Malvern-Netzsch Battery Brochure
Malvern-Netzsch Battery Brochure
Malvern-Netzsch Battery Brochure
The age of the battery is well underway. Lithium-ion also improvements in production efficiency to minimize
batteries, for example, have already revolutionized our production costs. When success is defined by such fine
day-to-day lives – from smart mobile devices to pollution- margins, today’s manufacturers must be able to ensure
free electric cars and intelligent power management total quality and performance – every time.
solutions. And, looking ahead, batteries also have the
potential to provide an economical solution for mass At Malvern Panalytical and NETZSCH Analyzing & Testing,
energy storage and complement renewable energy we leverage over six decades of experience in the design,
resources for power grid applications. manufacture, and supply of analytical instruments to
offer a complete range of laboratory and online analytical
Despite these successes, gaps in battery technology solutions. Whether you are a battery component
remain, both in terms of safety and performance. What’s manufacturer looking for greater process efficiency and
more, for their mass-scale adoption in applications like better quality control, or a researcher trying to determine
electric vehicles, large cost reductions will be needed. the performance parameters of newly emerging battery
Indeed, with regulators becoming more stringent and materials, our solutions will offer you the new levels of
consumers more demanding, these core issues are insight and control needed to power the production of
driving not only research into new battery materials, but superior-quality batteries.
Evaporator
Anode slurry
Anode coated
Cu foil
Cathode /
Anode powder
3
Table 1. Battery materials and analytical solutions along the battery value chain.
Coat weight
Coating thickness Photon sensor Photon and Micro caliper sensors
Electrode and Thermal management Micro caliper thickness sensor from NDC technologies
electrode coating (thermal diffusivity/ Laser/Light Flash LFA 467 HyperFlash®
conductivity) Differential Scanning Calorimetry DSC 404 Pegasus®
Specific heat capacity
Simultaneous Thermal
STA 449 Jupiter® - QMS 403 Aëolos®
Electrolyte Thermal Stability Analysis coupled to Evolved
Quadro
Gas Analysis (e.g., QMS)
Composition,
thermal behavior Simultaneous Thermal Analysis STA 449 Jupiter®
Binder, additives
Viscosity Rheology Rotation Rheometer Kinexus Prime
Viscoelasticty
Differential Scanning
Specific heat capacity, DSC 404 Pegasus®,
Separator Calorimetry,
length change TMA 402 Hyperion®
Thermomechanical Analysis
Cathode coated
Al foil Electrolyte
Porous polymer
separator
Battery cell
4
Co-precipitation
Cathode materials of current interest, such as NCA and
NMC, are produced via co-precipitation of a transition metal
hydroxide precursor, followed by calcination (lithiation and Precursor: particle 1
oxidation) with a lithium compound.
Our morphological, structural and elemental insights can
size and zeta
help to: potential analysis 6
• Optimize process parameters.
• Ensure consistent quality and reduce production costs.
2 3 4
Li compund Precursor Precursor: particle size
(NMC / NCA) and shape, and elemental
composition analysis
Calcination 7
2 3 4 5
Mill
CHARACTERIZATION TOOLS
Particle size
1 Consistent cathode-material particle size starts with the
precursor – with our Insitec online tool, manufacturers
can analyze particle size in real time at the precursor or
milling stage.
3 Particle shape
Particle shape influences critical parameters like electrode
slurry rheology and packing density. Analyze particle size
and shape at the precursor stage with Morphologi 4
imaging - automatic analysis of thousands of particles with Rough Smooth Regular Elongated
Na Mg Al Si P S Cl Ar
electrode materials. L La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
A Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
5 Crystalline phase
Crystalline phase and crystallite size are the key
attributes defining the quality of electrode materials. Our
Aeris compact X-ray diffractometer sets the industry
benchmark for crystalline phase composition analysis,
which can be used to optimize the calcination process.
6 Zeta potential
Zeta potential can be used to optimize process
parameters like pH and concentration to control slurry
stability, agglomeration, and sedimentation behavior.
Our Zetasizer can analyze zeta potential of a dispersion
and also the size and agglomerate state of nanosized
materials.
7 Heat treatment
Characterization of raw materials and calcination:
Simultaneous monitoring of the thermal behavior and
gases released during heat treatment enables coupling of
the NETZSCH QMS Aëolos® Quadro mass spectrometer
to the NETZSCH STA 449 Jupiter ® Simultaneous Thermal
Analyzer (Differential Scanning Calorimetry (DSC) and
Thermogravimetric Analysis (TGA)). This combination
provides a deep insight into both the raw materials and
the calcination process.
