View
225
Download
0
Category
Preview:
Citation preview
8/16/2019 Nikita Project 01-06-2016
1/38
REVIEW OF HIGH ENERGY CATHODE MATERIALSFOR NEXT GENERATION ENERGY STORAGE DEVICES
submitted in partial fulfillment of the requirements for the degree of
Master of Science
In
Chemistry
by
NIKITA YADAV
(Roll No. 14!"!#!1$%
Under the supervision of
Dr. D. AR&M&'AM
Assistant rofessor
to the
De)artment of A))lie* Science an* +,manities
INV-RTIS &NIV-RSITY
In/ertis /illa0e areilly 2 3,cno5 +i0h5ay 2 4 areilly 4616
(&..% INDIA
May2 !17
1
8/16/2019 Nikita Project 01-06-2016
2/38
C-RTI8ICAT-
This is to certify that Miss. Nikita Yadav is student of M.Sc
(Ch!ist"#$% (R&'' N&.)*+,+-+$ Department of Applied
Science and Humanities, INVERTIS UNIVERSIT, !areilly, Uttar
"radesh# The pro$ect %or& entitled 'Rvi/ &0 hi1h 2"1#
cath&d !at"ia's 0&" 23t 12"ati&2 2"1# st&"a1
dvics (for the partial ful)llment of the de*ree of Mast" &0
Sci2c i2 Ch!ist"##
Date9 Si0nat,re of the S,)er/isor
lace9 areilly
( Dr.D.Ar,m,0am%
Assistant Professor in Chemistry,
Department of Applied Science and Humanities,
INV!"IS UNIV!SI"#,
$areilly % &uc'no( Hi)h(ay%*+,
$areilly % *+-*, Uttar Pradesh,
INDIA
+
8/16/2019 Nikita Project 01-06-2016
3/38
ASTRACT
&i battery is a ener)y stora)e device it applicable for laptop smart phone,
cell phone etc. it play a very si)nificant role in today/s life A carbon%coated plate
li'e &i0eP1+ particle space )roup (as prepared by employin) a hydrothermal
method at -234C. "he obtained particle had a preferred crystal orientation (ith
53*36 te7ture, (hich (as revealed by transmission electron microscopy and
electron diffraction. After the hydrothermal treatment, further heat%treatments at
hi)h temperatures 5+336 58334C6 (ere carried out to increase the electrical
conductivity of the carbon layer, and the conductivity (as considerably improved
by heat%treatment at temperatures hi)her than 9334C. "he obtained &i0eP1+:C
particle e7hibited a hi)h%rate char)e;dischar)e capability in a li:ethylene carbonate ? diethyl carbonate 5-@-6 volume ratio.
"he dischar)e capacity of the particle (as more than -33 mAh )=- at a dischar)e
rate of -3 C. 0urthermore, an all%solid%state cell comprisin) &i:polymer
electrolyte:&i0eP1+ (as fabricated usin) a bloc' copolymer electrolyte consistin)
of polyethylene o7ide and polystyrene, and the char)e;dischar)e performance of
the cell (as e7amined at 34C. In this paper, the speci)c capacities as a
function of dischar*e rate of oer -. di/erent 0ie"2- materials
3
8/16/2019 Nikita Project 01-06-2016
4/38
reported %ere reie%ed and analy4ed# The in5uence of synthesis
route, particle si4e, dopin*, car6on coatin*, and conductie
car6on loadin* on the rate performance %as discussed#
ACKN:;3-D'-M-NT
"his research proBect is made possible throu)h the help and support from everyone,
includin)@ parents, teachers, family, friends, and in essence, all sentient bein)s.
specially, please allo( me to dedicate my ac'no(led)ment of )ratitude to(ard the
follo(in) si)nificant advisors and contributors@
0irst and foremost, I (ould li'e to than' to our Honourable Chancellor, Vice
Chancellor, Pro. vice chancellor for provide the (ell facility for complete of my
.Sc. in Chemistry and my research proBect.
I also than's to Dean and n)ineerin) Prof. !. . Shu'la Ph.D and our H1D Prof.
Shalabh Sa7ena P.hDE for constant support of my completion of thesis.
I (ould li'e to specially than's to our Dr. D. AR&NM&'AM for his most support
and encoura)ement. He 'indly read my proBect and offered invaluable detailed
advices on )rammar, or)aniFation, hand the theme of the proBect
Second, I (ould li'e to sho( my )ratitude to(ards all people (ho help and sho(
their )uidance for completion of this proBect.
