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Malvern-Netzsch Battery Brochure

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BATTERY RESEARCH AND

QUALITY CONTROL SOLUTIONS


Benefit from physical, chemical and structural insight
2

DISCOVER NEW HORIZONS IN


BATTERY QUALITY
Empower your research and production
with advanced analytical solutions

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.

Cathode / Cathode slurry


Anode slurry

Evaporator

Anode slurry

(+carbon black + binder


+ solvent)

Anode coated
Cu foil

Cathode /
Anode powder
3

MONITOR AND OPTIMIZE AT EVERY STAGE


Battery component manufacturers must not only At Malvern Panalytical and NETZSCH Analyzing & Testing,
deliver consistent overall quality – they must deliver it a range of research and quality control solutions to help
throughout the manufacturing process. The continuity manufacturers monitor and optimize every part of
of the manufacturing process means errors or impurities the battery manufacturing process. The unique set of
at an early stage will accumulate, resulting in much larger physical, chemical and structural analysis possibilities
consequences further down the production line. Quality that our technologies offer can be utilized across various
needs to be monitored at every stage – from raw materials stages of battery component production. From improving
through to cell assembly – to maintain production electrode material quality to accelerating the successful
efficiency and minimize waste. Likewise, research into new development of new high-performance battery materials,
battery materials must ascertain all the critical parameters we’ve got you covered– enabling the development and
that could affect battery performance throughout the production of the highest-performing batteries.
entire manufacturing process.

Table 1. Battery materials and analytical solutions along the battery value chain.

Battery materials Critical Parameters Analytical techniques Product and solutions


Laser diffraction
Mastersizer 3000
Particle size Automated Imaging
Cathode precursor Morphologi 4
Particle shape X-ray fluorescence
and electrode Epsilon 4 / Zetium XRF
Chemical composition X-ray diffraction
materials Aeris compact XRD
Crystal phase Simultaneous Thermal Analysis
STA 449 Jupiter ® - QMS Aëolos® Quadro
– Mass Spectrometer
Particle size
Particle shape Laser diffraction Mastersizer 3000
Battery slurry Viscosity Automated Imaging Morphologi 4
Viscoelasticity Rotational Rheometry Kinexus Prime
Stability

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

Degradation mechanism In operando XRD


Empyrean XRD
Battery cell during cycling Calorimetry, Accelerating
MMC 274 Nexus®, ARC 244/305
Efficiency of full cells Rate Calorimetry

Cathode coated
Al foil Electrolyte
Porous polymer
separator

Battery cell
4

OPTIMIZE CATHODE MATERIALS


Cathode material production is just one example of Our solutions can be used as cathode characterization
how our solutions enable quality at every stage of the tools at several stages of the cathode production process,
manufacturing process. As one of the first stages in from co-precipitation and precursor quality control,
battery production, quality control is especially important down to optimizing calcination and the final material. By
to cathode manufacturing – and battery manufacturers providing manufacturers with morphological, structural,
must implement it all while minimizing costs. and elemental insights, these solutions enable them to
optimize process parameters accordingly to ensure the
highest cathode quality.

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

On-line partical 1 Particle size and


size analysis crystal phase

2 3 4 5

Mill

• Improve precursor quality and throughput Cathode material with


• Ensure right stoichiometry desired size distribution
• Optimize calcination process
• Control particle size and morphology
5

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.

2 Fine control over particle size distribution plays an


important role in the quality of the electrode coating. With
the Mastersizer 3000, you can analyze particle size with
accuracy and ease.

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

high statistical accuracy.


Z Possible to analyze with Epsilon 4

H Z Not possible to analyze with Epsilon 4 He

4 Elemental composition Li Be Z Possible with Epsilon 4 and optional detector B C N O F Ne

Na Mg Al Si P S Cl Ar

Combined with fusion sample preparation recipes, our K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr

Epsilon 4 benchtop X-ray fluorescence (XRF) spectrometer Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe

or high-end Zetium spectrometer can simplify the Cs Ba L Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn

chemical composition and elemental impurity analysis of Fr Ra A

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

OUR RESEARCH AND QUALITY


CONTROL SOLUTIONS
Superior particle size distribution measurement

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

REAL-TIME PROCESS AUTOMATION


Optimizing process parameters

Manufacturers also need to monitor particle size On-line


- analysis
as the production process continues. And, if you’re
Synergy Synergy with
manufacturing at industrial scale with limited human Smart factory
value
resources, finding an efficient way to analyze particle size process flow
in real time can be difficult. Usually, lab analysis will deliver
feedback in about an hour, whereas for optimum quality Waste
reduction/
control, a feedback loop of a few minutes is required. Commercial
process
value
efficiency
Our on-line, automated Insitec particle size analyzer is improvement
~2%
ideal to meet this need in a production environment,
delivering real-time analysis every few seconds using a Manpower saving ~
feedback loop. It can be used to control precursor particle 1 person
size evolution over time, or just after milling to control Lab analysis
electrode particle size – enabling manufacturers to
reduce waste and align their processes with smart factory Typical value gain for a cathode manufacturing plant with Insitec
manufacturing flows. online particle size analysis of precursor slurry, in comparison to
lab analysis.
8

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.

