BATTERY RESEARCH ANDQUALITY CONTROL SOLUTIONS
Benefit from physical, chemical and structural insight

2

3

DISCOVER NEW HORIZONS IN
BATTERY QUALITY

MONITOR AND OPTIMIZE AT EVERY STAGE

Empower your research and production
with advanced analytical solutions

The age of the battery is well underway. Lithium-ion
batteries, for example, have already revolutionized our
day-to-day lives – from smart mobile devices to pollutionfree electric cars and intelligent power management
solutions. And, looking ahead, batteries also have thepotential to provide an economical solution for massenergy storage and complement renewable energy
resources for power grid applications.
Despite these successes, gaps in battery technology
remain, both in terms of safety and performance. What’smore, for their mass-scale adoption in applications likeelectric vehicles, large cost reductions will be needed.
Indeed, with regulators becoming more stringent andconsumers more demanding, these core issues are
driving not only research into new battery materials, butalso improvements in production efficiency to minimize
production costs. When success is defined by such finemargins, today’s manufacturers must be able to ensure
total quality and performance – every time.
At Malvern Panalytical and NETZSCH Analyzing & Testing,
we leverage over six decades of experience in the design,
manufacture, and supply of analytical instruments tooffer a complete range of laboratory and online analyticalsolutions. Whether you are a battery component
manufacturer looking for greater process efficiency andbetter quality control, or a researcher trying to determine
the performance parameters of newly emerging battery
materials, our solutions will offer you the new levels of
insight and control needed to power the production ofsuperior-quality batteries.

Cathode slurry

Cathode /Anode slurry

Evaporator

Battery component manufacturers must not only
deliver consistent overall quality – they must deliver itthroughout the manufacturing process. The continuityof the manufacturing process means errors or impurities
at an early stage will accumulate, resulting in much larger
consequences further down the production line. Quality
needs to be monitored at every stage – from raw materials
through to cell assembly – to maintain production
efficiency and minimize waste. Likewise, research into newbattery materials must ascertain all the critical parametersthat could affect battery performance throughout theentire manufacturing process.

At Malvern Panalytical and NETZSCH Analyzing & Testing,a range of research and quality control solutions to help
manufacturers monitor and optimize every part ofthe battery manufacturing process. The unique set ofphysical, chemical and structural analysis possibilities
that our technologies offer can be utilized across various
stages of battery component production. From improving
electrode material quality to accelerating the successful
development of new high-performance battery materials,
we’ve got you covered– enabling the development andproduction of the highest-performing batteries.

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

Critical Parameters

Analytical techniques

Product and solutions

Cathode precursor
and electrodematerials

Particle size
Particle shape
Chemical composition
Crystal phase

Laser diffraction
Automated Imaging
X-ray fluorescence
X-ray diffraction
Simultaneous Thermal Analysis– Mass Spectrometer

Mastersizer 3000
Morphologi 4
Epsilon 4 / Zetium XRF
Aeris compact XRD
STA 449 Jupiter ® - QMS Aëolos® Quadro

Battery slurry

Particle size
Particle shape
Viscosity
Viscoelasticity
Stability

Laser diffraction
Automated Imaging
Rotational Rheometry

Mastersizer 3000
Morphologi 4
KinexusElectrode andelectrode coating

Coat weight
Coating thickness
Thermal management(thermal diffusivity/
conductivity)
Specific heat capacity

Photon sensor
Micro caliper thickness sensor
Laser/Light Flash
Differential Scanning Calorimetry

Photon and Micro caliper sensors
from NDC technologies
LFA 467 HyperFlash®
DSC 404 Pegasus®

Electrolyte

Thermal Stability

Simultaneous Thermal
Analysis coupled to Evolved
Gas Analysis (e.g., QMS)

