The further development of energy storage devices especially of lithium-ion batteries plays an important role in the
ongoing miniaturization process towards lightweight, flexible mobile devices. To improve mechanical stability and to
increase the power density of electrode materials while maintaining the same footprint area, a three-dimensional battery
design is necessary.
In this study different designs of three-dimensional cathode materials are investigated with respect to the electrochemical
performance. Lithium cobalt oxide is considered as a standard cathode material, since it has been in use since the first
commercialization of lithium-ion batteries.
Various electrode designs were manufactured in lithium cobalt oxide electrodes via laser micro-structuring. Laser
ablation experiments in ambient air were performed to obtain hierarchical and high aspect surface structures. Laser
structuring using mask techniques as well as the formation of self-organized conical surface structures were studied in
detail. In the latter case a density of larger than twenty million microstructures per square centimeter was obtained with a
significant increase of active surface area.
Laser annealing was applied for the control of the average grain size and the adjustment of a crystalline phase which
exhibits electrochemical capacities in the range of the practical capacity known for lithium cobalt oxide. An investigation
of cycling stability with respect to annealing parameters such as annealing time and temperature was performed using a
diode laser operating at 940 nm.
Information on the phase and crystalline structure were obtained using Raman spectroscopy and X-ray diffraction
analysis. The electrochemical performance of the laser modified cathodes was studied via cyclic voltammetry and
galvanostatic testing using a lithium anode and a standard liquid electrolyte.
Three-dimensional cathode architectures for rechargeable lithium-ion cells can provide better Li-ion diffusion due to
larger electrochemical active surface area and therefore, may stabilize the cycling behaviour of an electrochemical cell.
This features show great importance when aiming for long-life batteries, e.g. in stationary or portable power devices.
In this study, lithium manganese oxide thin films were used as cathode material with the goal to stabilize their cycling
behavior and to counter degradation effects which come up within the lithium manganese oxide system.
Firstly, appropriate laser ablation parameters were selected in order to achieve defined three-dimensional structures with
features sizes down to micro- and sub-micrometer scale by using mask imaging technique. Laser annealing was also
applied onto the laser structured material in a second step in order to form an electrochemically active phase. Process
development led to a laser annealing strategy for a flexible adjustment of crystallinity and grain size. Laser annealing
was realized using a high power diode laser system operating at a wavelength of 940 nm.
Information on the surface composition, chemistry and topography as well as studies on the crystalline phase of the
material were obtained by using Raman spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy
and X-ray diffraction analysis. The electrochemical activity of the laser modified lithium manganese oxide cathodes was
explored by cyclic voltammetry measurements and galvanostatic testing by using a lithium anode and standard liquid
electrolyte.
The development of future battery systems is mainly focused on powerful rechargeable lithium-ion batteries. To satisfy
this demand, current studies are focused on cathodes based on nano-composite materials which lead to an increase in
power density of the LIB primarily due to large electrochemically active surface areas. Electrode materials made of
lithium manganese oxides (Li-Mn-O) are assumed to replace commonly used cathode materials like LiCoO2 due to less
toxicity and lower costs. Thin films in the Li-Mn-O system were synthesized by non-reactive r.f. magnetron sputtering of
a LiMn2O4 target on silicon and stainless steel substrates. In order to enhance power density and cycle stability of the
cathode material, direct laser structuring methods were investigated using a laser system operating at a wavelength of
248 nm. Therefore, high aspect ratio micro-structures were formed on the thin films. Laser annealing processes were
investigated in order to achieve an appropriate crystalline phase for unstructured and structured thin films as well as for
an increase in energy density and control of grain size. Laser annealing was realized via a high power diode laser system.
The effects of post-thermal treatment on the thin films were studied with Raman spectroscopy, X-ray diffraction and
scanning electron microscopy. The formation of electrochemically active and inactive phases was discussed. Surface
chemistry was investigated via X-ray photoelectron spectroscopy. Interaction between UV-laser radiation and the thin
film material was analyzed through ablation experiments. Finally, to investigate the electrochemical properties, the
manufactured thin film cathodes were cycled against a lithium anode. The formation of a solid electrolyte interphase on
the cathode side was discussed.
