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Patent 2829224 Summary

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(12) Patent: (11) CA 2829224
(54) English Title: METAL-FREE AQUEOUS ELECTROLYTE ENERGY STORAGE DEVICE
(54) French Title: DISPOSITIF DE STOCKAGE D'ENERGIE SANS METAL A ELECTROLYTE AQUEUX
Status: Deemed expired
Bibliographic Data
(51) International Patent Classification (IPC):
  • H01M 10/12 (2006.01)
  • H01M 2/02 (2006.01)
  • H01M 2/10 (2006.01)
  • H01M 4/50 (2010.01)
  • H01M 4/68 (2006.01)
(72) Inventors :
  • WHITACRE, JAY (United States of America)
  • HUMPHREYS, DON (United States of America)
  • YANG, WENZHUO (United States of America)
  • LYNCH-BELL, EDWARD (United States of America)
  • MOHAMAD, ALEX (United States of America)
  • WEBER, ERIC (United States of America)
(73) Owners :
  • AQUION ENERGY INC. (United States of America)
(71) Applicants :
  • AQUION ENERGY INC. (United States of America)
(74) Agent: BERESKIN & PARR LLP/S.E.N.C.R.L.,S.R.L.
(74) Associate agent:
(45) Issued: 2016-10-04
(86) PCT Filing Date: 2012-03-08
(87) Open to Public Inspection: 2012-09-13
Examination requested: 2015-11-26
Availability of licence: N/A
(25) Language of filing: English

Patent Cooperation Treaty (PCT): Yes
(86) PCT Filing Number: PCT/US2012/028228
(87) International Publication Number: WO2012/122353
(85) National Entry: 2013-09-05

(30) Application Priority Data:
Application No. Country/Territory Date
61/450,774 United States of America 2011-03-09
13/043,787 United States of America 2011-03-09

Abstracts

English Abstract


An electrochemical device including a hermetically sealed, electrochemically
inert,
polymer housing, stacks of electrodes stacked in a prismatic configuration and
arranged side
by side m the housing, each stack including an anode electrode, a cathode
electrode, and an
electrolyte, separator sheets disposed between adjacent anode and cathode
electrodes of each
stack and extending continuously between at least two of the stacks, and anode
and cathode
current collectors extending continuously between at least two of the stacks.
Each separator
sheet extends over or under anode boundary areas between adjacent anode
electrodes in
adjacent stacks, and over or under cathode boundary areas between adjacent
cathode
electrodes in adjacent stacks. Each anode current collector extends between
adjacent anode
electrodes in each stack, and over or under anode boundary areas between
adjacent anode
electrodes in adjacent stacks. Each cathode current collector extends between
adjacent
cathode electrodes in each stack, and over or under cathode boundary areas
between adjacent
cathode electrodes in adjacent stacks.


French Abstract

L'invention concerne un dispositif électrochimique comprenant une enveloppe et une pile d'éléments électrochimiques dans l'enveloppe. Chaque élément électrochimique comprend une électrode d'anode, une électrode de cathode, un séparateur situé entre l'électrode d'anode et l'électrode de cathode, et un électrolyte. Le dispositif électrochimique comprend également un collecteur de courant situé entre des éléments électrochimiques adjacents, un bus d'anode relié fonctionnellement aux anodes des éléments électrochimiques de la pile et un bus de cathode relié fonctionnellement aux cathodes des éléments électrochimiques de la pile. L'enveloppe, l'électrode d'anode, l'électrode de cathode, le séparateur, le bus d'anode et le bus de cathode sont non métalliques.

Claims

Note: Claims are shown in the official language in which they were submitted.


