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NMR Studies of Cathode Materials for Lithium-Ion Rechargeable Batteries

NMR Studies of Cathode Materials for Lithium-Ion Rechargeable Batteries

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NMR Studies of Cathode Materials for Lithium-Ion Rechargeable Batteries
Clare P. Grey* and Nicolas Dupre´
Department of Chemistry, State University of New York at Stony Brook, Stony Brook, New York 11794-3400 Received February 24, 2004 
Contents 
1. Introduction 44932. NMR Background 44942.1. Lithium NMR Spectra of Cathode Materials:Introduction44942.2. NMR Spectra of Paramagnetic Materials 44942.2.1. Fermi-Contact Interaction 44962.2.2. Dipolar Coupling 44963. Extracting Chemical Information from the Spectraof Paramagnetic Materials44973.1. Fermi-Contact Interaction 44973.2. Dipolar Interaction 45004. Applications of NMR Spectroscopy to the Studyof Cathode Materials45014.1. Spinels 45014.1.1. Cation-Doped Spinels 45024.2. Cr
3
+
- and Ni
2
+
-Substituted Layered LithiumManganates45044.3. LiCoO
2
and Related Materials 45054.4. Lithium Phosphates 45064.5. Vanadates 45074.5.1.
51
V NMR 45074.5.2. NMR Studies of Vanadium Oxides 45074.5.3. Vanadium Phosphates 45095. Conclusions 45106. Acknowledgments 45107. References 4510
1. Introduction 
Lithiumintercalation or insertion materials havebeen widely investigated in the search for newelectrodematerialsfor usein high-voltagerecharge-able batteries.
1
-
6
 The first commercial Li-ion re-chargeable battery contains the layered materialsLiCoO
2
(Figure 1) and graphite as the cathode (orpositiveelectrode)andanode(or negativeelectrode),respectively.
7
Although this battery is the currentstandardinmanyapplicationsincludingcell phonesandlaptops,itsslowchargeanddischargeratesandcost have prevented its use in applications thatrequire cheap high power and capacity, such ashybrid electric vehicles and electric vehicles. Thetoxicity of Co is also an issue. A wide variety omaterialshavebeen studied,
5,6
which includedopedLiCoO
2
phases, layered compounds based on theLiCoO
2
structure(e.g.,LiNiO
28
andLiNi
0.5
Mn
0.5
O
29,10
),
* Towhomcorrespondenceshould beaddressed. E-mail: cgrey@notes.cc.sunysb.edu.
Clare P. Grey received her B.A. (1987) and D. Phil. (1990) degrees inChemistry from the University of Oxford. At Oxford she worked withProfessors Tony Cheetham and Christopher Dobson on the applicationof solid-state NMR to problems in solid-state chemistry. She then spenta year as a postdoctoral fellow at the University of Nijmegen in TheNetherlands with Professor Wiebren Veeman, where she developed newNMR methods for measuring internuclear distances in systems withquadrupolar nuclei. She was a visiting scientist at the DuPont ExperimentalStation in Wilmington (1992
1994), where she worked with Dr. AlexanderVega on NMR theory and on the application of NMR to molecular sievesand inorganic
organic composites. She joined the faculty at SUNY StonyBrook in 1994 as Assistant Professor and was promoted to Full Professorin 2001. She uses solid-state NMR spectroscopy, in combination withother characterization techniques such as diffraction, to understand therole that local structure plays in controlling the physical properties of awide range of materials. Current studies include the investigation ofelectrode materials for lithium-ion rechargeable batteries, anionic conduc-tors, and ion-exchange and sorption properties of soil minerals, molecularsieves, and layered materials.Nicolas Dupre´ was born in Chatillon-sous-Bagneux, France, in 1975. Hereceived his Ph.D. (2001) degree from Universite´ Pierre et Marie Curie
Paris VI working under the direction of Professor Michel Quarton. Hewas appointed as a postdoctoral associate at SUNY Stony Brook in 2002,where he works with Professor Clare P. Grey. His current researchinterests are focused on the study of the behavior of materials for lithiumbatteries using solid-state NMR.
