Effect of Metal (Mn, Ti) Doping on NCA Cathode …downloads.hindawi.com/journals/jnm/2018/8082502.pdfO, %, Sigma-Aldrich) in a molarratioof:.byhandgrinding,andthen,themixture wascalcinedagainat

Research ArticleEffect of Metal (Mn Ti) Doping on NCA Cathode Materials forLithium Ion Batteries

Dao YongWan 1 Zhi Yu Fan 1 Yong Xiang Dong 1 Erdenebayar Baasanjav1

Hang-Bae Jun1 Bo Jin 2 EnMei Jin 1 and SangMun Jeong 1

1School of Environmental Urban and Chemical Engineering Chungbuk National University 1 Chungdae-ro Seowon-GuCheongju Chungbuk 28644 Republic of Korea2Key Laboratory of Automobile Materials Ministry of Education College of Materials Science and EngineeringJilin University Changchun 130022 China

Correspondence should be addressed to En Mei Jin kujienavercom and Sang Mun Jeong smjeongchungbukackr

Received 25 September 2017 Revised 5 December 2017 Accepted 24 December 2017 Published 30 January 2018

Academic Editor Bhanu P Singh

Copyright copy 2018 Dao YongWan 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

NCA (LiNi085Co010Al005minusx MxO2 M=Mn or Ti 119909 lt 001) cathode materials are prepared by a hydrothermal reaction at 170∘Cand doped with Mn and Ti to improve their electrochemical properties The crystalline phases and morphologies of variousNCA cathode materials are characterized by XRD FE-SEM and particle size distribution analysis The CV EIS and galvanostaticchargedischarge test are employed to determine the electrochemical properties of the cathodematerialsMn andTi doping resultedin cell volume expansion This larger volume also improved the electrochemical properties of the cathode materials because Mn4+and Ti4+ were introduced into the octahedral lattice space occupied by the Li-ions to expand the Li layer spacing and therebyimproved the lithium diffusion kinetics As a result the NCA-Ti electrode exhibited superior performance with a high dischargecapacity of 1796mAh gminus1 after the first cycle almost 23mAh gminus1 higher than that obtained with the undoped NCA electrode and1667mAh gminus1 after 30 cycles A good coulombic efficiency of 886 for the NCA-Ti electrode is observed based on calculations inthe first charge and discharge capacities In addition the NCA-Ti cathode material exhibited the best cycling stability of 93 up to30 cycles

1 Introduction

Currently there is an increasing consumer demand for Li-ion batteries (LIBs) with long life high energy and highpower density LIBs can be used in many devices fromportable electronics to electric vehicles However there aremany issues that need to be addressed when using LIBs inelectric vehicles including those related to cost safety andenergy density considerations [1 2]

Recently transition metal-layered oxide LiMO2 (M=NiMn Co) materials have generated interest as suitable solu-tions to the aforementioned issues including specific capac-ity energy density safety and cost [3 4] Among thesematerials LiNiO2 is of low cost has a large theoreticalcapacity (275mAh gminus1) and ismore environmentally friendlythan LiCoO2 [5ndash8] However several limitations such as a

difficult synthesis protocol for stoichiometric LiNiO2 par-tially reversible phase for LiNiO2 and LiNi cation mixinghave to be overcome before LiNiO2 can be commerciallyused as a cathode material for LIBs To resolve theseissues different metals such as Co Al and Fe were studiedas dopantspartial substitutes for Ni which demonstratedpromising but limited performance Among these Co andAl codoped LiNi1minusxminusyCoxAlyO2 (NCA 005 le 119909 le 015001 le 119910 le 010) cathode materials exhibit the improvedelectrochemical properties and the thermal safety becausecation substitution of Co and Al increases the stability of thestructure [5 9] However a few drawbacks such as degrada-tion during chargendashdischarge cycles and thermal runaway areyet to be resolved Moreover higher Ni concentrations resultin highly unstableNi3+ andNi4+ ions remaining in the layeredstructure and their reaction with the electrolyte speeds up

HindawiJournal of NanomaterialsVolume 2018 Article ID 8082502 9 pageshttpsdoiorg10115520188082502

2 Journal of Nanomaterials

degradation of the materials and batteries [10 11] In orderto solve these problems the small amounts of dopants at thecationic sites have been considered for example it has beenreported that the addition of small amounts of Cl Mg F andNa improves the capacity and cycle performance [12ndash17]