WHAT IS CLAIMED IS:
1 An electrochemical device, comprising
a housing,
a plurality of stacks of electrodes arranged side by side in the housing, each
stack
comprising an anode electrode, a cathode electrode, and an electrolyte,
a plurality of separator sheets, wherein each separator sheet of the plurality
of
separator sheets extends continuously between at least two of the plurality of
stacks, such
that each separator sheet is located between adjacent anode and cathode
electrodes of each
stack, and
a plurality of current collectors;
wherein:
the housing comprises a hermetically sealed, electrochemically inert polymer
housing, and the electrodes in each of the stacks are stacked in a prismatic
configuration;
each current collector of the plurality of current collectors extends
continuously
between at least two of the plurality of stacks;
each separator sheet extends over or under anode boundary areas between
adjacent
anode electrodes in adjacent stacks;
each separator sheet extends over or under cathode boundary areas between
adjacent cathode electrodes in adjacent stacks;
each anode current collector of the plurality of current collectors extends
between
adjacent anode electrodes in each stack, and over and under the anode boundary
areas
between adjacent anode electrodes in adjacent stacks; and
each cathode current collector of the plurality of current collectors extends
between
adjacent cathode electrodes in each stack, and over and under the cathode
boundary areas
between adjacent anode electrodes in adjacent stacks
2. The electrochemical device of claim 1, wherein the anode and cathode
electrodes
are between 0 05 and 1 cm thick, and the current collectors comprise carbon
current
collectors.
3. The electrochemical device of claim 2, wherein the current collectors
comprise
carbon fiber paper, an inert substrate coated with carbon material or
exfoliated graphite
having a density of greater than 0 6 g/cm3.
4. The electrochemical device of claim 1, wherein the electrochemical device
is a
hybrid aqueous electrolyte energy storage device.
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5. The electrochemical device of claim 4, wherein the cathode comprises an
alkali
ion intercalation material and the anode is a pseudocapacitive or
electrochemical double
layer capacitive material that is electrochemically stable to less than ¨1.3 V
vs NHE
6. The electrochemical device of claim 5, wherein the cathode electrode
comprises a
doped or undoped cubic spinel .lambda.-MnO2-type material or Na4Mn9O18 tunnel
structured
orthorhombic material, the anode electrode comprises activated carbon,
titanium oxide
material or phospho-olivine material, and the electrolyte comprises sodium
ions.
7. The electrochemical device of claim 6, wherein the electrolyte is an
aqueous
solution containing dissolved alkali ions that are able to interact with both
anode and
cathode such that charge is stored via intercalation at the cathode electrode
and by
pseudocapacitive non-faradic surface reaction at the anode electrode.
8. The electrochemical device of claim 1, further comprising a first plurality
of tabs
operatively connected to the cathode current collectors of the plurality of
current collectors
and a second plurality of tabs operatively connected to the anode current
collectors of the
plurality of current collectors.
9. The electrochemical device of claim 2, wherein
the anode electrode comprises a pressed granular anode electrode; and
the cathode electrode comprises a pressed granular cathode electrode
10. The electrochemical device of claim 1, wherein each separator sheet of the

plurality of separator sheets extends continuously between a first stack and a
second stack of
the plurality of stacks, such that each separator sheet is located between
adjacent anode and
cathode electrodes of the first stack, and between adjacent anode and cathode
electrodes of
the second stack.
11. An electrochemical device, comprising.
a housing;
a plurality of stacks of electrodes arranged side by side in the housing, each
stack
comprising an anode electrode, a cathode electrode, and an electrolyte,
a plurality of separator sheets, such that each separator sheet is located
between
adjacent anode and cathode electrodes of each stack; and
a plurality of current collectors;
wherein.
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each separator sheet extends over or under anode boundary areas between
adjacent
anode electrodes in adjacent stacks,
each separator sheet extends over or under cathode boundary areas between
adjacent cathode electrodes in adjacent stacks,
each anode current collector of the plurality of current collectors extends
between
adjacent anode electrodes in each stack, and over and under the anode boundary
areas
between adjacent anode electrodes in adjacent stacks, and
each cathode current collector of the plurality of current collectors extends
between
adjacent cathode electrodes in each stack, and over and under the cathode
boundary areas
between adjacent anode electrodes in adjacent stacks.
12. The electrochemical device of claim 11, further comprising a first
plurality of
tabs operatively connected to the cathode current collectors of the plurality
of current
collectors and a second plurality of tabs operatively connected to the anode
current
collectors of the plurality of current collectors.
13. The electrochemical device of claim 12, wherein
the anode electrode comprises a pressed granular anode electrode, and
the cathode electrode comprises a pressed granular cathode electrode
14. The electrochemical device of claim 11, wherein at least 50% of the anode
boundary areas are not aligned with respective cathode boundary areas across
the separator
sheet.
-33-

Description

Note: Descriptions are shown in the official language in which they were submitted.


