Hanyang University
Polymer Electrolyte
공업화학과/정보통신소재연구실/석사2기
이인재
2000.11.27
Lithium secondary battery
Polymer electrolyte
Historical background
Electrochemical process
Cell configuration
Classifications
Requirements
Requirements
Advantage
Ion conduction mechanism
Solid Polymer electrolyte
Gel Polymer electrolyte
Ionic Conductivity
Information and Communication Materials Lab.
Hanyang University
Lithium secondary battery
Linden, Handbook of batteries, 1994
Jang Myoun Ko, Polymer Science ang Technology, 1998, 9, 203
Yang Kook Sun, Prospectives of Industrial chemistry, 2000, 3, 11
Historical Background
Electrochemical Process of Lithium
secondary battery
1789 개구리다리로부터 전지현상발견 (Galbani(Italy))
1799 구리-아연 전지 발명 (Cu/H2SO4/Zn,Volta(Italy))
1860 연축전지 발명(PbO2/H2SO4/Pb,Plante'(France))
1867 망간 건전지의 원형 발명
(MnO2/NH4Cl.ZnCl2/Zn,Lechlanche(France))
1899 니켈-카드뮴 전지 발명
(NiOOH/KOH/Cd,Jungner(Sweden))
1899 니켈-아연 전지 발명 (NiOOH/KOH/Zn)
1900 니켈-철 전지 발명 (NiOOH/KOH/Fe,Edison(USA))
1909 알카리 망간전지 발명(MnO2/KOH/Zn)
1917 공기 아연전지 발명(O2 in Air/KOH/Zn)
Charge
1942 수은전지 발명(HgO/KOH/Zn)
Cathode LiMO2 Discharge Li1-xMO2+xLi+xe
1970 리튬 1차전지실용화
Charge
1970 미국 GM Delco 칼슘 MF 연축전지 개발
C6+xLi+xe
LixC
1973 이산화망간-리튬 1차전지 실용화(MnO2/LiClO4/Li) Anode
Discharge
1981 리튬 이온2차전지발명
Charge
1990 리튬 이온2차전지실용화,생산개시(일본 SONY사) Overall LiMO +C
2
6 Discharge LixO6+Li1-xMO2
1990 밀폐형 닉켈-수소전지실용화(NiOOH/KOH/MH)
1990 미국 켈리포니아주 대기정화법(Clean Air Act)통
과 세계각국 전기자동차용 전지 본격적인 개발
1995 수은전지 생산중지
Information and Communication Materials Lab.
Hanyang University
Cell Configuration
•
•
Cathode
LiCoO2
LiNixCo1-xO2
LiNiO2
LiMn2O4
LiMnO2
결정구조
Layered
Layered
Layered
Spinel
Layered
이론용량
(mAh/g)
274
275
275
148
285
실제용량
(mAh/g)
>135
>185
>160
>120
>190
평균전압(V)
3.6
3.6
3.6
3.8
~2.8,~3.4
Cost
high
moderate
moderate
low
Low
Anode
음극물질
무게당 용량
(mAh/g)
부피당 용량
(mAh/l)
C6(Coke)(50%사용시)
186
372
C6(graphite)
372
515
Li metal(25%사용시)
965
837
Li metal(100%사용시
3861
2062
•
Electrolyte


