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The Influence of Solvents and Salts on the Properties of High-Voltage Cathode Materials

Abstract

Lithium - ion batteries play an increasingly important role in the battery industry and they have become the dominant source of energy in the recent years, especially for portable electronic devices due to their high gravimetric energy density. This article examines the influence of mixtures of solvents with different combinations of lithium salts on the stability of two types of high-voltage cathode materials: LiNi0.5Mn1.5O4 and LiCr0.1Ni0.4Mn1.5O4 produced by a solid phase reaction. These materials were combined with several different electrolytes, cycled at various loads and higher temperature. Various combinations of solvents ethylene carbonate (EC), dimethyl carbonate (DMC) and Tetrahydrothiophene 1.1-dioxide (Sulfolane) were used for these measurements. Salts LiPF6 , LiNO3 and LiTFSI were used. The influence of solvents and salts on the properties of high-voltage cathode materials was tested by cycling at different current loads and by cycling at high temperature. It was found out, by LSV analysis, that the addition of Sulfolane increases the stability of electrolyte. The addition of chromium to the cathode material LiNi0.5Mn1.5O4 causes increasing of capacity and stability at high temperature. The combination of the cathode material LiCr0.1Ni0.4Mn1.5O4 with the electrolyte 1.5 M LiPF6 EC:DMC:Sulfolane 1:2:1 w/w/w leads to increased stability in comparison with other electrolytes.

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The Influence of Solvents and Salts on the Properties of High-Voltage Cathode Materials

Author: Kazda, Tomáš; Vondrák, Jiří; Sedlaříková, Marie; Gómez-Romero, Pedro; Musil, Michal; Čudek, Pavel; Straková Fedorková, Andrea; Kašpárek, Vít
Publisher: ESG
Year: 2015
Source: https://dspace.vut.cz/bitstreams/6ec28b97-7788-4b93-980b-379dfd05d158/download
In . J. Elec ochem. Sci., 10 (2015) 6288 - 6301
In e na ional Jou nal o
ELECTROCHEMICAL
SCIENCE
www.elec ochemsci.o g
The In luence o Sol en s and Sal s on he P ope ies o High-
Vol age Ca hode Ma e ials
T. Kazda1,*, J. Vond ák1, M. Sedlaříko á1, P.Gómez-Rome o 2, M. Musil1,P Čudek1,
A. Fedo ko á S ako á1 and V. Kašpá ek3
1 Depa men o Elec ical and Elec onic Technology, Facul y o Elec ical Enginee ing and
Communica ion, BUT, Technická 10, 616 00 B no, Czech Republic
2 Ins i u Ca alà de Nanociència y Nano ecnologia, ICN2 (CSIC-ICN), Consejo Supe io de
In es igaciones Cien í icas, Campus UAB 08193, Bella e a (Ba celona), Spain
3 CEITEC BUT, B no Uni e si y o Technology, Technicka 10, 616 00 B no, Czech Republic
*E-mail: [email p o ec ed]c. u b .cz
Recei ed: 22 Ma ch 2015 / Accep ed: 29 May 2015 / Published: 24 June 2015
Li hium - ion ba e ies play an inc easingly impo an ole in he ba e y indus y and hey ha e
become he dominan sou ce o ene gy in he ecen yea s, especially o po able elec onic de ices
due o hei high g a ime ic ene gy densi y. This a icle examines he in luence o mix u es o
sol en s wi h di e en combina ions o li hium sal s on he s abili y o wo ypes o high- ol age
ca hode ma e ials: LiNi0.5Mn1.5O4 and LiC 0.1Ni0.4Mn1.5O4 p oduced by a solid phase eac ion. These
ma e ials we e combined wi h se e al di e en elec oly es, cycled a a ious loads and highe
empe a u e. Va ious combina ions o sol en s e hylene ca bona e (EC), dime hyl ca bona e (DMC)
and Te ahyd o hiophene 1.1-dioxide (Sul olane) we e used o hese measu emen s. Sal s LiPF6 ,
LiNO3 and LiTFSI we e used. The in luence o sol en s and sal s on he p ope ies o high- ol age
ca hode ma e ials was es ed by cycling a di e en cu en loads and by cycling a high empe a u e. I
was ound ou , by LSV analysis, ha he addi ion o Sul olane inc eases he s abili y o elec oly e.
