Electrochemical and Solid-State Letters, 6 共5兲 A75-A79 共2003兲 A75

0013-4651/2003/6共5兲/A75/5/$7.00 © The Electrochemical Society, Inc.

Structured Silicon Anodes for Lithium Battery Applications

Mino Green,a,*,z Elizabeth Fielder,a Bruno Scrosati,b,* Mario Wachtler,b
and Judith Serra Morenob
a
Department of Electrical and Electronic Engineering, Imperial College, London SW7 2BT, United Kingdom
b
Department of Chemistry, University of Rome ‘‘La Sapienza,’’ 00185 Roma, Italy

Pillar arrays fabricated on silicon substrates have been tested as potential anodes for lithium batteries. Electrodes of array
characteristics, diameter 580 ⫾ 150 nm; fractional surface coverage 0.34; height 810 nm are reported here. Cyclic voltammetry
共CV兲 and cyclic galvanostatic tests of alloying/dealloying of electrochemically produced lithium with silicon were carried out, and
results correlated with SEM studies. Aerial current densities in the low and fractional mA cm⫺2, and voltage 25 mV to 2 V 共vs.
L/Li⫹) were used. CV features correspond to various Zintl phase compounds 共ZPCs兲. Structured electrodes of Si pillars main-
tained their structural integrity throughout cycling; planar Si electrodes showed cracks 共2 ␮m features兲 after 50 cycles. A model
is advanced in which lithium diffuses through a layer of ZPC to react with Si: growing ZPCs plastically deforms where necessary.
Upon lithium dealloying vacancies coalesce to form voids at the ZPC/Si interface, Si rejoins the substrate, or precipitates out as
a nanocrystalline material, and the voids appear as a fine pattern of cracks, looking like dried mud. The extra surface area that a
pillar structure can confer on Si electrodes is essential and makes it practical to consider the possible eventual use of such anodes
in integrated battery structures.
© 2003 The Electrochemical Society. 关DOI: 10.1149/1.1563094兴 All rights reserved.

Manuscript submitted October 18, 2002; revised manuscript received January 22, 2003. Available electronically March 5, 2003.