In this work the NCA cathode material was preparedby one step of hydrothermal reaction at 170∘C and dopedwith either Mn or Ti This is because Mn and Ti havesimilar atomic radii as that of Ni and in coordinationwith oxygen can replace the transition metal atoms in theoctahedral interstitial sites The aforesaid process enhancesthermal and structural stability and in some cases decreaseselectronic andor ionic resistance [18 19] Herein we reportthe effects ofMn or Ti doping on the crystalline structure andelectrochemical properties of NCA

2 Experimental

The NCA cathode materials were prepared via one step ofhydrothermal reaction First 085M of nickel(II) sulfate hex-ahydrate (NiSO4sdot6H2O 99 Sigma-Aldrich) and 015M ofcobalt(II) sulfate heptahydrate (CoSO4sdot7H2O ge99 Sigma-Aldrich) were dissolved in 25M of NaOH solution Afterstirring vigorously for 1 h 005M of aluminum hydrox-ide hexahydrate (Al(OH)3sdot6H2O 98 Sigma-Aldrich) andammonia solution were added sequentially and the mixturewas stirred for another half hour Then the resultant solu-tion was transferred to a 100-mL Teflon-lined stainless-steelautoclave which was placed in a laboratory electric oven andheated at 170∘C for 18 h After the hydrothermal reactionthe autoclave was cooled to room temperature The obtaineddark-green Ni085Co010Al005(OH)2 powder was washed withdeionized water and ethanol and centrifuged several timesfollowed by vacuum drying overnight at 120∘C Next theNi085Co010Al005(OH)2 powder was calcined at 500

∘C for 5 hin air to obtain Ni085Co010Al005O2 which was mixed withlithium hydroxide (LiOHsdotH2O 99 Sigma-Aldrich) in amolar ratio of 1 105 by hand grinding and then the mixturewas calcined again at 700∘C for 10 h under an O2 atmosphere(O2 flow 3mLminminus1) to obtain the Li105Ni085Co010Al005O2(NCA) cathode material The NCA cathode materials weredopedwithMnandTi to improve their electrochemical prop-erties For the metal-doping process 001mol of titanium(IV) isopropoxide (C12H28O4Ti ge97 Aldrich) or 001molof manganese(II) sulfate monohydrate (MnSO4sdotH2O 98Samchun) was added during the addition of the Al sourceThe obtained pristine NCA and Mn- and Ti-doped NCAcathode materials were denoted as NCA NCA-Mn andNCA-Ti respectively

For electrode fabrication the cathode material (as-prepared NCA NCA-Mn or NCA-Ti) super-p carbon blackand polyvinylidene fluoride (PVdF 119872119908 sim400000 Sigma-Aldrich) in the weight ratio of 94 3 3 were ground with N-methyl-2-pyrrolidone (NMP Samchun Pure Chemical) as asolvent The slurry was coated on Al foil by doctor blademethod and then the electrode was dried for 1 h at 80∘CThe coated electrode was 20120583m thick and it was pressed to80 of the coating thickness After drying under vacuumat 110∘C for 24 h the electrode was cut into a round plate

10 20 30 40 50 60 70 80

(018

)(1

10)

(003

)

(101

)

(104

)

(015

)

(107

)

(113

)

(006

)(0

12)In

tens

ity (a

u)

2-Theta (degree)

(b)

(c)

(a)

182 184 186 188 190 192 194

(b)

(c)

(a)

Figure 1 XRD patterns of (a) NCA (b) NCA-Mn and (c) NCA-Tipowders

(Φ = 15958mm) The CR2032 coin-type cell was assembledin an argon-filled glove box with oxygen and moisture levelslt1 ppm Lithium foil polyethylene (PE W-SCOPE) and 1MLiPF6EC-DMC (3 7 vv) were used as the counter electrodeseparator and electrolyte respectively