-
8/16/2019 Nikita Project 01-06-2016
5/38
And also, I sincerely than' to my parents, family, and friends, (ho provide the
advice and financial support. "he product of this research proBect (ould not be
possible (ithout all of them.
IND-<
C+AT-R C:NT-NT A'- No.
1. Introduction 3-%->
. &iterature Survey -9%-8
6. Aim and Scope of this (or' -2%*-
4. 7perimental **%*G
$. !esults and Discussion *>%+
7. Conclusions G
#. !eferences 9
7
8/16/2019 Nikita Project 01-06-2016
6/38
1. INTR:D&CTI:N
1.1 -lectrochemistry
"he branch of Science (hich deals (ith the relationship bet(een electrical
and chemical ener)y and their inter conversion is called lectrochemistry. "he
device in (hich conversion of electrical ener)y into chemical ener)y is done is
called lectrolyte Cell (hile Jalvanic or Voltaic Cell is a device in (hich redo7
reaction is used to convert chemical ener)y into electrical ener)y. lectrochemistry
is the study of chemical processes that causes electrons to move . "his movements
of electrons is called lectricity, (hich can be )enerated by movements of
electrons from one elements to another in a reaction 'no(n as an o7idation
reduction 5redo76 "he main difference bet(een these t(o cells are in electrolytic
cell, anode is positive electrode (hile cathode is ne)ative electrode. 1n the other
hand , in )alvanic cell, anode is ne)ative electrode and cathode is positive
electrode.
1. atteries Contri=,tion in electrochemistry
8
8/16/2019 Nikita Project 01-06-2016
7/38
In electrochemistry, $atteries play numerous important roles in everyday life.
$atteries also have the potential to help reduce )reenhouse )as emissions by
efficiently storin) electricity )enerated from both conventional and rene(able
ener)y sources and as a sources of po(ers for electric vehicles. $atteries
Application 5a6 Automotive Application@% Start%Stop system, ild, 0ull and in
Hybrid lectric Vehicles 5HV6E 5b6 otive Application@% &ift truc's and handlin),
"rains, ships and aircraftE 5c6 Stationary application@% "elecommunication,
!ene(able ner)y System 5!S6, Jrid Support.
1.6 Classification of atteries
A Cell or battery is basically a )alvanic cell and used (here the chemical ener)y of
redo7 reaction is converted into electrical ener)y. $atteries are classified into t(o
types
- ) rimary atteries -"he batteries are those in (hich the cell reaction occurs
only once and the battery becomes dead after use over a period of time and cannot
be reused a)ain. e.).@% Dry Cell 5 li'e@ &aclanche Cell , ercury Cell 6. a6
&eclanche Cell @ A commercial dry cell containin) of a )raphite 5carbon6 cathode
in a Finc container E the later acts as a anode. b6 ercury Cell @ Here the reducin)
cell is Finc and the o7idiFin) a)ent is mercury 5II6 o7ide.
9
8/16/2019 Nikita Project 01-06-2016
8/38
% Secon*ary atteries - A Secondary cell can be rechar)ed by passin) current
throu)h it in opposite direction , so it can be used a)ain.
a% 3ea* Stora0e attery 2 "he most important secondary cell is lead stora)e
battery , commonly used in automobiles and invertors. b6 Nic'el Cadmium $attery
@% Another important secondary battery is Ni%Cd battery (ith lon)er life but more
e7pensive.
0i)@ Structure of $attery
1.4 3ithi,m attery Contri=,tion in Secon*ary atteries
A rechar)eable battery, stora)e battery, secondary cell, or accumulator is a type
of electrical battery (hich can be char)ed, dischar)ed into a load, and rechar)ed
many times, (hile a non%rechar)eable or primary battery is supplied fully char)ed,
and discarded once dischar)ed. It is composed of one or more electrochemical cell.
"he term KaccumulatorK is used as it accumulates and stores ener)y throu)h a
reversible electrochemical reactions. !echar)eable batteries are produced in many
:
8/16/2019 Nikita Project 01-06-2016
9/38
different shapes and siFes, ran)in) from button cells to me)a(att systems
connected to stabiliFean electrical distribution net(or'. Several different
combinations of electrode materials and electrolytes are used, includin) lead%acid
nic'el cadmium 5NiCd6, nic'el metal hydride5NiH6,lithium ion 5&i%ion6, and
lithium ion polymer 5&i%ion polymer6.
!echar)eable batteries initially cost more than disposable batteries, but have
a much lo( total cost of o(nership and environmental impact, as they can be
rechar)ed ine7pensively many times before they need replacin).
