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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

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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

+

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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

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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.

-

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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

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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

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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

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% 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

:

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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

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=% 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.

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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+

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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

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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

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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

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. 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

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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

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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

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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

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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. -

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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

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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

++

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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

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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.

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 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

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(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

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$.. 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

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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.

+:

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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#

+;

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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.

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  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

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re*ular cell# This sample %as synthesi4ed 6y a polyol B"0C method

%ith a uniform )ne particle si4e of +.

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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

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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-

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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

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* !. 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.

 

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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 :..=>#

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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*#