The addi ion o ch omium o he ca hode ma e ial LiNi0.5Mn1.5O4 causes inc easing o capaci y and
s abili y a high empe a u e. The combina ion o he ca hode ma e ial LiC 0.1Ni0.4Mn1.5O4 wi h he
elec oly e 1.5 M LiPF6 EC:DMC:Sul olane 1:2:1 w/w/w leads o inc eased s abili y in compa ison
wi h o he elec oly es.
Keywo ds: Li hium ion ba e y, LiNi0.5Mn1.5O4, elec oly e, sul olane
1. INTRODUCTION
Highe ol age ma e ials a e mos ly based on ma e ial LiMn2O4. I is i s spinel s uc u e ha
makes i mo e s able han LiCoO2. This ma e ial is less oxic because o he use o Mn, i has low
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exo he mic co up ion. I s speci ic capaci y is ~ 120 mAh/g and he ol age agains li hium is 4 V.[1-3]
I one ou h o manganese is subs i u ed by nickel, his ma e ial can be cha ged up o 5 V and he
ol age agains li hium abou 4.7 V. This ol age is he e o e abou 1 V mo e han by o he commonly
used ma e ials oday.[1-2] The heo e ical capaci y o LiNi0.5Mn1.5O4 ma e ial is ~ 147 mAh/g. I s
ene gy densi y is 700Wh/kg due o i s capaci y and high ol age which is app oxima ely 20% highe
han LiCoO2 and 30% highe han LiFePO4.[4] The ma e ial emains s able du ing cycling and handles
well by highe cu en loads hanks o he spinel s uc u e. This ca hode ma e ial eaches he high
ol age using se e al oxida ion s eps a which he e occu s con e sion
LiNi0.5IIMn1.5IIIO4/Ni0.5IVMn1.5IVO4. Mn3+ oxidizes o Mn4+ a 4 V s Li and subsequen ly Ni2+ is
oxidized o Ni3+ a he ol age ange 4.7 – 4.8 V s Li and hen o Ni4+.[5,6] The esul o hese
successi e changes o alence o nickel is joining wo discha ge pla eaus in one e y s able discha ge
pla eau. Two ypes o ca hode ma e ials (LiNi0.5Mn1.5O4 and i s modi ica ion LiC 0.1Ni0.4Mn1.5O4)
we e chosen o he expe imen in his a icle hanks o hese p ope ies. The Modi ica ion o he
ma e ial LiNi0.5Mn1.5O4 using ch omium is used o inc ease he s abili y o he ca hode ma e ial du ing
cycling and highe loads. [1,7-11] C is mos o en a pa ial eplacemen o Ni du ing he p ocess o
doping LiNi0.5Mn1.5O4 by ch omium. The ionic adius o C +3 is 0.615 Å which is close o he ionic
adius o Ni+2 (0.65 Å). This pa ial subs i u ion – o example in LiC 0.05Ni0.45Mn1.5O4 - leads o he
imp o ed elec ochemical p ope ies due o highe s eng h o he bond C -O han he bond be ween
Ni- and Mn-O. This s onge C -O bond leads o an inc ease in he s eng h o he s uc u e and
main ains i s p ope ies du ing long e m cycling e en a highe loads. [1,7,8] The modi ica ion
LiC 0.05Ni0.45Mn1.5O4 o al e na i ely LiC 0.2Ni0.4Mn1.4O4 a e mos equen ly men ioned in scien i ic
a icles. [8-11] The modi ica ion LiC 0.1Ni0.4Mn1.5O4 was chosen o his a icle o e i y whe he
doping by C in a speci ic a io can imp o e he ma e ial p ope ies. The main pa o his a icle
ocuses on in es iga ion o he e ec o u ilized elec oly es on he elec ochemical p ope ies o hese
wo ca hode ma e ials. EC (e hylene ca bona e), DMC (dime hyl ca bona e) and sul olane we e chosen
as sol en s. EC and DMC a e commonly used as sol en s and sul olane was chosen because o i s
highe he mal s abili y and i was also expec ed i would be mo e s able a highe ol ages.[12] LiPF6,
LiNO3 and LiTFSI we e chosen as sal s. The LiNO3 sal was selec ed o he assump ion ha i s
