U.S. patent application number 13/682788 was filed with the patent office on 2013-06-06 for electrochemical device and methods for energy conversion.
This patent application is currently assigned to SOFC Holdings LLC. The applicant listed for this patent is SOFC Holdings LLC. Invention is credited to Wei Bai, Tao T. Tao.
Application Number | 20130143139 13/682788 |
Document ID | / |
Family ID | 22731579 |
Filed Date | 2013-06-06 |
United States Patent
Application |
20130143139 |
Kind Code |
A1 |
Tao; Tao T. ; et
al. |
June 6, 2013 |
ELECTROCHEMICAL DEVICE AND METHODS FOR ENERGY CONVERSION
Abstract
The present invention relates to an electrochemical device. The
device features an anode constructed of materials such that the
device can be chemically recharged. In addition, the device is
capable of switching between operating as a fuel cell or as a
battery. The switch can occur without cessation of electrical
output. In certain aspects of the invention, the device is capable
of operating at a temperature of less than 1000.degree. C. Other
aspects feature a liquid anode which allows higher output,
dispersion of fuel and minimal stresses in an interface comprising
the anode. Preferably the anode is a liquid at a temperature of
less than 1000.degree. C. The invention also relates to methods for
energy conversion in which a continual electrical output can be
produced in both the presence of fuel without anode consumption or
the absence of fuel.
Inventors: |
Tao; Tao T.; (Hopkinton,
MA) ; Bai; Wei; (Westborough, MA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
SOFC Holdings LLC; |
Wilmington |
DE |
US |
|
|
Assignee: |
SOFC Holdings LLC
Wilmington
DE
|
Family ID: |
22731579 |
Appl. No.: |
13/682788 |
Filed: |
November 21, 2012 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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13075256 |
Mar 30, 2011 |
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13682788 |
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12625881 |
Nov 25, 2009 |
7943271 |
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13075256 |
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10627330 |
Jul 25, 2003 |
7678484 |
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12625881 |
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09837864 |
Apr 18, 2001 |
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10627330 |
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60197998 |
Apr 18, 2000 |
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Current U.S.
Class: |
429/465 ;
429/482 |
Current CPC
Class: |
Y02E 60/50 20130101;
Y02E 60/525 20130101; H01M 8/2484 20160201; Y02P 70/50 20151101;
H01M 8/2425 20130101; H01M 12/08 20130101; H01M 8/243 20130101;
Y02P 70/56 20151101; H01M 4/921 20130101; H01M 4/9025 20130101;
H01M 8/1246 20130101; B82Y 30/00 20130101; H01M 4/90 20130101 |
Class at
Publication: |
429/465 ;
429/482 |
International
Class: |
H01M 12/08 20060101
H01M012/08 |
Claims
1-113. (canceled)
114. An electrochemical device, comprising: a first electrode
comprising a liquid metal at a temperature at which the
electrochemical device is operated; a solid-state electrolyte in
ionic communication with the first electrode, the solid-state
electrolyte comprising a metal oxide and/or a mixed metal oxide and
remaining solid at the temperature at which the electrochemical
device is operated; and a second electrode in ionic communication
with the solid-state electrolyte.
115. The electrochemical device of claim 114, wherein the
solid-state electrolyte has a formula
(ZrO.sub.2)(HfO.sub.2).sub.a(TiO.sub.2).sub.b(Al.sub.2O.sub.3).sub.c(Y.su-
b.2O.sub.3).sub.d(Y.sub.dO.sub.3).sub.d(M.sub.xO.sub.y).sub.e where
a is from 0 to about 0.2, b is from 0 to about 0.5, c is from 0 to
about 0.5, d is from 0 to about 0.5, x is greater than 0 and less
than or equal to 2, y is greater than 0 and less than or equal to
3, e is from 0 to about 0.5, and M is selected from the group
consisting of calcium, magnesium, manganese, iron, cobalt, nickel,
copper, and zinc.
116. The electrochemical device of claim 114, wherein the
solid-state electrolyte comprises YSZ.
117. The electrochemical device of claim 114, wherein the
solid-state electrolyte comprises ZrO.sub.2.
118. The electrochemical device of claim 114, wherein the second
electrode comprises a metal.
119. The electrochemical device of claim 114, wherein the first
electrode comprises tin.
120. The electrochemical device of claim 114, wherein the first
electrode comprises silver.
121. The electrochemical device of claim 114, wherein the first
electrode comprises copper.
122. The electrochemical device of claim 114, wherein the first
electrode comprises bismuth.
123. The electrochemical device of claim 114, wherein the first
electrode further comprises a current collector.
124. The electrochemical device of claim 123, wherein the current
collector comprises LSM.
125. The electrochemical device of claim 114, further comprising a
source of fuel exposable to the first electrode.
126. The electrochemical device of claim 125, wherein the fuel
comprises a carbonaceous material.
127. The electrochemical device of claim 125, wherein the fuel
comprises syngas.
128. The electrochemical device of claim 125, wherein the fuel
comprises hydrogen gas.
129. The electrochemical device of claim 125, wherein the fuel
comprises natural gas.
130. The electrochemical device of claim 114, wherein the first
electrode comprises a chemically reducing environment.
131. The electrochemical device of claim 114, wherein the first
electrode is substantially tubular.
132. The electrochemical device of claim 114, wherein the first
electrode is substantially surrounded by the solid-state
electrolyte.
133. The electrochemical device of claim 114, wherein the
solid-state electrolyte is substantially surrounded by the second
electrode.
134. The electrochemical device of claim 114, wherein the first
electrode is the anode and the second electrode is the cathode.
135. An apparatus, comprising: at least first and second
electrochemical devices, each of the electrochemical devices
independently comprising a first electrode comprising a liquid
metal at a temperature at which the electrochemical device is
operated, a solid-state electrolyte in ionic communication with the
first electrode, and a second electrode in ionic communication with
the solid-state electrolyte, wherein the solid-state electrolyte
comprises a metal oxide and/or a mixed metal oxide and remains
solid while supplying the fuel to the electrochemical device; and
an interconnect in electrical communication with the first
electrode of the first electrochemical device and the second
electrode of the second electrochemical device.
136. A method, comprising: supplying fuel to an electrochemical
device comprising a first electrode comprising a liquid metal at a
temperature at which the electrochemical device is operated, a
solid-state electrolyte in ionic communication with the first
electrode, and a second electrode in ionic communication with the
solid-state electrolyte, wherein the solid-state electrolyte
comprises a metal oxide and/or a mixed metal oxide and remains
solid while supplying the fuel to the electrochemical device.
Description
RELATED APPLICATIONS
[0001] This application is a continuation of U.S. application Ser.
No. 10/627,330, filed Jul. 25, 2003, by Tao T. Tao et al., which is
a divisional of U.S. application Ser. No. 09/837,864, filed Apr.
18, 2001, by Tao T. Tao et al., which claims the benefit under
Title 35 U.S.C. .sctn.119(e) of co-pending U.S. provisional
application Ser. No. 60/197,998, filed Apr. 18, 2000, by Tao T. Tao
et al., each of which is incorporated herein by reference.
FIELD OF INVENTION
[0002] The present invention relates to an electrochemical device
that can operate either as a fuel cell or a battery. The device
features a chemically rechargeable anode, particularly where the
anode comprises a liquid such as a metal or a metal alloy. Methods
for generating electricity in the presence or absence of a fuel are
also disclosed.
BACKGROUND OF THE INVENTION
[0003] In a fuel cell comprising a solid oxide, a cathode reduces
oxygen to oxygen ions and an anode oxidizes a fuel accompanied by a
release of electrons provided by the fuel. The oxidized fuel
combines with the oxygen ions to counteract a resulting flow of
released electrons through an external circuit. The anode is not
consumed during operation of the fuel cell. Theoretically, the fuel
cell can operate as long as fuel is supplied to the anode.
[0004] Electrical output depends on several factors, including the
type of fuel used and the operational temperature, as well as the
electrode and electrolyte components. To provide a high electrical
output, new materials have been devised that can withstand high
operational temperatures. Such high temperatures may not be
practical for many applications, however. In addition, a
combination of currently known materials results in a heavy device,
which is not practical for variable load applications. Attempts to
improve the performance of fuel cells include the discovery of new
materials for anode, electrolyte and cathode components. Each
device, however, is generally specific for a certain type of
fuel.
[0005] In a metal/air battery, a cathode reduces oxygen to oxygen
ions in a similar manner to a fuel cell, but the anode itself
oxidizes and provides electrons which are released to an external
circuit. Thus, the anode is consumed. For charge balance, the
oxidized anode reacts with oxygen ions produced by the cathode. The
battery does not require fuel in order to generate electricity. The
battery, however, has only a defined lifetime as determined by the
lifetime of the anode.
[0006] Attempts have been made to combine the attributes of a fuel
cell and a battery. For example, a device may comprise separate
battery and fuel cell components, thus combining the storage
capacity of a battery with the longevity of fuel cells. This
arrangement, however, only adds to the weight of the device.
[0007] Much effort has been made, and continues to be made, to
improve the performance of fuel cells and batteries, particularly
for mobile applications where lightweight components and increased
power output are essential.
SUMMARY OF THE INVENTION
[0008] One aspect of the present invention provides an
electrochemical device. The device comprises an anode constructed
of a material such that the anode is a chemically rechargeable
anode. The device also comprises a source of fuel exposable to the
anode.
[0009] Another aspect of the present invention provides an anode
being constructed of a material such that the anode is a chemically
rechargeable anode.
[0010] Another aspect of the present invention provides an
electrochemical device comprising an anode comprising a liquid. The
device is operable at a temperature of no more than 1,000.degree.
C. The device also comprises a source of a fuel exposable to the
anode.
[0011] Another aspect of the present invention provides an
electrochemical device comprising an anode and an intermittent fuel
source deliverable to the anode to produce a continuous electrical
output from the device.
