U.S. patent application number 15/844199 was filed with the patent office on 2018-09-20 for method of fabricating structured particles composed of silicon or a silicon-based material and their use in lithium rechargeable batteries.
The applicant listed for this patent is Nexeon Limited. Invention is credited to Mino Green, Feng-Ming Liu.
Application Number | 20180269470 15/844199 |
Document ID | / |
Family ID | 38476463 |
Filed Date | 2018-09-20 |
United States Patent
Application |
20180269470 |
Kind Code |
A1 |
Green; Mino ; et
al. |
September 20, 2018 |
METHOD OF FABRICATING STRUCTURED PARTICLES COMPOSED OF SILICON OR A
SILICON-BASED MATERIAL AND THEIR USE IN LITHIUM RECHARGEABLE
BATTERIES
Abstract
Pillared particles of silicon or silicon-comprising material and
a method of fabricating the same are disclosed. These particles may
be used to create both a composite anode structure with a polymer
binder, a conductive additive and a metal foil current collector,
and an electrode structure. The structure of the particles
overcomes the problems of charge/discharge capacity loss.
Inventors: |
Green; Mino; (London,
GB) ; Liu; Feng-Ming; (Reading, GB) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Nexeon Limited |
Oxfordshire |
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GB |
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|
Family ID: |
38476463 |
Appl. No.: |
15/844199 |
Filed: |
December 15, 2017 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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14593674 |
Jan 9, 2015 |
9871244 |
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15844199 |
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12669216 |
Feb 26, 2010 |
8940437 |
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PCT/GB2008/002452 |
Jul 17, 2008 |
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14593674 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
H01M 4/386 20130101;
H01M 4/134 20130101; Y02P 70/50 20151101; Y10T 117/102 20150115;
H01M 4/0492 20130101; Y10T 428/2982 20150115; H01M 4/1395 20130101;
H01M 10/52 20130101; H01M 2004/027 20130101; Y02E 60/10 20130101;
Y02P 70/54 20151101; Y10T 29/49108 20150115 |
International
Class: |
H01M 4/134 20060101
H01M004/134; H01M 10/52 20060101 H01M010/52; H01M 4/38 20060101
H01M004/38; H01M 4/1395 20060101 H01M004/1395; H01M 4/04 20060101
H01M004/04 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 17, 2007 |
GB |
0713898.5 |
Claims
1. A particle comprising a particle core and a plurality of
elongate structures coating one or more surfaces of the particle,
each extending outwardly from the particle core from a first end to
a second end, wherein each of the plurality of elongate structures
is attached to the core at the first end of the elongate structure
and the second end of the elongate structure is an unattached free
end, and wherein the elongate structures are formed from
silicon.
2. A particle as claimed in claim 1, wherein the fraction of the
surface area of the particle core occupied by the elongate
structures is in the range of 0.10 to 0.50.
3. A particle as claimed in claim 2, wherein the particle has a
diameter of at least 0.5 .mu.m and the elongate structures have an
aspect ratio of greater than 20:1.
4. A particle as claimed in claim 1 wherein the particles have a
first dimension in the range of 10 .mu.m to 1 mm.
5. A particle as claimed in claim 1, wherein the elongate
structures have a diameter in the range of 0.08 to 0.70
microns.
6. A particle as claimed in claim 1 in which the elongate
structures have a length from the first end to the second end in
the range of 4 to 100 microns.
7. A particle as claimed in claim 1, wherein the elongate
structures are formed from n-type silicon, p-type silicon, or
metallurgical grade silicon.
8. A particle as claimed in claim 1 wherein the elongate structures
have a silicon purity of 90.00 to 99.95% by mass.
9. A particle as claimed in claim 1 in which the plurality of
elongate structures coat one or more surfaces of each particle.
10. A particle as claimed in claim 1, wherein in each of the
plurality of discrete particles, the plurality of elongate
structures extend over all the surfaces of the particle core.
11. A particle as claimed in claim 1, wherein the elongate
structures and the particle core are formed from the same
material.
12. A particle as claimed in claim 1, wherein the fraction of the
surface area of the particle core occupied by the elongate
structures is in the range of 0.10 to 0.50; the elongate structures
have an aspect ratio of greater than 20:1; the elongate structures
have a diameter in the range of 0.08 to 0.70 microns; the elongate
structures have a length from the first end to the second end in
the range of 4 to 100 microns; the elongate structures have a
silicon purity of 90.00 to 99.95% by mass; and the plurality of
elongate structures coat one or more surfaces of each particle.