Silicon is recognized as a potentially high energy per unit vol- Experimental

ume host material for lithium in lithium battery applications.1 At-
Structured electrode surfaces.—The structured electrode may be
tempts at realizing this potential have met with only partial success
made using conventional deep UV lithographic methods, but we
when nanocomposites of silicon powder and carbon black have been chose to use an economical method available to us, namely, ‘‘island
used.2 The major technical problem associated with the use of lithography.’’ This method employs cesium chloride as the resist in
silicon/lithium appears to be the mechanical failure brought about the lithographic step in the fabrication of pillar arrays. It works as
by the repeated large volume expansion associated with alloying.1c,3 follows. A thin film of CsCl is vacuum deposited on the clean,
Metallic and intermetallic anodic host materials, other than layer hydrophilic surface of the Si substrate. This system is then exposed
materials such as graphite, are reported to disintegrate after a few to the atmosphere at a controlled relative humidity. A multilayer of
lithium insertion/extraction cycles3,4 unless in fine powder form water adsorbs on the surface, the CsCl is soluble in the water layer
共submicrometer range兲. Since we are interested in finding a way to 共being more soluble at places of higher radius of curvature兲. The
make a lithium battery integrated onto a silicon chip we need to find CsCl reorganizes into a distribution of hemispherical islands, driven
a solution to this materials problem. Our proposal is to use a nano- by the excess surface energy associated with CsCl surface curvature.
structured silicon anode, discussed below. It is envisaged that the Such arrays are useful 共as a resist in reactive ion etching兲 in making
principle applications area for lithium batteries integrated into a chip structures for various studies involving nanoscale phenomena. A
study of the kinetics of the formation of island arrays has been
is in the medical field. Thus the well-developed practice of cochlea
carried out on GaAs surfaces9 and, more recently, and more exten-
implants appears to be an area that would benefit from an integrated
sively, on Si/SiO2 surfaces10 where the technique and results are
battery supply.5
described in detail. The process variables are CsCl film thickness
The characteristics of the silicon-lithium system, with its set of 共L兲; humidity 共RH兲, time of exposure 共t兲. The resulting island array
Zintl phase compounds 共ZPCs兲 is central to this work. Wen and has a Gaussian distribution of diameters, average diameter 共具d典兲
Huggins6 reported equilibrium emf data for the liquid system at standard deviation 共⫾␴兲, and surface fractional coverage 共F兲. Hav-
415°C 共shown in parentheses below兲 and the solid system at room ing made the CsCl resist array the next step is reactive ion etching
temperature7 共shown without parentheses below兲. Their results 共in 共RIE兲 to produce the corresponding array of pillars.11 The RIE pro-
millivolt vs. Li兲 are Si/Li12Si7 -582 (332); Li12Si7 /Li7 Si3 - cess variables are feed-gas composition, flow rate, and chamber
520 (288); Li7 Si3 /Li13Si4 -428 (158); Li13Si4 /Li21Si5 -⬃300 (44). pressure; rf power; dc bias; etch time. The results are characterized
It is proposed here that structured electrodes consisting of sub- by the etch depth, corresponding to pillar height 共H兲, and the wall
micrometer diameter pillars of silicon fabricated on an n-type silicon angle, namely, the angle that the pillar wall makes with the wafer
plane; it is chosen in this study to be close to 90°. The samples
wafer should be made 共see later Fig. 3兲. 共In a final version these
reported in this work were etched in an Oxford Plasmalab 80 appa-
pillar structures may be made on wafer-bonded silicon-on-insulator8
ratus. The etch gas was (O2 :Ar:CHF3 ) in the ratio 1:10:20; feed
substrates.兲 The basic notion is that such submicrometer anode
rate 20 sccm; chamber pressure, 50 mPa; rf power, 73 W; dc bias
structures, by virtue of their small size and configuration, should be 200 V.
able to tolerate the massive volume changes occasioned by lithium The pillar structure reported in this study 共K series兲 was charac-
alloying/dealloying. The volume of the first ZPC, Li12Si7 , is 2.17 terized as 具 d 典 ⫽ 580 ⫾ 150 nm; F ⫽ 0.34; H ⫽ 810 nm: it was
times larger than that of the host silicon from which it is made 共we made using, L ⫽ 80 nm; RH ⫽ 40%; t ⫽ 17.5 h. After fabrication
envisage that integrated batteries will be restricted mainly to this the silicon samples were washed in water; etched for 20 s in
composition兲. Therefore, any structure must be potentially capable NH4 OH (28 wt % NH3 ):H2 O2 (100 v/v):H2 O in equal volume ra-
of accommodating this increase: such a restriction means that the tios; the etchant was flooded away with deionized water and blow
silicon pillars should not exceed a fractional surface coverage 共F兲 of dried.
⬃0.5. SEM pictures were taken of the structured and planar electrodes
before and after galvanostatic cycling using a LEO 1450 scanning
electron microscope. Some micrographs contain insets showing the
* Electrochemical Society Active Member. image contrast along the line indicated in the main picture; this
z
E-mail: m.green@ic.ac.uk helped to improve the estimation of lateral dimensions.
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 A76 Electrochemical and Solid-State Letters, 6 共5兲 A75-A79 共2003兲

Figure 1. CVs for structured Si electrodes over the range 25 mV to 2 V; scan times: 共a兲 1, 共b兲 0.1, and 共c兲 0.01 mV s⫺1. 共d兲 Capacity 共␮Ah cm⫺2兲 and coulombic
efficiency vs. cycle number. The sequence of cycles was run without a break, starting at scan rate 1 mV s⫺1.