STA 449 Jupiter® - QMS 403 Aëolos®
QuadroBinder, additives

Composition,
thermal behavior
Viscosity
Viscoelasticty

Simultaneous Thermal Analysis
Rheology

STA 449 Jupiter®
Rotation Rheometer Kinexus

Separator

Specific heat capacity,
length change

Differential Scanning
Calorimetry,
Thermomechanical Analysis

DSC 404 Pegasus®,
TMA 402 Hyperion®

Battery cell

Degradation mechanism
during cycling
Efficiency of full cells

In operando XRD
Calorimetry, Accelerating
Rate Calorimetry

Empyrean XRD
MMC 274 Nexus®, ARC 244/254

Anode slurry
Cathode coated
Al foilElectrolyte

Porous polymer
separator(+carbon black + binder+ solvent)Anode coated
Cu foil

Battery cell

Cathode /Anode powder

45

OPTIMIZE CATHODE MATERIALSCHARACTERIZATION TOOLS

Cathode material production is just one example of
how our solutions enable quality at every stage of the
manufacturing process. As one of the first stages inbattery production, quality control is especially importantto cathode manufacturing – and battery manufacturers
must implement it all while minimizing costs.

Particle size

Our solutions can be used as cathode characterization
tools at several stages of the cathode production process,from co-precipitation and precursor quality control,
down to optimizing calcination and the final material. By
providing manufacturers with morphological, structural,and elemental insights, these solutions enable them tooptimize process parameters accordingly to ensure thehighest cathode quality.

1

Consistent cathode-material particle size starts with theprecursor – 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 animportant role in the quality of the electrode coating. With
the Mastersizer 3000, you can analyze particle size withaccuracy and ease.

3

Particle shape7

Co-precipitation
Cathode materials of current interest, such as NCA and
NMC, are produced via co-precipitation of a transition metalhydroxide precursor, followed by calcination (lithiation andoxidation) with a lithium compound.
Our morphological, structural and elemental insights canhelp to:• Optimize process parameters.
• Ensure consistent quality and reduce production costs.

Precursor: particle
size and zeta
potential analysis

Particle shape influences critical parameters like electrodeslurry rheology and packing density. Analyze particle sizeand shape at the precursor stage with Morphologi 4
imaging - automatic analysis of thousands of particles withhigh statistical accuracy.

1
6

4

Elemental composition

Rough

H
Li

Be

SmoothRegularZ

Possible to analyze with Epsilon 4

Z

Not possible to analyze with Epsilon 4

Z

Possible with Epsilon 4 and optional detector

He

Na Mg

Li compund

2

Precursor(NMC / NCA)

3

Combined with fusion sample preparation recipes, ourEpsilon 4 benchtop X-ray fluorescence (XRF) spectrometeror high-end Zetium spectrometer can simplify thechemical composition and elemental impurity analysis ofelectrode materials.

4

Precursor: particle sizeand shape, and elemental
composition analysis

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.

Calcination

7

6

On-line particalsize analysis

1

Zeta potential can be used to optimize processparameters like pH and concentration to control slurrystability, agglomeration, and sedimentation behavior.
Our Zetasizer can analyze zeta potential of a dispersion
and also the size and agglomerate state of nanosizedmaterials.

Particle size andcrystal phase2

3

4

Zeta potential

5

Mill
7

•

Improve precursor quality and throughput•

Ensure right stoichiometry•

Optimize calcination process•

Control particle size and morphology

Cathode material withdesired size distribution

Heat treatment
Characterization of raw materials and calcination:
Simultaneous monitoring of the thermal behavior andgases released during heat treatment enables coupling of
the NETZSCH QMS Aëolos® Quadro mass spectrometerto 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 andthe calcination process.

Elongated

B

C

N

O

F

Ne

Al

Si

P

S

Cl

Ar

Co

Ni

Cu

Zn

Ga

Ge

As

Se

Br

Kr

Ru

Rh

Pd

Ag

Cd

In

Sn

Sb

Te

I

Xe

Re

Os

Ir

Pt

Au

Hg

Tl

Pb

Bi

Po

At

Rn

Ce

Pr

Nd Pm Sm Eu

Gd

Tb

Dy

Ho

Er

Tm Yb

Lu

Th

Pa

U

Np Pu Am Cm Bk

CfEs

Fm Md No

Lr

K

Ca

Sc

Ti

V

Cr Mn Fe

Rb

Sr

Y

Zr

Nb Mo

Tc

Cs

Ba

L

Hf

Ta

W

Fr

Ra

A
L

La

A

Ac

6

7

OUR RESEARCH AND QUALITYCONTROL SOLUTIONSSuperior particle size distribution measurement
Delivering an optimal and consistent particle size
distribution doesn’t just add value to electrode materials,
it’s key to ensuring final product quality – enabling
manufacturers to optimize; slurry viscosity and flow
behavior; coating packing density and porosity; battery
cell charge rate capacity and cycling durability.
To meet this need, Malvern Panalytical offers an industrystandard particle size measuring tool; theMastersizer 3000. Based on laser diffraction, it offers
industrial-level performance, delivering more reliable

