Review Article Aging Mechanisms of Electrode Materials in Lithium-Ion Batteries …downloads.hindawi.com/journals/jchem/2015/104673.pdf · 2019-07-31 · Review Article Aging Mechanisms

Review ArticleAging Mechanisms of Electrode Materials in Lithium-IonBatteries for Electric Vehicles

Cheng Lin12 Aihua Tang123 Hao Mu12 Wenwei Wang12 and Chun Wang123

1National Engineering Laboratory for Electric Vehicles School of Mechanical Engineering Beijing Institute of TechnologyBeijing 100081 China2Collaborative Innovation Center of Electric Vehicles in Beijing Beijing Institute of Technology Beijing 100081 China3School of Mechanical Engineering Sichuan University of Science amp Engineering Zigong 643000 China

Correspondence should be addressed to Aihua Tang tahme163com

Received 16 March 2015 Revised 24 May 2015 Accepted 26 May 2015

Academic Editor Noshin Omar

Copyright copy 2015 Cheng Lin et al This is an open access article distributed under the Creative Commons Attribution Licensewhich permits unrestricted use distribution and reproduction in any medium provided the original work is properly cited

Electrode material aging leads to a decrease in capacity andor a rise in resistance of the whole cell and thus can dramaticallyaffect the performance of lithium-ion batteries Furthermore the aging phenomena are extremely complicated to describe dueto the coupling of various factors In this review we give an interpretation of capacitypower fading of electrode-oriented agingmechanisms under cycling and various storage conditions for metallic oxide-based cathodes and carbon-based anodes Forthe cathode of lithium-ion batteries the mechanical stress and strain resulting from the lithium ions insertion and extractionpredominantly lead to structural disordering Another important aging mechanism is the metal dissolution from the cathode andthe subsequent deposition on the anode For the anode the main aging mechanisms are the loss of recyclable lithium ions causedby the formation and increasing growth of a solid electrolyte interphase (SEI) and the mechanical fatigue caused by the diffusion-induced stress on the carbon anode particles Additionally electrode aging largely depends on the electrochemical behaviourunder cycling and storage conditions and results from both structuralmorphological changes and side reactions aggravated bydecomposition products and protic impurities in the electrolyte

1 Introduction

Lithium-ion cells are attractive candidates for power storageowing to their high power and energy-density and low self-discharge rate At present they are widely used in portableinstruments communication equipment and so forth Dur-ing the past few years lithium-ion cells have been extensivelyapplied in automobiles such as hybrid electrical vehicles(HEVs) plug-in hybrid electric vehicles (PHEV) and bladeelectric vehicles (BEVs) [1] The goals of the Freedom CARresearch initiated by the United States Advanced BatteryCouncil (USABC) require a 15-year lifespan of batterysystems for HEVs and a 10-year lifespan for BEVs As sucha lifetime of lithium-ion cells of up to 1000 cycles at an80 depth-of-discharge (DOD) is required according to thecycling life [2]

Unfortunately the life span of a lithium-ion cell as isgenerally known is restricted by side reactions that may

be detrimental to the cellrsquos component parts which includethe active lithium binder current collectors the separatorconducting salt and solvents and these reactions result in acapacity decreaseresistance rise of the cell [3ndash5] In particu-lar the electrolytersquos components are sensitive to exposure todifferent temperatures and operating conditions [6]

Understanding the electrode aging mechanisms inlithium-ion batteries is of great importance to address thelife time and safety challenges to make precise lifetimepredictions and to improve the battery performance [7]For lithium-ion batteries the impacts of the multiple factorscontributing to electrode aging are not independent butinstead have synergistic effects on battery aging [4] Thus theexplanations for capacitypower fading and the resistance riseare not given in terms of a single factor which complicatesthe understanding of electrode material aging and manyresearchers have been making great efforts to explore theaging mechanisms for many years [8]

Hindawi Publishing CorporationJournal of ChemistryVolume 2015 Article ID 104673 11 pageshttpdxdoiorg1011552015104673

2 Journal of Chemistry

Gas evolution

Electrolytedecomposition

Surface layerformation

Migration of soluble species

Re-precipitation of new phases

Loss of contact toconductive particles

Corrosionof currentcollector

Oxidationof conductive

particles

Binderdecomposition

Microcracking

Structuraldisordering

dissolutionMetal

Figure 1 Schematic diagram of the aging mechanisms of cathode materials

This paper attempts to study and summarize the presentresearch regarding the predominant agingmechanisms of thepositive electrode (metallic oxide cathode) and the negativeelectrode (carbon anode) of lithium-ion cells applied to EVsBecause the aging mechanisms of the cathode and anode areobviously different they are discussed in separate sectionsFirst the aging mechanisms of the positive electrode materi-als are presented with explanations of the aging phenomenonoriginating from the dominant factors Later we elaborate onthe SEI evolution and some basic agingmechanisms affectingthe negative electrode Finally the influences of the electrolyteon the cathode and anode ageing itself the thermal stabilityand the hydrolysis reaction at ambient temperatures arediscussed in the corresponding sections

2 Aging Mechanisms of the Positive Electrode

Cathode materials determine significantly not only the per-formance of lithium-ion batteries but also their calendarand cycle lives Lithium-manganese-oxides (LiMn

2O4) with

spinel structures and lithium-nickel-cobalt-mixed-oxides(LiNiCoO

2) with layered structures arewidely accepted as the

choices of cathode materials for applications in high-energyand power-dense batteries according to the factors of costabundance and performance and they have been extensivelystudied in recent years [9 10]

Figure 1 from [11] is a schematic diagram showing themain aging mechanisms for cathode materials In the begin-ning aging occurs in the batteryrsquos electrolyte and the ori-gin can be electrochemical mechanical or thermal and isstrongly dependent on the electrode materials [2 9] Agingcauses degradation of cell parts over the whole life cycle

[10] which leads to changes of the structural characteristicsdecomposition of the blinderelectrolytes formation of asurface layer and metal dissolution and so forth [3] Somebasic aging mechanisms under cycling and different storageconditions for each type of cathode materials (LiMn

2O4

and LiNiCoO2) will be discussed separately because of their

obvious distinction moreover the capacity fading and theirpreventive measures are also studied in this section

21 Structural Factors The insertion and extraction oflithium ions cause variation of the molar volume of the cath-ode materials It also leads to mechanical stress and strain ofthe metallic oxide particles Then the emergence of phasetransitions can subsequently cause crystal distortion andfurther mechanical stress (Figure 1) The reversible electro-chemical reactions of the cathode materials are in progress asthe lithium ions are insertedextracted infrom the lithium-manganese-oxides and are expressed by

LiMn2O4 999448999471 Li119909Mn2O4 + (1minus119909) Li++ (1minus119909) eminus (1)

The LiMn2O4spinel has a cubic structure with Mn

located on octahedral 16d sites and Li ions on 8a tetrahe-dral sites in a cubic close-packed array of oxygen anionsAt low potentials below 3V versus LiLi+ Li ions areinserted into vacant octahedral sites and produce a Jahn-Teller distorted tetragonal phase Li

2Mn2O4 Furthermore a

significant phase conversion appears which causes fracturingdecrepitation of the electrode and loss of contact to conduc-tive particles thus resulting in rapid capacity fading duringthe charging and discharging operations [11 12]

In the most recent literature [13ndash19] further phasetransitions taking place within LiMn

2O4spinel have been

Journal of Chemistry 3

confirmed The shapes of the superstructure phase of thelithium at 119909 = 05 [20] and the double hexagonal phase [21]must bemaintained for the purpose of achieving good cyclingstability Some measures such as the partial replacementof manganese ions by excess lithium andor by divalent ortrivalent cations such as Al Mg Co and Cr [22ndash32] can beadopted to diminish the molar volume changes of particlesduring the cycle to improve the capacity retention

In the lithium-nickel-cobalt-oxide system the LiNiO2

and LiCoO2compounds have the 120572-NaFeO

2crystallized

layer structure consisting of a cubic close-packed oxygenarray with transition metal and lithium ions occupyingoctahedral sites in alternating layers [12] It is difficult tosynthesise a pure LiNiO

2compound because of the structural

disorder reaction which is given by

LiNiO2 999448999471 Li1minus119909Ni (II)1199092Ni (III)1minus119909O2minus119909 +119909

