batteries

Article
Influence of Laser-Generated Cutting Edges on the
Electrical Performance of Large Lithium-Ion
Pouch Cells
Tobias Jansen 1, *, Maja W. Kandula 1 , Sven Hartwig 1 , Louisa Hoffmann 2 ,
Wolfgang Haselrieder 3 and Klaus Dilger 1
1 Institute of Joining and Welding, Technische Universität Braunschweig, Langer Kamp 8,
38106 Braunschweig, Germany; m.kandula@tu-braunschweig.de (M.W.K.);
s.hartwig@tu-braunschweig.de (S.H.); k.dilger@tu-braunschweig.de (K.D.)
2 Institute for High Voltage Technology and Electrical Power Systems, Technische Universität Braunschweig,
Schleinitzstraße 23, 38106 Braunschweig, Germany; louisa.hoffmann@tu-braunschweig.de
3 Institute for Particle Technology, Technische Universität Braunschweig, Volkmaroder Straße 5,
38104 Braunschweig, Germany; w.haselrieder@tu-braunschweig.de
* Correspondence: tobias.jansen@tu-braunschweig.de; Tel.: +49-531-391-95596




Received: 5 November 2019; Accepted: 26 November 2019; Published: 3 December 2019


Abstract: Laser cutting is a promising technology for the singulation of conventional and advanced
electrodes for lithium-ion batteries. Even though the continuous development of laser sources, beam
guiding, and handling systems enable industrial relevant high cycle times, there are still uncertainties
regarding the influence of, for this process, typical cutting edge characteristics on the electrochemical
performance. To investigate this issue, conventional anodes and cathodes were cut by a pulsed fiber
laser with a central emission wavelength of 1059–1065 nm and a pulse duration of 240 ns. Based on
investigations considering the pulse repetition frequency, cutting speed, and line energy, a cell setup
of anodes and cathodes with different cutting edge characteristics were selected. The experiments
on 9 Ah pouch cells demonstrated that the cutting edge of the cathode had a greater impact on the
electrochemical performance than the cutting edge of the anode. Furthermore, the results pointed out
that on the cathode side, the contamination through metal spatters, generated by the laser current
collector interaction, had the largest impact on the electrochemical performance.

Keywords: production strategies; laser cutting; cell manufacturing; automotive pouch cells

1. Introduction
Due to continuing human-induced CO2 emissions, the global warming of the earth and associated
negative consequences of extreme weather are steadily increasing [1]. The impact of climate change
has increased awareness of the population in industrialized countries of environmentally friendly
or carbon-neutral behavior. These interests are driving the development of new, greener, and more
efficient technologies for the major CO2 producing sectors, which are electrical energy production and
individual mobility. To reduce CO2 emissions in the individual mobility sector, electric mobility is
considered a key technology [2,3]. In order to maintain the positive CO2 balance of electric mobility,
the use of electrical energy from renewable energy sources is required, but also the production of
cells must be made more efficient and, therefore, more ecological. In particular, a more efficient
large-scale cell production can be achieved by reducing rejects by optimizing existing or developing
new technologies, as material costs dominate over operating and investment costs [4].
Lithium-ion pouch cells are considered to be the most effective electrochemical technology. Due to
their advantages regarding the high volumetric utilization of the installation space of the battery pack,

Batteries 2019, 5, 73; doi:10.3390/batteries5040073 www.mdpi.com/journal/batteries

 Batteries 2018, 4, x FOR PEER REVIEW 2 of 21

Lithium-ion pouch cells are considered to be the most effective electrochemical technology. Due
to their advantages regarding the high volumetric utilization of the installation space of the battery
Batteries 2019, 5, 73 2 of 20
pack, they are especially well suited for automotive batteries. Because of the possibility to customize
the cell geometry, the pouch cell leads to less dead volume compared to conventional cylindrical
18,650
they cells [5]. Besides,
are especially the for
well suited high volumetric
automotive energy densities
batteries. Because of onthe
battery level to
possibility pouch cells have
customize the cellhigh
volumetric
geometry, the energy of 466
pouch cell leadsWhL −1 and a specific energy density of 241 Whkg−1 on cell level (Cathode:
to less dead volume compared to conventional cylindrical 18650 cells [5].
LG Chem.
Besides, NCM
the high 111, Anode:
volumetric energy LGdensities
Chem. Graphite)
on battery[6]. Even
level pouchthough
cells cylindrical 18,650 cells
have high volumetric have a
energy
of volumetric −1
466 WhL energy density,
and a specific whichdensity
energy is aboutof20%
241 Whkg −1
higher than those
on cell of pouch
level (Cathode:cellsLG[5],Chem.
the homogeneous
NCM 111,
mechanical
Anode: LG Chem. behavior during
Graphite) [6].charging and discharging
Even though of pouch
cylindrical 18650 cells alead
cells have to longer
volumetric cycledensity,
energy lifetime,
which
which is to be
is about considered
20% a long
higher than those term advantage
of pouch overthe
cells [5], the higher energy
homogeneous density [7].
mechanical For pouch
behavior during cells,
in general,
charging and it is fundamental
discharging of pouchto cut the
cells endlessly
lead to longer coated
cycle electrodes and make
lifetime, which is to bethem suitablea for
considered longthe
following
term advantagestacking
overprocess.
the higherIt isenergy
imperative to look
density [7]. more closely
For pouch at the
cells, in cutting
general,process itself since each
it is fundamental to
cutcut
thecould lead to
endlessly manufacturing
coated electrodes errors in terms
and make themofsuitable
contamination and cutting
for the following edge quality
stacking process. [8].It Due
is
to a large
imperative number
to look moreofclosely
processes, it is necessary
at the cutting to optimize
process itself since eachevery step lead
cut could to improve ecological
to manufacturing
productivity.
errors in terms ofFigure 1 shows the
contamination andevolution of the
cutting edge accumulated
quality [8]. Due toproduction
a large numberrejectsofofprocesses,
a conventional
it is
cell production
necessary line schematically.
to optimize every step to improve ecological productivity. Figure 1 shows the evolution of
the accumulated production rejects of a conventional cell production line schematically.

Figure 1. Influence of the reject rate of every single process on the total reject rate of a cell production line.
Figure 1. Influence of the reject rate of every single process on the total reject rate of a cell production
Asline.
shown in Figure 1, each process can contribute to the overall efficiency of the production
line. Due to the numerous processes of battery production, even small reject rates can lead to a high
overallAs reject rate in
shown and, therefore,
Figure 1, eachtoprocess
low utilization of raw to
can contribute materials. Already
the overall at a reject
efficiency of therate of only 1%
production line.
per process, the accumulated rejects at the end of the line reach almost 14%. Therefore,
Due to the numerous processes of battery production, even small reject rates can lead to a high overall each process
should
reject be at and,
rate leasttherefore,
in the range of a utilization
to low 4σ reject rate, respectively,
of raw materials.with a reject
Already at arate of under
reject rate of0.09% with
only 1% per
regard to ecological
process, production.
the accumulated Investigating
rejects at the endand of improving the singulation
the line reach almost 14%. process can contribute
Therefore, each processto
accomplishing thesein
should be at least high
thestandards.
range of a 4σ reject rate, respectively, with a reject rate of under 0.09% with
Besides
regard the established
to ecological shearingInvestigating
production. or die-cuttingand (DIN 8588) [9], laser
improving cutting is becoming
the singulation increasingly
process can contribute
common in cell production lines
to accomplishing these high standards. due to its process-immanent advantages over the contact-based
singulation
Besidesmethod
the [10]. Especially
established for veryorthick
shearing and fragile
die-cutting electrodes,
(DIN or pure
8588) [9], laserlithium
cuttingmetal anodes,
is becoming
laser cutting is no
increasingly longer an
common in alternative
cell production but state of the
lines duearttotechnology due to the lack
its process-immanent of contact and
advantages overthethe
associated lack of mechanical stress [11]. In the following section, we
contact-based singulation method [10]. Especially for very thick and fragile electrodes, orhave given a summary of the
pure
numerous studies
lithium metal in this laser
anodes, field cutting
and laser is ablation
no longer generally.
an alternative but state of the art technology due to
the lack of contact and the associated lack of mechanical stress [11]. In the following section, we have
State of the
given Art Laser Cutting
a summary of Electrodes
of the numerous studies in this field and laser ablation generally.
The interactions between the material and the laser-generated photons during the cutting process
is very dynamic and very complex due to a large number of possible and partly mutually dependent
influencing factors. The key factors of a laser cutting plant are wavelength (λ), average power (Pavg ),
Batteries 2018, 4, x FOR PEER REVIEW 3 of 21

State of the Art Laser Cutting of Electrodes

The interactions between the material and the laser-generated photons during the cutting
process2019,
Batteries is very
5, 73 dynamic and very complex due to a large number of possible and partly mutually 3 of 20
dependent influencing factors. The key factors of a laser cutting plant are wavelength (λ), average
power 𝑃 ,spot size 𝑑 , laser profile and Rayleigh length in focus, cutting speed 𝑣 , the
spot size dspot , laser profile and Rayleigh length in focus, cutting speed (vc ), the number of passes,
number of passes, and cutting angle. In the case of pulsed laser beam sources, the additional factors
and cutting angle. In the case of pulsed laser beam sources, the additional factors are pulse peak
are pulse
 peak power 𝑃 , pulse energy 𝐸 , pulse repetition frequency (𝑃𝑅𝐹), and pulse shape,
power Ppeak , pulse energy (EP ), pulse repetition frequency (PRF), and pulse shape, as well as pulse
as well as pulse duration (τ). The relevant material properties of the electrode are the composition of
duration (τ). The relevant material properties of the electrode are the composition of the coating
the coating (anode/cathode), collector material, coating thickness, collector thickness, absorption
(anode/cathode), collector material, coating thickness, collector thickness, absorption coefficient, and
coefficient, and degree of compaction of the electrode (Figure 2).
degree of compaction of the electrode (Figure 2).