[0012] Another aspect of the present invention provides an
electrochemical device comprising an anode and a source of a fuel
exposable to the anode. The anode is constructed of a material such
that the device is capable of producing electricity by using the
anode in both the presence of the fuel without anode consumption,
and in the absence of the fuel.
[0013] Another aspect of the present invention provides an
electrochemical device, comprising a liquid anode comprising an
alloy. Each metal in the alloy comprises a standard reduction
potential greater than -0.70 V versus the Standard Hydrogen
Electrode.
[0014] Another aspect of the present invention provides a stack of
electrochemical devices. The stack comprises a first and second
electrochemical device. Each device includes an anode comprising a
liquid. The anode is in ionic communication with an electrolyte and
the electrolyte is in ionic communication with the cathode. The
stack comprises an interconnect positioned intermediate and
adjacent both the anode of the first device and the cathode of the
second device.
[0015] Another aspect of the present invention provides a method
for energy conversion. The method comprises providing an
electrochemical device comprising an anode. The method also
involves causing electricity to be produced in the presence of a
fuel provided to the anode without anode consumption. The method
further comprises causing electricity to be produced in the device
in the absence of the fuel provided to the anode.
[0016] Another aspect to the present invention provides a method
for energy conversion comprising providing an anode and delivering
a fuel to the anode intermittently while producing a continuous
electrical output by using the anode.
[0017] Another aspect to the present invention provides a method
comprising the steps of providing an anode and causing a portion of
the anode to be oxidized such that electricity is produced. The
method further comprises exposing the oxidized portion of the anode
to a chemical reductant to reduce the oxidized portion.
[0018] Another aspect of the present invention provides an
electrochemical device comprising a battery comprising an anode and
a fuel cell comprising the anode. The fuel is exposable to the
anode and comprises a material different from the anode.
[0019] Another aspect of the present invention provides a method
for energy conversion, comprising the steps of providing a battery
and supplying a fuel to an anode in the battery. The fuel is of a
different material than that of the anode.
[0020] Another aspect of the present invention provides a method
for energy conversion comprising the steps of providing a fuel cell
and switching the fuel cell to a battery by ceasing a supply of a
fuel to an anode in the fuel cell.
[0021] Another aspect of the present invention provides an
electrochemical device comprising at least two fuel sources for
supplying at least two different types of fuel to the device, the
two fuel sources being interchangeable to allow selection of a type
of fuel.
[0022] Another aspect of the present invention provides a
solid-state electrolyte material, the housing containing a liquid
anode.
[0023] Another aspect of the present invention provides a method
for energy conversion. The method comprises the steps of providing
a device comprising a liquid metal anode and oxidizing a portion of
the anode to form a metal oxide concurrent with the generation of
electricity.
[0024] Other advantages, novel features, and objects of the
invention will become apparent from the following detailed
description of the invention when considered in conjunction with
the accompanying drawings, which are schematic and which are not
intended to be drawn to scale. In the figures, each identical or
nearly identical component that is illustrated in various figures
is represented by a single numeral. For purposes of clarity, not
every component is labeled in every figure, nor is every component
of each embodiment of the invention shown where illustration is not
necessary to allow those of ordinary skill in the art to understand
the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0025] FIG. 1 shows a cross-sectional schematic diagram of a device
of the present invention, highlighting the electrode and
electrolyte components;
[0026] FIG. 2 shows a cross-sectional schematic diagram of a
tubular device of the present invention, highlighting the electrode
and electrolyte components;
[0027] FIG. 3 shows a cross-sectional schematic diagram of a
tubular device of the present invention, highlighting the
positioning of solid fuel positioned on the anode;
[0028] FIG. 4 shows a cross-sectional schematic diagram of a
tubular device of the present invention, highlighting the
positioning of an inlet positioned on one end of the anode,
allowing exhaust to exit the other end of the anode;
[0029] FIG. 5 shows a cross-sectional schematic diagram of a planar
stack of the present invention which utilizes liquid or gaseous
fuels;
[0030] FIG. 6 shows a cross-sectional schematic diagram of a planar
stack of the present invention which utilizes solid fuels;
[0031] FIG. 7 shows a three-dimensional schematic representation of
the planar stack of FIG. 5;
[0032] FIG. 8 shows an interconnect positioned between two tubular
devices of the present invention; and
[0033] FIG. 9 shows a scheme of the various electrochemical
processes that can be carried out by the anode of the present
invention within a single device.
DETAILED DESCRIPTION
[0034] The present invention provides new electrochemical devices
that display at least one or any combination of the following
advantageous features: (1) a capability for chemical recharging;
(2) simplified construction; (3) increased electrical output; and
(4) a capability for providing a stack of electrochemical devices
that afford low mechanical and thermal stresses. Certain aspects of
the invention exploit the construction of an anodic material in
conjunction with the use of different fuel types. The various
embodiments of the present invention also provides novel methods
for the generation of electricity.
[0035] One aspect of the present invention provides an
electrochemical device. In one embodiment, electrochemical devices
of the present invention are capable of converting chemical energy,
via an electrochemical reaction, into electrical energy to produce
an electrical output. Examples of electrochemical devices include a
fuel cell and a battery. Other examples include an oxygen purifier
and an oxygen sensor.
[0036] In one embodiment, the electrochemical device has a
dual-mode capability in that the device can operate both as a fuel
cell and as a battery. Thus, not only is the anode capable of
oxidizing a fuel source and releasing electrons (e.g., as in a fuel
cell), but the anode itself is capable of being oxidized with the
release of electrons (e.g., as in a battery).
[0037] An advantage of this dual-mode capability can be illustrated
by the following scenario. A typical prior art fuel cell can
produce power so long as there is a supply of fuel. When the fuel
supply is exhausted, the electrical output ceases almost
instantaneously. This situation can be disastrous especially when a
fuel cell device is being used for variable load applications in
which replacement fuel is not immediately available. To circumvent
this problem, certain prior art fuel cell devices have been
provided with a battery back-up. The addition of a separate
battery, however, adds weight and complexity to the fuel cell
device, which is undesirable especially for variable load
applications.
[0038] The use of batteries as a sole source of power also has its
disadvantages. In a typical battery, electrical power is generated
at the expense of anode consumption, as the anode is consumed to
release electrons. This anode consumption causes batteries to have
a defined lifetime which is dictated, in large part, by the
lifetime of the anode. To circumvent this problem, certain prior
art electrically rechargeable batteries have been developed in
which an input of electrons from an outside source reduces the
consumed anode and restores the anode to its initial state.
However, an external power source is required for electric
recharging.
[0039] In contrast, the device of the present invention is capable
of switching between "battery mode" and "fuel cell mode." For
example, if the fuel supply is exhausted, the device can continue
to generate electricity while operating in battery mode thereby
eliminating the need for an external battery back-up. Furthermore,
when the fuel supply is replenished the device in battery mode can
switch back to fuel cell mode if so desired. These features will be
discussed more fully below.
[0040] Another aspect of the invention provides an electrochemical
device which comprises an anode constructed of a material such that
the anode is a chemically rechargeable anode.
[0041] A "chemically rechargeable anode" refers to an anode capable
of being recharged by the addition of a chemical reductant, as
opposed to conventional electrically rechargeable devices. A
"chemically rechargeable device" as used herein refers to a device
comprising a chemically rechargeable anode. Prior to operation, the
device of this aspect of the invention provides an anode having an
initial oxidation state. When the device is operated in battery
mode, at least a portion of the anode is consumed and electrons are
released. A "consumed" anode or portion of the anode refers to an
anode having a higher oxidation state than the initial oxidation
state i.e., the anode is oxidized. Chemical recharging can be
initiated by exposing the portion of the consumed anode to a
chemical reductant resulting in that portion being reduced to a
more reduced state, such as the initial oxidation state. Thus, it
is the chemical reductant, not electricity (as in prior art
devices), that, at least in part, recharges the anode. In one
embodiment, the chemical reductant alone causes recharging of the
anode. In another embodiment, a combination of chemical and
electrical recharging results in restoration of the anode. An
advantage of chemical recharging is the provision of the recharging
species, (i.e., the chemical) located within the device itself.
Thus no external recharging species is needed. This feature is
particularly desired for use in areas where electrical power
sources for electrical recharging may not be readily available.
[0042] Certain metal anodes are capable of existing in more than
two oxidation states or in non-integral oxidation states. A metal
or alloy comprises metals having a neutral charge. Certain metals
can be oxidized to one or more oxidation states, any one of these
states being of a sufficient electrochemical potential to oxidize
the fuel. Conversely, if that metal is oxidized to its highest
oxidation state, it can be reduced to more than one lower oxidation
state (at least one having a higher oxidation state than neutral)
where the anode is capable of functioning in any of these states.
Alternatively, a metal oxide or mixed metal oxide may collectively
oxidize fuel where metal ions are reduced by formal non-integer
values.
[0043] In one embodiment, the chemical reductant is the fuel
itself. An advantage of this embodiment can be illustrated with the
previous scenario, in which the device is operating in battery
mode. Upon depletion of the anode, the device can convert back to
fuel cell mode where the fuel is consumed to produce electricity.
In addition, the fuel can chemically recharge the oxidized anode to
its initial state via a chemical reaction. A portion of the fuel
reduces the anode and another portion of the fuel is oxidized to
generate electricity. When the anode is restored (or a portion
restored) to a reduced state, such as its initial state, the device
regains its internal "battery back-up" for future emergency
situations. The use of the fuel itself as a recharging source
provides another advantage in that the device automatically
contains the recharging source, thus eliminating the need to store
additional chemicals into the device. In other embodiment, however,
it may be desired to incorporate another chemical reductant
specifically for recharging the anode and having sufficient
electrochemical activity to carry out this function.
[0044] In one embodiment, the chemically rechargeable device can be
configured to allow recharging with electricity in addition to the
chemical recharging capability. For certain anode materials and
certain fuel types, it may be more feasible to recharge
electrically if such an electrical power supply is readily
available. For mobile applications, it is preferred that the anode
is chemically rechargeable as well for the reasons described
previously, e.g. eliminate need to carry a separate battery back-up
for a lighter device.
