U.S. patent application number 16/437248 was filed with the patent office on 2019-09-26 for electrochemical cells.
The applicant listed for this patent is IFBattery Inc.. Invention is credited to John H. Cushman.
Application Number | 20190296383 16/437248 |
Document ID | / |
Family ID | 67985814 |
Filed Date | 2019-09-26 |
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United States Patent
Application |
20190296383 |
Kind Code |
A1 |
Cushman; John H. |
September 26, 2019 |
Electrochemical Cells
Abstract
Electrochemical cells and batteries that can operate with a
single electrolyte solution, such as those comprising an anode, a
cathode current collector, and a porous, non-conductive spacer
between the cathode current collector and anode. Membraneless
electrochemical cells and batteries are also disclosed. The
electrochemical cells and batteries disclosed herein may be used,
for example, to produce electricity or to generate hydrogen or
both, and to deliver electricity or hydrogen or both to process
applications.
Inventors: |
Cushman; John H.; (West
Lafayette, IN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
IFBattery Inc. |
West Lafayette |
IN |
US |
|
|
Family ID: |
67985814 |
Appl. No.: |
16/437248 |
Filed: |
June 11, 2019 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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PCT/US2018/021981 |
Mar 12, 2018 |
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16437248 |
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62470772 |
Mar 13, 2017 |
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62479548 |
Mar 31, 2017 |
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62506422 |
May 15, 2017 |
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62518523 |
Jun 12, 2017 |
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62530687 |
Jul 10, 2017 |
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62531274 |
Jul 11, 2017 |
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62595171 |
Dec 6, 2017 |
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62684135 |
Jun 12, 2018 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
H01M 8/188 20130101;
H01M 4/905 20130101; H01M 8/083 20130101; H01M 2300/0014
20130101 |
International
Class: |
H01M 8/18 20060101
H01M008/18; H01M 8/083 20060101 H01M008/083 |
Claims
1-237. (canceled)
238. An electrochemical cell, which comprises: a. an anode selected
from aluminum, gallium, indium, thallium and alloys comprising at
least one of these; b. a cathode current collector; and c. a
porous, non-conductive spacer between the cathode current collector
and anode.
239. The electrochemical cell of claim 238, wherein the anode is
aluminum or an alloy comprising aluminum.
240. The electrochemical cell of claim 238, wherein the cathode
current collector is selected from steel, the graphite allotrope of
carbon, carbon impregnated with a metal and carbon foam.
241. The electrochemical cell of claim 238, wherein the porous,
non-conductive spacer is selected from an organic polymer,
fiberglass film, glass wool, wood, paper, cloth, cardboard and
nylon.
242. The electrochemical cell of claim 238, further comprising a
single electrolyte solution in contact with both the anode and
cathode current collector of the cell.
243. The electrochemical cell of claim 242, wherein the electrolyte
solution comprises water as a solvent.
244. The electrochemical cell of claim 242, wherein the electrolyte
solution comprises an alcohol as a solvent.
245. The electrochemical cell of claim 244, wherein the alcohol is
ethanol.
246. The electrochemical cell of claim 242, wherein the electrolyte
solution comprises an oxidant and a metal salt.
247. The electrochemical cell of claim 246, wherein the oxidant is
a salt, and wherein the oxidant and metal salt have different anion
components.
248. The electrochemical cell of claim 247, wherein the oxidant is
a salt of peroxydisulfate and the metal salt is a metal salt of
sulfate.
249. The electrochemical cell of claim 248, wherein the
peroxydisulfate salt is sodium peroxydisulfate and the metal
sulfate salt is sodium sulfate.
250. The electrochemical cell of claim 242, wherein the electrolyte
solution comprises a base.
251. The electrochemical cell of claim 250, wherein the base is
sodium hydroxide.
252. The electrochemical cell of claim 242, wherein the electrolyte
solution comprises water, an oxidant, a metal salt and a base.
253. A method of generating electricity, which comprises connecting
an electrochemical cell of claim 242 to a load.
254. A method of generating hydrogen, which comprises contacting
both the anode and cathode current collector of the cell of claim
238 with a single electrolyte solution.
255. A method of operating an electrochemical cell of claim 238 as
a flow cell, which comprises: contacting both the anode and cathode
current collector of the cell with a single electrolyte solution;
operating the electrochemical cell to generate electricity,
hydrogen, or both electricity and hydrogen; and providing
additional electrolyte solution, or one or more components thereof,
to the electrochemical cell during its operation.
256. The method of claim 255, which further comprises: withdrawing
spent electrolyte solution, or one or more components thereof, from
the electrochemical cell during its operation.
257. The method of claim 256, which comprises withdrawing spent
electrolyte solution, or one or more components thereof,
simultaneously with providing additional electrolyte solution, or
one or more components thereof.
258. An electrochemical cell comprising a single aqueous
electrolyte solution in contact with a non-metallic current
collector, an oxidant, and a metal solid wherein current travels
from the metal solid to the current collector via a load, or an
electrochemical cell comprising a single aqueous electrolyte
solution in contact with a non-metallic current collector, an
oxidant, and a metal solid wherein current travels from the metal
solid to the current collector via a load, and wherein the pH is
greater or equal to 12, or an electrochemical cell comprising a
single aqueous electrolyte solution in contact with a non-metallic
current collector, an oxidant, and one or more anodes wherein
current travels from the one or more anodes to the current
collector via a load, and wherein the pH is greater or equal to
10.
259. An electrochemical cell comprising: a. a cathode; b. an anode
adjacent to the cathode at a distance; c. a first polar electrolyte
solution in contact with the cathode and disposed within the
distance comprising an oxidant; d. a second polar electrolyte
solution in contact with the anode and disposed within the distance
comprising a suitable metal ion; and e. a separation agent; wherein
the first and second electrolyte solutions are in contact with each
other and are immiscible, and wherein there is no membrane in
between the first and second electrolyte solutions, or an
electrochemical cell comprising: a. a cathode; b. an anode adjacent
the cathode at a distance; c. a first polar aqueous electrolyte
solution in contact with the cathode and disposed within the
distance comprising S.sub.2O.sub.8.sup.2-; d. a second polar
electrolyte alcoholic solution in contact with the anode and
disposed within the distance comprising Al.sup.3+; and e.
borosilicate within both the first and second electrolyte
solutions; wherein the first and second electrolyte solutions are
in contact with each other and are immiscible, and wherein there is
no membrane in between the first and second electrolyte solutions,
or an electrochemical cell comprising: a. a non-metallic cathode;
b. a non-metallic anode adjacent the cathode at a distance; c. a
first polar aqueous electrolyte solution in contact with the
cathode and disposed within the distance comprising
S.sub.2O.sub.8.sup.2-; and d. a second polar electrolyte alcoholic
solution in contact with the anode and disposed within the distance
comprising a metal solid; wherein the first and second electrolyte
solutions are in contact with each other and are immiscible, and
wherein there is no membrane in between the first and second
electrolyte solutions, or an electrochemical cell comprising: a. a
cathode; b. an anode adjacent to the cathode at a distance; c. a
first aqueous electrolyte solution in contact with the cathode and
disposed within the distance comprising an oxidant; d. a second
polar electrolyte solution in contact with the anode and disposed
within the distance comprising a metal and an oxidant; and e. a
separation agent; wherein the first and second electrolyte
solutions are in contact with each other and are immiscible, and
wherein there is no membrane in between the first and second
solutions.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation-in-part of international
application no. PCT/US2018/021981, filed on Mar. 12, 2018, which
claims priority to, and benefit of, U.S. Provisional Application
No. 62/470,772, filed on Mar. 13, 2017; U.S. Provisional
Application No. 62/479,548, filed on Mar. 31, 2017; U.S.
Provisional Application No. 62/506,422, filed on May 15, 2017; U.S.
Provisional Application No. 62/518,523, filed on Jun. 12, 2017;
U.S. Provisional Application No. 62/530,687, filed on Jul. 10,
2017; U.S. Provisional Application No. 62/531,274, filed on Jul.
11, 2017; and U.S. Provisional Application No. 62/595,171, filed on
Dec. 6, 2017. The entire contents of international application no.
PCT/US2018/021981, filed on Mar. 12, 2018, are specifically
incorporated by reference herein.
[0002] This application also claims priority to, and benefit of,
U.S. Provisional Application No. 62/684,135, filed on Jun. 12,
2018, the entire contents of which are specifically incorporated by
reference herein.
BACKGROUND
[0003] The U.S. Energy Information Agency projects a 48% increase
in world energy consumption by 2041 and global industries are
rapidly adapting to these new opportunities. At the center of their
efforts is the demand for a new battery that is more efficient,
more environmentally friendly, more affordable and more convenient.
The Department of Defense has stated a goal of generating 25% of
its energy from renewable sources by the year 2025. Additionally,
the military must have readily available sources of hydrogen when
fielding stealthy fuel-cell powered vehicles.
[0004] Liquid batteries, whether flow or no-flow, are known in the
art and work on the same principles as solid batteries, except the
electrolyte is liquid. Such batteries are comprised of
electrochemical cells which are based on reduction-oxidation
chemistry. Oxidation occurs on the anode side of the cell and
reduction on the cathode side. The solvents used in electrochemical
cells are varied. In many circumstances, aqueous solutions are used
on both sides of an electrochemical cell with each side (cathode
side and anode side) in contact with an electrode (i.e., the
cathode and anode respectively). The electrodes of the two-half
cells are placed in electrical contact to allow for current to
flow. To maintain charge balance, an electrochemical cell must also
allow for the passage of ions. In some batteries, this is done with
a salt bridge separating the cathode solution from the anode
solution. The bridge prevents mixing of the two solutions. The
prior art teaches that if the solutions were to mix, the half-cells
could be destroyed by direct chemical reaction.
[0005] Some electrochemical cells deploy membranes or salt bridges
to prevent shorting and to separate multiple electrolyte solutions.
Such membranes are costly and readily degrade over time.
WO2017/106215 reports electrochemical cells which may be used in
the absence of membranes and which use two or more immiscible
electrolytes.
[0006] The present disclosure includes improved designs for
electrochemical cells and batteries (including flow cells and flow
batteries) that, in certain embodiments, include a single
electrolyte solution, an anode, a cathode current collector, and a
porous, non-conductive spacer between the cathode current collector
and anode. In contrast to typical flow batteries, the anode and
cathode current collector in such embodiments need not be immersed
in an electrolyte. Additional embodiments include improved designs
for membraneless electrochemical cells and batteries that comprise
multiple electrolytes.
SUMMARY
[0007] Embodiments of the disclosure include electrochemical cells
and batteries that can operate with a single electrolyte solution.
In one such embodiment, an electrochemical cell comprising an
anode, a cathode current collector and a porous, non-conductive
spacer between the anode and the cathode current collector is
provided. Additional designs for electrochemical cells and
batteries that can operate with a single electrolyte solution are
also provided.
[0008] In a further embodiment of the disclosure, an
electrochemical battery comprising one or more of these
electrochemical cells and further comprising a load is
provided.
[0009] In yet a further embodiment of the disclosure, methods of
delivering electricity to applications with these electrochemical
cells or electrochemical batteries of the disclosure or both are
provided.
[0010] In additional embodiments of the disclosure, methods of
delivering hydrogen to applications with these electrochemical
cells or electrochemical batteries of the disclosure or both are
provided.
[0011] Additional embodiments include vehicles powered by
electrochemical cells of the disclosure.
[0012] Further embodiments include certain membraneless
electrochemical cells that contain separate first and second
electrolyte solutions at the cathode and anode, respectively;
batteries comprising these electrochemical cells; methods of
delivering hydrogen, electricity or both with the cells and
batteries to applications; capacitors; and various methods related
to these embodiments.
[0013] More embodiments and features are included in the detailed
description that follows, and will be readily apparent to those
skilled in the art from the description or recognized by practicing
the embodiments as described in the description, including in the
figures and claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] The accompanying figures constitute a part of this
disclosure. The figures serve to provide a further understanding of
certain exemplary embodiments. The disclosure and claims are not
limited to embodiments illustrated in the figures.
[0015] FIG. 1 is a schematic of one embodiment of electrochemical
cells of the disclosure.
[0016] FIG. 2 is a schematic of one embodiment of an
electrochemical battery of the disclosure.
[0017] FIG. 3 is a schematic block diagram of an embodiment of an
electrochemical cell according to the present disclosure.
[0018] FIG. 4A is a schematic block diagram of an embodiment of an
electrochemical cell according to the present disclosure.
[0019] FIG. 4B is a schematic block diagram of an embodiment of an
electrochemical cell according to the present disclosure.
[0020] FIG. 5 is a schematic of an embodiment of an electrochemical
cell of the disclosure.
[0021] FIG. 6 is a schematic of an embodiment of an electrochemical
cell of the disclosure.
[0022] FIG. 7 is a schematic of an embodiment of an electrochemical
cell of the disclosure.
[0023] FIG. 8 is a schematic of an embodiment of an electrochemical
cell of the disclosure in flow mode.
[0024] FIG. 9 is a schematic of an embodiment of an electrochemical
cell of the disclosure.
[0025] FIG. 10 is a schematic of a vehicle battery system of the
disclosure.
DETAILED DESCRIPTION
[0026] Various embodiments will now be explained in greater detail.
It is to be understood that both the foregoing general description
and the following detailed description are exemplary and
explanatory only, and are not restrictive of this disclosure or of
the claims. Any discussion of certain embodiments or features,
including those depicted in the figures, serve to illustrate
certain exemplary aspects of the disclosure. The disclosure and
claims are not limited to the embodiments specifically discussed
herein or illustrated in the figures.
[0027] Embodiments of the disclosure include electrochemical cells
and batteries that can operate with a single electrolyte solution.
Such cells and batteries do not require multiple electrolyte
solutions separated by a membrane, by a salt bridge or by other
techniques. In one such embodiment, an electrochemical cell
comprising an anode, a cathode current collector and a porous,
non-conductive spacer between the anode and the cathode current
collector is provided.
[0028] The electrochemical cells of the disclosure, including this
embodiment and other embodiments of electrochemical cells described
herein, may be used to form batteries to supply electricity,
hydrogen, or both to applications. Electrical applications include,
for example, grid applications such as cell phone tower backup
power or backup power for wind farms or solar farms. The
electricity could also be used to power vehicles, household
appliances, consumer goods or toys. When configured to run to
produce hydrogen, the hydrogen may be delivered to an application
such as a fuel cell for electricity production or a vehicle or to,
for example, an engine or furnace for burning. The electrochemical
cells may be configured such that electricity is primarily
delivered, hydrogen is primarily delivered, or both are delivered
in various ratios. In some embodiments, the cells and batteries of
the disclosure run in flow mode in that electrolyte is added to the
cell or battery and then removed after use, thereby replenishing
the supply of electrolyte to the cell or battery. When run in
hydrogen mode, electricity mode, or combination of hydrogen and
electricity, the batteries of the disclosure may be configured to
power a number of different devices such as electric vehicles and
other electric devices. Examples of such vehicles include scooters,
motorized grocery cars, battery backups, forklifts, trucks,
passenger cars, lift trucks, motorcycles, fork trucks, planes,
boats, quads, tractors and other industrial and agricultural
vehicles. The hydrogen from the batteries of the disclosure can be
delivered to a fuel cell which generates electricity for a motor
for vehicle transport. The electricity from the batteries of the
disclosure may be used to power the fuel cell controller and/or
power other vehicle electronics such as an electric motor.
[0029] In an example electrochemical cell of the disclosure, the
anode is in physical contact with the porous, non-conductive
spacer, such as non-conductive screen, which in turn is in physical
contact with the cathode current collector such as carbon foam. In
other embodiments, the spacer is not in physical contact with the
anode, the cathode current collector, or both, but is instead
positioned at a distance from the anode, cathode current collector,
or both.
[0030] The purpose of the porous, non-conductive spacer is to
prevent physical contact of the cathode current collector with the
anode. The term "non-conductive" with reference to the porous
spacer means that the spacer is not electrically conductive. The
spacer is porous to electrolyte, and is also porous in a
non-selective manner to anions and cations in the electrolyte
solution. Being electrically non-conductive, the porous spacer does
not permit the passage of electrons through it. Non-conductive
materials include those that are classified as electrical
insulators. Thus, any electrical insulator can be used as a spacer.
These features of the spacer differentiate it from salt bridges and
membranes in conventional batteries, which are often used to
maintain separation of multiple electrolyte solutions. Many
different types of non-conductive porous materials can be used for
the spacer, such as an organic polymer, surgical tape, fiberglass
film, glass wool, wood, paper, cloth, cardboard, and nylon. One
such organic polymer is vinyl coated polyester. The thickness of
the spacer is often between about 0.1 mm and about 0.8 mm.
[0031] A microporous material, such as surgical tape, may be used
to wrap the electrochemical cell so as to help maintain its
physical integrity. The wrapping need not completely encase the
electrochemical cell.