Figure 2. Relevant primary process parameters and material properties of a continuous wave (cw) and
Figure laser
pulsed 2. Relevant
cutting primary process
process for parameters
electrodes [10,12].and material properties of a continuous wave (cw)
and pulsed laser cutting process for electrodes [10,12].
For a simplified description of the influence of the primary process parameters in Figure 2, the
For a parameters
secondary simplified description
energy density of the influence
(ED) of the primary
[13], intensity (I), pulseprocess
fluenceparameters in Figure
(Hp ), and number of 2, the
laser
secondary
pulses parameters
per surface energy
increment (ndensity
line ) [13] (ED)
for [13],
pulsed intensity
beam (I),
sources pulse
can fluence
be used (𝐻
to ), and
explain number
the of
ablation laser
or
pulses per surface increment (𝑛 ) [13] for pulsed beam sources can be
cutting behavior. Considering a certain wavelength, average power, and spot size, these parameters used to explain the ablation
or cutting
can behavior.
be adjusted by vc , PRF, and τ. The
Considering a secondary
certain wavelength,
parameters average are defined power,
by theand spot size,
following these
equations:
parameters can be adjusted by 𝑣 , 𝑃𝑅𝐹, and τ. The secondary parameters are defined by the
P
" #
following equations: avg j
ED = (1)
vc dspot cm2
𝐸𝐷 (1)
𝐼 4 Pavg 𝑎𝑛𝑑 𝐼 Pavg
I =𝑓𝑜𝑟 𝑐𝑤 f or cw and IP = 𝑓𝑜𝑟Peak
4 P 𝑝𝑢𝑙𝑠𝑒𝑑 l𝑎𝑠𝑒𝑟 𝑤𝑖𝑡ℎ 𝑃 W
 
f or pulsed laser with PPeak ≈ (2)
(2)
π dspot
2 π dspot
2 PRF τ cm2
𝐻 (3)
" #
EP j
𝑛 Hp = (3)
(4)
π dspot
2 cm 2

The energy density describes the energy input per surface increment (cutting length times const.
PRF (dspot + τ vc )
spot size) on the material to be processed, nline =depending on the cutting speed, photonic power, and spot (4)
size. This parameter can be used to describe the scalability vc of the cutting speed for a defined
The energy
laser/scanner density
system anddescribes
materialthe or energy
to define input
the per surfaceenergy
necessary increment (cutting
input length times
for a quality const.
cut and the
spot size) onlimit.
cut-through the material
Since the toenergy
be processed,
density depending
represents the on average
the cutting speed,
power inputphotonic power,ofand
independent the
spot
peaksize. This
power, theparameter
intensity iscan be usedtotofurther
necessary describe the scalability
describe the cutting ofprocess
the cutting
withspeed forlaser
a pulsed a defined
beam
laser/scanner system and material or to define the necessary energy input for a quality cut and the
cut-through limit. Since the energy density represents the average power input independent of the
peak power, the intensity is necessary to further describe the cutting process with a pulsed laser beam
Batteries 2019, 5, 73 4 of 20
Batteries 2018, 4, x FOR PEER REVIEW 4 of 21

source. In addition, the pulse fluence and the number of pulses, which hit per surface increment,
source. In addition, the pulse fluence and the number of pulses, which hit per surface increment, must
must be specified. Based on the energy density, the intensity, the pulse fluence, and the number of
be specified. Based on the energy density, the intensity, the pulse fluence, and the number of hits per
hits per area increment, the amount of material removal and the material removal behavior can be
area increment, the amount of material removal and the material removal behavior can be derived.
derived. Figure 3 schematically shows the number of hits per surface increment as a function of the
Figure 3 schematically shows the number of hits per surface increment as a function of the vc , PRF, τ,
𝑣 , 𝑃𝑅𝐹, τ, and the 𝑑 , as well as the effects on the electrode cutting edge characteristics. The
and the dspot , as well as the effects on the electrode cutting edge characteristics. The ablation thresholds
ablation thresholds a and b, as well as the heat-affected zone c shown in Figure 3, can be derived from
a and b, as well as the heat-affected zone c shown in Figure 3, can be derived from the mentioned
the mentioned secondary parameters.
secondary parameters.

Figure 3. Laser scanning microscope image of a laser-cut electrode (left); Ablation thresholds depending
Figure
on 3. Laserof scanning
the number microscope
hits, intensity, imageenergy
pulse fluence, of a laser-cut
density, aselectrode (left);
well as the laser-Ablation thresholds
and corresponding
depending on the number
plasma-intensity-profile of hits,(a)intensity,
(right): pulsethreshold,
cut-through fluence, energy density,
(b) ablation as well as
threshold, the(c)
and laser- and
thermic
corresponding
influencing plasma-intensity-profile
threshold [10]. (right): (a) cut-through threshold, (b) ablation threshold, and
(c) thermic influencing threshold [10].
As the type of energy input can lead to different removal mechanisms, a comparison of continuous
waveAs (cw)theandtype of energy
pulsed systems input
based canonleadthe to different
energy densityremoval
is onlymechanisms,
conditionallya possible.
comparison of
Here,
acontinuous
distinctionwave can be(cw) and pulsed
made between systems
thermal based on the energy
(cw/pulsed) density is(pulsed)
and athermal only conditionally
dominant possible.
removal
Here, a distinction
processes. The thermal canablation
be madegenerally
betweenproceeds
thermal in (cw/pulsed) and athermal
three successive phases, and,(pulsed)
in thedominant
case of a
removal processes.
continuous cut, also The thermal
in parallel ablation
phases. generally
In the proceeds
first phase, in threeare
the photons successive
absorbedphases, and, inand
by the surface the
case of a continuous
penetrate a near-surface cut,area.
also Inin the
parallel phases.
following In the
second first phase,
phase, the photons
the temperature are absorbed
increases by the
at the surface
surface and penetrate a near-surface area. In the following second phase,
as a result of the absorption, and in deeper zones by thermal conductive effects. The rising temperature the temperature increases
at theto
leads surface as a result of the state
a transformation absorption,
of matter and in deeper
from solid tozones
liquidby thermal
and liquid conductive effects.from
to gas, or directly The
risingtotemperature
solid gas. In the thirdleadsphase,
to a transformation
the penetration of depth
the state of matter
increases andfrom
thussolid to liquid
the melting orand liquid to
evaporation
gas, or
zone, directlythe
wherein from solidistoexpelled
material gas. In in the thirdorphase,
liquid gaseous theform
penetration
from the depth
kerf. Theincreases
materialand thus can
ejection the
melting
be furtheror distinguished
evaporation zone, into wherein the materialand
fusion, sublimation, is expelled in liquidcutting/ablation.
photochemical or gaseous form from the kerf.
The athermal
The material
removal process ejection can be further
is characterized by the distinguished into fusion,
fact that the duration sublimation,
of the photonic energy andinput
photochemical
is too short
cutting/ablation.
for initiating heat The athermalThis
conduction. removal
removal process
process is characterized
can be achieved by with
the fact that
pulse the duration
durations of lessofthan
the
photonic
10 energy input
ps. Furthermore, due is too short
to the shortexposure
for initiating
time of heat conduction.
pulses Thisfsremoval
in the ps and range, the process
spatialcan be
extent
achieved with pulse durations of less than 10 ps. Furthermore, due to
of the resulting plasma is negligibly small [14]. Considering the high intensities, athermal processes the short exposure time of
pulses
can in the ps
be further and fs range,
distinguished the spatial
between extent cutting
sublimation of the andresulting plasma isablation.
photochemical negligibly small [14].
Considering the high
Figure 4 shows intensities,that
the processes athermal
occur afterprocesses
the firstcan impactbe of
further distinguished
the photons between
on the processed
sublimation cutting and photochemical ablation.
material. On average, the photons are absorbed in 10 fs, where the photonic energy is converted into
thermalFigure 4 shows
energy within the100processes that occur afterrelaxation
fs by electron-electron the first impact of the photons
of the electrode systems onofthe
theprocessed
covalent
material.
bonds. Onisaverage,
This followed thebyphotons are absorbedrelaxation
an electron-phonon in 10 fs, where the photonic
after about energy
1 to 10 ps, whichis converted into
leads to a heat
thermal energy within 100 fs by electron-electron relaxation of the electrode
transfer of the electrons into the lattice structure. Parallel to this process, the ablation begins, and aftersystems of the covalent
bonds.100
about Thisps,isthe
followed by an electron-phonon
phonon-phonon relaxation leads relaxation
to heat after about 1[15].
conduction to 10 ps, which leads to a heat
transfer of the electrons into the lattice structure. Parallel to this process, the ablation begins, and after
about 100 ps, the phonon-phonon relaxation leads to heat conduction [15].
Batteries 2019, 5, 73 5 of 20
Batteries 2018, 4, x FOR PEER REVIEW 5 of 21

Figure 4. Time-scaled
Figure 4. Time-scaled processes
processes during
during aa laser
laser pulse
pulse material interaction, based
material interaction, based on
on [16,17].
[16,17].

By
Bymeans
means of of the
the beam
beam source
source used used in this study,
in this study, it it is possible to
is possible to generate
generate pulses
pulsesin inthe
thensnsrange.
range.
Due to the relatively long pulse duration of 240 ns, we can only
Due to the relatively long pulse duration of 240 ns, we can only realize a thermally affected cutting realize a thermally affected cutting
process
process(thermal
(thermal removal
removal process)
process) with with this
this system
system [14].[14]. AsAs aa result
result of of the
the composite
composite structurestructure and and
the
theassociated
associated varying
varying material
material properties
properties over over thethe thickness
thickness of of the electrode, it
the electrode, it can
can bebe assumed
assumed that that
several removal mechanisms take place simultaneously and/or
several removal mechanisms take place simultaneously and/or serially during cutting. The cutting ofserially during cutting. The cutting of
the
theporous
porous coating
coating will will be be characterized
characterized by by aa photochemical
photochemical and and sublimation proportion, whereas
sublimation proportion, whereas
the cutting of the metallic collector will be characterized by sublimation
the cutting of the metallic collector will be characterized by sublimation and a fusion proportion. In and a fusion proportion.
In addition
addition to to
the thedirect
directinteraction
interactionbetween betweenlaser laserand andmaterial,
material,aaplasma plasmawhich which correlates
correlates to to the
the
intensity
intensitydistribution
distributionofof thethelaserlaserwillwill
alsoalso
interact with with
interact the electrode.
the electrode.This can lead
This can to material removal
lead to material
or thermal loading of the active material, in addition to thermal
removal or thermal loading of the active material, in addition to thermal conduction effects. conduction effects.
The
Thelaser-induced
laser-induced plasma plasma is is caused
caused by by the
the high
high intensities
intensities of of the individual pulses,
the individual pulses, whichwhich leads
leads
to
tostrong
strongoscillations
oscillationsof of the
the free
free electrons,
electrons, enabling
enabling them them to knock bounded
to knock bounded electrons
electrons out out ofof neutrally
neutrally
charged
charged atoms. The avalanching increase of free and strong oscillating electrons leads to number
atoms. The avalanching increase of free and strong oscillating electrons leads to a large a large
of free electrons
number of free and positively
electrons charged species.
and positively charged The resulting
species. Thehigh-energy plasma absorbs
resulting high-energy plasma the photons
absorbs
of the
the laser radiation
photons of the laser by the inverseby
radiation Bremsstrahlung (IB) and the photoionization
the inverse Bremsstrahlung (PI). In this case,
(IB) and the photoionization IBIn
(PI). is
considered to be the main absorption mechanism. The photons
this case, IB is considered to be the main absorption mechanism. The photons in this mechanism arein this mechanism are absorbed by free
electrons
absorbedas bythey
freecollide
electrons withas neutral or ionized
they collide species.orThis
with neutral leadsspecies.
ionized to an increase
This leads in the
to an energy of the
increase in
electrons and thus to an increase in the degree of ionization and the
the energy of the electrons and thus to an increase in the degree of ionization and the temperature of temperature of the plasma. If the
temperature
the plasma. and If thedensity of the plasma
temperature and density rise above
of theaplasma
certain rise
level, the plasma
above a certain canlevel,
shield thethe area from
plasma can
being
shieldcutthefrom
areathe laserbeing
from radiation.
cut from This the
effect is referred
laser radiation. to as the effect
This plasmais shielding
referred effect
to as [18].
the plasma
Investigations
shielding effect [18]. on cw and pulsed laser beam cutting of electrodes have already been carried out in
previous studies. The
Investigations onresults
cw andshowed pulsed that laserthe beamusecutting
of single-mode
of electrodes cw fiber
havelasers
already madebeenit carried
possibleout to
achieve very studies.
in previous high, industry-relevant
The results showed cuttingthatspeeds
the use due of to the high average
single-mode cw fiber power
lasers andmadethe itachievable
possible
low spot sizes. Studies −1 and a
to achieve very high, showed that it was possible
industry-relevant cutting speedsto cut andue anodeto the(120highµm) with
average 11,666powermmsand the
cathode
achievable(130lowµm)spot withsizes.
10,000 mms−1
Studies with a that
showed single-mode cw fiber
it was possible tolaser
cut an at anode
a wavelength
(120 µm) in with
the infrared
11,666
range
mms−1(1070
and nm),
a cathodean average
(130 µm) power withof10,000
5000 W, mmsand−1 awith
spotasize of 25 µm [19].
single-mode Thislaser
cw fiber resulted
at a in an energy
wavelength
density of 2000 jcm −2 for the cut-through limit of the cathode and an energy density of 1714 jcm−2 for
in the infrared range (1070 nm), an average power of 5000 W, and a spot size of 25 µm [19]. This
the anode.
resulted in The lower required
an energy density of energy
2000 jcm density
−2 for forthethe anode waslimit
cut-through probably
of the due
cathodeto the andlowancollector
energy
thickness
density ofand 1714 the jcmlower
−2 fordegree
the anode. of compaction.
The lower required In another study,
energy an anode
density (50 anode
for the µm) with wasaprobably
collector
thickness
due to the oflow
30 µm was cutthickness
collector with a cutting and the speedlowerof 2000
degree mms of−1 using a single-mode
compaction. In another cwstudy,
Ytterbium fiber
an anode
laser (1070
(50 µm) nm,a250
with W, andthickness
collector 23 µm spot size).
of 30 µm Thewasmuchcut with lower required
a cutting energy
speed density
of 2000 mms of−1543 jcma−2single-
using could
mode
be cw Ytterbium
explained by the lower fiber material
laser (1070 nm, 250
thickness andW,byand the23 µm spot
higher size).[20].
intensity The Based
much on lowertheserequired
results,
energy investigations
further density of 543 using jcm the
−2 could be explained
same system showed by thethat lower material (56
compacted thickness
µm) and andnon-compacted
by the higher
intensity
anodes (70[20].
µm) Based on these thickness
with a collector results, further
of 20 µm investigations
could be cut at using
a speed the ofsame mms−1 showed
5000system [21]. Thethat low
compacted
energy density(56 µm)
of 217 andjcm −2 required foranodes
non-compacted (70 µm) with
the singulation a collector
suggested thatthickness
the collector of 20thickness
µm couldwas be
cut at a speed of 5000 mms [21]. The low energy density of 217 jcm required for the singulation
−1 −2