1.$ Classification of 3ithi,m2Ion atteries
"hey are classified into si7 types
a% 3ithi,m Co=alt :>i*e- It is also 'no(n &ithium Cobalt or &ithium ; Ion
Cobalt batteries. &ithium Cobalt o7ide batteries are made from lithium carbonate
and cobalt. Due to their very hi)h capacity , these batteries are used for
cellphones , laptops and electronic cameras. "he battery has a cobalt o7ide cathode
and a )raphite carbon anode E durin) dischar)e , lithium ion move from the anode
to the cathode (ith the flo( reversin) on char)e. Dra(bac's @ It has a shorter
lifespan and a limited specific po(er.
;
https://en.wikipedia.org/wiki/Grid_energy_storagehttps://en.wikipedia.org/wiki/Grid_energy_storage
8/16/2019 Nikita Project 01-06-2016
10/38
=% 3ithi,m Man0anese :>i*e% It is also called &ithium man)anate or &ithium ;
ion man)anese batteries. "hey may also be referred to as &i%an)anese or Spinel.
"he first commercial lithium ion cell made (ith a lithium man)anese o7ide as a
cathode materials. It is safer than other types of &ithium ;ion batteries .0or this
reasons , they are often used in medical ei*e% It is also 'no(n as lithium ;
man)anese% cobalt% o7ide batteries or NC. &ithium nic'el man)anese cobalt
o7ide batteries are made of several materials common in other lithium iron
batteries ."hese involves a cathode combination of nic'el , man)anese and cobalt.
1.
8/16/2019 Nikita Project 01-06-2016
11/38
8/16/2019 Nikita Project 01-06-2016
12/38
Application for these batteries can include military and aerospace uses and they
may also be used for storin) (ind and solar ener)y and creatin) smart )rids#
1.7. Com)onents of 3ithi,m2Ion attery (Ano*e ? Catho*e
-lectrolyte%
K"he three primary functional components of a lithium%ion battery are a positive
and ne)ative electrode and electrolyte. Jenerally, the ne)ative electrode of a
1+
8/16/2019 Nikita Project 01-06-2016
13/38
conventional lithium%ion cell is made from carbon . "he positive electrode is a
metal o7ide, and the electrolyte is a lithium salt in an or)anic solvents.K
1.# Catho*e Materials for 3ithi,m2 Ion attery
Cathode aterials are the main element dictatin) the differences in composition
(hile buildin) positive electrodes for battery cells. "he table belo( brea's do(n
the most commonly used &ithium%ion battery cathode chemistries on the mar'et
into four )roups@ Cobalt, an)anese, NC and Phosphate. 1ne of the challen)es
for improvin) the performance of lithium ion batteries to meet increasin)ly
demandin) re
8/16/2019 Nikita Project 01-06-2016
14/38
family of batteries includes a variety of products that cater to different user needs
for hi)h ener)y density and:or hi)h load capacity.
1." -lectrolytes 8or 3ithi,m2Ion attery
Hi)h purity lithium ion battery electrolytes made (ith &iP0> salt as (ell as
hi)h phosphorus content flame retardant , DP. lectrolytes are available for all
lithium;ion applications from consumer electronic to V cells. "he Principles
advanta)es of our lectrolytes products are as follo(s% Jood cycle life, 7cellent
thermal and hydrolytic stability, Hi)h conductivity, Hi)h dischar)e rate, Jood
performance at hi)h temperatures , Jood performance at lo( temperatures
7cellent anti%overchar)in) performance. &i
8/16/2019 Nikita Project 01-06-2016
15/38
1.@ Se)arator 8or 3ithi,m Ion attery
$attery Separator play an important role in &i%ion battery manufacturin).
1ur Scientist carries &ithium ;ion battery )rade Polypropylene 5PP6 and
Polyethylene 5P6. Separator (hich play a critical role of separatin) the cathode
from the anode. It is the separation of char)e that allo(s the battery to )enerate
electricity. $attery Separator are po(er driven spacers and can be produced (ith
fiber)lass cloth or fle7ible plastics films made from nylon, polyethylene or
polypropylene. It must be absorbant and slim to allo( the char)ed lithium ion to
pass (ithout obstruction and it should ta'e up the minimum of space allo(ed ,
leavin) available apace for the cathode active elements. If the separator brea's
do(n or infiltration, this (ill (ea'en hi)h po(er cells end results. Durin) char)in)
cycle, the positively char)ed lithium ion move from the cathode , throu)h the
separator to the anode. Durin) dischar)e, the positively char)ed lithium ions move
from the anode throu)h the battery separator to the cathode (hile electrons move
throu)h the e7ternal load from the anode to the cathode , resultin) in the current
that provides po(er to the load. "he lithium ion move throu)h the separator via an
electrolyte solution. 0actors to selectin) the ri)ht separators are @ lectronic
insulators, inimal electrolyte ionic resistance, echanical and dimensional
stability, Sufficient physical stren)th to allo( easy handlin), !eadily (etted by
electrolyte, Uniform in thic'ness and other properties, etc...