[0032] Cathode current collectors and anodes in electrochemical
cells in this disclosure, including in this embodiment and other
embodiments of electrochemical cells described herein, may be
selected from suitable materials. Examples of suitable cathode
current collector materials include steel, carbon such as in the
graphite allotrope of carbon, carbon impregnated with a metal, and
carbon foam. Conducting carbon cloth (which is also referred to as
carbon foam), for example, is a suitable cathode current collector
for many embodiments and is a conducting material. Suitable anodes
for embodiments having a single electrolyte solution include metals
in Column 13 of the Periodic Table and their alloys. These metals
and alloys include, for example, aluminum, gallium, indium and
thallium, as well as alloys comprising at least one of these. One
example alloy has the name of Galinstan, which is an alloy of
gallium, indium and tin.
[0033] In many embodiments, the electrochemical cell further
comprises a single electrolyte solution. The term "single
electrolyte solution" refers to one common electrolyte solution
shared between the anode and cathode current collector of the cell,
as opposed to multiple physically separated electrolyte solutions.
This contrasts with conventional liquid batteries, which require at
least two electrolyte solutions, i.e., an electrolyte solution for
each of the half cells. The single electrolyte solution may
comprise any appropriate number of components as described herein,
including multiple components that could be considered
electrolytes.
[0034] The electrochemical cell may be saturated with respect to
the electrolyte. In some embodiments, the cell is not immersed in
an electrolyte bath. By saturating via drip, spray or atomization
of the electrolyte, for example, one can activate the cells to
produce electricity or hydrogen or both. One example of a cathode
current collector is carbon foam. The electrolyte may be sprayed
onto the cell until or before the carbon foam is saturated in such
an example. As electricity or hydrogen or both is produced,
additional electrolyte (or other materials such as salts, oxidants,
or bases) may be sprayed or otherwise delivered to the cell to
maintain its saturation and replace salts and oxides. Indeed, a
recirculator could be used to continuously recycle and deliver
electrolyte or other materials to the cell. Thus, it is not
necessary to keep a large supply of electrolyte present, which
saves on both cost and weight compared with flow cells of the prior
art.
[0035] In these and other embodiments, the anode of the
electrochemical cell is made from aluminum, for example. In many
embodiments the aluminum is in the form of a sheet. In many other
embodiments it is in the form of a screen or other thin porous
structure. The thickness of the aluminum screen may be, for example
between about 0.05 mm and about 0.5 mm, or between about 0.1 mm and
about 0.3 mm. In some embodiments, the cathode current collector
can be carbon foam and the porous, non-conductive spacer can be a
non-conductive screen such as an organic polymer or surgical tape.
One such polymer is vinyl coated polyester.
[0036] Additional embodiments include 1) an electrochemical cell
comprising an anode, a cathode current collector, a porous,
non-conductive spacer between the anode and the cathode current
collector, and a single electrolyte solution; 2) an electrochemical
cell consisting essentially of an anode, a cathode current
collector, a porous, non-conductive spacer between the anode and
the cathode current collector, and a single electrolyte solution;
and 3) an electrochemical cell consisting of an anode, a cathode
current collector, a porous, non-conductive spacer between the
anode and the cathode current collector, and a single electrolyte
solution.
[0037] Electrochemical cells are often connected to one another by
metal conductors to form electrochemical batteries. An example of a
metal conductor is copper such as copper wire or wires. Thus, for
example, an aluminum anode on one electrochemical cell is in
contact with a porous, non-conductive spacer on the cell and the
spacer is in turn in contact with a carbon foam current collector.
The aluminum anode is also in contact with a metal conductor to the
cathode current collector on an adjacent electrochemical cell,
which in turn is in contact with its own porous, non-conductive
spacer and corresponding aluminum anode. In this manner, a series
of electrochemical cells may be connected. At the termination of
the series, the terminal electrochemical cells may be connected to
a load, such as an application or to additional electrochemical
cell series so that the overall electrochemical battery has both a
series and parallel arrangement of electrochemical cells.
[0038] In some embodiments, the electrochemical cells are also
configured to operate as flow cells. The cells may be configured as
flow cells so as to support a flow battery, for example. In such a
battery, electrolyte can be provided to cells during the operation
of the battery continuously during operation so that electrical
charging is not required.
[0039] In many embodiments of the disclosure, the electrolyte
comprises water and one or more salts. Examples of solvents for use
in the electrolyte, including water and others, may be found in
Table 1.
TABLE-US-00001 TABLE 1 Polar Solvents Solvent Dielectric constant
Water 80 Sulfuric acid 101 Ammonia 26.7 Ethanol 24.3 Acetonitrile
36.2 Pyridine 12.3 Methanol 30 Glycerol 47 Ethylene glycol 37
Hydrofluoric acid 134 Furfural 42 Hydrazine 52 Formamide 84
Hydrogen peroxide 128 Hydrocyanic acid 158
[0040] In many embodiments, there are two salts that are added to
the electrolyte. Examples of such salts include salts of
peroxydisulfate (such as sodium peroxydisulfate), hypochlorite, and
sulfate (such as sodium sulfate). The electrolyte may additionally
comprise a base, such as sodium hydroxide. One of the salts is an
oxidant. Thus, in many embodiments, the electrolyte contains an
oxidant and also contains an additional salt, such as a metal salt
found in Table 3, wherein the anion portion of the metal salt and
the oxidant differ.
[0041] The non-limiting list of compounds in Table 2, or their
corresponding salts and acids as the case may be, may be delivered
and dissociate to form oxidants. As used herein, the term "oxidant"
refers to the compound added to perform oxidation as well as the
resulting anion that results from dissociation of that compound.
Thus, peroxydisulfuric acid (H.sub.2S.sub.2O.sub.8), sodium
peroxydisulfate (Na.sub.2S.sub.2O.sub.8) and the peroxydisulfate
anion (S.sub.2O.sub.8.sup.2-) are all oxidants as used herein. When
the acid or salt form of the peroxydisulfate oxidant, for example,
is added to an electrolyte of the disclosure, there will be
dissociation into the anion form. The anion form is the form which
acts to oxidize another species and which in turn is reduced.
TABLE-US-00002 TABLE 2 Oxidants Hydrogen peroxide Nitric acid
Sulfuric acid Peroxydisulfuric acid Sodium peroxydisulfate
Peroxymonosulfuric acid Chlorite, chlorate, perchlorate, and other
analogous halogen compounds Hypochlorite and other hypohalite
compounds, including NaClO Hexavalent chromium compounds such as
chromic and dichromic acids and chromium trioxide, pyridinium
chlorochromate (PCC), and chromate/dichromate compounds
Permanganate compounds such as potassium permanganate Sodium
perborate Nitrous oxide Potassium nitrate Sodium bismuthate Oxygen
Ozone Halogens
[0042] The other salt may be, for example, any one of the compounds
found in Table 3.
TABLE-US-00003 TABLE 3 Metal Salts KI NaI LiI BaI.sub.2 CaI.sub.2
MgI.sub.2 ZnI.sub.2 AlI.sub.3 KBr NaBr LiBr BaBr.sub.2 CaBr.sub.2
MgBr.sub.2 ZnBr.sub.2 AlBr.sub.3 KCl NaCl LiCl BaCl.sub.2
CaCl.sub.2 MgCl.sub.2 ZnCl.sub.2 AlCl.sub.3 K.sub.2SO.sub.4
Na.sub.2SO.sub.4 Li.sub.2SO.sub.4 BaSO.sub.4 CaSO.sub.4 MgSO.sub.4
ZnSO.sub.4 Al.sub.2(SO.sub.4).sub.3 KNO.sub.3 NaNO.sub.3 LiNO.sub.3
Ba(NO.sub.3).sub.2 Ca(NO.sub.3).sub.2 Mg(NO.sub.3).sub.2
Zn(NO.sub.3).sub.2 Al(NO.sub.3).sub.3 KF NaF LiF BaF.sub.2
CaF.sub.2 MgF.sub.2 ZnF.sub.2 AlF.sub.3 K.sub.3PO.sub.4
Na.sub.3PO.sub.4 Li.sub.3PO.sub.4 Ba.sub.3(PO.sub.4).sub.2
Ca.sub.3(PO.sub.4).sub.3 Mg.sub.3(PO.sub.4).sub.2
Zn.sub.3(PO.sub.4).sub.2 AlPO.sub.4 K.sub.2SO.sub.3
Na.sub.2SO.sub.3 Li.sub.2SO.sub.3 BaSO.sub.3 CaSO.sub.3 MgSO.sub.3
ZnSO.sub.3 Al.sub.2(SO.sub.3).sub.3 K.sub.2CO.sub.3
Na.sub.2CO.sub.3 Li.sub.2CO.sub.3 BaCO.sub.3 CaCO.sub.3 MgCO.sub.3
ZnCO.sub.3 Al.sub.2(CO.sub.3).sub.3 K.sub.2S Na.sub.2S Li.sub.2S
BaS CaS MgS ZnS Al.sub.2S.sub.3 K.sub.2SiO.sub.3 Na.sub.2SiO.sub.3
Li.sub.2SiO.sub.3 BaSiO.sub.3 CaSiO.sub.3 MgSiO.sub.3 ZnSiO.sub.3
Al.sub.2(SiO.sub.3).sub.3 KOH NaOH LiOH Ba(OH).sub.2 Ca(OH).sub.2
Mg(OH).sub.2 Zn(OH).sub.2 Al(OH).sub.3
[0043] The second salt should be a compound that dissociates so as
to produce a metal ion. An example of such a metal salt is sodium
sulfate.
[0044] In many embodiments, the electrolyte further contains a base
such as a strong base. Examples of strong bases include LiOH, RbOH,
CsOH, Sr(OH).sub.2, Ba(OH).sub.2, NaOH, KOH, Ca(OH).sub.2, or a
combination thereof. One particular example is NaOH.
[0045] In further embodiments, the electrolyte comprises one of
water or an alcohol. The electrolyte can be a catholyte, for
example. When an oxidant and a metal salt are present in this
electrolyte, the two can have different anion components. An
example oxidant includes sodium peroxydisulfate and an example
metal salt is sodium sulfate. This electrolyte may further comprise
a base, such as sodium hydroxide.
[0046] A further embodiment includes an electrochemical cell
comprising: [0047] a. an anode; [0048] b. a cathode current
collector; and [0049] c. a porous, non-conductive spacer between
the cathode current collector and anode; wherein the
electrochemical cell does not comprise an electrolyte.
[0050] The anode, cathode current collector, and spacer may have
one or more characteristics or features described above for those
components. Such an embodiment may, for example, be constructed in
one location then transported to another location where it is
contacted with electrolyte (such as a single electrolyte solution)
for use.
[0051] Cells that do not comprise an electrolyte solution may be
contacted with electrolyte solution such that they do then comprise
an electrolyte solution. Those skilled in the art understand that
the cells are to be contacted with the electrolyte solution in
order to generate electricity or hydrogen.
[0052] The disclosure includes additional embodiments of
electrochemical cells that can operate with a single electrolyte
solution. For example, an electrochemical cell comprising a single
aqueous electrolyte solution in contact with a non-metallic cathode
current collector, an oxidant, and a metal solid wherein current
travels from the metal solid to the cathode current collector via a
load, is provided.
[0053] In such a cell, the electrolyte solution can be basic and
the oxidant can be S.sub.2O.sub.8.sup.2-, for example. The
electrolyte solution may further comprise, for instance, sodium
hydroxide. Suitable metal solids include those in Column 13 of the
Periodic Table and their alloys. These metals and alloys include,
for example, aluminum, gallium, indium and thallium, as well as
alloys comprising at least one of these. One example metal solid is
aluminum, such as aluminum in the form of a foil. The cell may
further comprise a porous stabilizer. In one example, the cell may
comprise a metal sulfate (such as Na.sub.2SO.sub.4) where the
cathode current collector is carbon foam and the porous stabilizer
is glass wool or a borosilicate or both. The pH of the cell may,
for example, be greater than 12, greater than 13 or greater than
14.
[0054] Cells such as this, which can use a single electrolyte
solution, may produce, for example, between about 10 Watt-hours/(kg
of electrolyte+anode metal) and about 680 Watt-hours/(kg of
electrolyte+anode metal). When measured per kg of electrolyte, the
cell may produce, for example, between about 10 Watt-hours/kg of
electrolyte and about 100 Watt-hours/kg of electrolyte, between
about 40 Watt-hours/kg of electrolyte and about 80 Watt-hours/kg of
electrolyte, or between about 10 Watt-hours/kg of electrolyte and
about 60 Watt-hours/kg of electrolyte. The power produced per
square centimeter of metal solid can be, for example, between about
600 mW and about 1000 mW. As with other electrochemical cells in
this disclosure, the cell may be configured to operate in flow
mode. The cell may include an inflow stream that comprises, for
example, an aqueous electrolyte solution that may further comprise
an oxidant such as sodium peroxydisulfate or a solution comprising
peroxydisulfate anion or both. Oxidant (such as solid
Na.sub.2S.sub.2O.sub.8 or Na.sub.2S.sub.2O.sub.8 in solution) can
be provided to the cell, for example, Na.sub.2S.sub.2O.sub.8 in an
aqueous basic solution, where the base may be, for example, sodium
hydroxide. The cell may further comprise an outflow stream. The
outflow stream may comprise an aqueous solution and may also
include, for example, metal sulfate.
[0055] A further embodiment includes a method of creating a
capacitor comprising the step of disconnecting the load from one
side of an electrochemical cell of the disclosure that can operate
using a single electrolyte solution. The method further comprises
the step of reconnecting the load. A further embodiment includes a
capacitor, prepared by the process of alternatively disconnecting
and reconnecting the load from at least one of the cathode current
collector or anode in the electrochemical cell.
[0056] An additional embodiment that can operate with a single
electrolyte solution is an electrochemical cell comprising a single
aqueous electrolyte solution in contact with a non-metallic cathode
current collector, an oxidant, and a metal solid wherein current
travels from the metal solid to the cathode current collector via a
load, and wherein the pH is greater or equal to 12. As an example,
the non-metallic cathode current collector can be carbon foam, the
oxidant can be a peroxydisulfate salt, and the metal solid can be
aluminum.
[0057] An additional embodiment that can operate with a single
electrolyte solution is an electrochemical cell comprising a single
aqueous electrolyte solution in contact with a non-metallic cathode
current collector, an oxidant, and one or more anodes wherein
current travels from the one or more anodes to the cathode current
collector via a load, and wherein the pH is greater or equal to
10.
[0058] Suitable anodes include metals in Column 13 of the Periodic
Table and their alloys. These metals and alloys include, for
example, aluminum, gallium, indium and thallium, as well as alloys
comprising at least one of these. One example metal is aluminum,
such as aluminum in the form of foil. The anodes can also be
separated by an insulator. In some embodiments, the pH is greater
or equal to 12.
[0059] An example of an electrochemical cell that can operate with
a single electrolyte solution is provided in Example 7 and is
illustrated in FIG. 9.
[0060] An additional embodiment of the disclosure includes a method
of making an electrochemical cell of the disclosure. The method
comprises 1) providing an electrochemical cell comprising an anode,
a cathode current collector and a porous, non-conductive spacer
between the anode and the cathode current collector; and 2)
contacting the cell with a single electrolyte solution. The cell
can be contacted with electrolyte solution, for example, by
spraying the electrolyte solution onto the cell. The electrolyte
could also be applied in bulk such as by immersion. The electrolyte
solution could also be applied to the cell as droplets via drip or
as an atomized mist. The electrolyte can also be supplied in bulk
compartments, or in any combinations of the techniques provided
herein.
[0061] A further embodiment includes a method, such as a method of
operating an electrochemical cell in flow mode, that comprises 1)
providing an electrochemical cell according to any of the
embodiments above and that comprises a single electrolyte solution,
2) operating the cell to produce electricity, hydrogen, or both
electricity and hydrogen (such as when the cell is connected to a
load), and 3) providing additional electrolyte solution (or one or
more components thereof) to the cell during its operation. Such an
embodiment can further comprise 4) withdrawing spent electrolyte
solution (or one or more components thereof) from the cell during
its operation, for example, simultaneously with providing the
additional electrolyte solution (or one or more components thereof)
to the cell. The electrolyte solution in these embodiments may have
any composition appropriate for the cells as described herein.
Components of the electrolyte solution can include, for example, an
oxidant, a metal salt, and a base. A further embodiment includes
the method performed on a battery that comprises the cell.
[0062] In other aspects of the disclosure, electrochemical
batteries comprising electrochemical cells of the disclosure are
provided. An electrochemical battery contains one or more cells and
is electrically connected to a load. The load could be the
resistance in a wire or it could be to an application, or both. The
electrochemical batteries of the disclosure may be used to generate
electricity through the load, hydrogen, or both. The battery can be
configured, for example, to favor electricity or hydrogen. Hydrogen
production may be controlled by adjusting pH and the specific
surface area of the anode. Starting with an alkaline solution, as
the pH increases and the larger specific surface of the anode used,
the more hydrogen produced. For example the surface area of the
aluminum may be increase by folding over an aluminum screen
multiple times. Electricity may be favored when oxidant
concentration is increased and the solution is made increasingly
alkaline.
[0063] Embodiments of the disclosure further include methods of
delivering electricity, hydrogen, or both electricity and hydrogen,
produced by the cells or batteries disclosed herein to an
application. Such applications can include, for example, cell phone
towers, vehicles and fuel cells.