13. A plurality of discrete particles as claimed in claim 1.
14. A solvent-based slurry comprising a solvent and a plurality of
discrete particles as claimed in claim 1.
15. A porous composite structure for an electrode comprising a
plurality of discrete particles, each discrete particle comprising
a particle core and a plurality of elongate structures coating one
or more surfaces of the particle, each extending outwardly from the
particle core from a first end to a second end, wherein each of the
plurality of elongate structures is attached to the core at the
first end of the elongate structure, and wherein the elongate
structures are formed from silicon; and a binder binding the
particles into the composite structure.
16. A porous composite structure as claimed in claim 15, further
comprising an electronic additive bound into the composite
structure by the binder.
17. A porous composite structure according to claim 16, having a
pore volume of 10-30%.
18. An electrochemical cell comprising an anode and a cathode, the
anode comprising a porous composite structure according to claim 15
disposed against a current collector.
19. A method of fabricating a porous composite structure according
to claim 15, the method comprising providing a solvent-based slurry
of the plurality of discrete particles and a binder; coating the
slurry onto a surface; and evaporating the solvent to create the
porous composite structure.
20. A method of fabricating a plurality of discrete particles, each
particle comprising a particle core and a plurality of elongate
structures coating one or more surfaces of the particle, each
extending outwardly from the particle core from a first end to a
second end, wherein each of the plurality of elongate structures is
attached to the core at the first end of the elongate structure and
the second end of the elongate structure is an unattached free end,
and wherein the elongate structures are formed from silicon, the
method comprising providing a plurality of silicon particles, and
etching the silicon particle to form the elongate structures.
21. A method as claimed in claim 20 in which the elongate
structures are created by galvanic exchange etching.
Description
[0001] This application is a continuation of U.S. patent
application Ser. No. 14/593,674, filed Jan. 9, 2015, which is a
continuation of U.S. patent application Ser. No. 12/669,216, filed
Feb. 26, 2010, which is a U.S. National State application of
International Patent Application no. PCT/GB2008/002452, which
claims priority to U.K. Patent Application no. GB0713898.5, filed
Jul. 17, 2007, each of which is hereby incorporated herein by
reference in its entirety.
[0002] The invention relates to a particle comprising silicon, a
method of fabricating a particle, an electrode containing particles
as its active material, an electrochemical cell, a lithium
rechargeable cell anode, a cell, a device powered by a cell, a
method of creating a composite electrode, a method of fabricating a
lithium rechargeable cell and a method of fabricating
silicon-comprising fibres.
[0003] The recent increase in the use of portable electronic
devices such as mobile telephones and notebook computers and the
emerging trend of using rechargeable batteries in hybrid electric
vehicles has created a need for smaller, lighter, longer lasting
rechargeable batteries to provide the power to the above mentioned
and other battery powered devices. During the 1990s, lithium
rechargeable batteries, specifically lithium-ion batteries, became
popular and, in terms of units sold, now dominate the portable
electronics marketplace and are set to be applied to new, cost
sensitive applications. However, as more and more power hungry
functions are added to the above mentioned devices (e.g. cameras on
mobile phones), improved and lower cost batteries that store more
energy per unit mass and per unit volume are required.
[0004] It is well known that silicon can be used as the active
anode material of a rechargeable lithium-ion electrochemical
battery cell (see, for example, Insertion Electrode Materials for
Rechargeable Lithium Batteries, M. Winter, J. O. Besenhard, M. E.
Spahr, and P. Novak in Adv. Mater. 1998, 10, No. 10). The basic
composition of a conventional lithium-ion rechargeable battery cell
is shown in FIG. 1 including a graphite-based anode electrode, the
component to be replaced by the silicon-based anode. The battery
cell includes a single cell but may also include more than one
cell.
