Applications note

Lithium Ion Battery note

LIBnote
Morphology Observation & Surface Analysis Instruments
XRF / XPS / EPMA / AES / SEM / TEM / CP / FIB

Chemical Analysis Instruments

GC-MS / NMR

Fabrication Systems
Roll to Roll Electron Beam Deposition Systems
RF Induction Thermal Plasma System for Nano Particle Synthesis
1. Morphology Observation & Surface Analysis Instruments

LIB
B
LIBnote
Lithium Ion Battery

Introduction
The applications for lithium ion batteries (LIB) cover a wide range, from power sources for personal computers
and mobile devices to automobiles, and there is always a demand for even better performance and safety.
In order to ensure the performance and quality of LIB, analysis and evaluation using high-performance
assessment systems is necessary. JEOL offers a full line-up off equipment to support the development of new LIB
technologies and to improve product quality, including instruments for morphology observation and surface
analysis, chemical analysis systems to perform structural analysis on a molecular level, as well as fabrication
systems to create high-performance coatings and powders. This LIB note offers solutions for researchers and
engineers who are looking for the best equipment for their application.

INDEX
Introduction P01

Lithium Ion Battery Basic Structure & Fabrication Process P02

1.Morphology Observation & Surface Analysis Instruments

1-1. Features to Consider for Instrument Selection P03

1-2. XRF: X-ray Fluorescence Spectrometer P04

1-3. XPS: X-ray Photoelectron Spectrometer P05

1-4. EPMA: Electron Probe Micro Analyzer P07

1-5. AES: Auger Electron Spectrometer P09

1-6. SEM: Scanning Electron Microscope P11

1-7. TEM: Transmission Electron Microscope P17

1-8. CP: Specimen Preparation Equipment: Air Isolation & Cooling CP, FIB P18

2.Chemical Analysis Instruments

2-1. GC-MS: Gas Chromatograph Mass Spectrometer P20

2-2. NMR: Nuclear Magnetic Resonance Spectrometer P21

3.Fabrication Systems

3-1. Roll to Roll Electron Beam Deposition Systems P23

3-2. RF Induction Thermal Plasma System for Nano Particle Synthesis P24

Conclusion Analysis Item and Applicable Instruments P25

1 LIBnote
B
Lithium Ion Battery Basic Structure & Fabrication Process

The basic structure of LIB consists of various


    

These components have a variety of formats,


 

  
to assess for the various material evaluations. It is
also necessary to make assessments after assembly,
and after repeating the charge/ discharge operations.

     

that is suitable for materials assessment at the R&D
level, and the equipment useful for making the
evaluations for each step of the fabrication process.
■ Positive electrode materials ■ Separator ■ Negative electrode ■ Electrolyte
materials

JEOL offers analytic instrument solutions for each process

Transmission Electron
Microscope / TEM Auger Electron Spectrometer / AES
Cathode/ Anode materials

R&D

Separator

Quality
Control
Nuclear Magnetic
Resonance Spectrometer
Electrolyte / NMR
Fabrication
Electron Spin Resonance
Spectrometer / ESR

Preparation of raw materials Cathode/ Anode materials X-ray Fluorescence

Spectrometer / XRF

Coating / Press Cathode/ Anode materials

Scanning Electron Electron Probe Micro Analyzer / EPMA

Microscope / SEM
Cell assembly Winding, Extrusion, Drawing
(cathode, anode, current collector,
  separator, electrolyte)

Aging Check battery performance

Charging cycle test Check deterioration process

X-ray Photoelectron Gas Chromatography

Spectrometer / XPS – Mass Spectrometer / GC-MS

LIBnote 2
1. Morphology Observation & Surface Analysis Instruments

1-1 Features to Consider for Instrument Selection

The tables below show the criteria for selecting instruments for material assessment purposes. Table 1 lists the
   
         

Features of instruments to support the development of LI ion batteries 1

Instrument Features
Micro scale Suitable for rapid specimen average composition analysis（just a few minutes
to obtain a result, including sampling and measurement). Measurements are
possible for both vaccum and atmosphere.
Fluid samples as well as solid samples can be used.
Can be used for screening of transition metals, such as Fe, Co, and Ni: for
XRF：X-ray Fluorescence Spectrometer cathode materials.

Li is observable, An ideal system for chemical bonding state analysis of the

sample surface. Chemical state analysis of the electrode interface is possible
  !
XPS：X-ray Photoelectron Spectrometer

Multi-channel WDS allows micro area element analysis with a high energy
resolution. Secondary electron images and backscattered electron images
make it possible to observe the surface morphology.
EPMA：Electron Probe Micro Analyzer

"   chemical bonding state analysis as well
as surface analysis for micro area is possible. Secondary electron images
and backscattered electron images make it possible to observe the surface
AES：Auger Electron Spectrometer morphology.