[0064] Without being bound by theory, the following explanation is
believed to explain how some embodiments of the electrochemical
cells and batteries of the disclosure work. For example, in many
embodiments the anode is aluminum, the cathode is a catholyte in
contact with a carbon foam current collector, and the catholyte is
an electrolyte comprising water, sodium sulfate, sodium hydroxide,
and sodium peroxydisulfate where the carbon current collector and
anode are stacked and separated by a porous, non-conductive spacer
and each stack is electrically connected by a conductor such as
copper wire. Such a configuration can generally be seen in FIG. 1
and FIG. 2.
[0065] Without being bound by theory, in such embodiments, the
aluminum is oxidized per equation (A) at the anode and persulfate
reduction occurs at the surface of the cathode current collector
via equation (B)
2Al(s).fwdarw.2Al.sup.3++6e.sup.- (A)
2Na.sub.2S.sub.2O.sub.8(aq)+4NaOH(aq)+4e.sup.-.fwdarw.4Na.sub.2SO.sub.4(-
aq)+4(OH).sup.- (B)
[0066] There are, however, two extra electrons available from the
oxidation of aluminum. In many embodiments, it is observed that
protons are reduced to form hydrogen gas at the aluminum anode.
Thus, it is further believed that water dissociates to form H.sup.+
and OH.sup.- and then the two extra electrons are available to
reduce H.sup.+ into hydrogen gas and such hydrogen gas evolution is
observed at the aluminum anode and not the current collector where
oxidant is reduced. It is also possible that the hydroxide ion
itself may be dissociating to form H.sup.+ because the same
hydrogen evolution is observed when the electrolyte is ethanol.
Accordingly, and as disclosed previously, the electrolyte could
also be an alcohol and water or an alcohol with one example being
ethanol.
[0067] In view of the above, the current collector could be
characterized as a "cathode current collector," because it
distributes electrons that reduce oxidant within the electrolyte
solution at the surface of the current collector (according to
equation B above), wherein the electrolyte solution can be
characterized as a catholyte. The cathode current collector can be,
for example, embedded in or otherwise suitably contacting the
catholyte, wherein the catholyte is the source of oxidant for
reduction at the cathode current collector.
[0068] In FIG. 1, a series of three electrochemical cells are
shown. Each cell contains an anode 100, such as aluminum in the
form of a sheet or screen. The anode 100 is in physical contact
with a porous, non-conductive spacer 110. The spacer is a screen
that prevents physical contact between the anode and the cathode
current collector 120. The cathode current collector is often a
carbon foam and the spacer may be surgical tape, for example, or
vinyl coated polyester. The stack 160 of anode 100, cathode current
collector 120 and spacer 110 may be optionally wrapped in surgical
tape for physical integrity. Each cell is in electrical contact
with an adjacent cell wherein the anode 100 and the cathode current
collector 120 of adjacent cells are in electrical contact via a
conductor, such as copper wire 130.
[0069] Electrolyte is deposited onto the cell, but the cell of FIG.
1 is not immersed in the electrolyte. The electrolyte may be
sprayed on or delivered via atomization or compartmentalized. Often
this is done so when carbon foam is the cathode current collector,
the carbon foam is saturated. In other embodiments, the cell is
immersed in electrolyte solution. In a wet condition, the
electrolyte acts as a catholyte such that reduction occurs in the
solution when a circuit is made.
[0070] FIG. 2 represents a battery wherein the cell components of
FIG. 1 in series are further connected to a Load 150 via a
conductor, such as copper 140. In this state, when electrolyte is
deposited onto the battery, current and/or hydrogen is produced,
with hydrogen reduction occurring at the anode. Depending on the
pH, the surface area of the anode and the amount of oxidant used,
one can determine whether the battery produces primarily
electricity, hydrogen, or a combination of the two. The Load 150
could be an application such as cell tower or other grid
application. Alternatively, when hydrogen is produced, the hydrogen
can be collected at each anode for delivery to, for example a fuel
cell or to a furnace or engine for burning hydrogen.
[0071] Additional embodiments described below include certain
membraneless electrochemical cells that contain separate first and
second electrolyte solutions at the cathode and anode,
respectively; batteries comprising electrochemical cells of the
disclosure; methods of delivering hydrogen, electricity or both
with the cells and batteries to applications; methods for boosting
current in electrochemical cells of the disclosure; and various
methods related to these embodiments.
[0072] For example, one embodiment of the disclosure includes an
electrochemical cell comprising: [0073] a. a cathode; [0074] b. an
anode adjacent to the cathode at a distance; [0075] c. a first
polar electrolyte solution in contact with the cathode and disposed
within the distance comprising an oxidant; [0076] d. a second polar
electrolyte solution in contact with the anode and disposed within
the distance comprising a suitable metal ion; and [0077] e. a
separation agent; wherein the first and second electrolyte
solutions are in contact with each other and are immiscible, and
wherein there is no membrane in between the first and second
electrolyte solutions.
[0078] In this embodiment, each polar electrolyte solution may
comprise a porous stabilizer such as borosilicate. The first polar
electrolyte solution may be aqueous and may also comprise a base
such as KOH, NaOH, Ca(OH).sub.2, LiOH, RbOH, CsOH, Sr(OH).sub.2, or
Ba(OH).sub.2. The pH of the first polar electrolyte solution may
be, for example, between about 8 and about 14 or between about 11
and about 14. The oxidant may be, for example, a Vanadium ion,
S.sub.2O.sub.8.sup.2- or ClO.sup.-. An example separating agent in
this embodiment includes a salt, such as a calcium chloride or
sodium sulfate.
[0079] The electrochemical cell may be configured to operate in
flow mode. It may comprise, for example, an inflow solution
comprising a base (such as sodium hydroxide), an oxidant (such as
S.sub.2O.sub.8.sup.2-) and a separation agent (such as sodium
sulfate). Outflow from the cell may include a base (including an
aqueous solution of a base) and sodium sulfate, where the base may
be sodium hydroxide.
[0080] A current collector may be placed within the first
electrolyte solution, the second electrolyte solution, or in both.
Example current collectors include metals as well as non-metals
such as carbon foam. The electrochemical cell may also comprise
glass wool placed in between the first and second polar electrolyte
solutions.
[0081] In some embodiments, the second polar electrolyte solution
comprises an alcohol. It may be an alcoholic solution that further
comprises a base such as KOH or NaOH. The pH of the second polar
electrolyte solution may be, for example, between about 8 and about
14 or between about 11 and about 14. Suitable metal ions in the
second polar electrolyte include Zn.sup.2+ and Al.sup.3+.
[0082] In some embodiments, the separation agent is a salt (such as
CaCl.sub.2 or sodium sulfate) and the alcohol in the second polar
electrolyte solution is ethanol, methanol, or both. In some
embodiments, the second polar electrolyte comprises an alcohol and
is configured to operate in flow mode with an inflow stream
comprising a polar solution comprising an alcohol (such as ethanol,
methanol, or both), a base (such as sodium hydroxide), a separation
agent, and a metal capable of dissociating into a suitable metal
ion (such as Al.sup.3+). An outflow stream for the cell may
comprise an alcohol (such as ethanol), a base (such as sodium
hydroxide) and a separation salt (such as sodium sulfate).
[0083] The electrochemical cell described here may, for example,
generate hydrogen gas in the second electrolyte solution and may
direct the gas to a hydrogen compressor. A further embodiment of
the disclosure therefore includes a battery system comprising one
or more of the electrochemical cells and a hydrogen compressor.
Such a system may be used, for example, to power a process
application such as a fuel cell.
[0084] Another embodiment of the disclosure includes an
electrochemical cell comprising: [0085] a. a cathode; [0086] b. an
anode adjacent the cathode at a distance; [0087] c. a first polar
aqueous electrolyte solution in contact with the cathode and
disposed within the distance comprising S.sub.2O.sub.8.sup.2-;
[0088] d. a second polar electrolyte alcoholic solution in contact
with the anode and disposed within the distance comprising
Al.sup.3-; and [0089] e. borosilicate within both the first and
second electrolyte solutions; wherein the first and second
electrolyte solutions are in contact with each other and are
immiscible, and wherein there is no membrane in between the first
and second electrolyte solutions.
[0090] The first polar electrolyte solution and second polar
electrolyte solution may be of different densities, where the first
electrolyte solution may comprise a halide salt (such as
CaCl.sub.2) and the second electrolyte solution may comprise a
metal sulfate salt (such as Na.sub.2SO.sub.4). The second polar
electrolyte alcoholic solution may comprise, for example, ethanol
or methanol.
[0091] In some embodiments, the pH of the first electrolyte and
second electrolyte solutions can be adjusted, for example, to
between about 11 to about 13 each. Each solution may comprise a
base, such as sodium, calcium, or potassium hydroxide. In some
embodiments, the cathode is copper (such as a copper brush),
carbon, or both and the anode is aluminum. The borosilicate may be,
for example, Pyrex.RTM. wool. In some embodiments, the borosilicate
has a pore size of about 8 microns.
[0092] This electrochemical cell may be configured to run in flow
mode. An additional embodiment includes an electrochemical battery
comprising one or more of the cells. When the battery comprises
more than one of the electrochemical cells, the cells may be
aligned, for example, in parallel geometry and arranged in a
voltaic pile. The electrochemical cell or battery could deliver
electricity to a process application, including solar farms, wind
farms, household appliances, consumer goods, and toys.
[0093] Another embodiment of the disclosure includes an
electrochemical cell comprising: [0094] a. a non-metallic cathode;
[0095] b. a non-metallic anode adjacent the cathode at a distance;
[0096] c. a first polar aqueous electrolyte solution in contact
with the cathode and disposed within the distance comprising
S.sub.2O.sub.8.sup.2-; and [0097] d. a second polar electrolyte
alcoholic solution in contact with the anode and disposed within
the distance comprising a metal solid; wherein the first and second
electrolyte solutions are in contact with each other and are
immiscible, and wherein there is no membrane in between the first
and second electrolyte solutions.
[0098] In some embodiments, the metal solid is dispersed through
the second electrolyte solution in powder form while borosilicate
is placed within both the first and second electrolyte solutions.
Example metals include zinc and aluminum. Metal in powder form may
have, for example, an average particle size less than about 5
microns, or an average particle size between about 5 and about 30
microns. Non-metallic cathodes and non-metallic anodes can be made
of carbon foam, for instance. A further embodiment includes a
method of boosting current in an electrochemical cell comprising
the steps of adding oxidant to the second electrolyte solution of
this electrochemical cell.
[0099] Another embodiment of the disclosure includes an
electrochemical cell comprising: [0100] a. a cathode; [0101] b. an
anode adjacent to the cathode at a distance; [0102] c. a first
aqueous electrolyte solution in contact with the cathode and
disposed within the distance comprising an oxidant; [0103] d. a
second polar electrolyte solution in contact with the anode and
disposed within the distance comprising a metal and an oxidant; and
[0104] e. a separation agent; wherein the first and second
electrolyte solutions are in contact with each other and are
immiscible, and wherein there is no membrane in between the first
and second solutions.
[0105] In some embodiments, the second polar electrolyte solution
is an alcoholic solution such as ethanol or methanol. Also in some
embodiments, the oxidant is S.sub.2O.sub.8.sup.2- or sodium
peroxydisulfate, or both, the metal is aluminum, the separation
agent is sodium sulfate, and the cathode and anode are carbon foam.
A porous stabilizer (such as glass wool, borosilicate, or both) may
optionally be provided in the first and second electrolyte
solutions.
[0106] The electrochemical cell may be configured to operate in
flow mode. The cell may comprise an inflow stream that comprises an
aqueous electrolyte solution and optionally also an oxidant (such
as sodium peroxydisulfate or a solution comprising peroxydisulfate
anion or both). Thus, an embodiment of the disclosure is a method
which comprises providing additional oxidant to the electrochemical
cell. The oxidant (such as Na.sub.2S.sub.2O.sub.8) may be provided
in an aqueous basic solution, for example, where the base may be
NaOH. The oxidant may also be provided as a solid. The cell may
further comprise an aqueous solution that outflows from the cell
and that may comprise, for example, metal sulfate.
[0107] In some embodiments, the cell may produce between about 10
Watt-hours/(kg of electrolyte+anode metal) and about 680
Watt-hours/(kg of electrolyte+anode metal). When measured per kg of
electrolyte, the cell may produce, for example, between about 10
Watt-hours/kg of electrolyte and about 100 Watt-hours/kg of
electrolyte, and such as between about 40 Watt-hours/kg of
electrolyte and about 80 Watt-hours/kg of electrolyte.
[0108] The following disclosure provides further description of the
embodiments detailed above and other embodiments of this
disclosure.
[0109] Various embodiments of the disclosure, such as ones
mentioned above, include an electrochemical cell that contains a
single electrolyte solution. In some embodiments, a single
electrolyte solution contains a metal solid, water, base, an
oxidant, and a cathode current collector. The solution is basic in
some embodiments. Electrical contact is made between the cathode
current collector, such as carbon foam, and the metal solid via an
external load. A common metal example is aluminum, such as aluminum
foil, a base, such as sodium hydroxide, and the oxidant added may
be sodium peroxydisulfate, which in turn dissociates. When
operating, the peroxydisulfate reduces to sulfate. Additional
sulfate, such as by the addition of a metal sulfate such as sodium
sulfate, may be added. A porous stabilizer, such as glass wool or a
borosilicate may be used. In such embodiments, there is only a
single electrolyte solution and it may be operated in a flow mode
whereby oxidant is refilled into the cell. The added oxidant may be
as an aqueous solution such as with a base like sodium hydroxide or
added as solid such as with granular sodium peroxydisulfate. As
sodium sulfate forms in the cell, it may optionally be removed by
an apparatus for desalinization or by other mechanisms.
[0110] Supercharging may also be achieved with two electrolyte
solutions. In these embodiments, oxidant, such as sodium
peroxydisulfate is added to the second electrolyte solution. In
these embodiments, the metal in the second electrolyte solution can
be aluminum and the solution is an alcoholic solution such as
methanol, ethanol, or both. A porous stabilizer such as glass wool
or a borosilicate may also be used. A base such as sodium hydroxide
is present as is a separating agent such as sodium sulfate. The
first electrolyte solution in such embodiments can be aqueous and
is kept basic such as with NaOH. An oxidant such as sodium
peroxydisulfate is used and a metal sulfate such as sodium sulfate
is optionally added. A porous stabilizer such as glass wool or a
borosilicate may also be used. In such embodiments,
peroxydisulfate, or another suitable oxidant, is added to the
second electrolyte solution and this addition causes a boost in
current production. Such current boosts may be on the order of
50%.
[0111] The power produced by the single-solution embodiments may
be, for example, between about 10 Watt-hours/(kg of
electrolyte+anode metal) and about 680 Watt-hours/(kg of
electrolyte+anode metal). When measured per kg of electrolyte, the
cell may produce, for example, between 10 and 100 Watt-hours/kg of
electrolyte, including between about 40 and about 80 Watt-hours/kg
electrolyte and further including between about 10 and about 60
Watt-hours/kg electrolyte. When measured against the surface area
of the metal solid used, such as with aluminum, power densities of
between about 600 and about 1000 mW/cm.sup.2 are observed.
[0112] Without being bound by theory, it is believed that upon
opening the circuit in a single electrolyte system, the anode
becomes negatively charged and is surrounded by an ionic double
layer and, for example, when considering a capacitor based on the
electrochemical cell of FIG. 9, the sodium and sulfate ions make up
the ionic double layer. The sodium concentrates next to the
negatively charged surface (the stern layer) and both the sodium
and sulfate ions form a diffuse layer out from the surface. Such a
capacitor is in fact a self-charging capacitor. With respect to the
cell of FIG. 9, for example, when the battery circuit is opened,
the S.sub.2O.sub.8.sup.2- anion or 2H.sup.+ cations continue to
interact with the solid aluminum atoms while trying to place them
into the unstable +2 oxidation state. To compensate for this
instability, the oxidized aluminum atoms shed a third electron to
the solid aluminum, but because the circuit is open, the solid
aluminum cannot transfer the electron to the cathode current
collector. This effect negatively charges the solid aluminum, and
to maintain charge neutrality, a classical double layer
distribution of ions is formed, with the cations packed near the
solid aluminum surface. When the circuit is closed these stored
electrons are shipped to the cathode current collector, but again
because of the need to maintain charge neutrality, they are not all
shipped at once, but rather released with a peak initially that
gradually declines over time owing to the gradual redistribution of
ions in the double layer which relaxes on an electro-chemical
diffusion gradient. By staggering the opening and closing of
circuits, multiple anodes can be employed to maximize the current
(while one anode circuit is open it charges and another can be
closed and discharging).
[0113] Without being bound by theory, aluminum can exist in the
non-negative oxidation states +3, +2, +1 and 0, but only the +3 and
0 states are energetically stable under standard battery operating
conditions, with the 0 state being the solid aluminum phase. When a
strong oxidant such as S.sub.2O.sub.8.sup.2- or 2H.sup.+ reacts
with an aluminum atom in the 0 state, it strips 2 electrons from
the solid aluminum atom (reducing itself to 2SO.sub.4.sup.2-) while
trying to put the aluminum atom into the energetically unstable +2
oxidation state. Because this state is energetically unfavorable,
the aluminum atom sheds a third electron to put it in the stable +3
state. The third electron is conducted through the solid aluminum
to the load and subsequently to the cathode current collector,
wherein the catholyte reduces another S.sub.2O.sub.8.sup.2-
anion.