[0005] The battery cell generally comprises a copper current
collector 10 for the anode and an aluminium current collector 12
for the cathode which are externally connectable to a load or to a
recharging source as appropriate. A graphite-based composite anode
layer 14 overlays the current collector 10 and a lithium containing
metal oxide-based composite cathode layer 16 overlays the current
collector 12. A porous plastic spacer or separator 20 is provided
between the graphite-based composite anode layer 14 and the lithium
containing metal oxide-based composite cathode layer 16 and a
liquid electrolyte material is dispersed within the porous plastic
spacer or separator 20, the composite anode layer 14 and the
composite cathode layer 16. In some cases, the porous plastic
spacer or separator 20 may be replaced by a polymer electrolyte
material and in such cases the polymer electrolyte material is
present within both the composite anode layer 14 and the composite
cathode layer 16.
[0006] When the battery cell is fully charged, lithium has been
transported from the lithium containing metal oxide via the
electrolyte into the graphite-based layer where it reacts with the
graphite to create the compound, LiC.sub.6. The graphite, being the
electrochemically active material in the composite anode layer, has
a maximum capacity of 372 mAh/g. It will be noted that the terms
"anode" and "cathode" are used in the sense that the battery is
placed across a load.
[0007] It is generally believed that silicon, when used as an
active anode material in a lithium-ion rechargeable cell, provides
a significantly higher capacity than the currently used graphite.
Silicon, when converted to the compound Li.sub.21Si.sub.5 by
reaction with lithium in an electrochemical cell, has a maximum
capacity of 4,200 mAh/g, considerably higher than the maximum
capacity for graphite. Thus, if graphite can be replaced by silicon
in a lithium rechargeable battery the desired increase in stored
energy per unit mass and per unit volume can be achieved.
[0008] Existing approaches of using a silicon or silicon-based
active anode material in a lithium-ion electrochemical cell have
failed to show sustained capacity over the required number of
charge/discharge cycles and are thus not commercially viable.
[0009] One approach disclosed in the art uses silicon in the form
of a powder (say as particles or spherical elements with a 10 .mu.m
diameter), in some instances made into a composite with or without
an electronic additive and containing an appropriate binder such as
polyvinylidene difluoride coated onto a copper current collector.
However, this electrode system fails to show sustained capacity
when subjected to repeated charge/discharge cycles. It is believed
that this capacity loss is due to partial mechanical isolation of
the silicon powder mass arising from the volumetric
expansion/contraction associated with lithium insertion/extraction
to and from the host silicon. In turn this gives rise to electrical
isolation of the silicon elements from both the copper current
collector and themselves. In addition, the volumetric
expansion/contraction causes the spherical elements to be broken up
causing a loss of electrical contact within the spherical element
itself.
[0010] Another approach known in the art designed to deal with the
problem of the large volume changes during successive cycles is to
make the size of the silicon elements that make up the silicon
powder very small, that is to use spherical particles that have
diameters in the 1-10 nm range. This strategy assumes that the
nano-sized elements can undergo the large volumetric
expansion/contraction associated with lithium insertion/extraction
without being broken up or destroyed. However, this approach is
problematic in that it requires the handling of very fine,
nano-sized powder that may pose a health and safety risk and it
does not prevent the electrical isolation of the spherical elements
from both the copper current collector and themselves as the
silicon powder undergoes the volumetric expansion/contraction
associated with lithium insertion/extraction. Importantly, the
large surface area of the nano-sized elements can give rise to the
creation of a lithium-containing surface film that introduces a
large irreversible capacity into the lithium-ion battery cell. In
addition, the large number of small silicon particles creates a
large number of particle-to-particle contacts for a given mass of
silicon and these each have a contact resistance and may thus cause
the electrical resistance of the silicon mass to be too high. The
above problems have thus prevented silicon particles from becoming
a commercially viable replacement for graphite in lithium
rechargeable batteries and specifically lithium-ion batteries.
[0011] In another approach described by Ohara et al. in Journal of
Power Sources 136 (2004) 303-306 silicon is evaporated onto a
nickel foil current collector as a thin film and this structure is
then used to form the anode of a lithium-ion cell. However,
although this approach gives good capacity retention, this is only
the case for very thin films (say .about.50 nm) and thus these
electrode structures do not give usable amounts of capacity per
unit area. Increasing the film thickness (say >250 nm) causes
the good capacity retention to be eliminated. The good capacity
retention of these thin films is considered by the present
inventors to be due to the ability of the thin film to absorb the
volumetric expansion/contraction associated with lithium
insertion/extraction from the host silicon without the film being
broken up or destroyed. Also, the thin film has a much lower
surface area than the equivalent mass of nano-sized particles and
thus the amount of irreversible capacity due to the formation of a
lithium-containing surface film is reduced. The above problems have
thus prevented a thin film of silicon on a metal foil current
collector from becoming a commercially viable replacement for
graphite in lithium rechargeable batteries and specifically
lithium-ion batteries.
