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Silicon is a very promising candidate to replace graphite as the anode in Li-ion batteries because of its very high theoretical
capacity. It has not yet made its way into commercial cells because of severe problems with the charge and discharge cycling of
the material. It seems that amorphous silicon and amorphous silicon-containing alloys exhibit much improved cycling perfor-
mance. Therefore, it is desirable to fully understand the reaction of Li with a-Si. To this end, an in situ X-ray diffraction study of
the reaction of lithium with a-Si has been performed. The results confirm that a new crystalline Li15Si4 phase is formed below 30
mV vs. Li/Li⫹ as first reported by Obrovac and Christensen in an article published in Electrochemical and Solid-State Letters.
However, the crystalline phase only forms for films of a-Si above a critical thickness of about 2 m.
© 2004 The Electrochemical Society. 关DOI: 10.1149/1.1739217兴 All rights reserved.
In the portable electronics industry, the recent trend has been formed in a-Si thin films on cycling. These columns then cycled
toward smaller and more powerful devices. This requires batteries reversibly with little capacity loss. Maranchi et al.13 also found re-
made from materials with very high energy densities. The battery of sults similar to those of Beaulieu with excellent cycling and high
choice is currently the Li-ion battery, which typically consists of a capacities 共⬃3500 mAh/g兲 in 250 nm thick a-Si films on copper
graphite negative electrode and a LiCoO2 positive electrode. How- substrates. Netz et al.14 experimented with several alloys containing
ever, to meet the ever-increasing energy demands of modern de- silicon. Their materials were promising in terms of charge/discharge
vices, researchers are seeking new materials that will lead to smaller, cycling, but suffered from large first-cycle irreversible capacity.
lighter, and longer-lasting batteries. Many other alloy systems also experience a very large first-cycle
For the negative electrode, some of the most promising materials irreversible capacity.15-18 Wachtler et al. 15 reported irreversible ca-
include silicon, tin, and alloys containing these elements.1-5 Silicon pacities for Sn/SnSb alloys as high as 65% of first discharge. As
has a theoretical specific capacity of nearly 4200 mAh/g 共⬃9800 pointed out in the article, these high irreversible capacities may have
mAh/mL兲, which corresponds to a fully lithiated state of Li22Si5 共4.4 more to do with structure than composition.
Li per Si兲. This value is very favorable when compared to the spe- Several authors have reported that crystalline silicon be-
cific capacity of graphite, which is only 372 mAh/g (LiC6 ). comes amorphous upon alloying with lithium.19-21 Limthongkul
A crucial hurdle must still be overcome before these materials et al.20,21 collected high resolution electron microscopy and X-ray
diffraction 共XRD兲 data showing the conversion of a crystalline Si
can be used in commercial Li-ion cells. Although their capacities are
electrode into an amorphous Li-Si alloy. They proposed an electro-
very high, they do not retain this capacity over a large number of
chemically driven solid-state amorphization mechanism similar to
cycles.5 Some actually fall below 50% of their initial capacity after
thin-film solid-state amorphization.
less than five cycles. For use in a commercial cell, the capacity
Obrovac and Christensen22 recently reported that a-Si crystal-
retention must be much better than this.
The capacity loss in these alloy materials can occur for several lizes very rapidly to a new Li15Si4 phase below 50 mV vs. Li. The
reasons. In crystalline materials, new intermetallic phases are crystalline phase then converts back to a-Lix Si during the subse-
formed on lithium insertion.5 This leads to inhomogeneous volume quent charge. This fully lithiated phase of Li15Si4 seems to be more
expansions in the two-phase regions which can cause cracking and consistent with capacities reported in the literature, despite the fact
pulverization of the material. As a result of this cracking, some of that equilibrium phase diagrams do not predict it, but instead predict
the particles may lose electrical contact with the electrode, and ca- a fully lithiated state of Li22Si5 . The theoretical capacity for this
pacity is lost. phase is about 3500 mAh/g, which is very close to the capacities
In amorphous alloys, the capacity loss occurs for a different reported in.13 This has also been discussed previously in Ref. 23 and
reason. Beaulieu et al.6-9 have shown that in amorphous alloys of has been used to help explain capacities found in a-Si1⫺x Snx films.