[0114] By comparison, Zn can exist in the non-negative oxidation
states +2, +1 and 0, but only the 0 and +2 states are energetically
favored. Thus when the S.sub.2O.sub.8.sup.2- anion reacts with a
zinc atom in the 0 oxidation state it strips two electrons from the
zinc atom putting it in the stable +2 state, and no current is
generated. However, if there is an oxidant in the -1 state which is
capable of striping a single electron from the zinc, then as in the
aluminum case, a current can be generated.
[0115] In such single-electrolyte systems, pairs of oxidants and
reductants may be selected such that the oxidant removes sufficient
electrons to create an unstable oxidation state in the reductant
which may spontaneously transition to a stable oxidation state with
the release of one or more additional electrons. In such pairs, the
unstable oxidation state is a lower oxidation state than the stable
oxidation state. The stable oxidation state may have an oxidation
state that is +1 or +2 or more compared with the unstable oxidation
state. In aluminum, for example, the stable oxidation state, +3 is
one more (+1) than the unstable oxidation state.
[0116] In many embodiments of such single-electrolyte
electrochemical systems, multiple anodes may be used with a single
cathode current collector. For example, when the anode is aluminum,
aluminum foil packets may be separated from each other such as with
an insulator to create multiple aluminum anodes. If particulate
aluminum is used, such individual particles may act as multiple
anodes.
[0117] The pH can also be used to control current. When the pH is
neutral, the S.sub.2O.sub.8.sup.2- is unable to oxidize the solid
aluminum because an Al.sub.2O.sub.3 film forms on the solid
surface. When the system is very alkaline, such as greater than pH
of 12 or even higher, the OH.sup.- anion destroys the aluminum
oxide film and allows the S.sub.2O.sub.8.sup.2- anion to thereby
create a current. By adjusting the pH, either with the addition of
OH- ions, such as from NaOH, or by the addition of H+ ions, such as
with the addition of sulfuric acid, the availability of OH- and
thus control the current can be regulated. Lower pHs may also work,
such as at around 10, provided the surface is sufficiently
activated.
[0118] In other embodiments, electrochemical cells and batteries of
the disclosure operate without the need for membranes or other
devices to separate a first electrolyte solution (at the cathode)
from a second electrolyte solution (at the anode). When the terms
"membraneless" or "without a membrane" or "wherein there is no
membrane" or words to that effect are used, what is meant is that
there is no membrane or other kind of separator between the first
and second electrolyte solutions (and third electrolyte solutions
in those embodiments).
[0119] Electrochemical batteries of one or more cells, including
greater than one cell, may be prepared by combining electrochemical
cells of the disclosure in parallel or in series. Examples include
a voltaic pile of cells. Such cells and batteries may be used to
deliver electricity to process applications such as solar farms and
wind farms, hydrogen compressors, vehicles, such as electric
vehicles, electrical grids, household appliances, consumer
products, and toys.
[0120] Cathodes and anodes in electrochemical cells in this
disclosure, including in this embodiment and other embodiments of
electrochemical cells described herein, may be selected from
suitable materials. Examples of suitable cathodes include steel,
carbon such as in the graphite allotrope of carbon, carbon
impregnated with a metal, and carbon foam. Conducting carbon cloth
(which is also referred to as carbon foam), for example, is a
suitable cathode for many embodiments and is a conducting material.
Suitable anodes for embodiments of the membraneless cells with
multiple electrolytes include platinum, zinc, lithium, nickel,
calcium, magnesium or aluminum as well as non-metallic materials
such as carbon, including carbon foam.
[0121] First and second electrolyte solutions included in
embodiments of the disclosure may be polar and of different
densities. In many examples, one or more of the first polar
electrolyte solution contains water and a separation agent. In
these and other embodiments of the disclosure, the two polar
electrolyte solutions are immiscible. When the first electrolyte
solution comprises H.sub.2O and the second electrolyte solution
comprises ethanol, methanol, or a combination thereof, the
solutions would normally be miscible. However, the separation agent
may be used to make such fluids immiscible. The separation agent
may be added to a mixture of an alcohol and water and at sufficient
concentration it will separate the two solutions and maintain their
immiscibility. The separation agent is often a salt. In some
embodiments, the solution is saturated with respect to the salt.
Examples of salts include metal halides or ammonium salts such as
sodium chloride, magnesium chloride, calcium chloride, lithium
chloride and ammonium chloride. Other such salts include sodium
sulfate, calcium sulfate, potassium sulfate, and ammonium sulfate
among others. The same or different salts may be present in the
first or second electrolyte solutions. For example, sodium sulfate
may be present in both. In other embodiments, a salt such as sodium
sulfate or sodium chloride may be present in the first electrolyte
solution and ammonium chloride in the second electrolyte solution.
In still other embodiments calcium chloride may be present in the
first electrolyte solution and sodium sulfate in the second. The
salts are often saturated in the respective solution at or near
their solubility limit.
[0122] In many cells of the disclosure, the first electrolyte
solution is an aqueous solution and the second electrolyte solution
is an alcoholic solution. The solution at each electrode must
contain the necessary components so that oxidation-reduction will
occur, thus generating electricity. Suitable alcohols for use in
the second electrolyte solution include methanol and ethanol.
[0123] Examples of polar solvents for use in first or second
electrolyte solutions may be found in Table 1 above. The solvent
for the particular system selected should be of sufficient dipole
moment so as to dissociate the corresponding salts placed in the
solvent. In some embodiments, a strong acid, such as sulfuric acid
(e.g., 1M) may be used to make the first polar electrolyte solution
acidic while the second polar electrolyte solution is neutral.
[0124] In other embodiments, both the first and second polar
solutions are basic. These solutions may be made basic such as by
the addition of a base such as LiOH, RbOH, CsOH, Sr(OH).sub.2,
Ba(OH).sub.2, NaOH, KOH, Ca(OH).sub.2, or a combination thereof. To
complete an electrochemical circuit, an oxidant is added to the
first polar electrolyte solution and a suitable metal ion is added
to the second polar electrolyte solution. A common polar solvent
used for the first polar electrolyte solution is water. Common
solvents used for the second electrolyte solution include ethanol,
methanol, acetonitrile, or combinations thereof.
[0125] Examples of oxidants can be found in Table 2 above and
examples of compounds which may dissociate into suitable metal ions
in solution can be found in Table 3 above. Any metal ion oxidant
pair may be chosen provided the metal oxidation by the oxidant is
thermodynamically spontaneous. Metal ions which are commonly used
in the disclosure include Al, Zn, Sn, and V.
[0126] FIG. 3 illustrates an embodiment of an electrochemical cell
that comprises first and second electrolytes. The electrochemical
cell 10 includes a cathode 12 and an anode 14 separated by a first
electrolyte solution 20 and a second electrolyte solution 22 such
that the first electrolyte solution 20 is in contact with the
cathode 12 and such that the second electrolyte solution 22 is in
contact with the anode 14. The first electrolyte solution 20 and
the second electrolyte solution 22 are immiscible and in contact
with each other and thus can enable ion and electron exchange
(e.g., H.sup.+ and e.sup.-) between the anode 14 and the cathode
12. Each cell 10 may be electrically connected to a load 16 by a
circuit 18 to enable a current flow via the circuit. Note that the
vertical lines connecting the electrolyte solutions and the cathode
and anode electrodes in the schematic are not conduits but are
merely to aid in the viewing of the schematic.
[0127] In certain embodiments, the first electrolyte solution 20
may be a positive electrolyte or catholyte, and the second
electrolyte solution 22 may be a negative electrolyte or analyte
(and immiscible). In many embodiments, the densities of the first
electrolyte solution and the second electrolyte solution are
different with the first electrolyte solution 20 being denser than
the second electrolyte solution 22 such that when the cell 10 is
oriented vertically with cathode 12 at the bottom, the buoyancy
effect causes the second electrolyte solution 22 to layer above the
first electrolyte solution 20.
[0128] In many embodiments, the cell 10 may optionally be
configured to run in flow mode so as to support a flow battery for
example. In such a battery, electrolyte solutions are provided to
the cell during the operation of the battery continuously during
operation. For example, the first electrolyte solution 20 and the
second electrolyte solution 22 may flow into the cell 10 and
between the cathode 12 and the anode 14 from a first source, such
as a tank, 30, or other suitable storage device, and a second
source, such as a tank, 32, or other suitable storage device,
respectively, as shown in FIG. 3 via conduits 21 and 25
respectively. The first electrolyte solution 20 and second
electrolyte solution 22 may further flow out of the cell 10 via
conduits 23 and 27 respectively. They may be directed to waste or
to other tanks. In some embodiments, flow could be reversed from
said other tanks to recharge cell 10. The flows may be generated by
pumps 50, 52 or by capillarity, reverse osmosis, a ratchet,
swelling pressure, or gravity. The flows of the first electrolyte
solution 20 and the second electrolyte solution 22 may be
maintained within a laminar flow regime. In alternative
embodiments, the first electrolyte solution 20 and the second
electrolyte solution 22 may not flow through the cell 10 but may be
replaceable.
[0129] When an electrolyte solution is prepared, typically an
electrolyte, often a solid, is disposed within a solvent which then
becomes an electrolyte solution. For example, when an electrolyte
is disposed within a solvent where it can dissolve, the dissolution
of the electrolyte solid will create ions and, if they dissociate
sufficiently, the solvent becomes an electrolyte solution. In
addition, other components are added to the solvent so that
oxidation will occur at the anode and reduction at the cathode.
Examples of such a component is zinc metal. When added at the anode
of an operating electrochemical cell, zinc will oxidize to
Zn.sup.2+. On the cathode side, one such component example is
NH.sub.4VO.sub.3 which dissolves and dissociates to produce
V.sup.5+, which will be reduced to V.sup.4+ in an operating
electrochemical cell. In many such embodiments of the disclosure,
the first electrolyte solution comprises a component which
dissociates into an ion selected from ClO.sup.-, Fe.sup.3+,
V.sup.5+, Br.sub.2, and S.sub.2O.sub.8.sup.2-, which ions are
reduced at the cathode. In these and other embodiments, the second
electrolyte solution comprises a component which oxidizes into an
ion selected from Li.sup.+, Ca.sup.2+, Al.sup.3+, Mg.sup.2+,
V.sup.2+, Zn.sup.2+, SiO.sub.3.sup.2+, [Zn(CN).sub.4].sup.2-, and
[Zn(OH).sub.4].sup.2, which ions result from oxidation at the
anode.
[0130] In some embodiments, the cathode, vanadium undergoes
reduction from V.sup.5+ to V.sup.4+. In that embodiment, at the
anode, zinc is oxidized from Zn(s) to Zn.sup.2+. To enable the flow
of positively charged ions, a methanol solvent with zinc solid on
the anode side is further charged with ammonium chloride. The
ammonium chloride dissolves and dissociates sufficiently to provide
NH.sub.4.sup.+ in solution as a positively charged ion and Cl.sup.-
as a negatively charged ion. On the cathode side, positively
charged ions are provided by adding both sulfuric acid
(H.sub.2SO.sub.4) and sodium sulfate (Na.sub.2SO.sub.4) to an
aqueous V.sup.5+ solution. The dissolution and dissociation into
H.sup.+ and Na.sup.+ provides positively charged ions and
SO.sub.4.sup.2- as a negatively charged ion on the cathode side of
the electrochemical cell. In addition, the sodium sulfate prevents
the mixing of the first and second electrolyte solutions and
maintains their immiscibility. Further, since water is denser than
methanol, buoyancy forces cause the methanol solution to layer on
top of the denser aqueous solution. This layering of immiscible
fluids (salt water is immiscible with methanol or ethanol)
effectively and advantageously eliminates the need for a membrane
for separation. Such embodiments may be configured for flow or for
no-flow operation as described further herein. Further, in such
embodiments the zinc may be in contact with a conducting material
such as conducting carbon and the cathode solution may also be in
contact with such a conducting material.
[0131] In some embodiments, the anode is aluminum and the cathode
is carbon or steel, the first electrolyte solution contains water
and ClO.sup.-, and the second electrolyte solution contains ethanol
or methanol. In such embodiments, for example, each electrolyte
contains a base such as NaOH, and a salt, LiCl which results in
immiscible electrolyte solutions. The voltage supplied by such an
electrochemical cell is between 1.5 and 2.1 volts. Such an
electrochemical cell may create amperages of between about 0.1 and
about 0.4 amps including about 0.2 and about 0.3 amps. Examples of
components providing ClO.sup.- include Na(ClO) and Ca(ClO).sub.2.
In such a cell, ClO.sup.- will be reduced at the cathode according
to equation 1:
ClO.sup.-+H.sub.2O+2e.sup.-.fwdarw.Cl.sup.-(aq)+2OH.sup.-(aq) EQ.
1
[0132] The second electrolyte may contain a component that is a
metal that oxidizes, such as aluminum oxidizing to Al.sup.3+ as per
equation 2:
Al(s).fwdarw.Al.sup.3+(aq)+3e.sup.- EQ. 2
[0133] Another anode choice may be magnesium which oxidizes per
equation 3:
Mg(s).fwdarw.Mg.sup.2+(aq)+2e.sup.- EQ. 3
or Vanadium which oxidizes per equation 4:
V(s).fwdarw.V.sup.2+(aq)+2e.sup.- EQ. 4
[0134] In some embodiments, the anode is lithium solid and the
solvent is propylene carbonate and dimethoxyethane. The cathode may
be a suitable metal such as copper, with sodium sulfate also added.
In these embodiments, both the anode and cathode electrolyte
solutions contain a salt. An example salt is a metal halide salt
such as MgCl.sub.2. When MgCl.sub.2 is used in the electrolyte
solutions, a voltage of 3.15 V and a current of 0.1 A/cm.sup.2 may
be achieved at 1 ohm resistance. When amperages are recorded as
A/cm.sup.2 what is meant is amperage per areal area as opposed to
specific area. For example, a 2 square centimeter piece of carbon
foam has a much higher specific area than its 2 square centimeter
areal area.
[0135] In other embodiments, the first polar aqueous electrolyte
solution contains S.sub.2O.sub.8.sup.2-, NaOH, a salt, such as a
metal sulfate or metal halide salt such as CaCl.sub.2, and a metal
cathode such as a copper, such as a copper brush, carbon foam, or a
combination thereof. An example of a metal sulfate salt is
Na.sub.2SO.sub.4. The S.sub.2O.sub.8.sup.2- ion originates from a
salt which dissociates into that ion in, for example, the first
electrolyte solution. The salt may be, for example,
Na.sub.2S.sub.2O.sub.8. The copper may be in wire form such as a
brush, for example. The second polar alcoholic electrolyte
solution, for example of a different density that the first
electrolyte solution, contains an alcohol such as methanol,
ethanol, or both, NaOH, a salt such as a sulfate, including metal
sulfates such as Na.sub.2SO.sub.4. An example anode is a metal
anode such as aluminum. Alternatively, the anode may be a
non-metallic material such as carbon foam and a metal solid, such
as in a powder form, may be dispersed within the anode solution.
Examples of such metal powders, include aluminum and zinc. The
metal powder in the solution is oxidized by the action of the
electrochemical cell in a similar manner as it would oxidize if the
anode itself were the metal.
[0136] In some embodiments, the first polar solution is aqueous and
contains a separation agent such as a salt like CaCl.sub.2 or
Na.sub.2SO.sub.4. The cathode in contact with the first electrolyte
solution in such embodiments may be a metal like copper or a
non-metal like carbon foam. A stabilizer such as glass wool or a
borosilicate such as Pyrex.RTM. may be used. The oxidant in such
solutions is often S.sub.2O.sub.8.sup.2- which may be sourced from
Na.sub.2S.sub.2O.sub.8, for example. In such embodiments, the
second polar solution is often an alcohol such as ethanol or
methanol. The anode in contact with the second electrolyte
solutions in such embodiments is often aluminum or carbon foam.
Separation agents, such as Na.sub.2SO.sub.4 are often deployed at
or near saturation concentrations in the first polar electrolyte
solution, the second polar electrolyte solution, or both. Suitable
metal ions are often Aluminum such as Al.sup.3+ which may be
sourced, for example from Aluminum foil or Aluminum powder.
Zn.sup.2+ may also be used, for example, in such embodiments. Both
the first and second polar electrolyte solutions can be rendered
basic by a base such as NaOH where the pH is greater than and often
between 11 and 14. In many such embodiments, hydrogen gas is
generated in the second polar electrolyte solution. Such gas may be
vented and delivered to a process application like a fuel cell. The
hydrogen can be fed to a hydrogen compressor prior to delivery, for
example. Electricity generated from one or more cells may be used
to power the hydrogen compressor. The electrochemical cell may be
run in a flow mode in such operations where electrolyte solution is
replenished and spent solution removed.