4493
Chem. Rev.
2004,
104,
4493
451210.1021/cr020734p CCC: $48.50 © 2004 American Chemical SocietyPublished on Web 09/03/2004
 
and a series of materials with two- and three-dimensional hosts for Li (e.g., Li
1
+
x
Mn
2
-
x
O
411
andLiFePO
412
).Whilelong-rangestructural informationistypicallyavailablefromdiffractionmethods,solid-stateNMR isan extremelyuseful tool for character-izinglocal structureinthesematerials,eveninhighlydisorderedsystems.Thelithiumnuclei (
7
Li and
6
Li)aretypically (but by nomeans exclusively) used asprobesbecauseitisthelithiumionsthataredirectlyinvolvedintheelectrochemical processes.TheNMRspectra are strongly influenced by the electronicstructureof thematerials,andit isoften possibletodistinguish between insulators and conductors andbetween diamagnetsandparamagnets.Themethodis quantitativeand can beused todeterminewhichspeciesareremovedonchargingthebatteryandhowthelocal structureschangeonextendedcycling.NMRisalsosensitivetodynamicsthat occur on theNMRtime scale, and one-dimensional (1D) and two-dimensional (2D)NMR have,for example,beenusedtoinvestigateLi-ionmotioninvanadates(1D)
13
andbetweentwodifferentnanosizeddomainsinanatase,Li
y
 TiO
2
.
14
 This paper describes theapproaches taken by usand other researchers over the past few years tointerpretandextractchemical informationfromthisclass of materials. We focus on ex-situ analysis of electrode materials (i.e., samples that have beenextracted from cycled batteries) since these ap-proaches allow higher resolution spectra to be ob-tained. Useof a toroid detector (toobtain theNMRsignal) has allowed workingbatteries tobestudiedin situ by spectroscopy and imagingmethods,
15
andmore recent studies have shown that NMR signalsmaybeobtainedfromplasticbagbatteries.
16
In-situmethods havenot, todate, been combined with thehigh-resolutionmethodmagicanglespinning(MAS)duetoanumber ofexperimental difficultiesthatstillneed to be surmounted and are, therefore, notdiscussedhere.Thetheoryrequiredtointerpret theNMR spectraisfirstpresented(section2);theuseothis theory to extract chemical information is thendescribed(section 3).Thisisfollowedbyillustrativerecent examples from the field. In so far as this ispossible, section 4 has been written so that it doesnot require a detailed understanding of NMRtheory (beyond that discussed in section 2.1) andshould be accessible to the non-NMR audience. Amorecomprehensivediscussionofsomeofthetechni-cal aspects associated with obtaining NMR spectraofcathodematerialscanbefoundinanearlier reviewarticle.
17
2. NMR Background 
2.1. Lithium NMR Spectra of Cathode Materials:Introduction
 Thechemical shift rangefor lithiumNMR spectraisverysmall,andit isnot alwayspossibletoresolveresonancesduetodifferentlocal environmentsintheNMR spectra of diamagneticmaterials based solelyon the chemical shift interaction. Sometimes im-proved resolution can be obtained at higher fieldstrengths, allowing chemical information to be ex-tractedfromthespectra.
18,19
Fortunately,thelithiumNMR spectra of most battery samples are stronglyaffected by a series of larger interactions whichincludequadrupolecoupling(
6
Li,
I
)
1;
7
Li,
I
)
3/2)and interactions with unpaired electrons for para-magneticsamples(hyperfineinteractions)andwiththeconductionelectronsinmetals(theKnightshift).