[0045] In one embodiment, the anode comprises a liquid, preferably
at temperatures for which the device is operable. A liquid is a
material which exhibits flow properties. In one embodiment, a
liquid is a material which exhibits a tendency to flow in response
to an applied force under given operating conditions of temperature
and pressure. Liquids generally have little or no tendency to
spontaneously disperse. Preferably, materials which flow within a
time scale that is not visually perceptible by the human eye are
generally excluded from this definition.
[0046] One advantageous feature of a liquid anode is that fuel can
be dispersed throughout the anode regardless of the physical state
of the fuel, i.e., a gaseous, liquid or solid fuel can be dispersed
throughout the anode. It is known that electrical output can be
increased by increasing the surface area of an anode. Dispersing
fuel throughout the anode allows maximization of the surface area
exposed to the fuel. In addition, the liquid can be agitated by
stirring or bubbling (or any other agitation methods) to help
disperse the fuel throughout the liquid. In one embodiment,
agitating the anode has further advantages where the anode
undergoes oxide formation when consumed. The oxidized portion of
the anode can be displaced with agitation to expose the unoxidized
anode portions to the fuel. In contrast, a solid anode would form
an oxidized portion at the anode/fuel interface, and the oxidized
portion may block the fuel from accessing the anode. Additionally,
a liquid anode reduces a need to machine the anode, as the anode
can conform to any shape of casing used to house the device
components. Where the electrolyte is a solid state electrolyte, the
anode can conform to the shape of the electrolyte, maximizing the
surface area of contact between the anode and the electrolyte.
[0047] In one embodiment, the device is operable, with the anode in
a liquid state, at a temperature of less than about 1500.degree.
C., preferably at a temperature of less than about 1300.degree. C.,
more preferably less than about 1200.degree. C., even more
preferably less than about 1000.degree. C., and even more
preferably less than about 800.degree. C. By "operable", it is
meant that the device is able to generate electricity, either as a
fuel cell or as a battery with the anode in a liquid state, and the
anode may not necessarily be a liquid at room temperature. It is
understood by those of ordinary skill in the art that anodic
temperature can be controlled by selection of anode materials or in
the case of an alloy, composition and percentages of the respective
metal components, i.e., composition can affect a melting point of
the anode. Other exemplary operating temperature ranges include a
temperature between about 300.degree. C. to about 1500.degree. C.,
between about 500.degree. C. to about 1300.degree. C., between
about 500.degree. C. to about 1200.degree. C., between about
500.degree. C. to about 1000.degree. C., between about 600.degree.
C. to about 1000.degree. C., between about 700.degree. C. to about
1000.degree. C., between about 800.degree. C. to about 1000.degree.
C., between about 500.degree. C. to about 900.degree. C., between
about 500.degree. C. to about 800.degree. C., and between about
600.degree. C. to about 800.degree. C.
[0048] In one embodiment, the device is operable at a temperature
at which any of the solid state components (e.g. a cathode or
electrolyte) are not easily susceptible to cracking, i.e., the
solid state components should maintain their structural integrity
at the operating temperature of the device. In another embodiment,
the device is operable at a temperature at which the cathode does
not react with the electrolyte. In another embodiment, the device
is operable at a temperature at which the anode comprises a liquid.
One or any combination of these factors can be practiced
independently or in combination, and those of ordinary skill in the
art can balance these factors with the knowledge that increasing
operational temperatures generally result in an increase in
electrical output.
[0049] In one embodiment, the anode can be a pure liquid or can
have solid and liquid components, so long as the anode as a whole
exhibits liquid-like properties.
[0050] In one embodiment, the anode comprises a metal. The metal
can be a pure metal or can comprise an alloy comprising two or more
metals. Upon consumption of a portion of the anode, the portion of
the anode is oxidized to form a metal oxide. A mixed metal oxide
can be formed in the case where the anode is an alloy. In one
embodiment, the metal has a standard reduction potential greater
than -0.70 V versus the Standard Hydrogen Electrode (determined at
room temperature). These values can be obtained from standard
reference materials or measured by using methods known to those of
ordinary skill in the art. In another embodiment, where the anode
comprises more than one metal, all metals preferably have a
standard reduction potential greater than -0.70V versus the
Standard Hydrogen Electrode. Balancing the various electrochemical
potential requirements can be determined by those of ordinary skill
in the art. In certain embodiments, an alloy can be used where at
least one of the metals does not have a standard reduction
potential greater than -0.70V, but is included in the alloy to
enhance flow properties, consistency, or other properties not
related to electrochemical potential. In other embodiments, the
anode can comprise a mixture of a metal and non-metals to enhance
flow properties, consistency, or other properties not related to
electrochemical potential.
[0051] In one embodiment, the anode comprises a conducting polymer.
Typical conducting polymers have a conjugated n-system extending
throughout a substantial portion of the polymer backbone. Because
of this conjugation, conducting polymers can be reduced or oxidized
many times over, creating radicals which can be delocalized over at
least a portion of the backbone. Conducting polymers can comprise
organic components, or a mixture of organic and metal components.
In the latter situation, the metals can themselves be oxidized or
reduced. Preferably, the conducting polymer anode is a liquid at
the operating temperatures disclosed herein. Examples of conducting
polymers can be found in the "Desk Reference of Functional
Polymers," R. Arshady Ed., American Chemical Society, Washington,
D.C. (1997) in which the portions relating to conducting polymers
are incorporated herein.
[0052] In one embodiment, the anode comprises a conducting ceramic,
preferably one that is molten at any of the operating temperatures
disclosed herein.
[0053] In one embodiment, where the fuel is used to chemically
recharge the anode, the oxidation potential of the fuel can dictate
the anode composition, i.e., the oxidized state of the anode is of
a sufficient electrochemical potential to oxidize the fuel.
[0054] In one embodiment, the anode is chemically rechargeable from
the oxidized state. For example, where the oxidized state is a
metal oxide or mixed metal oxide, the chemical recharging results
in restoration (i.e. reduction) of the anode back to being a metal
or metal alloy. In another embodiment, the chemical recharging
results in reduction of the anode to an oxidation state capable of
oxidizing the fuel.
[0055] In one embodiment, the anode comprises a metal or alloy
comprising at least one of a transition metal, a main group metal,
an alkaline metal, an alkaline earth metal, a lanthanide, an
actinide and combinations thereof. In another embodiment, the anode
comprises material such as copper, molybdenum, mercury, iridium,
palladium, antimony, rhenium, bismuth, platinum, silver, arsenic,
rhodium, tellurium, selenium, osmium, gold, lead, germanium, tin,
indium, thallium, cadmium, gadolinium, chromium nickel, iron,
tungsten, cobalt, zinc, vanadium or combinations thereof. For
example, the anode can comprise a pure metal such as antimony,
indium, tin, bismuth, mercury and lead. In another embodiment, the
anode comprises an alloy of at least one element such as copper,
molybdenum, mercury, iridium, palladium, antimony, rhenium,
bismuth, platinum, silver, arsenic, rhodium, tellurium, selenium,
osmium, gold, lead, germanium, tin, indium, thallium, cadmium,
gadolinium, chromium nickel, iron, tungsten, vanadium, manganese,
cobalt, zinc and combinations thereof. Examples of alloys include
5% lead with reminder antimony, 5% platinum with reminder antimony,
5% copper with reminder indium, 20% lead, 10% silver, 40% indium,
5% copper.
[0056] In one aspect of the invention, the anode comprises a
material that is different from the fuel composition, thus
distinguishing the devices of the present invention from metal/air
batteries. Metal/air batteries are sometimes referred to as "fuel
cells" because the lifetime of metal/air batteries can be increased
by adding more anodic material. These batteries, however, do not
provide the benefits of the devices of the present invention, as
described herein. In one embodiment, the invention provides a
method for energy conversion comprising the step of providing a
battery and supplying a fuel to an anode in the battery. The fuel
is of a different material than the anode material. This embodiment
allows the device to operate as a fuel cell and a battery. With
other batteries, supplying a fuel that is of a different material
than the anode material is an irrelevant step and serves no
function.
[0057] In one aspect of the invention, the device comprises a
source of fuel exposable to the anode. "Exposable to the anode"
refers to a capability for delivering fuel to the anode. For
example, the fuel can be added directly to the anode.
Alternatively, the fuel can be contained in a reservoir and can be
deliverable to the anode, when needed, via a conduit leading from
the reservoir to the anode. When the device is operating in battery
mode, the fuel source can be shut off but remains exposable or
capable of being exposed to the anode at a later time when fuel
cell mode is desired. Alternatively, the fuel can be in contact
with the anode, i.e. dispersed throughout the anode, positioned on
a surface of the anode or otherwise contacted with the anode during
operation and/or storage. In other embodiments, where the anode is
a metal, the fuel can be in contact with metal oxide formed from
the anode. The anode can be supplied with a new charge of fuel
either continuously or periodically. This may be one viable
arrangement for solid fuels. Depending on the physical state of the
fuel (i.e., solid, liquid or gas), and other physical properties
(powder, viscous liquid, etc.), those of ordinary skill in the art
can readily construct a delivery mechanism to expose the fuel to
the anode.
[0058] Examples of classes of fuels include a carbonaceous
material; sulfur; a sulfur-containing organic compound such as
thiophene, thiourea and thiophenol; a nitrogen-containing organic
compound such as nylon and a protein; ammonia, hydrogen and
mixtures thereof. Typically, the fuel selected for the device is
mission dependent.