CA 02829224 2016-06-07
METAL-FREE AQUEOUS ELECTROLYTE ENERGY STORAGE DEVICE
RELATED APPLICATIONS
[0001] This application claims the priority benefit of U.S. Application
61/450,774, filed
March 9, 2011, and of U.S. Application 13/043,787, filed March 9, 2011.
FIELD
[0002] The present invention is directed to aqueous batteries and hybrid
energy storage
devices, and in particular to electrochemical storage devices without metal
parts in contact
with the aqueous electrolyte.
BACKGROUND
[0003] Small renewable energy harvesting and power generation technologies
(such as
solar arrays, wind turbines, micro sterling engines, and solid oxide fuel
cells) are
proliferating, and there is a commensurate strong need for intermediate size
secondary
(rechargeable) energy storage capability. Batteries for these stationary
applications typically
store between 1 and 50 kWh of energy (depending on the application) and have
historically
been based on the lead-acid (Pb acid) chemistry. Banks of deep-cycle lead-acid
cells are
assembled at points of distributed power generation and are known to last 1 to
10 years
depending on the typical duty cycle. While these cells function well enough to
support this
application, there are a number of problems associated with their use,
including: heavy use of
environmentally unclean lead and acids (it is estimated that the Pb-acid
technology is
responsible for the release of over 100,000 tons of Pb into the environment
each year in the
US alone), significant degradation of performance if held at intermediate
state of charge or
routinely cycled to deep levels of discharge, a need for routine servicing to
maintain
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performance, and the implementation of a requisite recycling program. There is
a strong
desire to replace the Pb-acid chemistry as used by the automotive industry.
Unfortunately the
economics of alternative battery chemistries has made this a very unappealing
option to date.
[0004] Despite all of the recent advances in battery technologies, there
are still no low-
cost, clean alternates to the Pb-acid chemistry. This is due in large part to
the fact that Pb-
acid batteries are remarkably inexpensive compared to other chemistries
($200/kWh), and
there is currently a focus on developing higher-energy systems for
transportation applications
(which are inherently significantly more expensive than Pb-acid batteries).
SUMMARY
[0005] An embodiment relates to an electrochemical device including a
housing and a
stack of electrochemical cells in the housing. Each electrochemical cell
includes an anode
electrode, a cathode electrode, a separator located between the anode
electrode and the
cathode electrode and an electrolyte. The electrochemical device also includes
a current
collector located between adjacent electrochemical cells, an anode bus
operatively connected
to the anodes of the electrochemical cells in the stack and a cathode bus
operatively
connected to the cathodes of the electrochemical cells in the stack. The
housing, the anode
electrode, the cathode electrode, the separator, the anode bus and the cathode
bus are non-
metallic. "Non-metallic" in the context of this patent specification means
electrically
conductive materials which are not made of pure metal or metal alloys.
Examples of non-
metallic materials include, but are not limited to, electrically conductive
metal oxides or
carbon.
[0006] Another embodiment relates to a method of making an electrochemical
device.
The method includes stacking a first non-metallic anode electrode, stacking a
first non-
metallic separator on the anode electrode and stacking a first non-metallic
cathode electrode
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on the separator. The method also includes operatively connecting the first
anode electrode
to a non-metallic anode bus and operatively connecting the first cathode
electrode to a non-
metallic cathode bus.
[0007] An embodiment relates to an electrochemical device that includes a
housing and a
stack of electrochemical cells in the housing. Each electrochemical cell
includes an anode
electrode, a cathode electrode, a separator located between the anode
electrode and the
cathode electrode and an electrolyte. The device also includes a plurality of
carbon cathode
and anode current collectors alternately located between adjacent
electrochemical cells and a
plurality of tabs operatively connected to the plurality of carbon cathode and
anode current
collectors, the plurality of tabs configured to connect to an electrical bus.