6
Delivering an optimal and consistent particle size and faster measurements than sieving, faster
distribution doesn’t just add value to electrode materials, measurements than sedimentation, and statistically
it’s key to ensuring final product quality – enabling superior information compared to microscopy. The
manufacturers to optimize; slurry viscosity and flow Mastersizer 3000 laser diffraction particle size analyzer
behavior; coating packing density and porosity; battery delivers rapid, accurate particle size distributions for
cell charge rate capacity and cycling durability. both wet and dry dispersions with the minimum of effort.
Measuring over the nanometer to millimeter particle
To meet this need, Malvern Panalytical offers an industry- size ranges, it packs exceptional performance into the
standard particle size measuring tool; the smallest of footprints, bringing operator-independent
Mastersizer 3000. Based on laser diffraction, it offers measurements that every user can rely on.
industrial-level performance, delivering more reliable
30 16
NCM Cathode Synthetic Graphite
Cathode-A
12 Anode-1
20 Cathode-B
Anode-2
Volume (%)
Volume (%)
Cathode-C Anode-3
8
10
4
0 0
0,1 1 10 100 1000 0,1 1 10 100 1000
Size (µm) Size (µm)
Figure 1. Particle size distribution of three batches of NCM811 Figure 2. Particle size distribution of three batches of synthetic
cathode materials synthesized with different processing graphite synthesized with different heating conditions.
parameters.
7
THERMAL MANAGEMENT
Controlling battery thermal characteristics – Separator,
Electrode and Electrode Coating
Like the human body, the operating temperature of a of electrodes, electrode coating, separators, the LFA
battery should always be monitored, protected and 467 HyperFlash® is the right instrument. Between -100°C
kept at an optimal level. If the ambient temperature is and 500°C, this LFA system contactless measures the
too low, it will not deliver its full power. If the ambient temperature increase of samples between 6 mm and
temperature rises too high, the battery can even swell, 25.4 mm with an IR detector. The patented ZoomOptics
catch fire, explode and release toxic gases. Proper allows the detector’s field of view to be adjusted until the
battery thermal management ensures longer lifespan only temperature increase registered is that of the sample
by keeping the cells within a limited temperature range and no influences by the surroundings may have any
during storage, operation and charging. Understanding effect.
how much heat can be dissipated by the cells requires
understanding of the basic heat transfer properties of the Differential Scanning Calorimetry
cell design. Measuring the thermal diffusivity and thermal
conductivity along with the specific heat capacity form the
basis for comprehensive understanding. To investigate
these thermophysical properties, NETZSCH offers Laser/
Light Flash Analysis systems (LFA) as well as Differential
Scanning Calorimeters (DSC). Thermal management
system failures can be avoided.
dL/Lo /%
2 2 2
0,5
0,2 -8
0,5 0,5
Thermal Diffusivity -10
0,1 Conductivity
-12
Spec. Heat
0 0
0 -14
0 10 20 30 40 50 60
20 40 60 80 100 120 140 160 180
Temperature /°C Temperature /°C
Figure 3. Aluminum electrode coated on both sides: The thermal Figure 4. TMA measurement on a polymer film between RT
conductivity (petrol curve) is determined by measuring the and 190°C at a tensile force of 5 mN . Shrinkage starts at 159°C
thermal diffusivity with the NETZSCH LFA 467 HyperFlash® (rubine (extrapolated onset).
red curve) and specific heat capacity, cp (gray curve). In this
example, cp was determined using the DSC 404 F1 Pegasus®.
THERMAL STABILITY
Safety is ensured when deterioration of stability is avoided
Electrolytes are characterized by high conductivity, good However, nickel reduces the stability of the battery as
electrochemical stability and the ability to perform at low it reacts easily to the external environment. The nickel
temperatures. However, the thermal stability of many content in batteries can increase to 80% or higher, and the
electrolyte solutions is restricted even at moderate consequent deterioration in stability must be improved to
temperatures. Due to overcharging, batteries can ensure safety.
overheat to the point that they catch fire.
The thermal stability can be investigated by means
Besides various metals (e.g., cobalt, aluminum or of Differential Scanning Calorimetry (DSC) and
manganese, etc.), the cathode material of Li-ion batteries Thermogravimetry (TG or called Thermogravimetric
contains nickel. There is a positive correlation between Analysis TGA). A combination of both methods represents
the nickel content and the battery capacity. Since nickel is the Simultaneous Thermal Analyzer (STA).
relatively cheaper than cobalt, adding more nickel lowers The STA 449 Jupiter ® series combines configuration
the unit cost of, e.g., electric vehicle (EV) batteries. flexibility and unmatched performance in just one
instrument. Pluggable interchangeable DSC and
TGA sensors and various furnaces allow for precise
thermoanalytical measurements. By supplementary MS
coupling, even more comprehensive analyses are possible.