2

Li2O

+

119909

4

O2

(2)

However lithium-nickel-disorder will decrease as thecobalt content increases Meanwhile monoclinichexagonalphase transitions arise in pure lithium-nickel-oxide duringthe process of electrochemical lithiationdelithiation and canbe prevented by a cobalt content of approximately 20 mole[12 22]

Additionally there are two kinds of new electrodematerials LiNi

08Co015

Al005

O2

(NCA) [33 34] andLiNi13

Mn13

Co13

O2(NMC) [35] Compared with LiNiO

2

and LiCoO2 they have higher specific capacitiesmdashdespite

their isostructuremdashand improved structural chemical andthermal stabilities [36] The reduction in the amount ofcobalt will improve the structure of the materials and reducethe cost compared to the parent compounds like LiNiO

2and

LiNi12

Mn12

O2 The doping of Al in LiNiO

2will improve

the thermal stability and low-level partial substitution of Al[37 38] orMn [39 40] for cobalt inNMCalso has been shownto improve the thermal behaviour [41] and cycling stability[42] whereas the addition of small amounts of Ti appears toincrease the practical capacities and improves cycling overan extended voltage range [12 22] Hence incorporationof Al Mg or Cl in LiNiCoO

2leads to better cycle stability

compared to undoped oxides [43ndash48] moreover the charge-discharge tests show that both the specific capacities andcapacity retentions of Cl-doped cathodes increase comparedto those of the undoped materials especially for the capacityretention in the high-voltage region [49ndash54]

22 Surface EffectsChemical Decomposition in ElectrolytesThe formation of surface membranes because of electrolyteoxidation and decomposition is mentioned in the litera-ture [55ndash59] At elevated temperatures high-voltage storageinduces side reactions such as some electrolyte decompo-sitions at the cathodeelectrolyte interface accompanied byCO2gas evolution [60ndash62] Then the metallic oxide-coated

cathode can contribute to oxidation reactions as an oxygensource itself by the formation of a subsurface membrane ofoxide-phase defects of the rock-salt construction [63 64]

The surface membrane on a lithium metallic oxide cathodeis shown in Figure 1 The formation of a surface film onLiMO

119909-based (M = Co Ni Mn) cathodes as the source of

an observed impedance increase upon cell cycling has beenidentified by Electrochemical Impedance Spectroscopy (EIS)techniques [65ndash71] This means that Li+ ions must also travelthrough an additional (solid electrolyte interphase- (SEI-)type) layer between the cathode and electrolyte which will befurther discussed in the next sectionThis rock-salt structureembodies the low conductivity character of lithium ions andcauses the surface resistance rise of the electrode [11 16 72ndash82]

23 Metal Dissolution Metal dissolution especially man-ganese dissolution occurring between lithium-manganese-oxides (spinel) and the electrolyte is an important issueat elevated temperatures [16 83ndash92] The manganese dis-solution causes a loss of active material and a subsequentcapacity fading of the electrode Apparently manganese ionsthat are dissolved from the cathode move towards the anodeafter which they merge into the SEI there which will befurther discussed in next section This phenomenon canaccelerate the electrolyte decomposition and aggravate theanode self-discharge Accordingly the existence of even asmall amount of manganese in the electrolyte will affect thelife span of the lithium-ion cell Generally two kinds ofmanganese dissolution are discussed especially at elevatedtemperatures dissolution occurring at low potentials andacid dissolution accelerated by hydrofluoric acid (HF) [11 22]Moreover the precipitation of various lithium-manganese-oxides on the cathode and loss of electronic contact of themanganese compound such as MnF

2and MnCO

3 resulting

in resistance rise of the electrode have been investigated byscanning electron microscopy (SEM) and energy dispersiveX-ray analysis (EDX) [16] In contrast to lithium-manganese-oxides metal dissolution of lithium-nickel-cobalt-mixed-oxides in an electrolyte appears to be negligible Only a tinyamount of dissolution occurs and a small amount of cobaltcan be found on the anode when lithium-nickel-cobalt-mixed-oxides are charged beyond a stable potential windowof 42 V versus LiLi+ [93 94]

24 Conclusion on Cathode Aging Table 1 provides a sum-mary of the principal characteristics of cathode aging and thediscussedmeasures that reduce the effects As for the cathodeaging phenomena may be primarily ascribed to changes ofthe cathode materialsrsquo structures surface effects and electro-chemical reactions at the electrodeelectrolyte interface andmetal dissolution Furthermore electrode aging is catalyzedby elevated temperatures high ΔSOC (state of charge) andhigh charge and discharge rates among others We concludethat the predominant agingmechanisms of themetallic oxidecathode can be summarized as follows

(i) The aging of electrode materials that results fromstructural disordering and phase transitions can bereduced by using new active materials or by adjustingtheir compositions and controlling the charge cutoffvoltage


Table 1 Aging mechanisms of lithium-ion cathode materialsmdashcauses effects and results

Cause Effect Result Reduced by Enhanced by

Li+ insertionextraction Structural disordering Capacitypower fading New materialsMaterial combinations Undoped materials

Phase transitions Crystal distortionFurther mechanical stress Capacity fading Control charge

cutoff voltage Overcharge

Metal dissolutionReprecipitation of new phases

Loss of active materialSurface layer formation

Capacity fadingImpedance rise Temperature control Elevated temperature

Electrolyte decomposition Gas evolutionSurface layer formation Impedance rise Alternative

conductive salts

Protic impuritiesElevated temperatureHigh storage potentials

Negativeelectrode

Graphitecarbon

SEI evolution

Particle isolation

Binderdecomposition

Currentcollectorcorrosion

Impedanceincrease

Power fading

Loss of lithium

Loss of active material

Inactivecomponent

Binderdecomposition

Oxidationconductive agent

Corrosioncurrent collector

Capacity fading

Impedanceincrease

Power fading

Capacity fading

Capacity fading

Capacity fading

Loss of lithium

Loss of mechanical

stability

Impedance rise

Overpotentials

Figure 2 Aging mechanisms of the anode materialsmdashcauses effects and results

(ii) Both electrochemical decomposition and formationof surface membranes can be reduced by operatingwithin an appropriate temperature range and bycontrolling the charge cutoff voltage

(iii) Metal dissolution mainly in the form of Mn disso-lution can be restrained by avoiding deep dischargeblending the lithium-manganese spinel powder withlithium-nickel-cobalt-oxides and using an alternativeelectrolyte

3 Aging of the Negative Electrode

Generally the most critical part of the cell is the anodeelectrolyte interface because of the high reactivity of theorganic electrolyte with any type of electrode material andlithium ions Graphite carbon amorphous silicon andlithium titanium oxide are the main candidates for the anodematerials [53 71 95ndash97] Figure 2 from [11] shows a flowchartof the aging mechanisms for anodematerials of a lithium-ionbattery To further the discussion the anode aging under the


Electrolyte decompositionand SEI formation

SEI

Donor solvent

Graphite exfoliation cracking(gas formation solvent cointercalation)

SEI conversionstabilization and growth

SEI dissolution precipitation

Positivenegative interactions

Lithium plating andsubsequent corrosion

Graphene layer

Li+

H+

Mn2+

Figure 3 SEI evolution at the anodeelectrolyte interface

conditions of storage and use will be summarized in terms ofthe following (i) SEI formation stable growth dissolutionand precipitation at the interface between the anodes andelectrolytes (ii) anode mechanical failure and (iii) anodeelectrochemical aging

31 Evolution of the Passivated Surface Layer at the AnodeElectrolyte Interface Graphite is commonly adopted as theanode material for lithium-ion batteries with organic elec-trolytes such as LiPF

6 with cosolvents like ethylene car-

bonate (EC) dimethyl carbonate (DMC) diethyl carbonate(DEC) and methyl ethyl carbonate (EMC) [98] Becausethe interface reactions take place between the compositeanode and the electrolyte solution changes at the anode andelectrolyte interface are regarded by many researchers to bethe main source of anode aging [7 11 16 72ndash79] When theanode operates at a potential that exceeds the electrochem-ically stable window of the electrolyte components somemajor reactions in a LiPF

