锂离子电池负极材料Li4Ti5O12的结构和性能

Li4Ti5O12∗

(,361005)

(Li4Ti5O12),,

.,650TiO2,, 650TiO2,80024h Li4Ti5O12,.

,,,

TB321,TM9111005-3093(2007)01-0082-05

Structure and performance of lithium battery anode

material Li4Ti5O12

HE Hui CHENG Xuan ZHANG Ying∗∗

(Department of Materials Science and Engineering,State Key Laboratory for Physical Chemistry of Solid Surfaces,

Xiamen University,Xiamen361005)

*Supported by National Natural Science Foundation of China No.10472098.

Manuscript received April20,2006;in revised form August20,2006.

**To whom correspondence should be addressed,Tel:(0592)2180999,E–mail:yzh@xmu.edu.cn ABSTRACT The precursors of Li4Ti5O12were prepared by sol–gel method and the Li4Ti5O12sam-ples were synthesized by calcining.The structure and surface species of Li4Ti5O12were characterized by thermogravimetry(TG),X–ray diffraction(XRD),infrared spectroscopy(IR)and Raman spectroscopy.

The effects of the synthesis temperatures on the structure and species of Li4Ti5O12were systematically investigated.The results revealed that two types of TiO2were formed and coexisted when the synthesis temperature was below650,which adversely influenced the structure of Li4Ti5O12,and TiO2gradually disappeared after the synthesis temperature was above650.Single–phase and pure Li4Ti5O12with excellent electrochemical performance was obtained after the sample was prepared at800and kept heated for24h.

KEY WORDS inorganic non–metallic materials,lithium titanate,sol–gel method,anode material

/.,

,

,[1∼3].,

.

F d–3m Li[M2]O4,

.[M2]O4M–O,[M2]O4

[4].,

[Li]8a[Li1/3Ti5/3]16d[O4]32e,,

*10472098.

20020;2006820.

:,

1%[5],

[6∼8],

,.

Li4Ti5O12TiO2( )Li2CO3LiOH·H2O

,[9∼11].

,,

,[11].

,,

Li4Ti5O12,

.

1

"c":

(

1:5),

,,,Li

Ti4:5.80,

,–50

,.400∼800

24h,

30min,.

Netzsch STA400

,50mL

/min,10/min,

25∼1000.DTG

,.Philips Panalytical X pert X

XRD,(Cu Kα1,λ=1.5406nm),

0.0167◦,10◦∼90◦.Nico-let OMNIC

.4000∼400cm−1,

32.Dilor LabRam I

Raman.

He–Ne,632.8nm,50 ,4mW,

10s.

600,650,75080024h

,.

,(::PVDF=85 :10:5),NMP,

,,,

,(Lab master100),

,LiPF6/EC+DMC(1:1), Celgerd2300,2035.

,0.5∼2.1V,0.1C Arbin.

2

1,200

7.35%,103,

.200400

,,

.,

Ti–O,

51.4%.400,

,.

2,450,

TiO2(I41/amd),

400,TiO2.

1

Fig.1TG and DTG curves of precursor

2XRD

Fig.2XRD patterns of samples calcined at different temperatures for24h(•:anatase TiO2,◦:ru-

tile TiO2, :spinel Li4Ti5O12)

500,TiO2

TiO2,TiO2.

,Li4Ti5O12,

,.650Li4Ti5O12 ,TiO2. 750TiO2,

Li4Ti5O12.750800

XRD,750

.800

,,750

.,

(Fd–3m),

8a,16d ,Li:Ti=4:5,32e[9,12].

3,1500cm−1C–O

[13],, 800.,8421

3

Fig.3IR spectra samples calcined at different tem-peratures

Li2CO3,

,Li2CO3Ti

.Li2CO3, XRD.400,Ti–O(460cm−1650cm−1)[13] ,,Ti–O

,,, Ti–O,.

4300∼800cm−1

.,,

,TiO2,

.TiO2Li4Ti5O12

1.500

TiO2(I41/amd),500TiO2

,TiO2;550

(F d–3m),

TiO2(P42/mmm),800

.400,,

,,TiO2

,550

.800,

(F d–3m).XRD

Raman,75080024h

4

Fig.4Raman spectra samples calcined at different temperatures

XRD;Raman

,

,TiO2

.,750800

.

,Li4Ti5O12: ,

,Ti(OH)4[13∼16],,

,TiO2 (T<450),TiO2 (T≈500),TiO2(T< 650);750,

Li2CO3,TiO2Li4Ti5O12.

5,

600,650,75080024h.

,600

.600∼650

24h,;750 80024h, 1.5V

,800.

2,600,

88mAh/g,33mAh/g,

,20mAh/g,

1TiO2,Li4Ti5O12

Table1Raman active phonon and vibration sources for TiO2and Li4Ti5O12

Position of peak/cm−1

Sample

A1g B1g A1g+B1g E g T2g TiO2[15](P42/mmm)610448

TiO2[16](I41/amd)3985150

Li4Ti5O12[17,18](F d–3m)659425,3531:Li4Ti5O1285

51,2

Fig.5Cyclic discharge curves of thefirst and second cycle of of samples calcined at different temperatures

21,2

Table2Properties of cycling performance from Fig.5

Material

600650750800

Charge capacity/(mAh/g)88169170191 First

Discharge capacity/(mAh/g)33140146169

Charge capacity/(mAh/g)20123153177 Second

Discharge capacity/(mAh/g)19115144165

Loss/%7727107

77%.650,

169mAh/g,

27%.750,

170mAh/g,

(175mAh/g[9]),10%,

800,,

191mAh/g,,

7%.

,600,

Li4Ti5O12,

TiO2,

;,TiO2

,F d–3m,

Li4Ti5O12,.

3

Li4Ti5O12.

650,TiO2

Li4Ti5O12,

750Li4Ti5O12,

TiO2,800,

Li4Ti5O12.

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