High resolution morphology observations of the surface, including structural

analysis of materials at a nano-level with low accelerating voltages. Available
attachments include EDS and WDS, enabling element analysis.
SEM：Scanning Electron Microscope

Offers structural analysis at atomic resolution, element analysis with EDS, and
   #     $$"% '       * +
directly detect Li with EELS
Nano scale TEM：Transmission Electron Microscope
EDS：Energy dispersive X-ray spectrometer  EELS：Electron Energy Loss spectrometer  WDS：Wavelength Dispersive X-ray spectrometer

：Function to perform analysis while etching the surface with Ar ion

Features of instruments to support the development of LI ion batteries 2

Element analysis function

Excitation Main detected Sample Resolution
Instrument Environment Analysis Detectable Energy Detection*3
source signals formats guideline concentration
depth element range resolution limit
Vacuum Fluorescent Bulk 1 to 12 mmΦ   About 150 eV Several ppm
XRF Normal atmosphere X-ray X-ray Fluids (analysis area)
1 mm*3 Na to U (Mn Kα) or more

30 μm to a few mm About 0.1%

XPS Vacuum X-ray Photoelectron Bulk (analysis area)
6 nm Li to U About 0.1 eV or more

Secondary electron           Tens of 10 ppm

EPMA Vacuum Electron Backscattered electron Bulk 0.1 to 1 μm*1 1 μm Be to U*2 About 10 eV
beam or more
Characteristic X-ray      
Electron Auger electron 3 nm (Secondary electron) About 0.1 %
AES Vacuum Bulk 6 nm Li to U About 0.1 eV
beam Secondary electron 8 nm (Auger electron) or more

Secondary electron       E

D  B to U About 130 eV About 0.1 % or more
SEM Vacuum Electron Backscattered electron Bulk 1.2 nm or more*1 1 μm
S

beam W
Characteristic X-ray D
S
 B to U About 10 eV Tens of 10 ppm or more
E

Electron Transmission electron       100 nm

D
S
 B to U About 130 eV About 0.1 % or more
TEM Vacuum  0.1 nm or more*1   1.0 eV(Schottky)*4
beam Characteristic X-ray (sample thickness) E
E
L H to U About 0.1 % or more
S 0.50 eV(Cold-FEG)*4

*1 Depend on the system *2 When the optional analyzing crystal for Be is installed *3 Differs depending on the specimen and conditions *4：Varies according to the conditions of use
For details, refer to the catalogs and data sheets for each instrument

3 LIBnote
 1. Morphology Observation & Surface Analysis Instruments

1-2 Energy Dispersive X-ray Fluorescence Spectrometer (XRF)

 03#    #4 #   
 #   03#   03# 5 # 
for applications like assessing grades of steel, controlling product quality, and RoHS compliance (Cd, Pb, Hg,
+
6*     # 
 #  
preparation until a result is obtained.

Excellent for element analysis of trace metals!

Features
・Analysis elements: Na to U
・Analysis region: 1 to 12 mmφ
・Specimen form: solid, powder, liquid
・Non-destructive analysis
・Detection lower limit: from several ppm

Element Analyzer

Analysis
example Positive electrode material analysis (tablet of a powder sample)

Tablets are formed of a powder material that is used for lithium ion batteries, and 30 second measurements are made,
providing results that allow quantitative analysis of the element composition. The results shown here indicate that the
specimen is composed of the expected mixture of Mn : CO : Ni in a 1 : 1 : 1 ratio.

[ Measurement conditions ]
Tube voltage : 50 kV
Collimator : 1.0 mmφ
Atmosphere : Air
Li Mn Co Ni Ox Measurement time : 30 s
X-ray intensity（CPS）

Component Mass % Atomic %

Mn 16.1 7.3

Co 16.9 7.1

Ni 16.4 7.0

Balance 50.6 78.6

   
Mn : Co : Ni = 1 : 1 : 1
X-ray energy（keV）

LIBnote 4
1. Morphology Observation & Surface Analysis Instruments

1-3 X-ray Photoelectron Spectrometer (XPS)

%           #   03#   

 0!%     
of being able to analyze surface-sensitive solids with high energy resolution. As a result, for LIB analyses, it
is possible to detect Li, a key component, and to analyze the chemical bonding state. Furthermore, depth
 #  #  
      

Direct detection of Li !
Features
・Analysis elements: Li to U
・Surface analysis instrument (detection depth of about 6 nm)
・Chemical bonding state analysis
・Detectable elements from Li to U
・Detection lower limit of about 0.1 %
JPS-9200 ・%  

Analysis
example Photoelectron image, Analysis of chemical bonding state

Li C ・       

The stage scanning method makes it possible to
acquire wide images of up to 50 mm x 18 mm.
Performing photoelectron imaging is useful for
identifying locations with different wettability due to
differences in the chemical bonding state or sample
contamination that cannot be determined from optical
information.
2mm

・
         
Since peak position differences occure due to variations in the chemical bonding state, it is possible to identify the
chemical bonding state of the Li by interpreting the peak positions.

