纳米复合材料在高性能锂电池中的应用

Nanocomposite

Electrode

Materials

forHigh

Energy

Lithium

BatteriesOutline•

Status

of

Lithium

Battery

Industry

in

Taiwan•

High

Capacity

Li-rich

Composite

Cathode

Materials•

High

Capacity

Si/Carbon

NanocompositeAnode

MaterialsTaiwan

Lithium

Battery

Industry

Cell•能元(E-ONE

Moli)•有量(Amita)•必翔電能(Pihsiang)•興能(SYNergy)•動能(EXAEnergy)•昇陽(PSI)

etc.

total

11s

SystemEV•華創(Haitec)•勝榮(Kortus)•中華(China

Motor)ES•中華(China

Motor)•光陽工業(Kymco)•三陽(Sanyang)•益通(E-Ton)•必翔(Pihsiang)•山葉(Yamaha)

etc.

total

10sEB•巨大(Giant)•美利達(Merida)...Power

Scooter•必翔(Pihsiang)

Battery

Module/

Power

ManagementBattery

Module•新普(Simplo)•順達科(DynaPack)•正崴(Foxlink)•能元(E-ONE

Moli)•加百裕(Celxpert)•達振(CT

Hitech)

etc.

total

20sPowerManagement•台達電(Delta)•光寶(Liteon)•能元(E-ONE

Moli)•致茂(Chroma)•達振(CT

Hitech)

Material

Cathode

•台塑長園(Formosa

Energy

)

•立凱(Aleees)

•尚志精密(Tatung)

•宏瀨(Hirose)

etc.

total

10s

Anode

•中碳(China

Steel

Carbon)

•義芳(Yee

Fong

)Electrolyte•台塑(Formosa)Separator•明基材料(BenQ

Materials)

Substrate•南亞(Nan

Ya)•金居(Golden

Copper)

Li

Battery

Industry

Supply

Chain

in

Taiwan•

Taiwan

Li-ion

battery

industry,

with

a

domestic

industrial

chain

of

upstream

materials,

midstream

electrode/module

and

downstream

system

,

has

successfully

penetrated

in

power

battery

market.•

For

energy

saving

and

CO2

reduction,

E-scooter

and

E-bus

subsidization

programs

are

applied

in

Taiwan.Additives•中碳(CSCC)•高銀化學•榮碳(Long

Time)(Formosa

Plastic)(HOPAX)•明基材料新永裕Components

Li-ion

Battery

Material

Industry

in

Taiwan•Material

Industry:

Cathode

Materials•康普(Comax)•鋰科(LICO)•鐵研(TAK)•宏森•台塑鋰鐵(Formosa

Energy

)•立凱(Aleees

)•尚志(Tatung)•宏瀨(Hirose)•倍特利Anode

Separator

ElectrolyteMaterials

(Coin

Chem.)

•義芳(Yee

Fong)

(BenQ

Materials)

•

前瞻能源

Battery

Facility•宏全(Hon

Chuan)

•亞泰金屬(AMI)•沖壓精密(CIPC)

•海金•長春

•友煜(Unitronic)•台日古河

•固緯(Good

Will)•金居(Golden

Copper)

•世宏•和勤(CFTC)•新德•聚鼎

LiFePO41.

About

the

LFPpositive

material’s

investment

and

production

contain

Formosa

Energy

(

invested

0.8

BNT$/annual

capacity

of

4800T),

Aleees

(

sales

up

to

200T

in

2009

and

additional

0.6

BNT$

investment/annual

capacity

of

3600T),

Tatung

(

0.7

BNT$

investment/annual

capacity

of

4320T)

and

Hirose

(

0.6

NT$

investment/annual

capacity

of

3600T).2.

The

W.W.

market

share

of

LFPpositive

material

is

higher

than

43%

(Taiwan:1800T/

W.W.

4200T)•台塑

•聚和ITRI

–

Where

Taiwan’s

High-tech

BeganKodakLithium

Battery

StandardTaiwan/

Ph.

D.Joint

Lab.Joint

ProgramOpticalUCBerkeleyUSA/

NorthWestern

U.Testing

TCO

FilmRussia/MSU-ITRI

Joint

Lab.Russia/

IoffeUkrain/

Inst.

of

TEEnergyHarvestingBiomassSolar

TechFlexibleElectronicsEvonikDegussaTaiwan/

ITRI-NCU

Joint

Lab.InternationalLC

SimulationRheology

Simulation

Fuel

CellLocalAcademia

Taiwan/

ITRI-NTU

Energy

Material

Eco

Material

Bio

Material

6studentsBASFDow

Fuel

CellIC

MaterialsBattery

SONY

Electronic

Material

NokiaPrecisionCoatingInternational

&Academia

CooperationAnti

UV/

Self

Cleaning

Nano

Coating

Behr

Taiwan,

China

Bureau

of

Standard

Swiss/

Fribourg

U.