and faster measurements than sieving, fastermeasurements than sedimentation, and statisticallysuperior information compared to microscopy. The
Mastersizer 3000 laser diffraction particle size analyzer
delivers rapid, accurate particle size distributions forboth wet and dry dispersions with the minimum of effort.
Measuring over the nanometer to millimeter particle
size ranges, it packs exceptional performance into thesmallest of footprints, bringing operator-independentmeasurements that every user can rely on.

1630

Synthetic Graphite

Cathode-A
Cathode-B

20

Cathode-C
100

Anode-1

12
Volume (%)

Volume (%)

NCM Cathode

Anode-2Anode-3

8

REAL-TIME PROCESS AUTOMATION

4
0

0,1

1

10

100

1000

Size (µm)
Figure 1. Particle size distribution of three batches of NCM811
cathode materials synthesized with different processing
parameters.

0,1

1

10

100

1000

Size (µm)
Figure 2. Particle size distribution of three batches of synthetic
graphite synthesized with different heating conditions.

Optimizing process parameters
Manufacturers also need to monitor particle sizeas the production process continues. And, if you’re
manufacturing at industrial scale with limited humanresources, finding an efficient way to analyze particle sizein real time can be difficult. Usually, lab analysis will deliver
feedback in about an hour, whereas for optimum quality
control, a feedback loop of a few minutes is required.
Our on-line, automated Insitec particle size analyzer isideal to meet this need in a production environment,delivering real-time analysis every few seconds using a
feedback loop. It can be used to control precursor particle
size evolution over time, or just after milling to control
electrode particle size – enabling manufacturers to
reduce waste and align their processes with smart factory
manufacturing flows.

On-lineanalysis
Synergy with
Smart factory
process ﬂow

Synergyvalue

Commercial
value

Waste
reduction/
processeﬃciency
improvement~2%

Manpower saving ~1 person
Lab analysis

Typical value gain for a cathode manufacturing plant with Insitec
online particle size analysis of precursor slurry, in comparison tolab analysis.

8

9

THERMAL MANAGEMENT
dL/Lo /%

2of electrodes, electrode coating, separators, the LFA
467 HyperFlash® is the right instrument. Between -100°C
and 500°C, this LFA system contactless measures thetemperature increase of samples between 6 mm and25.4 mm with an IR detector. The patented ZoomOptics
allows the detector’s field of view to be adjusted until the
only temperature increase registered is that of the sample
and no influences by the surroundings may have any
effect.

Thermal Diﬀusivity /(mm^2/s)

Like the human body, the operating temperature of abattery should always be monitored, protected andkept at an optimal level. If the ambient temperature is
too low, it will not deliver its full power. If the ambient
temperature rises too high, the battery can even swell,catch fire, explode and release toxic gases. Properbattery thermal management ensures longer lifespanby keeping the cells within a limited temperature range
during storage, operation and charging. Understanding
how much heat can be dissipated by the cells requires
understanding of the basic heat transfer properties of thecell design. Measuring the thermal diffusivity and thermal
conductivity along with the specific heat capacity form thebasis 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.

0,4

1,5

0,3

1

0,2
0,5

Thermal Diﬀusivity
0,1

0

1,5

1

0,5

Conductivity
0

0
10

20

-2
-4
-6
-8
-10
-12

Spec. Heat
0

2

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

Controlling battery thermal characteristics – Separator,
Electrode and Electrode Coating

2
Thermal Conductivity / (W/(m*K))

0,5

30

40

50

0

-14

60

Temperature /°C

20

40

60

80

100

120

140

160

180

Temperature /°C

Figure 3. Aluminum electrode coated on both sides: The thermal
conductivity (petrol curve) is determined by measuring thethermal diffusivity with the NETZSCH LFA 467 HyperFlash® (rubine
red curve) and specific heat capacity, cp (gray curve). In thisexample, cp was determined using the DSC 404 F1 Pegasus®.