addi ion in o he mix will inc ease he s abili y o he elec oly e. LiTFSI is used as a s able sal o Li-
S ba e ies and i was chosen o he alida ion o he s abili y o hese ca hode ypes. [13]
2. EXPERIMENTAL
The me hod o eac ion in solid s a e was chosen o he p oduc ion o his ma e ial. P ecu so s
based on ca bona es and oxides we e chosen as basic ma e ials o he p oduc ion. Li2CO3 (Li hium(II)
ca bona e), MnCO3 (Manganese ca bona e), NiO (Nickel oxide) and C 2O3 (Ch omium(III) oxide)
we e chosen in ou case; hese ma e ials we e mixed in a s oichiome ic a io o 0.02 mol/l. The wo-
s ep annealing p ocess was selec ed o he p epa a ion. Selec ed p ecu so s a e milled oge he o 4h
du ing he i s s ep o his p ocess. In he i s annealing s ep, he esul an mix u e is annealed a 600
°C o 10h. The second s ep is annealing a 900 °C o 15h. [14] A e his syn hesis we ob ain
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ma e ials wi h ace-cen e ed spinel s uc u e he e o e known as diso de ed. The p epa ed ma e ial was
hen mixed in o a mix u e consis ing o NMP (N-Me hyl-2-py olidon) (sol en ), PVDF
(Poly inyliden luo id) (binde ) and ca bon Supe P. The weigh a io o he ma e ials was: ac i e
ma e ial 80%, Supe P 10%, PVDF 10%. The esul ing mix u e was subsequen ly deposi ed on an Al
oil, d ied and p essed by he p essu e o 3200 kg/cm2. A disk wi h a diame e o 18 mm was cu ou
o he coa ed aluminium oil and inse ed in o he elec ochemical es cell El-Cell© ECC-STD. The
assembly was done in a glo e box illed wi h a gon a mosphe e. Me al Li hium was used as a ma e ial
o he anode and he elec oly e was soaked in a glass ib e sepa a o .
1 M LiPF6 EC:DMC 1:1 w/w, 1.5 M LiPF6 EC:DMC 1:2 w/w, 1.5 M LiPF6 + 0.1 M LiNO3
EC:DMC 1:2 w/w, 1.5 M LiPF6 EC:DMC:Sul olane 1:2:1 w/w/w, 1.5 M LiPF6
+ 0.1 M LiNO3 EC:DMC:Sul olane 1:2:1 w/w/w, 0.75 M LiTFSI + 0.1 M LiNO3 EC:DMC 1:2 w/w
and 0.75 M LiTFSI + 0.1 M LiNO3 EC:DMC:Sul olane 1:2:1 w/w/w we e used as elec oly es.
Linea Sweep Vol amme y (LSV) was used o es ing o he s abili y o elec oly es in he
ol age window om 3.0 o 5.2 V e sus li hium. Scan a e was se o 5 mV/s and 1 mV/s.
Gal anos a ic cycling was used o measu ing elec odes wi h di e en elec oly es; he po en ial
window was se om 3.0 o 5.1 V e sus li hium. Two cycles o cha ging and discha ging ha e always
been ca ied ou du ing which he used cha ging and discha ging cu en s we e 0.5 C (calcula ed om
he weigh o he deposi ed ma e ial p o ided ha he capaci y o he ma e ial is 120 mAh/g). The eal
alue o capaci y o he sample was deduc ed om hese wo cycles and he sample was hen
exposu ed o long e m cycling du ing which i was cycled en imes by 0.5 C cu en . I was
subsequen ly cycled i e imes by 1 C cu en , hen i e imes by 2 C cu en and hen i e imes by
5 C cu en . Nex s ep was cycling again i e imes by 2 C cu en , again i e imes by 1 C cu en ,
again i e imes by 0.5 C cu en , and inally he e we e en cycles by 0.5 C cu en a he empe a u e
o 50 °C. SEM mic oscope TESCAN VEGA3 XMU whi B uke EDAX analyze was used o
de e mine he dis ibu ion o he elemen s in he ma e ials. TGA analysis was used o he compa ison
o s uc u al s abili y o he syn hesized ca hode ma e ial.