suggested that the collector thickness was the dominating speed-influencing parameter of the
Batteries 2019, 5, 73 6 of 20

the dominating speed-influencing parameter of the electrode. Considering the strong influence of the
collector thickness, as well as the intensity of the focused laser spot, it was plausible that an energy
density of 818 jcm−2 at 5000 mms−1 led to a cut-through of an anode (100 µm) with a current collector
thickness of 10 µm by using a single-mode cw fiber laser (1070 nm, 450 W, 11 µm spot size) [22].
In principle, the investigations with cw laser systems showed that the achievable chamfer width (total
ablated area) was less than 50 µm and increased with increasing energy densities [21].
The trend of these dependencies was also found in investigations with pulsed laser beam sources.
In addition to this, the investigations showed that with pulsed beam sources in the nanosecond
range, higher pulse repetition frequencies enabled higher cutting speeds and led to a smaller chamfer
width [19]. By using an ns pulsed fiber laser (1070 nm, 100 W, 50 µm spot size, 500 kHz, and 30 ns),
it was possible for Kronthaler et al. [23] to cut an anode (114 µm) with a collector thickness of 10 µm
at a speed of 1200 mms−1 . Using the same system parameter, a slightly higher cut-through limit of
1250 mms−1 could be achieved for a 124 µm thick cathode with a collector thickness of 20 µm [23].
From the given parameters, an energy density of 160 jcm−2 resulted, for the cut-through limit, in an
intensity per pulse of 3.4 × 108 Wcm−2 and a hit number of 20. Lutey et al. showed in their research
that the number of hits per area increment caused an increase in the plasma shielding effect. With
higher numbers of hits, a higher average power was needed to realize a cut. At 125 hits per area
increment (500 kHz), an energy density of 660 jcm−2 was needed, whereas, with a hit number of 5
(20 kHz), only an energy density of 352 jcm−2 sufficed [24].
Further results on laser cutting of electrodes showed that low energy densities and intensities
were necessary for singulation for a smaller wavelength. At a wavelength of 1064 nm, an energy
density of 448 jcm−2 and an intensity of 28.5 × 108 Wcm−2 were necessary [24], whereas, at 355 nm,
an energy density of 340 jcm−2 and an intensity of 1.7 × 108 Wcm−2 were sufficient to cut a 120 µm thick
anode [19]. These results could not be confirmed by studies with a laser in the green electromagnetic
spectrum (532 nm, 1 ns, 6 W). For the singulation of an anode (130 µm), with the same collector
thickness, an energy density of 560 jcm−2 and an intensity of 50.8 × 108 Wcm−2 were needed. This
could be attributed to the fact that the number of hits per surface increment of 165 increased the plasma
shielding effect, and thus reduced the maximum cutting speed [25].
In order to realize the most dynamic and fast cutting processes possible in a cutting plant,
the beam guidance on the workpiece is conventionally carried out by means of a remote scanner
system. As a result of the low mass and the associated low inertia of the deflection mirrors, very
high speeds and repetition accuracies can be achieved in the horizontal plane. Due to the varying
distance of the electrode to the scanner system, a focus adjustment in the vertical direction is necessary.
This adjustment can be produced by means of additional lenses (focus-shifter) or by a static f-theta
objective. Considering the static beam refocusing, the advantage of an f-theta objective over a focus
shifter is the higher repetition accuracy and wear-freedom. However, the dynamic focus by means of a
focus shifter allows us to adjust the working field and to customize the focus in certain areas.

2. Experimental

2.1. Materials
To investigate the influence of the laser process parameters on the properties of the cutting edge
and the influence on the electrochemical performance, double-sided coated electrodes with industrially
available material components were used. For the anode, the active material SMGA4 (91 wt.%; Hitachi,
Japan), with a specific capacity of 360 mAhg−1 , was coated on a 10 µm thick copper collector (Sumisho
Metallex, Japan). Subsequently, the coating was compacted to a density of 1.5 gcm−3 , which results
in the porosity of 32.25% and a total thickness of 123 µm. On the cathode side, the active material
NMC 111 (90 wt.%; BASF, Germany), with a specific capacity of 165 mAhg−1 , was coated on 20 µm
thick aluminum collector (Hydro Aluminum Rolled Products, Germany) and compacted to a degree
of 2.8 gcm−3 . The described compaction led to porosity of 31.35% and a total electrode thickness of
Batteries 2019, 5, 73 7 of 20

143 µm.
Batteries For
2018, 4, xthe
FORanode and cathode,
PEER REVIEW a conductivity additive SFG6L (2 wt.% anode, 2 wt.% cathodes; 7 of 21
Imerys, Switzerland), a carbon black C65 (2 wt.% anode, 4 wt.% cathodes; Imerys, Switzerland), and a
Imerys, Switzerland),
PVDF binder (5 wt.%and a PVDF
anode, binder
4 wt.% (5 wt.%Solvay,
cathodes; anode, 4Italy)
wt.%were
cathodes; Solvay,
utilized. TheItaly) were utilized.
cell manufacturing
The
wascell manufacturing
carried out with a was
27 µmcarried
thick out with a (Separion)
separator 27 µm thick separator
and (Separion)
a conventional and
LiPF a conventional
6 electrolyte (UBE
LiPF 6 electrolyte
Industries (UBE Industries
Ltd., Japan). Ltd., Japan).
The conductive The
salt LiPF 6
conductive
was solved salt
in a LiPF 6 was solved
concentration of in
one a concentration
mole in a solvent
of one mole in a solvent consisting of ethylene carbonate (EC), dimethyl carbonate
consisting of ethylene carbonate (EC), dimethyl carbonate (DMC), and ethyl methyl carbonate (DMC), and(EMC),
ethyl
methyl carbonate (EMC),
with a volumetric ratio ofwith a volumetric
the solvent ratio ofofthe
components solvent
1:1:1. components
To suppress of 1:1:1. of
the evolution Togas
suppress
duringthe
the
evolution of gas during the first charging, the electrolyte contained 2 wt.% of Vinylene
first charging, the electrolyte contained 2 wt.% of Vinylene Carbonate (VC). As further additives for Carbonate
(VC).
reducingAs hydrogen
further additives
formationfor reducing
at high hydrogen
voltages, formation
the electrolyte at high
contained voltages,
3 wt.% the electrolyte
of cyclohexylbenzene
contained
(CHB). 3 wt.% of cyclohexylbenzene (CHB).

2.2.Analysis
2.2. Analysisofofthe
theCutting
CuttingEdge
EdgeCharacteristics
Characteristics
The
Theprescriptive
prescriptive characteristics of the
characteristics of theelectrode
electrodecutting
cuttingedge
edgeare
are shown
shown in in Figure
Figure 5a means
5a by by means
of a
of a microsection.
microsection. TheseThese characteristics
characteristics were determined
were determined by light by light microscopy
microscopy (VHX 2000(VHX 2000 light
light microscope
microscope (LM),
(LM), Keyence, Keyence,
Osaka, Japan)Osaka, Japan)
and laser and laser
scanning scanning
microscope microscope
(VK-X Series 3D (VK-X Series 3D
Laser Scanning Laser
Confocal
Scanning
MicroscopeConfocal
(LSM), Microscope (LSM),
Keyence, Osaka, Keyence,
Japan). Here,Osaka, Japan). Here,
the parameters chamferthewidth
parameters chamfer width
and heat-affected zone
and
(HAZ)heat-affected zone to
were considered (HAZ)
be the were considered
significant to be
influencing the significant
factors influencingperformance
on the electrochemical factors on and,
the
electrochemical performance
therefore, investigated and,
further. Thetherefore, investigated
HAZ is defined further.
as an area where The
theHAZ
activeismaterial
defined isasthermally
an area
where thebut
stressed active
not material
removed.isThe
thermally
chamfer stressed
width but not removed.byThe
is characterized chamfer
active width
material is characterized
removal and a melt
by active material
formation zone. removal and a melt formation zone.

(b)

(a) (c)
Analysisofofthe
Figure5.5. Analysis
Figure theprescriptive
prescriptivecutting
cuttingedge
edgecharacteristics:
characteristics:(a)(a)Schematic
Schematicmicrosection
microsectionofofaa
laser-generatedcutting
laser-generated cuttingedge,
edge, 1.1. Chamfer
Chamferwidth
width(chw),
(chw), 2.2. The
Theheat-affected
heat-affectedzone
zone (HAZ),
(HAZ), 3.
3. Melt
Melt
formation, 4. Ablation, 5. Melt superelevation, α Chamfer angle; (b) LSM image of a cutting
formation, 4. Ablation, 5. Melt superelevation, α Chamfer angle; (b) LSM image of a cutting edge; (c) edge; (c)
Analysis of a cutting edge by LSM data, based on
Analysis of a cutting edge by LSM data, based on [10]. [10].