6salt system with EC and DMC are

supposed to take place and these reactions are listed below toshow the processes and products ((3)ndash(8)) [99ndash102]

As the reactions continue the consumption of lithiumions and the electrolyte solvents are inevitable as the electrodeis in a state of charge then the electrolyte decomposesand produces deposits This process subsequently resultsin the formation of a protective ionically conductive butelectrically insulating passivation layer on the surface of theanode during the first charge cycle the so-called SEI (egLiCO3 (CH

2OCO2Li)2 CH3OCO2Li Li2O and LiF) and

the SEI evolution is illustrated in Figure 3 which is from[11] Furthermore the ROCO

2Li can undergo a reduction

reaction with traces of H2O and CO

2in the electrolyte to

form LiCO3[102ndash109] which further reacts with EC to form

transesterification products [11 99ndash102] Additionally anioncontaminates such as Fminus from LiPF

6 readily react with

lithium ions to form insoluble reaction products LiF whichare nonuniform are electrically insulating and are unstableon the surface of the graphite particles When the sidereactions continue during prolonged cycling the produceddeposits accumulate in the SEI and consequently lead tostable growth of the SEI which in turn leads to the loss ofactive lithium and further decomposition of the electrolyte[110 111] Subsequently restructuring of the damaged SEI ora reprecipitation of the dissolved SEI products might occuras the SEI membrane begins to dissolve or to decompose[16 102]

O O

O

C(EC)

2Li+ + 2eminus +

H2C CH2

Li2CO3 darr + CH2 = CH2 uarr

(CH2OCO2Li)2 darr

middot middot middotmiddot middot middot

(3)

O O

O

C(DMC)

Li+ + eminus +

CH3CH3

CH3OCO2Li darr + CH3∙ (4)


Li+ + eminus + Trace H2O 997888rarr LiOH darr +12H2 uarr (5)

LiOH + eminus + Li+ 997888rarr Li2O darr +1

2H2 uarr (6)

2Li+ + 2eminus + 2CO2 997888rarr LiCO3darr +CO uarr (7)

119899Li+ + 119899eminus + PF6minus997888rarr LiF darr + Li

119909POF119910darr (8)

In addition interactions of the anode with the cathodemust also be taken into account For instancemetal is presenton the anode surface Dissolution of the cathode electrodemetal from the lattice into the electrolyte can be caused by twomain reaction mechanisms in the cell [11] These reactionscan be due to the disproportionation of Mn3+ to Mn2+ andMn4+ ions at low states of charge or due to traces of HFwithinthe LiPF

6electrolyte Because manganese ions do not change

their oxidation state to Mn3+ during storage within the NMCand the spinel phase manganese dissolution caused by HFis more likely Dissolved transition metals are transportedthrough the electrolyte to the surface of the anode resultingin the deposition of cation contaminates such asMn Co andFe which are incorporated into the SEI layer [3 4 21 98 102]

Moreover the graphite electrodematerials are susceptibleto lithium plating and lithium dendrite growth because of theclose proximity of its reversible potential to that of Li+LiBoth effects are especially aggravated when the unmodifiedgraphite anode operates at low temperatures (below 25∘C)[112] andor a high charging rate Thus these factors areattributed to the lithium plates on the SEI surface of theanode If these moss-like metallic deposits and dendritescontinue to grow between the polymer separator and theanode a short circuit is created which then can lead tothermal runway and battery failure [11 98]

32 Anode Mechanical Failure Fracture and decrepitation ofthe electrodes are critical challenges existing in lithium-ionbatteries as a result of lithium diffusion during the chargingand discharging operations When lithium ions intercalateand deintercalate intofrom the graphite electrode a largevolume change on the order of a few to several hundredpercent can occur Diffusion-induced stresses (DISs) cantherefore cause the nucleation and growth of cracks leadingto mechanical degradation of the active electrode materials[113] Cuenot et al [114] have clarified the influence of thenanowire radius on the mechanical properties including theapparent stiffness and tensile modulus Hence for nanoscaleelectrode structures surface energies and surface stresses canbe expected to have a significant impact on the mechanicalproperties of the electrodematerials Additionally cycling thelithium-ion batteries at high C-rate and high state of charge(SOC) induce mechanical strain on the graphite lattice ofthe anode electrode due to the steep gradient of lithium ions[98] Nevertheless graphite exfoliation and particle crackingrising from solution cointercalation electrolyte reductionand gas evolution inside the graphite will definitely cause

a rapid decay of the electrode [96 97] In particular the gasevolution which accelerates cell aging is considered to exerta tremendous influence on the changes of the activematerials[53]

33 Anode Electrochemical Aging The resistance rise of theelectrode which has a significant correlation with power fad-ing of the whole cell has been measured by many researchers[56ndash59 110ndash118] The resistance rise is considered to resultfrom the thickening of the SEI alongwith the continual chem-ical changes of the SEI [60ndash64] Additionally the thicknessand constituents of the SEI membranes deposited on agedelectrodes were further researched by inductively coupledplasma (ICP) and EDX measurements [6]

The effects of different temperatures on the anode elec-trochemical characteristics are prominent The kinetics ofthe lithium intercalationdeintercalation intofrom the anodematerials are significantly accelerated at elevated temper-atures and the structure and morphology of the SEI areexpected to change with a rise of temperature [55ndash64] Thethermal runaway may lead to fire or explosion of the cellin some extreme cases Thus the SEM and X-ray diffraction(XRD) have been adopted by different groups to explore theelectrode or cell thermal characteristics at elevated tempera-tures [119ndash121]

Furthermore it is generally accepted that some basicmechanisms exist that account for the general aging phe-nomena in the lithium batteries although each battery maypossess different electrochemical behaviours The strongreactivity of the electrolyte and lithium ions and the stabilityof the SEI are the main contributors to the stability of theoverall cellThus amodified graphite electrode with properlychosen active materials and electrolyte results in an anodethat is stable during both storage and cycling [53 98]

34 Conclusion on Anode Aging The aging mechanisms ofthe anode in addition to those intrinsic to the anode maypredominantly be ascribed to changes of the electrode andelectrolyte at the interface between them Summarizing inbrief we can conclude that themainmechanisms of the anodeaging occur for the following reasons

(i) Changes at the anodeelectrolyte interface the SEImembrane is fabricated during the first electrochemi-cal charge and then further evolves with precipitationon the anode during cycling and storage Moreoverinteractions of the anode with the cathode andmetal-lic lithium plating must be considered as significantfactors in the anode aging

(ii) Mechanical failure such as graphite exfoliation andparticle cracking leads to isolation of active materialswhich subsequently aggravates electrode aging

(iii) Anode electrochemical aging characteristics someside reactions at the electrodesolution interface orthe SEI and electrolytes together with the contact losswithin the composite anode materials consequentlyresult in a resistance rise of electrode


4 Conclusions

Battery aging generally manifests in the form of a powercapacity decrease and impedanceinner resistance rise dur-ing storage and cycle This review presented the agingmechanisms of electrode materials in lithium-ion batterieselaborating on the causes effects and their results takingplace during a batteryrsquos life as well as the methods adoptedto mitigate the aging phenomena in lithium-ion batteriesStructural disordering and mechanical effects are the pre-dominant aspects of aging of cathode materials used inlithium-ion batteries upon cycling However the cathode byapplying state-of-the-art doped materials such as Al Mgand Cl-doped lithium-nickel-cobalt-mixed-oxides exhibitsgood cycling stability Additionally phase transitions aredependent on the high state of charge and upper cutoffvoltage Moreover the lifespan of cathode materials forexample lithiumndashmanganese spinel extended by operatingwithin reasonable electrochemical potential windows andtemperature ranges Further the capacity fading can beattributed to the loss of cyclable lithium and active materialsdue to the formation and development of an irreversible SEImembrane at the anode Additionally the SEI membraneis unstable when exposed to elevated temperatures whichis another cause of continuous lithium consumption andthe consequent capacity fading as the surface membrane isincreasingly rebuilt Elevated temperatures and high stor-age potentials initiate the decomposition of the electrolytersquoscomponents This effect is probably not caused by electrolytedecomposition alone and may be caused by a porous surfacelayer that is permeable for the electrolytes but acts as ahindering layer

