of LIBs by 40-60%.In short , Si-Li-on battery
caged with graphene has 63% higher capacity and 40%less in weight when compared wit LIBs.

CONCLUSION :

With Graphene-caged Si-Li-on battery , we can see our batteries become full from 0to 100%
within 15 minutes. And can use our battery for long 2 days without charging often.This be a
solution to the present problem of smartphone batteries.We can live with super-thin batteries for
our super-slim mobiles.With large volume and energy density , all these are possible.With high
capacity retention,we can really move into the smartphone world.Moreover , this method is a
cheapest method to produce the most efficient battery as it involves the Silicon wastes for the
production of anode.
REFERENCES :

1.Ren, J.et al.Silicon-graphene composite anodes for high-energy lithium batteries.Energy

Technol.1,77-84 ( 2013 )

2.Obrovac , M.N. &Cristensen , L. Structural changes in silicon anodes during lithium insertion /
extraction.Electrochem.Solid-State Lett. 7, A93-A96 ( 2004 )

3.Xiao , J.et al. Stabilization of silicon anode for Li-on batteries. J.Electrochem.soc.157,A1047-
A1051 ( 2010 )

4.Lu,Z.etal.Nonfilling carbon coating of porous silicon micrometer-sized particles for high-

performance lithium battery anodes.ACS Nano 9, 2540-2547 (2015)

5.Yuzhang Li,Kai Yan, Yi Cui ,Growth of conformal graphene cages on micrometer-sized

silicon particles as stable battery anodes , Nature Energy 1, A15029 ( 2016 )