17
8/16/2019 Nikita Project 01-06-2016
16/38
. 3IT-RAT&R- S&RV-Y!esearch on cathode materials has been continuously studied since early
-2>3/s. "he cathode materials prepared (ere focused mainly on the preparation
method,as (ell as the structural analysis. "hose &iV1+ cathode (here, M Cu ,
Ni, Co, n, Cd, ) and $e are the most cathode materials that have been
synthesiFed usin) various types of techni
8/16/2019 Nikita Project 01-06-2016
17/38
driven the demand of hi)h po(er ener)y sources for li)ht electronics , alternative
materials to avoid the poisonous Pb and Cd for environmental protection . "hus, the
commercialiFation of &ithium battery (as finally achieved in late -283/s. "oday/s
lar)est manufacture for both lithium rechar)eable and nic'el metal hydride
batteries.
"he demand for the lithium ion batteries has created everyone attentions since their
commencement in the mar'et in -22-. "o date, the necessity for portable po(er
sources (ith hi)h ener)y density has tremendously increase due to the
advancement of the portable po(er sources such as cell phones , noteboo',
computers , camcordors and so on. "he famous cathode materials such as &iC1*,
&iNi1* AND &in1* are amon) various transition metal o7ides used in most
reported (or'. Oe also discussin) about NCA Cathode material 5Nic'el%based
Cathode aterials6 @ &iNiCoAl1* "he features of K Hi)h capacity and Hi)h specific
ener)yK in comparison to &ithium cobalt o7ide5&C16. In recent years, even hi)her
capacity &ithium%ion !echar)eable $attery 5&I$6 is re
8/16/2019 Nikita Project 01-06-2016
18/38
1% :)timie* 3i8e:4 2 olyacene Catho*e Materials for 3ithi,m ion attery
1ur scientist Jood%enou)h co%(or'ers reported that the fact that
&i0eP1+ could be used as a cathode material for lithium ion batteries. "hrou)h
different synthetic techni
8/16/2019 Nikita Project 01-06-2016
19/38
6% +y*rothermal Synthesis :f Car=on2Coate* 3i8e:4 an* its a))lication of
3ithi,m olymer attery
Serosatietal have reported that the all%solid state cell
&i:P1:&i0eP1+ can be stably operated for more than -33 char)e%dischar)e cycles
at 23 de)ree. "hus, &i0eP1+ is a promisin) cathode materials for all solid state
lithium polymer batteries. A dra(bac' of &i0eP1+ is its lo( electrical conductivity
(hich causes the &i0eP1+ cathode to have a hi)h resistance. In this study, a carbon%
coated plate li'e &i0eP1+ particles (as prepared by employin) hydrothermal
method, and heat treatments (ere carried out at hi)h temperature to increase the
electrical conductivity of the carbon layer. "he electrochemical properties of
&i0eP1+:C (ere characteriFed in a conventional li
8/16/2019 Nikita Project 01-06-2016
20/38
5!J16 and detailed of modelin) and calculation. In Nano composite Jenerator (e
are studied about Production process of p%NC stretchin) and bendin) test of p%NC,
Po(er Jeneration of NCJ durin) periodical commercial &D usin) Self%Po(ered
ner)y.
4. -
8/16/2019 Nikita Project 01-06-2016
21/38
deioniFed (ater. In this reaction, the flu7 of the solution of 0e5N16 and HP1 (as
controlled at a rate of -*3cm h, (hile the flu7 of the a or hi)her. "he
product (as dried for h in a dryin) bo7 at 23 de)ree. 0inally, the spherical iron
(as obtained.