To measure
To measure these
thesecharacteristics, LM
characteristics, andand
LM LSMLSMimages were were
images taken taken
of the upper
of theside of the
upper electrodes
side of the
at the cutting edges. The areas of the heat-affected zone and the chamfer width could
electrodes at the cutting edges. The areas of the heat-affected zone and the chamfer width could be clearly
be
separated by a combined measuring method. By means of the LSM topography
clearly separated by a combined measuring method. By means of the LSM topography images images (Figure 5b,c),
the chamfer
(Figure 5b,c),width was measured.
the chamfer width wasBy subtracting
measured. Bythe subtracting
chamfer widththe from the entire
chamfer widthaffected
from the area (LM
entire
affected area (LM images), the heat-affected zone could be quantified. For the determination of
contaminant products as a result of the laser-material interaction, SEM (FEI Quanta 650, Thermo
Fisher, Waltham, MA, USA) and EDX (Oxford X-Max 80 mm², Oxford Instruments, Abingdon,
England) images of the cut electrodes were taken.
Batteries 2019, 5, 73 8 of 20

images), the heat-affected zone could be quantified. For the determination of contaminant products as
a result of the laser-material interaction, SEM (FEI Quanta 650, Thermo Fisher, Waltham, MA, USA) and
EDX (Oxford X-Max 80 mm2 , Oxford Instruments, Abingdon, England) images of the cut electrodes
Batteries 2018, 4, x FOR PEER REVIEW 8 of 21
were taken.
2.3.
2.3. Cell
Cell Format
Format andand Manufacturing
Manufacturing
To evaluate the
To evaluate the influence
influence of of the
the cutting
cutting edge
edge on on the
the electrochemical
electrochemical performance,
performance, pouch pouch cells
cells
with
with 15 compartments were built (total cell capacity about 9 Ah). The relatively high number
15 compartments were built (total cell capacity about 9 Ah). The relatively high number of of
compartments was chosen to emphasize the effect of the cutting edge
compartments was chosen to emphasize the effect of the cutting edge properties of the electrodes, properties of the electrodes,
maximizing
maximizing the the effects
effects ofof the
the cutting
cutting edgeedge characteristics
characteristics on on the
the electrochemical
electrochemical performance.
performance. The The
surface of the anode coated with active material was 16,484 mm² 2
surface of the anode coated with active material was 16,484 mm and, based on the geometry and, based on the geometry shown
shown in
in Figure 6a, gave a cutting edge to surface ratio of 0.030 mm −1−1. The cathode is defined by an area of
Figure 6a, gave a cutting edge to surface ratio of 0.030 mm . The cathode is defined by an area of
15,209
15,209 mmmm²2 andand aa ratio
ratio of cutting edge
of cutting edge to to the
the surface
surface ofof 0.031
0.031 mmmm−1 −1. For the anode, a circumferential
. For the anode, a circumferential
overlap
overlap of of 2.5
2.5mm mmresulted
resulted fromfromthethe illustrated
illustrated geometries
geometries for theforanode
the anode
and theand the cathode.
cathode. This
This overlap
overlap
guaranteed guaranteed
the total the total
stress stress
of the of theas
cathode cathode as a in
a reference reference in these examinations
these examinations and ensured andtheensured
correct
the correct balancing
balancing of the compartment. of the compartment.
By
By means
means of of aaz-folding
z-foldingprocess
process(prototype
(prototypeplant,plant,Jonas
Jonas& Redmann,
& Redmann, Berlin, Germany),
Berlin, Germany), the
singularized
the singularized electrodes were stacked
electrodes were stacked alternating betweenbetween
alternating a separator to form an
a separator toelectrode-separator-
form an electrode-
composite (ECS). Subsequently, the individual collectors of the
separator-composite (ECS). Subsequently, the individual collectors of the electrodes were electrodes were joinedjoined
to a tab
to a via
tab
ultrasonic welding (Ultraweld F20, Branson Ultraschall, Hannover, Germany).
via ultrasonic welding (Ultraweld F20, Branson Ultraschall, Hannover, Germany). For this purpose, the For this purpose, the
15
15 single anode collectors
single anode collectorswere
werewelded
weldedtotoaanickelnickeltabtabwith
withananenergy
energyofof 200
200 j, and
j, and cathodes
cathodes collectors
collectors to
to an aluminum tab with an energy of 100 j at an oscillating sonotrode
an aluminum tab with an energy of 100 j at an oscillating sonotrode amplitude of 30 µm. Subsequently, amplitude of 30 µm.
Subsequently,
the ECS was dried the ECS
under wasvacuum
dried underfor 120 vacuum
◦ C for for
16 h.120In°C
theforfollowing
16 h. In thestep, following
the ECSstep, the ECS
was inserted
was inserted into the pouch bag and filled under argon atmosphere
into the pouch bag and filled under argon atmosphere with electrolyte and sealed. Finally, the with electrolyte and sealed.
filled
Finally, the filled cells were tempered ◦ for 4 h at 60 °C to support the complete
cells were tempered for 4 h at 60 C to support the complete wetting of the electrodes. The finished wetting of the electrodes.
The finished
assembled assembled
cell is shown cell is shown
in Figure in Figure 6b [12].
6b [12].

(a) (b)
Cell format
Figure 6. Cell format and
and pouch
pouch cell design: (a)
(a) Electrode
Electrode format,
format, (b)
(b) Complete
Complete pouch
pouch cell.

2.4. Cell Diagnostic

2.4. Cell Diagnostic
After assembly and wetting, the manufactured cells were placed in a climate chamber (WKM
After assembly and wetting, the manufactured cells were placed in a climate chamber (WKM
Inc., Lachendorf, Germany) at 20 ◦ C and connected to a battery tester (Series XCTS, Basytec Inc.,
Inc., Lachendorf, Germany) at 20 °C and connected to a battery tester (Series XCTS, Basytec Inc.,
Asselfingen, Germany) with a fixed torque of 2.54 Nm. Due to the high capacity of the battery cells,
Asselfingen, Germany) with a fixed torque of 2.54 Nm. Due to the high capacity of the battery cells,
the tests required a high safety environment. Therefore, the climate chambers were equipped with a
the tests required a high safety environment. Therefore, the climate chambers were equipped with a
fire extinguishing system (Wagner Group Inc., Langenhagen, Germany). In the event of an accident,
fire extinguishing system (Wagner Group Inc., Langenhagen, Germany). In the event of an accident,
the climate chamber is flooded with nitrogen gas. Furthermore, an activated carbon filter (Stöbich
technology Inc., Goslar, Germany) will filter the exhaust air in the pipe duct.
Batteries2018,
Batteries 2019,4,5,x73FOR PEER REVIEW 9 9ofof21
20

In our experiments, the cells were formed in two cycles. They were first charged and discharged
the climate chamber is flooded with nitrogen gas. Furthermore, an activated carbon filter (Stöbich
at 1/10 C, and in the second formation cycle with 1/2 C. Upper and lower cut-off voltages were 4.2 V
technology Inc., Goslar, Germany) will filter the exhaust air in the pipe duct.
and 2.9 V, respectively, for all charge-discharge cycles. To characterize the cells, a capacity test at 1/10
In our experiments, the cells were formed in two cycles. They were first charged and discharged
C and a pulse test (1 C for 1 s) to determine the internal resistance were performed. After the
at 1/10 C, and in the second formation cycle with 1/2 C. Upper and lower cut-off voltages were 4.2 V
formation process, the cells were matured over eight days with a state of charge (SOC) of 50% at 20
and 2.9 V, respectively, for all charge-discharge cycles. To characterize the cells, a capacity test at 1/10 C
C. Then, the aging of the cells began with a C-rate test with different discharge-rates from 1/5 to 2 C,
and a pulse test (1 C for 1 s) to determine the internal resistance were performed. After the formation
which lasted 20 cycles. Long-term cycling was then started at 1 C for 100 cycles. After this, the
process, the cells were matured over eight days with a state of charge (SOC) of 50% at 20 C. Then, the
cyclization was paused, and the internal resistance was measured in a pulse test before the C-rate test
aging of the cells began with a C-rate test with different discharge-rates from 1/5 to 2 C, which lasted
was repeated. These aging investigations were repeated periodically until at least 450 cycles were
20 cycles. Long-term cycling was then started at 1 C for 100 cycles. After this, the cyclization was
reached. In this study, 5 cells per laser variation were analyzed, and only the long-term cycling was
paused, and the internal resistance was measured in a pulse test before the C-rate test was repeated.
considered.
These aging investigations were repeated periodically until at least 450 cycles were reached. In this
study, 5 cells per laser variation were analyzed, and only the long-term cycling was considered.
2.5. Laser Cutting Plant and Key Parameter
2.5. Laser Cutting
The laser Plantplant
cutting and Key
used Parameter
in this study was an in-house development and construction. Due
to its The
modular structure
laser cutting andused
plant the process-immanent
in this study was anadvantages of the scanner
in-house development andsystem, it is suitable
construction. Due to
for a large number of different electrode formats. The beam source used
its modular structure and the process-immanent advantages of the scanner system, it is suitable was a nanosecond pulsed
for a
fiber laser with a central emission wavelength of 1059–1065 nm (G4 Pulsed
large number of different electrode formats. The beam source used was a nanosecond pulsed fiber Fiber Laser, SPI Lasers
UK Ltd.,
laser withSouthampton,
a central emissionUK). The average of
wavelength power of thenm
1059–1065 fiber laser
(G4 was Fiber
Pulsed 72 W Laser,
with aSPIpeak pulseUK
Lasers power
Ltd.,
of up to 13 kW and an M² of <1.6. Guidance and focusing of the laser beam
Southampton, UK). The average power of the fiber laser was 72 W with a peak pulse power of up were performed by a 3-to
axis laser beam deflection system (AXIALSCAN 30/FOCUSSHIFTER,
13 kW and an M of <1.6. Guidance and focusing of the laser beam were performed by a 3-axis laser
2 Raylase AG, Wessling,
Germany) with asystem
beam deflection working field of 40030/FOCUSSHIFTER,
(AXIALSCAN × 400 mm². The firstRaylase two dimensions
AG, Wessling,of the scannerwith
Germany) werea
needed to drive the spot over the workpiece to create the cutout. The third dimension
working field of 400 × 400 mm2 . The first two dimensions of the scanner were needed to drive the spot was needed to
ensure
over the a workpiece
constant spot size ofthe
to create ~74 µm with
cutout. Theathird
focus depth of was
dimension 0.6 mm on one
needed level over
to ensure the entire
a constant spot
working field. All laser cuts were made in one pass. The fully automated handling
size of ~74 µm with a focus depth of 0.6 mm on one level over the entire working field. All laser system was carried
cuts
out by simple roll to roll and pick and place operation (Figure 7a), controlled
were made in one pass. The fully automated handling system was carried out by simple roll to roll by an Arduino Mega
2560. Sinceand
and pick theplace
cut could only be
operation realized
(Figure 7a),in the focus by
controlled level
an of the laser
Arduino spot,2560.
Mega a special
Sincenegative form
the cut could
for
only be realized in the focus level of the laser spot, a special negative form for the positioning ofThe
the positioning of the electrode had to be built for each electrode format (Figure 7b). the
positioning of the electrode was done by negative pressure on holes surrounding
electrode had to be built for each electrode format (Figure 7b). The positioning of the electrode was the cutting curve.
Even
done though a cutting
by negative on the
pressure onfly wassurrounding
holes possible with thethe used remote
cutting scanner
curve. Even system,
though a static
a cutting oncutting
the fly
operation was used to guarantee constant cutting speed over the complete cutting
was possible with the used remote scanner system, a static cutting operation was used to guarantee length and an easy
format
constant change.
cutting speed over the complete cutting length and an easy format change.