 
Li2CO3
Li2O

Li3PO4 Li
Chemical bonding state Li1s

Li 52.6 eV

Li2O 53.5 eV
Standard
sample
Li2CO3 54.6 eV

Li3PO4 55.5 eV

Metallic lithium

5 LIBnote
 1. Morphology Observation & Surface Analysis Instruments

Analysis
example 
    

・! 
     "  
The image on the left is a powder of the raw material for a lithium-ion battery positive electrode that has been formed
             
surface, as shown in the graph on the right.

Li

Co
Mn
Ni

Analysis region：1 mmφ

・#   "   $ 

The graph below shows the qualitative analysis results for the negative electrode material. Li is detected. There is also Co
detected, which was not present in the negative electrode originally.
F
Co Co

O
C
Li

Comparing the spectrum of the Co in the negative electrode material (below left) with the standard sample spectra of
simple Co and Co oxides (below right) clearly shows that the Co in the negative electrode material exists in a metallic
state. It can be inferred that the Co in the positive electrode has ionized, migrated to the negative electrode, and
precipitated as metallic Co.

Measured data Co oxides standard spectrum

Co
CoO
Co3O4

LIBnote 6
1. Morphology Observation & Surface Analysis Instruments

1-4 Electron Probe Micro Analyzer (EPMA)

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capable of elemental analysis of micro areas with a high energy resolution. In addition, the SEM functionality
 
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secondary electron images and backscattered electron images.

Features
・ G    'G%*
KQ
・ Analysis elements: (Be) B to U
・ Analysis region: several μm to several cm
・ Analysis depth: up to about 1 μm
・ Detection lower limit: several 10 ppm

JXA-8530F

Comparison of WDS and EDS

WDS
( Wavelength dispersive X-ray spectrometer )

Incident
X-ray intensity (a.u.)

electron beam Analyzing crystal

Rowland circle

Sample
Detector

X-ray energy (keV)

WDS principles WDS-EDS spectra comparison

EDS (Energy dispersive X-ray spectrometer The detection principles and structures for WDS
!" #$  !"
Au coating Au coating
(lower left), which simultaneously detects all the
P layer N layer characteristic X-rays that are generated, WDS
only detects the characteristic X-ray of the target
Characteristic X-ray Electron
detection element.
Hole measurement system
  ' 
of the EDS and WDS analyses of SI oxides and Ta
Intrinsic region
-1000V +  ;# "<
overlapped in the EDS spectrum, but are separated
EDS principles
in the WDS spectrum, demonstrating the high
energy resolution attainable with WDS.

7 LIBnote
 1. Morphology Observation & Surface Analysis Instruments

Analysis
example Qualitative analysis of positive electrode materials, Wide region analysis

The spectra shown below on the right are the results of qualitative analysis for Co and F contained in a positive electrode
material after a charge/discharge cycle. The EDS result has a low energy resolution and a high background level, and
the F-Kα># ? <     !" ?;α line effect, and the
F-Kα line can be detected.

X-ray intensity (a.u.)

■ Positive electrode materials ■ Separator ■ Negative electrode materials

Positive electrode materials： LiCoO2, LiMn2O4, LiFePO4, etc. X-ray energy (keV)
Negative electrode materials： C, Si, SnO2, etc.
Electrolyte： LiPF6, LiClO4, etc.

The images on the right show an example F C

of element mapping with WDS for a cross
section of Li-ion battery positive electrode
material through repeated charge/discharge
cycles. The signal intensity of the F and C
that have migrated from the collector (Al) in
the center portion increases.
The profile in the element mapping is
obtained by averaging the signal intensity in
the longitudinal direction. What should have
 
originally been a uniform distribution of the Composition image
Co
elements is now shown to be biased, which
is considered to be one of the factors in the
deterioration of battery performance.
A feature of EPMA is the ability to confirm
minute changes in the element distribution.
The analysis area is 180 μm × 180 μm.

 

LIBnote 8
1. Morphology Observation & Surface Analysis Instruments

1-5 Auger Electron Spectrometer (AES)

V   #

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   #  #  " Z V   
     
     " 
single particle of positive electrode material can be obtained.

Li can be detected directly !

Features
・ High spatial resolution of Auger analysis: 8 nm
・ Variable energy resolution: From 0.05 % to 0.6 %
・ Analysis range: Up to 95 mmΦ with the large stage
・ Insulating materials can be analyzed using the
neutralizing gun and sample tilting method
・ Wide range of options (BEI, EBSD etc.)
・  
JAMP-9510F

Li sensitivity

Because the JAMP-9510F uses a concentric hemispherical electrostatic analyzer, it is possible to obtain peaks even in
'# '   ##  
right below shows the results of measurements with the JAMP-9510F for standard samples of Li, Li2O, and Li2CO3. This
clearly illustrates the changes in the peak position and shape for each of the different chemical bonding states.

・#%  &     "   

Since the Auger Electron Spectrometer uses an electron beam as the excitation source, it is possible to acquire element
maps for micro areas corresponding to the secondary electron images and backscattered electron images.

SEI Li

9 LIBnote
 1. Morphology Observation & Surface Analysis Instruments

       

 

・   " 
The Li sensitivity with Auger Electron Spectrometry (AES) is higher than that of X-ray photoelectron spectrometry (XPS).
Assuming that the C sensitivity is about the same for AES and XPS, using the C peak as the base line, and comparing the
peak intensities for metallic Li, the peaks from AES are 70 times higher than those from XPS.