Laser Flash Analysis

Specific heat capacity (cp) is determined by means of the


LFA method or Differential Scanning Calorimetry (DSC).
DSC is the most employed Thermal Analysis method. It
allows for the precise detection of thermal characteristics
such as melting/crystallization temperatures and
enthalpies, glass transition temperatures, reaction
temperatures and enthalpies, cross-linking reactions
(curing), and more.

Thermal conductivity and diffusivity are the most


important thermophysical parameters for the description
of the heat transport properties of a material or a
component (Figure 3). The Laser/Light Flash technique
has proven itself a fast, versatile and absolute method for
measurement of the thermal diffusivity. NETZSCH offers
three models, covering the widest temperature range for
the broadest spectrum of materials. For the investigation
9

dL/Lo /%
2 2 2
0,5

Thermal Conductivity / (W/(m*K))


0
Thermal Diffusivity /(mm^2/s)

0,4 1,5 1,5 -2

Spec. Heat /(J/(g*K))


-4
0,3
1 1 -6

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®.

Thermomechanical Analysis This is achieved by Thermomechanical Analysis (TMA),


Each time a material is exposed to temperature changes expressed by the coefficient of thermal expansion (CTE).
– it shows a variation in its dimension. Whether it is in the The length change phenomena can be studied by means
course of its regular thermal expansion or by passing a of thus revealing information regarding their thermal
phase transition, the substance will either be shrunk or behavior and about process parameters or curing kinetics.
elongated. For example, polymer separators can shrink
significantly at elevated temperatures which affects the Under a defined mechanical force, the TMA 402 Hyperion®
battery performance. To predict the deformation and series allows for monitoring the volumetric and linear
stresses in the separator in battery cells, it is necessary to thermal expansion, shrinkage steps, glass transition
measure the expansion/shrinkage behavior. temperature, density change, and anisotropic behavior.

TMA 402 Hyperion®


10

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.

The NETZSCH QMS 403 Aëolos® Quadro is a compact


mass spectrometer with a heated capillary inlet system
for routine analysis of gases and, in particular, volatile
decomposition products. The software is unique: fully
integrated MS software for measurement and analysis
allows for direct correlation between the mass-loss steps
and gases released. This coupling is especially suitable for
studying the thermal degradation of electrolytes.

TG /% QMID *10-12 /A TG /% QMID *10-12 /A


EC-DEC-LiPF6 - Untreated
[s:1, m:45] EC-DEC-LiPF6 - Untreated
[s:1, m:43]
152.3 °C
100 20 100 274.5 °C 60
50 15 50
152.3 °C 40
0 10 0
5 -50 274.5 °C 20
-50 s:1, m:45 [2]
152.3 °C 0 -100 s:1, m:43 [2]
s:1, m:91 [2] 274.5 °C 0
-100 -150 s:1, m:88 [2]
154.7 °C
s:1, m:63 [2] -5 274.5 °C s:1, m:58 [2]
-150 s:1, m:75 [2] -200 -20
150.0 °C -10 274.5 °C s:1, m:56 [2]
-250
-200 s:1, m:59 [2]
-15
s:1, m:73 [2]
-40
50 100 150 200 250 300 350 400 450 50 100 150 200 250 300 350 400 450
Temperature /°C
Temperature /°C

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​

The role of particle shape in battery electrode materials


is usually ignored or underestimated. However, this
may be the key to unlock full potential of a given battery
material to be translated into the best performing battery.
Particle shape affects slurry rheology as well as the Rough Smooth Regular Elongated
electrode coating in terms of packing density, porosity
and uniformity. To achieve the highest level of battery
performance, manufacturers must also understand and Do your particles have the right morphology?
optimize the particle morphology.

To help manufacturers resolve these critical questions,


we offer our powerful optical imaging tool, Morphologi 4.
Equipped with fully automated image analysis, it enables
manufacturers to measure parameters such as circularity,
elongation/aspect ratio, Circular Equivalent (CE) diameter,
and transparency.