3. RESULTS AND DISCUSSION
I is e iden ha he decomposi ion o elec oly es wi h sal s LiTFSI and LiNO3 occu s a e
exceeding o 3.7 V when compa ing wi h he cu es in Fig. 1. The elec oly e 1.5 M LiPF6 EC:DMC
1:2 showed lowe s abili y om he o he elec oly es. The s abili y o he elec oly e was inc eased
a e he addi ion o sal LiNO3 and i was e en be e a e he addi ion o Sul olane. The elec oly e
1.5 M LiPF6 EC:DMC:Sul olane 1:2:1 appea ed o be he mos s able. The LSV a a scan a e o
1 mV/s is shown in Fig. 2. I is e iden om hese g aphs ha he lowes s abili y again exhibi he
elec oly es wi h he sal mix u e o LiTFI and LiNO3. Be e s abili y was again disco e ed, like in he
p e ious measu emen , a e he addi ion o LiNO3 sal in o he elec oly e 1.5 M LiPF6 EC:DMC 1:2.
1.5 M LiPF6 EC:DMC:Sul olane 1:2:1 seems o be he mos s able elec oly e again. The elec oly es
wi h a mix u e o LiTFI and LiNO3 sal s we e disca ded o he nex measu emen s o he p ope ies o
ca hode ma e ials wi h di e en elec oly es due o hei high ins abili y. A simila ins abili y in he
In . J. Elec ochem. Sci., Vol. 10, 2015
6291
egion abo e 4 V was shown also by he commonly used elec oly e 1 M LiPF6 EC: DMC 1:1 which is
e iden a bo h scan a es. Fo his eason, he con en ional elec oly e 1 M LiPF6 EC: DMC 1:1 was
excluded om he nex measu emen .
-0.05
0.00
0.05
0.10
0.15
0.20
0.25
2.5 3.0 3.5 4.0 4.5 5.0 5.5
I [mA/cm2]
UWE [V]
1.5M LiPF₆ EC:DMC 1:2
1.5M LiPF₆ EC:DMC:Sul olane 1:2:1
1.5M LiPF₆+ 0.1 M LiNO₃ EC:DMC
1.5M LiPF₆+ 0.1M LiNO₃ EC:DMC:Sul olane
0.75M LiTFSI+ 0.1M LiNO₃ EC:DMC
0.75M LiTFSI+ 0.1M LiNO₃ EC:DMC:Sul olane
1M LiPF₆ EC:DMC 1:1
Figu e 1. LSV cu es o hal -cells using di e en elec oly es a he scan a e o 5 mV/s. The wo king
elec ode used in he hal -cells is Al
-0.05
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
2.5 3.0 3.5 4.0 4.5 5.0 5.5
I [mA/cm2]
UWE [V]
1.5M LiPF₆ EC:DMC 1:2
1.5M LiPF₆ EC:DMC:Sul olane 1:2:1
1.5M LiPF₆+ 0.1 M LiNO₃ EC:DMC
1.5M LiPF₆+ 0.1M LiNO₃ EC:DMC:Sul olane
0.75M LiTFSI+ 0.1M LiNO₃ EC:DMC
0.75M LiTFSI+ 0.1M LiNO₃ EC:DMC:Sul olane
1M LiPF₆ EC:DMC 1:1
Figu e 2. LSV cu es o hal -cells using di e en elec oly es a he scan a e o 1 mV/s. The wo king
elec ode used in he hal -cells is Al
The ma e ials LiNi0.5Mn1.5O4 and LiC 0.1Ni0.4Mn1.5O4 we e analysed using SEM mic oscopy.