A cathode
electrode of a first electrochemical cell electrically contacts a first
cathode current collector.
A cathode electrode of a second electrochemical cell electrically contacts the
first cathode
current collector. The second electrochemical cell is located adjacent to a
first side of the
first electrochemical cell in the stack. An anode electrode of the first
electrochemical cell
electrically contacts a second anode current collector. An anode electrode of
a third
electrochemical cell electrically contacts the second anode current collector.
The third
electrochemical cell is located adjacent to a second side of the first
electrochemical cell in the
stack.
[0008] Another embodiment relates to an electrochemical device including a
housing and
a stack of electrochemical cells in the housing. Each electrochemical cell
includes a pressed
granular anode electrode, a pressed granular cathode electrode, a separator
located between
the anode electrode and the cathode electrode and an electrolyte. The
electrochemical device
also includes a plurality of cathode and anode current collectors alternately
located between
adjacent electrochemical cells. A cathode electrode of a first electrochemical
cell electrically
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contacts a first cathode current collector. A cathode electrode of a second
electrochemical
cell electrically contacts the first cathode current collector. The second
electrochemical cell
is located adjacent to a first side of the first electrochemical cell in the
stack. An anode
electrode of the first electrochemical cell electrically contacts a second
anode current
collector and an anode electrode of a third electrochemical cell electrically
contacts the
second anode current collector. The third electrochemical cell is located
adjacent to a second
side of the first electrochemical cell in the stack.
[0009] Another embodiment relates to an electrochemical device that
includes a housing
and a plurality of stacks of electrochemical cells arranged side by side in
the housing. Each
electrochemical cell includes an anode electrode, a cathode electrode, a
separator located
between the anode electrode and the cathode electrode and an electrolyte. The
device also
includes a current collector located between adjacent electrochemical cells in
each of the
stacks. The separator of at least one cell comprises a separator sheet which
extends
continuously between at least two of the plurality of stacks.
[0010] An embodiment relates to an electrochemical device including a
housing and a
stack of electrochemical cells in the housing. Each electrochemical cell
includes an anode
electrode, a cathode electrode, a separator located between the anode
electrode and the
cathode electrode and an electrolyte. The electrochemical device also includes
a graphite
sheet located between adjacent electrochemical cells in the stack. The
graphite sheet is a
current collector for adjacent electrochemical cells.
[0011] Another embodiment relates to an electrochemical cell including an
anode
electrode with a plurality of discrete anode electrode members separated by
anode boundary
areas and a cathode electrode with a plurality of discrete cathode electrode
members
separated by cathode boundary areas. The electrochemical cell also includes a
separator
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located between the anode electrode and the cathode electrode and an
electrolyte. The
electrolyte is located in the separator and in the anode electrode and cathode
electrode
boundary areas. Further, at least 50% of the anode boundary areas are not
aligned with a
respective cathode boundary areas across the separator.
[0012] Another embodiment relates to a method of making an electrochemical
device
having a stack of electrochemical cells. The method includes forming a stack
electrochemical cells and pouring an electrically insulating polymer around
the stack of
electrochemical cells and solidifying the polymer to form a solid insulating
shell or providing
a preformed solid insulating shell around the stack of electrochemical cells.
[0013] Another embodiment relates to a method of making an electrochemical
device.
The method includes stacking an anode electrode comprising a plurality of
discrete anode
electrode members separated by anode boundary areas, stacking a separator on
the anode
electrode and stacking a cathode electrode comprising a plurality of discrete
cathode
electrode members separated by cathode boundary areas on the separator. At