With analysis based on 10,000 – 500,000 particles from


0.5 µm onwards, manufacturers can gain reliable insight
into the shape of the smallest particles with high statistical
accuracy. What’s more, the Morphologi 4-ID combines
automated static imaging features of the Morphologi 4
with chemical identification of individual particles using
Raman spectroscopy - enabling automated measurement
of particle size, particle shape and chemical identity, on a
single platform.

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

Deviations in chemical composition or impurities in


electrode materials can significantly affect final battery
performance. For this reason, chemical composition and
elemental impurity analysis are an integral part of the
battery manufacturing process. However, the often-used
inductively coupled plasma (ICP) analysis is not always the
best tool for this. Requiring sample digestion and frequent
calibration, ICP is inefficient and expensive for most
elemental analysis needs.

To provide a simpler way to analyze elemental


composition and detect impurities down to ppm level,
we offer X-ray fluorescence (XRF) solutions that require
no sample digestion or frequent calibration and are up
to three times cheaper in terms of per sample analysis.
In particular, chemical composition analysis of cathode
materials at low-percentage elemental levels is more
reliably measured with X-ray fluorescence.

Specifically, our Epsilon 4 benchtop energy dispersive


XRF spectrometer can accurately measure elemental
composition in just a few minutes. When better light
element sensitivity is desired, our Zetium wavelength
dispersive XRF spectrometer is recommended. These
Mn% measured with Omnian standardless
solutions can help manufacturers optimize cost and use
of human resources, while saving ICP for very low-level 100,00

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.

Composition and impurities analysis on five samples of


LiFexMn1-xPO4 measured on the Epsilon 4 is shown in the table
below. Measured Mn composition (Figure 7) shows a straight-line
calibration with Target Mn composition in these samples.

Table 2. Typical elemental composition analysis on a LFMP cathode material using XRF

Sample Target Material Measured composition and impurities


Mn
% Zr Al Ca Cl Co Cr Cu Ni S Si Ti Y Zn
SMP1 LiFe 02Mn 08PO 4 80.2 0.11 0.011 0.014 0 0 0.017 0 0.026 0.008 0.022 0.009 0.006 0
SMP2 LiFe 04Mn 06PO 4 59.9 0.19 0.012 0 0 0.001 0.024 0.018 0.013 0.004 0.02 0.01 0.009 0.006
SMP3 LiFe 06Mn 04PO 4 40.2 0.117 0.041 0 0 0.003 0.034 0.011 0.023 0.006 0.024 0 0.007 0.005
SMP4 LiFe 08Mn 02PO 4 20.4 0.161 0.008 0.014 0.037 0 0.042 0.009 0.015 0 0.02 0 0.006 0.006
SMP5 LiFePO 4 0.1 0.155 0.015 0 0 0 0.055 0.009 0.024 0.007 0.024 0 0.009 0.004
13

SAMPLE PREPARATION FOR XRF


Ensuring more accurate analysis

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.

At Malvern Panalytical, you can count on our 40-plus years


of expertise in designing and delivering fusion recipes for
various kinds of complex samples. What’s more, we offer
two fusion instruments. Our robust LeNeo instrument is
ideal for battery sample fusion. This automatic electric
instrument can prepare glass disks for XRF analysis, as
well as borate and peroxide solutions for AA and ICP
analysis. With one fusion position, it delivers excellent
ease of use, operator safety, and superior analytical
performance in the laboratory – eliminating doubt and
driving high-precision quality control. To meet high sample
throughput, our TheOx advanced instrument, which has
six fusion positions, can be used.
14

CRYSTALLINE PHASE COMPOSITION


Unlocking atomic-level exploration

Counts
LMFP-Mn20Fe80

30000

20000

10000

20 30 40 50 60 70 80

Figure 11. Typical XRD pattern of a Lithium Manganese Iron


Phosphate (LFMP) cathode material.

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

to estimate the size of primary particles (from the


measurement of crystallite size), which plays an important
10000
role in ion migration. In anode materials, XRD can measure
the degree of graphitization in synthetic graphite, which
significantly affects anode energy density. 26 28 30

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

Figure 13. Figure 14.