[0059] Examples of a fuel comprising a carbonaceous material
include conductive carbon, graphite, quasi-graphite, coal, coke,
charcoal, fullerene, buckminsterfullerene, carbon black, activated
carbon, decolorizing carbon, a hydrocarbon, an oxygen-containing
hydrocarbon, carbon monoxide, fats, oils, a wood product, a biomass
and combinations thereof. Examples of a hydrocarbon fuel include
saturated and unsaturated hydrocarbons, aliphatics, alicyclics,
aromatics, and mixtures thereof. Other examples of a hydrocarbon
fuel include gasoline, diesel, kerosene, methane, propane, butane,
natural gas and mixtures thereof. Examples of oxygen-containing
hydrocarbon fuels include alcohols which further include
C.sub.1-C.sub.20 alcohols and combinations thereof. Specific
examples include methanol, ethanol, propanol, butanol and mixtures
thereof. However, almost all oxygen-containing hydrocarbon fuels
capable of being oxidized by the anode materials disclosed herein
can be used so long as the fuel is not explosive or does not
present any danger at operating temperatures.
[0060] Gaseous fuels such as hydrogen and SynGas (a mixture of
hydrogen and carbon monoxide) can also be used in certain
embodiments of the invention.
[0061] In another aspect of the invention, the electrochemical
device is capable of operating with more than one type of fuel. The
vast majority of prior art fuel cells are designed to operate with
a specific fuel type, usually hydrogen and less often methanol.
This aspect of the invention makes it possible to capitalize on the
benefits of different fuel types. For example, one type of fuel may
provide a higher power output whereas another may provide a lower
power output but affords lightweight properties. Enhanced
performance may be achieved with one type of fuel, yet another type
of fuel recharges the anode more efficiently. Other benefits for
using different fuel types may be realized, for example, in
situations where the price of one fuel type rises and economics
dictate the use of a cheaper fuel. Environmental concerns may also
be a deciding factor in changing the fuel type. Short term benefits
may be realized, for example, in the situation where the supply of
one fuel type is exhausted and only another fuel type is readily
available.
[0062] In one embodiment, the device comprises a variable source of
fuel for at least two different fuels. For example, the source of
fuel can comprise at least two different reservoirs for two or more
different fuels. Each fuel type can be accessed on demand
individually, or in combination. In another embodiment, the source
of fuel is capable of being interchanged with a different source of
fuel. For example, an electrochemical device running on a gaseous
fuel can run with a solid carbonaceous fuel dispersed throughout
the anode. Those of ordinary skill in the art can readily devise a
device comprising various delivery mechanisms.
[0063] Examples of electrochemical devices of the invention are
illustrated in FIGS. 1 and 2. FIG. 1 shows a cross-sectional
schematic diagram of electrochemical device 2 having anode 4 in
ionic communication with electrolyte 5. "Ionic communication"
refers to a positioning and/or interconnecting of an electrode to
an electrolyte to allow ions to migrate between the electrode and
electrolyte. When anode 4 is in ionic communication with
electrolyte 5, negative ions can migrate from electrolyte 5 to
anode 4. An alternative arrangement (not shown here) can be
provided where anode 4 is in ionic communication with electrolyte 5
even with an intervening layer of another material disposed between
and contacting anode 4 and electrolyte 5. For example, a layer of a
catalyst can be used as the intervening layer to increase the
reaction rate between the oxidized fuel and oxygen anions.
Electrolyte 5 is also in ionic communication with cathode 6 to
allow negatively charged ions to migrate from cathode 6 to
electrolyte 5. In the specific embodiment shown in FIG. 1, the
electrodes (anode 4 and cathode 6) and electrolyte 5 are shown as
solid-state layers in which electrolyte layer 5 is disposed between
and contacting anode layer 4 and cathode layer 6.
[0064] Leads (or current collectors) 8a and 8b are in electronic
communication with anode 4 and cathode 6 respectively. "Electronic
communication" refers to any pathway which provides for the
transport of electricity. The electrochemical circuit is completed
with external circuit 9 which electrically connect leads 8a and 8b.
Circuit 9 is typically a metal wire or any material capable of
conducting electricity. In one embodiment, lead 8a can comprise
graphite and can serve the double function of collecting current
and providing a fuel if at least partially submersed in anode
4.
[0065] Inlet 10 is a conduit for introducing fuel to the anode.
Inlet 10 can be positioned, at least in part, within anode 4 to
disperse fuel throughout the anode efficiently. Alternatively,
inlet 10 does not have to contact anode 4 but can be positioned at
a minimally close distance to allow all the fuel released through
inlet 10 to contact anode 4. Inlet 10 can be further connected to a
reservoir (not shown) that comprises a source of fuel with or
without the use of a conduit. A variety of reservoirs have been or
can be developed for the delivery of solid, gaseous or liquid fuel.
For example, the reservoir can comprise a pressurized tank of
gaseous or liquid fuel. It is not necessary to provide liquid fuels
in pressurized form although pressurization advantageously compacts
the fuel volume. Solid fuel can be provided as a powder or other
deliverable forms poured, sprayed or otherwise distributed from a
reservoir in pure form or as a slurry. Optionally other mechanisms
can be attached which forces the fuel from the reservoir through a
conduit and through inlet 10.
[0066] Not shown in FIG. 1 is a casing for containing and/or
protecting device 2. The casing is preferably constructed of a
material that can withstand the desired operating temperature. Also
not shown in FIG. 1 is a housing to isolate the anode from
atmospheric oxygen, and this housing can be the same or different
as the casing that contains device 2. In these embodiments, a
conduit which penetrates the casing and/or housing can be provided
for delivering the oxygen-containing flow 7 to cathode 6. The
device can further comprise another conduit to release waste
products, such as gases or liquids, from the casing and/or
housing.
[0067] The cathode ionizes oxygen to oxygen ions as represented by
the electrochemical half reaction shown in eq. 1:
1/2O.sub.2+2e.sup.-.fwdarw.O.sub.2- (1)
This ionization occurs when the device operates in battery or fuel
cell mode. The cathode can be exposed to air, pure oxygen or any
oxygen-containing gas 7, at atmospheric pressures or greater.
Alternatively, the device can include an inlet to expose cathode 6
to the oxygen-containing gas 7. Typically, oxygen is reduced at an
interface between cathode 6 and the oxygen-containing gas 7.
Cathode 6 preferably comprises a material which allows oxygen ions
to migrate through cathode 6 and access electrolyte 5.
[0068] When the fuel cell operates in battery mode, the anode
itself is consumed as represented by the electrochemical half
reaction of eq. 2:
M.fwdarw.M.sup.n++ne.sup.- (2)
where M represents a metal or metal alloy (and accordingly,
M.sup.n+ represents an oxidized metal or alloy), "e.sup.-" denotes
an electron, and n is greater than or equal to 1, depending on the
metal or metal alloy. M.sup.n+ is typically present as a metal
oxide (or mixed metal oxide). As described previously, the portion
of the anode that is oxidized, as shown in eq. 2, forms an oxidized
portion on or within the anode.
[0069] When the device is in fuel cell mode, a variety of reactions
can occur. The fuel is oxidized at the anode, thereby releasing
electrons, as represented in eq. 3:
1/2nO.sup.2-+fuel.fwdarw.aCO.sub.x+bNO.sub.y+cSO.sub.z+dH.sub.2O+(option-
ally other oxidation products)+ne.sup.- (3)
[0070] The oxygen anions shown in eq. 3 are, for the most part,
supplied by the cathode reaction of eq. (1). Eq. 3 is intended to
represent some of the various possible oxidation products. The
coefficients a, b, c, d, x, y, and z can be the same or different
and each are greater than or equal to zero and their values depend
on the type of fuel used, and at least one of a, b, c, d, x, y, and
z will be greater than zero. The coefficient "n" is greater than 0.
The fuel may comprise a combination of "a" carbon atoms and/or "b"
nitrogen atoms and/or "c" sulfur atoms and/or d hydrogen atoms,
etc. For example, CO.sub.x can represent CO.sub.2, CO or a mixture
thereof. If hydrogen is the fuel, water is the sole oxidation
product. Not all possible oxidation products are represented by eq.
3 and depending on the composition of the fuel, those of ordinary
skill in the art can determine the resulting oxidation product.
Thus, a net reaction of the anode in fuel cell mode involves
oxidation of the fuel with no consumption of the anode.
[0071] Without wishing to be bound by any theory, the recharging of
the anode by the fuel is represented by eq. (4).
nMO.sub.v+fuel.fwdarw.nM+aCO.sub.x+bNO.sub.y+cSO.sub.z+dH.sub.2O+(option-
ally other oxidation products) (4)
[0072] The reaction of eq. (4) is similar to that of eq. (3),
except the oxygen anions are provided, at least in part, by the
metal or mixed metal oxide, "MO.sub.v" where "v" is greater than
0.
[0073] In one embodiment, the device is capable of electrical
output of at least about 10 mWatt/cm.sup.2, preferably at least
about 50 mWatt/cm.sup.2, preferably at least about 100
mWatt/cm.sup.2, even more preferably at least about 200
mWatt/cm.sup.2, even more preferably at least about 300
mWatt/cm.sup.2, and even more preferably at least about 500
mWatt/cm.sup.2
[0074] In one embodiment, the cathode is a solid state cathode.
Examples of solid state cathodes include a metal oxide and a mixed
metal oxide. Specific examples include tin-doped In.sub.2O.sub.3,
aluminum-doped zinc oxide and zirconium-doped zinc oxide. Another
example of a solid state cathode is a perovskite-type oxide having
a general structure of ABO.sub.3, where "A" and "B" represent two
cation sites in a cubic crystal lattice. A specific example of a
perovskite-type oxide has a structure
La.sub.xMn.sub.yAaB.sub.bCcO.sub.d where A is an alkaline earth
metal, B is selected from the group consisting of scandium, yttrium
and a lanthanide metal, C is selected from the group consisting of
titanium, vanadium, chromium, iron, cobalt, nickel, copper, zinc,
zirconium, hafnium, aluminum and antimony, x is from 0 to about
1.05, y is from 0 to about 1, a is from 0 to about 0.5, b is from 0
to about 0.5, c is from 0 to about 0.5 and d is between about 1 and
about 5, and at least one of x, y, a, b and c is greater than zero.