[0137] When being replenished, the inflow solution may be an
aqueous solution comprising a base, an oxidizing agent, and a
separation agent for the first polar electrolyte solution and
comprising an alcohol, a metal capable of dissociating into a
suitable metal ion, a base and a separation agent. The outflow
solutions comprise an aqueous solution of base and separation agent
for the first electrolyte solution and alcohol, base, and
separation agent for the second polar electrolyte solution. When
the suitable metal ion is Al, the outflow may also contain
Al.sub.2O.sub.3.
[0138] In certain aspects of these embodiments, the pH of each
solution is made basic by the use of NaOH, KOH, Ca(OH).sub.2, or
another base. With such a base, the pH may be adjusted to between
about 8 and about 14, between about 9 and about 14, between about
10 and about 14, between about 11 and about 14, between about 12
and about 14, between about 11 and about 13 and all values between
about 8 and about 14 including about 8, 9, 10, 11, 12, 13, and
14.
[0139] The electrochemical cells may further contain a porous
stabilizer. The porous stabilizer allows for the passage of fluid
and also can be placed across the first and second electrolyte
solutions and help maintain the separation between the solutions
including during turbulent movement. A porous stabilizer may be any
porous media, Examples of porous stabilizers are glass wool and
borosilicates including Pyrex.RTM.. The porous stabilization may be
used in each of the first and second electrolyte solutions and it
enables the electrochemical cell containing the two electrolyte
solutions to spin, bounce or rotate rapidly with little fluid
displacement. Examples of borosilicate include such borosilicate
with a pore size of about 8 .mu.m. Pyrex.RTM. wool is one such
borosilicate. Such electrochemical cells may be run in a flow or
non-flow mode. Such electrochemical cells can have superior current
density and voltages than cells of the prior art. For example,
electrochemical cells of these embodiments have been measured for
18 hours at 1 ohm resistance with starting voltages and amperages
of about 2.07 V and 0.16 A/cm.sup.2 and concluding at about 1.55 V
and 0.088 A/cm.sup.2.
[0140] The use of porous stabilizers affects some or all of the
following characteristics of batteries and electrochemical cells of
the disclosure: wettability boundary conditions; no slip and slip
boundary conditions; conductivity, including resistivity and
friction; dispersivity or mixing between adjacent fluids; porosity
(e.g., relative volume for flow); tortuosity (e.g., length and
complexity of trajectories); connectivity (e.g., species and
electrical); particle size distribution (e.g., packing); relative
conductivity (e.g., multiphase resistivity); multiscale (e.g.,
discrete scale separation); surface absorptivity (e.g., double
layer capacitance); surface reactivity (e.g., pseudo capacitance);
diagenesis (e.g., dissolution or deposition); and swelling (e.g.,
interfacial forces). The porous media may include nanostructures or
nanoparticles. Such porous media may be used, for example, at the
cathode or anode. Further examples of such porous media include
micro-porous or nano-porous graphite.
[0141] Separators or interconnects may be used to separate adjacent
cells to prevent short circuiting such batteries but still provide
for electrical communication. Stabilizers may also be used in
between the first and second electrolyte solutions of an
electrochemical cell.
[0142] When the anode is non-metallic, such as carbon foam, and a
metal, such as aluminum or zinc, is added as a solid to the anode
solution, it is often in the form of a powder and a common particle
size is one where the average size is less than 5 microns. In other
embodiments, the average size is between about 5 microns and 30
microns. In many embodiments, the powder is dispersed throughout
the solution so that the solution appears cloudy. Such a dispersion
is useful for the performance of the cell. Generally, the smaller
the particle, the longer it takes for the particles to settle out
from the dispersion in accordance with Stokes' law. Thus, from a
suspension stability stand point, smaller particles are
favored.
[0143] At the cathode, the half-cell reaction for some such
embodiments is:
S.sub.2O.sub.8.sup.2-+2e.sup.-.fwdarw.2SO.sub.4.sup.2- EQ. 5
whereas the half-cell reaction at the anode for some such
embodiments is:
Al(s).fwdarw.Al.sup.3++3e.sup.- EQ. 6
when aluminum is the anode or is suspended in the anode solution as
a solid and
Zn(s).fwdarw.Zn.sup.2++2e.sup.- EQ. 7
is the half-cell reaction at the anode the anode itself is zinc, or
is suspended in the anode solution as a solid.
[0144] In these and other embodiments, hydrogen gas may be
liberated by the chemical reactions within the electrochemical cell
under basic conditions. Advantageously, and unlike with hydrogen
production from petroleum products, hydrogen may be created without
the liberation of CO.sub.2 or CO. The resulting hydrogen may be
collected for storage or redistribution or routed to a second
electrochemical cell with a platinum membrane for additional energy
generation. For example, when the suitable metal ion is Al.sup.3+
and the second polar electrolyte solution contains a polar solvent
such as a methanol, ethanol or both, hydrogen gas may be liberated
as a result of subsequent reactions in such electrochemical cells.
A suitable oxidant herein is S.sub.2O.sub.8.sup.2-.
[0145] Thus, there are three separate reactions that are occurring.
In one, protons are being reduced to form hydrogen gas at the
anode. In another, aluminum is being oxidized and forms
NaAl(OH).sub.4. Lastly, at the cathode, oxidant (such as
S.sub.2O.sub.8.sup.2-) is reduced to SO.sub.4.sup.2-.
[0146] The rate at which hydrogen gas is generated, for fixed
concentrations of reactants, is a function of the distance between
the copper/carbon and metal, such as aluminum, in the second polar
electrolyte solution, for example, aluminum. The greater the
distance, the lower the rate hydrogen gas is released and the lower
the current. In addition surface area affects the rate in that the
greater the surface area, generally the greater the rate of
hydrogen produced. Hydrogen may be produced in a flow or non-flow
mode.
[0147] In order for the electrochemical cell to produce electricity
spontaneously, the metal anode is oxidizable by the oxidant and the
oxidant is reduced at the cathode. When the electrochemical cell of
the disclosure is further used to generate hydrogen gas, then a
suitable metal ion is present in the anode side along with a base
such as NaOH in a polar solution comprising for example, methanol
or ethanol. Suitable metals are those which produce hydrogen when
placed in contact with a base in the second polar electrolyte
solution. Such metals have a metal-metal ion redox potential that
is negative. Examples of such fluids include alcohols such as
methanol, ethanol, propyl alcohol, or isopropyl alcohol. Water is
another such fluid such as in a mixture with an alcohol, however,
in the presence of a separating salt, water tends to collect on the
cathode side of an electrochemical cell of the disclosure. The
amount of hydrogen that is created from a battery may be up to
about 100 kg of hydrogen per day including between about 10 kg and
100 kg and all values in between. Hydrogen gas may be collected for
use in such electrochemical cells. A single electrochemical cell
with 3 cm.sup.2 Al metal placed in the second polar electrolyte
solution was measured in an electrochemical cell set up generally
in accordance with FIG. 8 to produce about 0.5 kg of the H.sub.2
per hour. A larger surface area metal placed in the second polar
electrolyte solution will produce more hydrogen. Metals placed in
the second polar electrolyte solution to produce suitable metal
ions may be provided as sheets such as Aluminum sheets, folded over
or serpentine in shape may also be provided. Other forms of
Aluminum solid include powders such as in a slurry, or nano
structures. The hydrogen may be stored for future use, such as
under compressed conditions. Examples of uses of hydrogen includes
fuel cells. Such fuel cells may be used to power vehicles, for
instance.
[0148] In some embodiments of the disclosure, the current may be
boosted or "super charged" by the addition of oxidant to the second
polar electrolyte solution. For example, in electrochemical cells
where aluminum is disposed with an alcohol or aqueous solution,
sodium peroxydisulfate may be added to the alcohol solution to
boost the current observed from the electrochemical cell. In still
other embodiments, a second polar electrolyte solution is not
needed to create such boosted current. In electrochemical batteries
of the disclosure, it may be useful to stack more than one
electrochemical cell. The stacking of cells may be enabled, for
example, by the use of three or more immiscible fluids having three
or more different densities. In such embodiments, a second cathode
opposite the first cathode at a second distance from the anode is
provided and a third electrolyte solution in contact with the
second cathode and the second electrolyte solution is further
provided wherein the third and second electrolyte solutions are in
contact with each other and are immiscible, and wherein there is no
membrane in between the third and second electrolyte solutions. The
third electrolyte solution may be polar and will be a greater
density than the first two electrolyte solutions. An example of a
third electrolyte solution that is denser than water is one that
contains propylene carbonate as a solvent. The third electrolyte
solution may contain a salt and may be saturated with respect to
that salt. Batteries with such cells may be configured in flow or
no flow mode.
[0149] In at least one embodiment according to the present
disclosure, as shown in FIG. 4A, a battery may include a cell 11
including a first electrolyte solution 20, a second electrolyte
solution 22, and a third electrolyte solution 24. In such an
embodiment, the cell 11 includes one cathode 12 operating with two
anodes 14 to generate electricity supplied to the load 16 via
circuit 18. In such an embodiment, the third electrolyte solution
24 is denser than the first electrolyte solution 20 and the second
electrolyte solution 22. The third electrolyte solution 24 is
immiscible relative to the first electrolyte solution 20 and/or the
second electrolyte solution 22. Accordingly, the second electrolyte
solution 20 is disposed in a layer above the first electrolyte
solution 22, and the first electrolyte solution 22 is disposed in a
separate layer above the third electrolyte solution 24. Optional
tanks 30 and 32, acting as sources for electrolyte solutions, and
pumps 50 and 52 (or by capillarity, reverse osmosis, a ratchet,
swelling pressure, or gravity), may be used to deliver electrolyte
solutions to the cell in flow mode, for example via conduits 21 and
25 respectively. The first electrolyte solution 20 and second
electrolyte solution 22 may further flow out of the cell 11 via
conduits 23 and 27 respectively. They may be directed to waste or
to other tanks. In some embodiments, flow could be reversed from
said other tanks to recharge cell 11. In other embodiments, the
cell can be arranged with a cathode on top and bottom and an anode
in the middle.
[0150] As shown in FIG. 4A, the third electrolyte solution 24 may
be supplied to the cell 11 from a third source 34 via conduit 31
with pump 54 (or by capillarity, reverse osmosis, a ratchet,
swelling pressure, or gravity) which may be used in flow mode. The
third electrolyte solution 24 may further flow out of cell 11 via
conduit 33. This may be directed to waste or to another tank. In
some embodiments, flow could be reversed from said another tank to
recharge cell 11. In embodiments in which the third electrolyte
solution 24 flows through the cell 11, the third electrolyte
solution 24 may be directed to waste or to other tanks. In some
embodiments, flow could be reversed and from the other tanks to
recharge the cells. Alternatively, the third electrolyte solution
24 may not flow through the cell 11 but may be replaceable. Note
that the vertical lines connecting the electrolyte solutions and
the cathode and anode electrodes in the schematic are not conduits
but are merely to aid in the viewing of the schematic.
[0151] In FIG. 4B, electrochemical cell 11a is a three-layer system
presented with two cathodes 12 and one anode 14. First electrolyte
solution 20 is in contact with cathode 12 and second electrolyte
solution 22 which in turn is in contact with anode 14 and third
electrolyte solution 24. Cathode 12 is in contact with the third
electrolyte solution 24 and load 16 via circuit 18. An optional
reductant (such as H.sub.2 gas) 26 may supply the H.sub.2 to anode
14 via conduit 31a. Flow tanks, conduits, and pumps (or by
capillarity, reverse osmosis, a ratchet, swelling pressure, or
gravity) may be used to run electrochemical cell 11a in flow mode
and thus allow for recharging. Note that the vertical lines
connecting the electrolyte solutions and the cathode and anode
electrodes in the schematic are not conduits but are merely to aid
in the viewing of the schematic.
[0152] In some embodiments, a first and second electrolyte solution
are of different densities and immiscible due to the presence of a
salt in the first electrolyte solution and are in contact without a
membrane. Further, the cell is configured to run in a no flow mode.
Batteries may be made of such cells such as in parallel or series
geometry and/or a voltaic pile. The electricity from such batteries
may be delivered to a process application such as solar farms, wind
farms, household appliances, consumer goods, or toys.
Example 1--Creating an Electrochemical Cell
[0153] Al Anode: A strip of aluminum screen which is 200 mm by 25
mm is cut and the screen is folded in half lengthwise three times,
resulting in a 25 mm by 25 mm square 8 layers thick.
[0154] Carbon foam current collector: A strip of carbon felt which
is 100 mm by 25 mm is cut. The carbon felt is folded in half
lengthwise two times, resulting in a 25 mm by 25 mm square 4 layers
thick.
[0155] Copper wire: A length of bare copper wire is cut which is
about 100 mm long.
[0156] Assembly of copper wire and Al Anode: The piece of copper
wire is slid through the middle of the aluminum screen, so there
will be four layers on top of the copper and four layers below the
copper. 10 mm on the end of the wire is bent so it partially wraps
around resulting in copper wire, 4 layers aluminum, copper wire,
and 4 layers aluminum. Once the wire is bent, the assembly is
stapled together to avoid the wire falling out and to ensure good
contact.
[0157] Assembly of copper wire and Carbon Foam Collector: The piece
of copper wire is slid through the middle of the carbon foam,
resulting in two layers on top of the copper and two layers below
the copper. 10 mm on the end of the wire is bent so it partially
wraps around the copper wire, 2 layers carbon foam, copper wire,
and 2 layers of carbon foam. Once the wire is bent, the assembly is
stapled together to avoid the wire falling out and to ensure good
contact.
[0158] The overall assembly of aluminum, copper wire, and carbon
foam is referred herein as a "unit".
Example 2--Assembling Units Together
[0159] Cutting the porous, non-conductive spacer: A 35 mm by 35 mm
piece of vinyl coated polyester screen is cut. This screen will act
as a spacer to ensure that the aluminum anode of one unit will not
touch the carbon foam collector of a separate unit, preventing a
short in the battery.
[0160] Assembling two units together: A sandwich of the aluminum
from a first unit, the spacer, and the carbon foam from a second
unit is made. This sandwich is then wrapped in one layer of 3M
surgical tape, which ensures that there is light compression of the
sandwich construct so that the gap between the aluminum and carbon
is the thickness of the spacer. The surgical tape also works as a
sponge to absorb the electrolyte when so exposed to ensure adequate
saturation of the battery. This sandwich may be referred to as a
stack.
[0161] The assembly can be repeated for as many units as desired to
create electrochemical cells in series. The ends of the cells can
be connected via a common load to create an electrochemical
battery. Upon exposure to electrolytes of the disclosure,
electricity or hydrogen or both may be generated and may be
delivered to an application.
Example 3--Al/Peroxydisulfate Electrochemical Cell/Battery with
Immiscible Electrolyte Solutions without a Membrane
[0162] A no flow electrochemical cell/battery configured in
accordance with the schematic of FIG. 5 (other than the flow
portion of the schematic) was prepared. The figure represents both
an electrochemical cell and a battery with a battery being defined
as containing one or more electrochemical cells. The cell/battery
was made in a glass beaker. Aluminum solid was used as anode 62 and
electrically connected via circuit 18 and Load 16 to cathode 63,
conducting carbon cloth or copper depending on the specific
experiment. The anode was placed in an electrolyte solution 22c
containing ethanol or methanol (multiple were tested), which was
loaded with sodium sulfate and sodium hydroxide. The cathode was
placed in contact with an electrolyte solution 20c and loaded with
sodium hydroxide, calcium chloride, and Na.sub.2S.sub.2O.sub.8.
Although each solution is polar, the different electrolyte
solutions are immiscible. Further, they have different densities
with the peroxydisulfate solution being denser, and thus on the
bottom and the less dense neutral alcohol (ethanol or methanol)
solution on top. The anode electrode is aluminum. Pyrex.RTM. wool
is loaded into the beaker in between the cathode and anode. The
Pyrex.RTM. wool forms a porous medium in which fluids are imbedded.
Other porous media materials, such as other borosilicates, may be
used.
[0163] The concentrations of sodium and calcium salts were such
that they were near or at their solubility limit for the system.
The cell/battery of FIG. 5 could be run in flow mode by attaching
optional tanks 30 and 32 and pumps 50 and 52 (or by capillarity,
reverse osmosis, a ratchet, swelling pressure, or gravity) via
conduits 21 and 25 respectively. The outflow from the cell/battery
23 and 27 could be routed to waste or to an external tank for
recharge purposes via reversing polarity. In flow operation, the
rate of addition of a fluid to increase or decrease the thickness
of a layer can be used to change the pressure in the layer. The
anode oxidation reaction rate, such as Al(s).fwdarw.Al.sup.3+, can
be controlled by adjusting the two pressures in electrolyte
solutions (by adjusting the rate which controls the thickness of
the two solutions) which in turn changes the proximity of the
aluminum to the ions in the cathode solution such as, for example,
the S.sub.2O.sub.8.sup.2- ion).