Si and Sn, the expansion on lithium insertion is homogeneous and In this study, we performed an in situ XRD study of the reaction
that 10-30 m pieces of thin films expand and contract reversibly of lithium with a sputtered a-Si film. The XRD and electrochemical
without further pulverization. It appears that in these amorphous data are presented. Also, in Ref. 13 it was shown that the film
films, the capacity loss occurs because contact is lost because of thickness had a strong effect on the electrochemical performance.
expanding and contracting particles undergoing large volume Here we show that film thickness also has an effect on structural
changes and not because of the pulverization that occurs in crystal- changes that occur during the lithiation of a-Si films.
line films. It was shown in a previous work that amorphous alloys of
Experimental
Si-Al-Sn do tend to cycle better than their crystalline counterparts.10
Similar results were found by Song et al. for Mg2 Si films, although Samples were prepared by magnetron sputtering using a Corona
their amorphous films were 30 nm thick as compared to their nano- Vacuum Coater’s 共Vancouver, British Columbia, Canada兲 V3T sys-
crystalline films, which were 380 nm thick.11 tem. The system holds up to five targets, is turbopumped, and
To take advantage of the capacity available from silicon and to reaches a base pressure of 5 ⫻ 10⫺8 Torr. 2-in. diam targets of
overcome the problems with cycling, it is necessary to study it in boron-doped Si 共Pure Tech, 99.9%兲 were used. Films were deposited
detail. Many researchers have begun studying amorphous silicon using either a radio frequency 共rf兲 power supply with a net forward
and amorphous silicon-containing alloys. Sayama et al.12 found power of 200 W, or a dc power supply of 100 W.
similar results to those of Beaulieu, in that ⬃6 m columns were Films were deposited on a preweighed Be window 共Electro-
fusion, Fremont, CA兲 and on 1.3 cm diam preweighed Cu disks. The
Cu disks were cleaned with steel wool, and all substrates were
rinsed with methanol. To remove organic contaminants, substrates
* Electrochemical Society Student Member.
** Electrochemical Society Active Member. were exposed to an O2 plasma and an Ar plasma for 20 min, each
z
E-mail: jeff.dahn@dal.ca created with an rf power supply 共50 W net兲 attached to a Cu elec-
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Journal of The Electrochemical Society, 151 共6兲 A838-A842 共2004兲 A839
Figure 1. XRD pattern of 12 m a-Si film on a Be window for use in an Figure 2. Plot of potential vs. capacity for the in situ XRD cell. The arrow
in situ XRD test cell. indicates a change in slope near 0.03 V.
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A840 Journal of The Electrochemical Society, 151 共6兲 A838-A842 共2004兲
Obrovac and
Parameter This work Christensen 共Ref. 22兲
Lattice constant 10.777 Å 10.685 Å
Si 共16c兲 共x, y, z兲 共0.462, 0.462, 0.462兲 共0.459, 0.459, 0.459兲
Li 共48e兲 共0.130, 0.177, 0.865兲 共0.118, 0.156, 0.961兲
Li 共12a兲 共0.375, 0.0, 0.250兲 共0.375, 0.0, 0.250兲
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Journal of The Electrochemical Society, 151 共6兲 A838-A842 共2004兲 A841
Figure 6. Plot of data collected for the second discharge and charge of the in
Figure 7. Plots of 共a兲 potential vs. capacity for a 4.5 m thick a-Si film, 共b兲
situ XRD cell showing 共a兲 potential vs. time and 共b兲 selected XRD scans. The
circled numbers in 6a show the start time of the XRD scans. The numbers to dQ/dV vs. potential for a 4.5 m thick a-Si film, 共c兲 potential vs. capacity
the right of 6b show the scan numbers. Diffraction peaks from cell parts have for a 2.4 m thick a-Si film, 共d兲 dQ/dV vs. potential for a 2.4 m thick a-Si
been subtracted. film, 共e兲 potential vs. capacity for a 0.5 m thick a-Si film, and 共f兲 dQ/dV vs.
potential for a 0.5 m thick a-Si film.
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A842 Journal of The Electrochemical Society, 151 共6兲 A838-A842 共2004兲
References 14. A. Netz, R. A. Huggins, and W. Weppner, J. Power Sources, 119-121, 95 共2003兲.
15. M. Wachtler, M. Winter, and J. O. Besenhard, J. Power Sources, 105, 151 共2002兲.
1. C. J. Wen and R. A. Huggins, J. Electrochem. Soc., 128, 1636 共1981兲. 16. M. M. Thackeray, J. T. Vaughey, C. S. Johnson, A. J. Kropf, R. Benedek, L. M. L.