(a) (b)

Figure7.
Figure Lasercutting
7.Laser cuttingplant:
plant:(a)
(a)Front
Frontview
viewof
ofthe
thelaser
lasercutting
cuttingplant;
plant;(b)
(b)Negative
Negativeform.
form.

3. Results and Discussion

3. Results and Discussion
The presentation of the results has been divided into three sections. In the first section, the results
The presentation of the results has been divided into three sections. In the first section, the results
of the influence of the laser parameters on the cutting edge characteristics, chamfer width, and
of the influence of the laser parameters on the cutting edge characteristics, chamfer width, and heat-
heat-affected zone have been considered and discussed. The investigations focused on the pulse
affected zone have been considered and discussed. The investigations focused on the pulse repetition
repetition frequency, the cutting speed, and the pulse length, as well as the influence of the number of
frequency, the cutting speed, and the pulse length, as well as the influence of the number of hits per
surface increment, and intensity at a constant energy density. In the second section, the influence of
Batteries 2019, 5, 73 10 of 20

hits per surface increment, and intensity at a constant energy density. In the second section, the influence
of the cutting edge characteristics and corresponding laser process parameters on the electrochemical
performance has been examined. Building on these results, the last section would present further
investigations of the cutting process and the cutting edge, explaining the electrochemical behavior.

3.1. Influence of the Laser Process Parameters on the Cutting Edge Characteristics
In a first step, we investigated the influence of the laser parameters on the cutting edge properties.
For this purpose, the pulse repetition frequency (PRF) and the cutting speed (Vc ) were deliberately
varied with constant power and pulse duration. The resulting cut edges were evaluated according
to the analysis methods presented. On the basis of the obtained data, models could be developed
by means of the analysis program Design Expert 11, which describes the examined parameter space.
The experimental design was made with a D-optimal strategy and comprised 13 experiments with five
repeated measurements each. The response surface model was adapted to the measured values by
fitting it to a quadratic polynomial of the form of Response = Intercept * + A + B + AB + AB2 + A2 B A2
B2 . The results for the anode (Figure 8) showed that both parameters influenced the formation of the
chamfer width and the heat-affected zone. In Figure 8a model, it could be seen that the formation of
the chamfer width steadily decreased with increasing PRF. This tendency could also be observed with
increasing cutting speed. The smallest chamfer width for this model was obtained at the maximum
achievable speed of 700 mms−1 , with a pulse repetition frequency of 490 kHz. Considering the
additional laser parameters, this resulted in a number of hits per area increment of 51 and an energy
density of 141 jcm−2 . The decrease in the chamfer width with increasing speed or decreasing energy
density could be explained by the lower energy input per area. The dependence on energy density
has already been confirmed by previous publications [24]. The decrease of the chamfer width with
increasing pulse repetition frequency could be attributed to different mechanisms, which result from
the adjusted mode of the energy input. Due to the constant average power and the constant pulse
duration, the pulse peak power had to drop with increasing pulse repetition frequencies to reduce the
energy per pulse. As a consequence, the intensity and the energy decreased with increasing pulse
repetition frequency, and thus the width of the threshold intensity or the spot diameter, which led
to an ablation, becoming smaller due to the Gaussian intensity distribution. Besides, the increased
number of hits of 360 (at 490 kHz and 100 mms−1 ) could lead to a more intensive harmonic laser-plasma
interaction, which reduced the energy impinging on the target by shielding effects and thus reduced
the energy density. In addition, the reduced pulsed peak power could lead to a smaller broadening of
the plasma formation. Since the plasma was also involved in the removal of material and the thermal
load on the surface, the proportion of the total material removal became less at higher frequencies.
Literature regarding ns laser-induced breakdown spectroscopy describes threshold pulse fluences for
forming a plasma of 1.01 jcm−2 for aluminum and 1.46 jcm−2 for copper. As the smallest pulse fluence
at 490 kHz for this System was 3.45 jcm−2 , the plasma formation, in general, would always occur for
the examined parameter space [26].
Batteries2018,
Batteries 2019,4,5,x73FOR PEER REVIEW 1111ofof21
20

(a) (b)
Figure 8.
Figure Modelfor
8. Model forthe
theinfluence
influenceof ofthe
thepulse
pulserepetition
repetitionfrequency
frequencyand
andcutting
cuttingspeed
speedon onthe
the anode
anode
cuttingedge:
edge:7272w,w,240
240ns;ns; 2 = 0.77, Adjusted
cutting (a)(a) Influence
Influence ononthethe chamfer
chamfer width
width (Cubic
(Cubic fitting:
fitting: R² =R0.77, Adjusted R² =
R2 =Predicted
0.75, 0.75, Predicted R2 = 0.73);
R² = 0.73); (b) Influence
(b) Influence onheat-affected
on the the heat-affected
zonezone (Cubic
(Cubic fitting:
fitting:
2 = 0.94, Adjusted
R² =R0.94, Adjusted R²
R 2 = 0.93, Predicted R 2
= 0.93, Predicted R² = 0.93).= 0.93).

From the
From the heat-affected
heat-affectedzone zonemodel
model (Figure
(Figure 8b),8b),
it could
it couldbe seen that increasing
be seen that increasingthe PRF thecould
PRF reduce
could
reduce the heat-affected zone. The cause for the dependence of the thermal load on the PRFexplained
the heat-affected zone. The cause for the dependence of the thermal load on the PRF could be could be
by the reasons
explained by thegiven abovegiven
reasons for theabove
dependence
for the of the chamferofwidth
dependence on the PRF.
the chamfer widthTheon correlation
the PRF.ofThe the
HAZ with the cutting speed showed the opposite behavior to the
correlation of the HAZ with the cutting speed showed the opposite behavior to the chamfer width. chamfer width. As the cutting speed
increased,
As the cutting the HAZ
speed increased
increased, in thetherange
HAZ of increased
70–350 kHz. in This
the could
range be ofexplained
70–350 kHz. by the factcould
This that with be
increasing cutting speed, the chamfer width and the kerf were
explained by the fact that with increasing cutting speed, the chamfer width and the kerf were becoming steadily smaller. This means
that less material
becoming steadilywas removed
smaller. for higher
This means thatcutting speeds.
less material was Due to the Gaussian
removed for higherintensity distribution
cutting speeds. Due
and the increasing speed, the energy input profile changed to the
to the Gaussian intensity distribution and the increasing speed, the energy input profile changed toeffect that the material which was no
longer ablated underwent such high thermal stress that there
the effect that the material which was no longer ablated underwent such high thermal stress thatwas an optical change. This means that
the final
there wasproduct
an optical cutchange.
with high Thisspeed
means contained
that theafinal larger active cut
product material area that
with high speed is contained
thermally stressed,
a larger
which would be completely removed at lower speeds. The investigations
active material area that is thermally stressed, which would be completely removed at lower speeds. on the cathode were carried
out in smaller parameter space (Figure 9a) with respect to the speed (100–400 mms −1 ) because due
The investigations on the cathode were carried out in smaller parameter space (Figure 9a) with
to the higher −1 , the cut-through limit for high
respect to the material thickness
speed (100–400 mmsof the collectordue
−1) because already
to the at higher
455 mms material thickness of the collector
PRF was reached. The results for the formation of the chamfer
already at 455 mms , the cut-through limit for high PRF was reached. The results for
−1 width as a function of the
thePRF and Vc
formation
showed similar tendencies as the anodic model. Both with increasing
of the chamfer width as a function of the PRF and Vc showed similar tendencies as the anodic model. PRF and with increasing Vc , the
chamfer
Both withwidth decreased
increasing PRF significantly.
and with increasing The resultsVc, theshowed
chamfer thatwidth
the smallest
decreasedchamfer widths could
significantly. The
results showed that the smallest chamfer widths could only be achieved through the combination for
only be achieved through the combination of low energy densities and high PRF. Possible causes of
these
low dependencies
energy densitiescould
and high be transferred
PRF. Possible from the explanations
causes to the anode.could
for these dependencies The bemodel presented
transferred fromfor
theexplanations
developmentto ofthe
theanode.
heat-affected zonepresented
for cathodes 2 of 0.93
the The model for(Figure 9b) could be
the development of adjusted with an Rzone
the heat-affected for
and allowed
cathodes a 92%
(Figure 9b)reliable
could be prediction.
adjusted with Withan increasing
R² of 0.93PRF, the HAZadecreased
and allowed 92% reliable significantly
prediction.until Withit
approachedPRF,
increasing zerotheat 490
HAZ kHz. Here, thesignificantly
decreased influence of the untilcutting speed played
it approached zeroonly
at a490minorkHz. role. Despite
Here, the
the low significance, an increase in the cutting speed led to a reduction
influence of the cutting speed played only a minor role. Despite the low significance, an increase in in the HAZ. These results were
opposite
the cuttingtospeedthe results
led tofor the anode.inThe
a reduction thedifference
HAZ. These in behavior
results were was opposite
explainedtobythe two facts.for
results Firstly,
the
the intensity
anode. and energy
The difference in difference
behavior between
was explained the ablationby two threshold and the
facts. Firstly, thethermal
intensity stress
andthreshold
energy
were smaller
difference for the the
between cathode active
ablation material and
threshold than thefor the anodestress
thermal activethreshold
material. were Secondly, the ablation
smaller for the
threshold
cathode of thematerial
active cathodethan activeformaterial
the anode wasactive
highermaterial.
than thatSecondly,
of the anode the active
ablation material.
threshold of the
cathode active material was higher than that of the anode active material.
Batteries2018,
Batteries 2019,4,5,x73FOR PEER REVIEW 1212ofof21
20

(a) (b)
Figure9.
Figure Modelfor
9.Model forthe
theinfluence
influenceof ofthe
thepulse
pulserepetition
repetitionfrequency
frequencyand
andcutting
cuttingspeed
speedon onthe
thecathode
cathode
cuttingedge:
edge:7272w,w,240
240ns;ns; 2 = 0.91, Adjusted
cutting (a)(a) Influence
Influence ononthethe chamfer
chamfer width
width (Cubic
(Cubic fitting:
fitting: R² =R0.91, Adjusted R² =
R2 =Predicted
0.90, 0.90, Predicted R2 = 0.88);
R² = 0.88); (b) Influence
(b) Influence onheat-affected
on the the heat-affected
zonezone (Cubic
(Cubic fitting:
fitting:
2 = 0.94, Adjusted
R² =R0.94, Adjusted R²
R 2 = 0.93, Predicted R 2
= 0.93, Predicted R² = 0.92).= 0.92).