Figure 4. TMA measurement on a polymer film between RT
and 190°C at a tensile force of 5 mN . Shrinkage starts at 159°C(extrapolated onset).

Thermomechanical Analysis

This is achieved by Thermomechanical Analysis (TMA),
expressed by the coefficient of thermal expansion (CTE).
The length change phenomena can be studied by meansof thus revealing information regarding their thermal
behavior and about process parameters or curing kinetics.

Differential Scanning Calorimetry
Each time a material is exposed to temperature changes– it shows a variation in its dimension. Whether it is in thecourse of its regular thermal expansion or by passing aphase transition, the substance will either be shrunk orelongated. For example, polymer separators can shrink
significantly at elevated temperatures which affects thebattery performance. To predict the deformation andstresses in the separator in battery cells, it is necessary tomeasure the expansion/shrinkage behavior.

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 andenthalpies, glass transition temperatures, reaction
temperatures and enthalpies, cross-linking reactions(curing), and more.

Thermal conductivity and diffusivity are the mostimportant thermophysical parameters for the descriptionof the heat transport properties of a material or acomponent (Figure 3). The Laser/Light Flash technique
has proven itself a fast, versatile and absolute method formeasurement of the thermal diffusivity. NETZSCH offers
three models, covering the widest temperature range forthe broadest spectrum of materials. For the investigation

TMA 402 Hyperion®

Under a defined mechanical force, the TMA 402 Hyperion®
series allows for monitoring the volumetric and linear
thermal expansion, shrinkage steps, glass transition
temperature, density change, and anisotropic behavior.

10

11

THERMAL STABILITY

PARTICLE MORPHOLOGY

Safety is ensured when deterioration of stability is avoided

Enabling better insight into electrode material morphology​

Electrolytes are characterized by high conductivity, goodelectrochemical stability and the ability to perform at low
temperatures. However, the thermal stability of manyelectrolyte solutions is restricted even at moderatetemperatures. Due to overcharging, batteries canoverheat to the point that they catch fire.
Besides various metals (e.g., cobalt, aluminum or
manganese, etc.), the cathode material of Li-ion batteries
contains nickel. There is a positive correlation between
the nickel content and the battery capacity. Since nickel isrelatively cheaper than cobalt, adding more nickel lowers
the unit cost of, e.g., electric vehicle (EV) batteries.

However, nickel reduces the stability of the battery as
it reacts easily to the external environment. The nickel
content in batteries can increase to 80% or higher, and theconsequent deterioration in stability must be improved toensure safety.
The thermal stability can be investigated by meansof Differential Scanning Calorimetry (DSC) and
Thermogravimetry (TG or called ThermogravimetricAnalysis TGA). A combination of both methods represents
the Simultaneous Thermal Analyzer (STA).
The STA 449 Jupiter ® series combines configuration
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, volatiledecomposition 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 forstudying the thermal degradation of electrolytes.

The role of particle shape in battery electrode materials
is usually ignored or underestimated. However, thismay 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 theelectrode coating in terms of packing density, porosity
and uniformity. To achieve the highest level of battery
performance, manufacturers must also understand andoptimize the particle morphology.

RoughSmoothRegularElongated

Do your particles have the right 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 statisticalaccuracy. What’s more, the Morphologi 4-ID combines
automated static imaging features of the Morphologi 4with chemical identification of individual particles using
Raman spectroscopy - enabling automated measurementof particle size, particle shape and chemical identity, on asingle platform.
2,55Cathode-A

4

Cathode-C

Cathode-A

3

1,5

2

1

1

0,5

0

0,1

1

10

100

HS Circularity of 3 cathode materials

2

Cathode-B

1000

Cathode-B
Cathode-C

0
0,6

0,7

0,8

0,9

1

Size (µm)
Figure 6.