DispersionTohoku

U.

Kyoto

U.

Nano

Materials

Testing

Clay

AIST

NanoblendingPALS

Calibration

LCD

Rubbing

Cloth．

Electrode

and

Jelly

Roll．

Conducting

Mechanism．

Simulation．

Safety

VerificationPerformance

TestModule

TestCell

Fab.Safety

Test

•Anode

/

Cathode

synthesis

•

micro-structure

Design

•

High

V

electrolyte

•

Capacity

controlMaterial

Development•Paste

control•Thermal/ElectricalDesign/

simulation•

Safety

control•

sealing

Cell

Design．

Recipe

of

Material

System

．

．

．．

Mathematical

Model

and

．

．

．Capacity

and

Energy

DensitySpecific

PowerHigh

Current

CapabilityCycle

life

and

Storage/Shelf

LifeImpedance

AnalysisFailure

Mechanism．．．．•Thermal

/Electrical

conduction•Mechanical

design/simulation•SOC

Information•Cell

Equalization•Protection

Battery

Module

DesignMechanical

Abuse

．Performance

TestElectrical

AbuseAbnormalEnvironmentFrom

Cell

toApplicationLithium

Ion

Battery

Verification

Platform

in

ITRI

Anode

Material•

High-Rate

Charge•

High

Capacity

CathodeMaterial•High

Capacity•High

Voltage

Separator•

Low

Cost•

Safety

Electrolyte•

Safety•

High

VoltageInnovation

and

Goal

for

Each

Li

Battery

MaterialsHigh

Capacity

Li-rich

Composite

Cathode

MaterialVoltage(V)Capacity

(mAh/g)0100200300400Capacity(mAh/g)2.03.04.05.0A104231S20.5C

D(2-4.8V):211.31

mAh/gQirr=55Q=25001020304050607050

0100200150250Cycle

number0.2C/0.2D

0.6

Li[Li1/3Mn2/3]O2–

0.4

LiNi0.4Co0.2Mn0.4O2A10423-1S

mixer

c-rate

retest(0.1C/0.1C*2-0.2C/0.2C*1-0.2C/0.5C)

(11)

For

C(0.1C-1st:2-4.8V):305.12

mAh/g

For

D(0.1C-1st:2-4.8V):250.54

mAh/g

For

C(0.1C-2nd:2-4.8V):253.76

mAh/g

For

D(0.1C-2nd:2-4.8V):248.77

mAh/g

0.2C

C(2-4.8V):243.22

mAh/g

0.2C

D(2-4.8V):228.02

mAh/g

0.2C

C(2-4.8V):232.41

mAh/gElectrochemical

Properties

of

Composite

CathodeTap

density=1.78Voltage(V)Z''Capacity(mAh/g)1105010015020025030035040005010015020025080%Cycle

no.Tap

density=

2.1

g/cm30.2C/0.5C0501001502002503003502.04.03.53.02.54.5Capacity(mAh/g)

0.1C(4.8V):309.36

0.1D(4.8V):231.71

0.1C(4.6V):211.31

0.1D(4.6V):210.59

0.2C:198.76

0.2D:192.08

0.2C:193.71

0.5D:179.58

0.2C:179.31

1D:168.18

0.2C:167.83

2D:151.45

0.2C:151.64

3D:138.72Irriversible

:77.65A1-0626-5S

.7620408010012010

0302040506070Z'5cycle85cycle

60(

)(

)AC

impedanceD50

~21

md~100

nm0RsRseiRctRctRseiLi1.2Ni0.16Co0.08Mn0.56O2

Electrochemical

Properties

of

Composite

Cathode•

Nanocomposite

powders

increase

RT

the

rate

capability

of

composite

cathode

5.0Voltage

(

V

)0501001502002505.04.54.03.53.02.52.00.2C/0.5C10th210.600.2C/0.5C100th194.530.2C/0.5C200th182.710.2C/0.5C350th171.14

(mAh/g)Capacity(

mAh/g

)

Cycle

Life

of

Composite

Cathode•

Long

cycle

life

and

voltage

decay

issue

for

composite

cathode

0.6

Li[Li1/3Mn2/3]O2–

0.4

LiNi0.4Co0.2Mn0.4O2Voltage(V)Z''0501001502002503003502.04.03.53.02.54.5Capacity(mAh/g)0.1C(4.8V):288.500.1D(4.8V):251.830.1C(4.6V):239.690.1D(4.6V):238.320.2C:227.640.2D:218.270.2C:215.570.5D:199.560.2C:197.951D:181.170.2C:180.212D:156.110.2C:155.833D:135.26Irriversible