Comparison of ionization cross section (Al-kα) for Li and C with XPS Comparison of peak intensities of Li and C measured with the same
conditions using AES
X-ray：Al Kα (1487 eV)

 ) $*
H 1 0.0002
He 2 0.0082
Li 3 0.0568
Be 4 0.1947
B 5 0.486
C 6 1.000
N 7 1.80
O 8 2.93
F 9 4.43
Ne 10 6.30

Ref : J.Electron Spec,

Relat.Phenom,8,129(1976)
ILi / IC ≒ 1/18 ILi / IC ≒ 4
( Li sensitivity is about1/18 that of C ) ( Li sensitivity is about4 times greater than C )

・'   & (%

 "%   
The quantitative analysis results from various methods using positive electrode material particles containing Li (NMC
particles) as the specimen are shown in the table below. Even for analysis from the surface, and analysis of a CP cross-
               #@   Y"
shows that there is a difference of a few percent, and that comparable quantitative accuracy is obtained.

Surface analysis Standardized atomic concentrations, excluding carbon

Li O Mn Co Ni
AES (average of 50 μmΦ ) 19.6 55.0 8.5 8.5 8.4
XPS (average of 3 mmΦ ) 14.8 60.5 7.4 8.1 9.2

Bulk analysis Standardized atomic concentrations, excluding carbon

Li O Mn Co Ni
AES 5.1 53.8 13.6 14.4 13.1
SEM-EDS - 64.8 11.0 12.1 12.1
NMC particles used for the actual test XRF - 59.8 13.1 13.7 13.4
(Mn : Co : Ni = 1:1:1)

LIBnote 10
1. Morphology Observation & Surface Analysis Instruments

1-6 Scanning Electron Microscope (SEM)

   '%$K*        
SEM is especially useful for tracking minute changes in the structure of electrode materials as the charge/
discharge is repeated. SEM system performance, such as spatial and lateral resolution, varies significantly
depending on the electron gun and lens type. Here, we introduce the basic technology and application of the
JSM-7800F, a high-end model SEM. The JSM-7800F utilizes a Super Hybrid Lens (SHL) combining superposed
     3    # 3 
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electron gun incorporates a wealth of the latest technologies, including a Gentle Beam mode for high-resolution
image acquisition with a bias voltage applied to the specimen, and also various types of detectors.

Features
・ In-lens Schottky electron gun
・ Super Hybrid Lens (SHL) and TTL detector
・ Specimen bias (Gentle Beam (GB)) function
・ Wide range of options (EDS, WDS, EBSD, etc.)

JSM-7800F

Arrangement of detectors

・+ %  

''          Z"\;^_`   
SHL and these detectors makes it possible to selectively detect the various kinds of information that are generated from
the specimen.
JSM-7800F structural diagram *Option

,,  

Detection over a wide range is possible, from low energy secondary Schottky electron gun
electrons to high energy backscattered electrons. Controlling the
voltage that is applied to the electrode grid of the lower portion of the
UED enables selection of the signals over a range from secondary
electrons to backscattered electrons. Condenser lens

,-,-    ACL

(Aperture-angle control lens)
Detects the secondary electrons that have been eliminated with the grid
voltage of the UED lower section. It is possible to simultaneously obtain
USD (Upper Secondary Electron Detector)
2 types of information; a backscattered electron image with the UED, # 
and a secondary electron images with the USD. USD*
(Upper Secondary Electron Detector)
 &  
The E-T detectors used for a wide range of SEM allow the use of a long
working distance, unlike the UED and USD. Since a large number of
backscattered electrons that have been generated at low angles are SHL objective lens
    # "\ >   
topology of the specimen.

./.   LED

A detector mainly used to acquire backscattered electron images using (Lower Electron Detector)
BED*
a semiconductor detector. (Backscattered electron detector)
Specimen bias voltage (GB)
Specimen

11 LIBnote
 1. Morphology Observation & Surface Analysis Instruments

Principles of Gentle Beam mode (GB)

In the Gentle Beam (GB) mode when the electron probe with a high accelerating voltage passes through the objective
lens, the landing energy of the electron probe on the specimen is reduced by a bias voltage that is applied to the
specimen. This is an effective method for obtaining high resolution with extremely low accelerating voltages.

Conventional Gentle Beam

(Specimen with no bias voltage) (Bias voltage applied to the Specimen)

Accelerating voltage
2 kV
Accelerating voltage
Electron probe
0.5 kV

Objective lens

Landing energy:0.5 kV
Bias voltage
Specimen
1.5 kV

( For a bias voltage of 1.5 kV )

A comparison of the resolution with a low accelerating voltage for a conventional sample without any bias voltage (left)
and for the GB mode (right) is shown. The specimen is gold particles on carbon. For the specimen with no bias voltage (left),
the image shows the gold particles observed with an accelerating voltage of 500 V. In the GB mode shown on the right, it
            #

Accelerating voltage : 500 V

( No GB mode, no ) Landing voltage : 500 V ( Using GB mode )

20nm 20nm

Specimen : Gold particles on carbon

LIBnote 12
1. Morphology Observation & Surface Analysis Instruments

1-6 Scanning Electron Microscope (SEM)

Observation
example Observation
電池材料の観察例 of battery materials

SEM is highly suitable for observing the morphology of various types of battery materials. Several examples are
shown below.