The crystalline phases of various NCA cathode materialswere identified using X-ray diffraction (XRD Dmax1200Rigaku) using CuK120572 radiation (120582 = 15406 nm 40 kV 40mA)over the range 2120579 = 10ndash80∘ The morphologies of variousNCA cathodematerials were characterized by field-emission-scanning electron microscopy (FE-SEM LEO-1530 CarlZeiss) The electrical conductivities and particle size distri-bution of the NCA cathode materials were analyzed by apowder resistivity measurement system (HPRM-M2 HANTECH) and a particle size analyzer (Mastersizer 3000 Mar-vern) Cyclic voltammetry was carried out in an automatedchargendashdischarge equipment (WBCS 3000L WonATech) ata scanning rate of 01mV sminus1 in the voltage range 28ndash45 VThe chargendashdischarge test (WonATech WBCS 3000L) wasperformed at potentials ranging from 30 to 43 V at 01CThe electrochemical impedance measurements were per-formed using electrochemical impedance spectroscopy (EISPGSTAT302NMetrohmAutolab BV) in the frequency range001ndash100 kHz at an amplitude of 10mV All electrochemicalmeasurements were performed at 25∘C

3 Results and Discussion

Figure 1 shows the XRD patterns of pristine NCA NCA-MnandNCA-Ti powders in the 2120579 range 10ndash80∘ All the peaks canbe indexed to a hexagonal 120572-NaFeO2 structure (space groupR3m)The sharp and intense peaks at 188∘ 367∘ 445∘ 482∘and 583∘ were representative of the (003) (101) (104) (015)and (107) diffraction planes respectively [20] Furthermorethe splitting of the two peaks (006)(102) and (108)(110) wasobserved clearly at 377ndash387∘ and 636ndash654∘ respectivelyconfirming that a typical layered structure formed in the

Journal of Nanomaterials 3

1 휇m

(a)

1 휇m

(b)

1 휇m

(c)

Figure 2 FE-SEM images of (a) NCA (b) NCA-Mn and (c) NCA-Ti powders

Table 1 Lattice parameters of the NCA NCA-Mn and NCA-Ti powders

Samples 119886 (A) 119888 (A) 119881 (A3) 119888119886 119868003119868104NCA 28674 140433 999999 48976 14708NCA-Mn 28705 141362 1008809 49246 16331NCA-Ti 28727 142648 1019534 49656 19255

crystal lattice [21] In particular the (003) peak of NCA-Mn and NCA-Ti shifted slightly toward the lower-angleregion (inset of Figure 2) because Mn4+ and Ti4+ ions wereintroduced into the octahedral lattice space occupied by theLi-ions to expand the Li layer spacing and thereby improvethe lithium diffusion kinetics [22] The variations in thelattice parameters were calculated by the Rietveld refinementmethod the results are provided in Table 1 The integratedintensity ratio I(003)I(104) has been used as an indicator ofLi+Ni2+ cation mixing (Ni2+ at the 3a site and Li+ at the 3bsite in the space group R3m) values smaller than 13 indicatea high degree of cation mixing because of the presence ofother ions in the lithium interslab regionThus the reversiblecapacity of the cathode material tends to decrease when theratio is lt12 [23ndash27] As shown in Table 1 the I(003)I(104)diffraction peaks are higher for NCA-Ti which could begreatly affected by the presence of Ti-metal ions in the lithiumlayer thus leading to better electrochemical properties

The typical morphology of the NCA NCA-Mn andNCA-Ti powders is shown in Figure 2 Here the smallprimary particles are organized into larger agglomeratesas secondary particles These three NCA cathode materialscomprise almost spherical particles

To investigate the doping results element mapping andenergy dispersive X-ray spectrometry (EDS) analyses wereperformed on the NCA NCA-Mn and NCA-Ti cathodematerials Figure 3 shows the Al Co Ni Mn and Tielement mapping results for NCA (Figure 3(a)) NCA-Mn(Figure 3(b)) andNCA-Ti (Figure 3(c))The signals fromMnand Ti (bright yellow and green spots respectively) clearlydemonstrate thatMn andTi were homogeneously distributedthroughout the NCA-Mn and NCA-Ti particles TheMn andTi contents in the NCA cathode materials were analyzed byEDS The weight percent of Mn and Ti was 08385 and07049 and their atomic percent was 08557 and 08529respectively