TG /%
100

EC-DEC-LiPF6 - Untreated

QMID *10-12 /A[s:1, m:45]

152.3 °C

20
15

50

152.3 °C

0-50

10s:1, m:45 [2]152.3 °C-100

154.7 °C

-150

150.0 °C

-200
50

100

150

s:1, m:91 [2]0s:1, m:63 [2]-5s:1, m:75 [2]-10s:1, m:59 [2]

200
250
300
Temperature /°C

350

400

5

450

-15

TG /%

QMID *10-12 /A[s:1, m:43]

EC-DEC-LiPF6 - Untreated

100
50
0
-50
-100
-150
-200
-250

274.5 °C

60

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 thesesamples is compared in Figure 7. Circularity index 1 corresponds to perfect spheres and smaller values to larger deviation fromcircularity. A narrow distribution in circularity means uniform shape particles, whereas broad distribution represents large variance inparticle shapes. Cathode A has circular particles, whereas B and C are irregularly shaped with large shape variations.

40
20

274.5 °C
s:1, m:43 [2]274.5 °C

s:1, m:88 [2]274.5 °C

s:1, m:58 [2]274.5 °C

s:1, m:56 [2]s:1, m:73 [2]

50

100

150

200
250
300
Temperature /°C

350

400

450

0

0,5

1,2

0,4

Sample A
Sample B-20-40

HS Circularity

Particle size distribution (μm)

0,8

0,2

0,4
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.

0

Sample A
Sample B

0,3
0,1

1

Figure 8.

10

100

1000

0

0

0,2

0,4

0,6

0,8

1

Figure 9

Example Graphite electrode material: size distribution of two samples as measured with Mastersizer 3000 (Figure 8) and circularityof 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

13

ELEMENTAL COMPOSITION
Simplifying chemical composition and impurity analysis
Deviations in chemical composition or impurities inelectrode materials can significantly affect final battery
performance. For this reason, chemical composition andelemental impurity analysis are an integral part of thebattery manufacturing process. However, the often-usedinductively coupled plasma (ICP) analysis is not always thebest tool for this. Requiring sample digestion and frequentcalibration, ICP is inefficient and expensive for mostelemental 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 cathodematerials at low-percentage elemental levels is morereliably measured with X-ray fluorescence.

SAMPLE PREPARATION FOR XRF
Ensuring more accurate analysis

Specifically, our Epsilon 4 benchtop energy dispersive
XRF spectrometer can accurately measure elemental
composition in just a few minutes. When better lightelement sensitivity is desired, our Zetium wavelength
dispersive XRF spectrometer is recommended. These
solutions can help manufacturers optimize cost and useof human resources, while saving ICP for very low-level
impurity detection.

Sample preparation is a major source of error in elemental
composition analysis. All too often, preparation methods
such as pressed pellets (in XRF) or acid digestion (in ICP)
are affected by mineralogical or particle size effects inmetal samples, compromising the accuracy of the results.

Mn% measured with Omnian standardless

Measured Mn %100,00
80,00

80,17

60,00

59,90

40,00

40,19
20,35

20,00
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 tablebelow. 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

80.2

0.11

0.011

0.014

0

Cl

SMP1

LiFe 02Mn 08PO 4

SMP2

LiFe 04Mn 06PO 4

59.9

0.19

0.012

0

0

SMP3

LiFe 06Mn 04PO 4

40.2

0.117

0.041

0

0

SMP4

LiFe 08Mn 02PO 4

20.4

0.161 0.008

0.014

0.037

SMP5

LiFePO 4

0.1

0.155 0.015

0

0

Co
0

To meet the need for reliable sample preparation for XRF
or ICP, Malvern Panalytical offers a high-performance
fusion solution. Fusion involves dissolving a fully oxidized
sample at high temperature in a suitable solvent (a flux)
in a platinum, zirconium or graphite crucible. The melted
mixture is agitated and poured into a mold to create aglass disk for XRF analysis. It can also be poured intoa beaker to create a solution for Atomic Absorption
Spectroscopy (AAS) or ICP analysis.

Cr

Cu

Ni

S

Si

Ti

Y

0.026

0.008

0.022

0.009

0.006

0

0.018

0.013

0.004

0.02

0.01

0.009

0.006

0.011

0.023

0.006

0.024

0

0.007

0.005

0.042

0.009

0.015

0

0.02

0

0.006

0.006

0.055

0.009

0.024

0.007

0.024

0

0.009

0.004

0.017

0

0.001

0.024

0.003

0.034

0
0

Zn

At Malvern Panalytical, you can count on our 40-plus yearsof expertise in designing and delivering fusion recipes forvarious kinds of complex samples. What’s more, we offer
two fusion instruments. Our robust LeNeo instrument isideal for battery sample fusion. This automatic electric
instrument can prepare glass disks for XRF analysis, aswell 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 anddriving high-precision quality control. To meet high sample
throughput, our TheOx advanced instrument, which has
six fusion positions, can be used.

