Lithium ion Cell DCA

Disassembly of batteries, cleaning of electrodes, and other pre-treatment

processes are performed in the glove box, in which temperature and the
oxygen concentration are maintained at -60
o
C or below and 10 ppm or
below, respectively, in argon atmosphere. fter a battery is disassembled
in the glove box, its electrode components are put in transfer containers
for each analysis system that are tightly closed with argon gas. !ach
container is transferred to each analysis system and attached to its
loader, and then the electrode component is moved into the analysis
system.
"able 1Analyses that can be performed in the absence of air
Analysis Purpose
SEM-EDX
Determination of the crystallographic structure
and morphology of electrode components and
separators at the micrometer level
EM-EDX-EELS-
ED
Determination of the crystallographic structure!
elements! and state! and structural analysis of
positive and negative active materials of
electrodes at the nanometer level
X"D
Determination of the crystallographic structure
of positive and negative active materials of
electrodes
XPS
Analysis of the state of surface coating #SE$
film%
Determination of elements of the electrode
surface
"eflection EELS Structural analysis of the electrode surface
&$-"'PE
Structural analysis of the electrode surface
Analysis of the state of surface coating #SE$
film%
AES
Determination of elements of electrode
components in the micrometer region
(D-)ES
Determination of the elemental distribution in a
region of electrode components from the surface
to depth #including the distribution of Li%
#ntroduction
"o enhance the characteristics of lithium-ion batteries, elucidation of how
batteries deplete and structural analysis of how positive and negative
active materials, which are ma$or components of batteries, degrade are
essential. %owever, parts of each battery component are made up of very
active substances including lithium, whose states would change if they are
handled in the atmosphere. "o maintain the their states that they are in
the battery during analysis, we have created a system that allows for all
processes from disassembly of batteries to pre-treatment, transfer to
analytical e&uipment, and analysis procedure in the absence of air. "his
article presents some examples of such analysis.
1. 1. 'ystem for nalysis in (on-air tmosphere
2. ). !xamples of surface analysis
3. *. (anostructure nalysis +sing "ransmission !lectron
,icroscopy -"!,.
4. /. 'canning !lectron ,icroscopy -'!,.
*+ System for Analysis in ,on-air Atmosphere
Disassembly of batteries, cleaning of electrodes, and other pre-treatment
processes are performed in the glove box, in which temperature and the
oxygen concentration are maintained at -60
o
C or below and 10 ppm or
below, respectively, in argon atmosphere. fter a battery is disassembled
in the glove box, its electrode components are put in transfer containers
for each analysis system that are tightly closed with argon gas. !ach
container is transferred to each analysis system and attached to its
loader, and then the electrode component is moved into the analysis
system.
able *Analyses that can be performed in the absence of air
Analysis Purpose
'!,-!D0
Determination of the crystallographic structure and
morphology of electrode components and separators
at the micrometer level
"!,-!D0-!!1'-
!D
Determination of the crystallographic structure,
elements, and state, and structural analysis of
positive and negative active materials of electrodes at
the nanometer level
02D
Determination of the crystallographic structure of
positive and negative active materials of electrodes
03'
nalysis of the state of surface coating -'!# film.
Determination of elements of the electrode surface
2eflection !!1' 'tructural analysis of the electrode surface
%#-2+3!
'tructural analysis of the electrode surface
nalysis of the state of surface coating -'!# film.
!'
Determination of elements of electrode components in
the micrometer region
4D-5!'
Determination of the elemental distribution in a region
of electrode components from the surface to depth
-including the distribution of 1i.
-+ E.amples of surface analysis
)-1 0-ray 3hotoelectron 'pectroscopy -03'.
6igure 1 shows results of 03' of the negative electrode removed from a
degraded 1i-ion battery for mobile phones7batteries described in this
article were all discharged. 6or comparison, results of analysis in air are
also shown. "he positions of the 1i 1s photoelectron spectrum are different
between the analyses in the presence8absence of air, indicating that the
chemical state of 1i has changed. "his result, combined with those from
the photoelectron spectra of C 1s and 5 1s, suggest that oxide, hydroxide,
fluoride, and other complex compounds of 1i in the absence of air mostly
altered to 1i
)
C5
*
in the presence of air. s shown in this example, it is
obvious that components of the negative electrode undergo alteration in
the presence of air. "herefore, analysis in the absence of air is
indispensible to inhibit alteration.