SEI Landing voltage: 0.7 kV（in GB mode） SEI Landing voltage: 1 kV（in GB mode）

Separator ( polyethylene ) Conductive additive ( Acetylene black )

SEI Landing voltage: 1 kV（in GB mode ） SEI Landing voltage: 1 kV（in GB mode）

Cathode active material：LiCoO2

SEI Landing voltage: 1 kV（in GB mode） SEI Landing voltage: 1 kV（in GB mode）

Cathode active material：LiMn2O4 ( Spinel )

13 LIBnote
 1. Morphology Observation & Surface Analysis Instruments

Observation
example Imaging with various detectors and EDS analysis at ultra-low accelerating voltage
電池材料の観察例

・     "  

(Simultaneous acquisition of surface topography and composition information using a low accelerating voltage)

With the JSM-7800F, it is possible to acquire a variety of information about the surface of a specimen by selectively
using the various detectors. The two photos below show an example of the simultaneous observation with the USD (left)
and UED (right) of a lithium-ion battery positive electrode. With the USD, information about the surface roughness and
topology is obtained, while composition information for the specimen is acquired with the UED.

USD: surface information (mainly topography) UED: Composition information

CK

・- &  &

 " 
The photo on the right shows an
example of EDS analysis of the
surface of a positive electrode
material for Li ion batteries at
a low accelerating voltage of  
1 kV. It is possible to observe
OK Co L
the carbon distribution in an
extremely thin film layer on the
uppermost surface, which cannot
b e d e t e c t e d u n d e r o rd i n a r y
acquisition conditions.
Even at an accelerating voltage of
1 kV, the JSM-7800F can deliver
an sufficient probe current (15
nA) for EDS analysis. This is quite
 
useful for bot image observation
and EDS analysis. Sample：Li-ion battery cathode material ( Vacc: 1kV, Probe current: 15 nA ）

LIBnote 14
1. Morphology Observation & Surface Analysis Instruments

1-6 Scanning Electron Microscope (SEM)

Transfer Vessel

The transfer vessel is a device for transferring a specimen that has been prepared in an inert gas environment ( such as
in a glove box ) to the specimen exchange chamber without exposing the specimen to the atmosphere, so that it can be
observed using the FE-SEM. This is especially useful for handling specimens that alter rapidly when exposed to air.

Air-tight cover
detachment knob

Glove box

Transfer vessel

First, the vessel is transferred from

the glove box to the SEM specimen
Specimen-exchange rod
e x c h a n g e c h a m b e r. W h e n t h e
evacuation of the specimen exchange
chamber is started, the vacuum valve
that is embedded in the air-tight cover Air-tight cover
opens, and the inert gas contained
within the vessel is evacuated. Specimen holder

When the pressures inside the vessel

and outside the vessel are both at
atmospheric pressure, this valve is Fig.1 Cross section view of the specimen exchange chamber with the transfer vessel mounted
designed to maintain the air-tight seal
by the force of a spring. When the
pressure outside the vessel is reduced,
the force of the pressure inside the Fig.2 Air tight cover closed Fig.3 Air tight cover open
vessel pushes the valve open.

As shown in Fig. 1, there is an “air-tight

cover detachment knob” on the top
of the specimen exchange chamber.
When evacuation is completed, the
threaded rod on the end of this knob
is screwed into the tap in the air-tight
cover and used to pull it up. Fig. 2 and
3 show this knob being used.
Specimen size：Φ25.4 mm X 20 mm h

15 LIBnote
 1. Morphology Observation & Surface Analysis Instruments

Effect of Preventing Air Exposure using the Transfer Vessel

For the evaluation of lithium ion battery materials that react with air, it is indispensable to have techniques to prevent the
exposure of the specimen to the atmosphere. Data demonstrating the effect of the transfer vessel is shown below.
In the example here, specimens of a lithium-ion battery positive electrode material containing LiCoO2 
without being exposed to the atmosphere, and then the same location is observed after exposing the specimen to air.
A comparison is made between a specimen that has never been charged/ discharged and a specimen that has been
subjected to a charge/discharge cycle 5 times. There are no deposits observed on the unexposed specimens, but when
the same locations are observed after exposure to air, the deposits are observed. This demonstrates the effect of the
transfer vessel for preventing specimen exposure to the air.

・."
Deposits that are not observed on the LiCoO2 particles that have not been exposed to the atmosphere are seen here and
there after exposure to the air.