More specific examples of perovskite-type oxides include
LaMnO.sub.3, La.sub.0.84Sr.sub.0.16MnO.sub.3,
La.sub.0.84Ca.sub.0.16MnO.sub.3, La.sub.0.84Ba.sub.0.16MnO.sub.3,
La.sub.0.65Sr.sub.35Mn.sub.0.8Co.sub.0.2O.sub.3,
La.sub.0.79Sr.sub.0.16Mn.sub.0.85Co.sub.0.015O.sub.3,
La.sub.0.84Sr.sub.0.16Mn.sub.0.8Ni.sub.0.2O.sub.3,
La.sub.0.84Sr.sub.0.16Mn.sub.0.8Fe.sub.0.2O.sub.3,
La.sub.0.84Sr.sub.0.16Mn.sub.0.8Ce.sub.0.23,
La.sub.0.84Sr.sub.0.16Mn.sub.0.8Mg.sub.0.2O.sub.3,
La.sub.0.84Sr.sub.0.16Mn.sub.0.8Cr.sub.0.2O.sub.3,
La.sub.0.6Sr.sub.0.35Mn.sub.0.8Al.sub.0.2O.sub.3,
La.sub.0.84Sc.sub.0.16MnO.sub.3, La.sub.0.84Y.sub.0.16MnO.sub.3
La.sub.0.7Sr.sub.0.3CoO.sub.3, LaCoO.sub.3,
La.sub.0.7Sr.sub.0.3FeO.sub.3, and
La.sub.0.5Sr.sub.0.5Co.sub.0.8Fe.sub.0.2O.sub.3.
[0075] Other examples of solid state cathodes include LaCoO.sub.3,
LaFeO.sub.3, LaCrO.sub.3, and a LaMnO.sub.3-based perovskite oxide
cathode, such as La.sub.0.75Sr.sub.0.25CrO.sub.3,
(La.sub.0.6Sr.sub.0.4).sub.0.9CrO.sub.3,
La.sub.0.6Sr.sub.0.4FeO.sub.3, La.sub.0.6Sr.sub.0.4CoO.sub.3 or
Ln.sub.0.6Sr.sub.0.4CoO.sub.3, where Ln can be any one of La, Pr,
Nd, Sm, or Gd.
[0076] Alternatively, the cathode can comprise a metal. Exemplary
metal cathodes include platinum, palladium, gold, silver, copper,
rhodium and combinations thereof.
[0077] The electrolyte allows conduction of ions between the
cathode and anode. The electrolyte allows migration of oxygen ions
from the cathode to the anode. In one embodiment, the electrolyte
is a solid state electrolyte. Example solid state electrolytes
include a metal oxide and mixed metal oxides.
[0078] An example of a solid state electrolyte is an electrolyte
having a formula
(ZrO.sub.2)(HfO.sub.2).sub.a(TiO.sub.2).sub.b(Al.sub.2O.sub.3).su-
b.c(Y.sub.2O.sub.3).sub.d(M.sub.xO.sub.y).sub.e where a is from 0
to about 0.2, b is from 0 to about 0.5 c is from 0 to about 0.5, d
is from 0 to about 0.5, x is greater than 0 and less than or equal
to 2, y is greater than 0 and less than or equal to 3, e is from 0
to about 0.5, and M is selected from the group consisting of
calcium, magnesium, manganese, iron, cobalt, nickel, copper, and
zinc. More specifically, examples of solid state electrolytes
include (ZrO.sub.2), (ZrO.sub.2)(Y.sub.2O.sub.3).sub.0.08,
(ZrO.sub.2)(HfO.sub.2).sub.0.02(Y.sub.2O.sub.3).sub.0.08,
(ZrO.sub.2)(HfO.sub.2).sub.0.02(Y.sub.2O.sub.3).sub.0.05,
(ZrO.sub.2)(HfO.sub.2).sub.0.02(Y.sub.2O.sub.3).sub.0.08(TiO.sub.2).sub.0-
.10,
(ZrO.sub.2)(HfO.sub.2).sub.0.02(Y.sub.2O.sub.3).sub.0.08(Al.sub.2O.su-
b.3).sub.0.10,
(ZrO.sub.2)(Y.sub.2O.sub.3).sub.0.08(Fe.sub.2O.sub.3).sub.0.05,
(ZrO.sub.2)(Y.sub.2O.sub.3).sub.0.08(CoO).sub.0.05,
(ZrO.sub.2)(Y.sub.2O.sub.3).sub.0.08(ZnO).sub.0.05,
(ZrO.sub.2)(Y.sub.2O.sub.3).sub.0.08(NiO).sub.0.05,
(ZrO.sub.2)(Y.sub.2O.sub.3).sub.0.08(CuO).sub.0.05,
(ZrO.sub.2)(Y.sub.2O.sub.3).sub.0.08(MnO).sub.0.05 and
ZrO.sub.2CaO.
[0079] Other examples of solid state electrolytes include a
CeO.sub.2-based perovskite, such as Ce.sub.0.9Gd.sub.0.1O.sub.2 or
Ce.sub.1-xGd.sub.xO.sub.2 where x is no more than about 0.5;
lanthanum-doped ceria, such as (CeO).sub.1-n(LaO.sub.5).sub.n where
n is from about 0.01 to about 0.2; a LaGaO.sub.3-based perovskite
oxide, such as La.sub.1-xA.sub.xGa.sub.1-yB.sub.yO.sub.3 where A
can be Sr or Ca, B can be Mg, Fe, Co and x is from about 0.1 to
about 0.5 and y is from about 0.1 to about 0.5 (e.g.
La.sub.0.9Sr.sub.0.1Ga.sub.0.8Mg.sub.0.2O.sub.3); a
PrGaO.sub.3-based perovskite oxide electrolyte, such as
Pr.sub.0.93Sr.sub.0.07Ga.sub.0.85Mg.sub.0.15O.sub.3 or
Pr.sub.0.93Ca.sub.0.07Ga.sub.0.85Mg.sub.0.15O.sub.3; and a
Ba.sub.2In.sub.2O.sub.5-based perovskite oxide electrolyte, such as
Ba.sub.2(In.sub.1-xGa.sub.x).sub.2O.sub.5 or
(Ba.sub.1-xLa.sub.x)In.sub.2O.sub.5, where is x is from about 0.2
to about 0.5.
[0080] In one embodiment, the electrochemical device is a
solid-state device which comprises solid-state cathode and
electrolyte components as described previously. Preferably, the
anode is a liquid as described previously.
[0081] In one embodiment, the device provides an electrolyte having
small thicknesses. A small thickness provides at least one of many
advantageous features: (1) efficient migration of ions; (2)
provision of the oxygen-containing gas at relatively low pressures;
and (3) facile design of miniature devices. In one embodiment, the
electrolyte has a thickness of less than about 200 .mu.m, and more
preferably less than about 100 .mu.m.
[0082] FIG. 1 shows a cross-section of a device in which each
component can be provided as a flat layer or a shaped layer. For
example, FIG. 1 can also represent a cross-section of a shaped
device such as a tubular device. By "shaped device" it is meant
that the electrode-electrolyte configuration can be provided as any
shape besides a flat layer, as known to those of ordinary skill in
the art.
[0083] FIG. 2 shows a schematic cross-section of one type of shaped
layer, i.e. tubular device 12. Device 12 of FIG. 2 has similar
components as device 2 of FIG. 1. In FIG. 2, anode 14 is centrally
positioned within and enclosed by electrolyte 15. Encircling
electrolyte 15 is cathode layer 16. Leads 18a and 18b contact anode
14 and cathode 16 respectively. Inlet 20, for introducing gaseous
or liquid fuels if applicable, is shown submersed in the anode but
can be positioned anywhere that allows the fuel to be exposable to
anode 14. Optionally, cathode layer 16 can be positioned within a
casing to protect cathode layer 16 from breakage, as cathode layer
16 is typically provided as a thin layer. The casing may be
sufficiently porous to allow oxygen to access cathode layer 16.
Alternatively, device 12 can further comprise one or more conduits
(not shown) to provide an oxygen-containing gas flow 17 to the
cathode, or for removing exhaust from the device.
[0084] Another aspect of the present invention provides a housing
for the anode comprising a solid-state electrolyte material. This
feature provides an efficient design for an electrochemical device
as the solid-state electrolyte serves two functions: (1) as a
medium for the transport of ions to and from the electrodes; and
(2) for containing a liquid anode. Design efficiency is
advantageous, particularly when stacks of electrochemical devices
are employed. In this aspect, a separate housing is eliminating,
thus reducing cost of materials and resulting in a more lightweight
device. The electrolyte housing can be constructed solely of
electrolyte material, or partially of electrolyte material.
Ideally, the housing should comprise enough electrolyte material to
span a dimension of the anode, such as in FIG. 2 (electrolyte makes
up essentially the entire housing) or FIGS. 3 and 4 (electrolyte
makes up wall 25 only). Of course, the electrolyte material can be
of any dimension, depending on the electrical output and/or
economic requirements. Generally, efficient device design results
from maximizing the surface area which provides ionic communication
between the electrode/electrolyte components.
[0085] Alternatively, the housing can comprise a mixture of
electrolyte and non-electrolyte materials. Preferred
non-electrolyte materials in this mixture have thermal expansion
coefficients substantially similar to the electrolyte material. In
one embodiment, the thermal expansion coefficients of the
electrolyte and non-electrolyte materials differ by less than about
30% at a temperature of less than about 1500.degree. C., preferably
less than about 20% and more preferably less than about 10%.
Example non-electrolyte materials that can be included in this
mixture include .alpha.-Al.sub.2O.sub.3.
[0086] In one embodiment, an electrolyte housing is surrounded and
in ionic communication with a cathode material. In this embodiment,
the cathode conforms to the shape of the electrolyte, or at least
to the dimension of the electrolyte which spans a dimension of the
anode. FIG. 2 shows cathode 16 in conforming contact with
electrolyte which also functions as a housing for the anode. FIG. 3
shows another embodiment, where cathode 26 only surrounds the walls
of electrolyte 25, leaving base 29 free of contact with cathode
material.