Solid polymer electrolyte + Lithium salt
Gel polymer electrolyte + Lithium Salt +
Solvent
Lithium salt ; LiClO4, Li(CF3SO2)2N, LiCF3SO3,
LiAsF6, LiPF6, LiBF6
Solvent ; PC, EC, DMC, EMC, DEC, -BL, etc
Information and Communication Materials Lab.
Hanyang University
이론 용량과 실제 용량
Faraday’s Low of Electrolysis
; 1g당량의 원자 또는 원자단이 석출하는데 필요한 전기량은 물질에 관계없이 항상 일정한
96487C을 갖는다.
Ex)Li1-xMO2(M=Co, Ni, Mn, …)
1.
LiCoO2(MW=97.87)
1F=96487C=96487A•s  1h/3600s  1000mA/A = 26800mAh
∴ 26800mAh/97.87g = 273mAh/g ⇒ LiCoO2 의 이론용량
실제용량은 x=0.5이하이므로 137mAh/g
2.
Li1-xMn2O4(MW=180.8)
똑같은 계산으로 26800mAh/180.8g = 148mAh/g
Spinel structure의 Li1-xMn2O4는 x=1이므로 실제용량이 이론용량값과 거의 일치
Information and Communication Materials Lab.
Hanyang University
Classifications of
Lithium secondary battery
Requirements of
Lithium secondary battery
Lithium Ion
Lithium Ion
Polymer
Lithium Metal
Polymer
음극
탄소
탄소
리튬
전해질
액체 전해질
고분자 전해
질
고분자 전해질
양극
금속 산화물
(LiCoO2,
LiN2O2,
LiMn2O4 등)
금속 산화물
(LiCoO2,
LiN2O2,
LiMn2O4 등)
금속 산화물,
유기 Sulfur, 전
도성 고분자
평균전압
3.6V
3.6V
2.0~3.6V

보존 특성 (충전보존, 가역성보존)
에너지밀도
High
High
Very High

자기 방전
사이클특성
Excellent
High
Poor

안전성
저온특성
Good
Medium
Poor

Memory effect
안전성
Poor
Medium
Good

형상 자유성
Cell 디자인
자유도
Poor
Good
Good

Cost
용도 및
개발시기
3C시장
91년 Sony
3C시장
97년 Ultralife
3C, EV(대용량)
개발중

환경문제

Energy density(Wh/g or Wh/l)
Wh=Ah(용량)  V(전압)

Cycle life (100% DOD 기준)

Rate performance (C-Rate)