[0012] In another approach described in US2004/0126659, silicon is
evaporated onto nickel fibres which are then used to form the anode
of a lithium battery.
[0013] However this is found to provide an uneven distribution of
silicon on the nickel fibres hence significantly affecting
operation. In addition, these structures have a high ratio of
nickel current collector mass to active silicon mass and thus do
not give usable amounts of capacity per unit area or per unit
mass.
[0014] A review of nano- and bulk-silicon-based insertion anodes
for lithium-ion secondary cells has been provided by Kasavajjula et
al (J. Power Sources (2006), doi:10.1016/jpowsour.2006.09.84),
herewith incorporated by reference herein.
[0015] Another approach described in UK Patent Application
GB2395059A uses an silicon electrode comprising a regular or
irregular array of silicon pillars fabricated on a silicon
substrate. These structured silicon electrodes show good capacity
retention when subjected to repeated charge/discharge cycles and
this good capacity retention is considered by the present inventors
to be due to the ability of the silicon pillars to absorb the
volumetric expansion/contraction associated with lithium
insertion/extraction from the host silicon without the pillars
being broken up or destroyed. However, the structured silicon
electrodes described in the above publication is fabricated by
using a high purity, single crystal silicon wafer and hence
produces an electrode with a potentially high cost.
[0016] The first aspect of the invention provides a particle
comprising silicon having a particle core and an array of
silicon-comprising pillars extending therefrom.
[0017] The pillars may be regular or irregular. The pillars of the
present invention are 0.08 to 0.70 microns in one dimension,
preferably 0.1 to 0.5 microns, more preferably 0.2 to 0.4 microns,
and most preferably 0.3 microns or above. In a second dimension,
the pillars are 4 to 100 microns, preferably 10 to 80 microns, more
preferably 30 microns or above. The pillars thus have an aspect
ratio of greater than 20:1. The pillars may have a substantially
circular cross-section or a substantially non-circular
cross-section.
[0018] The pillared particle may comprise undoped silicon, doped
silicon or a mixture, such as a silicon-germanium mixture. In
particular, the particle may have a silicon-purity of 90.00% to
99.95% by mass, preferably 90.0% to 99.5%. The silicon can be doped
with any material for example, phosphorous, aluminium, silver,
boron and/or zinc. The particle may be relatively low purity
metallurgical grade silicon.
[0019] The particles may be regular or irregular in cross section
and can be from 10 .mu.m to 1 mm in diameter, preferably 20 .mu.m
to 150 .mu.m, more preferably 25 .mu.m to 75 .mu.m.
[0020] The second aspect of the invention provides a method of
fabricating a particle of the first aspect, comprising the steps of
etching a particle comprising silicon. In particular, the pillars
can be created by chemical reaction etching or galvanic exchange
etching.
[0021] The third aspect of the invention provides a composite
electrode containing particles as defined in the first aspect of
the invention as one of its active materials. In particular, the
third aspect provides a composite electrode which uses copper as a
current collector. In a feature of the third aspect, the electrode
can be an anode.
[0022] The third aspect therefore further provides an
electrochemical cell containing an electrode as defined above. In
particular, there is provided an electrochemical cell in which the
cathode comprises a lithium-containing compound capable of
releasing and reabsorbing lithium ions as its active material. In
particular, there is provided an electrochemical cell in which the
cathode comprises lithium-based metal oxide or phosphate as its
active material preferably LiCoO.sub.2 or
LiMn.sub.xNi.sub.xCo.sub.1-2xO.sub.2 or LiFePO.sub.4.
[0023] The invention further provides a lithium rechargeable cell
anode comprising particles of the first aspect. In particular,
there is provided an anode in which the particles are part of a
composite.
[0024] The third aspect further provides a cell comprising an anode
and a cathode wherein the cathode preferably comprises
lithium-based material, more preferably lithium cobalt dioxide.
[0025] There is further provided a device powered by a cell as
defined above. The fourth aspect of the invention provides a method
of creating a composite electrode comprising the steps of preparing
a solvent-based slurry containing pillared particles, coating the
slurry onto a current collector and evaporating the solvent to
create a composite film.