7
Li has the much higher natural abundance (93%)andlarger quadrupolar andgyromagneticmoments.In contrast,
6
Li isonly7%abundant,but itssmallerquadrupoleandgyromagneticmomentscanresultinhigher resolution spectra that are often easier tointerpret.Thequadrupolar interaction,whichresultsfromtheinteractionofthequadrupolar nucleuswiththe electric field gradient (EFG) at the nucleus, istypicallyverysmall for
6
Li but can result in charac-teristicbroadeninginstaticandaseriesof spinningsidebands in magicanglespinning(MAS)
7
Li NMRspectraduetothesatellite(
|
+
3/2
-
|
1/2
and
|
-
1/2
-
|
-
3/2
) transitions. This (anisotropic) interactioncontains information concerning the local environ-ments at the lithium nucleus and can be used todistinguish between ions in distorted and moresymmetricenvironments.Manybatterymaterialsareparamagneticinthedischargedor chargedstate.Forexample, thecathodematerial LiMn
2
O
4
is a mixed-valencecompoundcontainingMn
3
+
(d
4
)andMn
4
+
(d
3
)ions. Although the Co
3
+
d electrons in Li
x
CoO
2
arepairedinthefullydischargedstate,Li
x
CoO
2
containsCo
4
+
d
5
ions when charged. The NMR spectra oparamagneticmaterialsaredominatedbytheinter-actions between the nuclear and electronic spins(Figures 2 and 3). Theseinteractions may bemuchlarger than any of the other interactions and candominatethespectraofthesematerials,buttheycanalso contain valuable information concerning bothlocal crystallographicandelectronicstructure.Hence,we will now consider these interactions in somedetail.
2.2. NMR Spectra of Paramagnetic Materials
Paramagneticions with electronicspin,
S
(e.g.,
S
)
3/2for d
3
ionsMn
4
+
andCr
3
+
),areassociatedwithmagneticmoments,
µ
e
, that align in thepresenceoastaticmagneticfield,
B
0
(Figure2),typicallydefinedtobethe
z
-direction.
S
z
representsthecomponent othespinalongthisdirection.Electronspinresonance(ESR) probes the transitions between the differentspin(or Zeeman)states
|
m
s
.Oftenthelifetimeofanioninaparticular electronicstate(
 T
1e
)isveryshorton the relatively long time scale probed by NMR(frommanysecondsto10
-
8
s,dependingon thesize
Figure 1.
Structure of the cathode material LiCoO
2
,showing the alternating layers formed by edge-sharingCoO
6
octahedra and Li
+
.
4494
Chemical Reviews, 2004, Vol. 104, No. 10 Grey and Dupre´
 
oftheelectron
-
nuclear interaction).Inthissituation,theNMR spinscannotcoupleto
S
z
(i.e.,thedifferentspin states
|
m
s
) and instead couple with the timeaverageofthelocal field,
S
z
.Thisisnonzeroduetothe differences in populations of the different
|
m
s
states in a magneticfield. Thetimeaverageo
S
z
isproportional to the net magnetic moment of anensemble, which is the quantity measured in amagneticsusceptibility measurementwhere
 µ
0
isthepermeability,
g
theelectron
g
-factor,
 µ
B
theBohr magneton,
N
0
Avogadro’s number, and
 χ
M
the magnetic molar susceptibility in m
3
mol
-
1
.
20
 Thesizeoftheelectron
-
nuclear interactioncanbequantifiedviaahyperfinecouplingconstant,
A/ h
(inHz) (seebelow), and NMR experiments arefeasiblefor ions with short
T
1e
s, such that
21
As the
 T
1e
s lengthen and 1/
 T
1e
(s
-
1
) approaches thesizeoftheelectron
-
nuclear interaction,considerableNMR linebroadening can occur, and it may not bepossible to acquire high-resolution NMR spectraunder these conditions. The effect o
T
1e
on thenuclear relaxation timesisdiscussedin moredetailinref22.Largehyperfineconstantsareobserved(omany MHz) when the nuclear and electronic spinsare on the same atom. For example, a hyperfineconstant
A/ h
o
-
324MHzwasmeasuredbyelectronspin resonance (ESR) for the
S
)
1
/
251
V
4
+
vanadylionsinVO(H
2
O)
52
+
,
23
andthe
 T
1e
sfor theseionsare10
-
8
-
10
-
9
s.