The material development for advanced lithium-ion batteries plays an important role in future mobile applications and
energy storage systems. It is assumed that electrode materials made of nano-composited materials will improve battery
lifetime and will lead to an enhancement of lithium diffusion and thus improve battery capacity and cyclability. A major
problem concerning thin film electrodes is, that increasing film thickness leads to an increase in lithium diffusion path
lengths and thereby a decrease in power density. To overcome this problem, the investigation of a 3D-battery system
with an increased surface area is necessary. UV-laser micromachining was applied to create defined line or grating
structures via mask imaging. SnO2 is a highly investigated anode material for lithium-ion batteries. Yet, the enormous
volume changes occurring during electrochemical cycling lead to immense loss of capacity. The formation of micropatterns
via laser ablation to create structures which enable the compensation of the volume expansion was investigated
in detail. Thin films of SnO2 were deposited in Ar:O2 atmosphere via r.f. magnetron sputtering on silicon and stainless
steel substrates. The thin films were studied with X-ray diffraction to determine their crystallinity. The electrochemical
properties of the manufactured films were investigated via electrochemical cycling against a lithium anode.
The material development for advanced lithium ion batteries plays an important role in future mobile applications and
energy storage systems. It is assumed that electrode materials made of nano-composited materials will improve battery
lifetime and will lead to an enhancement of lithium diffusion and thus improve battery capacity and cyclability. Lithium
cobalt oxide (LiCoO2) is commonly used as a cathode material. Thin films of this electrode material were synthesized by
non-reactive r.f. magnetron sputtering of LiCoO2 targets on silicon or stainless steel substrates. For the formation of the
high temperature phase of LiCoO2 (HT-LiCoO2), which exhibits good electrochemical performance with a specific
capacity of 140 mAh/g and high capacity retention, a subsequent annealing treatment is necessary.
For this purpose laser annealing of thin film LiCoO2 was investigated in detail and compared to conventional furnace
annealing. A high power diode laser system operating at a wavelength of 940 nm with an integrated pyrometer for
temperature control was used. Different temperatures (between 200°C and 700°C) for the laser structured and
unstructured thin films were applied.
The effects of laser treatment on the LiCoO2 thin films studied with Raman spectroscopy, X-ray photoelectron
spectroscopy and X-ray diffraction to determine their stoichiometry and crystallinity. The development of HT-LiCoO2
and also the formation of a Co3O4 phase were discussed. The electrochemical properties of the manufactured films were
investigated via electrochemical cycling against a lithium anode.
The material development of improved lithium ion batteries will play an important role in future mobile applications and
energy storage systems. Electrode materials made of nano-composited materials are expected to improve battery lifetime
and will lead to an enhancement of lithium diffusion and thus improve battery capacity and cyclability. In this study,
research was conducted to further improve the electrochemical properties of thin film cathodes by increasing the surface
to volume ratio and thereby the lithium intercalation rate. Cathode materials were synthesised by r.f. magnetron
sputtering of LiCoO2 targets in a pure argon plasma. LiCoO2 films 3 μm thick and with a grain size of 10 to 500 nm were
deposited on silicon and stainless steel substrates. The deposition parameters (argon pressure, substrate bias) were varied
to create stoichiometric films with controlled nano-crystalline texture and morphology. During laser-assisted surface
treatment, cone-shaped periodic surface structures were produced. For this purpose high repetition excimer laser
radiation at wavelengths of 193 nm and 248 nm and with short laser pulse widths (4-6 ns) were used. Structure sizes
varied with laser and processing parameters, e.g. laser fluences, pulse number, wavelength and processing gas. Laser
annealing in air or furnace annealing in a controlled argon/oxygen environment were then used to create the high
temperature phase of LiCoO2 (HT-LiCoO2). The sputtered films were studied with Raman spectroscopy, x-ray
photoelectron spectroscopy and x-ray diffraction to determine their stoichiometry and crystallinity before and after laser
treatment. The development of HT-LiCoO2 and also the formation of a Co3O4 phase were discussed. By means of
electrochemical cycling, the performance of the manufactured films was investigated.
Two types of laser patterning are of interest for application in microsystem technology: direct ablation of polymer
material for the generation of two or three dimensional shapes such as microfluidic channels, curved shapes or micro-holes
and alternatively photo-induced change of chemical or physical properties. An appropriate choice of laser and
process parameters enables new approaches for the fabrication of lab-on-chip devices with integrated functionalities.
We will present our current research results in laser-assisted ablation and modification of polystyrene (PS) with respect
to the fabrication of polymer devices for high throughput planar patch clamping. Patch clamping is a highly sensitive
technique used to measure the electrical activity of a cell. It is used in applications which include drug screening where
there is demand for high throughput systems (HTS). While there are a few commercially available HTS patch clamping
systems on the market using traditional patch clamping materials, there are no systems on the market using novel
materials, or for dealing with cell networks - a physiologically important consideration for the developing fields of
tissue engineering and understanding cell to cell interactions. This paper presents potential design approaches and
processes for producing a polymer based automated patch clamping system.