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

Acknowledgments

This work was supported by the National Sci-Tech SupportPlan (no 2014BAG02B02) and International SampT Coop-eration Program of China (ISTCP) (no 2015DFG81930)The authors would like to thank Dr Rui Xiong at BeijingInstitute of Technology for many helpful discussions Theyare also grateful to all of the anonymous reviewers forproviding useful comments and suggestions that resulted inthe improved quality of this paper

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[3] H Kim and J Cho ldquoHard templating synthesis of mesoporousand nanowire SnO

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Materials Chemistry vol 18 no 7 pp 771ndash775 2008

[4] M FHassan ZGuo Z Chen andH Liu ldquo120572-Fe2O3as an anode

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[5] S Vyazovkin ldquoOn the phenomenon of variable activationenergy for condensed phase reactionsrdquo New Journal of Chem-istry vol 24 no 11 pp 913ndash917 2000

[6] TWaldmannMWilka M Kasper M Fleischhammer andMWohlfahrt-Mehrens ldquoTemperature dependent ageing mecha-nisms in Lithium-ion batteriesmdasha Post-Mortem studyrdquo Journalof Power Sources vol 262 pp 129ndash135 2014

[7] W Waag S Kabitz and D U Sauer ldquoExperimental investi-gation of the lithium-ion battery impedance characteristic atvarious conditions and aging states and its influence on theapplicationrdquo Applied Energy vol 102 no 2 pp 885ndash897 2013

[8] A Barre B Deguilhem S Grolleau M Gerard F Suard andD Riu ldquoA review on lithium-ion battery ageing mechanismsand estimations for automotive applicationsrdquo Journal of PowerSources vol 241 pp 680ndash689 2013

[9] U Troltzsch O Kanoun and H-R Trankler ldquoCharacterizingaging effects of lithium ion batteries by impedance spec-troscopyrdquo Electrochimica Acta vol 51 no 8-9 pp 1664ndash16722006

[10] G-B Cho T-H Kwon T-H Nam et al ldquoStructural andelectrochemical properties of lithium nickel oxide thin filmsrdquoJournal of Chemistry vol 2014 Article ID 824083 5 pages 2014

[11] J Vetter P Novak M R Wagner et al ldquoAgeing mechanisms inlithium-ion batteriesrdquo Journal of Power Sources vol 147 no 1-2pp 269ndash281 2005

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2nanotube anode material

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[14] M Kunduraci J F Al-Sharab and G G Amatucci ldquoHigh-power nanostructured LiMn

2minus119909Ni119909O4high-voltage lithium-ion

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[15] Y Idota T Kubota A Matsufuji Y Maekawa and T MiyasakaldquoTin-based amorphous oxide a high-capacity lithium-ion-storage materialrdquo Science vol 276 no 5317 pp 1395ndash1397 1997

[16] J-M Tarascon and M Armand ldquoIssues and challenges facingrechargeable lithium batteriesrdquo Nature vol 414 no 6861 pp7359ndash7367 2001

[17] X W Lou D Deng J Y Lee J Feng and L A ArcherldquoSelf-supported formation of needlelike Co

3O4nanotubes and

their application as lithium-ion battery electrodesrdquo AdvancedMaterials vol 20 no 2 pp 258ndash262 2008

[18] K A Smith C D Rahn and C-Y Wang ldquoControl oriented 1Delectrochemical model of lithium ion batteryrdquo Energy Conver-sion and Management vol 48 no 9 pp 2565ndash2578 2007

[19] Y-D Li S-X Zhao C-W Nan and B-H Li ldquoElectrochemicalperformance of SiO

2-coated LiFePO

4cathode materials for

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[20] H Ikuta K Takanaka and M Wakihara ldquoThe effect ofchromium substitution on the phase transition of lithiummanganese spinel oxidesrdquo Thermochimica Acta vol 414 no 2pp 227ndash232 2004


[21] J Lv YWang L Zhu andYMa ldquoPredicted novel high-pressurephases of lithiumrdquo Physical Review Letters vol 106 no 1 ArticleID 015503 2011

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[23] E Rezlescu L Sachelarie P D Popa and N Rezlescu ldquoEffectof substitution of divalent ions on the electrical and magneticproperties of Ni-Zn-Me ferritesrdquo IEEE Transactions onMagnet-ics vol 36 no 6 pp 3962ndash3967 2000

[24] H-M Zhang N Yamazoe and Y Teraoka ldquoEffects of Bsite partial substitutions of perovskite-type La

06Sr04CoO3on

oxygen desorptionrdquo Journal of Materials Science Letters vol 8no 9 pp 995ndash996 1989

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[26] S-H Park H-S Shin S-T Myung C S Yoon K Amine andY-K Sun ldquoSynthesis of nanostructured Li[Ni

13Co13Mn13]O2

via a modified carbonate processrdquo Chemistry of Materials vol17 no 1 pp 6ndash8 2005

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2O5filmsrdquo Journal of

Materials Chemistry vol 20 no 48 pp 10841ndash10846 2010[28] D-W Han W-H Ryu W-K Kim J-Y Eom and H-S Kwon

ldquoEffects of Li and Cl codoping on the electrochemical perfor-mance and structural stability of LiMn

2O4cathode materials

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3familyrdquoNew Journal of Chemistry vol

39 pp 829ndash835 2015[30] V Cicek and A Apblett ldquoSynthesis and characterization of salts

and esters of hydroxy acids as corrosion inhibitors for mildsteel and aluminum alloysrdquo Journal of Chemistry and ChemicalEngineering vol 5 pp 1160ndash1170 2011

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2minus119910Al119910O4prepared by a

wet-chemistry methodrdquo Journal of Materials Chemistry vol 11no 7 pp 1837ndash1842 2001

[32] M Kaneko S Matsuno T Miki et al ldquoLocal structural studiesof LiCryMn

2minus119910O4cathode materials for Li-Ion batteriesrdquo Jour-

nal of Physical Chemistry B vol 107 no 8 pp 1727ndash1733 2003[33] J R Dahn E W Fuller M Obrovac and U von Sacken

ldquoThermal stability of Li119909CoO2 Li119909NiO2and 120582-MnO

2and

consequences for the safety of Li-ion cellsrdquo Solid State Ionicsvol 69 no 3-4 pp 265ndash270 1994

[34] S Albrecht J Kumpers M Kruft et al ldquoElectrochemical andthermal behavior of aluminum- andmagnesium-doped spheri-cal lithium nickel cobalt mixed oxides Li

1minus119909(Ni1minus119910minus119911

CoyM119911)O2

(M=AlMg)rdquo Journal of Power Sources vol 119-121 pp 178ndash1832003

[35] N Yabuuchi and T Ohzuku ldquoNovel lithium insertion materialof LiCo

13Ni13Mn13O2for advanced lithium-ion batteriesrdquo

Journal of Power Sources vol 119ndash121 pp 171ndash174 2003[36] J Choi and A Manthiram ldquoRole of chemical and struc-

tural stabilities on the electrochemical properties of layered

LiNi13Mn13Co13O2cathodesrdquo Journal of the Electrochemical

Society vol 152 no 9 pp A1714ndashA1718 2005[37] A Manthiram A V Murugan A Sarkar and T Murali-

ganth ldquoNanostructured electrode materials for electrochemicalenergy storage and conversionrdquo Energy amp Environmental Sci-ence vol 1 no 6 pp 621ndash638 2008

[38] G T-K Fey Y Y Lin and T Prem Kumar ldquoEnhancedcyclability and thermal stability of LiCoO

2coated with cobalt

oxidesrdquo Surface and Coatings Technology vol 191 no 1 pp 68ndash75 2005

[39] X Zhang F Cheng J Yang and J Chen ldquoLiNi05Mn15O4

porous nanorods as high-rate and long-life cathodes for Li-ionbatteriesrdquo Nano Letters vol 13 no 6 pp 2822ndash2825 2013

[40] S Banerjee S Roy J W Chen and D Chakravorty ldquoMagneticproperties of oxide-coated iron nanoparticles synthesized byelectrodepositionrdquo Journal of Magnetism and Magnetic Materi-als vol 219 no 1 pp 45ndash52 2000