[0087] Another advantageous feature of a liquid anode in certain
embodiments involves the ability of the anode to act as a sealant
precursor to seal a flaw in the device. In this embodiment, the
device is "self-repairing", and does not require any active human
intervention for the repair. For example, when a solid state
electrolyte develops a crack or other flaw, a liquid metal anode
can flow to substantially cover and/or substantially fill the
crack. Subsequently, the anode can react with oxygen to form a
metal oxide (or mixed metal oxide in the case where the anode is an
alloy). The resulting oxide formed substantially conforms to the
crack due to the flow properties of the initially liquid anode.
Even though the present device minimizes thermal and mechanical
stresses due to the liquid properties of the anode, the
self-repairing capability helps to ensure the integrity of the
device, particularly when repair is not feasible, e.g. during
operation of the system.
[0088] FIGS. 3 and 4 display various methods of exposing an anode
to a source of fuel. FIG. 3 shows a cross-sectional schematic
diagram of a tubular device 22 having electrolyte 25 in ionic
communication with anode 24 and cathode 26. Base 29 can be of the
same material as electrolyte 25, or of a different material and the
connection between electrolyte 25 and base 29 can be integral or
non-integral. Lead 28a (which can comprise a graphite material) is
submersed in anode 24 and is electrically connected to lead 28b
which is in electronic communication with cathode 26. Fuel 23 is
shown positioned on top of anode 24 and can either be consumed in
this manner or can be dispersed throughout the anode. This
arrangement is useful in the situation where the fuel is not easily
transferred from an inlet, such as in the case of certain solid
fuels. Optionally, the device can further comprise a mechanism for
urging fuel 23 towards the anode as fuel 23 is consumed. An urging
mechanism allows maximum contact surface area between fuel 23 and
anode 24. Examples of urging mechanisms include various mechanical
devices, such as a spring, a clamp, a rod or a diaphragm, or other
urging mechanisms known to those of ordinary skill in the art.
Mixing or agitation can also accomplish the urging.
[0089] FIG. 4 shows a cross-sectional schematic diagram of tubular
device 32, featuring another position of inlet 40 with respect to
device 32. Device 32 comprises electrolyte in ionic communication
with anode 34 and cathode 36. Base 39 can be of the same or a
different material as electrolyte 35 and the connection between
electrolyte 35 and base 39 can be integral or non-integral. Lead
38a is partially submersed in anode 34 and does not extend all the
way to base 39. Inlet 40 penetrates through base 39 to the extent
that a space exists between inlet 40 and lead 38a. Upon release of
fuel 41 into anode 34 through inlet 40, the fuel can be readily
dispersed throughout a maximum portion of anode 34. Another
advantage to this arrangement is that any waste products will
naturally travel to an aperture opposite, or at a distance from
inlet 40, for example, areas 42 in which anode 34 contacts the
atmosphere. Alternatively, the device of the present invention can
further comprise an exhaust conduit to remove any waste from the
device.
[0090] Certain prior art devices require operating temperatures of
greater than 1000.degree. C. It is generally desired to lower these
operating temperatures to minimize thermal energy provided to the
device. Exceedingly high temperatures may also lead to electrolyte
or cathode cracking or the formation of other flaws in the device.
In addition, rapid start-up heating times provides an advantage in
the situation where electrical power is required quickly. The
higher the operating temperature, however, the greater the time
needed for start-up heating of the device.
[0091] Thus, another aspect of the present invention provides an
electrochemical device comprising an anode comprising a liquid at a
temperature of no more than about 1000.degree. C. The ability to
provide a liquid anode at lower operating temperatures, such as a
temperature below 1000.degree. C., reduces a temperature range
required for start-up heating. In addition to reducing start-up
heating times, lower temperatures afford a more hospitable
environment for maintaining the integrity of an interface between
different components such as the anode/electrolyte or
electrolyte/cathode components.
[0092] Another aspect of the present invention provides an
electrochemical device comprising an anode and an intermittent fuel
source deliverable to the anode to produce a continuous electrical
output from the device. "Intermittent fuel source" refers to any
fuel source arranged to allow cessation between a period of
delivery of the fuel to the anode. In one embodiment, the cessation
can be periodic or random. Cessation can be a multiple occurrence
or a one-time occurrence. It is a feature of this aspect of the
invention that even with this cessation of fuel delivery a
continuous electrical output is produced. In one embodiment, an
intermittent fuel source can be used when the device is switched
from fuel cell mode to battery mode where fuel is not delivered to
the anode. When fuel is supplied to the device, electricity can be
generated via fuel cell operation. Ceasing delivery of fuel to the
anode causes the device to switch to battery mode for continuous
generation of electricity. An electrical device can be
manufactured, using the methods and materials described herein, to
derive power continuously while experiencing minimal or almost no
shut down time as the electrical device switches between fuel cell
and battery modes. During intermittent fuel delivery, the fuel
source can also be changed or replenished.
[0093] In one embodiment, switching from fuel cell mode to battery
mode and vice versa occurs automatically. For example, the device
of the present invention can operate in fuel cell mode until the
fuel is exhausted. Automatic switching is demonstrated when the
anode begins to oxidize, thereby releasing electrons, i.e., the
device automatically operates in battery mode. In one embodiment,
the switching can occur by simply shutting off fuel delivery to the
anode or turning on the fuel source. Alternatively, a switch can be
constructed which stops/starts introduction of fuel to the anode.
Other switching mechanisms can be readily envisioned by those of
ordinary skill in the art.
[0094] In one embodiment, the device can operate simultaneously in
fuel cell and battery mode. In this embodiment, fuel consumption
and fuel oxidation by the anode occur simultaneously. This may
occur when fuel is supplied to the anode at a low flow rate and/or
in low amounts. Alternatively, simultaneous fuel cell and battery
operation may inherently occur when fuel is supplied to the device.
Switching between fuel cell and battery mode can occur, not as a
sharp on/off event, but gradually as the amount of fuel supplied to
the anode is increased or decreased.
[0095] Another aspect of the invention provides an electrochemical
device comprising an anode and a source of fuel exposable to the
anode. The anode is constructed of a material such that the device
is capable of producing electricity by using the anode (the anode
is included in a circuit in which the electricity is produced) in
both the presence of fuel without anode consumption (or without net
anode consumption, i.e., less anode is consumed than regenerated)
and in the absence of fuel. In one embodiment, a device "capable of
producing electricity involving the anode in the presence of fuel
without anode consumption" refers to generation of electricity via
fuel cell operation. Conversely, the same anode can deliver
electrons to the device without exposure to fuel in which the anode
is consumed, such as when the device operates in battery mode. In
one embodiment, the electrochemical device is a fuel cell/battery
hybrid capable of operating in either fuel cell or battery mode,
while producing a continuous electrical output.
[0096] Another aspect of the present invention provides a stack of
electrochemical devices. Electrical output can be multiplied by
supplying a number of devices as described above into one system.
For variable load applications, it is usually desired that the
stack be lightweight and capable of miniaturization. FIG. 5 shows
an example of a stack 100 of planar electrochemical devices. Each
device in stack 100 comprises an anode 104 in ionic communication
with electrolyte 105. Electrolyte 105 in turn is in ionic
communication with cathode 106. Stack 100 further includes an inlet
110 for liquid or gaseous fuel to be provided to each device via
guide 111. Inlet 112 allows oxygen to be supplied via guide 113 to
each cathode 106. Conduit 114 and outlet 115 serve to remove any
exhaust gases from stack 100. The multi-device system is positioned
within casing 102. Stack 100 further includes preheating chamber
116 to heat each device to an operational temperature.
[0097] In this aspect, a liquid anode is particularly advantageous
due to its moldable properties. The liquid can function as a seal
between each device. Moreover, the liquid provides a soft contact
between the liquid anode and the adjacent device to reduce
mechanical and thermal stresses between the devices.
[0098] FIG. 5 shows each device in the stack arranged and
positioned in a repeat array to arrange identical components in the
same orientation. This arrangement may relieve stresses on each
device, particularly taking advantage of the soft contact provided
by the anode. A variety of arrangements of the devices in the stack
can be envisioned to maximize the number of devices that receive
fuel from guide 111.
[0099] In other embodiments, the devices in the stack can be
arranged in series, parallel or can comprise a series-parallel
configuration.
[0100] The stack need not necessarily be arranged in planar
configuration and can be arranged in any array, e.g. such as a
rectangular or hexagonal array.
[0101] Another advantageous feature of the liquid anode is that by
positioning a liquid adjacent a solid component, a non-permanent
seal is formed. This non-permanent attachment removes a need to add
further components to hold each device adjacent to each other such
as adhesives or mechanical attachments. In one embodiment, the
casing can provide a series of slots. Each device can simply be
guided through the slots to provide the stack. In the event of a
malfunction of an individual device, the malfunctioning device can
be removed and easily replaced with a new device. For other prior
art devices, when one individual device malfunctions, either the
permanent seal would have to be broken to replace the individual
device or the entire stack will need to be repaired. Of course,
other embodiments may provide a permanent seal in addition,
depending on the application.
[0102] FIG. 6 shows an alternative example of a stack utilizing
solid fuel. FIG. 6 shows stack 120 having anode 124 positioned
adjacent electrolyte 125 which in turn is positioned adjacent
cathode 126. Inlet 132 directs oxygen to individual devices via
conduit 133. Solid fuel 130 is positioned within anode 124. Solid
fuel 130 can also act as a lead to collect electricity from the
anode. Each device can be positioned within casing 122. Casing 122
can further comprise inlets to provide more solid fuel to the
device, or a reservoir for additional solid fuel sources. Each
device in stack 120 can be tubular or planar.