Figure 4(a) shows the particle size distribution of theNCA NCA-Mn andNCA-Ti powders As shown in Figure 4three kinds of powders exhibited a bimodal distributionof particle sizes such as with small particle distribution at3ndash5 120583m and large particle at 10ndash30 120583m The NCA powderhas an almost 1 1 volume density of small and large particlehowever the large range (10ndash30120583m) of volume density wasincreased after doping of Mn or Ti into the NCA In resultstheNCA-Mnhas a higher volumedensity of large particle sizethan others The electrical conductivities of the NCA NCA-Mn and NCA-Ti powders were measured and the results aredepicted in Figure 4(b) The electrical conductivity (120590) wasmeasured at room temperature in the compression pressurerange 5ndash23MPa The sample weight of the powder wasapproximately 10 g and the diameter of the measuring diewas 11 cmThe electrical conductivity was determined by theequation120590 = ℎ(119877sdot119860) where119877 is the electrical resistance (Ω)119860 is the area of the pellet surface (m2) and ℎ is the distance(m) from the bottom to the top of the sample As shown inFigure 4(b) an increase in pressure increases the electricalconductivity for all the cathode materials considered in thisstudy The electrical conductivity of the metal-doped NCApowder exceeds that of pristine NCA under all pressureconditions possibly because of the metal ions in the lithiumlayerThe electrical conductivities of theNCANCA-Mn andNCA-Ti powders at 10MPa are 292 365 and 362 Smminus1respectively

The electrochemical properties of differentNCAcathodesfor LIBs were investigated by cyclic voltammetry (CV) usinga coin-type cell with a potential window of 28ndash45 V at scanrate of 01mV sminus1 as shown in Figure 5 In the CV curvethe peak currents represent the electrochemical propertiesof the material and express the phase transitions that occurduring the intercalationdeintercalation of lithium ions [2829] During the charge and discharge process three pairs ofpeaks can be observed (IndashI1015840 IIndashII1015840 and IIIndashIII1015840) in the CV

4 Journal of Nanomaterials

Co K 0 4 Ni K 0 8Al K 0 315Base (596)

65535

(a)

Co K 0 4 Ni K 0 7Al K 0 4 0 3Mn K0 255Grey

(b)

Co K 0 4 Ni K 0 8Al K 0 4 0 4Ti K15 65535Base (589)

(c)

Figure 3 EDS elemental mapping of (a) NCA (b) NCA-Mn and (c) NCA-Ti powders

01 1 10 100 1000

Volu

me d

ensit

y (

)

0

1

2

3

4

5

6

NCANCA-MnNCA-Ti

Particle size m)(휇

(a)

Pressure (MPa)4 8 12 16 20 24

15

20

25

30

35

40

45

50

55

NCANCA-MnNCA-Ti

smminus1)

Elec

tric

al co

nduc

tivity

(

(b)

Figure 4 (a) Particle size distribution and (b) electrical conductivity with applied pressure for NCA NCA-Mn and NCA-Ti powders

diagram which are attributed to hexagonal to monoclinicmonoclinic to hexagonal and hexagonal to hexagonal phasetransitions respectively [30 31] In the case of NCA theoxidation peaks around 384 402 and 420Vdenote I II andIII respectively The corresponding reduction peaks around

366 393 and 412 V denote I1015840 II1015840 and III1015840 The NCA-Mnand NCA-Ti electrodes exhibit a broad oxidation peak withshoulders near 394 and 379V respectively whichmay resultfrom the lower intensity of lithium clustering due to metaldoping [30]

Journal of Nanomaterials 5

28 30 32 34 36 38 40 42 44 46

Curr

ent (

mA

)

minus06

minus04

minus02

00

02

04

06

08

1 cycle5 cycles10 cycles

III

III

I㰀 II㰀III㰀

Voltage (V)

(a)

28 30 32 34 36 38 40 42 44 46minus06

minus04

minus02

00

02

04

06

08

1 cycle5 cycles10 cycles

Voltage (V)

Curr

ent (

mA

)

(b)

Voltage (V)28 30 32 34 36 38 40 42 44 46

Curr

ent (

mA

)

minus06

minus04

minus02

00

02

04

06

08

1 cycle5 cycles10 cycles

(c)

Voltage (V)28 30 32 34 36 38 40 42 44 46

Curr

ent (

mA

)

minus06

minus04

minus02

00

02

04

06

08

NCANCA-MnNCA-Ti

(d)

Figure 5 Cyclic voltammetry (CV) curves of (a) NCA (b) NCA-Mn (c) NCA-Ti electrodes and (d) CV curves of different electrodes at 10cycles