Example LMFP Cathode Materials with varying Mn content:


Lattice expansion along c-axis (Figure 13) with increasing Mn content. For unknown batch samples, c-parameter can be measured, and
composition deduced using calibration graph (Figure 13). XRD also reveals that crystallite size increases with Mn content (Figure 14) – higher
Mn facilitates larger crystallite size. Crystallite size usually has a close relationship to the primary particle size.
15

ZETA POTENTIAL ANALYSIS


Enabling slurry stability insight

In electrode slurry production, zeta potential (related to


charge charge on particle) plays an important role in slurry
stability. Low zeta potential can result in agglomeration
and aggregation of particles – causing unstable particle
dispersion in slurries and, in turn, compromising battery
quality. So, being able to accurately monitor and optimize
zeta potential isn’t just useful to battery manufacturers –
it’s essential.

High zeta potential Low zeta potential


= stable dispersion = unstable dispersion /
agglomeration

To meet this need, we offer the Zetasizer. Whether it’s


to understand agglomeration and sedimentation in
precursor slurry, or to ensure electrode slurry stability,
or to understand slurry wetting behavior on flat surfaces,
this tool measures zeta potential with excellent accuracy,
repeatability, and consistency. And, for high-concentration
and highly conducting samples, its specialized cell and
constant current mode have you covered – enabling
manufacturers to optimize Ph and concentration for
stable slurries to manufacture high quality electrodes.

Counts

640000 Syn Graphite mixed with Si reference

360000
0.3358 nm
Graphitization degree 95%
Graphite

160000

40000 Example Synthetic graphite:


Degree of graphitization and orientation index are important
attributes of synthetic graphite, which is a commonly used anode
0
material due to its superior consistency and purity compared to
26 28 30 32
natural graphite. Aeris can measure both the graphitization degree
and orientation index. Figure 15 shows the measurement of the
Figure 15. degree of graphitization in one such material.
16

PROCESSING PROPERTIES AND


LEVELING CHARACTERISTICS
How to apply battery slurry onto the electrode
A battery slurry is typically processed by blade coating
or slot die coating. During these processes, the slurry
is undergoing mid-level shear rates for a short period
of time, followed by gravitational stresses acting on the
slurry after the coating process. This has impact on the
leveling behavior at low shear rates and film uniformity.

Rheology provides access to these flow properties


of battery slurries. Different low-shear behavior can
influence the leveling. With high solid content, shear
thickening might occur in processing shear rate range
and causes difficulties during the coating process. In
addition to the shear viscosity function, the elasticity of
the slurry under shear flow is important. It can lead to
flow instabilities, such as film rupture or uneven edges of
the coating layer. Elasticity of the slurry, however, helps
prevent sedimentation of the particles at rest and needs
to be balanced against the negative impact of elastic
normal stresses on the processing.

Critical factors influencing rheology of the slurry:


• Volume fraction
• Particle size and distribution
• Shape
• Electrostatic interactions
• Molecular weight
• Intrinsic viscosity

Critical factors when processing battery slurries:


• Slurry stability
• Flow properties (viscosity and elasticity) during coating
• Flow instability
• Film structure / leveling behavior

Viscosity and visco-elasticity control of the coating process


The rheometer measurement with the NETZSCH Kinexus Prime
shows that the addition of PVDF to NMP drastically increases
Viscosity vs Shear rate
viscosity relative to NMP alone and the viscosity remains largely 101
independent of the shear rate (Newtonian behavior).Adding
carbon black increases viscosity and the resulting slurries both Carbon A
(with Binder)
showed shear rate dependence (non-Newtonian behavior). The
slurry made with Carbon A yielded a much higher viscosity than 100

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).

To avoid sedimentation at all, the slurry structure at rest needs to NMP/PVDF

be dominated by elasticity. This can be investigated by oscillatory 10-2

shear experiments, which allows for characterization of the


viscoelastic properties and thus enables a stability forecast for NMP

the slurry before it is coated.


10-3

10-1 100 101 102 103 104


.
The higher viscosity may also make the coating process more γ (s-1)

difficult to control, potentially leading to uneven coating and


Figure 16. Rheological measurements on 4 different slurries
variable layer density which, in turn, results in a variable ion measurement carried out at shear rates ranging between
transfer rate and hence battery lifetime (and recharge cycle time). 0.1 to 1000s-1.
17

CHARACTERIZATION OF COIN CELLS


AS A WHOLE
Heat signature as key information for battery development and testing
Specifically, understanding of the heat generation during Using the unique coin cell module of the NETZSCH MMC
charging/ discharging cycles is crucial for improving the 274 Nexus® Multiple Module Calorimeter allows for
cell efficiency, performance and lifetime of batteries. analysis of the behavior of a complete coin cell instead of
Measuring the heat signature of coin cells during individual components to mimic cell performance in the
cycling provides insight into the underlying processes real world. This special differential measuring principle
and provides a quantitative way of comparing changes for improved stability and sensitivity captures even weak
in chemistry above and beyond current and voltage heat signals from coin cells. Characterization of coin cells
measurements. Some of these processes are reversible, can be achieved by isothermal charging/discharging and
some occur during the initial few cycles, and others take scanning tests.
place over a period of weeks, months, or even years. The
amount of heat released or absorbed during all these
physicochemical changes and the rate of energy change
within the coin cell provide additional pieces of the puzzle
and can accelerate the development process.