Not exposed to air After exposure to air

・.  : 

" #   #  Y +   
of the LiCoO2 particles.
Not exposed to air After exposure to air

LIBnote 16
1. Morphology Observation & Surface Analysis Instruments

1-7 Transmission Electron Microscope (TEM)

The transmission electron microscope (TEM) is essential to capture the charge-and-discharge induced changes
 # $K   3 6
in addition to morphological observation, TEM provides elemental analysis by EDS and EELS. In particular,
EELS enables chemical-state analysis and direct analysis of Li.
Further, instruments with a STEM function to acquire transmission images by scanning the surface with a
 
 #
   6Z' *
V6Z' 
*
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#    V6Z
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ARM200F equipped with a spherical aberration corrector. The table below shows the main performance of
the JEM-ARM200F.

Schottky type Cold anode type

;   , / ;  </;

Guaranteed resolution: 82 pm 100 pm
STEM-HAADF images 78 pm (with CFEG) 100 pm (with CFEG)
TEM image (point-to-point) 110 pm 120 pm
With aberration corrector 100 pm (with CFEG) 120 pm (with CFEG)
Solid angle (EDS) 0.8 sr 0.98 sr
（*With100 mm2SDD mounted）

JEM-ARM200F external appearance

Observation
example Li column observation using ABF
電池材料の観察例

A BF B HAADF C ABF For an aberration-corrected STEM system, the angle

(Bright Field) (High Angle Annular Dark Field) (Annular Bright Field)
of the incident electron beam onto the specimen
Incident
angle α
is 20 to 25 mrad. The STEM detector detects the
electrons that pass through the specimen and are
scattered.

As shown in Figure A, a BF image can be obtained

by detecting electrons at angles lower than the
incidence angle. Figure B illustrates acquisition of an
HAADF image by detecting electrons scattered at
Detection larger angles than the incidence angle, 50 mrad or
angleβ more. The ABF image is obtained using a detector
with a beam stopper to detect electrons scattered
Detection angle Annular detector Annular detector
β＜α βin ＞ 50mrad βin to 0.5xα,βout to α at about 10 to 25 mrad.

STEM-HAADF STEM-ABF
'; "\ 
of LiMn 2O4 positive electrode materials for a
lithium-ion battery obtained with the JEM-
ARM200F. In the HAADF image shown on
the left, only Mn can been seen, while in the
ABF image on the right it is possible to directly
observe the column sites of the light elements
such as lithium and oxygen. This allows
evaluation of the lithium-ion battery material at
the atomic level.
Specimen: LiMn2o4 ○ Li ○ O ○ Mn

17 LIBnote
 1. Morphology Observation & Surface Analysis Instruments

1-8 Specimen Preparation Equipment:

Air Isolation & Cooling Cross Section Polisher

We introduce a cross section polisher IB-19510 with the added functionality to cool the specimen and prevent
                        %$K    3
melting point metals, like solder, which are easily deformed by heat, materials with a low glass-transition
temperature, like resins, and battery materials that react with air.

Features
・ Special transfer vessel can be used to transfer
 
+!%$K
   
・ Cooling the specimen during ion milling
reduces thermal damage
・ Thermal damage can also be reduced by using
intermittent milling
Air Isolation + Cooling Cross Section Polisher

Transfer vessel

Observation
example Metallic lithium processing and observation
電池材料の観察例

・;  &  %! %  

The photo on the left below is a SEM image of a cross section of metallic lithium processed without being exposed to the
atmosphere. The image on the right shows the SEM image of the same location on the same sample after it was exposed
to air for 2 minutes. The reaction products caused by the exposure to air are clearly seen covering the entire sample. This
also demonstrates the value of transferring the specimens without exposure to air.

Accelerating voltage: 5kV Accelerating voltage: 5kV

Processed without exposure to the air Appearance after exposure to the air for 2 minutes

LIBnote 18
1. Morphology Observation & Surface Analysis Instruments

1-8 Specimen Preparation Equipment: FIB (Focused Ion Beam)

The FIB system is an instrument with an electrostatic lens system to focus a Ga ion beam and scan the beam across a
 _4` 
  #      
 
  '%5K*   # #  `
 
   
 # x#
 K3
Beam system allows immediate SEM observation and EDS analysis of specimen surfaces that have been processed
 Z56   #    3
$K 
{ #  
{ #Z56 |%$K 
Available attachments include a specimen cooling system and a transfer vessel system.

Features
・ For SEM, a Schottky electron gun (JIB-4601F) and the
LaB6 (JIB-4501F) are available
・ Supporting not only 3D analysis of the morphology,
but also EBSD (analysis of crystal orientation) and EDS
(element analysis)
JIB-4601F

Observation
example Solder電池材料の観察例
Cold processing, 3D analysis

An example of using the cooling stage to process lead solder is shown below. At the upper left is an example of lead
   ' ~€    ‚ƒ#  #
image that was reconstructed using 3D analysis shows that these voids are distributed quite uniformly. In comparison,
    ' ;€    ‚ !   
checked, the contrast of voids cannot be recognized. This indicates that the voids at the interface found in lead solder
that was processed at room temperature are the result of thermal damage during the processing.