Electrochemical characterization.—The electrochemical tests of the electrode during the first Li discharge. After the first and
were performed in a three-electrode glass cell where the Si sample second cycles, the scans assumed a repeatable general shape. Be-
was the working electrode and metallic Li was used for both the cause these were scans in which the potential was changed slowly
counter and reference electrodes. A 1 M solution of LiClO4 共Merck and the current densities were therefore small, there was no IR drop
Selectipur兲 in ethylene carbonate:diethyl carbonate 共Merck Selec- or diffusion overpotential terms, and, assuming no activation over-
tipur兲, 共1:1兲 w/w solvent was used as the electrolyte. The cell was potential, the electrode potential was a measure of the surface
assembled under a dry argon atmosphere in a glove box. Ohmic lithium activity. The first cathodic feature was the rapid increase in
contact was made to the rear side of the silicon sample electrodes current at ⬃330 mV that, according to room-temperature data,7 cor-
using a 1:1 InGa eutectic alloy.12 The electrode area was delineated responded to the presence of Li12Si7 . The lowest potential reached
using an O-ring configuration in a polytetrafluoroethylene 共PTFE兲 was 25 mV and this was taken to be associated with the presence of
holder, the complete assembly being immersed in the electrolyte. No higher Li compounds, e.g., Li21Si5 . The capacity 共␮Ah cm⫺2兲 of the
adhesive was used and a good electrolyte/atmosphere seal was ob- pillars alone converted to Li12Si7 is given by
tained. In an earlier study we found that epoxy adhesive, used to 关 (FH/M ) ⌽ (12/7) 278兴 , where F and H are given above, M is the
mount a Si electrode, contaminated the active electrode surface molar volume of silicon, and ⌽ is the Faraday constant. For Li21Si5
causing spurious currents at high voltages 共⬎2 V兲. the above fraction 共12/7兲 is replaced by 共21/5兲. The cycling sequence
The electrochemical behavior of the cell was investigated by shows a progressive ‘‘activation’’ of the sample, associated with
cyclic voltammetry 共CV兲 and by galvanostatic measurement 共volt- increasing breakdown of the crystalline silicon structure 共see Dis-
age vs. time at constant current兲, using an electrochemical worksta- cussion兲. The anodic part of the CV curve is associated with pro-
tion 共VMP PerkinElmer Instruments兲. The capacity referred to here gressive delithiation of the electrode according to the various ZPC
is the total charge inserted into the projected electrode surface area equilibrium potentials. For a scan rate of 1 mV s⫺1 the capacity 共260
exposed to the electrolyte 共this ignores any surface area due to struc- ␮Ah cm⫺2兲 of the electrodes is roughly comparable to the pillar
turing兲, given as ␮Ah cm⫺2 共microampere-hours per centimeter
volume being converted to Li21Si5 , while for the slower scan rates
squared兲.
the capacity exceeds that of the pillar volume. The latter results
point to the participation of the substrate in the alloying/dealloying
Results
process.
⫹
The response of the Li兩 Li -electrolyte 兩Si cell was measured: for Figure 2 shows the results for a series of galvanostratic measure-
this cell the cathodic process was discharge of lithium onto silicon to ments on structured Si at two different charge depths 共amounts of
form an alloy 共charging兲, and the anodic process was lithium extrac- charge兲 that was obtained by using different cutoff potentials and
tion or dealloying 共discharging兲. Figure 1 shows one series of CV current densities: see captions for detail. Figure 3 shows the SEM
scan sets 共details in caption兲. The first cycle, and to a large extent the structure of the K series of silicon electrodes that were used in this
second, differs from those that follow. It is conjectured that this study and the effects of extensive galvanostatic cycling upon that
difference is due to a ‘‘formation’’ effect, associated with the filming structure. The structures are clearly intact, but at the higher charge
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 Electrochemical and Solid-State Letters, 6 共5兲 A75-A79 共2003兲 A77

Figure 2. Galvanostatic cycling tests on separate electrodes in the K series. The electrodes were first activated by 3 CV cycles at 1 mV s⫺1. 共a, b兲 Electrode
12K was charged at 415 ␮A cm⫺2 down to 150 mV and discharged at 41.5 ␮A cm⫺2 up to 2 V. 共c, d兲 Electrode 11K was charged at 1016 ␮A cm⫺2 down to
25 mV and discharged at 101.6 ␮A cm⫺2 up to 2 V. The charge currents of 415 ␮A cm⫺2 and 1016 ␮A cm⫺2 are those calculated currents that allow the
conversion of all of the Si contained in the pillars into Li12Si7 and Li21Si5 , respectively, within 15 min. The charge/discharge capacities and coulombic
efficiencies are shown in the corresponding graphs.