22
1/
 T
1e
is similar in magnitudeto
A
/
h,
and high-resolution NMR spectra arenot observed.Whenthenuclei under observationarefurther fromthe paramagnet,
A
is much smaller (the proton
-
electron hyperfinecouplingconstants areonly 2.1
-
0.01 MHz for water molecules in thesamevanadylcomplex
24
-
26
)andtheconditionineq2ismorereadilyachieved. This is the case for lithium spins, whicharegenerally separated by twoor morebonds fromtheparamagnet. In addition, bondinginvolvingLi
+
islargelyionic,againreducingthesizeo
A
.Shorter
 T
1e
s aregenerally observed for ions with
S
>
1/2(
S
*
5/2), such as Mn
3
+
, Ni
2
+
, and Co
2
+
, and higherresolutionspectraaremorereadilyachieved.
22
Broader
6
Li/
7
Li resonances have been observed for localenvironments containing the paramagnetic
S
)
1
/
2
ion Ni
3
+
(e.g., for LiNiO
227
and LiCo
1
-
x
Ni
x
O
228
), buttheresonancesarenot sufficiently broadtopreventdetailed analysis of thelocal environments in thesecompounds.
28,29
 The nuclear spins can interact with the time-averagedmagneticmomentsviaeither through-space(dipolar) or through-bond (Fermi-contact) interac-tions. The
6
Li MAS NMR spectrum of LiMn
2
O
4
is
Figure 2.
(a, b) Effect of a static magnetic field on aparamagnet withmagneticmoment
µ
e
andelectronicspin
S
)
1
/
2
.Notethat thelowest energylevel for
S
)
1
/
2
inthemagneticfieldisthe
|
-
1/2
stateduetonegativechargeothe electron. (The magnetic moment of the electron
µ
e
associatedwiththisstateisstill alignedalongthedirectionof the static magnetic field; in many of the subsequentdrawings,wewill usearrowstorepresentdirectionsofthenet magneticmomentson theelectrons/paramagnets.)(c)ESR probes thetransitions between thespins states
|
+
1/2
|
-
1/2
. Spins in thesestates relax with a rate1/
 T
1e
,whichistypicallymuchfaster thanthesizeofmanyoftheinteractions probed by NMR (i.e.,
T
1e
is shorter than theNMR timescale). Thus, NMR experiments aregenerallyonly sensitivetothetime-averagedvalueof themagneticmoment,
µ
j
e
(
-
g
 µ
B
S
z
).
S
z
)-
B
0
 µ
0
gN
0
 µ
B
 χ
M
(1)
|
A
/
h
|
,
1/
 T
1e
(2)
Figure 3.
(a)
6
Li MAS NMR spectrum of the spinelLiMn
2
O
4
synthesized at 850 °C acquired with a spinningspeedof 10kHz at a fieldstrength of 4.7T. Thespinningsidebandsandtheisotropicshiftaremarkedwithasterisksand its shift value (520 ppm), respectively. (b) Li localenvironment in LiMn
2
O
4
showing a tetrahedrally coordi-natedLi ionandthe12nearestMnions(intheoctahedralsitesofthespinel structure).Schematicsillustrating(c)thetransfer of unpaired electron spin density from the un-paired electrons in the t
2g
d electrons (on one of the 12nearby Mn ions) via the 2p orbitals on the interveningoxygenatomtothe2sorbital onLi,whichcausesthelargeshift seen for theLiMn
2
O
4
isotropicresonanceand(d)thedipolar coupling between a
6
Li nuclear spin and netmagnetic moment duetoa nearby Mn ion. Thespinningsidebandsshown in (a)primarilyresult fromthisinterac-tion, which is not completely removed by MAS.
34
Materials for Lithium-Ion Rechargeable Batteries Chemical Reviews, 2004, Vol. 104, No. 10
4495

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