14

15

CRYSTALLINE PHASE COMPOSITIONZETA POTENTIAL ANALYSIS

Unlocking atomic-level exploration

Enabling slurry stability insightCountsIn electrode slurry production, zeta potential (related tocharge charge on particle) plays an important role in slurrystability. 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.

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
electrode materials, governing lithium-ion transport at
atomic level. To analyze crystalline phase composition andquality in synthesized powder materials, X-ray diffraction(XRD) is routinely used.
In battery cathode materials, XRD can be used to ensurethat reactants have completely fused to the desired andstable crystalline phases during the calcination process.
It can also be used to measure chemical composition or
to estimate the size of primary particles (from themeasurement of crystallite size), which plays an importantrole in ion migration. In anode materials, XRD can measure
the degree of graphitization in synthetic graphite, whichsignificantly affects anode energy density.
These applications can be carried out easily with our Aeris
compact X-ray diffractometer. Thanks to its automatedanalysis, sample measurement on Aeris requires no prior
XRD expertise. Moreover, the Aeris is built for industrial
automation. It meets requirements for industrial highthroughput sampling, since typical sample measurementtakes just a few minutes. Samples can be fed either
manually or via a belt automation.
Counts

30000

20000

10000

26

28

30

10,5

CountsCrystallite size with Mn Content

64000080

size (nm)

10,4
10,35

0

20

40

60

80

Mn Content
Figure 13.

0.3358 nm
Graphite

Graphitization degree 95%

16000040
20

Syn Graphite mixed with Si reference

360000

60

10,3
10,25

To meet this need, we offer the Zetasizer. Whether it’sto 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-concentrationand highly conducting samples, its specialized cell andconstant current mode have you covered – enabling
manufacturers to optimize Ph and concentration forstable slurries to manufacture high quality electrodes.

Example LMFP Cathode Material:
Section of XRD pattern (Figure 8) showing peak shift to lower
angles as the Mn content increases, meaning lattice expansion
along c-axis.

100

10,45

Low zeta potential= unstable dispersion /agglomeration

Figure 12.

c-parameter variation with Mn Contentc (Å)

LFP LiFePO4
LMFP-Mn20Fe80
LMFP-Mn40Fe60
LMFP-Mn60Fe40
LMFP-Mn80Fe20

High zeta potential= stable dispersion

40000

0

20

40

60

80

Mn Content
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, andcomposition 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.

026

Figure 15.

28

30

32

Example Synthetic graphite:
Degree of graphitization and orientation index are important
attributes of synthetic graphite, which is a commonly used anodematerial due to its superior consistency and purity compared tonatural graphite. Aeris can measure both the graphitization degreeand orientation index. Figure 15 shows the measurement of thedegree of graphitization in one such material.

16

17

PROCESSING PROPERTIES ANDLEVELING CHARACTERISTICS

CHARACTERIZATION OF COIN CELLSAS A WHOLE

How to apply battery slurry onto the electrode

Heat signature as key information for battery development and testing

A battery slurry is typically processed by blade coatingor slot die coating. During these processes, the slurry
is undergoing mid-level shear rates for a short periodof time, followed by gravitational stresses acting on theslurry after the coating process. This has impact on theleveling behavior at low shear rates and film uniformity.

Specifically, understanding of the heat generation during
charging/ discharging cycles is crucial for improving thecell efficiency, performance and lifetime of batteries.
Measuring the heat signature of coin cells during
cycling provides insight into the underlying processes
and provides a quantitative way of comparing changes
in chemistry above and beyond current and voltage
measurements. Some of these processes are reversible,
some occur during the initial few cycles, and others takeplace 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.

Rheology provides access to these flow propertiesof 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 ofthe slurry under shear flow is important. It can lead toflow 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.