.Car=on2Nanot,=e2Decorate* Nano23i8e:4 BC Catho*e Material 5ith
S,)erior +i0h2Rate an* 3o52Tem)erat,re erformance for 3ithi,m2Ion
atteries
"he double nano%carbon decorated &0PQC:CN" (as prepared by usin) the
modified polyol route follo(ed by a carbon coatin) procedure, multi(alled CN"s
(ere added to tetraethylene )lycol and ultrasonically dispersed for several hours to
form a uniform suspension. Secondly, ferrous acetate, lithium acetate and
phosphoric acid (ere dissolved into the suspension at a molar ratio in the se
8/16/2019 Nikita Project 01-06-2016
22/38
6. +y*rothermal synthesis of car=on2coate* 3i8e:4 an* its a))lication of
lithi,m )olymer =attery
"he preparation of the &i0eP1+:C particle (as carried out usin) the
hydrothermal method at -23 de)ree C. "he ra( materials for the preparation of
&i0eP1+:C (ere 0eS1+, &i1H%H*1, 5NH+6*HP1+, HP1+ and ascorbic acid, (hich
(ere used as the 0e, &i, P and C sources respectively. "he &i and P sources (ere
dissolved in deioniFed (ater, and 0eS1+ and ascorbic acid (ere then added.
"o prevent the o7idation of 0e*? to 0e? the (ayer (as de)assed by N* )as bubblin)
for 3 min before preparin) the solution. "he mi7ture process (as carried out under
nitro)en atmosphere. &i1H, 0eS1+, 5NH+6*HP1+, HP1+ and ascorbic acid (ere
mi7ed in a molar ratio. "he concentration of 0eS1+ in the precursor solution (as
-.3 mol dm and the pH of the solution (as G.+3 ml of the solution (as poured into
a "eflon vessel sealed in a stainless steel autoclave and the reactor (as heated in an
oven at -23 de)ree C for -* hrs. Durin) the hydrothermal treatment, the formation
of &i0eS1+ and the decomposition of ascorbic acid occured inside the reactor. After
the hydrothermal reaction, the reactor (as cooled at room temperature. "he
precipitate po(der (as collected by filteration and (ashed throu)hly (ith
deioniFed (ater and acetone . "he obtained po(der (as dried at 8G de)ree C for -
hrs under vaccum condition. "o increase the electrical conductivity of the carbon
layer the precipitated po(der (as heat treated under a flo( of Ar containin) vol
++
8/16/2019 Nikita Project 01-06-2016
23/38
R H* for - hrs. "he carbon content of the prepared po(der (as determined by
elemental analysis.
4. Com)arision of the Rate Ca)acities of 3i8e:4 Catho*e MaterialsIn the preparation of the &i0eP1+ battery cell, it is common practice to add
conductive carbon po(der to improve the electronic contact bet(een the active &i%
ion po(der and the electronic conductor. In this process, the &i0eP1+ po(der (ere
mi7ed (ith carbon po(der and binder to form a cathode film on a conductive metal
foil. It (as noted that the loadin) of conductive and the mi7in) procedure had a
sin)nificant impact on that electrochemical performance of the prepared cells. A
hi)her conductive carbon loadin) )enerally improves the rate capacity by reducin)
the char)e transfer resistance, especially for bare &i0eP1+ po(der (ithout carbon
coatin). Unfortunately, a hi)her carbon loadin) reduce the volumetric ener)y
density of the cell and increases the total siFe and cost of the battery.
$. Res,lts an* Disc,ssions
$.1. :)timie* 3i8e:42olyacene Catho*e Material for 3ithi,m2Ion attery
+3
8/16/2019 Nikita Project 01-06-2016
24/38
0i)ure -. All diffraction lines are inde7ed to an orthorhombic crystal structure
5space )roup Pmnb, triphylite6. No phase impurity (as detected from our !D
measurements. The electronic conductiity of sample A decreases
sli*htly %hen the temperature falls from 8. to < 3. => # At room
temperature, the pure 0ie?"2- compound has an electronic
conductiity of 1.
8/16/2019 Nikita Project 01-06-2016
25/38
8i0,re 1. !D patterns of the prepared &i0eP1+ ;PAS po(ders. Sample Ais spherical po(der prepared by usin) a spherical 0eP1+T*H*1 precursorE sample $ is a disordered &i0eP1+ ;PAScomposite.