least 50% of
the anode boundary areas are not aligned with a respective cathode boundary
areas across the
separator and the plurality of anode electrode members and the plurality of
cathode electrode
members are arranged in an array of rows and columns.
[0014] Another embodiment relates to a secondary hybrid aqueous energy
storage device.
The secondary hybrid aqueous energy storage device includes a housing and a
stack of
electrochemical cells in the housing. Each electrochemical cell includes an
anode electrode,
a cathode electrode and a separator located between the anode electrode and
the cathode
electrode, an electrolyte and a graphite sheet located between adjacent
electrochemical cells.
The anode and cathode electrodes are between 0.05 and 1 cm thick.
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BRIEF DESCRIPTION OF THE DRAWINGS
[0015] FIG. 1 is a schematic illustration of a prismatic stack of
electrochemical cells
according to an embodiment.
[0016] FIG. 2 is a schematic illustration of a detail of a sandwiched
current collector
according to an embodiment.
[0017] FIG. 3 is a perspective view of an electrochemical device having a
plurality of
prismatic stacks of electrochemical cells according to an embodiment.
[0018] Fig. 4 is another perspective view of the embodiment illustrated in
FIG. 3.
[0019] FIG. 5 is a perspective view of an electrochemical device having a
single
prismatic stack of electrochemical cells according to an embodiment.
[0020] FIG. 6 is a perspective view of the embodiment of FIG. 5 with the
electrochemical
cells removed for clarity.
[0021] FIG. 7 is a schematic side cross sectional view illustrating details
of a portion of
the embodiment illustrated in FIG. 5.
[0022] FIG. 8 is a plot of cell potential versus cell capacity of an
embodiment.
[0023] FIG. 9 is a schematic illustration of an electrochemical cell
according to an
embodiment of the invention. The electrochemical cell may be stacked in a
bipolar or
prismatic stack configuration.
[0024] FIG. 10 is a cross sectional view of an electrochemical cell with an
anode
electrode composed of discrete anode electrode members and a cathode electrode
composed
of discrete cathode electrode members according to an embodiment. The
electrochemical
cell may be stacked in a bipolar or prismatic stack configuration.
[0025] FIG. 11 is a schematic illustration of an electrochemical device
comprising a
bipolar stack of electrochemical cells according to an embodiment of the
invention.
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CA 02829224 2016-06-07
[0026] Figure 12(a) is a plot of cell potential vs. accumulated capacity
under charge and
discharge conditions over 30 cycles. Figure 12(b) is a plot of cell charge and
discharge
capacity and efficiency as a function of cycle.
DETAILED DESCRIPTION
[0027] Embodiments of the invention are drawn to electrochemical energy
storage
systems, such as primary and secondary batteries and hybrid energy storage
systems
described below. While secondary hybrid aqueous energy storage systems
described below
are preferred embodiments of the invention, the invention is also applicable
to any suitable
electrochemical energy storage systems, such as aqueous and non-aqueous
electrolyte
containing batteries (e.g., having anodes and cathodes which intercalate ions
from the
electrolyte, including Li-ion batteries, etc.) or electrolytic capacitors
(also known as
supercapacitors and ultracapacitors, e.g., having capacitor or pseudocapacitor
anode and
cathode electrodes that store charge through a reversible nonfaradiac reaction
of cations on
the surface of the electrode (double-layer) and/or pseudocapacitance rather
than by
intercalating alkali ions).
[0028] Hybrid electrochemical energy storage systems of embodiments of the
present
invention include a double-layer capacitor or pseudocapacitor electrode (e.g.,
anode) coupled
with an active electrode (e.g., cathode). In these systems, the capacitor or
pseudocapacitor
electrode stores charge through a reversible nonfaradiac reaction of alkali
cations on the
surface of the electrode (double-layer) and/or pseudocapacitance, while the
active electrode
undergoes a reversible faradic reaction in a transition metal oxide that
intercalates and
deintercalates alkali cations similar to that of a battery.
[0029] An example of a Na-based system has been described in U.S. patent
publication
number US-2009-0253025-A1, published on October 8, 2009,
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which utilizes a spinel structure LiMn204 battery electrode, an activated