[0103] In one embodiment, the stack can further comprise an
interconnect positioned adjacent the anode of a first device and
the cathode of the second device. An interconnect has an air flow
pattern to allow oxygen flow in or out of the stack. In addition,
an interconnect can convey electrical currents and/or thermal
energy away from each device. Preferably, the interconnect has
sufficient electrical conductivity and thermal conductivity to
achieve this function. To reduce the likelihood of forming cracks
in the device, it is preferred that the interconnect and cathode
have similar thermal coefficients. In one embodiment, respective
thermal expansion coefficients of the cathode and interconnect
differ by less than about 30% at a temperature of less than about
1500.degree. C., preferably less than about 20% and more preferably
less than about 10%. In one embodiment, the interconnect comprises
substantially the same material as the cathode, and thus the
respective thermal coefficients would theoretically differ by about
0%.
[0104] Referring back to FIGS. 5 and 6, interconnects 107 and 127
are shown as being positioned adjacent cathodes 106 and 126,
respectively, and the adjacent anodes. FIG. 7 shows a close-up of a
stack of FIG. 5. Stack 100 features interconnect 107 positioned
adjacent cathode 106. Interconnect 107 is also positioned adjacent
an anode.
[0105] FIG. 8 shows another exemplary arrangement for connecting
two tubular devices of the invention together to form a stack via
an interconnect. In FIG. 8, stack 140 comprises individual units
each comprising anodes 144a and 144b positioned adjacent and within
electrolyte layers 145a and 145b, respectively. Cathodes 146a and
146b are provided as a layer which coats at least a portion of
electrolytes 145a and 145b. Fuel sources 150a and 150b can be
positioned adjacent anodes 144a and 144b. Where the fuel is a solid
fuel, fuel sources 150a and 150b can comprise a solid rod, such as
graphite. In addition, the solid rod can also function as a current
collector.
[0106] Alternatively, for liquid, gaseous or solid powder fuels,
fuel sources 150a and 150b can comprise an inlet positioned within
or near anodes 144a and 144b to guide and disperse the fuels
throughout anodes 144a and 144b. In any situation, a lead would be
required to be positioned in anode 144b and lead 154 can be
positioned adjacent cathode 146a. Interconnect 152 is positioned
adjacent electrolyte layer 145a and cathode layer 146b. To allow
interconnect 152 to contact anode 144a, holes can be provided in a
portion of electrolyte 145a which contacts interconnect 152. Thus,
the anode 144a can flow through the holes to eventually contact
interconnect 152. FIG. 8 shows tubular arrangements, but those of
ordinary skill in the art can readily design an analogous planar
device, in light of the description provided herein.
[0107] As discussed previously, typical fuel cell interconnects
include a gas flow pattern. In one embodiment, an interconnect of
the present invention is free of a gas flow pattern, particularly
when used with a liquid anode. Because fuel and waste are
dispersible throughout the anode and can enter or exit each device
via the liquid anode, a gas flow pattern is not essential for the
interconnect of the present invention. It is understood that other
fuel types may still require an interconnect with a gas flow
pattern for enhanced device performance.
[0108] As discussed previously, the interconnect is positioned
adjacent a liquid anode, thus reducing many problems associated
with thermal coefficients mismatches that may arise as the device
is heated to high temperatures. Accordingly, it has been discovered
that such moldability of the liquid anode allows the interconnect
to have much thinner dimensions than many prior art interconnects.
This allows interconnects to be more lightweight and less expensive
and these benefits can be extended to the manufacturer of the
device.
[0109] Thus, the interconnect of the present invention can provide
at least one of the following advantages: (1) a reduction in weight
by at least 20%, preferably by at least 30% and more preferably by
at least 40% compared to prior art interconnects; (2) elimination
of intricate, machined gas flow patterns, which reduces the cost
and manufacture time; and (3) rapid and repeated start-up heating
of the stack due to the minimal thermal and mechanical stresses
resulting from contact with adjacent anode and cathode
materials.
[0110] FIG. 9 shows a schematic diagram summarizing various
electrochemical processes that can be carried out by the anode of
the present invention. In FIG. 9, anode 200 is represented as "M"
in which anode 200 comprises a metal or metal alloy. Eq. 202 of
FIG. 9 schematically represents anode 200 functioning as a battery.
In eq. 202, anode 200 combines with "y" moles of O.sup.2- produced
from a cathode. In battery mode, anode 200 releases electrons
resulting in the oxidation of M to form a metal or mixed metal
oxide, M.sub.xO.sub.y. Eq. 203 schematically shows the chemical
rechargeability of the anode which, in the presence of fuel, is
reduced back to metal anode 200. In eq. 203, it is the metal oxide
that combines with the fuel to produce fuel oxidation products.
"M.sub.xO.sub.y" should be of a sufficient electrochemical
potential to be reduced by the fuel. Without wishing to be bound by
any theory, the combination of eqs. 202 and 203 schematically
illustrates the process undergone by anode 200 when operating in
fuel cell mode, in which there is no net consumption of anode.
Thus, FIG. 9 shows the capability of anode 200 to: (1) be oxidized
in the absence of a fuel and produce electricity, as shown in eq.
202; (2) regenerate from a corresponding metal oxide, as shown in
eq. 203; and (3) oxidize fuel with no net consumption of the anode,
as represented by eqs. 202 and 203.
[0111] Accordingly, another aspect of the present invention
provides a method for energy conversion. The method involves
providing an electrochemical device comprising an anode, such as
any anode described herein. The method also involves causing
electricity to be produced when the anode is exposed to a fuel,
such that electricity is produced without anode consumption (i.e.
anode acts as a catalyst). In one embodiment, this step is
exemplified by eqs. 202 and 203 of FIG. 9. The method also involves
causing electricity to be produced in the device in the absence of
fuel provided to the anode. This step is distinguished from other
devices which provide a back-up battery source having another
anode, in the event the fuel supply is exhausted. The present
invention allows the same anode to cause electricity to be produced
in the presence of a fuel (i.e., when in fuel cell mode) and to
cause electricity to be produced in the absence of the fuel. In one
embodiment, this step is exemplified by eq. 202 of FIG. 9.
[0112] In one embodiment, either step of causing electricity to be
produced in the presence or absence of a fuel involves providing an
electrolyte in ionic communication with the anode and a cathode in
ionic communication with the electrolyte. These steps can also
involve directing an oxygen-containing gas flow to the cathode. In
one embodiment, the causing steps can also include heating the
device from a temperature of about 300.degree. C. to about
1500.degree. C., or within other temperature ranges as described
previously. Preferably, the chosen temperature range involves
producing the anode in a liquid state.
[0113] In the embodiment where electricity is produced in the
absence of the fuel, the anode is typically consumed. Thus, in one
embodiment, the method further comprises providing fuel to the
anode to chemically recharge the anode. In one embodiment, this
step is exemplified by eq. 203 of FIG. 9.
[0114] Another aspect of the present invention provides a method
for energy conversion. The method involves providing an anode and
delivering a fuel to the anode intermittently while producing a
continuous electrical output by using the anode. As described
previously, "intermittently" can involve any cessation of fuel
delivery to the anode. "Producing a continuous electrical output by
using the anode" refers to use of the anode continuously, even
though fuel is provided to the anode intermittently.
[0115] A device comprising a fuel cell and a separate battery
back-up is excluded from this aspect of the invention, because when
fuel is supplied, the anode of the fuel cell is used to produce
electricity. When fuel delivery ceases in favor of the battery
backup, the anode of the battery and not the anode of the fuel
cell, is used to produce electricity. Thus, the anode of the fuel
cell is not used continuously in the continuous production of
electricity.
[0116] Another aspect of the present invention provides a method
involving providing an anode and causing a portion of the anode to
be oxidized such that electricity is produced. In one embodiment,
this causing step occurs when the anode is operated as a battery,
as exemplified by eq. 202 of FIG. 9. The "portion of the anode" is
described as follows. Initially, the portion of the anode that is
immediately adjacent the electrolyte is oxidized, as this portion
represents the shortest diffusion pathway by which oxygen ions
released by the cathode can access the anode. As device operation
continues, this oxidized portion grows from the anode/electrolyte
interface toward the bulk of the anode, as the anode continues to
be consumed.
[0117] At any stage of anode consumption, either initially or when
the entire anode has been consumed (i.e. at least a portion of the
anode is consumed), the method involves exposing the oxidized
portion of the anode to a chemical reductant such that the oxidized
portion is reduced. In one embodiment, reducing this oxidized
portion regenerates the anode to its initial state. In one
embodiment, the anode is a metal which is oxidized to a metal
oxide, and exposure of the metal oxide to a chemical reductant
results in re-formation of the metal anode or to an oxidation state
capable of oxidizing the fuel. In one embodiment, the chemical
reductant is a fuel. This is advantageous in that the device does
not require any new materials as the fuel available is capable of
reducing the oxidized portion of the anode to the initial state of
the anode.
[0118] In one embodiment, the reduced portion, which results from
reducing the oxidize portion, is capable of functioning as an anode
again. "Functioning as an anode" involves either the operation of
the anode as a battery or a fuel cell.
[0119] Another aspect of the invention provides a method for energy
conversion, comprising the step of providing a device comprising a
liquid metal anode. A portion of the anode is oxidized to form a
metal oxide concurrent with the generation of electricity in the
device. The anode can be oxidized by heating the device to any of
the preferred operable temperatures disclosed herein when exposed
to oxygen anions. Alternatively, the oxidized anode can be reduced
by exposing the anode to a fuel, preferably at the temperatures
disclosed herein.
[0120] The function and advantage of these and other embodiments of
the present invention will be more fully understood from the
examples below. The following examples are intended to illustrate
the benefits of the present invention, but do not exemplify the
full scope of the invention.
Example 1
An Electrochemical Device
[0121] A single electrochemical device, as exemplified by FIG. 2,
is constructed as follows. Tubular electrolyte 15 is made of YSZ
(yttria-stabilized zirconia,
(ZrO.sub.2)(HfO.sub.2).sub.0.02(Y.sub.2O.sub.3).sub.0.08) and has a
thickness of 180 .mu.m. Tubular cathode 16 is made of LSM
(La.sub.0.84Sr.sub.0.16MnO.sub.3) and has a thickness of 300 .mu.m.