Temperature
sensor
Top
guard
heater

Side
guard
heater

Leaf spring

Reference Sample

Heat flow
sensor

The MMC 274 Nexus® offers three interchangeable calorimeter


Bottom
guard modules: ARC for process safety investigations, Scanning for high
Coin Cell Module heater reaction enthalpies and Coin Cell for battery testing.

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

It features an innovative differential measurement design Charge efficiency @ 1C = 96.0%


Area...: 422.22E+03mW*S 100
31.0
40
based on thermopiles for improved sensitivity and 50 30.5

stability in heat-flow measurements. The calorimetric 30 0

block is equipped with a Resistance Temperature Device 30.0

-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

discharging or internal physical changes, the sensor


-200
28.5
Area: 17.04 J

detects this heat. To nullify the effect of external 0 -250

28.0
disturbances, the signal coming from the reference heat 1700 1750 1800 1850
-300

flow meter is subtracted from the signal detected by the Time/min

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

BATTERY CELL CHARACTERIZATION


Delivering in operando X-ray diffraction
The biggest issue faced when developing new battery In operando X-ray diffraction (XRD) can investigate these
materials with high energy density is capacity degradation failure mechanisms by analyzing underlying crystal
with cycling. Causes of capacity degradation can include structure changes during battery cycling. Our Empyrean
particle cracking, lithium retention in electrodes, XRD platform offers options for the in operando cycling
electrolyte degradation, and dendrite formation. of various types of battery cells – from coin cells and
Understanding these degradation mechanisms is electrochemical cells to pouch cells and prismatic cells.
therefore an important step towards the successful
development of new battery materials.

COIN AND ELECTROCHEMICAL CELLS


Opening possibilities for non-ambient exploration

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.

Lattice parameter variation with charge-discharge


14,6 2,88

2,86
14,4
2,84

2,82
14,2
c [Å]
2,8
a [Å]

14 2,78
3V 4,3 3V

Figure 18. Figure 19.

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.

An electrochemical cell supported on the Empyrean XRD platform:


it is also possible to heat or cool the cell and investigate cycling
durability at non-ambient temperatures.
19

POUCH AND PRISMATIC CELLS


Unlocking the full story with hard radiation transmission

What’s more, multilayer pouch cells up to 5 mm thick can Voltage [V]


Voltage [V]
also be analyzed on the Empyrean XRD platform, when
4.2 4 3.8 3.6 3.4
equipped with high energy Ag radiation and a GaliPIX 3D 160
detector. The Empyrean supports 60 kV excitation,
enabling the high-intensity 22.16 keV Ag radiation suitable 128

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.

The voltage variation (3.2V in discharged state to 4.3V in fully


charged state) is plotted in green line colour. The isoline plot
Voltage [V]
shows cathode and anode peak positions as the cell is charged or 4 3.5
discharged. The peak around 6.8° 2θ is the 003 peak of the NCM
cathode and its changing position reflects changes in c-parameter 104
with cycling. The discontinuous peak around 9° 2θ is from the 96
Scan number

graphite anode, which changes from C to LiC6 or LiC12 during the 88


charge cycle and then reverses back to LiC12 and then C during
the discharge cycle. 80
72
64
56
48
40
7 8 9
Position [°2θ] (Ag K-α12)

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.

MALVERN PANALYTICAL NETZSCH-Gerätebau GmbH


EN · 1122 · Technical specifications are subject to change.

Grovewood Road, Malvern, Lelyweg 1, Wittelsbacherstraße 42


Worcestershire, WR14 1XZ, 7602 EA Almelo, 95100 Selb
United Kingdom The Netherlands Germany

Tel. +44 1684 892456 Tel. +31 546 534 444 Tel. +49 9287 881-0
Fax. +44 1684 892789 Fax. +31 546 534 598 Fax. +49 9287 881 505

info@malvernpanalytical.com at@netzsch.com

www.malvernpanalytical.com/batteries www.netzsch.com/ta

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