Figure 5. STA-MS measurement on 8 to 10 mg 1.0 M LiPF6 in EC/DEC=50/50 (v/v). The left plot indicates that the 1st mass-loss step is most
likely due to the evaporation of DEC; the right plot shows mass numbers attributed to ethylene carbonate (43, 56, 58, 73 and 88) indicating
the evaporation of EC during the 2nd mass-loss step.
11
PARTICLE MORPHOLOGY
Enabling better insight into electrode material morphology
2,5
5
HS Circularity of 3 cathode materials
Cathode-A
4 Cathode-B 2
Cathode-C
3 1,5 Cathode-A
Cathode-B
2 1
Cathode-C
1 0,5
0 0
0,1 1 10 100 1000 0,6 0,7 0,8 0,9 1
Size (µm)
Figure 6. Figure 7.
Example Cathode Materials Circular Equivalent (CE) size distribution of three NCM cathode materials, as obtained from
Morphologi 4 (Figure 6). These are the same samples as those measured with the Mastersizer 3000 in Figure 1. Circularity for these
samples is compared in Figure 7. Circularity index 1 corresponds to perfect spheres and smaller values to larger deviation from
circularity. A narrow distribution in circularity means uniform shape particles, whereas broad distribution represents large variance in
particle shapes. Cathode A has circular particles, whereas B and C are irregularly shaped with large shape variations.
HS Circularity
Particle size distribution (μm) 0,5
1,2
Sample A 0,4
Sample B
Sample A
0,8 0,3 Sample B
0,2
0,4
0,1
0 0
1 10 100 1000 0 0,2 0,4 0,6 0,8 1
Figure 8. Figure 9
Example Graphite electrode material: size distribution of two samples as measured with Mastersizer 3000 (Figure 8) and circularity
of the same samples (Figure 9) as measured with Morphologi 4. Though the samples have similar circular equivalent size distribution,
sample A is more irregular in shape.
12
ELEMENTAL COMPOSITION
Simplifying chemical composition and impurity analysis
impurity detection.
80,00 80,17
Measured Mn %
60,00 59,90
40,00 40,19
20,00 20,35
0,00 0,12
0 20 40 60 80 100
Figure 10.
Table 2. Typical elemental composition analysis on a LFMP cathode material using XRF
Sample preparation is a major source of error in elemental To meet the need for reliable sample preparation for XRF
composition analysis. All too often, preparation methods or ICP, Malvern Panalytical offers a high-performance
such as pressed pellets (in XRF) or acid digestion (in ICP) fusion solution. Fusion involves dissolving a fully oxidized
are affected by mineralogical or particle size effects in sample at high temperature in a suitable solvent (a flux)
metal samples, compromising the accuracy of the results. in a platinum, zirconium or graphite crucible. The melted
mixture is agitated and poured into a mold to create a
glass disk for XRF analysis. It can also be poured into
a beaker to create a solution for Atomic Absorption
Spectroscopy (AAS) or ICP analysis.
Counts
LMFP-Mn20Fe80
30000
20000
10000
20 30 40 50 60 70 80
Crystalline phase is an important factor in battery throughput sampling, since typical sample measurement
electrode materials, governing lithium-ion transport at takes just a few minutes. Samples can be fed either
atomic level. To analyze crystalline phase composition and manually or via a belt automation.
quality in synthesized powder materials, X-ray diffraction
Counts
(XRD) is routinely used.
LFP LiFePO4
LMFP-Mn20Fe80
LMFP-Mn40Fe60
In battery cathode materials, XRD can be used to ensure 30000
LMFP-Mn60Fe40
LMFP-Mn80Fe20
that reactants have completely fused to the desired and
stable crystalline phases during the calcination process.
It can also be used to measure chemical composition or 20000
Figure 12.
These applications can be carried out easily with our Aeris Example LMFP Cathode Material:
compact X-ray diffractometer. Thanks to its automated Section of XRD pattern (Figure 8) showing peak shift to lower
analysis, sample measurement on Aeris requires no prior angles as the Mn content increases, meaning lattice expansion
along c-axis.