/igure *Comparison bet0een XPS of the degraded negative
electrode of a Li-ion battery in the presence1absence of air
#Photoelectron spectra of C *s! ) *s! and Li *s%
)-) "eflection Electron Energy Loss Spectroscopy #EELS%
2eflection !!1' provides smaller changes such as oxidation and bonding
of specific elements on the specimen surface by measuring photoelectrons
that are emitted from the specimen exposed to an electron beam. 9e
have our proprietary system that has been optimally designed to reflection
!!1'.
6igure ) shows comparison of reflection !!1' of core loss spectra of Co in
1iCo5
)
used in the positive electrode for a 1i-ion battery in the presence
and absence of air. "he entire pea: of the spectrum of Co in the presence
of air is broad, suggesting that the specimen surface has reacted with
compounds such as water and C5
)
and conse&uently presents a mix of
various states. 6igure * compares spectra of the positive electrode ta:en
out of normal and depleted batteries. new pea: of Co emerged at the
higher energy side because of depletion, suggesting an increase in the
valency of Co that is consistent with a general view that a depleted
battery loses 1i and has increased Co oxide.
/igure -Comparison of reflection EELS of #core loss spectra
of% Co in LiCo)
-
used in the positive electrode for a Li-ion
battery in the presence and absence of air
'pecimen of positive electrode -from a normal battery, in
absence of air.
'pecimen of positive electrode -exposed to the air after
disassembly of a normal battery.
Co5
/igure 2Comparison of reflective EELS #core loss% spectra of
the positive electrode ta3en out of normal and depleted
batteries
'pecimen of positive electrode -from a normal battery, in
absence of air.
'pecimen of positive electrode -depleted.
Co5
2+ ,anostructure Analysis 'sing
ransmission Electron Microscopy #EM%
5bservation of positive and negative electrodes using "!, re&uires preparation
of a thin film specimen using a focused ion beam -6#;. system. 9e modified
the specimen inlet of our 6#; system and created an air-tight specimen holder
so that a series of specimen preparation processes can be performed in the
absence of air.
6igure / shows "!, images of the vicinity of the surface of positive active
material 1iCo5). !nergy dispersive 0-ray -!D0. &uantitative line analysis
indicates that the oxygen concentration of the specimen surface decreased.
'hift of the 1 shell absorption edge of Co found by !!1' indicates that the
valency of Co has decreased on the surface of the positive active material.
/igure 4EM images of the positive active material of a Li-ion battery
6igure < shows "!, images of particles of 1iCo5
)
, the positive active material
ta:en out of a depleted battery. nalysis of electron diffraction images
indicates that 1iCo5
)
hexagonal. Depletion caused generation of voids along
'ide C of the hexagonal crystal. n electron diffraction image of the vicinity of
the void surface shows strea:s along 'ide C, indicating the presence of lattice
defects.
"!, images of the negative active material of the depleted battery in 6igure 6
show that voids were generated in graphite of the negative electrode. !D0
mapping indicates that there is a layer of reaction products. Combined with
!D0, !!1' determined in what state 1i existed, namely 1i6.
/igure 5EM images of the positive active material of a depleted Li-ion
battery
/igure 6EM images of the negative active material of a depleted Li-ion
battery
4+ Scanning Electron Microscopy #SEM%
6igure = shows '!, images of the surface of the negative electrode of a
depleted battery. Deposits are present on the electrode surface. !D0 indicates
that the electrode surface got crac:ed and oxidi>ed when it was exposed to the
air.
'!, images of a cross section of the positive electrode, which was treated
using a cross-section polisher while it was exposed to the air, are shown in
6igure ?. '!, enables analysis of the morphology and distribution of positive
active materials and conductive additives, as well as investigation of clogging
and deformation of the separator.
/igure 7SEM images of the surface of the negative electrode of a
depleted Li-ion battery
/igure 8SEM images of a cross section of the positive electrode of a Li-
ion battery
Conclusion
#n addition to the examples described here, our systems for uger
electron spectroscopy -!'. and glow discharge spectroscopy -4D-5!'.
are compatible with analysis in the absence of air. 6urther we are
developing a techni&ue that combines cross-section fabrication by
diagonal cutting with surface analysis. 9e at @obelco 2esearch #nstitute
hope that our uni&ue analysis techni&ues in the absence of air will help
analy>e depleted 1i-ion batteries and develop high-function batteries. 9e
are also planning to apply our techni&ues to analysis of surface-active
materials such as organic electroluminescent devices and catalysts.