:37.1202040608010012040302010

05060Z'85cycle(

)(

)AC

impedance

Performance

of

Composite

Cathode

by

Surface

Nanocoating•

Reduce

the

irreversible

capacity

loss

of

composite

cathode

by

VOx

nanocoating

VOx-coated

0.6

Li[Li1/3Mn2/3]O2–

0.4

LiNi0.4Co0.2Mn0.4O2

.95RT

5.0

70

5cycleHeat

Flow

(mW/mg)14240245250255260-30-35DSC

profiles

of

pristine

&

VOxsurface-coated

0.6

Li[Li1/3Mn2/3]O2–

0.4

LiNi0.4Co0.2Mn0.4O2

5

0

-5

-10

-15

-20

-25oxpristinesurface-coatedVoltage(V)Z''M-doped

0.6

Li[Li1/3Mn2/3]O2–

0.4

LiNi0.4Co0.2Mn0.4O20501001502002503003502.03.53.02.54.54.05.0Capacity(mAh/g)0.1C(4.8V):310.380.1D(4.8V):263.370.1C(4.6V):240.890.1D(4.6V):241.06

0.2C:227.16

0.2D:219.63

0.2C:217.46

0.5D:204.77

0.2C:203.73

1D:190.66

0.2C:190.00

2D:170.90

0.2C:171.50m

3D:156.93mIrriversible

:47.01A1-0626-20Cr.74RT020408010012040302010

06050705cycle85cycle60Z'(

)(

)AC

impedance•

Performance

of

Composite

Cathode

by

Metal

DopingReduce

the

voltage

decay

of

composite

cathode

by

metal

dopingAverage

VoltageVoltage(V)Pristine16•0501001502002502.04.03.53.02.54.55.0Capacity(mAh/g)10cycle30cycle50cycle84cycleA2-0709-1S.35RT0204060801001201401601803.253.403.353.303.453.50CyclePristine0729-1CrM-doped

Performance

of

Composite

Cathode

by

Metal

DopingReduce

the

voltage

decay

of

composite

cathode

by

metal

dopingPristine

vs.

M-dopedHigh

Capacity

Si/Carbon

NanocompositeAnode

Material

Composite

Cathode(+)

Capacity>250mAh/g

SiAlloy/Carbon

CompositeAnode(－)

Capacity>1000mAh/gNew

Entry

Barrier

18Energy

Density>350

Wh/Kg

Energy

Density>280

Wh/Kg

LiNiCo(M)O2(+)

Capacity>180mAh/g

Nano

Si/Carbon

NanocompositeAnode(－)

Capacity>600mAh/g

Energy

Density:200

Wh/Kg

LiNiCoMnO2(+)

Capacity:165mAh/gCapacity

limitation

fortraditional

anode

materials

Graphite(－)

Capacity:350mAh/g

Cylindrical

Li

Battery(18650)

CompositeAnode

Materials

for

High

Energy

Density

Li

Battery•High-capacity

anode

material

is

the

key

material

for

high-energy

density

Li

battery

High

Energy

Li

BatteryApproach:

Nanostructure

(nano-Si)

alleviates

cracking

problem

Core-Shelled

structure

reinforces

structural

integrity

Uniform

pores

absorb

volume

expansion

of

nano-Si

Reduce

the

irreversible

capacity

loss

of

Si/Carbonnanocomposite

anode

by

carbon

coating

layer.High-Capacity

Si/Carbon

NanocompositeAnode

MaterialIrreversible

capacity

loss<15%Voltage

(V)Voltage

(V)LFP-

Graphite

Cell0.20.40.60.81.01.21.41.62.0

0.04.44.03.63.22.82.4Capacity

(Ah)0.20.40.60.81.01.22.0

0.04.44.03.63.22.82.4Capacity

(Ah)

LFP-C-186500.1C

charge

/

0.1C

discharge

formationLFP-

Si/C

(20%)+Graphite

SiC-0829-5+FEC

0.1C

charge

/

0.1C

discharge

formation

>1,450mAh(80%)

CellDischarge

Capacity

of

NanocompositeAnode

Material

•

LiFePO4-Graphite

(Si/C

+

Graphite)

18650

power

Cell

•

Capacity

increase

more

than

35%Electrochemical

Properties

of

NanocompositeAnode

MaterialLiFePO4-Si/C

+

Graphite

18650

Cellafter

test

Safety

Test

-

Overcharge

LiFePO4-Si/C

+

Graphite

18650

Cell•

Standard:•

3C

charge

for

3

hours，the

cell

shall

not

explode

or

catch

fire•

Result:

Pass

Test

data

Before

test•

Standard:Before

testafter

test•

The

cell

is

to

be

crushed

between

2

flat

surface,

the

crushing

is

to

be

continued

to

13±1kN,

the

sample

shall

no

explode

or

catch

fire•

Result:

Pass

Test

data

Safety

Test

-

CrushLiFePO4-Si/C

+

Graphite

18650

Cellafter

test