depths slight cracking of the bulk Si surface, below the pillars, is 共iii兲 The amorphous13 ZPC film is deformable and so does not give
observed. rise to stress-induced cracking on volume change. The diffusion
Figure 4 shows the SEM pictures of the structures obtained on coefficient, D, for Li in crystalline Si14 is ⬃10⫺14 cm2 s⫺1 , Li in
planar 共unpillared兲 Si electrodes before cycling and, separately, after ZPC is expected to be faster; a value of D ⭓ 10⫺12 cm2 s⫺1 is
galvanostatic cycling. When cycled at the lower charge depths, the enough to account for all the processes carried out in this study. This
surface is deformed, although crack formation does not occur. Cy- model for ZPC film formation is in many ways analogous to the
cling at higher charge depths produces wide cracks. model of SiO2 layer formation on silicon due to Deal and Grove:15
Discussion but the details are different and will be treated elsewhere.
The model for ZPC decomposition is, in broad terms, the reverse
The electrochemical discharge of lithium on silicon and its sub- of the above steps. Discharge of Lio at the electrolyte interface pro-
sequent chemical reaction destroys the silicon lattice, giving rise to duces a surface vacancy in the ZPC. Locally Lio moves into the
the swelling of the solid, producing amorphous Si/Li phases.13 The vacancy so the vacancy diffuses back to the ZPC/Si interface: at the
first new phase to appear in the system is Li12Si7 . This compound, interface Sin rejoins the Si phase 共where it is said to be
and all the rest up to Li, is a so-called Zintl-phase compound, and polycrystalline13兲 and vacancies coalesce to produce larger void
consists of simple, electropositive cations and complex covalently spaces. These spaces, as they coalesce further and grow, give rise to
bound, multiply charged, electronegative anions. The charge as- the crack-like features seen in the SEM pictures in Fig. 3b, c and 4.
cribed to the ‘‘ions’’ is purely notional: the actual charge 共depending Such a process has been described by Beaulieu et al.16 for lithium
upon definition兲 is less than the formal value and may be consider- removal from silicon/tin alloys.
ably less, and we simply refer to bulk lithium as Lio and bulk silicon It has been shown that repeated Li alloying/dealloying of planar
as Sion . Si can be carried out without pulverization of the substrate, cf. Fig.
It is important to form some idea of the mechanism of lithiation 4. However, as noted, the alloy/dealloy process is limited by diffu-
and delithiation of silicon. We propose that 共i兲 Discharged lithium sion through the ZPC layer. To obtain charging rates suitable for
reacts with silicon forming a ZPC film with atomically continuous various applications it is necessary to increase the surface area of the
contact to the silicon. 共ii兲 Lithium excess diffuses 共via a vacancy Si/electrolyte interface; and this has been done using pillar fabrica-
mechanism兲 through the compact ZPC film to react with silicon at tion. Previous attempts using silicon particles have failed because
the Si/ZPC interface, thickening the ZPC film, without void forma- the particle-to-particle contacts change and part with cycling.2 The
tion. These processes may be represented by Li⫹(el) ⫹ e⫺(solid) pillar structures are largely maintained as evidenced by the flatness
→ Li(ads); Li(ads) ⫹ V(ZPC) → Lio (ZPC) s ; Lio (ZPC) s of the pillar tops after 50 cycles, cf. Fig. 3.
→ diffusion → Lio (ZPC) ZPC/Si ; xLio ⫹ ySio → ZPC (Lix/y Si) Efficiencies of ⬍100% reported here are attributed mainly to
共where Li共ads兲 is Li adsorbed on ZPC; V is a Lio vacancy in ZPC兲. reaction, on alloying, with the electrolyte, and to a lesser extent
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 A78 Electrochemical and Solid-State Letters, 6 共5兲 A75-A79 共2003兲

Figure 4. SEM pictures of flat, unstructured Si. 共a兲 Before and 共b, c兲 after 50
Figure 3. SEM pictures of structured Si. 共a兲 Before and 共b, c兲 after galvano- galvanostatic cycles. The cycling procedures used for the samples shown in
static cycling. 共b兲 A sample after three CV activation cycles and 50 cycles 共b兲 and 共c兲 are the same as those used for the structured Si samples shown in
using a charge current of 415 ␮A cm⫺2, a discharge current of 41.5 ␮A Fig. 3b and c, respectively.
cm⫺2, and a potential range of 150 mV to 2 V 共cf. Fig. 2a and b兲. 共c兲 A
sample after three CV activation cycles and 50 cycles using a charge current
of 1016 ␮A cm⫺2, a discharge current of 101.6 ␮A cm⫺2, and a potential
range of 25 mV to 2 V 共cf. Fig. 2c and d兲.
⫻ 10⫺4 cm3 /cm2 , which is equivalent, when converted to Li12Si7 ,
to a capacity of 3.81 ⫻ 103 v ⫽ 914 ␮Ah cm⫺2 . The surface area
isolation of regions of ZPC. The data presented here show that re- enhancement of such a pillar structure is ⬃4FH/d, which is the
duced current density on both alloying and dealloying results in basis of the much improved characteristics.
improving efficiency. We suppose that this improvement comes
mainly from a reduced surface concentration of adsorbed Li on al- Acknowledgment
loying and accessing all the lithium in the ZPC on dealloying.
There is large scope for further increasing the surface-to-volume We thank the CEC for funding this work under the Assess
ratio of the pillar construction, and we may look forward to, for Scheme in the Information Technology Program 共contract no. IST-
example, pillars of diameter 共d兲 ⬃0.3 ␮m and 6 ␮m height 共H兲. The 2000-29694兲.
pillar volume ( v ) would be, FH, and for F ⫽ 0.4, v ⫽ 2.4 Imperial College assisted in meeting the publication costs of this article.

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 Electrochemical and Solid-State Letters, 6 共5兲 A75-A79 共2003兲 A79

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