[41] M R Palacın G G Amatucci M Anne et al ldquoElectrochemicaland structural study of the 33 V reduction step in defectiveLi119909Mn2O4and LiMn

2O(4minus119910)

F119910compoundsrdquo Journal of Power

Sources vol 81-82 pp 627ndash631 1999[42] B L Ellis K T Lee and L FNazar ldquoPositive electrodematerials

for Li-Ion and Li-batteriesrdquo Chemistry of Materials vol 22 no3 pp 691ndash714 2010

[43] C Vogler B Loffler WWeirather MWohlfahrt-Mehrens andJ Garche ldquoDoped lithium nickel cobalt mixed oxides for thepositive electrode in Lithium Ion Batteriesrdquo Ionics vol 8 no1-2 pp 92ndash99 2002

[44] M Broussely P Blanchard P Biensan J P Planchat K Nechevand R J Staniewicz ldquoProperties of large Li ion cells using anickel basedmixed oxiderdquo Journal of Power Sources vol 119-121pp 859ndash864 2003

[45] C-J Kim I-S Ahn K-K Cho S-G Lee and J-K ChungldquoCharacteristics of LiNiO

2thin films synthesized by Li diffusion

on the surface oxidized epitaxial layer of Ni-alloyrdquo Journal ofAlloys and Compounds vol 449 no 1-2 pp 335ndash338 2008

[46] N N Bramnik K Nikolowski G Baehtz K G Bramnikand H Ehrenberg ldquoPhase transitions occurring upon lithiuminsertion-extraction of LiCoPO

4rdquo Chemistry of Materials vol

19 no 4 pp 908ndash915 2007[47] D R Macfarlane J Huang and M Forsyth ldquoLithium-doped

plastic crystal electrolytes exhibiting fast ion conduction forsecondary batteriesrdquo Nature vol 402 no 6763 pp 792ndash7941999

[48] W-S Yoon S Iannopollo C P Grey et al ldquoLocal structureand cation ordering in O

3lithium nickel manganese oxides

with stoichiometry Li[ NixMn(2 minusx)3Li(1minus2x)3]O2 NMR studies

andfirst principles calculationsrdquoElectrochemical and Solid-StateLetters vol 7 no 7 pp A167ndashA171 2004

[49] A Hirano R Kanno Y Kawamoto K Oikawab T Kamiyamaand F Izumi ldquoNeutron diffraction study of the layeredLi05minusxNi1+xO2rdquo Solid State Ionics vol 86ndash88 no 2 pp 791ndash796

1996[50] B Xu C R Fell M Chi and Y S Meng ldquoIdentifying surface

structural changes in layered Li-excess nickelmanganese oxidesin high voltage lithium ion batteries a joint experimental andtheoretical studyrdquo Energy and Environmental Science vol 4 no6 pp 2223ndash2233 2011

[51] M S Whittingham ldquoLithium batteries and cathode materialsrdquoChemical Reviews vol 104 no 10 pp 4271ndash4301 2004


[52] M Tang W C Carter and Y-M Chiang ldquoElectrochemicallydriven phase transitions in insertion electrodes for lithium-ionbatteries examples in lithiummetal phosphate olivinesrdquoAnnualReview of Materials Research vol 40 pp 501ndash529 2010

[53] M A L Nobre and S Lanfredi ldquoPhase transition in sodiumlithium niobate polycrystal an overview based on impedancespectroscopyrdquo Journal of Physics and Chemistry of Solids vol62 no 11 pp 1999ndash2006 2001

[54] Y Chen Q Jiao L Wang et al ldquoSynthesis and characterizationof Li105

Co13Ni13Mn13O195

X005

(X =Cl Br) cathode materi-als for lithium-ion batteryrdquo Comptes Rendus Chimie vol 16 no9 pp 845ndash849 2013

[55] S Komaba W Murata T Ishikawa et al ldquoElectrochemicalNa insertion and solid electrolyte interphase for hard-carbonelectrodes and application to Na-ion batteriesrdquo Advanced Func-tional Materials vol 21 no 20 pp 3859ndash3867 2011

[56] E Hosono T Kudo I Honma H Matsuda and H ZhouldquoSynthesis of single crystalline spinel LiMn

2O4nanowires for a

lithium ion battery with high power densityrdquo Nano Letters vol9 no 3 pp 1045ndash1051 2009

[57] L M L Fransson J T Vaughey R Benedek K Edstrom J OThomas and M M Thackeray ldquoPhase transitions in lithiatedCu2Sb anodes for lithium batteries an in situ X-ray diffraction

studyrdquo Electrochemistry Communications vol 3 no 7 pp 317ndash323 2001

[58] J Morales C Perez-Vicente and J L Tirado ldquoCation distribu-tion and chemical deintercalation of Li

1minus119909Ni1+119909

O2rdquo Materials

Research Bulletin vol 25 no 5 pp 623ndash630 1990[59] S P Lin K Z Fung YMHon andMHHon ldquoCrystallization

mechanism of LiNiO2synthesized by Pechini methodrdquo Journal

of Crystal Growth vol 226 no 1 pp 148ndash157 2001[60] K Xu ldquoNonaqueous liquid electrolytes for lithium-based

rechargeable batteriesrdquo Chemical Reviews vol 104 no 10 pp4303ndash4417 2004

[61] K Kumai K Takei Y Kobayashi H Mlyashiro and RIshikawa ldquoMechanism of electrolyte decomposition in practicallithium-ion cell after long charge and discharge cyclesrdquo DenkiKagaku vol 66 no 3 pp 314ndash320 1998

[62] S A Freunberger Y Chen N E Drewett L J Hardwick FBarde and P G Bruce ldquoThe lithium-oxygen battery with ether-based electrolytesrdquo Angewandte Chemie International Editionvol 50 no 37 pp 8609ndash8613 2011

[63] D P Abraham R D Twesten M Balasubramanian I PetrovJ McBreen and K Amine ldquoSurface changes on LiNi

08Co02O2

particles during testing of high-power lithium-ion cellsrdquo Elec-trochemistry Communications vol 4 no 8 pp 620ndash625 2002

[64] S Venkatraman Y Shin and A Manthiram ldquoPhase rela-tionships and structural and chemical stabilities of chargedLi1minus119909

CoO2minus120575

and Li1minus119909

Ni085

Co015

O2minus120575

cathodesrdquo Electrochem-ical and Solid-State Letters vol 6 no 1 pp A9ndashA12 2003

[65] Z Chen and J R Dahn ldquoStudies of LiCoO2coated with metal

oxidesrdquo Electrochemical and Solid-State Letters vol 6 no 11 ppA221ndashA224 2003

[66] L Gao S Liu and R A Dougal ldquoDynamic lithium-ionbattery model for system simulationrdquo IEEE Transactions onComponents and Packaging Technologies vol 25 no 3 pp 495ndash505 2002

[67] A Magasinski P Dixon B Hertzberg A Kvit J Ayala andG Yushin ldquoHigh-performance lithium-ion anodes using ahierarchical bottom-up approachrdquo Nature Materials vol 9 no4 pp 353ndash358 2010

[68] S Akao M Yamada and T Kodera ldquoPowder characteriza-tion and electrochemical properties of LiNi

05Mn15O4cathode

materials produced by large spray pyrolysis using flame com-bustionrdquo Advances in Materials Science and Engineering vol2011 Article ID 768143 6 pages 2011

[69] J-Y Luo and Y-Y Xia ldquoAqueous lithium-ion batteryLiTi2(PO4)3LiMn

2O4with high power and energy densities

as well as superior cycling stabilityrdquo Advanced FunctionalMaterials vol 17 no 18 pp 3877ndash3884 2007

[70] K A Smith C D Rahn and C-Y Wang ldquoModel-basedelectrochemical estimation and constraint management forpulse operation of lithium ion batteriesrdquo IEEE Transactions onControl Systems Technology vol 18 no 3 pp 654ndash663 2010

[71] Z-S Wu W Ren L Wen et al ldquoGraphene anchored withCo3O4nanoparticles as anode of lithium ion batteries with

enhanced reversible capacity and cyclic performancerdquo ACSNano vol 4 no 6 pp 3187ndash3194 2010