Furtherinvestigations
Further investigations outsideoutside of of the
theconsidered
considered parameter
parameter space space inin the
therange
rangeof ofvery
verylow lowcutting
cutting
speeds (50 mms -1 ) and very high energy densities, respectively, showed that on the cathode and anode
speeds (50 mms-1) and very high energy densities, respectively, showed that on the cathode and
cuttingcutting
anode edge, edge,
eithereitherno or novery
or small HAZHAZ
very small couldcould
be identified.
be identified.ThisThis
waswas caused by the
caused by theslope of the
slope of
intensity distribution and the very high energy input. As a result, the areas
the intensity distribution and the very high energy input. As a result, the areas that were previously that were previously only
thermally
only stressed
thermally at lower
stressed intensities
at lower were subjected
intensities to material
were subjected removalremoval
to material at higheratenergy
higherdensities.
energy
Furthermore, the high energy density at 50 mms −1 led to an increase in the ablation area, since the
densities. Furthermore, the high energy density at 50 mms led to an increase in the ablation area,
−1

ablation thresholds of the collector and active material differ

since the ablation thresholds of the collector and active material differ significantly. significantly.
With regard
With regard to to the
the strong
strong influence
influence of of the
the PRF
PRF ononthe
thechamfer
chamferwidth widthand andthetheHAZ,
HAZ,the theinfluence
influence
of the pulse duration and the pulse peak power on different PRF was
of the pulse duration and the pulse peak power on different PRF was investigated in a further study. investigated in a further study.
For this purpose, cuts were performed at a constant energy density
For this purpose, cuts were performed at a constant energy density with a variation of the pulse with a variation of the pulse
durationand
duration andpulse
pulse peak peak power.
power. Pulse
Pulseduration
durationwas waskept
keptconstant
constant(240 (240ns)ns)with
withthe theeffect
effect that
that the
the
pulse peak power decreased with increasing frequency (70 kHz: 13
pulse peak power decreased with increasing frequency (70 kHz: 13 kW, 102 kHz: 6 kW, 200 kHz: 2 kW, 102 kHz: 6 kW, 200 kHz: 2 kW,
291 kHz:
kW, 1 kW,
291 kHz: 403 403
1 kW, kHz:kHz:0.7 kW,
0.7 kW,490 490kHz: 0.550.55
kHz: kW). TheThe
kW). pulse pulseduration
duration waswasshortened
shortened (240–20
(240–20ns)
to keep the pulse peak power quasi constant (70 kHz: 13 kW, 102/200/291
ns) to keep the pulse peak power quasi constant (70 kHz: 13 kW, 102/200/291 kHz: 10 kW, 403/490 kHz: 10 kW, 403/490 kHz:
9 kW).
kHz: 9 The
kW).results for the chamfer
The results width and
for the chamfer the heat-affected
width zone derived
and the heat-affected from
zone these experiments
derived from these
are shown inare
experiments Figure
shown 10. The PRF variation
in Figure 10. The PRF with variation
constant pulse
with duration
constant showed the same
pulse duration tendencies
showed the
as in the previously presented models in Figures 8
same tendencies as in the previously presented models in Figures 8 and 9. and 9.
AAreduction
reductionof ofthethepulse
pulselength
lengthwithwithaaquasi-constant
quasi-constantpulse pulsepeak peakpower
powerled ledtotoaalarger
largerchamfer
chamfer
width and
width and HAZ,
HAZ, bothboth at at the
the anode
anode and and at at the
the cathode
cathode (Figure
(Figure 10).10). OnOnthetheanode
anodeside,
side,thethereduction
reduction
of the pulse length led to a significant enlargement of the heat-affected
of the pulse length led to a significant enlargement of the heat-affected zone for the PRF 102 and zone for the PRF 102 200
and
200 kHz.
kHz. Due to Due
theto the higher
higher PRF and PRF theand
high the high intensities,
intensities, the plasmathe plasma
formed was formed was ofenergy,
of higher higherleading
energy,
leading to enhanced thermal stress of the electrode surface and, thus,
to enhanced thermal stress of the electrode surface and, thus, potentially to a higher ablation. The potentially to a higher ablation.
The reduction
reduction of theofHAZ the HAZ
by theby the increased
increased frequencyfrequency
of the nsof laser
the nspulseslaser was
pulses
thuswas thus determined
determined largely
largely
by the lowby the lowenergy.
pulse pulse energy.
Only by Only
a much by a much
greater greater reduction
reduction of theofpulse
the pulse
lengthlength
of lessof less
thanthan
10
10 picoseconds, a cold cutting is
picoseconds, a cold cutting is possible [14]. possible [14].
Batteries 2018, 4, x FOR PEER REVIEW 13 of 21
Batteries 2019, 5, 73 13 of 20

(a) (b)
Figure 10. Influence
Figure 10. Influenceofofthe pulse
the duration
pulse durationat different pulse
at different repetition
pulse frequencies
repetition on theon
frequencies chamfer width
the chamfer
and heat-affected
width zone ofzone
and heat-affected the anode
of the (a) and(a)
anode theand
cathode (b) cutting
the cathode edge. edge.
(b) cutting

The
The increased
increasedchamfer
chamferwidthwidthforfor
thethe
anode andand
anode the cathode
the cathodeat higher pulse pulse
at higher peak powers at higher
peak powers at
PRF confirmed the assumption that was previously made on the anode and
higher PRF confirmed the assumption that was previously made on the anode and cathode model. cathode model. In addition
to
In the decrease
addition in pulse
to the peak
decrease inpower, the decrease
pulse peak in pulse
power, the energy
decrease at higher
in pulse energyPRFatled to a reduction
higher PRF led toofa
the chamfer
reduction ofwidth.
the chamfer width.
In
In the followingexperiment,
the following experiment,the thescalability
scalabilityofofthe
thecutting
cuttingspeed
speed oror
thethe
influence
influence of of
thethe
number
number of
hits at constant energy density was investigated (Figure 11). The results for the
of hits at constant energy density was investigated (Figure 11). The results for the anode showed that anode showed that at
constant
at constant energy
energydensity, the chamfer
density, width
the chamfer increased
width at a reduced
increased rate. A
at a reduced reason
rate. for this
A reason forwas
thisthe
waslower
the
intensity and the correlated intensity distribution, as well as the lower energy
lower intensity and the correlated intensity distribution, as well as the lower energy of the pulse, of the pulse, which
narrowed
which narrowed the profile
the of the material
profile removal threshold.
of the material As a result,
removal threshold. Asthe geometric
a result, distance between
the geometric distance a
full cut and the ablation of the active material increased (see Figure 3.). In general,
between a full cut and the ablation of the active material increased (see Figure 3.). In general, the the cutting kerf,
as well as
Batteries
cutting the
2018,
kerf, entire
4,as
x FOR area
wellPEER in which
REVIEW
as the material
entire area was removed,
in which material wasbecame smallerbecame
removed, as a result. Because
smaller of of
14 the21
as a result.
displacement
Because of theof the removalof
displacement thresholds,
the removal a larger chamfer
thresholds, width
a larger was produced
chamfer width was at lower
producedspeeds for a
at lower
specific energy density.
speeds for a specific energy density.
The fluence resulting from the reduction of the average power to 33.3% was still 1.15 jcm−2 and
was thus above the limit for the formation of plasma for aluminum. Despite the high number of hits,
it could be assumed that shielding effects were negligible as the intensity was much lower, and the
larger plasma formation led to increased removal of the active material. When the average energy
was reduced to one-third of the maximum power, no cut could be made through the copper collector
at a frequency of 490 kHz for the energy density being studied. Due to the strong reduction of the
pulse energy and peak pulse power, the beam could no longer be coupled because of the low
absorption of the copper. When cutting copper, it is first heated by the radiation until it oxidizes [10].
As soon as the material oxidizes, the radiation can be much better coupled into the material, and only
then leads to the sufficiently high absorption of the laser radiation for a complete cut.

Figure 11. Influence of the intensity and the number of hits per area increment on the chamfer width at
aFigure
constant
11.energy density
Influence 328 jcm−2and
of theofintensity . the number of hits per area increment on the chamfer width
at a constant energy density of 328 jcm–2.
The fluence resulting from the reduction of the average power to 33.3% was still 1.15 jcm−2 and
was thus above investigations
Cathode the limit for theshowed
formation of plasma
similar for aluminum.
tendencies, which Despite the high
were much number
less of hits,
pronounced.
itCompared
could be assumed that shielding effects were negligible as the intensity was much lower,
to the anode, the cathode could be cut at 33% of the maximum average power, although and the
larger plasma formation
the cathode’s aluminum ledcollector
to increased
was removal
twice asofthick
the active
as thematerial.
anode’sWhen thecollector.
copper average energy was
The results
basically showed that the necessary energy density could be used as a second parameter to define a
cut-through limit.

3.2. Influence of the Cutting Edge Characteristics and the Process Parameters on the Electrochemical
Performance
Batteries 2019, 5, 73 14 of 20

reduced to one-third of the maximum power, no cut could be made through the copper collector at a
frequency of 490 kHz for the energy density being studied. Due to the strong reduction of the pulse
energy and peak pulse power, the beam could no longer be coupled because of the low absorption of
the copper. When cutting copper, it is first heated by the radiation until it oxidizes [10]. As soon as the
material oxidizes, the radiation can be much better coupled into the material, and only then leads to
the sufficiently high absorption of the laser radiation for a complete cut.
Cathode investigations showed similar tendencies, which were much less pronounced. Compared
to the anode, the cathode could be cut at 33% of the maximum average power, although the cathode’s
aluminum collector was twice as thick as the anode’s copper collector. The results basically showed
that the necessary energy density could be used as a second parameter to define a cut-through limit.

3.2. Influence of the Cutting Edge Characteristics and the Process Parameters on the Electrochemical
Performance
Based on the knowledge gained from the experiments, a parameter study was developed to
investigate the influence of the presented product and process properties on the electrochemical
performance of the electrode, or the cell. In a first study, a cell was built with anodes and cathodes cut
using the same laser and system parameters. The parameter configuration for this cell was referred
to as V0 and served as a reference system for the variation of the parameter configuration. This
parameter configuration was very reliable in terms of possible fluctuations in the focus position and
the layer thickness. In a first limitation, it was examined whether the cutting edge on the anode side,
or the cathode side, had a greater influence on the electrochemistry and, thus, the performance of
the cell. In further experiments, only the cutting edge of the performance controlling electrode was
examined. For the first experiments, cells with anodes (V1) and cathodes (V2) with a very large chamfer
width were built. To produce this very large chamfer width, the electrodes were cut with a very high
energy density and intensity. In the following, the parameters PRF (V3), Vc (V4), and τ (V5) were
varied at a constant energy density at the electrode. Based on the parameter configurations shown in
Table 1, it was possible to evaluate the previously presented cutting edges characteristics and process
characteristics with regard to their influence on the electrochemical performance of the cell.

Table 1. Set laser parameters to investigate the impact on electrochemical performance.

Parameter Unit V0 V1 V2
Vc mms–1 300 50 300
PRF kHz 70 70 70
τ ns 240 240 240
Anode
ED jcm–2 328 1968 328
IPeak Wcm–2 3.02 × 108 3.02 × 108 3.02 × 108
nline - 17 103 17
Vc mms–1 300 50 300 100 300
PRF kHz 70 70 490 490 490
τ ns 240 240 240 240 20
Cathode
ED jcm–2 328 1968 328 328 328
IPeak Wcm–2 3.02 × 108 3.02 × 108 0.17 × 108 0.1 × 108 2.09 × 108
nline - 17 103 120 362 120
Cutting speed (Vc ), Pulse repetition frequency (PRF), Pulse duration (τ), Energy density (ED), Intensity (IPeak ),
Number of laser pulses per surface increment (nline ).

