Department of Chemical Engineering, National Chung Cheng ...

1
Synthesis of Porous Silicon from Rice Husks as Anode Material for Li-ion Batteries Material Identification Electrochemical performance Chung-Chu, Chou (周盅車) and Chao-Hong, Wang (王朝弘)* Department of Chemical Engineering, National Chung Cheng University, Chia-yi, Taiwan (MOST 104-2218-E-194-005) In this study, we demonstrated a new and simple method for successfully preparing the porous Si powders from the agricultural waste - rice husks, which contains up to ~ 20% silica. A mixture of Si and Li x Si y O z is synthesized by thermal treatment of blending biogenic silica and reducing agents. After the removal of Li 4 SiO 4 , the pure Si particles characterized by FIB microscopy clearly revealed the porous structure with pore sizes of about 0.3-1.2 μm. Notably, the homogenous and high-porosity microstructure can accommodate the volume expansion of Si and enhance the lithiation/delithiation during the cycling. In addition, fluoroethylene carbonate (FEC) was added to the electrolyte, leading to the formation of a dense and less resistant SEI film on porous Si particle. The Si electrode exhibited the high capacity of ~2000 mAh/g, (0.1C) and good cycle life (69% capacity retention after 100 cycles) ). The approach has a scalable synthetic potential for the transformation of rice husk to obtain high-performance porous Si for many applications. Heat treatment Leaching with Acid Rice Husks- SiO 2 Etching with B.O.E. Morphology Capacity (mAh/g) 1 st cycle 1 st CE% Max. capacity 100 th cycle 100 th retention No FEC addition 2048.26 80.23% 2104.09 642.07 30.52% 5wt% FEC addition 1770.17 78.37% 1992.64 1365.75 68.54% 0 40 80 120 160 200 240 0 40 80 120 160 200 240 -Z(ohm) Z(ohm) After 100th cycle test 5wt% FEC addition no FEC addition Introduction We synthesized porous Si via thermal reduction of SiO 2 . The significant improvement of electrochemical performance could be achieved by electrolyte addition. The porous Si electrode have a good reversible capacity of 1365.75 mAh/g at the current density of 0.1C. Surface area : 48.5 m 2 /g Abstract Cross section Experimental Method Reducing agent Li 4 SiO 4 Porous Si Rice Husks- SiO 2 Pyrolysis Ball milled Calcination Rice Husks Leaching Si Pore MTES Rice Husks TEOS Sand Magnesiothermic Reduction Porous Si Etching Pore SiO 2 Assembling Cross section Zoom In Zoom In Conclusion New Thermal Reduction Carbothermic Magnesiothermic Aluminothermic Calciothermic New method Si Etching Etching MgO Si Si SiO 2 Li 4 SiO 4 SiO 2 Si a b c d (a) (b) (c) (d) 10 20 30 40 50 60 70 80 90 Leaching with Acid ● Li 2 SiO 3 Li 4 SiO 4 ● Si Intensity (a.u.) 2 (degree) Etching with B.O.E. Heat treatment Rice Husk - SiO 2

Transcript of Department of Chemical Engineering, National Chung Cheng ...

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Synthesis of Porous Silicon from Rice Husks as Anode Material for Li-ion Batteries

Material Identification

Electrochemical performance

Chung-Chu, Chou (周盅車) and Chao-Hong, Wang (王朝弘)*

Department of Chemical Engineering, National Chung Cheng University, Chia-yi, Taiwan

(MOST 104-2218-E-194-005)

In this study, we demonstrated a new and simple method for successfully preparing the porous Si powders from the agricultural waste - rice husks, which

contains up to ~ 20% silica. A mixture of Si and LixSiyOz is synthesized by thermal treatment of blending biogenic silica and reducing agents. After the

removal of Li4SiO4, the pure Si particles characterized by FIB microscopy clearly revealed the porous structure with pore sizes of about 0.3-1.2 µm.

Notably, the homogenous and high-porosity microstructure can accommodate the volume expansion of Si and enhance the lithiation/delithiation during the

cycling. In addition, fluoroethylene carbonate (FEC) was added to the electrolyte, leading to the formation of a dense and less resistant SEI film on porous

Si particle. The Si electrode exhibited the high capacity of ~2000 mAh/g, (0.1C) and good cycle life (69% capacity retention after 100 cycles) ). The

approach has a scalable synthetic potential for the transformation of rice husk to obtain high-performance porous Si for many applications.

Heat treatment

Leaching with Acid

Rice Husks- SiO2

Etching with B.O.E.

Morphology

Capacity (mAh/g) 1st cycle 1st CE% Max. capacity 100th cycle 100th retention

No FEC addition 2048.26 80.23% 2104.09 642.07 30.52%

5wt% FEC addition 1770.17 78.37% 1992.64 1365.75 68.54%

0 40 80 120 160 200 240

0

40

80

120

160

200

240

-Z(

ohm

)

Z(ohm)

After 100th cycle test

5wt% FEC addition

no FEC addition

Introduction

We synthesized porous Si via thermal reduction of SiO2. The significant improvement

of electrochemical performance could be achieved by electrolyte addition. The porous Si

electrode have a good reversible capacity of 1365.75 mAh/g at the current density of 0.1C.

Surface area : 48.5 m2/g

Abstract

Cross section

Experimental Method

Reducing

agent Li4SiO4

Porous Si

Rice Husks- SiO2

Pyrolysis Ball milled

Calcination

Rice Husks

Leaching

Si

Pore

MTES

Rice Husks

TEOS

Sand

Magnesiothermic Reduction

Porous Si

Etching

Pore

SiO2

Assembling

Cross section

Zoom In

Zoom In

Conclusion

New Thermal Reduction

Carbothermic

Magnesiothermic

Aluminothermic

Calciothermic

New method

Si

Etching

Etching

MgO

Si

Si SiO2

Li4SiO4

SiO2 Si

a b

c

d

(a)

(b) (c)

(d)

10 20 30 40 50 60 70 80 90

Leaching with Acid

●●

●●●

● ● ●

● Li2SiO

3

Li4SiO

4

●●

●●

●● ●

● Si

Inte

nsi

ty (

a.u

.)

2(degree)

Etching with B.O.E.

Heat treatment

Rice Husk - SiO2