carbon capacitor
electrode, and an aqueous Na2SO4 electrolyte. In this system, the negative
anode electrode
stores charge through a reversible nonfaradiac reaction of Na-ion on the
surface of an
activated carbon electrode. The positive cathode electrode utilizes a
reversible faradiac
reaction of Na-ion intercalation/deintercalation in spinel lambda-Mn02.
[0030] In an alternative system, the cathode electrode may comprise a non-
intercalating
(e.g., non-alkali ion intercalating) Mn02 phase. Example non-intercalating
phases of
manganese dioxide include electrolytic manganese dioxide (EMD), alpha phase
and gamma
phase.
[0031] Figure 1 illustrates a prismatic stack 100P of electrochemical cells
102 according
to an embodiment. In this embodiment, each of the electrochemical cells 102 in
the prismatic
stack 100P includes an anode electrode 104, a cathode electrode 106, and a
separator 108
located between the anode electrode 104 and the cathode electrode 106. The
electrochemical
cells 102 also include an electrolyte located between the anode electrode 104
and the cathode
electrode 106 (i.e., impregnated in the separator and/or the electrodes). Each
of the
electrochemical cells 102 of the prismatic stack 100P may be mounted in a
frame 112 (see
Figures 9-10). Further, the prismatic stack 100P may be enclosed in a housing
116 (see
Figures 3-6) instead of or in addition to. Additional features of the housing
116 are provided
in more detail below in relation to the embodiments illustrated in Figures 3-
6. Further
embodiments of the electrochemical cells 102 are illustrated in Figures 9 and
10 and
discussed in more detail below. The prismatic stack 100P also includes a
plurality of carbon
cathode and anode current collectors 110a, 110c alternately located between
adjacent
electrochemical cells 102. The current collectors may comprise any suitable
form of
electrically conductive carbon, such as, exfoliated graphite, carbon fiber
paper, or an inert
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CA 02829224 2015-11-26
substrate coated with carbon material. Preferably, the collectors comprise
graphite having a
density greater than 0.6 g/cm3.
[0032] In an embodiment, the prismatic stack 100P includes a plurality of
electrically
conductive contacts (e.g., tabs) 120 operatively connected to the plurality of
carbon cathode
and anode current collectors 110a, 110c. The electrically conductive contacts
120 may be
affixed to one side of the carbon cathode and anode current collectors 110a,
110c.
Alternatively, as illustrated in Figure 2, the electrically conductive
contacts 120 may be
located in between two carbon current collectors 110a or 110c, making a
sandwich structure
110s. Preferably, the prismatic stack 100P also includes two electrical buses
122a, 122c.
One electrical bus 122a electrically connected to the anode current collectors
110a in the
prismatic stack 100P and one electrical bus 122c connected to the cathode
current collectors
110c in the prismatic stack 100P. In an embodiment, the electrical connection
from the
anode and cathode current collectors 110a, 110c to the electrical buses 122a,
122c is via the
electrically conductive contacts 120. In this manner, the electrochemical
cells 102 in the
stack 100P can be electrically connected in parallel.
[0033] In an embodiment, the positive cathode bus 122c electrically
connects the cathode
electrodes 106 of the electrochemical cells 102 in the stack 100P in parallel
to a positive
electrical output of the stack, while the negative anode bus 122a electrically
connects the
anode electrodes 104 of the electrochemical cells 102 in the stack 100P in
parallel to a
negative electrical output of the stack 100P.
[0034] In the prismatic stack 100P, the cathode current collector 110c may
be located in
between adjacent electrochemical cells 102. That is, pairs of electrochemical
cells 102 are
configured "front-to-front" and "back-to-back." As an example, consider a
prismatic stack
100P in which the first electrochemical cell 102 is in the center of the stack
100P. In a first
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pair of cells 102 the first cathode current collector 110c is located such
that a cathode
electrode 106 of the first electrochemical cell 102 electrically contacts the
first cathode
current collector 110c and a cathode electrode 106 of a second electrochemical
cell 102 also
electrically contacts the first cathode current collector 110c. The second
electrochemical cell