The evaluation of the electrochemical performance showed that the cutting edge of the cathode
exerted the greater influence. Therefore, the influence of cut edge characteristics and process
configurations at the cathode was investigated. In the following, the characteristics chamfer width and
heat-affected zone have been shown for the examined parameter configurations V0 to V5.
The comparison of the features in Figure 12 showed that the total affected area consisting of the
heat-affected zone and chamfer width was the largest for the reference parameter V0 for both the
anode and the cathode. The largest chamfer width with almost identical characteristics showed the
configurations at the cathode was investigated. In the following, the characteristics chamfer width
and heat-affected zone have been shown for the examined parameter configurations V0 to V5.
The comparison of the features in Figure 12 showed that the total affected area consisting of the
heat-affected zone and chamfer width was the largest for the reference parameter V0 for both the
anode and the cathode. The largest chamfer width with almost identical characteristics showed the
Batteries 2019, 5, 73 15 of 20
parameters V1 for the anode and V2 for the cathode. The further investigations with the parameters
V3 to V5 showed, on the cathode side, the smallest influenced area with an average chamfer width
of 70 µm toV1
parameters 80 for
µm.the anode and V2 for the cathode. The further investigations with the parameters
V3 to V5 showed, on the cathode side, the smallest influenced area with an average chamfer width of
70 µm to 80 µm.

Figure 12. Response to the parameters, shown in Table 1.

The investigation of Figure

the 12. Response of
influence to the
theparameters,
presentedshown in Table
cutting edge 1. characteristics on the
electrochemical performance was carried out by means of the cyclization routine defined in Section 2.4.
The investigation
The result of the diagnosis of ofthe
theinfluence of the performance
electrochemical presented cutting
is shown edge characteristics
in the form of normalizedon the
electrochemical performance was carried out by means of the cyclization routine
cyclization curves in Figure 13. The cyclization curves showed that in comparison to the reference (V0), defined in Section
2.4.cathode
the The result of theedge
cutting diagnosis of the electrochemical
(V2) exerted a significantly performance
greater influence is shown
on thein cycle
the form of normalized
stability than the
cyclization curves in Figure 13. The cyclization curves showed that in comparison
anode (V1). In this case, the mean value for all cells, with the anode (V1), lied on the mean value of the to the reference
(V0), the cathode
reference cells (V0)cutting
with aedge (V2)
similar exerted deviation
standard a significantly
after greater influence
350 cycles. on the
The cells withcycle
the stability
cathode than
(V2)
the anode (V1). In this case, the mean value for all cells, with the anode (V1), lied
were far above this value and thus had significantly higher cycle stability. All tests to determine the on the mean value
of the reference
influence cells (V0)width
of the chamfer with a(V3–V5)
similar standard deviation
on the cathode sideafter
showed350 that
cycles. The
with cells
low with the
chamfer cathode
width, no
(V2) were far above
improvement of the this
cyclevalue and thus
stability couldhad
be significantly higher cycle
achieved compared to V2. stability.
Since the Allcells
testsV2to to
determine
V5 had
the influence
higher of the chamfer
cycle stability than the width (V3–V5)
reference cellsonV0,
thethe
cathode side showed
statement could bethat madewith low
that thechamfer width,
heat-affected
zone on the cathode side had a greater influence on the electrochemical stability of the cell than had
no improvement of the cycle stability could be achieved compared to V2. Since the cells V2 to V5 the
higher cycle
chamfer width. stability than thethe
Furthermore, reference cells V0,
cycling curves the statement
of cells V3 and V5could be made
were nearly that the
identical heat-affected
after 350 cycles.
zone this,
From on the cathode
it could be side had athat
deduced greater influence
the pulse on the
duration electrochemical
or pulse peak powerstability
as processof the cell thandid
parameters the
not exert a significant influence on the electrochemical performance. The cells with cathodes cut at
constant line energy at reduced speed (V4) showed greater cycle stability after 350 cycles than the V3
and V5 cells. Despite the optimized process control, the cycle stability of the cells V4 was below that
of V2.
The cells V3 to V5 showed a greater capacity drop than the cells from the series V2, although
they had a small chamfer width and no heat-affected zone. This was an indication that in addition
to the previously known and analyzed product features, another, previously unrecognized feature,
influenced the electrochemical performance.
parameters did not exert a significant influence on the electrochemical performance. The cells with
cathodes cut at constant line energy at reduced speed (V4) showed greater cycle stability after 350
cycles than the V3 and V5 cells. Despite the optimized process control, the cycle stability of the cells
V4 was below that of V2.
Batteries 2019, 5, 73 16 of 20

Figure 13. Capacity fading during the long-time cyclization of the investigated electrode/
cell configuration.
Figure 13. Capacity fading during the long-time cyclization of the investigated electrode/cell
3.3. configuration.
Further Investigations of the Cutting Process and the Electrode Surface to Explain the
Electrochemical Behavior
The cells V3 to V5 showed a greater capacity drop than the cells from the series V2, although
In addition to the physical characteristics of the cutting edge, it was found that the different
they had a small chamfer width and no heat-affected zone. This was an indication that in addition to
parameters led to a different degree of flying sparks, as shown in Figure 14. This could be recorded
the previously known and analyzed product features, another, previously unrecognized feature,
by imaging techniques. The sparking could lead to contamination of the electrode and thus affect
influenced the electrochemical performance.
the electrochemical performance. The images showed that with increased pulse repetition frequency
(V0 → V3),Investigations
3.3. Further the distanceofofthe theCutting
spark Process
flight increased by 2.5 times.
and the Electrode Surface This couldthe
to Explain beElectrochemical
explained by the
increased number of hits if the cutting speed remained the same. If the number of hits on the active
Behavior
material, as well as on the solid and molten collector, increased, the number and acceleration of the
In addition
ablation products to would
the physical
increasecharacteristics
too. A reduction of theofcutting edge, speed
the cutting it waswith
found that theline
constant different
energy
parameters led to a different degree of flying sparks, as shown in Figure 14.
(V4) showed a strong reduction of the sparks. The lower level of the spark formation was due to the This could be recorded
by imaging
lower energytechniques.
and intensityThe per
sparking
pulse,could
as well lead to contamination
as the reduced travelofspeed.
the electrode andof
The profile thus
theaffect the
sparkling
electrochemical performance. The images showed that with increased pulse repetition
flight was very similar to the sparking profile at low pulse repetition frequency and traversing speed frequency (V0
→ V3),Since
(V2). the distance
variation ofV2
thewas
spark
cutflight
withincreased
a lower pulseby 2.5 times. This
repetition could bethan
frequency explained by the
variation V4, increased
this could
number of hits
lead to less if the cutting
contamination ofspeed remained
the electrode andthethussame. If the
explain thenumber of hitsofon
impairment thethe active material,
performance of V4
as well as on
compared to V2. the solid and molten collector, increased, the number and acceleration of the ablation
products would increase
In addition too. A reduction
to the assessment of the
of the flying cutting
sparks, speed
the with constant
recordings line energy
could strengthen the(V4) showed
assumptions
amade
stronginreduction
the previous of the sparks.
sections The lower
concerning level
the of the spark
formation of the formation
plasma. Awas due to the
qualitative lower energy
comparison of the
and intensity per pulse, as well as the reduced travel speed. The profile
images in Figure 14 showed that V0, V2, and V5 showed a clearly purple-colored plasma formation, of the sparkling flight was
very similar
whereas, fortothe
theother
sparking profile at lowand
parameters—V3 pulseV4,repetition
the plasma frequency and traversing
presumably lied belowspeed (V2). Since
the ablation gas
variation V2 was cut with a lower pulse repetition frequency than variation V4,
phase, and thus was significantly smaller. This also explained why at shorter pulse lengths or higher this could lead to less
contamination
pulse peak powers, of thetheelectrode
materialand thus explain
removal and the the impairment
formation of the
of the HAZ performance
at a constant ofenergy
V4 compared
density
to
wasV2.greater.
In addition to the assessment of the flying sparks, the recordings could strengthen the
assumptions made in the previous sections concerning the formation of the plasma. A qualitative
comparison of the images in Figure 14 showed that V0, V2, and V5 showed a clearly purple-colored
plasma formation, whereas, for the other parameters—V3 and V4, the plasma presumably lied below
Batteries 2018, 4, x FOR PEER REVIEW 17 of 21

the ablation gas phase, and thus was significantly smaller. This also explained why at shorter pulse
lengths2019,
Batteries or higher
5, x73FORpulse peak powers, the material removal and the formation of the HAZ at a constant
Batteries 2018, 4, PEER REVIEW 1717of
of 21
20
energy density was greater.
the ablation gas phase, and thus was significantly smaller. This also explained why at shorter pulse
lengths or higher pulse peak powers, the material removal and the formation of the HAZ at a constant
energy density was greater.

(V0) (V2)

(V0) (V2)

(V3) (V4)

(V3) (V4)

(V5)
Figure 14. Optical process investigations regarding the flying sparks.

The
The change
changeininspark travel
spark might
travel leadlead
might to a change
to in the degree
a change
(V5) in the of contamination
degree of the electrodes
of contamination of the
and, thus, in addition to the cut edge quality, adversely affect the electrochemical
electrodes and, thus, in addition to the cut edge quality, adversely affect the electrochemical performance.
The contaminations Figure
of the14. Optical process
electrode investigations regarding images
the flying sparks.
performance. The contaminations of were analyzed
the electrode by SEM/EDX
were analyzed by SEM/EDXand are shown
images andinare
Figure
shown15.
Contamination
in Figure products
15. Contamination in the form
products of metal spatters could be identified on all electrodes tested.
The change in spark travel might inleadthetoform of metal
a change spatters
in the degreecould be identified of
of contamination on the
all
The reference
electrodes cathode
tested. The had the strongest
reference cathode metal
had the spatter contaminations.
strongest metal spatter The lowest contamination
contaminations. The lowest
electrodes and, thus, in addition to the cut edge quality, adversely affect the electrochemical
occurred with the
contamination parameter
occurred withvariations V2 and
the parameter V4.
variations V2 and V4.
performance. The contaminations of the electrode were analyzed by SEM/EDX images and are shown
These results showed that fewer sparks formation led to less contamination of the electrode surface
in Figure 15. Contamination products in the form of metal spatters could be identified on all
in the area of the cutting edge. Based on the results of the electrochemical diagnosis and the analysis of
electrodes tested. The reference cathode had the strongest metal spatter contaminations. The lowest
the cutting edges, it could be assumed that the contaminations on the cathode surface exerted a greater
contamination occurred with the parameter variations V2 and V4.
influence on the electrochemical performance than the heat-affected zone and the chamfer width.

(V0) (V2)
+

(V0) (V2)
Figure 15. Cont.
Batteries 2019, 5, 73 18 of 20
Batteries 2018, 4, x FOR PEER REVIEW 18 of 21

(V3) (V4)

(V5)
Figure 15. SEM/EDX analysis of the cathode surface next to the cutting
cutting edge:
edge: Contamination of the
surface by molten aluminum splashes are marked turquoise:
turquoise: 1. Electrode
Electrode surface, 2. Cut
Cut zone.
zone.