Temperature
sensorTop
guard
heaterCritical factors influencing rheology of the slurry:• Volume fraction• Particle size and distribution• Shape• Electrostatic interactions• Molecular weight• Intrinsic viscosity

Side
guard
heaterLeaf spring

To avoid sedimentation at all, the slurry structure at rest needs tobe dominated by elasticity. This can be investigated by oscillatory
shear experiments, which allows for characterization of theviscoelastic properties and thus enables a stability forecast forthe slurry before it is coated.
The higher viscosity may also make the coating process moredifficult to control, potentially leading to uneven coating andvariable layer density which, in turn, results in a variable iontransfer rate and hence battery lifetime (and recharge cycle time).

SampleReference

Heat ﬂow
sensorCritical factors when processing battery slurries:• Slurry stability• Flow properties (viscosity and elasticity) during coating• Flow instability• Film structure / leveling behavior

Coin Cell Module

Bottomguard
heater

The MMC 274 Nexus® offers three interchangeable calorimeter
modules: ARC for process safety investigations, Scanning for highreaction enthalpies and Coin Cell for battery testing.

Viscosity vs Shear rate
101

Efficiency Tests for Coin Cells

Carbon A(with Binder)100

η (Pa s)Viscosity and visco-elasticity control of the coating process
The rheometer measurement with the NETZSCH Kinexus
shows that the addition of PVDF to NMP drastically increases
viscosity relative to NMP alone and the viscosity remains largely
independent of the shear rate (Newtonian behavior).Adding
carbon black increases viscosity and the resulting slurries bothshowed shear rate dependence (non-Newtonian behavior). The
slurry made with Carbon A yielded a much higher viscosity than
Carbon B at low and high shear rates, which would likely increase
the resistance to sedimentation on standing (low shear process)and result in a thicker electrode film on coating (high shear
process).

Using the unique coin cell module of the NETZSCH MMC
274 Nexus® Multiple Module Calorimeter allows foranalysis of the behavior of a complete coin cell instead ofindividual components to mimic cell performance in thereal world. This special differential measuring principle
for improved stability and sensitivity captures even weakheat signals from coin cells. Characterization of coin cells
can be achieved by isothermal charging/discharging andscanning tests.

Carbon B(with Binder)
10-1

NMP/PVDF
10-2

NMP

10-3
10-1

100

101

.
γ (s-1)

102

103

104

Figure 16. Rheological measurements on 4 different slurries
measurement carried out at shear rates ranging between
0.1 to 1000s-1.

The key component of the coin cell module is the sensor.
It features an innovative differential measurement design
based on thermopiles for improved sensitivity andstability in heat-flow measurements. The calorimetricblock is equipped with a Resistance Temperature Device(RTD) in order to precisely monitor and control its
temperature using the surrounding furnace. When thecoin cell releases or absorbs any heat due to charging/discharging or internal physical changes, the sensor
detects this heat. To nullify the effect of external
disturbances, the signal coming from the reference heatflow meter is subtracted from the signal detected by the
sample heat flow meter, thus yielding a true differential
measurement. This technique is much more accurate andsensitive than that of a single-sensor system.

Power /mW
Temp. /°C

Heat ﬂow /mW Discharge eﬃciency @ 1C = 87.9%
Area...: 371.44E+03mW*S
50

↑ exo

150
Charge eﬃciency @ 1C = 96.0%
Area...: 422.22E+03mW*S

40

100
50

30

0

31.0

30.5

30.0

-50
20

Heat ﬂow
Temp.
Area: 45.04 J

Power

-100
-150

10

29.5

29.0

-200
Area: 17.04 J
0

28.5
-250
-300

1700

1750

1800

28.0

1850

Time/minFigure 17. From the heat signature of the LiR2032 during three cycles
of discharging and charging, the efficiency is calculated by dividing theelectrical energy by the total energy (electrical energy + heat flow)
during discharging and charging.

18

19

BATTERY CELL CHARACTERIZATIONPOUCH AND PRISMATIC CELLS

Delivering in operando X-ray diffraction

Unlocking the full story with hard radiation transmission

In operando X-ray diffraction (XRD) can investigate thesefailure mechanisms by analyzing underlying crystal
structure changes during battery cycling. Our Empyrean
XRD platform offers options for the in operando cyclingof various types of battery cells – from coin cells andelectrochemical cells to pouch cells and prismatic cells.

