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All-solid-state batteries: An overview for bio applications

Conference Paper · February 2013

DOI: 10.1109/ENBENG.2013.6518400

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 All-solid-state batteries:
an overview for bio applications
R. Sousa J.F. Ribeiro
Algoritmi Centre: Industrial Electronics Department Algoritmi Centre: Industrial Electronics Department
University of Minho University of Minho
Guimarães, Portugal Guimarães, Portugal
[email protected] [email protected]

J.A. Sousa L.M. Goncalves

Industrial Electronics Department Algoritmi Centre: Industrial Electronics Department
University of Minho University of Minho
Guimarães, Portugal Guimarães, Portugal
[email protected] [email protected]

J.H. Correia
Algoritmi Centre: Industrial Electronics Department
University of Minho
Guimarães, Portugal
[email protected]

Abstract — Batteries are crucial for most of bio applications.

Batteries based on a liquid or polymer electrolyte needs a weight
protective packaging which decreases their energy density and
increases their size. This paper aims to identify, on the one hand,
the efforts performed in thin-film batteries until now, and on the
other hand, to provide an overview about the future perspectives
in integration of batteries with flexible electronic circuits and
energy harvesting systems. The overview highlights the need for
an on-going investigation that aims to replace metallic lithium
anode of batteries through different approaches. Other materials,
namely silicon or germanium, seem promising when combined
with nanostructures. Three dimensional and integrated batteries
will increase its volumetric capacity.

Keywords — all-solid-state batteries; bio applications; integration,

overview.

I. INTRODUCTION
Figure 1: Battery capacity for different technologies [2].
Nowadays, the diversity of electronic autonomous and
portable devices requires on board energy. Batteries convert
chemical energy into electric energy, which increases the Conventional lithium-ion batteries use a liquid electrolyte
volumetric energy density, when compared with capacitors. and polymer lithium batteries use a polymer-based electrolyte.
Many of these devices rely on rechargeable batteries since can This implies a hermetically and heavy packaging which
delivery higher volumetric and gravimetric energy densities increase batteries weight and decreases their energy density.
[1]. In figure 1 is compared the battery capacity for different Furthermore, the use of liquid/polymer electrolytes, create
technologies, namely, conventional lithium-ion batteries (Li- several safety issues, like leaking, becoming crucial the
ion), batteries based on polymer lithium electrolyte (Li- emergence and continuous development of all-solid-state
polymer) and also lithium-ion batteries in thin-films (Film batteries due to the rigid safety requirements for bio
Li/Li-ion). applications. Taking advantage of weight and size reduction
with batteries fabricated only by thin-films opens up the
opportunity of devices miniaturization and, at the same time external circuit. Conversely, during the discharge, the reverse
and most importantly, the integration of micro/nano batteries process occurs with cathode receiving lithium ions internally
directly into the electronic chips [3]. In the present research our and electrons externally. Figure 3 illustrates the battery charge/
aim is to integrate batteries, energy harvesting systems and discharge with Li ions passing through the electrolyte and
electronic circuits with MPPT algorithms, at the same electrons passing through the lamp.
substrate, that can be flexible. Therefore, our broader purpose
is to enable the supplying of electrical energy in sensing and
monitoring applications for autonomous wireless
microsystems. Human body applications and other bio
applications can benefit of these characteristics.

II. BATTERIES WORKING PRINCIPLE

A battery is composed by two electrodes and one
electrolyte between them, acting as an electrical isolator. In the
positive electrode, cathode, reduction reactions occurs, and in
the negative electrode, anode, the oxidation reactions takes
place. The anode in lithium batteries is normally composed by
metallic lithium. The electrolyte ensures the isolation among
cathode and anode allowing the exchange of lithium-ions Figure 3: Representation of a battery charge/discharge [9].
through it. Thus, the main features of an electrolyte must be
excellent ionic conductivity; high electric resistivity, forcing
the movement of electrons through an external circuit and good The cathode and anode current collectors, platinum and
adhesion with the electrodes. Furthermore, an electrolyte must titanium, respectively, are deposited by e-beam technique. The
be electrochemical stable for the range voltage of battery. most common cathode of a thin-film battery is lithium cobalt
Figure 2 represents a schematic of a typical planar all-solid- oxide (LiCoO2) and the electrolyte is lithium phosphorus
state battery. oxynitride (LiPON), both deposited by RF sputtering. Within
the scope of the present research, extensive investigation have
been developed in order to improved and achieve better
characteristics for these two materials [4][10].
Promising results have been achieved, in our study, using
the electrodes and electrolyte materials mentioned above.
Figure 4 presents a thin film lithium-ion battery made on a
flexible substrate.

Figure 2: Schematic of a typical planar all-solid-state battery with a lithium

metal anode [4].