The initial chargendashdischarge curves of the NCA NCA-Mn and NCA-Ti cathodes are shown in Figure 6(a) Thechargendashdischarge test is performed in the voltage range30ndash43 V at a rate of 01C The first discharge capaci-ties of NCA NCA-Mn and NCA-Ti are 1565 1714 and1796mAh gminus1 and the first charge capacities are 1971 2099and 2026mAh gminus1 with initial coulombic efficiencies of794 817 and 886 respectively Studies have shownthat the coulombic efficiency of NCA cathode is closelyrelated to the interfacial resistance which can be reducedsignificantly bymetal doping [30 31]The cycle performancesofNCANCA-Mn andNCA-Ti are shown in Figure 6(b)Thedischarge capacity of NCA is lower than that of metal-dopedNCA-Mn orNCA-TiThe best discharge capacity is found for

the NCA-Ti because Ti4+ is introduced into the octahedrallattice space occupied by Li+ to expand the Li layer spacingthereby the Li+ diffusion kinetics are improvedThedischargecapacities of NCA NCA-Mn and NCA-Ti at the end of 30cycles are 1501 1629 and 1667mAh gminus1 respectively Betterelectrochemical performance of NCA-Ti is closely related toits excellent crystallization layered structure and electricalconductivity from the aforementioned analysis

To investigate the variation in surface morphology ofthe different electrodes after 10 cycles cross-sectional FE-SEM analysis was performed as depicted in Figure 7 Figures7(a)ndash7(c) show the fresh NCA NCA-Mn and NCA-Tielectrodes while Figures 7(d)ndash7(f) depict the same NCANCA-Mn and NCA-Ti electrodes after the 10th discharge

6 Journal of Nanomaterials

0 50 100 150 200 250

Cell

pote

ntia

l (V

)

30

32

34

36

38

40

42

44

NCANCA-MnNCA-Ti

Capacity (mA hgminus1)

(a)

Cycle number5 10 15 20 25 30

0

50

100

150

200

Capa

city

(mA

hgminus1)

NCANCA-MnNCA-Ti

(b)

Figure 6 (a) Chargendashdischarge profiles at first cycle and (b) cycling performance of NCA NCA-Mn and NCA-Ti electrodes in a voltagerange of 30 to 43 V at 01C

10 휇m

500 nm

(a)

10 휇m

500 nm

(b)

10 휇m

500 nm

(c)

10 휇m

500 nm

(d)

10 휇m

500 nm

(e)

10 휇m

500 nm

(f)

Figure 7 Enlarged cross-sectional FE-SEM images of (a)-(c) fresh electrodes and (d)-(f) after discharging 10 cycles of (a) (d) for NCA (b)(e) for NCA-Mn and (c) (f) for NCA-Ti electrodes The inset images are low magnification FE-SEM images of each electrode

respectively The insertion figures in Figure 7 show theenlarged images for the rectangular part of the cross-sectionalimages of the electrodes As can be seen in the cross-sectional FE-SEM images the electrodes show clear changeafter cycling when compared with the fresh electrodes Thelarger primary particle size of NCA is found after 10th cycledischarged compared to before cycling However the NCA-Mn and NCA-Ti are almost unchanged even after cycling

This suggests that the NCA-Mn and NCA-Ti electrodes havea stable structure with much less structural change duringcycling Thus the electrochemical properties of NCA can beimproved by doping with Mn or Ti

Nyquist plots of the fresh NCA NCA-Mn and NCA-Ti electrodes and the electrodes after the 10th cycle areshown in Figure 8 Experimental results shown in solid linesare fitted by the equivalent circuit in the inset of Figure 8

Journal of Nanomaterials 7

0 100 200 300 4000

100

200

300

400

500

600

NCANCA-Mn

NCA-TiFitting line

Z㰀㰀

(Ω)

Z㰀 (Ω)

Rs

R2 R3

Q2 Q3 W

(a)

0 100 200 300 400 500 6000

50

100

150

200

Z㰀㰀

(Ω)

Z㰀 (Ω)

Rs

R2R1 R3

Q2Q1 Q3

NCANCA-Mn

NCA-TiFitting line

W

(b)

Figure 8 EIS analysis of NCA NCA-Mn and NCA-Ti electrode (a) before cycling and (b) after 10 cycles discharged