COIN AND ELECTROCHEMICAL CELLS

What’s more, multilayer pouch cells up to 5 mm thick canalso be analyzed on the Empyrean XRD platform, whenequipped with high energy Ag radiation and a GaliPIX 3D
detector. The Empyrean supports 60 kV excitation,
enabling the high-intensity 22.16 keV Ag radiation suitablefor pouch cell research. Special multilayer focusing mirrorsdeliver high resolution and a high brilliance X-ray beam,further shortening the measurement times.

160

Scan number

The biggest issue faced when developing new battery
materials with high energy density is capacity degradation
with cycling. Causes of capacity degradation can include
particle cracking, lithium retention in electrodes,
electrolyte degradation, and dendrite formation.
Understanding these degradation mechanisms istherefore an important step towards the successful
development of new battery materials.

2,88

14,6

2,86
14,4

2,84
2,82
c [Å]

2,8

a [Å]

14

Figure 18.

3V

4,3

3V

2,78

3.6

3.4

15

20

25

32

Position [°2θ] (Ag K-α12)Voltage [V]Scan number

Lattice parameter variation with charge-discharge

3.8

64

Example of in operando cycling of a pouch cell. Measurements
were performed on the Empyrean XRD platform configured withAg 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 plotshows cathode and anode peak positions as the cell is charged ordischarged. The peak around 6.8° 2θ is the 003 peak of the NCM
cathode and its changing position reflects changes in c-parameterwith cycling. The discontinuous peak around 9° 2θ is from thegraphite anode, which changes from C to LiC6 or LiC12 during thecharge cycle and then reverses back to LiC12 and then C during
the discharge cycle.

Voltage [V][V]
Voltage96

10

Another solution is the electrochemical cell, with an
X-ray transparent window made from beryllium or glassy
carbon. We supply the electrochemical cells with theoption of heating and cooling that are mounted on the
Empyrean XRD.

14,2

4

128

Opening possibilities for non-ambient exploration
All types of coin cells with at least one side with an X-ray
transparent window can be studied on the Empyrean XRD.
We provide a specialized coin cell holder, which can beused for charge-discharge cycling.

4.2

4

3.5

7

8

104
96
88
80
72
64
56
48
40
9

Position [°2θ] (Ag K-α12)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 isusually 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.

Pouch and prismatic cell mounting on the Empyrean XRD.
A mechanism to apply pressure on the pouch cell is also
supported.

Our GaliPIX3D detector with 100% efficiency from Cu to Ag
radiation makes fast measurements possible on cells up
to 5 mm thick.

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NETZSCH

When you make the invisible visible,
the impossible is possible.

We partner with many of the world’s biggest companies,
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only for the power of our solutions, but also for the depth of
our expertise, collaboration and integrity.
With over 2200 employees, we serve the world, andwe are part of Spectris plc, the world-leading precision
measurements group.

The NETZSCH Group is an owner-managed, international
technology company with headquarters in Germany. The
Business Units Analyzing & Testing, Grinding & Dispersing
and Pumps & Systems represent customized solutions at
the highest level. More than 3,800 employees in
36 countries and a worldwide sales and service network
ensure customer proximity and competent service.
Our performance standards are high. We promise ourcustomers Proven Excellence – exceptional performancein everything we do, proven time and again since 1873.

Malvern Panalytical. We’re BIG on small™.

When it comes to Thermal Analysis, Accelerating
Rate Calorimetry, the determination of
Thermophysical Properties, Rheology andFire Testing, NETZSCH has it covered.
Our 50 years of applications experience, broad state-ofthe-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 PANALYTICALNETZSCH-Gerätebau GmbH

Grovewood Road, Malvern,
Worcestershire, WR14 1XZ,
United Kingdom

Lelyweg 1,7602 EA Almelo,
The Netherlands

Wittelsbacherstraße 42
95100 Selb
Germany

Tel. +44 1684 892456
Fax. +44 1684 892789

Tel. +31 546 534 444
Fax. +31 546 534 598

Tel. +49 9287 881-0
Fax. +49 9287 881 505
at@netzsch.com

www.malvernpanalytical.com/batteries

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EN · 0321 · Technical specifications are subject to change.

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