We can see s uc u es o bo h syn hesised ma e ials in Fig. 3, he ield o iew o bo h samples is 41.5
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6292
μm. I is possible o obse e he c ys al s uc u e o syn hesized samples in bo h cases. We can see ha
he c ys al size o he ma e ial LiC 0.1Ni0.4Mn1.5O4 is somewha smalle han in he ma e ial
LiNi0.5Mn1.5O4.
Figu e 3. SEM analysis o he samples A) LiNi0.5Mn1.5O4 and B) LiC 0.1Ni0.4Mn1.5O4 iew ield used -
41.5μm
The las analysis ca ied ou on samples LiNi0.5Mn1.5O4 and LiC 0.1Ni0.4Mn1.5O4 was EDX
analysis o hei composi ion. Resul s o bo h ma e ials a e shown in Fig. 4. As shown in Fig. 4-1) he
dis ibu ion o elemen s in he ma e ial is uni o m and he esul ing ma e ial con ains oxygen, nickel
and manganese. Fig. 4-2) shows he esul o EDX analysis o he sample LiC 0.1Ni0.4Mn1.5O4, i is
again e iden ha , like in he ma e ial LiNi0.5Mn1.5O4, uni o m dis ibu ion o elemen s on he su ace
o he sample was achie ed, and he e a e nickel, oxygen, manganese and ch omium.
Figu e 4. Mapping o he sample o 1) LiNi0.5Mn1.5O4 A) SEM pa icles LiNi0.5Mn1.5O4 B)
dis ibu ion o oxygen C) dis ibu ion o manganese D) dis ibu ion o nickel 2)
LiC 0.1Ni0.4Mn1.5O4 A) SEM pa icles LiC 0.1Ni0.4Mn1.5O4 B) dis ibu ion o oxygen C)
dis ibu ion o manganese D) dis ibu ion o nickel E) dis ibu ion o ch omium

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The s uc u al s abili y o he ca hode ma e ials LiNi0.5Mn1.5O4 and LiC 0.1Ni0.4Mn1.5O4 was
in es iga ed by he mal analysis (Fig. 5).
95
96
97
98
99
100
101
0200 400 600 800 1000
Weigh loss [%]
Tempa a u e [ C]
O₄
₄ O₄
Figu e 5. TGA analysis o he samples A) LiNi0.5Mn1.5O4 and B) LiC 0.1Ni0.4Mn1.5O4
-1000
-800
-600
-400
-200
0
200
400
600
800
1000
3.8 4 4.2 4.4 4.6 4.8 5
I [mA/g]
UWE [V]
LiNi0.5Mn1.5O4
Mn3+ → 4+
Ni2+ → 3+
Ni3+ → 4+
Ni3+ ← 4+
Ni2+ ← 3+
Mn3+ ← 4+
a)
-800
-600
-400
-200
0
200
400
600
800
3.8 4 4.2 4.4 4.6 4.8 5
I [mA/g]
UWE [V]
LiC 0.1Ni0.4Mn1.5O4
Mn3+ → 4+
Ni2+ → 3+
Ni3+ → 4+
C 2+ ← C 3+
Ni3+ ← 4+
Ni2+ ← 3+
Mn3+ ← 4+
b)
Figu e 6. CV o a) LiNi0.5Mn1.5O4 b) LiC 0.1Ni0.4Mn1.5O4 and alence changes ongoing du ing cycling.
Hal -cell whi elec oly e 1.5 M LiPF6 EC:DMC 1:2 a he scan a e o 0.5 mV/s.
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6294
TGA analysis was pe o med in he empe a u e ange om oom empe a u e o 900 °C and
he empe a u e was inc eased a 10 °C/min a e. I is e iden ha he la ges weigh loss was obse ed
in he ange be ween 600 °C o 900 °C. This d op o weigh is caused by losing o oxygen and li hium
om he ca hode ma e ial s uc u e. [15] Ma e ial wi h C exhibi s he highes s abili y du ing hea ing.
Adding o ch omium caused s abiliza ion o he s uc u e o he ca hode ma e ial which leads o a
signi ican s abiliza ion o weigh in compa ison wi h he p is ine ma e ial.