[0026] The invention further provides a method of fabricating a
lithium rechargeable cell comprising the steps of creating an anode
as defined above and adding a cathode an electrolyte. In
particular, the method further comprising adding a separator
between cathode and the anode. A casing may be provided around the
cell.
[0027] There is also provided a method of fabricating
silicon-comprising fibres in which the pillars are detached from a
particle of the first aspect by one or more of scraping, agitating
or chemical etching.
[0028] The production of an anode electrode structure using the
structured particles of the invention further overcomes the
problems of reversibly reacting silicon with lithium. In particular
by arranging the particles in a composite structure, that is a
mixture of particles, a polymer binder and an conductive additive,
or by directing bonding the structured particles to the current
collector, the charge/discharge process becomes reversible and
repeatable and good capacity retention is achieved. This good
reversibility is considered by the present inventors to be due to
the ability of the silicon pillars forming part of the structured
silicon particle to absorb the volumetric expansion/contraction
associated with lithium insertion/extraction from the host silicon
without the pillars being broken up or destroyed. Importantly, the
silicon electrodes described in this invention are fabricated by
using a low purity, metallurgical grade silicon and hence produces
an electrode with a potentially low cost.
[0029] Embodiments of the invention will now be described, by way
of example, with reference to the figures, of which:
[0030] FIG. 1 is a schematic diagram showing the components of a
battery cell;
[0031] FIG. 2 is a electron micrograph of a pillared particle
according to embodiments of the present invention;
[0032] FIG. 3 shows the overall galvanic exchange etching
mechanism; and
[0033] FIG. 4 shows hypothetical kinetic curves in the form of the
partial currents in the galvanic exchange etching process.
[0034] In overview the invention allows creation of pillared
particles of silicon or silicon-comprising material and the use of
these particles to create both a composite anode structure with a
polymer binder, an conductive additive (if required) and a metal
foil current collector and an electrode structure. In particular it
is believed that the structure of the particles that make up the
composite overcomes the problem of charge/discharge capacity loss.
By providing a particle with a plurality of elongate or long thin
pillars the problem of charge/discharge capacity loss is
reduced.
[0035] Typically the pillars will have a length to diameter ratio
of approximately 20:1. The insertion and removal of lithium into
the pillars, although causing volume expansion and volume
contraction, does not cause the pillars to be destroyed and hence
the intra-fibre electronic conductivity is preserved.
[0036] The pillars can be made on the particles by wet
etching/using a chemical galvanic exchange method for example as
described in our co-pending application GB 0601318.9 with common
assignees and entitled "Method of etching a silicon-based
material", incorporated herewith by reference. A related method
which may also be used has been disclosed in Peng K-Q, Yan, Y-J
Gao, S-P, Zhu J., Adv. Materials, 14 (2004), 1164-1167 ("Peng"); K.
Peng et al, Angew. Chem. Int. Ed., 44 2737-2742; and K. Peng et
al., Adv. Funct. Mater., 16 (2006), 387-394; K. Peng, Z. Huang and
J. Zhu, Adv. Mater., 16 (2004), 127-132; and T. Qui, L. Wu, X.
Yang, G. S. Huang and Z. Y. Zhang, Appl. Phys. Lett., 84 (2004),
3867-3869. The above-mentioned methods are used to produce pillars
from a high purity silicon wafer.
[0037] In a preferred embodiment of the present invention, pillars
are produced on crystalline particles of relatively low purity
silicon such as metallurgical grade silicon. The method comprises
the five steps of: grinding and sieving; washing; nucleation;
etching; and silver removal, as explained, by way of example only,
later. An electron micrograph of pillared particle made in
accordance with present invention is shown in FIG. 2.
[0038] Any appropriate grinding process is suitable such as power
grinding or ball milling. The skilled person will appreciate that a
minimum particle size will exist below which pillars cannot be
etched onto the surface and instead the particle will be
homogeneously etched away. Particles having a diameter less than
0.5 .mu.m may be too small.
[0039] A more uniform pillar array, in terms of density and height,
is produced by nucleating before etching. This step produces a
uniform distribution of silver nuclei/islands (nuclei combine and
form silver islands that are the site for pillar growth).