[72] I Hadjipaschalis A Poullikkas and V Efthimiou ldquoOverviewof current and future energy storage technologies for electricpower applicationsrdquoRenewable and Sustainable Energy Reviewsvol 13 no 6-7 pp 1513ndash1522 2009

[73] D Aurbach B Markovsky A Rodkin et al ldquoOn the capacityfading of LiCoO

2intercalation electrodes the effect of cycling

storage temperature and surface film forming additivesrdquo Elec-trochimica Acta vol 47 no 27 pp 4291ndash4306 2002

[74] H-W Lee P Muralidharan R Ruffo C M Mari Y Cui andD K Kim ldquoUltrathin spinel LiMn

2O4nanowires as high power

cathode materials for Li-ion batteriesrdquo Nano Letters vol 10 no10 pp 3852ndash3856 2010

[75] C H Chen J Liu and K Amine ldquoSymmetric cell approachtowards simplified study of cathode and anode behavior inlithium ion batteriesrdquo Electrochemistry Communications vol 3no 1 pp 44ndash47 2001

[76] C K Chan H Peng G Liu et al ldquoHigh-performance lithiumbattery anodes using silicon nanowiresrdquo Nature Nanotechnol-ogy vol 3 no 1 pp 31ndash35 2008

[77] Y Moritomo M Takachi Y Kurihara and T Matsuda1ldquoSynchrotron-radiation X-ray investigation of Li+Na+ inter-calation into prussian blue analoguesrdquo Advances in MaterialsScience and Engineering vol 2013 Article ID 967285 17 pages2013

[78] R Xiong F Sun H He and T D Nguyen ldquoA data-drivenadaptive state of charge and power capability joint estimator oflithium-ion polymer battery used in electric vehiclesrdquo Energyvol 63 pp 295ndash308 2013

[79] R Kostecki and F McLarnon ldquoDegradation of LiNi08Co02O2

Cathode surfaces in high-power lithium-ion batteriesrdquo Electro-chemical and Solid-State Letters vol 5 no 7 pp A164ndashA1662002

[80] R Xiong F Sun Z Chen andHHe ldquoA data-drivenmulti-scaleextendedKalman filtering based parameter and state estimationapproach of lithium-ion olymer battery in electric vehiclesrdquoApplied Energy vol 113 no 1 pp 463ndash476 2014

[81] N Sato KHirao E Hayashi andG Katagiri ldquoCharacterizationof electrode materials during degradation process of Li-ionbatteriesrdquo Nippon Kagaku Kaishi vol 2002 no 2 pp 189ndash1942002

[82] K S Ng C S Moo Y P Chen and Y C Hsieh ldquoEnhancedcoulomb counting method for estimating state-of-charge andstate-of-health of lithium-ion batteriesrdquoApplied Energy vol 86no 9 pp 1506ndash1511 2009


[83] L Li J Ge F Wu R Chen S Chen and B Wu ldquoRecoveryof cobalt and lithium from spent lithium ion batteries usingorganic citric acid as leachantrdquo Journal of Hazardous Materialsvol 176 no 1ndash3 pp 288ndash293 2010

[84] S M Shin N H Kim J S Sohn D H Yang and Y H KimldquoDevelopment of a metal recovery process from Li-ion batterywastesrdquo Hydrometallurgy vol 79 no 3-4 pp 172ndash181 2005

[85] H Li and H Zhou ldquoEnhancing the performances of Li-ion batteries by carbon-coating present and futurerdquo ChemicalCommunications vol 48 no 9 pp 1201ndash1217 2012

[86] Z Y Chen X Q Liu L Z Gao and Z L Yu ldquoElectrochemicalcapacity fading in high temperature of spinel LiMn

2O4and its

improvementrdquo Chinese Journal of Inorganic Chemistry vol 17no 3 pp 325ndash330 2001

[87] U Mehmood S-U Rahman K Harrabi I A Hussein andB V S Reddy ldquoRecent advances in dye sensitized solar cellsrdquoAdvances inMaterials Science and Engineering vol 2014 ArticleID 974782 12 pages 2014

[88] J Cho G B Kim and H S Lim ldquoImprovement of structuralstability of LiMn

2O4cathode material on 55∘C cycling by

solminusgel coating of LiCoO2rdquo Electrochemical and Solid-State

Letters vol 2 no 12 pp 607ndash609 1999[89] J NanDHanMYangMCui andXHou ldquoRecovery ofmetal

values from amixture of spent lithium-ion batteries and nickel-metal hydride batteriesrdquo Hydrometallurgy vol 84 no 1-2 pp75ndash80 2006

[90] S Komaba N Kumagai T Sasaki and YMiki ldquoManganese dis-solution from lithium doped Li-Mn-O spinel cathode materialsinto electrolyte solutionrdquo Electrochemistry vol 69 no 10 pp784ndash787 2001

[91] H Oka S Kasahara T Okada et al ldquoStructural analysisof lithium-excess lithium manganate cathode materials by7Li magic-angle spinning nuclear magnetic resonance spec-troscopyrdquo Solid State Ionics vol 144 no 1-2 pp 19ndash29 2001

[92] L Sun and K Qiu ldquoVacuum pyrolysis and hydrometallurgicalprocess for the recovery of valuable metals from spent lithium-ion batteriesrdquo Journal of Hazardous Materials vol 194 pp 378ndash384 2011

[93] H Liu J Li Z Zhang Z Gong and Y Yang ldquoThe effects of sin-tering temperature and time on the structure and electrochem-ical performance of LiNi

08Co02O2cathode materials derived

from sol-gel methodrdquo Journal of Solid State Electrochemistryvol 7 no 8 pp 456ndash462 2003

[94] G G Amatucci J M Tarascon and L C Klein ldquoCobalt dis-solution in LiCoO

2-based non-aqueous rechargeable batteriesrdquo

Solid State Ionics vol 83 no 1-2 pp 167ndash173 1996[95] B Saha S Poll K Goebel and J Christophersen ldquoAn inte-

grated approach to battery health monitoring using bayesianregression and state estimationrdquo in Proceedings of the IEEEAutotestcon pp 646ndash653 September 2007

[96] M Winter J O Besenhard M E Spahr and P Novak ldquoInser-tion electrode materials for rechargeable lithium batteriesrdquoAdvanced Materials vol 10 no 10 pp 725ndash763 1998

[97] R Xiong F Sun X Gong and C Gao ldquoA data-driven basedadaptive state of charge estimator of lithium-ion polymerbattery used in electric vehiclesrdquo Applied Energy vol 113 no1 pp 1421ndash1433 2014

[98] V Agubra and J Fergus ldquoLithium ion battery anode agingmechanismsrdquoMaterials vol 6 no 4 pp 1310ndash1325 2013

[99] D Aurbach E Zinigrad Y Cohen and H Teller ldquoA shortreview of failure mechanisms of lithium metal and lithiated

graphite anodes in liquid electrolyte solutionsrdquo Solid StateIonics vol 148 no 3-4 pp 405ndash416 2002

[100] P Lu C Li E W Schneider and S J Harris ldquoChemistryimpedance and morphology evolution in solid electrolyteinterphase films during formation in lithium ion batteriesrdquoTheJournal of Physical Chemistry C vol 118 no 2 pp 896ndash9032014

[101] R Fu S-Y Choe V Agubra and J Fergus ldquoDevelopment ofa physics-based degradation model for lithium ion polymerbatteries considering side reactionsrdquo Journal of Power Sourcesvol 278 pp 506ndash521 2015

[102] P Handel G Fauler K Kapper et al ldquoThermal aging ofelectrolytes used in lithium-ion batteriesmdashan investigation ofthe impact of protic impurities and different housingmaterialsrdquoJournal of Power Sources vol 267 pp 255ndash259 2014

[103] P Roder B Stiaszny J C Ziegler N Baba P Lagaly and H-DWiemhofer ldquoThe impact of calendar aging on the thermal sta-bility of a LiMn

2O4ndashLi(Ni

13Mn13Co13)O2graphite lithium-

ion cellrdquo Journal of Power Sources vol 268 pp 315ndash325 2014[104] T E Furtak ldquoAnomalously intense Raman scattering at the

solid-electrolyte interfacerdquo Solid State Communications vol 28no 11 pp 903ndash906 1978