Table 2 EIS results of lithium ion batteries with NCA NCA-Mn and NCA-Ti electrodes

Samples 1198771 (Ω) 1198772 (Ω) 1198773 (Ω) 119877119904 (Ω)

FreshNCA - 348 1571 30NCA-Mn - 290 1302 20NCA-Ti - 292 950 15

After 10th dischargingNCA 311 805 2774 51NCA-Mn 524 902 2106 53NCA-Ti 242 487 1897 61

using the NOVA program (Version 1104 Metrohm AutolabBV) Constant phase elements (CPEs) describing nonidealcapacitances with parametersQ analogous to capacitance andthe ideality factor 119899 are necessitated due to the existenceof spatial and chemical nonuniformity across the electrodeas well as the solid electrolyte interphase (SEI) surface Theinclined line at lower frequencies indicates the Warburgimpedance (W) which represents the lithium ion diffusionprocess within the electrodes and 119877119904 is the solution resistance[32ndash36] The Nyquist plots exhibit identical electrochemicalbehaviors with semicircles in the high-frequency region anda straight sloping line at low frequencies The semicirclein the high-to-medium frequency region is related to thesolidelectrolyte interphase (SEI) layer resistance (1198771) andthe semicircle at medium frequency is related to the chargetransfer resistance (119877119888119905 = 1198772 + 1198773) The EIS data forvarious electrodes used in LIBs are listed in Table 2 119877119904 forall electrodes are increased after 10th discharging becauseof continuous SEI formation on the surface of the particles[34 35] The 119877ct values of the LIBs with the fresh NCANCA-Mn andNCA-Ti electrodes are 1919 1592 and 1242Ωrespectively while the corresponding values after 10 cyclesare 3579 3008 and 2384Ω Moreover it can be observedthat the NCA-Ti electrode has the smallest SEI film resistance

(1198771) This suggests that the NCA-Ti electrode has superiorelectrochemical properties and allows for rapid electrontransport during the electrochemical Li+ insertionextractionreaction [32 33]The EIS results agree well with the electricalconductivity (Figure 4(b)) and discharge behavior (Figure 6)

4 Conclusions

NCA cathode materials were successfully prepared by ahydrothermal reaction and their electrochemical propertieswere improved by doping with the transition metals Mn andTi In particular the Ti-doped cathode material (NCA-Ti)had a good crystalline structure and showed higher electricalconductivity than the other sample materials In additionthe NCA-Ti electrode exhibited enhanced electrochemicalperformance NCA-Ti showed the best discharge capacity of1796mAh gminus1 after the first cycle and an initial coulombicefficiency of 886

Conflicts of Interest

The authors declare that there are no conflicts of interestregarding the publication of this paper

8 Journal of Nanomaterials

Acknowledgments

This work was funded by the MOTIEKIAT [R0004144development of high energy density cathode materials fordischarge capacity 215mAhg or more] Also this researchwas supported by Basic Science Research Program throughthe National Research Foundation of Korea (NRF) funded bythe Ministry of Education (2017R1D1A1B03028311)

References

[1] Y Fu and A Manthiram ldquoCore-shell structured sulfur-polypyrrole composite cathodes for lithium-sulfur batteriesrdquoRSC Advances vol 2 pp 5927ndash5929 2012

[2] M S Whittingham ldquoLithium batteries and cathode materialsrdquoChemical Review vol 10 pp 4271ndash4302 2004

[3] N Leifer O Srur-Lavi I Matlahov B Markovsky D Aurbachand G Goobes ldquoLiNi08Co015Al005O2 Cathode material newInsights via 7Li and 27Al magic-angle spinning NMR spec-troscopyrdquoChemistry of Materials vol 28 no 21 pp 7594ndash76042016

[4] E M Jin G E Lee B K Na and S M Jeong ldquoElectrochemicalproperties of commercial NCA Cathode materials for highcapacity of lithium ion batteryrdquo Korean Chemical EngineeringResearch vol 55 pp 163ndash169 2017

[5] F chipper E M Erickson C Erk J Y Shin F F Chesneauand D Aurbacha ldquoReviewmdashrecent advances and remainingchallenges for lithium ion battery CathodesI Nickel-RichLiNi119909Co119910Mn119911O2rdquo Journal of The Electrochemical Society vol164 no 1 pp A6220ndashA6228 2017