Example 4--Zn/Peroxydisulfate Electrochemical Cell/Battery with
Immiscible Electrolyte Solutions without a Membrane
[0164] A no flow electrochemical cell/battery configured in
accordance with the schematic of FIG. 6 (other than the flow
portion of the schematic) was prepared. The figure represents both
an electrochemical cell and a battery with a battery being defined
as containing one or more electrochemical cells. The cell/battery
was made in a glass beaker. Carbon foam was used as an
anode-electrode 62a and electrically connected via circuit 18 and
Load 16 to cathode 63a, which was also carbon foam. The anode was
placed in an electrolyte solution 22d containing ethanol or
methanol depending on the experiment (multiple runs were
performed), which was loaded with zinc powder, sodium sulfate and
sodium hydroxide. The cathode was placed in contact with an
electrolyte solution 20c in water and loaded with sodium hydroxide,
calcium chloride, and Na.sub.2S.sub.2O.sub.8. Although each
solution is polar, the different electrolyte solutions are
immiscible. Further, they have different densities with the
peroxydisulfate solution being denser, and thus on the bottom and
the less dense neutral alcohol (ethanol or methanol) solution on
top. Pyrex.RTM. wool was loaded into the beaker in between the
cathode and anode. The Pyrex.RTM. wool forms a porous medium in
which fluids are imbedded. Other porous media materials, such as
other borosilicates, may be used.
[0165] The concentrations of sodium and calcium salts were such
that they were near or at their solubility limit for the system.
The cell/battery of FIG. 6 could be run in flow mode by attaching
optional tanks 30 and 32 and pumps 50 and 52 (or by capillarity,
reverse osmosis, a ratchet, swelling pressure, or gravity) via
conduits 21 and 25 respectively. The outflow from the cell/battery
23 and 27 could be routed to waste or to an external tank for
recharge purposes via reversing polarity. After running for three
hours, voltages of between 1.75V and 1.89 V were recorded and a
current of 0.12 A/cm.sup.2 were recorded at one ohm in ethanol and
about 1.52V at 0.12 A/cm.sup.2 in methanol.
[0166] In flow operation, the rate of addition of a fluid to
increase or decrease the thickness of a layer can be used to change
the pressure in the layer. The anode oxidation reaction rate, such
as Zn(s).fwdarw.Zn.sup.2+, can be controlled by adjusting the two
pressures in electrolyte solutions (by adjusting the rate which
controls the thickness of the two solutions) which in turn changes
the proximity of the zinc to the ions in the cathode solution such
as, for example, the S.sub.2O.sub.8.sup.2- ion. The reaction may
also be reversible so that the cell or a battery with multiple
cells may be recharged.
Example 5--Additional Embodiment of Al/Peroxydisulfate
Electrochemical Cell/Battery with Immiscible Electrolyte Solutions
without a Membrane
[0167] A no flow electrochemical cell/battery configured in
accordance with the schematic of FIG. 7 (other than the flow
portion of the schematic) was prepared. The figure represents both
an electrochemical cell and a battery with a battery being defined
as containing one or more electrochemical cells. The cell/battery
was made in a glass beaker. Carbon foam was used as an
anode-electrode 62a and electrically connected via circuit 18 and
Load 16 to cathode 63a, which was also carbon foam. The anode was
placed in an electrolyte solution 22e containing ethanol or
methanol depending on the experiment (multiple runs were
performed), which was loaded with aluminum powder, sodium sulfate
and sodium hydroxide. The cathode was placed in contact with an
electrolyte water solution 20c and loaded with sodium hydroxide,
calcium chloride, and Na.sub.2S.sub.2O.sub.8. Although each
solution is polar, the different electrolyte solutions are
immiscible. Further, they have different densities with the
peroxydisulfate solution being denser, and thus on the bottom and
the less dense neutral alcohol (ethanol or methanol) solution on
top. Pyrex.RTM. wool is loaded into the beaker in between the
cathode and anode. The Pyrex.RTM. wool forms a porous medium in
which fluids are imbedded. Other porous media materials, such as
other borosilicates, may be used.
[0168] The concentrations of sodium and calcium salts were such
that they were near or at their solubility limit for the system.
The cell/battery of FIG. 7 could be run in flow mode by attaching
optional tanks 30 and 32 and pumps 50 and 52 (or by capillarity,
reverse osmosis, a ratchet, swelling pressure, or gravity) via
conduits 21 and 25 respectively. The outflow from the cell/battery
23 and 27 could be routed to waste or to an external tank for
recharge purposes via reversing polarity. After running for three
hours, a voltage of 1.9 V was recorded and a current of 0.14
A/cm.sup.2.
[0169] In flow operation, the rate of addition of a fluid to
increase or decrease the thickness of a layer can be used to change
the pressure in the layer. The anode oxidation reaction rate, such
as Al(s).fwdarw.Al.sup.3+, can be controlled by adjusting the two
pressures in electrolyte solutions (by adjusting the rate which
controls the thickness of the two solutions) which in turn changes
the proximity of the aluminum to the ions in the cathode solution
such as, for example, the S.sub.2O.sub.8.sup.2- ion).
Example 6--Al/Peroxydisulfate Flow Battery and Hydrogen
Production
[0170] FIG. 8 is a schematic of an electrochemical cell in flow
mode. Flow batteries have the advantage that they are instantly
rechargeable via continual replacement of the electrolytes. In many
ways flow batteries are like fuel cells, but rather than using
hydrogen and oxygen, they employ liquid electrolytes. The metal
that is often on the anode side of redox flow-batteries is in the
form of a very fine powder that is premixed with the analyte to
form a colloidal suspension and pumped through a porous carbon
current collector where oxidation takes place. On the cathode side
a strong oxidant is dissolved in the catholyte for the reduction
step. Example single cell amperages range from 0.25 A/cm.sup.2 to
0.1 A/cm.sup.2 with voltages ranging from 1.5V to 3.25V. A first
electrolyte solution is made by loading water with NaOH,
Na.sub.2SO.sub.4 and Na.sub.2S.sub.2O.sub.8. Inflow and outflow
ports are provided so that electrolyte solution can be replenished
and removed for flow purposes. The first electrolyte solution uses
a carbon foam current collector and is stabilized with glass wool.
Inflowing solution contains water, NaOH, Na.sub.2SO.sub.4, and
Na.sub.2S.sub.2O.sub.8 whereas outflow is water, NaOH, and
Na.sub.2SO.sub.4. A material, often made of plastic, with holes may
be used to separate the first electrolyte solution from the second
and may contain glass wool.
[0171] A second electrolyte is made by adding NaOH, Al powder and
Na.sub.2SO.sub.4 to ethanol. The Na.sub.2SO.sub.4 is added at a
sufficiently high concentration to keep separate the aqueous first
electrolyte solution from the ethanolic second electrolyte
solution. Inflows and outflows are provided for the second
electrolyte solution with an inflow being an ethanolic solution of
NaOH and Na.sub.2SO.sub.4 with added Al in powder form. The outflow
contains ethanol, sodium hydroxide, Al.sub.2O.sub.3,
Na.sub.2SO.sub.4, and NaAl(OH).sub.4. The current collector is
carbon foam which is in electrical contact via a load with the
current collector of the first electrolyte solution. Glass wool
stabilizes the second electrolyte solution. During the
electrochemical process hydrogen gas is formed in the second
electrolyte solution and may be removed as set forth in FIG. 8 to,
for example, a hydrogen compressor, for hydrogen delivery to a
process application such as a fuel cell. The electricity generated
by the electrochemical cell may be used to power the hydrogen
compressor. For example, a 900 cm.sup.2 Aluminum sheet placed in
the second electrolyte solution should provide current of at least
0.1 A/cm.sup.2 resulting in 90 A of current, at 1 ohm and 2 volts,
this provides 180 watts of power. Thus, 6 electrochemical cells in
series would be more than sufficient to run a typical hydrogen
compressor.
[0172] Thus, on the anode side (ethanol), solid aluminum produces
electrons and on the cathode side a strong oxidant (like
S.sub.2O.sub.8.sup.2- or ClO.sup.-) accepts electrons. The
Al(s).fwdarw.Al.sup.3++3e.sup.- and the
S.sub.2O.sub.8.sup.2-+2e.sup.-.fwdarw.2SO.sub.4.sup.2- half
reactions yield a substantial current (1.4 A/cm.sup.2-anode) which
can be used to drive a compressor. Without being bound by theory,
if these reactions are carried out in a basic environment, then
there are three other very important reactions on the anode side
that take place which also lead to the oxidation of aluminum and
the resulting production of hydrogen gas.
Example 7--Electrochemical Cell with Single Solution which May be
Used as a Capacitor
[0173] An electrochemical cell was prepared in accordance with FIG.
9 in a no-flow mode. The cell could be run in flow mode, however,
and FIG. 9 illustrates how that could be done.
[0174] An electrolyte solution was made from 10 grams of sodium
peroxydisulfate, 10 grams of sodium hydroxide, 10 grams of sodium
sulfate and 200 mls of water. Within an electrochemical cell, 1.5
grams of Al foil was compressed into a 1.times.2.times.1 cm block
and connected via copper wire to a meter in the cell and 20 mls of
the electrolyte solution was added to the cell. A carbon foam
current collector was also connected to the meter in the cell.
Electrochemical cell 20d, therefore, is similar to 20c, except for
the addition of sodium sulfate. Over the course of about 45
minutes, concentrated (2M) sodium peroxydisulfate and NaOH (pH15)
was added dropwise to the cell near the Al foil. Drops were added
so that the current provided by the cell ranged between about 400
and 600 milliwatts until a total of about 20 ml were added.
Subsequently, a small amount of solid sodium peroxydisulfate was
added near the anode and it was observed that the power spiked to
750 milliwatts and then reached a steady state of 600 milliwatts
for about 10 minutes. The addition of solid peroxydisulfate also
caused the release of heat and substantial hydrogen gas.
[0175] Spikes in power may be obtained by adding oxidant, such as
with the addition of sodium peroxydisulfate and sodium hydroxide
followed by opening the electrochemical circuit such as by
disconnecting the lead. The disconnection may be used to build a
capacitor. The capacitor charge may then be discharged by
reconnecting the lead and closing the circuit. It is believed that
reduction-oxidation capacitance is charged chemically by continuous
oxidation of the aluminum while the circuit is open creating a net
negative charge on the aluminum, which in turn induces a double
ionic layer (sodium and sulfate) to form next to the aluminum
surface with cations favored toward the surface. Subsequent closing
the circuit causes the anode to rapidly discharge through the load,
with the coincident breakdown of the double layer, creating what is
commonly known as a capacitor. Rapidly cycling an open and closed
circuit can create a large and sustainable current. This capacitor
is self-charging and can be controlled by the amount of oxidant
deployed and pH.
[0176] This cycle, of opening and closing the circuit may be
repeated at the same time that bulk electrolyte and solid aluminum
is passed through the system. Alternatively, the resulting sodium
sulfate, aluminum oxide and sodium aluminate may be removed.
Example 8--a Battery-Powered Vehicle
[0177] A fuel-cell powered vehicle (Drive Medical Spitfire Scout 4
wheel scooter) is reconfigured to be powered by a battery of
Example 9 by manually replacing the installed-battery with the
battery and system as set forth in this Example 8. As illustrated
in FIG. 10, a battery of Example 9, 200, is placed in the vehicle
and connected via electrical connection 205 to a DC-DC converter
210A, which was electrically connected to fuel cell controller 245.
All electrical connections between the provided components are
provided as 205. The controller is a small computer which controls
the fuel cell values, the cooling system, and other components of
the fuel cell. One function of the controller is to control the
temperature of the fuel cell via a cooling system (not shown)
inside 240. The amount of hydrogen let into the fuel cell is
controlled by valves connected to or within the fuel cell. The fuel
cell controller is in electrical contact with the fuel cell.
[0178] Hydrogen from Battery 200 is dried prior to entering fuel
cell 240. Here, hydrogen from IFBattery 200 is delivered via
hydrogen gas line 215 to cooling coil 220 which is in fluid contact
with water pump 260 via 250 and radiator/fan 255 via. Electricity
from battery 200 through DC-DC converter 210A may be used to power
both the radiator/fan 255 and water pump 260. All hydrogen gas
lines between listed components are listed as 215. The cooled
hydrogen is transferred via gas line over a water accumulator 255
and through molecular sieve 230 via a gas line and pressure
regulator 235 via a gas line for delivery to fuel cell 240 via a
gas line.
[0179] Fuel cell 240 converts hydrogen to electricity for delivery
to DC-DC converter 210C for delivery to electric motor 265 for use
in powering the vehicle. Optional DC-DC converter 210B may be used
to power electric motor 265 also or in lieu of a fuel cell.
[0180] Battery 200 may be positioned within a system as described
below. In such as system, bulk battery fluid can be stored at the
bottom of a tank, then transported to a fluid manifold via a pump.
The fluid can then flow through to one or more series of cells of
the disclosure, and then to a fluid outlet where the flow rate is
controlled. The fluid may cycle from the battery fluid tank, to the
pump, to the fluid manifold, through the cells, to the fluid
outlet, and return to the battery fluid tank. This cycle can repeat
for as long as the battery is running. In the battery fluid tank,
electrolyte components such as NaOH and Na.sub.2S.sub.2O.sub.8 can
be added to maintain a steady concentration. A radiator may also be
added to keep temperature to a specified range, for example within
40-80 C.
[0181] Electric wires can all be connected at a central port.
Hydrogen is released at H.sub.2 ports and may go into the hydrogen
purification stream on the block diagram.
[0182] The block diagram includes a battery fluid pump 270, NaOH
dispenser 275, Na.sub.2S.sub.2O.sub.8 dispenser 280, and another
water pump 260/radiator 255 combination which will maintain the
temperature of the battery pack. These can all be powered with the
DC-DC converter (210A) which utilizes electrical power from the
battery. The NaOH 275 and Na.sub.2S.sub.2O.sub.8 280 dispensers are
used to add more of each chemical into the battery fluid tank to
either maintain the concentration as the chemicals are used up, or
to increase the concentrations. The battery fluid pump takes fluid
from the tank to the fluid manifold. The fluid flow is used in the
context of a flow battery.
[0183] In the various descriptions above, electrochemical cells are
stacked vertically. In alternative embodiments, adjacent
electrochemical cells, for example, may be disposed in other
orientations to make batteries.
Example 9--Battery
[0184] The electrochemical cells in Example 8 were prepared by
making electrochemical cells as described in this Example 9. Each
cell was constructed as follows: 10 g of Al were used as anodes and
were placed in containers of ABS plastic, a carbon foam was used as
a cathode current collector, and a vinyl coated polyester was used
as a separator to separate the aluminum and carbon foam. Then each
battery cell was filled with approximately 30 mL of 2M NaOH, 1/6M
Na.sub.2S.sub.2O.sub.8, 1/6M Na.sub.2SO.sub.4. The battery cells
were connected so that 6 battery cells were in series, and then 3
sets of 6 batteries in series were connected in parallel. The
connections between cells, as well as the parallel connections were
made with tin coated copper wire.
[0185] A variety of embodiments according to the present disclosure
are contemplated. Such embodiments may be employed in a variety of
methods, processes, procedures, steps, and operations as a means of
providing electrochemical cells and batteries. While the disclosure
has been illustrated and described in detail in the drawings and
foregoing description, the same is to be considered as illustrative
and not restrictive in character, it being understood that only
certain exemplary embodiments have been shown and described. Those
skilled in the art will appreciate that many modifications are
possible in the example embodiments without materially departing
from this disclosure. Accordingly, all such modifications are
intended to be included within the scope of this disclosure as
defined in the following claims. Indeed, this disclosure is not
intended to be exhaustive or to limit the scope of the
disclosure.
[0186] An additional list of non-limiting embodiments of this
disclosure is provided below in the form of clauses.
[0187] Clause 1. An electrochemical cell comprising: [0188] a. an
anode; [0189] b. a cathode current collector; and [0190] c. a
porous, non-conductive spacer between the cathode current collector
and anode.
[0191] Clause 2. The electrochemical cell of Clause 1, further
comprising a single electrolyte solution.
[0192] Clause 3. The electrochemical cell of Clause 2, wherein the
cell is saturated with electrolyte.
[0193] Clause 4. The electrochemical cell of Clause 3, wherein the
cell is not immersed in an electrolyte bath.
[0194] Clause 5. The electrochemical cell of Clause 1, wherein the
cell is wrapped in a microporous material.
[0195] Clause 6. The electrochemical cell of Clause 1, wherein the
anode is selected from aluminum, gallium, indium, thallium and
alloys comprising at least one of these.
[0196] Clause 7. The electrochemical cell of Clause 6, wherein the
anode is aluminum.
[0197] Clause 8. The electrochemical cell of Clause 1, wherein the
cathode current collector is selected from steel, the graphite
allotrope of carbon, carbon impregnated with a metal and carbon
foam.
[0198] Clause 9. The electrochemical cell of Clause 8, wherein the
cathode current collector is carbon foam.
[0199] Clause 10. The electrochemical cell of Clause 1, wherein the
porous, non-conductive spacer is selected from an organic polymer,
surgical tape, fiberglass film, glass wool, wood, paper, cloth,
cardboard and nylon.
[0200] Clause 11. The electrochemical cell of Clause 10, wherein
the spacer is vinyl coated polyester.
[0201] Clause 12. The electrochemical cell of Clause 2, wherein the
electrolyte comprises water and one or more salts.