0i)ure*. sho(s selected volta)e profiles as a function of the delivered capacity. A
char)e;dischar)e )alvanostatic cell (as used (ith different specific currents,
ran)in) from 3.+ to G C. "his material had an e7cellent flat volta)e plateau. At the
lo(est dischar)e rate 53.+ C6, the volta)e profile dropped rapidly from the end%
char)in) volta)e 5+.* V6 to about .G V. "his volta)e (as 'ept almost constant
durin) the follo(in) intercalation and more than >3R of the char)e occurred at a
flat operatin) volta)e of .G V. Durin) the remainin) part of the char)e, the
volta)e
8/16/2019 Nikita Project 01-06-2016
26/38
(tR carbon blac', and 8 (tR polyvinylidene fluoride, ;G m)cm;* loadin)6 a)ainst a lithium
metal counter electrode. "he dischar)e rates are the same as the char)e rates separately in cycle
0i)ure sho(s the cycle performance of the e7periment cells operate dat ;*3, ;-3,
3, *3, +3, and >3 4C. "he cycle performance (as e7cellent at various temperatures.
"he dischar)e capacity of the cell increased as the operatin) temperature (as
raised. At>34C the initial dischar)e capacity reached -+G m Ah );- 5- C6,
appro7imately -*R hi)her than (hat (as observed at *3 4C. At 3 4C, the initial
dischar)e capacity (as --* m Ah );-,-GRlo(er than (hat (as observed at *3 4C.
8i0,re 6. Specific capacities and cyclic performances of &i0eP1+;PAS 5sample A6 at different
temperatures. "he e7periment cells (ere char)ed and dischar)ed at the same rate of - C.
+8
8/16/2019 Nikita Project 01-06-2016
27/38
$.. Car=on2Nano t,=e2Decorate* Nano23i8e:4 BC Catho*e Materials
5ith S,)erior +i0h2Rate an* 3o52Tem)erat,re erformance foe 3ithi,m2Ion
atteries
0i)ure -a sho(s the %ray diffraction 5!D6 pattern of the as obtained
&0PQC:CN" nano composite. In addition to the (ea' diffraction pea' at about
*>.+ 4 for multi (alled CN"s, all intense pea's in the spectrum can be (ell inde7ed
to orthorhombic &i0eP1+ indicatin) the hi)h phase purity of the &0PQC:CN"
nanocomposite. "he mean crystallite siFe of &i0eP1+ is ca. 23 nm.
Bi*ure 1 6 and i*ure S1C# The si4e, morpholo*y, and structure of
the as?prepared products %ere characteri4ed 6y SE, hi*h?
resolution transmission electron microscopy BHRTEC, and
correspondin* fast?ourier transformation BTC#
+9
8/16/2019 Nikita Project 01-06-2016
28/38
8i0,re 4 . a6 !D pattern, b6 S, d6 schematic illustration of the prepared &0PQC:CN" nanocomposite.
$.6. +y*rothermal Synthesis of Car=on2Coate* 3i8e:4 an* Its
A))lication to 3ithi,m olymer attery
0i)ure +.sho(s the !D patterns of the &i0eP1+:C samples. All the obtained
samples had an orthorhombic structure (ith a space )roup of Pnma, and no
impurity phase (as detected in any sample. An important feature of the !D
pattern (as the intensity ratio of the pea's. "he 53*36 pea' intensity (as the
stron)est for all the samples. "his indicated that the particles had a preferred
crystal orientation alon) the 53*36 direction.
+:
8/16/2019 Nikita Project 01-06-2016
29/38
8i0,re $. !D patterns of the &i0eP1+:C samples annealed at various temperatures after hydrothermal
treatment@ 5a6 unannealed, 5b6 +33, 5c6 G33, 5d6 >33, 5e6 933, and 5f6 8334C.
i*ure 8 sho%s the char*e annealed at 9..=> ehi6ited a hi*h rate
capa6ility, and the dischar*e capacity measured at a dischar*e
rate of 1. > %as 1.- m Ah *F1#
+;
8/16/2019 Nikita Project 01-06-2016
30/38
8i0,re 7. Char)e;dischar)e curves of &i0eP1+:C samples bet(een 3.- C+8 A cm=* and -3 C +.8>
m A cm=*@ 5a6 unannealed sample and 5b6 sample annealed at 9334C.
i*ure 9sho%s the rate capa6ilities of 0ie"2-/> heated to arious
temperatures# The char*e particle, althou*h the electrical
conductiity of pure 0ie"2- is ery lo@
3.