[6] D L Vu and J W Lee ldquoProperties of LiNi08Co01Mn01O2 as ahigh energy cathode material for lithium-ion batteriesrdquo KoreanJournal of Chemical Engineering vol 33 no 2 pp 514ndash526 2016

[7] J Y Lee S H Shin and S H Moon ldquoFlame retardant coatedpolyolefin separators for the safety of lithium ion batteriesrdquoKorean Journal of Chemical Engineering vol 33 pp 285ndash2892016

[8] S H Park K S Park Y K Sun K S Nahm Y S Lee andM Yoshio ldquoStructural and electrochemical characterization oflithium excess and Al-doped nickel oxides synthesized by thesolndashgel methodrdquo Electrochimica Acta vol 46 pp 1215ndash12222001

[9] X Li Z Xie W Liu W Ge H Wang and M Qu ldquoEffects offluorine doping on structure surface chemistry and electro-chemical performance of LiNi08Co015Al005O2rdquo ElectrochimicaActa vol 174 pp 1122ndash1130 2015

[10] B Huang X Li ZWang et al ldquoEnhanced electrochemical per-formance in LiNi08Co015Al005O2 cathode material ResultingfromMn-surface-modification using a facile oxidizingndashcoatingmethodrdquoMaterials Letters vol 115 pp 49ndash52 2014

[11] S U Woo C S Yoon K Amine I Belharouak and Y KSun ldquoSignificant Improvement of Electrochemical Performanceof AlF3-Coated Li [ Ni08Co01Mn01] O2 Cathode MaterialsrdquoJournal of The Electrochemical Society vol 154 pp A1005ndashA1009 2007

[12] Y Chen Q Jiao L Wang et al ldquoSynthesis and characterizationof Li105Co13Ni13Mn13O195X005 (X = Cl Br) cathode materi-als for lithium-ion batteryrdquo Comptes Rendus Chimie vol 16 pp845ndash849 2013

[13] W Luo F Zhou X Zhao Z Lu X Li and J R DahnldquoSynthesis Characterization and Thermal Stability of

LiNi13Mn13Co13minus119911minusMg119911O2 LiNi13minus119911Mn13Co13Mg119911O2 andLiNi13Mn13minuszCo13MgzO2rdquo Chemistry of Materials vol 22pp 1164ndash1172 2010

[14] P Yue Z Wang X Li et al ldquoThe enhanced electrochemicalperformance of LiNi06Co02Mn02O2 cathode materials by lowtemperature fluorine substitutionrdquo Electrochimica Acta vol 95pp 112ndash118 2013

[15] B Huang X Lin Z Wang H Guo and X Xiong ldquoSynthesis ofMg-doped LiNi08Co015Al005O2 oxide and its electrochemicalbehavior in high-voltage lithium-ion batteriesrdquo Ceramics Inter-national vol 40 pp 13223ndash13230 2014

[16] W Hua J Zhang Z Zheng et al ldquoNa-doped Ni-richLiNi05Co02Mn03O2 cathode material with both high ratecapability and high tap density for lithium ion batteriesrdquoDaltonTransactions vol 43 pp 14824ndash14832 2014

[17] M N Ates Q Jia A Shah A Busnaina S Mukerjee and K MAbraham ldquoMitigation of layered to spinel conversion of a Li-Rich Layeredmetal oxide cathodematerial for Li-Ion batteriesrdquoJournal of The Electrochemical Society vol 161 no 3 pp A301ndashA301 2014

[18] Z Q Deng and A Manthiram ldquoInfluence of Cationic Substitu-tions on the Oxygen Loss and Reversible Capacity of Lithium-Rich Layered Oxide Cathodesrdquo Journal of Physical Chemistry Cvol 115 no 14 pp 7097ndash7103 2011

[19] H Chen J A Dawson and J H Harding ldquoEffects of cationicsubstitution on structural defects in layered cathode materialsLiNiO2rdquo Journal of Materials Chemistry A vol 2 pp 7988ndash7996 2014

[20] B Huang X Li Z Wang and H Guo ldquoA facile process forcoating amorphous FePO4 onto LiNi08Co015Al005O2 and theeffects on its electrochemicalrdquo Materials Letters vol 131 pp210ndash213 2014