[0202] Clause 13. The electrochemical cell of Clause 12, wherein at
least one salt is an oxidant.
[0203] Clause 14. The electrochemical cell of Clause 12, wherein
the electrolyte comprises two salts.
[0204] Clause 15. The electrochemical cell of Clause 14, wherein
the electrolyte comprises a salt of peroxydisulfate and a salt of
sulfate and further comprises a base.
[0205] Clause 16. The electrochemical cell of Clause 15, wherein
the peroxydisulfate salt is sodium peroxydisulfate and the sulfate
salt is sodium sulfate and the base is sodium hydroxide.
[0206] Clause 17. The electrochemical cell of Clause 2, wherein the
electrolyte comprises one of water or an alcohol.
[0207] Clause 18. The electrochemical cell of Clause 17, wherein
the electrolyte is a catholyte.
[0208] Clause 19. The electrochemical cell of Clause 17, further
comprising an oxidant.
[0209] Clause 20. The electrochemical cell of Clause 19, further
comprising a metal salt.
[0210] Clause 21. The electrochemical cell of Clause 20, wherein
the oxidant and metal salt have different anion components.
[0211] Clause 22. The electrochemical cell of Clause 21, wherein
the oxidant is sodium peroxydisulfate and the metal salt is sodium
sulfate.
[0212] Clause 23. The electrochemical cell of Clause 17, further
comprising a base.
[0213] Clause 24. The electrochemical cell of Clause 23, wherein
the base is NaOH.
[0214] Clause 25. An electrochemical cell of any one of Clauses
1-24, wherein the cell is electrically connected to a load.
[0215] Clause 26. An electrochemical battery comprising one or more
electrochemical cells of any one of Clauses 1-24, wherein the
battery is electrically connected to a load.
[0216] Clause 27. A method which comprises producing electricity or
hydrogen with an electrochemical cell of Clause 25 and delivering
the electricity to an application.
[0217] Clause 28. A method which comprises producing electricity or
hydrogen with an electrochemical battery of Clause 26 and
delivering the electricity or hydrogen to an application.
[0218] Clause 29. A method of making an electrochemical cell, which
comprises:
[0219] 1) providing an electrochemical cell of any one of Clauses 1
and 5-11, wherein the electrochemical cell does not comprise an
electrolyte; and
[0220] 2) contacting the cell with a single electrolyte
solution.
[0221] Clause 30. The method of Clause 29, which comprises
contacting the cell with the single electrolyte solution by
spraying the electrolyte solution onto the cell.
[0222] Clause 31. The method of Clause 29, which comprises
contacting the cell with droplets of the single electrolyte
solution via drip.
[0223] Clause 32. The method of Clause 29, which comprises
contacting the cell with an atomized mist of the single electrolyte
solution.
[0224] Clause 33. A method of operating an electrochemical cell,
which comprises:
[0225] 1) providing an electrochemical cell of Clause 1, wherein
the electrochemical cell further comprises a single electrolyte
solution;
[0226] 2) electrically connecting the electrochemical cell to a
load such that the electrochemical cell operates to produce
electricity, hydrogen, or both electricity and hydrogen; and
[0227] 3) providing additional electrolyte solution, or one or more
components thereof, to the cell during its operation.
[0228] Clause 34. The method of Clause 33, which further
comprises:
[0229] 4) withdrawing spent electrolyte solution, or one or more
components thereof, from the electrochemical cell during its
operation.
[0230] Clause 35. The method of Clause 34, which comprises 4)
withdrawing spent electrolyte solution, or one or more components
thereof, simultaneously with 3) providing additional electrolyte
solution, or one or more components thereof.
[0231] Clause 36. The method of any one of Clauses 33-35, wherein
the single electrolyte solution comprises one or more of the
following components: solvent, oxidant, metal salt, and base.
[0232] Clause 37. A method of creating a capacitor, which comprises
disconnecting a load from the cathode current collector or anode
side of the electrochemical cell of any one of Clauses 1-25.
[0233] Clause 38. The method of Clause 37, further comprising the
step of reconnecting the load.
[0234] Clause 39. A capacitor prepared by the process of
alternately disconnecting and reconnecting a load from at least one
of the cathode current collector or anode in an electrochemical
cell of any one of Clauses 1-25.
[0235] Clause 40. The electrochemical cell of any one of Clauses
1-4, wherein the cell is wrapped in a microporous material.
[0236] Clause 41. The electrochemical cell of any one of Clauses
1-4 and 40, wherein the anode is selected from aluminum, gallium,
indium, thallium and alloys comprising at least one of these.
[0237] Clause 42. The electrochemical cell of Clause 41, wherein
the anode is aluminum.
[0238] Clause 43. The electrochemical cell of Clause 42, wherein
the aluminum is in the form of a screen.
[0239] Clause 44. The electrochemical cell of Clause 43, wherein
the aluminum thickness in the screen is between about 0.1 mm and
about 0.3 mm.
[0240] Clause 45. The electrochemical cell of any one of Clauses
1-4 and 40-44, wherein the cathode current collector is carbon
foam.
[0241] Clause 46. The electrochemical cell of any one of Clauses
1-4 and 40-45, wherein the porous, non-conductive spacer is
selected from an organic polymer, surgical tape, fiberglass film,
glass wool, wood, paper, cloth, cardboard and nylon.
[0242] Clause 47. The electrochemical cell of Clause 46, wherein
the spacer is vinyl coated polyester.
[0243] Clause 48. The electrochemical cell of Clause 46, wherein
the spacer is a screen.
[0244] Clause 49. The electrochemical cell of Clause 48, wherein
the spacer thickness in the screen is between about 0.1 mm and
about 0.8 mm and the spacer is vinyl coated polyester.
[0245] Clause 50. The electrochemical cell of Clause 1, further
comprising a metal conductor between the anode and an adjacent
cathode current collector from a second electrochemical cell and
wherein the electrochemical cell of Clause 1 is configured to
operate as a flow cell.
[0246] Clause 51. The electrochemical cell of Clause 50, wherein
the metal conductor is copper wire.
[0247] Clause 52. The electrochemical cell of any one of Clauses
40-51, wherein the microporous material is surgical tape.
[0248] Clause 53. The electrochemical cell of any one of Clauses
2-4 and 40-52, wherein the electrolyte comprises water and one or
more salts, wherein at least one of the salts is an oxidant.
[0249] Clause 54. The electrochemical cell of Clause 53, wherein
the electrolyte comprises two salts.
[0250] Clause 55. The electrochemical cell of Clause 54, wherein
the electrolyte comprises a salt of peroxydisulfate and a salt of
sulfate and further comprises a base.
[0251] Clause 56. The electrochemical cell of Clause 55, wherein
the peroxydisulfate salt is sodium peroxydisulfate and the sulfate
salt is sodium sulfate and the base is sodium hydroxide.
[0252] Clause 57. An electrochemical battery comprising one or more
electrochemical cells of any one of Clauses 1-4 and 40-56, wherein
the battery is electrically connected to a load.
[0253] Clause 58. The electrochemical battery of Clause 57,
comprising two or more electrochemical cells arranged in
series.
[0254] Clause 59. The electrochemical battery of Clause 57,
comprising two or more electrochemical cells arranged in
parallel.
[0255] Clause 60. The electrochemical battery of Clause 57,
comprising electrochemical cells arranged in series and in
parallel.
[0256] Clause 61. The electrochemical battery of any one of Clauses
57-60, further comprising an electrolyte wherein the electrolyte
comprises water and one or more salts, wherein at least one of the
salts is an oxidant.
[0257] Clause 62. The electrochemical battery of Clause 61, wherein
the electrolyte comprises two salts.
[0258] Clause 63. The electrochemical battery of Clause 62, wherein
the electrolyte comprises a salt of peroxydisulfate and a salt of
sulfate and further comprises a base and wherein the
electrochemical battery is configured as a flow battery.
[0259] Clause 64. The electrochemical battery of Clause 63, wherein
the peroxydisulfate salt is sodium peroxydisulfate and the sulfate
salt is sodium sulfate and the base is sodium hydroxide.
[0260] Clause 65. The electrochemical battery of any one of Clauses
57-64, which produces electricity.
[0261] Clause 66. The electrochemical battery of any one of Clauses
57-64, which produces hydrogen.
[0262] Clause 67. The electrochemical battery of any one of Clauses
57-64, which produces electricity and hydrogen.
[0263] Clause 68. A method which comprises delivering electricity
produced by the electrochemical battery of Clause 65 to an
application.
[0264] Clause 69. A method which comprises delivering hydrogen
produced by the electrochemical battery of Clause 66 to an
application.
[0265] Clause 70. The method of Clause 68, wherein the application
is a cell phone tower or a vehicle.
[0266] Clause 71. The method of Clause 69, wherein the application
is a fuel cell or a vehicle.
[0267] Clause 72. The electrochemical cell of any one of Clauses
2-4 and 40-56, wherein the electrolyte comprises one of water or an
alcohol.
[0268] Clause 73. The electrochemical cell of Clause 72, wherein
the electrolyte is a catholyte.
[0269] Clause 74. The electrochemical cell of Clause 72 or 73,
further comprising an oxidant.
[0270] Clause 75. The electrochemical cell of Clause 74, further
comprising a metal salt.
[0271] Clause 76. The electrochemical cell of Clause 75, wherein
the oxidant and metal salt have different anion components.
[0272] Clause 77. The electrochemical cell of Clause 76, wherein
the oxidant is sodium peroxydisulfate and the metal salt is sodium
sulfate.
[0273] Clause 78. The electrochemical cell of any one of Clauses
72-77, further comprising a base.
[0274] Clause 79. The electrochemical cell of Clause 78, wherein
the base is NaOH.
[0275] Clause 80. The electrochemical battery of any one of Clauses
57-60, further comprising an electrolyte wherein the electrolyte
comprises one of water or an alcohol.
[0276] Clause 81. The electrochemical battery of Clause 80, wherein
the electrolyte is a catholyte.
[0277] Clause 82. The electrochemical battery of Clause 80 or 81,
further comprising an oxidant.
[0278] Clause 83. The electrochemical battery of Clause 82, further
comprising a metal salt.
[0279] Clause 84. The electrochemical battery of Clause 83, wherein
the oxidant and metal salt have different anion components.
[0280] Clause 85. The electrochemical battery of Clause 84, wherein
the oxidant is sodium peroxydisulfate and the metal salt is sodium
sulfate.
[0281] Clause 86. The electrochemical battery of any one of Clauses
80-85 further comprising a base.
[0282] Clause 87. The electrochemical battery of Clause 86, wherein
the base is NaOH.
[0283] Clause 88. An electrochemical cell comprising: [0284] a) an
anode; [0285] b) a cathode current collector; and [0286] c) a
porous, non-conductive spacer between the cathode current collector
and anode; wherein the electrochemical cell does not comprise an
electrolyte.
[0287] Clause 89. The electrochemical cell of Clause 88, wherein
the cell is wrapped in a microporous material.
[0288] Clause 90. The electrochemical cell of Clause 88 or Clause
89, wherein the anode is selected from aluminum, gallium, indium,
thallium and alloys comprising at least one of these.
[0289] Clause 91. The electrochemical cell of Clause 90, wherein
the anode is aluminum.
[0290] Clause 92. The electrochemical cell of Clause 90 or Clause
91, wherein the anode is in the form of a screen.
[0291] Clause 93. The electrochemical cell of Clause 92, wherein
the anode thickness in the screen is between about 0.1 mm and about
0.3 mm.
[0292] Clause 94. The electrochemical cell of any one of Clauses
88-93, wherein the cathode current collector is selected from
steel, the graphite allotrope of carbon, carbon impregnated with a
metal and carbon foam.
[0293] Clause 95. The electrochemical cell of Clause 94, wherein
the cathode current collector is carbon foam.
[0294] Clause 96. The electrochemical cell of any one of Clauses
88-95, wherein the porous, non-conductive spacer is selected from
an organic polymer, surgical tape, fiberglass film, glass wool,
wood, paper, cloth, cardboard and nylon.
[0295] Clause 97. The electrochemical cell of Clause 96, wherein
the spacer is vinyl coated polyester.
[0296] Clause 98. The electrochemical cell of any one of Clauses
88-97, wherein the spacer is a screen.
[0297] Clause 99. The electrochemical cell of Clause 98, wherein
the spacer thickness in the screen is between about 0.1 mm and
about 0.8 mm and the spacer is vinyl coated polyester.
[0298] Clause 100. The electrochemical cell of Clause 1, wherein
the electrochemical cell comprises a single electrolyte solution
and is electrically connected to a load, and wherein the cell
produces between about 10 Watt-hours/(kg of electrolyte+anode
metal) and about 680 Watt-hours/(kg of electrolyte+anode
metal).
[0299] Clause 101. The electrochemical cell of Clause 1, wherein
the electrochemical cell comprises a single electrolyte solution
and is electrically connected to a load, and wherein the cell
produces between about 10 Watt-hours/kg of electrolyte and about
100 Watt-hours/kg of electrolyte.
[0300] Clause 102. An electrochemical cell comprising a single
aqueous electrolyte solution in contact with a non-metallic cathode
current collector, an oxidant, and a metal solid wherein current
travels from the metal solid to the current collector via a
load.
[0301] Clause 103. The electrochemical cell of Clause 102, wherein
the aqueous electrolyte solution is basic and the oxidant is
S.sub.2O.sub.8.sup.2-.
[0302] Clause 104. The electrochemical cell of Clause 102, wherein
the aqueous electrolyte solution further comprises sodium
hydroxide.
[0303] Clause 105. The electrochemical cell of any one of Clauses
102-104, wherein the metal solid is selected from aluminum,
gallium, indium, thallium and alloys comprising at least one of
these.
[0304] Clause 106. The electrochemical cell of Clause 105, wherein
the method solid is aluminum in foil form.
[0305] Clause 107. The electrochemical cell of any one of Clauses
102-106, further comprising a porous stabilizer.
[0306] Clause 108. The electrochemical cell of any one of Clauses
102-107, further comprising a metal sulfate and wherein the cathode
current collector is carbon foam and the porous stabilizer is glass
wool or a borosilicate or both.
[0307] Clause 109. The electrochemical cell of Clause 108, wherein
the metal sulfate is Na.sub.2SO.sub.4.
[0308] Clause 110. The electrochemical cell of any one of Clauses
102-109 wherein the pH is greater than 12.
[0309] Clause 111. The electrochemical cell of Clause 110, wherein
the pH is greater than 13.
[0310] Clause 112. The electrochemical cell of Clause 111, wherein
the pH is greater than 14.
[0311] Clause 113. The electrochemical cell of any one of Clauses
102-112, wherein between about 10 Watt-hours/kg of electrolyte and
about 100 Watt-hours/kg of electrolyte is produced.
[0312] Clause 114. The electrochemical cell of Clause 113, wherein
the power produced per square centimeter of metal solid is between
about 600 mW and about 1000 mW.
[0313] Clause 115. The electrochemical cell of any one of Clauses
102-114 configured to operate in a flow mode.
[0314] Clause 116. A method which comprises providing additional
oxidant to the electrochemical cell of any one of Clauses
102-115.
[0315] Clause 117. The electrochemical cell of Clause 115, further
comprising an inflow stream comprising an aqueous electrolyte
solution.
[0316] Clause 118. The electrochemical cell of Clause 117, wherein
the inflow stream further comprises an oxidant.
[0317] Clause 119. The electrochemical cell of Clause 118, wherein
the oxidant is sodium peroxydisulfate or a solution comprising
peroxydisulfate anion or both.
[0318] Clause 120. The electrochemical cell of any one of Clauses
115-119, wherein an aqueous solution outflows from the cell.
[0319] Clause 121. The electrochemical cell of Clause 120, wherein
the aqueous solution outflowing from the cell comprises a metal
sulfate.
[0320] Clause 122. The electrochemical cell of Clause 118 or 119,
wherein the oxidant is in an aqueous basic solution.
[0321] Clause 123. The electrochemical cell of Clause 122, wherein
the base is NaOH.
[0322] Clause 124. The electrochemical cell of Clause 118 or 119
wherein the oxidant is solid Na.sub.2S.sub.2O.sub.8.
[0323] Clause 125. The electrochemical cell of any one of Clauses
115-124, wherein between about 10 Watt-hours/kg of electrolyte and
about 100 Watt-hours/kg of electrolyte is produced.
[0324] Clause 126. The electrochemical cell of Clause 125, wherein
between about 40 Watt-hours/kg of electrolyte and 80 Watt-hours/kg
of electrolyte is produced.
[0325] Clause 127. A method of creating a capacitor comprising the
steps of disconnecting the load from one side of the
electrochemical cell of any one of Clauses 115-126.
[0326] Clause 128. The method of Clause 127, further comprising the
step of reconnecting the load.
[0327] Clause 129. A capacitor, prepared by the process of
alternatively disconnecting and reconnecting the load from at least
one of the cathode current collector or anode in the cell of any
one of Clauses 102-126.
[0328] Clause 130. The electrochemical cell of Clause 125, wherein
between about 10 Watt-hours/kg of electrolyte and about 60
Watt-hours/kg of electrolyte is produced.