We can see CV o bo h ypes o high- ol age ca hode ma e ials (LiNi0.5Mn1.5O4 and
LiC 0.1Ni0.4Mn1.5O4) used in combina ions wi h 1.5 M LiPF6 EC:DMC 1:2 elec oly e in Fig. 6. The
peaks co esponding o he changes o alence ongoing in hese ma e ials a e isible in he cha s.
The e is an e iden edox peak o abou 4 V in bo h ca hode ma e ials which is caused by he change in
he alence o Mn3+ o Mn4+ and back. This peak is mo e signi ican in he case o he ma e ial
LiC 0.1Ni0.4Mn1.5O4 whe e i leads o an inc ease o he 4 V discha ge pla eau. We can see edox peaks
ela ed o he change o he oxida ion s a e o nickel in bo h ca hode ma e ials. In he ma e ial
LiC 0.1Ni0.4Mn1.5O4, we can ano he educ ion peak co esponding o he change in he alence o
ch omium a abou 4.85 V.
We can see a compa ison o he wo discha ge cycles o he ma e ials LiNi0.5Mn1.5O4 and
LiC 0.1Ni0.4Mn1.5O4 in Fig. 7. I is e iden om hese cu es ha he ma e ial LiC 0.1Ni0.4Mn1.5O4 has a
sligh ly highe discha ge pla eau due o he inco po a ion o ch omium in i s s uc u e and i s s eepe
decline due o he la ge spacing o changes in he alence o nickel. This ma e ial also shows a g ea e
pla eau a 4 V. This change is also caused by ch omium doping which leads o g ea e change in he
alence o manganese. These changes co espond wi h he da a ob ained by using CV.
2.5
3.0
3.5
4.0
4.5
5.0
5.5
020 40 60 80 100 120 140
UWE [V]
Capaci y [mAh/g]
O₄
₄ O₄
Figu e 7. Compa ison o i s discha ge cu es o Li/LiNi0.5Mn1.5O4 (do -dash line)
and Li/LiC 0.1Ni0.4Mn1.5O4 (blue line) in hal -cells a 0.5 C using
he 1.5 M LiPF6 EC:DMC 1:2 elec oly e
Fig. 8 shows he cycling o he ma e ial LiNi0.5Mn1.5O4 in combina ion wi h di e en
elec oly es a di e en loads. I is e iden ha all ou samples achie e simila capaci ies o abou 112
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6295
mAh / g du ing he i s 10 cycles a 0.5C and he mos s able sample seems be he elec oly e
1.5M LiPF6 EC:DMC 1:2 which eached 100.5 % o he capaci y o he i s cycle in he en h cycle.
The leas s able was he sample wi h he elec oly e 1.5M LiPF6 + 0.1M LiNO3 EC:DMC:Sul olane
1:2:1 which los 2.3 % o i s capaci y in he i s cycle a e en cycles. Di e en declines o capaci y
can be seen o ca hode ma e ials wi h di e en elec oly es du ing nex cycling a highe loads up o
5 C. The ma e ial LiNi0.5Mn1.5O4 wi h he elec oly e 1.5M LiPF6 EC:DMC 1:2 appea s o be he mos
s able one eaching 89.2 % o he capaci y om he i s cycle a he end o cycling a 5 C (99.5
mAh/g) ollowed by he sample wi h he elec oly e 1.5M LiPF6 EC:DMC:Sul olane 1:2:1 which
eached 82.2 % capaci y hus 92.1 mAh/g. I we compa e hese esul s wi h he esul s which we e
epo ed in he p e ious a icle [16] we can see ha bo h he capaci y and he s abili y achie ed du ing
cycling in he expe imen desc ibed in he pape a e highe han hose in he case o using a s anda d
elec oly e 1M LiPF6 EC: DMC (1: 1) and he o e all esul s a e be e han he ones achie ed in he
case o using sal LiBOB. We can see simila esul s in compa ison wi h he da a om he a icle [17]
in his a icle he au ho again epo ed lowe capaci ies in all es ed C- a es in he case o s anda d
elec oly e 1M LiPF6 EC: DMC (1: 1). In his a icle he e is also epo ed inc ease o achie ed
capaci ies in he case o use o he elec oly e wi h addi ion o Sul olane bu he eached capaci y and
s abili y a e again lowe han he ones achie ed in ou measu emen s. The highes dec ease was
eco ded o he ma e ial wi h elec oly e LiPF6 + 1.5M 0.1M LiNO3 EC:DMC:Sul olane 1:2:1 which
a he end o cycling a 5 C had 72.8 % o he capaci y om he i s cycle, hus 81.8 mAh/g. The load
was a e wa ds educed again o he alue o 0.5 C. Fi e cha ge and discha ge cycles we e ca ied ou
by his load, ollowed by cycling a 50 °C.