XRD expertise. Moreover, the Aeris is built for industrial
automation. It meets requirements for industrial high
100
c-parameter variation with Mn Content Crystallite size with Mn Content
10,5
80
10,45
size (nm)
10,4 60
c (Å)
10,35
40
10,3
10,25 20
0 20 40 60 80 0 20 40 60 80
Mn Content Mn Content
Counts
360000
0.3358 nm
Graphitization degree 95%
Graphite
160000
Carbon B at low and high shear rates, which would likely increase
the resistance to sedimentation on standing (low shear process) Carbon B
(with Binder)
and result in a thicker electrode film on coating (high shear
η (Pa s)
10-1
process).
Temperature
sensor
Top
guard
heater
Side
guard
heater
Leaf spring
Reference Sample
Heat flow
sensor
Efficiency Tests for Coin Cells Heat flow /mW Discharge efficiency @ 1C = 87.9%
Area...: 371.44E+03mW*S
Power /mW
Temp. /°C
50
The key component of the coin cell module is the sensor. ↑ exo
150
-50
(RTD) in order to precisely monitor and control its 20 Heat flow 29.5
-100
temperature using the surrounding furnace. When the Area: 45.04 J
Temp.
Power
-150
coin cell releases or absorbs any heat due to charging/
29.0
10
28.0
disturbances, the signal coming from the reference heat 1700 1750 1800 1850
-300
sample heat flow meter, thus yielding a true differential Figure 17. From the heat signature of the LiR2032 during three cycles
of discharging and charging, the efficiency is calculated by dividing the
measurement. This technique is much more accurate and
electrical energy by the total energy (electrical energy + heat flow)
sensitive than that of a single-sensor system. during discharging and charging.
18
All types of coin cells with at least one side with an X-ray Another solution is the electrochemical cell, with an
transparent window can be studied on the Empyrean XRD. X-ray transparent window made from beryllium or glassy
We provide a specialized coin cell holder, which can be carbon. We supply the electrochemical cells with the
used for charge-discharge cycling. option of heating and cooling that are mounted on the
Empyrean XRD.
2,86
14,4
2,84
2,82
14,2
c [Å]
2,8
a [Å]
14 2,78
3V 4,3 3V
Example of in operando cycling of an NCM cathode and graphite anode in an electrochemical cell. Fig. 17 shows how the 003 peak shifts
during cycling. Fig. 18 shows how c and a lattice parameters change during charge and discharge. Any abrupt change in lattice parameter is
usually associated with crystal phase changes and may cause particle cracking.
Scan number
for pouch cell research. Special multilayer focusing mirrors
deliver high resolution and a high brilliance X-ray beam, 96
further shortening the measurement times.
64
32
10 15 20 25
Position [°2θ] (Ag K-α12)
Example of in operando cycling of a pouch cell. Measurements
were performed on the Empyrean XRD platform configured with
Ag Kα radiation and the GaliPIX 3D detector. Every XRD scan over
5-30 2θ range was measured in just five minutes. A total of 166
scans were measured over five complete charge-discharge cycles.
Pouch and prismatic cell mounting on the Empyrean XRD. Our GaliPIX3D detector with 100% efficiency from Cu to Ag
A mechanism to apply pressure on the pouch cell is also radiation makes fast measurements possible on cells up
supported. to 5 mm thick.
WHY CHOOSE NETZSCH
MALVERN PANALYTICAL?
We are global leaders in materials The NETZSCH Group is an owner-managed,
characterization, creating superior, customer- international technology company with
focused solutions and services which headquarters in Germany. The Business Units
supply tangible economic impact through Analyzing & Testing, Grinding & Dispersing
and Pumps & Systems represent customized
chemical, physical and structural analysis.
solutions at the highest level. More than 4,000
Our aim is to help you develop better employees in 36 countries and a worldwide
quality products and get them to sales and service network ensure customer
market faster. Our solutions support proximity and competent service.
excellence in research, and help maximize
Our performance standards are high. We
productivity and process efficiency.
promise our customers Proven Excellence –
Malvern Panalytical is part of Spectris, the exceptional performance in everything we
productivity-enhancing instrumentation do, proven time and again since 1873.
and controls company.
When it comes to Thermal Analysis, Accelerating
www.spectris.com Rate Calorimetry, the determination of
Thermophysical Properties, Rheology and
Fire Testing, NETZSCH has it covered.
Our 60 years of applications experience, broad
state-of-the-art product line and comprehensive
service offerings ensure that our solutions
will not only meet your every requirement
but also exceed your every expectation.
Tel. +44 1684 892456 Tel. +31 546 534 444 Tel. +49 9287 881-0
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