A platinum wire functions as a cathode current collector (lead
18b), and a graphite rod functions as an anode current collector
(lead 18a). The tube has a length of 3 cm, a diameter of 1 cm. The
anode comprised either 8 g antimony; antimony alloy with 5% lead;
indium; lead; antimony alloy with 10% tin; antimony alloy with 5%
silver; antimony alloy with 50% indium; tin; or tin alloy with 5%
Pb. The device is placed on a heating block with a temperature
control.
Example 2
Propane Gas and Natural Gas as Fuel for Recharging
[0122] To demonstrate that a device of the present invention can be
operated without the addition of fuel, the device of Example 1 was
heated and maintained at 960.degree. C. The device registered an
open circuit voltage of 0.78V and a short current of 1.5 amp. After
operating for 30 min., there was no visible decrease in the power
output. After a time from 2-8 h, the current dropped to zero and
the open circuit voltage was 0.3-0.6 V.
[0123] Propane gas (Bernzomatic) or natural gas was introduced
through an alpha-alumina tube (outside diameter 1.2 mm and inside
0.8 mm) into the liquid metallic anode. The end of the tube was
submerged beneath the surface of the liquid at a gas flow rate of
50 mL/min.
[0124] After charging the device for 2 min. with propane gas, the
short circuit current increased from zero to 0.3 amp and the open
circuit voltage measured 0.79. After a 7 minute charge, the device
registered a current of 1.2 amp and a voltage of 0.76 V. Exhaust
gas started to show some smoke or carbon soot. With an additional 2
min. charge, the current reached 1.5 amp and voltage 0.76 V. The
amount of light smoke was another indication of the degree of
charge. More charge did not change the current and voltage.
[0125] Delivery of propane gas was ceased and the device continued
to run for a time greater than 1 h until it was exhausted. The
device was then recharged with propane gas as described in this
Example. This cycle was repeated for three days without noticeable
change of power output.
Example 3
Diesel, Gasoline and Alcohol (Denatured) as Fuel for Recharging
[0126] The device of Example 1 was heated and maintained at
990.degree. C. without the addition of fuel. After the cell was
exhausted (current was zero and open circuit voltage was 0.3-0.6V),
5 .mu.L of gasoline was injected through a microsyringe into the
liquid metallic anode. A total of 5 injections was made within 5
min at a rate of 5 .mu.L/min. Gray smoke was observed during each
injection. After recharging with gasoline, the cell gave a current
of 2.0 amp (from zero) and voltage of 0.75 V.
[0127] To demonstrate the ability of the device to operate with
different fuels, the cell was then heated and maintained at
990.degree. C. After the cell was exhausted (current was zero and
open circuit voltage was 0.3-0.6V), 2 .mu.L of denatured alcohol
was injected through a microsyringe into the liquid anode. A total
of 40 injections were made in 13 minutes at a rate of 6.2
.mu.L/min. Little smoke was observed during each injection. After
recharging with alcohol, the cell gave a current of 0.3 to 0.5 amp
and voltage of 0.72 V.
[0128] The cell was then heated and maintained at 990.degree. C.
After the cell was exhausted (current was zero and open circuit
voltage was 0.3-0.6V), 4 .mu.L of diesel was injected through a
microsyringe up to the surface of the liquid metallic anode. A
total of 20 injections were made within 20 minutes at a rate of 4
.mu.L per minute. Heavy smoke was observed during each injection.
After recharging with diesel, the cell gave a current of 0.3 to 0.5
amp and voltage of 0.72 V.
Example 4
Carbon Black as Fuel for Recharging
[0129] This Example demonstrates the ability of the device of the
present invention to operate with a solid fuel. The device of
Example 1 was heated and maintained at 980.degree. C. After the
cell was exhausted (current was zero and open circuit voltage was
0.3-0.6V), carbon grains (size 0.3-0.6 cm) were added inside the
cell. After recharging with 0.1 g of carbon, the cell gave a
current of 0.3 to 0.5 amp and voltage of 0.72 V. After recharging
with 0.1 g more carbon, the cell gave a current of 0.5-1.0 amp and
voltage of 0.763. After recharging with 0.21 gram more carbon, the
cell gave a current of 1.1 to 1.3 amp and voltage of 0.79 to 0.87
volt. After recharging with 0.17 gram more carbon, the cell gave a
current of 1.5 amp and 0.9 to 0.92 V.
Example 5
Weight Analysis for Multi-Unit Stack for Liquid Fuel
[0130] FIG. 5 shows exemplary dimensions of a stack of the present
invention. Table 1 lists a weight for each component of the stack.
Weights of liquid fuels such as gasoline, kerosene and diesel are
based on a power density of 4 kW/m.sup.2. Fuel and tank are not
included.
TABLE-US-00001 TABLE 1 Component Dimension and size Weight, lb
Ceramic electrolyte 25,000 .times. 0.01 cm.sup.3 (250 cm.sup.3) 3.3
Ceramic cathode 25,000 .times. 0.015 cm.sup.3 (375 cm.sup.3) 5.0
Ceramic interconnect 3,500 cm.sup.3 (1,500 cm.sup.3) 46 Liquid
metallic anodic 3,750 cm.sup.3 (2,500 cm.sup.3) 50 Air delivery
system 2 Fuel delivery system 2 Insulation 3 Case & support 20
Total Weight 131
[0131] An example stack can comprise a 60-stack of planar
electrochemical devices.
[0132] Each stack can have a size of 8 in. (203 cm).times.8 in.
(203 cm)=64 in..sup.2 (412 cm.sup.2), with a power output of 412
cm.sup.2.times.0.4 watt/cm.sup.2=165 watt each. Each stack can have
a thickness of 0.4 cm (0.01 cm for the electrolyte, 0.02 cm for the
cathode, 0.22 cm for the interconnect and 0.15 cm for the liquid
metallic anodic component). In this example, the total stack length
is 60.times.0.4 cm=24 cm (9.5'').
[0133] The liquid fuel cell is rated at 10 kW (165
watt/stack.times.60 stacks) with the stack size of 8 in. (203
cm).times.8 in. (203 cm).times.9.5 in. (24 cm).
[0134] Including insulation (1.5'' thickness), Case & Support,
air and exhaustive flow conduits, and a preheating, the stack can
have a volume of one cubic foot and a weight of 131 lb. This does
not include the fuel and a fuel tank.
Example 6
Weight Analysis for Multi-Unit Stack for Solid Fuel
[0135] FIG. 6 shows exemplary dimensions of a stack of the present
invention for a solid fuel such as carbon. The carbon can be placed
inside as part of the device or can be charged from the outside
periodically. Table 2 lists a weight for each component of the
stack. 46 lb of carbon can be stored inside the device. Of course,
the amount of carbon stored inside could be more or less, depending
on the mission.
TABLE-US-00002 TABLE 2 Component Dimension and size Weight, lb
Ceramic electrolyte 25,000 .times. 0.01 cm.sup.3 (250 cm.sup.3) 3.3
Ceramic cathode 25,000 .times. 0.015 cm.sup.3 (375 cm.sup.3) 5.0
Ceramic interconnect 3,500 cm.sup.3 (1,500 cm.sup.3) 46 Liquid
metallic anodic 3,750 cm.sup.3 (2,500 cm.sup.3) 50 Air delivery
system 2 Carbon plate as fuel 0.3 cm .times. 25 cm .times. 20 cm
.times. 60 46 Carbon & liquid guide 5 Insulation 5 Case &
support 25 Total Weight 187 lb
[0136] An example stack can comprise a 60-stack of planar fuel cell
stacks. In this example, each stack has a surface area of 8 in.
(203 cm).times.8 in. (203 cm)=64 in..sup.2 (412 cm.sup.2), with a
projected power output of 412 cm.sup.2.times.0.4 watt/cm.sup.2=165
watt each. A gap of 0.6 cm between each stack may be longer than
that of the liquid fuels (cf. 0.4 cm). Exemplary dimensions:
electrolyte=0.01 cm; cathode=0.02 cm; interconnect=0.22 cm; and
carbon and liquid anode=0.35 cm. In this example, a total stack
length is 60.times.0.6 cm=36 cm (14'').
[0137] An additional guide (5 lb) extending out of the stack can be
provided for guiding carbon plate and storing excess liquid
metals.
[0138] The carbon cell is rated at 10 kW (165 watt/stack.times.60
stacks) and has a dimension of 15''.times.16''.times.12'' and
weighs 187 lb with 46 lb of carbon stored inside as fuel.
[0139] With the 46 lb carbon fuel and at 40% fuel efficiency, the
unit will produce 73 kW-hours, equivalent to 860
watt-hours/kilogram.
[0140] Increasing carbon fuel load, will improve the energy
density. The theoretical limit for carbon is 3,520
watt-hours/kilogram at 40% fuel efficiency.
Example 7
Analysis of Device Components after Operation
[0141] After operating the device of Example 1 as described in
Example 2, the device was smashed to allow observation of the
internal components. In the interface between the anode and the
electrolyte, a yellow powder or white powder was observed. Without
wishing to be bound by any theory, it is proposed that this yellow
or white powder comprises consumed anode, i.e., a metal oxide such
as antimony oxide or a mixed antimony/lead, antimony/tin,
antimony/silver, tin and antimony/indium oxide. Interestingly, in
the anode/electrolyte interface immediately adjacent the fuel
source, no powder was observed. It is believed that the absence of
powder in this portion of the cell provides evidence that the fuel
is capable of reducing any metal oxide back to the metal.
[0142] Those skilled in the art would readily appreciate that all
parameters listed herein are meant to be examples and that actual
parameters will depend upon the specific application for which the
methods and apparatus of the present invention are used. It is,
therefore, to be understood that the foregoing embodiments are
presented by way of example only and that, within the scope of the
appended claims and equivalents thereto, the invention may be
practiced otherwise than as specifically described.
* * * * *