All-solid-state batteries had already been under extensive

investigation and development using Physical Vapor
Deposition Techniques (PVD) [5–8]. Nowadays some of them Figure 4: Thin-film lithium-ion battery fabricated on flexible substrate.
are commercially available at companies like Cymbet (ORNL
technology), Infinite Power Solutions and Front Edge. Others
companies like Sakti3, Seeo, Toyota/AIST, Excellatron and This battery presents yet a low capacity. Figure 5 illustrates
Planar Energy are developing their products to briefly start its the capacity obtained in charge curves for ten charge/discharge
commercialization. cycles. The charge was performed applying a constant current
of 10 nA to the battery, until a voltage of 3.9 V was achieved.
The operating voltage, in lithium batteries, is defined
A gradual loss of capacity is revealed with decreasing of
through chemical composition of their electrodes, cathode and
charge times along charge/discharge cycles.
anode, and aren’t related with their dimensions, which affects
the batteries capacity.
During the charge of a battery, lithium ions are extracted
from cathode to anode through electrolyte and electrons by
 approach to replace the lithium anode where the anode is itself
its own current collector, normally copper [13].

IV. THREE DIMENSIONAL BATTERIES

A different approach, than planar batteries, are the three
dimensional batteries. One of the ways to increases the
volumetric capacity of batteries is increasing the contact area
between cathode, electrolyte and anode, allowing faster
charge/discharge times.
H.-S. Min, et al. [21] uses lithography, pyrolysis and
electrodeposition techniques to create micro-rods or micro-
stems on two separate contacts pads, represented in figure 6. A
half of the micro-rods are used as cathode and the other half as
anode. This approach presents some advantages since both
electrodes have their current collectors integrated, allowing
electrodeposition. The micro-rods can be used directly as
Figure 5: Capacity of the battery in charge curves for ten charge/discharge anode and offers large versatility on his design. Nevertheless, a
cycles applying a current of 10 nA. solid electrolyte deposition becomes difficult with PVD
techniques in order to guarantee a uniform layer with good
contact between electrodes.
III. CHALLENGES FOR FUTURE PLANAR BATTERIES
Despite the high gravimetric capacity of lithium,
3860 mAh/g, and lower molecular weight, lithium have several
drawbacks. One of them is its low melting point temperature,
around 180 ºC, incompatible with the solder process in
microelectronic industry. Another one is its high reactivity,
especially when in contact with water and air, turning
inflammable and explosive and therefore implying the use of
effective protective coatings, like silicon nitride [11], layers of
different materials [2] and interspersed layers of Ti and
parylene C [12]. Moreover the formation of dendrites in the
interface among electrolyte and anode, due to continuous
cycles of charge/discharge, resulting in a chemical inactivity of
anode, is another drawback of metallic lithium as anode [13].
Therefore, several studies, including the present
investigation, are looking for other materials to replace the
metallic lithium, such as, tin (Sn), silicon (Si) and germanium
(Ge), among others. Results showing that anode based on Sn
films reveals a decreasing of their gravimetric capacity, 560
mAh/g, after a few cycles of charge/discharge [14]. Silicon
based anode presents an high gravimetric capacity, 4200 Figure 6: Three dimensional micro-rods or micro-stems structure [22].
mAh/g, with the formation of Li4,4Si [15]. However, this
unbalance provokes large volume variations until 300%
leaving to film destruction [16]. Germanium films have a An alternative and recent structure is a trench
diffusion coefficient of lithium ions two orders of magnitude configuration, integrated on a silicon wafer using reactive ion
higher than silicon and supports better the volume variations etching (RIE) [23]. The main advantages are the better
during the insertion and extraction of lithium ions. Results accommodations of volume variations during charge/discharge
reveal a gravimetric capacity nearby of 1600 mAh/g [17]. cycles, the uses of Si as anode material to replace metallic
According to these results silicon and germanium emerge as lithium and the good knowledge in integrated circuit (IC)
the more promising materials to substitute metallic lithium in technologies allows the integration and miniaturization of
thin-film batteries. Therefore, they will be used in the current microsystems. However, as drawbacks, this alternative implies
investigation. an effective lithium barrier layer among substrate and active
Further approaches are in investigation namely carbon, materials, the possible secondary reactions which can increase
graphene and germanium nanotubes [18], nanostructures of Sn the self-discharge rate and the difficulty to obtain a
and Si (like honeycombs, nanotubes, nanowires, nanofibers or homogeneously layers by accessible deposition techniques, like
porous films) [19], composites of Sn-based [20] and Si-based PVD [23]. Figure 7 shows a schematic representation of a three
[16], among others. Lithium-free batteries constitute a different dimensional integrated all-solid-state battery.
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