0
20
40
60
80
100
120
010 20 30 40 50
Q discha ge [mAh/g]
Cycle numbe
LiNi0.5Mn1.5O4
1.5M LiPF₆ EC:DMC 1:2
1.5M LiPF₆ EC:DMC:Sul olane 1:2:1
1.5M LiPF₆+ 0.1 M LiNO₃ EC:DMC 1:2
1.5M LiPF₆+ 0.1M LiNO₃ EC:DMC:Sul olane 1:2:1
0.5 C
1 C5 C
2 C2 C1 C0.5 C0.5 C -50°C
Figu e 8. Compa ison o capaci y change depending on load and empe a u e changes o he ma e ial
LiNi0.5Mn1.5O4 wi h di e en elec oly es
In . J. Elec ochem. Sci., Vol. 10, 2015
6296
The ca hode ma e ial wi h he highes capaci y in he las cycle a 0.5 C a oom empe a u e
was he one wi h he elec oly e 1.5M LiPF6 EC:DMC 1:2 ha a e o y cycles a di e en loads los
2.1 % o he capaci y om he i s cycle. I was ollowed by he sample wi h elec oly e
1.5M LiPF6 EC:DMC:Sul olane 1:2:1 which los 5.8 % o i s capaci y in compa ison wi h he i s
cycle. The highes dec ease was obse ed in he sample wi h elec oly e 1.5M LiPF6 + 0.1M LiNO3
EC:DMC:Sul olane 1:2:1 which capaci y dec eased by 8.1 %. The dec ease o capaci y can be seen o
all samples du ing cycling a 50 °C. This is e y signi ican o he samples wi h elec oly e con aining
LiNO3 and he cell p ac ically s ops wo king. The mos s able ma e ial is he one wi h elec oly e
1.5M LiPF6 EC:DMC 1:2 whe e he dec ease o he capaci y is g adual and om he six h cycle he
capaci y s abilizes. The capaci y o his sample a he end o he cycling was 88.5 % o he capaci y
om he i s cycle. The cycling o he sample wi h elec oly e 1.5M LiPF6 EC:DMC:Sul olane 1:2:1
p o ided simila esul s. The capaci y was somewha lowe - i was equal o 78.4 % o he capaci y in
he i s cycle a he end o cycling a 50°C.
0
20
40
60
80
100
120
140
010 20 30 40 50
Q discha ge [mAh/g]
Cycle numbe
LiC 0.1Ni0.4Mn1.5O4
1.5M LiPF₆ EC:DMC 1:2
1.5M LiPF₆ EC:DMC:Sul olane 1:2:1
1.5M LiPF₆+ 0.1 M LiNO₃ EC:DMC 1:2
1.5M LiPF₆+ 0.1M LiNO₃ EC:DMC:Sul olane 1:2:1
0.5 C
1 C5 C
2 C2 C1 C0.5 C0.5 C -50°C
Figu e 9. Compa ison o capaci y change depending on load and empe a u e changes in ma e ials
LiC 0.1Ni0.4Mn1.5O4 wi h di e en elec oly es
Fig.9 shows he cycling o he ma e ial LiC 0.1Ni0.4Mn1.5O4 in combina ion wi h di e en
elec oly es a di e en loads simila ly as in he case o ma e ial LiNi0.5Mn1.5O4. Ma e ial
LiC 0.1Ni0.4Mn1.5O4 showed highe capaci y han LiNi0.5Mn1.5O4 du ing he i s en cycles. Thei
capaci y was a ound 130 mAh/g in he case o he elec ode an elec oly e o which did no con ain he