8/16/2019 Nikita Project 01-06-2016
31/38
Fi14" -. "lots of the dischar*ecapacities of the 0ie"2-/> samples as
a function of the > rate# The samples %ere annealed at arious temperatures afterhydrothermal treatment BaC unannealed, B6C -.., BcC 7.., BdC 8.., BeC 9.., and BfC:..=>#
$.4. Com)arison of the Rate Ca)acities of 3i8e:4 Catho*e Materials
0i)ure 8. sho(s the overall distribution of the specific capacity as a function of
dischar)e rate for most of the &i0eP1+ materials reported to date. "he specific
capacities of these materials varied in a %ide ran*e especially at hi*h >
rates#
Some of the materials had a sharp decreased capacity at hi*h
current rates sample ! in i*#1#2ther samples B> and DC
maintained their capacity at hi*h > rates %ith a 5at capacity
8/16/2019 Nikita Project 01-06-2016
32/38
re*ular cell# This sample %as synthesi4ed 6y a polyol B"0C method
%ith a uniform )ne particle si4e of +.
8/16/2019 Nikita Project 01-06-2016
33/38
procedure from %et miin* to dry miin* also dramatically
reduced the capacity at hi*h >rates, een thou*h the capacities
at lo% > rates %ere not chan*ed S0 s dry in i*#; These results
sho%ed that maintainin* *ood electronic conductiity 6et%een
0ie"2- po%ders and the current collector is critically important
for hi*h rate performance#
Fi14" 5. The in5uence of conductie car6on loadin* and po%der miin* procedurein cell preparation on the rate capacity of 0ie"2- materials# The S0?19> and S0?7>samples are sample no# 11 in Ta6le I prepared usin* a slurry miture %ith 19 and 7%t conductie car6on, respectiely# The dry?19> and dry?7> samples are sampleno# 11 in Ta6le I prepared usin* a dry miin* procedure containin* 19 and 7 %t conductie car6on, respectiely#
in i*# 1.# @ithout car6on coatin* dotted lines , the samples
doped %ith *, Ni, and N6, %hich %ere reported 6y t%o di/erent
*roups, hae their rate capacities fairly compara6le, althou*h the
33
8/16/2019 Nikita Project 01-06-2016
34/38
N6?doped sample BD2"?N6C had a small particle si4e of less than
1.. nm# Their speci)c capacities areJ1-. m Ah/* at .#+> and :.
mAhK* at 1.>, %hich are in the lo% ran*e of the reported data for
0ie"2-, as sho%n in i*#1.# The >u?doped sample BD2"?>uC
%ithout car6on coatin* had a relatiely hi*her rate capacity#
Ho%eer, all the car6on?coated and doped0ie"2- samples had
6etter rate capacities than the uncoated samples# The t%o 6est
samples in this *roup are ? and >r?doped 0ie"2-/>, %hich had a
capacity of 18- m AhK* at .#1> rate BD2"?>Cand 119 m AhK* at
1.> rate BD2"?>r?>C
Fi14" + . The rate capacities of doped 0ie"2- materials %ithoutcar6on?coatin*#
3-
8/16/2019 Nikita Project 01-06-2016
35/38
7.Concl,sions
lectrochemical measurements of &i%ion batteries have demonstrated that
&i0eP1+%PAS has hi)h dischar)e capacity and superior cyclin) performance in the
ran)e of %*3 to >3 de)ree C. "his idea is a promisin) aspect in the desi)n of novel
battery materials.
Oe have developed a ne( desi)n by decoratin) &i0eP1 + nanoparticles (ith
t(o types of carbonaceous materials to improve the electrochemical properties of
&i0eP1+ cathode materials. A carbon%coated plate li'e &i0eP1+ particles (as
prepared by usin) the hydrothermal method at a temperature of -+3 de)ree C.
Ho(ever, the electrical conductivity of the carbon layer (as very lo( (ithout
postannealin). !evie( of the specific capacities of various &i0eP1+ materials in the
literature indicates that the electronic conductivity bet(een the &i0eP1 + po(ders
and the current collector plays a determinin) role in the hi)h rate performance of
the battery cell.
#. References- a6 A.. Padhi, .S. NanBundas(amy, W.$. Joodenou)h, W. lectrochem. Soc.
1@@#, -++, --88E b6 A.. Padhi, .S. NanBundas(amy, C. as
8/16/2019 Nikita Project 01-06-2016
36/38
* !. Amin, P . $alaya, W. aier, lectrochem. Solid%State &ett. *339, -3, A-.
A. &. $ard, &.!. 0aul'er, lectrochemical ethods, *nd ed, Oiley, *33-.
+ $. an), J. Ceder, Nature *332, +G8, -23.
G W. Oan), . Sun, ner)y nviron. Sci. *3-*, G, G->.
> . . &iao, . 0. 0en), #. S. He, W. lectrochem. Soc. *33G, -G*, A -2>2.