[0040] Silver islands delineate the formation of pillars and
galvanic fluoride etching of the {100} planes: see FIG. 3.
Referring to FIG. 3 there is shown a silicon surface 301 having a
pillar 307. An electron 305 is transferred from a fluoride ion 303
to the silicon surface 301. The reaction of fluorine with silicon
301 and fluoride ions 303 gives rise to fluorosilicate ions 305.
This is the anodic etching process. The cathode process is the
discharge of silver ions 309 to produce metallic silver 311.
[0041] The structure is explained by supposing that
silicon-fluoride bonds are formed as an essential step in the etch
process. And furthermore that structures that are Si--F
(mono-fluoride) are stable and those that are F--Si--F
(di-fluoride) and Si[--F]3 (tri-fluoride) are not stable. This is
because of steric interference on the Si surface of nearest
neighbour groups. The case of the {111} plane is that, a
mono-fluoride surface, stable except at the edges, inevitably
proceeds to a tri-fluoride surface and consequent instability. The
{110} surface is the only stable major crystal plane of Si that
will have exclusively mono-fluoride bonds-hence its stability and
the etch rate ratio [etch rate <100>]:[etch rate <110>]
of about three orders of magnitude. So the sides of the pillars
will be terminated on {110} planes.
[0042] A pillar surface density may be used to define the density
of the pillars on the surface of the particle. Herein, this is
defined as F=P/[R+P] wherein: F is the pillar surface density; P is
the total surface area of the particle occupied by pillars; and R
is the total surface area of the particle unoccupied by
pillars.
[0043] The larger the pillar surface density, the larger the
lithium capacity per unit area of a silicon particle electrode and
the larger the amount of harvestable pillars available to create
fibres.
[0044] For example, using the above-mentioned silicon powder from
Elken of Norway having a pre-etching size of
400.times.300.times.200 .mu.m, pillars are produced all over the
surface having a pillar height of approximately 25 to 30 .mu.m, a
diameter of approximately 200 to 500 nm and a pillar surface
density, F, of 10-50%, more typically, 30%.
[0045] For example, particles having a pre-etching size of
approximately 63-80.times.50.times.35 .mu.m are found to produce
pillars with a height of approximately 10 to 15 .mu.m, with a
coverage of approximately 30% and a diameter of approximately 200
to 500 nm
[0046] In a preferred embodiment, pillars of for example 100
microns in length and 0.2 microns in diameter are fabricated on and
from a silicon-comprising particle. More generally pillars of
length in the range of 4 to 100 microns and diameter or transverse
dimension in the range of 0.08 to 0.70 microns are fabricated from
a particle having an initial size of 10 to 1000 .mu.m.
[0047] According to the process, the silicon particles may be
predominantly n- or p-type and, according to the chemical approach,
and may be etched on any exposed (100), (111) or (110) crystal
face. Since the etching proceeds along crystal planes, the
resulting pillars are single crystals. Because of this structural
feature, the pillars will be substantially straight facilitating
length to diameter ratio of greater than 20:1.
[0048] The pillared-particles may then be used to form a composite
electrode as described later. Alternatively, the pillars may be
detached from the particle and used to form a fibre-based
electrode. The detached pillars may also be described as
fibres.
[0049] The invention encompasses the detachment of the pillars from
the particle. The particle, with pillars attached, can be placed in
a beaker or any appropriate container, covered in an inert liquid
such as ethanol or water and subjected to ultra-sonic agitation. It
is found that within several minutes the liquid is seen to be
turbid and it can be seen by electron microscope examination that
at this stage the pillars have been removed from the particle.
[0050] In an embodiment, the pillars are removed from the particle
in a two stage process. In the first stage, the particles are
washed several times in water and, if necessary, dried in a low
vacuum system to remove the water. In the second stage, the
particles are agitated in an ultrasonic bath to detach the pillars.
These are suspended in water and then filtered using different
various filter paper sizes to collect the silicon fibres.
[0051] It will be appreciated that alternative methods for
"harvesting" the pillars include scraping the particle surface to
detach them or detaching them chemically. One chemical approach
appropriate to n-type silicon material comprises etching the
particle in an HF solution in the presence of backside
illumination.