[105] O Borodin and D Bedrov ldquoInterfacial structure and dynamicsof the lithium alkyl dicarbonate SEI components in contactwith the lithium battery electrolyterdquo The Journal of PhysicalChemistry C vol 118 no 32 pp 18362ndash18371 2014

[106] W Haiss and J K Sass ldquoAdsorbate-induced surface stress at thesolidelectrolyte interface measured with an STMrdquo Journal ofElectroanalytical Chemistry vol 386 no 1-2 pp 267ndash270 1995

[107] B Prelot C Poinsignon F Thomas E Schouller and FVillieras ldquoStructural-chemical disorder of manganese dioxides1 Influence on surface properties at the solid-electrolyte inter-facerdquo Journal of Colloid and Interface Science vol 257 no 1 pp77ndash84 2003

[108] S Zhang M S Ding K Xu J Allen and T R Jow ldquoUnder-standing solid electrolyte interface film formation on graphiteelectrodesrdquo Electrochemical and Solid-State Letters vol 4 no12 pp A206ndashA208 2001

[109] M LuHCheng andY Yang ldquoA comparison of solid electrolyteinterphase (SEI) on the artificial graphite anode of the aged andcycled commercial lithium ion cellsrdquo Electrochimica Acta vol53 no 9 pp 3539ndash3546 2008

[110] D Goers M E Spahr A Leone WMarkle and P Novak ldquoTheinfluence of the local current density on the electrochemicalexfoliation of graphite in lithium-ion battery negative elec-trodesrdquo Electrochimica Acta vol 56 no 11 pp 3799ndash3808 2011

[111] F-M Wang M-H Yu Y-J Hsiao et al ldquoAging effects tosolid electrolyte interface (SEI) membrane formation and theperformance analysis of lithium ion batteriesrdquo InternationalJournal of Electrochemical Science vol 6 no 4 pp 1014ndash10262011

[112] D Zhang B SHaranADurairajan R EWhite Y Podrazhan-sky and B N Popov ldquoStudies on capacity fade of lithium-ionbatteriesrdquo Journal of Power Sources vol 91 no 2 pp 122ndash1292000

[113] R Deshpande Y-T Cheng and M W Verbrugge ldquoModelingdiffusion-induced stress in nanowire electrode structuresrdquo Jour-nal of Power Sources vol 195 no 15 pp 5081ndash5088 2010

[114] S Cuenot C Fretigny S Demoustier-Champagne and BNysten ldquoSurface tension effect on the mechanical properties ofnanomaterials measured by atomic force microscopyrdquo PhysicalReview B vol 69 no 16 Article ID 165410 2004


[115] A Matasso D Wetz Jr and F Liu ldquoThe effects of internalpressure evolution on the aging of commercial Li-Ion cellsrdquoECSTransactions vol 58 no 46 pp 37ndash44 2014

[116] T Jiang S Zhang X Qiu W Zhu and L Chen ldquoPreparationand characterization of silicon-based three-dimensional cellu-lar anode for lithium ion batteryrdquo Electrochemistry Communi-cations vol 9 no 5 pp 930ndash934 2007

[117] S S Zhang ldquoA review on electrolyte additives for lithium-ionbatteriesrdquo Journal of Power Sources vol 162 no 2 pp 1379ndash13942006

[118] Q Y Chen and K XWei ldquoEstimation of electric vehicle batteryohmic resistance using dual extend kalman filterrdquo AppliedMechanics and Materials vol 391 pp 246ndash249 2013

[119] Y Wang J Jiang and J R Dahn ldquoThe reactivity of delithiatedLi(Ni

13Co13Mn13)O2 Li(Ni

08Co015

Al005

)O2or LiCoO

2with

non-aqueous electrolyterdquo Electrochemistry Communicationsvol 9 no 10 pp 2534ndash2540 2007

[120] W-M Zhang X-L Wu J-S Hu Y-G Guo and L-J WanldquoCarbon coated Fe

3O4nanospindles as a superior anode mate-

rial for lithium-ion batteriesrdquo Advanced Functional Materialsvol 18 no 24 pp 3941ndash3946 2008

[121] G Wang X Shen J Yao and J Park ldquoGraphene nanosheets forenhanced lithium storage in lithium ion batteriesrdquo Carbon vol47 no 8 pp 2049ndash2053 2009

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy


Carbohydrate Chemistry

International Journal of


Journal of

Chemistry


Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of


The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of


Chromatography Research International


Applied ChemistryJournal of



Theoretical ChemistryJournal of


Journal of

Spectroscopy

Analytical ChemistryInternational Journal of


Journal of


Quantum Chemistry


Organic Chemistry International

ElectrochemistryInternational Journal of



CatalystsJournal of


Gas evolution

Electrolytedecomposition

Surface layerformation

Migration of soluble species

Re-precipitation of new phases

Loss of contact toconductive particles

Corrosionof currentcollector

Oxidationof conductive

particles

Binderdecomposition

Microcracking

Structuraldisordering

dissolutionMetal

Figure 1 Schematic diagram of the aging mechanisms of cathode materials

This paper attempts to study and summarize the presentresearch regarding the predominant agingmechanisms of thepositive electrode (metallic oxide cathode) and the negativeelectrode (carbon anode) of lithium-ion cells applied to EVsBecause the aging mechanisms of the cathode and anode areobviously different they are discussed in separate sectionsFirst the aging mechanisms of the positive electrode materi-als are presented with explanations of the aging phenomenonoriginating from the dominant factors Later we elaborate onthe SEI evolution and some basic agingmechanisms affectingthe negative electrode Finally the influences of the electrolyteon the cathode and anode ageing itself the thermal stabilityand the hydrolysis reaction at ambient temperatures arediscussed in the corresponding sections

2 Aging Mechanisms of the Positive Electrode

Cathode materials determine significantly not only the per-formance of lithium-ion batteries but also their calendarand cycle lives Lithium-manganese-oxides (LiMn

2O4) with

spinel structures and lithium-nickel-cobalt-mixed-oxides(LiNiCoO

2) with layered structures arewidely accepted as the

choices of cathode materials for applications in high-energyand power-dense batteries according to the factors of costabundance and performance and they have been extensivelystudied in recent years [9 10]

Figure 1 from [11] is a schematic diagram showing themain aging mechanisms for cathode materials In the begin-ning aging occurs in the batteryrsquos electrolyte and the ori-gin can be electrochemical mechanical or thermal and isstrongly dependent on the electrode materials [2 9] Agingcauses degradation of cell parts over the whole life cycle

[10] which leads to changes of the structural characteristicsdecomposition of the blinderelectrolytes formation of asurface layer and metal dissolution and so forth [3] Somebasic aging mechanisms under cycling and different storageconditions for each type of cathode materials (LiMn

2O4

and LiNiCoO2) will be discussed separately because of their

obvious distinction moreover the capacity fading and theirpreventive measures are also studied in this section

21 Structural Factors The insertion and extraction oflithium ions cause variation of the molar volume of the cath-ode materials It also leads to mechanical stress and strain ofthe metallic oxide particles Then the emergence of phasetransitions can subsequently cause crystal distortion andfurther mechanical stress (Figure 1) The reversible electro-chemical reactions of the cathode materials are in progress asthe lithium ions are insertedextracted infrom the lithium-manganese-oxides and are expressed by

LiMn2O4 999448999471 Li119909Mn2O4 + (1minus119909) Li++ (1minus119909) eminus (1)

The LiMn2O4spinel has a cubic structure with Mn

located on octahedral 16d sites and Li ions on 8a tetrahe-dral sites in a cubic close-packed array of oxygen anionsAt low potentials below 3V versus LiLi+ Li ions areinserted into vacant octahedral sites and produce a Jahn-Teller distorted tetragonal phase Li

2Mn2O4 Furthermore a

significant phase conversion appears which causes fracturingdecrepitation of the electrode and loss of contact to conduc-tive particles thus resulting in rapid capacity fading duringthe charging and discharging operations [11 12]

In the most recent literature [13ndash19] further phasetransitions taking place within LiMn

2O4spinel have been





2crystallized





2

Li2O

+

119909

4

O2

(2)