SIM image 3D reconstruction

}   ~€ #'' ‚

SIM image 3D reconstruction

}   ;€ ‚

19 LIBnote
 2. Chemical Analysis Instruments

2-1 Gas Chromatograph - Mass Spectrometer (GC-MS)

GC-MS is a combination of a gas chromatograph (GC) and a mass spectrometer (MS).

}   # # `+
into the MS for mass analysis.
5   # #4 #  
qualitative and quantitative analysis.

Features
・ Supports analysis of volatile and semi-volatile
compounds via GC and solids via direct insertion
probe (DIP)
・Can use a variety of ionization methods (EI, CI, PI)
・ V # 
techniques.
- Thermal analysis： Pyrolyzer and TG/DTA
- Volatile components in liquids and solids:
JMS-Q1500GC head space autosampler
- Odor analysis： GC-Olfactometry-MS

Analysis
example Evolved gas in a over-discharged Lithium ion battery cell

The following example shows a measurement made using a gas chromatograph quadrupole mass spectrometer to
identify the components of the evolved gas in a over-discharged lithium ion battery cell. Many components have been
detected, including ethylene carbonate (EC, Peak No.20) and diethyl carbonate (DEC, Peak No.19), widely used as
 #  ''#>   

TIC chromatogram of evolved gas from over-discharged LIB cell

;   ;   ; 

'   '   '  
No. No. No.

1 Air ( N2, O2 ‚ _ ~;> „  #  

2 Methane 9 Methyl formate 16 Hexane

3 Carbon dioxide ( CO2 ‚ „ !>  # „^  #  # 

4 Fluoroethane 11 Butane 18 Ethyl propionate

  >  # „~  #   „† ! # !?‚

6 Propane 13 Ethyl ether 20 Ethylene carbonate ( EC )

7 Cyclopropane 14 Pentane

LIBnote 20
2. Chemical Analysis Instruments

2-2
NMR is a technique that focuses on specific
Nuclear Magnetic Resonance Spectrometer (NMR)

atoms in a material and analyzes molecular

structures and states of the peripheral regions
for relevant atomic nuclei. For LIB analysis in
particular, it is one of the few valuable methods
to directly observe and measure the Li nuclei,
enabling the acquisition of various information,
such as the quantit y, chemical state and
mobility of the Li in a sample, regardless of the
location, or whether it is a cathode, anode or
electrolyte material.

Nuclear Magnetic Resonance spectrometer / JNM-ECZ500R

Analysis
example Positive electrode material analysis with ultra high-speed MAS measurement

Solid state NMR is a powerful tool for analysis of the physical properties and structure of solid materials because it
allows us to observe the chemical state of different nuclei (ions) as different signals. In solid state NMR, in order to obtain
;      '        +    
magic angle (54.74°) and rotated at high speed (Magic Angle Spinning, hereafter abbreviated to MAS). However, for LIB
  #""‡‚     >  
' < # ` <    ""‡  '#   
peaks by using a 1 mm or 0.75 mm MAS probe and spinning at extremely high speeds (up to 110 kHz), which allows the
<  7Li spectrum for positive electrode material for a manganese dioxide lithium battery below
clearly shows that there are 2 kinds of Li in the vicinity of Mn around 800 ppm, and 1 type of Li distant from Mn at 0 ppm.

Li in the vicinity of Mn Li at a distance from Mn Magic Angle Spining

z
High Rotation Frequency

B0
54.74r

x y

Ultra high speed

MAS sample tubes

4 mm 3.2 mm 2.5 mm 1 mm 0.75 mm O.D.

7
Li spectra of positive electrode material for manganese dioxide lithium battery

21 LIBnote
 2. Chemical Analysis Instruments

2-2 Nuclear Magnetic Resonance Spectrometer (NMR)

!  "  
  #!$
NMR system is an instrument for observing the absorption Sample

and emission processes of the electromagnetic waves that

correspond to the energy differences arising from nuclear
  #' 
frequency of the nuclear spin) depends on the intensity of the
 # '#
Fast precession = High resonance frequency


*  
 #           



possible to obtain the position information for the atoms in a

Field intensity

Œ

 3  ' 
and ions). Since there is a strong correlation between the
self-diffusion coefficient of ions and the ion conductivity in
an electrolyte, this can be used as a method for evaluating
# Z 
      Slow Precession = Low resonance frequency
cations and anions can be obtained separately, it is possible to
obtain information about the ion conduction mechanisms.       

Analysis
example Analysis of 7   
    

+ ;   #    # 
magnetic field gradient is varied, the attenuation of the signal intensity obtained from the Li ion is described by the
equation below.
Y##    # ' ‚ ; !‘’“„-11 m2/s)
of Li ion in the electrolyte can be obtained as in indicator of the ionic conductivity.