[0052] Once the pillared particles have been fabricated they can be
used as the active material in a composite anode for lithium-ion
electrochemical cells. To fabricate a composite anode, the pillared
particles are mixed with polyvinylidene difluoride and made into a
slurry with a casting solvent such as n-methyl pyrrolidinone. This
slurry can then be applied or coated onto a metal plate or metal
foil or other conducting substrate for example physically with a
blade or in any other appropriate manner to yield a coated film of
the required thickness and the casting solvent is then evaporated
from this film using an appropriate drying system which may employ
elevated temperatures in the range of 50 degrees C. to 140 degrees
C. to leave the composite film free or substantially from casting
solvent. The resulting composite film has a porous structure in
which the mass of silicon-based pillared particles is typically
between 70 percent and 95 percent. The composite film will have a
percentage pore volume of 10-30 percent, preferably about 20
percent.
[0053] Fabrication of the lithium-ion battery cell thereafter can
be carried out in any appropriate manner for example following the
general structure shown in FIG. 1 but with a silicon-comprising
active anode material rather than a graphite active anode material.
For example the silicon particle-based composite anode layer is
covered by the porous spacer 20, the electrolyte added to the final
structure saturating all the available pore volume. The electrolyte
addition is done after placing the electrodes in an appropriate
casing and may include vacuum filling of the anode to ensure the
pore volume is filled with the liquid electrolyte.
[0054] Some embodiments provide an electrode containing as its
active material a plurality of pillared particles of silicon.
Capacity retention is improved as the pillared structure of the
silicon allows for accommodation of the volume expansion associated
with insertion/extraction (charging and discharging) of lithium.
Advantageously, the pillared particles may be created by etching
lumps of low purity, silicon (termed metallurgical grade silicon)
such that a core of silicon remains covered by pillars that are
between 0.08 .mu.m and 0.5 .mu.m in diameter and between 4 .mu.m
and 150 .mu.m in length.
[0055] A particular advantage of the approach described herein is
that large sheets of silicon-based anode can be fabricated and then
rolled or stamped out subsequently as is currently the case in
graphite-based anodes for lithium-ion battery cells meaning that
the approach described herein can be retrofitted with the existing
manufacturing capability.
[0056] The invention will now be illustrated by reference to one or
more of the following non-limiting examples:
Grinding and Seiving
[0057] In the first stage, widely-available metallurgical grade
silicon, such as "Silgrain" from Elkem of Norway, was ground and
sieved to produce particles in the range 10 to 1000 .mu.m,
preferably 30 to 300 .mu.m and more preferably 50 to 100 .mu.m.
Washing
[0058] The second stage comprised washing the ground and sieved
particles in water to remove any fine particles stuck to the big
particles. The washed particles were then treated in diluted
HNO.sub.3 (1 molL) or H.sub.2SO.sub.4/H.sub.2O.sub.2 (1:2 in
volume) or H.sub.2O.sub.2/NH.sub.3H.sub.2O/H.sub.2O.sub.2 (1:1:1 in
volume) in 10 minutes to get rid of the possible organic or metal
impurities.
Nucleation
[0059] In the third stage, a nucleation reaction was carried out in
a solution of 17.5 ml HF (40%)+20 ml AgNO.sub.3 (0.06 mol/l)+2.5 ml
EtOH (97.5%)+10 ml H.sub.2O for 7.about.10 minutes at room
temperature (.about.23.degree. C.) using 0.1 g of silicon particles
with the dimension of about 400.times.300.times.200 .mu.m. For the
same weight of silicon, smaller silicon particles required a larger
solution volume due to the increased surface area to volume
ratio.
[0060] The effect of ethanol at room temperature was to slow the
chemical processes which gives a more uniform distribution of
silver islands. The time (especially at the upper limit) was
sufficient to consume a significant amount of the solution
silver.
Etching
[0061] The fourth stage comprised etching. The etching reaction
used a solution of 17.5 ml HF (40%)+12.5 ml Fe(NO.sub.3).sub.3
(0.06 moll)+2 ml AgNO.sub.3 (0.06 moll)+18 ml H.sub.2O for
1.about.1.5 hours at room temperature (.about.23.degree. C.) using
0.1 g of silicon particles with the dimension of about
400.times.300.times.200 .mu.m. For the same weight of silicon,
smaller silicon particles required a larger solution volume due to
the increased surface area to volume ratio. In addition, as the
particle size decreases, a shorter time is needed for smaller
silicon particles, for example, 30 min for 100.about.120 .mu.m
(sieve size) sample and 20 min for 63.about.80 .mu.m sample.