08Co015

Al005

O2


Mn13

Co13


2



2and

LiNi12

Mn12


2will improve










2and MnCO

3 resulting














conductive salts


Negativeelectrode

Graphitecarbon

SEI evolution

Particle isolation

Binderdecomposition


Impedanceincrease

Power fading

Loss of lithium


Inactivecomponent

Binderdecomposition



Capacity fading

Impedanceincrease

Power fading

Capacity fading

Capacity fading

Capacity fading

Loss of lithium

Loss of mechanical

stability

Impedance rise

Overpotentials








SEI

Donor solvent






Graphene layer

Li+

H+

Mn2+


















O O

O

C(EC)

2Li+ + 2eminus +

H2C CH2


(CH2OCO2Li)2 darr


(3)

O O

O

C(DMC)

Li+ + eminus +

CH3CH3





2H2 uarr (6)



119909POF119910darr (8)















4 Conclusions




Acknowledgments


References

























3O4nanotubes and




2-coated LiFePO









06Sr04CoO3on




13Co13Mn13]O2



















2and




CoyM119911)O2










2coated with cobalt






2O(4minus119910)

























Co13Ni13Mn13O195

X005




2O4nanowires for a





1minus119909Ni1+119909

O2rdquo Materials








08Co02O2



CoO2minus120575

and Li1minus119909

Ni085

Co015

O2minus120575







05Mn15O4cathode





























2O4and its



























2O4ndashLi(Ni




















13Co13Mn13)O2 Li(Ni

08Co015

Al005

)O2or LiCoO

2with















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of





2crystallized





2

Li2O

+

119909

4

O2

(2)



08Co015

Al005

O2


Mn13

Co13


2



2and

LiNi12

Mn12


2will improve










2and MnCO

3 resulting














conductive salts


Negativeelectrode

Graphitecarbon

SEI evolution

Particle isolation

Binderdecomposition


Impedanceincrease

Power fading

Loss of lithium


Inactivecomponent

Binderdecomposition



Capacity fading

Impedanceincrease

Power fading

Capacity fading

Capacity fading

Capacity fading

Loss of lithium

Loss of mechanical

stability

Impedance rise

Overpotentials








SEI

Donor solvent






Graphene layer

Li+

H+

Mn2+


















O O

O

C(EC)

2Li+ + 2eminus +

H2C CH2


(CH2OCO2Li)2 darr


(3)

O O

O

C(DMC)

Li+ + eminus +

CH3CH3





2H2 uarr (6)



119909POF119910darr (8)















4 Conclusions




Acknowledgments


References

























3O4nanotubes and




2-coated LiFePO









06Sr04CoO3on




13Co13Mn13]O2



















2and




CoyM119911)O2










2coated with cobalt






2O(4minus119910)

























Co13Ni13Mn13O195

X005




2O4nanowires for a





1minus119909Ni1+119909

O2rdquo Materials








08Co02O2



CoO2minus120575

and Li1minus119909

Ni085

Co015

O2minus120575







05Mn15O4cathode





























2O4and its



























2O4ndashLi(Ni




















13Co13Mn13)O2 Li(Ni

08Co015

Al005

)O2or LiCoO

2with















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of











conductive salts


Negativeelectrode

Graphitecarbon

SEI evolution

Particle isolation

Binderdecomposition


Impedanceincrease

Power fading

Loss of lithium


Inactivecomponent

Binderdecomposition



Capacity fading

Impedanceincrease

Power fading

Capacity fading

Capacity fading

Capacity fading

Loss of lithium

Loss of mechanical

stability

Impedance rise

Overpotentials








SEI

Donor solvent






Graphene layer

Li+

H+

Mn2+


















O O

O

C(EC)

2Li+ + 2eminus +

H2C CH2


(CH2OCO2Li)2 darr


(3)

O O

O

C(DMC)

Li+ + eminus +

CH3CH3





2H2 uarr (6)



119909POF119910darr (8)















4 Conclusions




Acknowledgments


References

























3O4nanotubes and




2-coated LiFePO









06Sr04CoO3on




13Co13Mn13]O2



















2and




CoyM119911)O2










2coated with cobalt






2O(4minus119910)

























Co13Ni13Mn13O195

X005




2O4nanowires for a





1minus119909Ni1+119909

O2rdquo Materials








08Co02O2



CoO2minus120575

and Li1minus119909

Ni085

Co015

O2minus120575







05Mn15O4cathode





























2O4and its



























2O4ndashLi(Ni




















13Co13Mn13)O2 Li(Ni

08Co015

Al005

)O2or LiCoO

2with















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of



SEI

Donor solvent






Graphene layer

Li+

H+

Mn2+


















O O

O

C(EC)

2Li+ + 2eminus +

H2C CH2


(CH2OCO2Li)2 darr


(3)

O O

O

C(DMC)

Li+ + eminus +

CH3CH3





2H2 uarr (6)



119909POF119910darr (8)















4 Conclusions




Acknowledgments


References

























3O4nanotubes and




2-coated LiFePO









06Sr04CoO3on




13Co13Mn13]O2



















2and




CoyM119911)O2










2coated with cobalt






2O(4minus119910)

























Co13Ni13Mn13O195

X005




2O4nanowires for a





1minus119909Ni1+119909

O2rdquo Materials








08Co02O2



CoO2minus120575

and Li1minus119909

Ni085

Co015

O2minus120575







05Mn15O4cathode





























2O4and its



























2O4ndashLi(Ni




















13Co13Mn13)O2 Li(Ni

08Co015

Al005

)O2or LiCoO

2with















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of




2H2 uarr (6)



119909POF119910darr (8)















4 Conclusions




Acknowledgments


References

























3O4nanotubes and




2-coated LiFePO









06Sr04CoO3on




13Co13Mn13]O2



















2and




CoyM119911)O2










2coated with cobalt






2O(4minus119910)

























Co13Ni13Mn13O195

X005




2O4nanowires for a





1minus119909Ni1+119909

O2rdquo Materials








08Co02O2



CoO2minus120575

and Li1minus119909

Ni085

Co015

O2minus120575







05Mn15O4cathode





























2O4and its



























2O4ndashLi(Ni




















13Co13Mn13)O2 Li(Ni

08Co015

Al005

)O2or LiCoO

2with















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


4 Conclusions




Acknowledgments


References

























3O4nanotubes and




2-coated LiFePO









06Sr04CoO3on




13Co13Mn13]O2



















2and




CoyM119911)O2










2coated with cobalt






2O(4minus119910)

























Co13Ni13Mn13O195

X005




2O4nanowires for a





1minus119909Ni1+119909

O2rdquo Materials








08Co02O2



CoO2minus120575

and Li1minus119909

Ni085

Co015

O2minus120575







05Mn15O4cathode





























2O4and its



























2O4ndashLi(Ni




















13Co13Mn13)O2 Li(Ni

08Co015

Al005

)O2or LiCoO

2with















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of






06Sr04CoO3on




13Co13Mn13]O2



















2and




CoyM119911)O2










2coated with cobalt






2O(4minus119910)

























Co13Ni13Mn13O195

X005




2O4nanowires for a





1minus119909Ni1+119909

O2rdquo Materials








08Co02O2



CoO2minus120575

and Li1minus119909

Ni085

Co015

O2minus120575







05Mn15O4cathode





























2O4and its



























2O4ndashLi(Ni




















13Co13Mn13)O2 Li(Ni

08Co015

Al005

)O2or LiCoO

2with















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of





Co13Ni13Mn13O195

X005




2O4nanowires for a





1minus119909Ni1+119909

O2rdquo Materials








08Co02O2



CoO2minus120575

and Li1minus119909

Ni085

Co015

O2minus120575







05Mn15O4cathode





























2O4and its



























2O4ndashLi(Ni




















13Co13Mn13)O2 Li(Ni

08Co015

Al005

)O2or LiCoO

2with















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of






2O4and its



























2O4ndashLi(Ni




















13Co13Mn13)O2 Li(Ni

08Co015

Al005

)O2or LiCoO

2with















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of







13Co13Mn13)O2 Li(Ni

08Co015

Al005

)O2or LiCoO

2with















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of










Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of

Documents

Review Article Aging Mechanisms of Electrode Materials in Lithium-Ion Batteries …downloads.hindawi.com/journals/jchem/2015/104673.pdf · 2019-07-31 · Review Article Aging Mechanisms