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Making a lithium-ion battery with nanostructured silicon as an anode

material – advantages, problems and perspectives

Conference Paper · March 2014

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 08-P3-04 Making a lithium-ion battery with nanostructured silicon as
an anode material – advantages, problems and perspectives
EUGENIA MATVEEVA
EM-Silicon Nano-Technologies, S.L.; 46010, Valencia, Spain;
eumat@em-silicon.com; Tel: (34) 673 825 063
SUMMARY
Based on the latest scientific publications on the nanostructured silicon materials for Li-ion batteries we review in a present report the entire
structure of the device called the electrical battery and illustrate the role of the nanostructured materials in a full system. We bring attention to the
intrinsic problems of the reversible, stable and durable functioning of such a system that could lay in many components of the device including the
binder and the electrolyte used, as well as in its overall design. Comparison of a battery with a fuel cell makes feasible putting forward a battery
design similar to that used in cells with the Electrodes Membrane Assembly. We proposed, describe and discuss this new design attempted to
release the accumulated stresses and to prevent the capacity fading problems.

LOAD/ INTRODUCTION Battery, Fuel cell,

POWER SOURCE
Closed system Open system
Energy storage within electrical battery is based on usage

ANODE CATHODE of two half cells (anode and cathode) with different
electrochemical potentials. Those potentials are formed by
Ion-conductive membrane

the electrochemical processes (RedOx reactions) between

Red I – e = Product I
Electrolyte with RedOx I
Electrons pass through metal-like conductors
Cations pass through an ion-conductive membrane
Anions pass through an ion-conductive membrane
At the ANODE (Li-ion reduction to Li atom):
At the CATHODE (Li atom oxidation to Li-ion):
• Materials used for both, the anode and the cathode, allow intercalation/de-
intercalation of Li-ions/Li-atoms into their lattices and thus trap them in reversibly.
• The electrolyte where the electrodes are immersed is in fact a simple Li-ion pool
that assures a separation of electrons and ions movements in the designed spacial
arrangement.
Actually, silicon is considered as the most promising anode material as it can be
lithiated up to Li4.4Si composition. Its well-recognized drawback is a huge volume
expansion under lithiation and consequent mechanical instability that lead to:
• a pulverization,
• lost of electrical contact to the current collector and
• a fast capacity fade under cycling.
The nano-structuring of silicon, similarly to what has been proposed for bulk
carbon anode, actual Li-battery anode material, helps solving a problem. Although in
the actual literature there is still no consensus about the size of individual Si nano-
structures that would afford mechanical stresses under lithiation, the values form 50
to 350 nm have been proposed based in different original experimental works.
Nano-structuring of Si material further implies various important issues in the design
of the anode as well as of the entire battery. Among them are the two interfaces
that have to assure the two different electrical pathways in the battery, ionic
and electronic, between the anode and:
1. the current collector and
2. the Li+-ion containing electrolyte.
Consequently, the entire design of the battery should be re-considered.
Solid-Electrolyte Interface/
Ionic contact to nano-structured electrode:
This electrical path is obviously needed for the correct functioning of the battery. It
extends over the electrolyte (that could be made of an ionic conductive membrane),
Ox II + e = Product II the components presented in/on the electrodes and in the
Current collector,
surrounding electrolytes. Both half-cells are put together in
Composite anode,
a way that the two electrical passes are formed, electronic
and ionic, spatially separated one from another. In this way Composite cathode,
Electrolyte with RedOx II
electrons needed for electrochemical RedOx reactions are
Porous separator
moved through the electronic conductors (electrodes,
Membrane/ electrodes assembly
collectors and external wiring, electronic pathway) while
ions consumed in the same processes are moved through Design of the Battery with the Membrane/Electrodes
Assembly
the electrolyte or the ion-conductive membrane (ionic
Li+ + e = Li (1)
Li = Li+ + e (2) pathway). The last must also physically separate the two In contrast to the general design of the battery, the fuel cell uses an inverse design
baths to avoid shortcuts. where the most important part is the MEA, Membrane/ Electrode
Assembly, Figure below, for clarity a symmetrical cathode side is shown, too.
Current collector/
MEA consists of the ionically conductive membrane (this is the only electrolyte in the
Electronic contact to nano-structured electrode: system) and the two current collectors (catalysts) attached to the opposite sides of
The most evident solution in this case is using the fine powder of metal
the membrane..The current collectors are porous and permit an inert solvent to
or carbon and mixing both components together in a composite equilibrate the membrane maintaining in this way its high conductivity. Membrane is
electrode. In this case the continuity of the net electrical path in a in its Li+-ion form and assures a movement of the Li-ions ions through it; no other
final electrode material is good but not completely assured. Recovering ions are moved as the counter-ions are on the polymer chains and thus a Li+-ion
each particulate of the active electrode material by a thin continuous transference number in the membrane is practically one. An anode material is
layer of carbon can improve it drastically. Various ideas have been prepared as from active silicon particles, carbon and inert solvent, and then dried to
proposed: a direct carbon vacuum deposition, a polymer deposition compact the composite material from slurry to solid; finally it is porous as well. The
from solution with subsequent thermal carbonization or in-situ entire assembly is immersed into an inert solvent that does not contain any salts and
polymerization of conducting polymers on the surface of the active thus is dielectric.
material. In any case all these methods can assure only the continuity
of the electronic pathway in the nanostructured electrode.
Continuous carbon layer not permeable to electrolyte
b
Conductive
Carbon particles
Silicon particulates:
a) compact;
a b) porous with a mean
pore size lesser that a
thickness of the carbon
layer;
c) hollow