[0062] In further modifications, stirring increased the etch rate
possibly owing to the discharge of hydrogen. Here, the out
diffusion of fluorosilicate ion was rate limiting.
[0063] The skilled person will understand that oxidizing agents
other than Ag.sup.+ may be equally suitable. For example:
K.sub.2PtC.sub.16; Cu(NO.sub.3).sub.2; Ni(NO.sub.3).sub.2;
Mn(NO.sub.3).sub.2; Fe(NO.sub.3).sub.3; Co(NO.sub.3).sub.2;
Cr(NO.sub.3).sub.2; Mg(NO.sub.3).sub.2. Compounds involving Cu and
Pt, having potentials higher than hydrogen, give metal deposition
(Cu and Pt) but the others, except for Ni, do not.
[0064] The overall galvanic exchange etching mechanism can be
illustrated using FIGS. 3 and 4. In FIG. 3 the anodic process,
Si+6F.sup.-=SiF.sub.6.sup.2-+4e.sup.-(-1.24 Volts)
is the local etching of silicon. While the removal of the electrons
accompanied by the discharge of silver ions is the cathodic
process
Ag.sup.++e.sup.-=Ag(+0.8 Volts)
[0065] For standard conditions the overall cell voltage is 2.04
volts. The other cathodic couples of interest are Cu/Cu.sup.2+
(+0.35V); PtCl.sub.6.sup.2-/PtCl.sub.4.sup.2- (+0.74V);
Fe.sup.3+/Fe.sup.2+ (+0.77V), since they are all positive with
respect to hydrogen. Couples that are more negative than H+/H.sub.2
will be in competition with hydrogen and will be largely
ineffective. FIG. 4 shows a schematic version of the partial
electrode reactions.
Silver Removal
[0066] The final stage of the process involved removing the silver
which was left on the etched silicon particles from the third and
fourth stages. The silver was removed (and saved) using a solution
of 15% HNO.sub.3 for 5.about.10 min.
[0067] It will be appreciated, of course, that any appropriate
approach can be adopted in order to arrive at the approaches and
apparatus described above. For example the pillar detaching
operation can comprise any of a shaking, scraping, chemical or
other operation as long as pillars are removed from the
particles.
[0068] The particles can have any appropriate dimension and can for
example be pure silicon or doped silicon other silicon-comprising
material such as a silicon-germanium mixture or any other
appropriate mixture. The particles from which pillars are created
may be n- or p-type, ranging from 100 to 0.001 Ohm cm, or it may be
a suitable alloy of silicon, for example Si.sub.xGe.sub.1-x. The
particles may be metallurgical grade silicon.
[0069] The particles and/or the detached pillars can be used for
any appropriate purpose such as fabrication of electrodes generally
including cathodes. The cathode material can be of any appropriate
material, typically a lithium-based metal oxide or phosphate
material such as LiCoO.sub.2, LiMn.sub.xNi.sub.xCo.sub.1-2xO.sub.2
or LiFePO.sub.4. The features of different embodiments can be
interchanged or juxtaposed as appropriate and the method steps
performed in any appropriate order.
[0070] Although relatively high purity single crystal wafers of
silicon can be etched to produce pillars of the desired parameters,
the wafers themselves are very expensive owing to their high
purity. Furthermore, it is difficult to arrange a pillared-wafer
into an electrode-geometry. Embodiments of the present invention
are advantageous because metallurgical grade silicon is relatively
cheap and pillared particles may themselves be incorporated into a
composite electrode without further processing. Also, pillared
particles are a good source of silicon fibres and can be used
themselves as the "active" ingredient in a battery electrode.
[0071] The particles used for etching may be crystalline for
example mono- or poly-crystalline with a crystallite size equal to
or greater than the required pillar height. The polycrystalline
particle may comprise any number of crystals from example two or
more.
[0072] Advantageously, metallurgical grade silicon is particularly
suitable as a battery electrode because of the relatively high
density of defects (compared to silicon wafers used in the
semiconductor industry). This leads to a low resistance and hence
high conductivity.
[0073] As the skilled person will understand, both n-type and
p-type silicon can be etched and any density of charge carriers is
appropriate provided the material does not become significantly
degenerate.
* * * * *