2. J. Wang, I. D. Raistrick, and R. A. Huggins, J. Electrochem. Soc., 133, 457 共1986兲. Fransson, and K. Edstrom, J. Power Sources, 113, 124 共2003兲.
3. J. Yang, M. Wachtler, M. Winter, and J. O. Besenhard, Electrochem. Solid-State 17. I. Rom, M. Wachtler, I. Papst, M. Schied, J. O. Besenhard, F. Hofer, and M. Winter,
Lett., 2, 161 共1999兲.
Solid State Ionics, 143, 329 共2001兲.
4. I. A. Courtney, J. S. Tse, O. Mao, J. Hafner, and J. R. Dahn, Phys. Rev. B, 58, 15583
共1998兲. 18. J. T. Vaughey, L. Fransson, H. A. Swinger, K. Edström, and M. M. Thackeray, J.
5. Good review articles: M. Winter and J. O. Besenhard, Electrochim. Acta, 45, 31 Power Sources, 119-121, 64 共2003兲.
共1999兲; R. A. Huggins in Handbook of Battery Materials, J. O. Besenhard, Editor, 19. H. Li, X. Huang, L. Chen, G. Zhou, Z. Zhang, D. Yu, Y. J. Mo, and N. Pei, Solid
Part III, Chap. 5, Wiley-VCH, Weinheim 共1999兲. State Ionics, 135, 181 共2000兲.
6. L. Y. Beaulieu, K. W. Eberman, L. J. Krause, and J. R. Dahn, Electrochem. Solid- 20. P. Limthongkul, Y. I. Jang, N. J. Dudney, and Y. M. Chiang, J. Power Sources,
State Lett., 4, A137 共2001兲. 119-121, 604 共2003兲.
7. L. Y. Beaulieu, K. C. Hewitt, R. L. Turner, A. Bonakdarpour, A. A. Abdo, K. W. 21. P. Limthongkul, Y. I. Jang, N. J. Dudney, and Y. M. Chiang, Acta Mater., 51, 1103
Eberman, L. J. Krause, and J. R. Dahn, J. Electrochem. Soc., 150, A149 共2003兲. 共2003兲.
8. L. Y. Beaulieu, T. D. Hatchard, and J. R. Dahn, Abstract 251, poster presented at 22. M. N. Obrovac and L. Christensen, Electrochem. Solid-State Lett., 7, A93 共2004兲.
the 11th International Meeting on Lithium Batteries, Monterey, CA, 2002. 23. T. D. Hatchard and J. R. Dahn, J. Electrochem. Soc., To be published.
9. L. Y. Beaulieu, T. D. Hatchard, A. Bonakdarpour, M. D. Fleischauer, and J. R. 24. M. N. Richard, I. Koetschau, and J. R. Dahn, J. Electrochem. Soc., 144, 554
Dahn, J. Electrochem. Soc., 150, A1457 共2003兲. 共1997兲.
10. T. D. Hatchard, J. M. Topple, M. D. Fleischauer, and J. R. Dahn, Electrochem.
25. M. Doyle, J. Newman, and J. Reimers, J. Power Sources, 52, 211 共1994兲.
Solid-State Lett., 6, A129 共2003兲.
26. P. Villars and L. D. Calvert, Pearson’s Handbook of Crystallographic Data for
11. S. W. Song, K. A. Striebel, X. Song, and E. J. Cairns, J. Power Sources, 119-121,
110 共2003兲. Intermetallic Phases, 2nd ed., Vol. 3, ASM International, Detroit, MI 共1991兲.
12. K. Sayama, H. Yagi, Y. Kato, S. Matsuta, H. Tarui, and S. Fujitani, Abstract 52, 27. Rietica v1.7.7, Microsoft Windows version of LHPM; R. J. Hill and C. J. Howard,
poster presented at the 11th International Meeting on Lithium Batteries, Monterey, J. Appl. Crystallogr., 18, 173 共1985兲; D. B. Wiles and R. A. Young, J. Appl.
CA, 2002. Crystallogr., 14, 149 共1981兲.
13. J. P. Maranchi, A. F. Hepp, and P. N. Kumta, Electrochem. Solid-State Lett., 6, 28. M. D. Fleischauer, T. D. Hatchard, G. P. Rockwell, J. M. Topple, S. Trussler, S. K.
A198 共2003兲. Jericho, M. H. Jericho, and J. R. Dahn, J. Electrochem. Soc., 150, A1465 共2003兲.
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