작동온도구간
방전;-20~+60℃, 충전;0~40℃
Information and Communication Materials Lab.
Hanyang University
Ionic Conductivity
Richard G. Compton, Giles H.W. Sanders, Electrode Potentials, 1996
Peter G. Bruce, in “Polymer Electrolyte Reviews”, ed. By J.R.MacCallum, 1987, 237
Basic concept
 = 1/ = l/RA
Where, =conductivity(-1m-1),=resistivity,
R=resistance
Measurements of conductivity
Direct current measurement(D.C.)
simple, straightforward method
conductivity value를 바로 얻음
Conductivity is a property of the chemical
nature and composition of the electrolyte
solution
Ohm’s low V=IR ∴ =(I/A)/(V/l)
(I/A=current density, V/l=voltage gradient) Alternating current measurement(A.C.)
Basic electrical properties of a polymer
Vmax/Imax:the ratio of the voltage and current
electrolyte
maxima
1)the total conductivity of the electrolyte as a
function of Temp.
2)identification of the different charged
species contributing to conduction
3)transport numbers, i.e. the proportion of the
current carried by each charged species, as a
function of Temp.
 : the phase difference between the voltage
and current
Impedance Z=f(Vmax/Imax,,)
Z*=Z’-jZ”
Resistor : =0, Z=R
Capacitor :  =-2/, Z=1/C
Information and Communication Materials Lab.
Hanyang University
Polymer electrolyte
Fiona M. Gray, Polymer Electrolyte, 1997
Peter V. Wright, Br. Polym. J., 1975, 7, 319
Jung Ki Park, Polymer Science and Technology, 1998, 9, 125
한원길역, 폴리머 전지, 2000
Requirements of Polymer electrolyte
High ion conductivity (≥10-3S/cm @ R.T)
Ion Conduction Mechanism
Solid polymer electrolyte
Good compatibility between polymer matrix
and liquid electrolyte
Thermal and electrochemical stability
Good mechanical stability
High cation transference number
Availability
Advantage of Polymer electrolyte
Low barriers to rotation for atoms in the main
chain so as to ensure high flexibility and hence
facilitate segmental motion
Gel polymer electrolyte
Design flexibility
High energy density
Thin film
No leakage of liquid electrolyte
Low cost
Lithium cation dissociated
by organic solvent
Transported through the
free volume or micropore
polymer matrix and liquid
electrolyte
Information and Communication Materials Lab.
Hanyang University
Solid polymer electrolyte
PEO
CH 2CH 2O
n
<10-8S/cm
Tg=-64℃
PPO
<10-8S/cm
CH 2CH 2O
CH 3
n
-60℃
CH 2CH 2CO
n
O
n
Polyamine
CH2CH2NH
CH2CH2NR
n
n
@60℃
Gel electrolytes:systems containing low
molecular weight solvent
R=CH3,C3H7
Random polyether
Polysulfide
CH2
High molecular weigh amorphous or
reduced crystallinity polyether-based
host architectures
•Random copolymer
•Comb-branched copolymer
•Network
Polyester
OCH 2CH 2OC(CH 2)CO
O
O
Second Generation
POO
S
m
10-5~10-8S/cm
n
CH 2O
CH 2CH 2O
3  10-8S/cm
-66℃
Information and Communication Materials Lab.
Hanyang University
Comb-branched copolymer
CH 3
PMG
P(EO/MEEGE)
1  10-8S/cm
CH 2C
-50℃(amorphous)
CH 2CH 2O
x
CH 2CHO
1-x
n
CH 2OCH 2CH 2OCH 2CH 2OCH 3
P(EO/MEEGE)-5 (95:5) -61℃
P(EO/MEEGE)-9 (91:9) -65℃
O(CH 2CH 2O)9CH 3
O
Siloxane-based
CH 3
CH 3
SiO(CH 2CH 2O)4
Si
O
n
n
CH 3
O(CH 2CH 2O) 12CH 3
10-4S/cm
CH 3
Si
O
n
10-4~10-5S/cm
CH 2CH 2CH 2O(CH 2CH 2O) 12CH 3
MEEP
O(CH 2CH 2O)2CH 3
N
P
O(CH 2CH 2O)2CH 3
10-5S/cm
-83℃(amorphous) (M. Watanabe, A. Nishimoto, Electrochimica
Acta, 1998, 43, 1177)
Information and Communication Materials Lab.
Hanyang University
P(EO/MEEGE)73/27
Poly((amino)[(2-methoxyethoxy)ethoxy])phosphazenes
Tg=-65~-50℃
1.4  10-3 @ 60℃
3.3  10-4 @ 40℃
Improve dimensional stability
(Nishimoto et al, J. Power
Sources, 1999, 81-82, 786)
(Y.W.chen-Yang et al, macromolecules, 2000, 33, 1237)
Information and Communication Materials Lab.
Hanyang University
Networks
Poly(propylene oxide)
Ion conductivity of polymer 4 and polymer 5
(M. Watanabe, N. Ogata, in “Polymer Electrolyte
Reviews”, 1987, 39)
PEO based(via thermal with crosslinker)
(Nishimoto et al, Solid State Ionics, 1995, 79,
306)
Information and Communication Materials Lab.
Hanyang University
PEO based(via photo)
P(EO/MEEGE)470
P(EO/MEEGE)500
P(EO/MEEGE)710
P(EO/MEEGE)850
P(EO/MEEGE)990
P(EO/MEEGE)1500
P(EO/MEEGE)2000
-68.0℃
–68.9℃
–68.6℃
–71.3℃
–68.7℃
–67.4℃
–66.7℃
(Nishimoto et al, Macromolecules, 1999, 32, 1541)
Information and Communication Materials Lab.
Hanyang University
Gel Polymer electrolyte
PAN/MEEP based
PVC based
(M. Watanabe, A.
Nishimoto, Solid
State Ionics, 1996,
86-88, 385)
(L.M.Abraham, M.Alamgir, J.Electrochem.Soc.,
1990, 137, 1657)
Information and Communication Materials Lab.
Hanyang University
PVdF based
Acrylate based
(J. Y. Song et al, J. Electrochem. Soc., 2000, 147,
3219)
S. I. Moon et al,
J. Power
Sources, 2000,
87, 213
Information and Communication Materials Lab.
Hanyang University
Poly(p-phenylene) based
(Wolfgang H.Meyer, Adv. Mater., 1998, 10, 439
P.Baum, W. H. Meyer, G. Wegner, Polymer, 2000, 41, 965)
Information and Communication Materials Lab.