[0329] Clause 131. An electrochemical cell comprising a single
aqueous electrolyte solution in contact with a non-metallic cathode
current collector, an oxidant, and a metal solid wherein current
travels from the metal solid to the cathode current collector via a
load, and wherein the pH is greater or equal to 12.
[0330] Clause 132. The electrochemical cell of Clause 131, wherein
the non-metallic cathode current collector is carbon foam, the
oxidant is a peroxydisulfate salt, and the metal solid is
aluminum.
[0331] Clause 133. An electrochemical cell comprising a single
aqueous electrolyte solution in contact with a non-metallic cathode
current collector, an oxidant, and one or more anodes wherein
current travels from the one or more anodes to the cathode current
collector via a load, and wherein the pH is greater or equal to
10.
[0332] Clause 134. The electrochemical cell of Clause 133, wherein
the one or more anodes are a metal.
[0333] Clause 135. The electrochemical cell of Clause 134, wherein
the metal is aluminum, gallium, indium, thallium, or an alloy
comprising at least one of these.
[0334] Clause 136. The electrochemical cell of any one of Clause
133-135, wherein the anodes are separated by an insulator.
[0335] Clause 137. The electrochemical cell of Clause 135, wherein
the anode is aluminum and is in a foil form.
[0336] Clause 138. The electrochemical cell of any one of Clauses
133-137, wherein the pH is 12 or greater.
[0337] Clause 139. An electrochemical cell comprising: [0338] a. a
cathode; [0339] b. an anode adjacent to the cathode at a distance;
[0340] c. a first polar electrolyte solution in contact with the
cathode and disposed within the distance comprising an oxidant;
[0341] d. a second polar electrolyte solution in contact with the
anode and disposed within the distance comprising a suitable metal
ion; and [0342] e. a separation agent; wherein the first and second
electrolyte solutions are in contact with each other and are
immiscible, and wherein there is no membrane in between the first
and second electrolyte solutions.
[0343] Clause 140. The electrochemical cell of Clause 139, wherein
each polar electrolyte solution further comprising a porous
stabilizer.
[0344] Clause 141. The electrochemical cell of any one of Clauses
139-140, configured for flow-mode.
[0345] Clause 142. The electrochemical cell of any one of Clauses
139-141, wherein the first polar electrolyte solution is
aqueous.
[0346] Clause 143. The electrochemical cell of any one of Clauses
139-142, wherein the oxidant is a Vanadium ion.
[0347] Clause 144. The electrochemical cell of any one of Clauses
139-142, wherein the oxidant is S.sub.2O.sub.8.sup.2-.
[0348] Clause 145. The electrochemical cell of any one of Clauses
139-142, wherein the oxidant is ClO.sup.-.
[0349] Clause 146. The electrochemical cell of any one of Clauses
139-145, wherein the first polar electrolyte solution further
comprises a base.
[0350] Clause 147. The electrochemical cell of Clause 146, wherein
the base is selected from KOH, NaOH, Ca(OH).sub.2, LiOH, RbOH,
CsOH, Sr(OH).sub.2, and Ba(OH).sub.2.
[0351] Clause 148. The electrochemical cell of Clause 147, wherein
the base is NaOH.
[0352] Clause 149. The electrochemical cell of any one of Clauses
146-148, wherein the pH of the first polar electrolyte solution is
between about 8 and about 14.
[0353] Clause 150. The electrochemical cell of Clause 149, wherein
the pH of the first polar electrolyte solution is between about 11
and about 14.
[0354] Clause 151. The electrochemical cell of any one of Clauses
140-150, wherein the porous stabilizer is borosilicate.
[0355] Clause 152. The electrochemical cell of any one of Clauses
139-151, wherein the separation agent is a salt.
[0356] Clause 153. The electrochemical cell of Clause 152, wherein
the salt is calcium chloride.
[0357] Clause 154. The electrochemical cell of Clause 152, wherein
the salt is sodium sulfate.
[0358] Clause 155. The electrochemical cell of any one of Clauses
139-154, wherein the cell is configured to operate in a flow
mode.
[0359] Clause 156. The electrochemical cell of Clause 155, further
comprising an inflow solution comprising an aqueous solution
comprising a base, an oxidant, and a separation agent.
[0360] Clause 157. The electrochemical cell of Clause 156, wherein
the base is sodium hydroxide, the separate agent is sodium sulfate,
and the oxidant S.sub.2O.sub.8.sup.2-.
[0361] Clause 158. The electrochemical cell of any one of Clauses
155-157, wherein an aqueous solution comprising base and sodium
sulfate outflows from the cell.
[0362] Clause 159. The electrochemical cell of any one of Clauses
155-157, further comprising an outflow solution comprising an
aqueous solution of a base.
[0363] Clause 160. The electrochemical cell of Clause 159, wherein
the base is sodium hydroxide.
[0364] Clause 161. The electrochemical cell of any one of Clauses
139-160, wherein a current collector is placed within the first
electrolyte solution.
[0365] Clause 162. The electrochemical cell of Clause 161, wherein
the current collector is a metal.
[0366] Clause 163. The electrochemical cell of Clause 161, wherein
the current collector is a non-metal.
[0367] Clause 164. The electrochemical cell of Clause 163, wherein
the current collector is carbon foam.
[0368] Clause 165. The electrochemical cell of any one of Clauses
139-164, further comprising glass wool placed in between the first
and second polar electrolyte solutions.
[0369] Clause 166. The electrochemical cell of any one of Clauses
139-165, wherein the second polar electrolyte solution comprises an
alcohol.
[0370] Clause 167. The electrochemical cell of any one of Clauses
139-166, wherein the suitable metal ion is Zn.sup.2+.
[0371] Clause 168. The electrochemical cell of any one of Clauses
139-166, wherein the suitable metal ion is Al.sup.3+.
[0372] Clause 169. The electrochemical cell of any one of Clauses
139-168, wherein the second polar electrolyte solution is an
alcoholic solution and further comprises a base.
[0373] Clause 170. The electrochemical cell of Clause 169, wherein
the base is KOH.
[0374] Clause 171. The electrochemical cell of Clause 169, wherein
the base is NaOH.
[0375] Clause 172. The electrochemical cell of any one of Clauses
169-171, wherein the pH of the second polar electrolyte solution is
between about 8 and about 14.
[0376] Clause 173. The electrochemical cell of Clause 172, wherein
the pH of the second polar electrolyte solution is between about 11
and about 14.
[0377] Clause 174. The electrochemical cell of any one of Clauses
166-173, wherein the separation agent is a salt and the alcohol is
ethanol, methanol, or both.
[0378] Clause 175. The electrochemical cell of Clause 174, wherein
the salt is CaCl.sub.2.
[0379] Clause 176. The electrochemical cell of Clause 174, wherein
the salt is sodium sulfate.
[0380] Clause 177. The electrochemical cell of any one of Clauses
166-176, wherein the alcohol is ethanol.
[0381] Clause 178. The electrochemical cell of any one of Clauses
139-177, wherein a current collector is placed within the second
electrolyte solution.
[0382] Clause 179. The electrochemical cell of Clause 178, wherein
the current collector is a metal.
[0383] Clause 180. The electrochemical cell of Clause 178, wherein
the current collector is a non-metal.
[0384] Clause 181. The electrochemical cell of Clause 180, wherein
the current collector is carbon foam.
[0385] Clause 182. The electrochemical cell of any one of Clauses
166-181, wherein the cell is configured to operate in a flow
mode.
[0386] Clause 183. The electrochemical cell of Clause 182, further
comprising an inflow stream comprising a polar solution comprising
an alcohol, a base, a separation agent, and a metal capable of
dissociating into a suitable metal ion.
[0387] Clause 184. The electrochemical cell of Clause 183, wherein
the alcohol is ethanol or methanol or both, the base is sodium
hydroxide, and the suitable metal ion is Al.sup.3+.
[0388] Clause 185. The electrochemical cell of any one of Clauses
166-184, further comprising an outflow stream comprising an
alcohol, a base, and a separation salt.
[0389] Clause 186. The electrochemical cell of Clause 185, wherein
the separation salt is sodium sulfate, and the base is sodium
hydroxide.
[0390] Clause 187. The electrochemical cell of Clauses 185 or 186,
wherein the alcohol is ethanol.
[0391] Clause 188. The electrochemical cell of any one of Clauses
139-187, wherein hydrogen gas is generated in the second
electrolyte solution.
[0392] Clause 189. The electrochemical cell of Clause 188, wherein
the hydrogen gas is directed to a hydrogen compressor.
[0393] Clause 190. A battery system comprising one or more
electrochemical cells of any one of Clauses 139-189 and a hydrogen
compressor.
[0394] Clause 191. The battery system of Clause 190 wherein the
hydrogen is used to power a process application.
[0395] Clause 192. The battery system of Clause 191, wherein the
process application is a fuel cell.
[0396] Clause 193. An electrochemical cell comprising: [0397] a. a
cathode; [0398] b. an anode adjacent the cathode at a distance;
[0399] c. a first polar aqueous electrolyte solution in contact
with the cathode and disposed within the distance comprising
S.sub.2O.sub.8.sup.2-; [0400] d. a second polar electrolyte
alcoholic solution in contact with the anode and disposed within
the distance comprising Al.sup.3+; and [0401] e. borosilicate
within both the first and second electrolyte solutions; wherein the
first and second electrolyte solutions are in contact with each
other and are immiscible, and wherein there is no membrane in
between the first and second electrolyte solutions.
[0402] Clause 194. The electrochemical cell of Clause 193, wherein
the first polar electrolyte solution and second polar electrolyte
solution are of different densities and wherein the first
electrolyte solution further comprises a halide salt and the second
electrolyte solution further comprises a metal sulfate salt.
[0403] Clause 195. The electrochemical cell of Clause 194, wherein
the alcohol is methanol or ethanol, the halide salt is CaCl.sub.2
and the metal sulfate salt is Na.sub.2SO.sub.4.
[0404] Clause 196. The electrochemical cell of Clause 195, wherein
the pH of the first electrolyte and second electrolyte solutions
are adjusted to between about 11 to about 13 each.
[0405] Clause 197. The electrochemical solution of Clause 193,
wherein the first and second electrolyte solutions further comprise
a base.
[0406] Clause 198. The electrochemical solution of Clause 197,
wherein the base is sodium, calcium or potassium hydroxide.
[0407] Clause 199. The electrochemical cell of any one of Clauses
193-198, wherein the cathode is copper, carbon, or both and the
anode is aluminum.
[0408] Clause 200. The electrochemical cell of Clause 199, wherein
the cathode is a copper brush.
[0409] Clause 201. The electrochemical cell of any one of Clauses
193-200, wherein the borosilicate is Pyrex.RTM. wool.
[0410] Clause 202. The electrochemical cell of any one of Clauses
193-201 wherein the cell is configured to run in a flow mode.
[0411] Clause 203. An electrochemical battery comprising one or
more electrochemical cells of any one of Clauses 193-202.
[0412] Clause 204. The electrochemical battery of Clause 203,
wherein the number of electrochemical cells is greater than one and
the electrochemical cells are arranged in a parallel geometry.
[0413] Clause 205. The electrochemical battery of Clause 204,
wherein the cells are arranged in a voltaic pile.
[0414] Clause 206. The electrochemical battery of any one of
Clauses 203-205, wherein the battery delivers electricity to a
process application.
[0415] Clause 207. The electrochemical battery of Clause 206,
wherein the process application is selected from solar farms, wind
farms, household appliances, consumer goods, and toys.
[0416] Clause 208. A method of delivering electricity from an
electrochemical cell of any one of Clauses 193-202 to a process
application.
[0417] Clause 209. The method of Clause 208, wherein the process
application is selected from solar farms, wind farms, household
appliances, consumer products, and toys.
[0418] Clause 210. The electrochemical cell of Clause 201, wherein
the borosilicate has a pore size of about 8 microns.
[0419] Clause 211. An electrochemical cell comprising: [0420] a. a
non-metallic cathode; [0421] b. a non-metallic anode adjacent the
cathode at a distance; [0422] c. a first polar aqueous electrolyte
solution in contact with the cathode and disposed within the
distance comprising S.sub.2O.sub.8.sup.2-; and [0423] d. a second
polar electrolyte alcoholic solution in contact with the anode and
disposed within the distance comprising a metal solid; wherein the
first and second electrolyte solutions are in contact with each
other and are immiscible, and wherein there is no membrane in
between the first and second electrolyte solutions.
[0424] Clause 212. The electrochemical cell of Clause 211, wherein
the metal solid is dispersed through the solution in powder form
and wherein borosilicate is placed within both the first and second
electrolyte solutions.
[0425] Clause 213. The electrochemical cell of Clause 212, wherein
the metal is zinc.
[0426] Clause 214. The electrochemical cell of Clause 212, wherein
the metal is aluminum.
[0427] Clause 215. The electrochemical cell of any one of Clauses
211-214, wherein the non-metallic cathode is carbon foam.
[0428] Clause 216. The electrochemical cell of any one of Clauses
211-215, wherein the non-metallic anode is carbon foam.
[0429] Clause 217. The electrochemical cell of any one of Clauses
212-216 wherein the average particle size of the powder is less
than about 5 microns.
[0430] Clause 218. The electrochemical cell of any one of Clauses
212-216, wherein the average particle size of the powder is between
about 5 and about 30 microns.
[0431] Clause 219. A method of boosting current in an
electrochemical cell comprising the steps of adding oxidant to the
second electrolyte solution of any one of Clauses 211-218.
[0432] Clause 220. An electrochemical cell comprising: [0433] a. a
cathode; [0434] b. an anode adjacent to the cathode at a distance;
[0435] c. a first aqueous electrolyte solution in contact with the
cathode and disposed within the distance comprising an oxidant;
[0436] d. a second polar electrolyte solution in contact with the
anode and disposed within the distance comprising a metal and an
oxidant; and [0437] e. a separation agent; wherein the first and
second electrolyte solutions are in contact with each other and are
immiscible, and wherein there is no membrane in between the first
and second solutions.
[0438] Clause 221. The electrochemical cell of Clause 220, wherein
the second polar electrolyte solution is an alcoholic solution.
[0439] Clause 222. The electrochemical cell of Clause 221, wherein
the alcohol is ethanol or methanol.
[0440] Clause 223. The electrochemical cell of any one of Clauses
220-222, wherein the oxidant is S.sub.2O.sub.8.sup.2- or sodium
peroxydisulfate, or both, the metal is aluminum, the separation
agent is sodium sulfate, and the cathode and anode are carbon
foam.
[0441] Clause 224. The electrochemical cell of Clause 223, wherein
a porous stabilizer is in the first and second electrolyte
solutions.
[0442] Clause 225. The electrochemical cell of Clause 224, wherein
the porous stabilizer is glass wool, a borosilicate, or both.
[0443] Clause 226. The electrochemical cell of any one of Clauses
220-225, configured to operate in a flow mode.
[0444] Clause 227. A method which comprises providing additional
oxidant to the electrochemical cell of any one of Clauses
220-226.
[0445] Clause 228. The electrochemical cell of Clause 226 or 227,
further comprising an inflow stream comprising an aqueous
electrolyte solution.
[0446] Clause 229. The electrochemical cell of Clause 228, wherein
the inflow stream further comprises an oxidant.
[0447] Clause 230. The electrochemical cell of Clause 229, wherein
the oxidant is sodium peroxydisulfate or a solution comprising
peroxydisulfate anion or both.
[0448] Clause 231. The electrochemical cell of any one of Clauses
226 and 228-230, wherein an aqueous solution outflows from the
cell.
[0449] Clause 232. A method which comprises removing metal sulfate
from the electrochemical cell of any one of Clauses 226 and
228-230.
[0450] Clause 233. The electrochemical cell of Clause 229, wherein
the oxidant is in an aqueous basic solution.
[0451] Clause 234. The electrochemical cell of Clause 233, wherein
the base is NaOH.
[0452] Clause 235. The electrochemical cell of Clause 229 or 230
wherein the oxidant is solid Na.sub.2S.sub.2O.sub.8.
[0453] Clause 236. The electrochemical cell of any one of Clauses
220-235, which produces between about 10 Watt-hours/kg of
electrolyte and about 100 Watt-hours/kg of electrolyte.
[0454] Clause 237. The electrochemical cell of Clause 208, wherein
between about 40 Watt-hours/kg of electrolyte and about 80
Watt-hours/kg of electrolyte is produced.
[0455] Clause 238. A vehicle comprising one or more electrochemical
cells of clauses 1-25, 40-56, 72-79, 88-115, 117-126, or
130-138.
[0456] Clause 239. A vehicle comprising one or more batteries of
clauses 26, 57-67, or 80-87.
[0457] Clause 240. The vehicle of clause 238, wherein the vehicle
is selected from scooters, motorized grocery cars, battery backups,
forklifts, trucks, passenger cars, lift trucks, motorcycles, fork
trucks, planes, boats, quads, and tractors.
[0458] Clause 241. The vehicle of clause 239, wherein the vehicle
is selected from scooters, motorized grocery cars, battery backups
and other stationary applications, forklifts, trucks, passenger
cars, vehicular range extenders, battery chargers, lift trucks,
motorcycles, fork trucks, planes, boats, quads, and tractors.
* * * * *