>G$>0? !  @ F  H・G・I  2D  J F I $ K  Q

I : Signal intensity γ : Nuclear gyromagnetic ratio * For the measurement of electrolytes with small
Œ\     δ : \  ' 
self-diffusion coefficients, or nuclei with a small
‰!   ! ";
gyromagnetic ratio, a system that can apply a large
 

Data courtesy of：

Asahi Kasei Corporation
 Analysis & Simulation Center
Y. Hashimoto 0
Y. Horiike
H. Shobukawa

–1
（ I / I₀ ）

gth
re n
en t st –2
adi
ln

gr
field
tic
gne
Ma
–3
D = 5.6×10–11 (m2/s)

0.0 2.0×1010 4.0×1010 6.0×1010

γ G δ （‰Šδ/3）
2 2 2

LIBnote 22
3. Fabrication Systems

3-1 Roll to Roll Electron Beam Deposition Systems

This instrument can provide thin films using electron beam evaporation technique while the substrate of a
      #

 
     V 
  3 

Features
・High-frequency sweep system can control the electron beam irradiation and heating within a
 
・   3     Y  
・Deposition rates an order of magnitude higher than those from sputtering or CVD methods.
・The use of a dedicated controller enables co-deposition from 2 or 3 sources.

Roll section

Z”>   # 

beam source（16 kW） ?     

Roll to Roll electron beam deposition system for R&D

（Made by M-TECHNOLOGIES Corp.）

+ ;   +    

JEOL High powerr type

typ
pe JEOL High power type
electron beam source electron beam source
（30 kW, 100 kW, 300 kW） （100 kW）

＊ ! '  „ '      # ‚
＊Y  ' #  '  ' '   „ 

23 LIBnote
 3. Fabrication Systems

3-2 RF Induction Thermal Plasma System

for Nano Particle Synthesis
The plasma is generated using high frequency power and an inert gas like Ar to create a plasma state with an
ultrahigh temperature of nearly 10,000 degrees, called RF induction thermal plasma.
Raw materials (fine powder / liquid / gas) can be introduced into this RF induction thermal plasma and
instantaneously evaporated or melted to induce reactions or decomposition.
      Y 
4
powders for lithium-ion battery electrodes.

Features
・Since there is no electrode, it is possible to melt
or evaporate the raw material as is.
・T h e u l t r a - h i g h t e m p e r a t u r e e n a b l e s
instantaneous flash evaporation, even for
heterogeneous materials with different boiling
points.
・A variety of gases can be used to generate the
plasma, making it possible to induce reforming
and chemical reactions such as carbonization,

 
     3

・Raw materials are rapidly cooled after passing
through the ultra-high temperature region of the
6 kW experiment system
plasma (nucleation and condensation from the
Ar plasma Ar + H2 plasma rapid cooling process).

Application
example Silicon nanoparticles for negative electrode materials

Fig.1
R#"T%U
・Possible to use metallurgy silicon ( ∼ 99.5 %)
・High throughput ( ∼ 360 g/h)
・Higher-order composite structure
(higher-order nano composites formed by a
few 10-nm primary particles)
・Possible to synthesize composite particles
(core shell, support, etc.)

Fig.2 Fig.3 Fig.4

Charge-and-discharge energy
density variations depending on
CH4 doped concentrations

Core shell nanoparticle composed of silicon

core and carbon shell

Data courtesy: Kambara Laboratory, Department of Materials Engineering, The University of Tokyo
Fig.1, 4 : Reproduced with permission from J. Appl. Phys. 115, 143302 (2014). Copyright 2014, AIP Publishing LLC.
Fig.2, 3 : Sci. Technol. Adv. Mater. 15 (2014) 025006

LIBnote 24
 LIBnote
Conclusion
L
LIB
Lithium Ion Battery

Transmission Electron Scanning Electron Auger Electron

Microscope Microscope Spectrometer

!%  &'! *'! %'*

Positive electrode Morphology observation ○ ○ ○
material
Element composition analysis ○ ○ ○

Element distribution analysis ○ ○ ○

Crystalline structure analysis ○ ○

  V ○ ○

  + #   ○ ○

Chemical state analysis ○ ○

Binder qualitative analysis

Assessment of impurities
Negative electrode Morphology observation ○ ○
material
Element composition analysis ○ ○ ○

Element distribution analysis ○ ○ ○

Carbon crystallization analysis ○

Separator Morphology observation ○ ○ ○

Element composition analysis ○ ○ ○

Chemical structure analysis

Thermo degradation mechanism

Electrolyte Component / Impurity analysis

  V      

Fabrication Gas composition analysis

atmosphere gas
Continuous monitoring

General Defect failure analysis ○ ○ ○

25 LIBnote
 JEOL Instruments Best Suited to Lithium Ion Battery Analysis Tasks
]
        ^$}"
up for the LIB analyses and evaluations. The table indicates the instruments suited to each of various tasks,
including those that were not introduced in previous sections.
For more detailed information, please refer to the catalogs, specifications and data sheets for each
instrument, or contact a JEOL representative.

Electron Probe Micro X-ray Photoelectron X-ray Fluorescence Nuclear Magnetic Electron Spin Nuclear Gas Chromatograph
Analyzer Spectrometer Spectrometer Resonance Magnetic Resonance Mass Spectrometer

'+!% .+* .$/ #!$ '*$ !*

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LIBnote 26
No.0102C678C(Bn)