4. Conclusions
These results showed that fewer sparks formation led to less contamination of the electrode
surfaceBy in the area
means of the cutting
of a pulsed edge.fiber
nanosecond Based on electrodes
laser, the resultscould
of thebeelectrochemical diagnosisaffecting
cut without significantly and the
analysis of thestability.
the cell cycle cutting edges, it could be
The influence assumed
of the that the contaminations
laser parameters or the cutting onedge
the cathode
showed surface
only a
exerted a greater influence on the electrochemical performance than the
small influence on the examined variations. Considering a linear behavior, the parameter V1 led toheat-affected zone and thea
chamfer
theoreticalwidth.
number of cycles of 1670 until the cells reached a state of health (SOH) of 80%. The best
parameter V2 resulted in a cycle number of 1760. Since the capacity drop tended to decrease, it could
4.
beConclusions
assumed that the cells would also reach higher cycles up to a SOH of 80%.
Themeans
By examined of a characteristics—chamfer
pulsed nanosecond fiberwidth laser, and heat-affected
electrodes could bezone—could
cut without be significantly
adjusted by
means of the pulse duration, the pulse repetition frequency, and the cutting speed.
affecting the cell cycle stability. The influence of the laser parameters or the cutting edge showed only In principle, the
aresults
small showed
influencethat on the
the chamfer
examined width decreased
variations. with decreasing
Considering a linear energy
behavior,density or with increasing
the parameter V1 led to
a theoretical number of cycles of 1670 until the cells reached a state of health (SOH) ofpulse
cutting speed. Furthermore, with a constant pulse duration and energy density, higher 80%.repetition
The best
frequenciesV2
parameter could result
resulted inin a smaller
a cycle numberchamfer width.
of 1760. Since This
the was probably
capacity drop due to the
tended fact that both
to decrease, the
it could
decrease of the energy and the decrease of the intensity
be assumed that the cells would also reach higher cycles up to a SOH of 80%. led to a geometric shift of the removal and
the thermal load threshold.
The examined This shift was probably
characteristics—chamfer width explained by the Gaussian
and heat-affected zone—couldintensity profile and
be adjusted by
the corresponding
means of the pulse slope of the
duration, theintensity in relation
pulse repetition to the spot
frequency, andsize,
the as well as
cutting by the
speed. In intensity
principle,andthe
energy-dependent
results showed thatformation
the chamfer of the plasma.
width The experiments
decreased with decreasing with energy
different pulse durations
density with the
or with increasing
same pulse energy showed, for different pulse repetition frequencies
cutting speed. Furthermore, with a constant pulse duration and energy density, higher pulseand constant energy density, that
the material
repetition removal and
frequencies the result
could thermal in load, among
a smaller the pure
chamfer laser-material
width. interaction,
This was probably duedepended onthat
to the fact the
plasma or the intensity. The analysis of the size of the heat-affected zone revealed
both the decrease of the energy and the decrease of the intensity led to a geometric shift of the removalthat it was essentially
influenced
and by theload
the thermal pulsethreshold.
repetitionThis
frequencies.
shift wasThe cause of
probably this dependency
explained could be explained
by the Gaussian by the
intensity profile
and the corresponding slope of the intensity in relation to the spot size, as well as by the intensity
and energy-dependent formation of the plasma. The experiments with different pulse durations with
Batteries 2019, 5, 73 19 of 20

same assumptions that have been made previously for the formation of the chamfer width. Both the
anode and the cathode showed similar tendencies. In general, the anode could be cut much faster than
the cathode due to the double material thickness of the collector, so that the parameter space for the
model development in terms of speed for the cathode turned out smaller than for the cathode.
Investigations to evaluate the influence of the chamfer width and the heat-affected zone on the
electrochemical performance of large-sized multicompartment pouch cells showed that the HAZ had
a greater influence than the chamfer width. Furthermore, the results showed that contamination
products in the form of metal spatter influenced the electrochemical performance more than the width
of the chamfer and probably also the HAZ. It could be shown by imaging techniques that with very
low speeds and high intensities and pulse energies with a moderate number of hits, metal spatters
could be reduced.
Furthermore, it was possible to reduce the melting spatters even for a high number of hits per
surface increment with a low traversing speed, intensity, and pulse energy. The results showed, so far,
that the formation of the metal spatters was a function of the number of hits per surface increment,
the speed of travel, the intensity, and the energy per pulse.

5. Outlook
The results showed that the electrochemical performance of the electrodes, or the cells, was
essentially affected by contamination products and less by the chamfer width or heat-affected zone
investigated in this study. Based on this knowledge, it is imperative to find out which contaminations
and concentrations are to be considered critical with regard to the electrochemical performance.
Furthermore, the pulsed ns laser system should be used to investigate which parameters lead to which
contaminations and whether the cw laser system offers process-inherent advantages with regard to the
contamination of the electrode surface. On the basis of these further investigations, unknown new
laser systems could be designed process-safe to fulfill the minimum requirement of four Sigma rejects.

Author Contributions: T.J. and M.W.K. wrote and edited the main parts of the paper, S.H. analyzed the REM/EDX
data. L.H. analyzed the electrochemical data. W.H. analyzed the electrochemical data and administered the
funding acquisition. K.D. administered the research project. All authors contributed to scientific discussions.
Funding: The results were generated in the project DaLion (03ET6089) funded by the Federal Ministry of Economic
Affairs and Energy. The authors express their gratitude for the financial support by the Ministry and for the project
management by the ProjektträgerJülich.
Acknowledgments: Hereby I would like to thank my student assistant Julien Essers for his technical support.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Pachauri, R.K.; Allen, M.R.; Barros, V.R.; Broome, J.; Cramer, W.; Christ, R.; Church, J.A.; Clarke, L.; Dahe, Q.;
Dasgupta, P.; et al. Climate Change 2014: Synthesis Report. Contribution of Working Groups, I. II and III to the Fifth
Assessment Report of the Intergovernmental Panel on Climate Change; IPCC, Ed.; IPCC: Geneva, Switzeland, 2014.
2. Trenberth, K.E.; Fasullo, J.T. Tracking Earth’s Energy: From El Niño to Global Warming. Surv. Geophys. 2012,
33, 413–426. [CrossRef]
3. Hettesheimer, T. Strategische Produktionsplanung in Jungen Märkten. Ein Systemdynamischer Ansatz zur
Konzeption und Dynamischen Bewertung von Produktionsstrategien am Beispiel der Lithium-Ionen-Traktionsbatterie;
Fraunhofer Verlag: Stuttgart, Germany, 2018; ISBN 978-3-8396-1275-0.
4. Schüneman, J.-H. Modell zur Bewertung der Herstellkosten von Lithiumionenbatteriezellen; Sierke Verlag:
Göttingen, Germany, 2015; ISBN 978-3-86844-704-0.
5. Choi, J.W.; Aurbach, D. Promise and reality of post-lithium-ion batteries with high energy densities. Nat. Rev.
Mater. 2016, 1, 359. [CrossRef]
6. Ding, Y.; Cano, Z.P.; Yu, A.; Lu, J.; Chen, Z. Automotive Li-Ion Batteries: Current Status and Future
Perspectives. Electrochem. Energy Rev. 2019, 2, 1–28. [CrossRef]
Batteries 2019, 5, 73 20 of 20

7. Albright, G. Cylindrical vs. Prismatic Cells: Life, Safety, Cost. Available online: http://www.
batterypoweronline.com/images/Allcell.pdf (accessed on 3 October 2019).
8. Schröder, R.; Aydemir, M.; Seliger, G. Comparatively Assessing different Shapes of Lithium-ion Battery Cells.
Procedia Manuf. 2017, 8, 104–111. [CrossRef]
9. Beuth Verlag GmbH. DIN 8588:2013-08, Fertigungsverfahren Zerteilen_- Einordnung, Unterteilung, Begriffe;
Beuth Verlag GmbH: Berlin, Germany, 2013.
10. Jansen, T.; Kandula, M.W.; Blass, D.; Hartwig, S.; Haselrieder, W.; Dilger, K. Evaluation of the Separation
Process for the Production of Electrode Sheets. Energy Technol. Available online: https://www.researchgate.
net/publication/333333666_Evaluation_of_the_Separation_Process_for_the_Production_of_Electrode_Sheets
(accessed on 10 October 2019).
11. Jansen, T.; Blass, D.; Hartwig, S.; Dilger, K. Processing of Advanced Battery Materials—Laser Cutting of Pure
Lithium Metal Foils. Batteries 2018, 4, 37. [CrossRef]
12. Hoffmann, L.; Grathwol, J.-K.; Haselrieder, W.; Leithoff, R.; Jansen, T.; Dilger, K.; Dröder, K.; Kwade, A.;
Kurrat, M. Capacity Distribution of Large Lithium-Ion Battery Pouch Cells in Context with Pilot Production
Processes. Energy Technol. 2019, 21, 1900196. [CrossRef]
13. Kreling, S. Laserstrahlung mit Unterschiedlicher Wellenlänge zur Klebvorbehandlung von CFK; Shaker: Aachen,
Germany, 2015; ISBN 9783844037685.
14. Bliedtner, M. Lasermaterialbearbeitung; Carl Hanser Verlag GMBH: München, Germany, 2013; ISBN
9783446421684.
15. Chichkov, B.N.; Momma, C.; Nolte, S.; Alvensleben, F.; Tünnermann, A. Femtosecond, picosecond and
nanosecond laser ablation of solids. Appl. Phys. A 1996, 63, 109–115. [CrossRef]
16. Sundaram, S.K.; Mazur, E. Inducing and probing non-thermal transitions in semiconductors using
femtosecond laser pulses. Nat. Mater. 2002, 1, 217–224. [CrossRef]
17. Sugioka, K.; Meunier, M.; Piqué, A. Laser Precision Microfabrication; Springer-Verlag: Heidelberg, Germany;
New York, NY, USA, 2010; ISBN 978-3-642-10522-7.
18. Stafe, M.; Marcu, A.; Puscas, N. Pulsed Laser Ablation of Solids; Springer-Verlag: Berlin, Germany; Heidelberg
GmbH & Co. KG: Heidelberg, Germany, 2013; ISBN 978-3-642-40977-6.
19. Luetke, M.; Franke, V.; Techel, A.; Himmer, T.; Klotzbach, U.; Wetzig, A.; Beyer, E. A Comparative Study on
Cutting Electrodes for Batteries with Lasers. Phys. Procedia 2011, 12, 286–291. [CrossRef]
20. Lee, D. Investigation of Physical Phenomena and Cutting Efficiency for Laser Cutting on Anode for Li-Ion
Batteries. Appl. Sci. 2018, 8, 266. [CrossRef]
21. Lee, D.; Oh, B.; Suk, J. The Effect of Compactness on Laser Cutting of Cathode for Lithium-Ion Batteries
Using Continuous Fiber Laser. Appl. Sci. 2019, 9, 205. [CrossRef]
22. Lee, D.; Patwa, R.; Herfurth, H.; Mazumder, J. High speed remote laser cutting of electrodes for lithium-ion
batteries: Anode. J. Power Sources 2013, 240, 368–380. [CrossRef]
23. Kronthaler, M.R.; Schloegl, F.; Kurfer, J.; Wiedenmann, R.; Zaeh, M.F.; Reinhart, G. Laser Cutting in the
Production of Lithium Ion Cells. Phys. Procedia 2012, 39, 213–224. [CrossRef]
24. Lutey, A.H.A.; Fortunato, A.; Carmignato, S.; Ascari, A.; Liverani, E.; Guerrini, G. Quality and Productivity
Considerations for Laser Cutting of LiFePO4 and LiNiMnCoO2 Battery Electrodes. Procedia CIRP 2016, 42,
433–438. [CrossRef]
25. Demir, A.G.; Previtali, B. Remote cutting of Li-ion battery electrodes with infrared and green ns-pulsed fibre
lasers. Int. J. Adv. Manuf. Technol. 2014, 75, 1557–1568. [CrossRef]
26. Cabalín, L.M.; Laserna, J.J. Experimental determination of laser induced breakdown thresholds of metals
under nanosecond Q-switched laser operation. Spectrochim. Acta Part B At. Spectrosc. 1998, 53, 723–730.
[CrossRef]

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