and ends on the anode/ and cathode/ electrolyte interfaces, Solid Electrolyte Discontinuous carbon layer permeable to electrolyte

Interfaces, SEIs. The charge transfer process is realized here, determines the
electrochemical kinetics and thus all the electrical parameters of a battery.
In case of the Si anode (for Li-ion batteries) it is not a solely electron transfer from
the electrode to Li+ -ion in solution, eq. (1) above. A deposited Li metal must be
CONCLUSIONS
dissolved in the Si electrode thus forming a phase different from that of the initial
material. The general terminology used in a battery-related field is The next topics that are of great
interest for the further progresses in
intercalation/de-intercalation (of Li), which brings much more attention to
the Li-ion batteries with the
the diffusion like process of penetration of Li-atoms into the anode material than to a nanostructured Si anode:
true electrochemical one, the electron transfer at the SEI.
In case of composite electrodes, carbon and silicon are both conductive, so the
1.techniques for the scalable
two possibilities for a charge transfer reaction can exist, one at the carbon interface production of silicon
and another at the silicon interface. The rates for these two processes will determine nanostructured materials;
the most probable Li+-ion reduction route and also, indicate a space where the SEI
2.surface chemistry control in
those materials over the all
will be preferrently formed and grown.
fabrication processes;
The SEI formation concept 3.usage the Li-ion exchange
membranes and development
the techniques for its processing
actively presented in most publications is still is very poorly developed. A number of in non-water solvents to impart
recent works suggested that it contains the two sandwiched parts and its a sufficient conductivity;
4.techniques for covering the
chemical composition includes all the components of the system: from the nanostructures with these
very surface layer of the electrodes themselves, the electrolyte and even any ionomers;
additives used in the fabrication process. More theoretical considerations lead to a 5.new designs of the whole
battery
hypothesis that the denser SEI part formed closer to the electrode surface is
permeable only for the Li+-ions which moved there through it a Grotthuss-like
hopping mechanism. Only a naked Li+-ion (without any solvation sheath) can accept New insight into SEI: (a) the possible conduction mechanism of Li+ across the SEI, (b) dynamic
equilibrium of interface between growth and dissolution.
the electron, be thus reduced to an atom and then intercalated into the solid Si
(reproduced from: K. Xu and A. Cresce (J. Mater.Res. 27, 18, 2327-2341, 2012, Li+-solvation/
electrode. The outer SEI part closer to the electrolyte is the place where the desolvation dictates interphasial process on graphitic anode in Li ion cells), Fig.5 in a review)
desolvation of the Li+-ions occurs. Therefore, the denser SEI layer
performs as an ion exchange membrane.

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