[21] C T Hsieh H H Hsu J P Hsu Y F Chen and J K ChangldquoInfrared-assisted synthesis of lithium nickel cobalt aluminaoxide powders as electrode material for lithium-ion batteriesrdquoElectrochimica Acta vol 206 pp 207ndash216 2016

[22] S Myung S Komaba K Hosoya N Hirosaki Y Miuraand N Kumagai ldquoSynthesis of LiNi05Mn05minus119909Ti119909O2 by anEmulsion Drying Method and Effect of Ti on Structure andElectrochemical Propertiesrdquo Chemistry of Materials vol 17 no9 pp 2427ndash2435 2005

[23] T Ohzuku A Ueda and M Nagayama ldquoElectrochemistry andStructural Chemistry of LiNiO2(1198773119898) for 4 Volt SecondaryLithium Cellsrdquo Journal of The Electrochemical Society vol 140pp 1862ndash1870 1993

[24] G T K Fey J G Chen V Subramanian and T OsakaldquoPreparation and electrochemical properties of Zn-dopedLiNi08Co02O2rdquo Journal of Power Sources vol 112 pp 384ndash3942002

[25] G X Wang S Zhong D H Bradhurst S C Dou and H KLiu ldquoSynthesis and characterization of LiNiO2 compounds ascathodes for rechargeable lithium batteriesrdquo Journal of PowerSources vol 76 pp 141ndash146 1998

[26] TOhzuku AUedaMNagayama Y Iwakoshi andHKomorildquoComparative study of LiCoO2 LiNi12Co12O2 and LiNiO2 for 4volt secondary lithium cellsrdquo Electrochimica Acta vol 38 no 9pp 1159ndash1167 1993

[27] D Aurbach K Gamolsky B Markovsky et al ldquoStudy of surfacephenomena related to electrochemical lithium intercalationinto Li119909MO119910 host materials (M = Ni Mn)rdquo Journal of TheElectrochemical Society vol 147 no 4 pp 1322ndash1331 2000

Journal of Nanomaterials 9

[28] Y Zhang Z BWang J Lei et al ldquoInvestigation on performanceof Li(Ni05Co02Mn03)1minus119909Ti119909O2 cathode materials for lithium-ion batteryrdquoCeramics International vol 41 pp 9069ndash9077 2015

[29] H Xie K Du G Hu Z Peng and Y Cao ldquoThe Roleof Sodium in LiNi08Co015Al005O2 Cathode Material and ItsElectrochemical Behaviorsrdquo Journal of Physical Chemistry Cvol 120 pp 3236ndash3241 2016

[30] H Kondo Y Takeuchi T Sasaki et al ldquoEffects of Mg-substitution in Li(NiCoAl)O2 positive electrode materials onthe crystal structure and battery performancerdquo Journal of PowerSources vol 174 no 2 pp 1131ndash1136 2007

[31] X Li F Kang W Shen and X Bai ldquoImprovement of structuralstability and electrochemical activity of a cathode materialLiNi07Co03O2 by chlorine dopingrdquo Electrochimica Acta vol 53pp 1761ndash1765 2007

[32] C H Chen J Liu M E Stoll G Henriksen D R Vissersand K Amine ldquoAluminum-doped lithium nickel cobalt oxideelectrodes for high-power lithium-ion batteriesrdquo Journal ofPower Sources vol 128 no 2 pp 278ndash285 2004

[33] G Peng X Yao H Wan et al ldquoJournal of Power SourcesrdquoInsights on the fundamental lithium storage behavior of all-solid-state lithium batteries containing the LiNi08Co015Al005O2cathode and sulfide electrolyte vol 307 pp 724ndash730 2016

[34] GQian LWang Y Shang et al ldquoPolyimide binder a facile wayto improve safety of lithium ion batteriesrdquo Electrochimica Actavol 187 pp 113ndash118 2016

[35] Q C Zhuang X Y Qiu S D Xu Y H Qiang and S G SunDiagnosis of Electrochemical Impedance Spectroscopy in Lithium-Ion Batteries Chapter 8 2012

[36] J Huang Z Li H Ge and J Zhang ldquoAnalytical solution tothe impedance of electrodeelectrolyte interface in lithium-ionbatteriesrdquo Journal of The Electrochemical Society vol 162 ppA7037ndashA7048 2015

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