For this purpose laser micro-drilling of PS and subsequent surface functionalization was investigated as function of laser
and process parameters. A high power ArF-excimer laser radiation source with pulse length of 20 ns (repetition rate up
to 40 Hz) as well as high repetition ArF- and KrF-excimer laser sources with pulse lengths of 4-6 ns (repetition rates up
to 500 Hz) were used in order to study the influence of laser pulse length on laser drilling and laser-induced surface
modification. Micro-drilling of PS with diameters down to 1.5 μm were demonstrated. Furthermore the localized
formation of chemical structures suitable for improved adhesion of single cells and cell networks was achieved on PS
surfaces. A photolytic activation of specific areas of the polymer surface and subsequent oxidization in oxygen or
ambient air leads to a chemically modified polymer surface bearing carboxylic acid groups well-suited for controlled
competitive protein adsorption or protein immobilization. Finally, distinct areas for cell growth and adhesion are
obtained. The combination of laser ablation and modification will be discussed for the laser-assisted fabrication of
polymer devices for patch clamping.
In this paper the current state of the art and new trends in excimer laser processing of polymer materials are presented.
Two processing regimes are of general interest: below and above the ablation threshold. The modification of polymer
surface can be carried out by laser processing below ablation threshold. This is successfully demonstrated for the
fabrication of optical singlemode waveguides in PMMA for the visible optical range and for 1550 nm. The obtained
structures reveal absorption losses in the order of 1.4 dB/cm up to 5 dB/cm. Laser exposure using contact masks or
direct scanning of planar structures are appropriate methods for the integration of optical waveguides in PMMA sensor
devices (Y-branch). Above the ablation threshold excimer laser micromachining is a powerful tool for a rapid
manufacturing of complex three-dimensional micro-structures in polymer surfaces with depths between 0.1 μm and
1000 μm and aspect ratios up to 10. Typical application fields are presented in micro-optics, micro-fluidics and rapid
tooling. Micro-Laser-LIGA is established in order to fabricate nebulizer membranes, micro-fluidic devices and
integrated single mode waveguides. Furthermore, the fabrication of 3d-shapes in metallic mold inserts is successfully
demonstrated. Debris formation is completely suppressed. Polymer structuring with a low power short pulse excimer
laser with high repetition rates up to 500 Hz is compared to the structuring with a "conventional" high power excimer
laser with a repetition rate of about 10-100Hz as well as with a UV-Nd:YAG (1-2 kHz). These "high-repetition-rateexcimer
lasers" with relatively small pulse energies but with much shorter laser pulse duration (< 6 ns) provide a
significant improvement of pattern quality. Furthermore, the high repetition rate enables a fast material processing
which is discussed in detail for several application fields.
A new very small powerful air-cooled excimer laser (193, 248, 308 nm) with metal-ceramic technology was developed by ATL Lasertechnik in Germany. The laser won 1995 Prize for the best innovation awarded by German federal states of Berlin & Brandenburg. The pulse energy of 10 - 20 mJ at high rep rates (200 - 500 Hz) from an active volume of only 1 cm3 are reached. The raw laser beam produces energy density of > 100 mJ/cm2 which is comparable to the performance of standard (large) excimer lasers. Its very short pulse length (3 ns), permits extremely high peak power density (30 MW/cm2). The ATLEX SP laser uses a new type of pre-ionization technique providing high beam homogeneity at low discharge voltages. Small footprint and weight, low operation costs opens up new industrial (micro-machining) and biomedical applications. Recently the ATLEX SP laser (193 nm) has been used for corneal refractive surgery. The setup consists of splitting a 193 nm laser beam into couples of beams which simultaneously ablates the corneal surface in a symmetrical scan-like fashion. Refractive changes up to 20 diopters were realized. Results of an analysis by corneal topography showed homogeneous ablation throughout the entire ablation zone.
Access to the requested content is limited to institutions that have purchased or subscribe to SPIE eBooks.
You are receiving this notice because your organization may not have SPIE eBooks access.*
*Shibboleth/Open Athens users─please
sign in
to access your institution's subscriptions.
To obtain this item, you may purchase the complete book in print or electronic format on
SPIE.org.
INSTITUTIONAL Select your institution to access the SPIE Digital Library.
PERSONAL Sign in with your SPIE account to access your personal subscriptions or to use specific features such as save to my library, sign up for alerts, save searches, etc.