102 is located adjacent to a first (cathode) side of the first electrochemical
cell in the
prismatic stack 100P.
[0035] A third electrochemical cell 102 is located adjacent to the second
(anode) side of
the first electrochemical cell 102 in the prismatic stack 100P. The anode
electrode 104 of the
first electrochemical cell 102 electrically contacts a first anode current
collector 110a and the
anode electrode 104 of the third electrochemical cell 102 also electrically
contacts the first
anode current collector 110a. Stacking can continue in this manner. The
resulting prismatic
stack 100P therefore may include a plurality of electrochemical cells 102 that
are stacked in
pairs, front-to-front and back-to-back, alternating adjacent anode electrodes
104 and adjacent
cathode electrodes 106.
[0036] The prismatic stack 100P may be described in terms of an axial
direction. For the
stack 100P illustrated in Figure 1, the axial direction is parallel to the
buses 122a, 122c. The
electrochemical cells 102 in the stack 100P are stacked in an axial direction
along an axis of
the stack 100P. Each of the odd or even numbered electrochemical cells 120 in
the stack
have a cathode electrode 106 facing a first end of the axis of the stack 100P
and an anode
electrode 104 facing the opposite, second end of the axis of the stack 100P.
Each of the other
ones of the even or odd numbered electrochemical cells 102 in the stack 100P
have a cathode
electrode 106 facing the second end of the axis of the stack 100P and an anode
electrode 104
facing the opposite, first end of the axis of the stack 100P.
[0037] In an embodiment, the prismatic stack 100P includes electrochemical
cells 102 in
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CA 02829224 2016-06-07
which the anode electrode 104 and/or the cathode electrode 106 are made of
pressed granular
pellets. The anode electrode 104 and cathode electrode 106 may be between 0.05
and 1 cm
thick. Alternatively, the anode electrode 104 and cathode electrode 106 are
between 0.05 and
0.15 cm thick. Boundary areas between the pressed granular pellets may provide
reservoirs
for electrolyte, as will be described in more detail below.
[0038] In an embodiment, the electrochemical cells 102 are secondary hybrid
aqueous
energy storage devices. In an embodiment, the cathode electrode 106 in
operation reversibly
intercalates alkali metal cations. The anode electrode 104 may comprise a
capacitive
electrode which stores charge through a reversible nonfaradiac reaction of
alkali metal
cations on a surface of the anode electrode 104 or a pseudocapacitive
electrode which
undergoes a partial charge transfer surface interaction with alkali metal
cations on a surface
of the anode electrode 104. In an embodiment, the anode is a pseudocapacitive
or
electrochemical double layer capacitive material that is electrochemically
stable to less than -
1.3 V vs. a normal hydrogen electrode (NHE). In an embodiment, the cathode
electrode 106
may comprise a doped or undoped cubic spinel X,-Mn02-type material or NaMn9018
tunnel
structured orthorhombic material and the anode electrode 104 may comprise
activated
carbon. Alternatively, the cathode electrode may comprise a non-intercalating
Mn02 phase,
such as electrolytic manganese dioxide (EMD), alpha or gamma phase.
[0039] Another embodiment of the invention is illustrated in Figures 3 and
4. In this
embodiment, the electrochemical device 300 includes eight stacks 100P of
electrochemical
cells 102 shown in FIG. 1, in a two by four array. However, any number of
stacks 100P may
be included. For example, the electrochemical device 300 may include two
stacks 100P in a
one by two array, three stacks 100P in a one by three array, twelve stacks
100P in a three by
four array, or 25 stacks 100P in a five by five array. The exact number of
stacks 100P may
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CA 02829224 2016-06-07
be selected according to the desire or power needs of the end user.
[0040] The electrochemical device 300 preferably includes a housing 116. In
this
embodiment, the housing 116 includes a base 116b and a plurality of sidewall
members 116a.
In an embodiment, the anode electrodes 104 and the cathode electrodes 106 of
the
electrochemical cells 102 in each of the plurality of stacks 100P are exposed
along their
edges but are constrained by the housing 116. Preferably, the housing 116
provides pressure
through each stack 100P, thereby keeping the stacks 100P of the
electrochemical device 300
secure. In an alternative embodiment, the anode electrodes 104 and the cathode