9 S. Shi, C. 1uyan), . ion), Phys. !ev. $@ Condens. atter ater. Phys. *33G,
9-, -+++-+.
8 . Striebel, W. Shim,V. Srinivasan, W. lectrochem. Soc.*33G, -G*, A>>+.
2 H. S. S'im, $. O. Cho, W. Po(er Sources *33+, -* *G.
-3 J. . Oan), &. #an), #. Chen, lectrochem, Acta *33G, G3, +>+2.
-- A. . Padhi, . S. NanBundas(amy, and W. $. Joodenou)h, W ,lectrochem,
Soc.,-++, --88 5-2296.
-* A. #amada, S. C. Chun), and . Hino'uma, W. lectrochem, Soc., -+8, A**+
5*33-6.
- S. #. Chun), W. ". $lo'in), and #. . Chian), Nature ater., -, -* 5*33*6.
-+ $. Oan), #. Xiu, and S. Ni, Solid State Ionics, -98, 8+ 5*3396.
-G W. $ar'er, . #. Saidi, and W.&. S(oyer, lectrochem. Solid%State &ett., >, AG
5*336.
-> O. 0. Ho(ard and !. . SpontnitF, W. Po(er Sources, ->G, 889 5*3396.
-9 . S. Ohittin)ham, !S $ull., , +-- 5*3386
-8 C. S. Sun, . hou, . J. u, D.J. Oan), W. P. Oei, . . $ian, and W. #an, W.
Po(er Sources, -2, 8+- 5*3326.
-2 . u, &. u, X. &ai, and . Wi, ater. !es. $ull., +*, 88 5*3396.
*3 J. Ceder and $. an), W. Po(er Sources, -2+, -3*+ 5*3326.
38
8/16/2019 Nikita Project 01-06-2016
37/38
3IST :8 8I'&R-
8i0,re 1. !D patterns of the prepared &i0eP1+ ;PAS po(ders. Sample A isspherical po(der prepared by usin) a spherical 0eP1+T*H*1 precursorE sample $ is
a disordered &i0eP1+ ;PAS composite.
8i0,re . Dischar)e curves of &i0eP1+ ;PAS 5sample A6 cathode material at
different rates. "he material is used in a conventional lithium%ion battery electrode
desi)n 58+ (tR active materials, 8 (tR carbon blac', and 8 (tR polyvinylidene
fluoride, ;G m)cm;* loadin)6 a)ainst a lithium metal counter electrode. "he
dischar)e rates are the same as the char)e rates separately in cycle.
8i0,re 6. Specific capacities and cyclic performances of &i0eP1+ ;PAS 5sample A6
at different temperatures. "he e7periment cells (ere char)ed and dischar)ed at the
same rate of - C.
8i0,re 4 . a6 !D pattern, b6 S, d6 schematic illustration of the prepared
&0PQC:CN" nanocomposite
.
8i0,re $. !D patterns of the &i0eP1+:C samples annealed at various
temperatures after hydrothermal treatment@ 5a6 unannealed, 5b6 +33, 5c6 G33, 5d6
>33, 5e6 933, and 5f6 8334C.
8i0,re 7. Char)e;dischar)e curves of &i0eP1+:C samples bet(een 3.- C+8 A
cm=* and -3 C +.8> mA cm5*6@ 5a6 unannealed sample and 5b6 sample annealed
at 9334C.
Fi14" -# "lots of the dischar*e capacities of the 0ie"2-/>
samples as a function of the > rate# The samples %ere annealedat arious temperatures after hydrothermal treatment BaC
unannealed, B6C -.., BcC 7.., BdC 8.., BeC 9.., and BfC :..=>#
39
8/16/2019 Nikita Project 01-06-2016
38/38
8i0,re ". Color online "he specific capacity as a function of the dischar)e rate
of various &i0eP1+ cathode materials reported in the literature.%"he sample no. in
"able for samples A, $, C, and D is , and ,respectively.
Fi14" 5. The in5uence of conductie car6on loadin* and po%der
miin* procedure in cell preparation on the rate capacity of 0ie"2- materials# The S0?19> and S0?7> samples are sample no#
11 in prepared usin* a slurry miture %ith 19 and 7 %t
conductie car6on, respectiely# The dry?19> and dry?7> samples
are sample no# 11 in prepared usin* a dry miin* procedure
containin* 19 and 7 %t conductie car6on, respectiely#
Fi14" + . The rate capacities of doped 0ie"2- materials
%ithout car6on?coatin*#
Recommended