electrodes
106 of the electrochemical cells 102 in each of the plurality of stacks 100P
are partially or
completely covered and constrained along their edges. This may be
accomplished, for
example, by mounting the anode electrodes 104 and the cathode electrodes 106
of each cell
102 in a frame 112, as shown in Figure 9. Other housing configurations may
also be used.
For example, the housing 116 may include a base 116b and a single, unitary
sidewall member
116a, similar to a bell jar.
[0041] In this embodiment, the separator 108 and/or the anode current
collector 110a
and/or the cathode current collector 110c of at least one electrochemical cell
102 extends
continuously between at least two of the plurality of stacks 100P. Preferably,
the separator
108, the anode current collector 110a and the cathode current collector 110c
extend
continuously between all of the stacks 100P in the electrochemical device 300.
In this
manner, the electrochemical device 300 can be easily and inexpensively
fabricated. The
cathode electrode 106 and the anode electrode 104 of each cell 102 in the
stacks 100P of
cells, however, preferably do not extend continuously to another cell 102 in
another one of
the stacks 100P. In an embodiment, spaces between electrodes 104, 106 of
adjacent stacks
100P contain an electrolyte reservoir.
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[0042] In an embodiment, the electrochemical device 300 further includes a
combined
positive bus and first end plate 122c which electrically connects all positive
outputs of the
plurality of the stacks and a combined negative bus and second end plate 122a
which
electrically connects all negative outputs of the plurality of the stacks
100P. In addition, the
base 116b may include external electrical contacts 124which allow the
electrochemical
device 300 to be quickly and easily attached to a load.
[0043] In an embodiment, the electrochemical device 300 is a hybrid
electrochemical
device described above. Preferably in this embodiment, all of the
electrochemical cells 102
of the stacks 100P of electrochemical cells 102 are hybrid electrochemical
cells. As in the
embodiments discussed above, the hybrid electrochemical cell 102 may include a
cathode
electrode 106 that includes doped or undoped cubic spinel k-Mn02-type material
or
NaMn9018 tunnel structured orthorhombic material and an anode electrode 104
that includes
activated carbon and the electrolyte comprises an aqueous electrolyte
containing sodium ions.
Other cathode and anode materials may be used as discussed below. The device
may
comprise a secondary battery, such as a Li-ion or Na-ion battery in an
alternative
embodiment.
[0044] Another embodiment of the invention is illustrated in Figures 5 and
6. In this
embodiment, the electrochemical device 500 as illustrated includes a single
prismatic stack
100P of electrochemical cells 102. More than one stack may be used. The single
prismatic
stack 100P of electrochemical cells 102 is located in a housing 116. The
electrochemical
device 500 includes an anode bus 122a and a cathode bus 122c. Each of the
anodes 104 in
the electrochemical cells 102 in the prismatic stack 100P is electrically
connected via anode
current collectors 110a to the anode bus 122a. In this embodiment, the anodes
104 are
connected in parallel. Similarly, each of the cathodes 106 in the
electrochemical cells 102 in
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the prismatic stack 100P is electrically connected to the cathode bus 122c via
cathode current
collectors 110c. In this embodiment, the cathodes 106 are connected in
parallel. Preferably,
the anode current collectors 110a and the cathode current collectors 110c are
connected to
their respective anode bus 122a and cathode bus 122c with conductive tabs 120.
The current
collectors 110a. 110c may be operatively connected to the respective tabs 120
and/or anode
and cathode buses 122a, 122c with a pressure/friction fitting; a conducting,
electrochemically
inert cured paint; or a conducting, electrochemically inert cured epoxy. The
electrochemical
device 500 also includes external electrical contacts 124 to provide
electricity from the
electrochemical device 500 to an external device or circuit. In an embodiment,
the external
electrical contacts 124 are located on top of the anode bus 122a and the
cathode bus 122c.
Alternatively, the contacts may be located on the bottom or sides of the
buses. The contacts
may be located on the same or different sides of the device.
[0045] In an
embodiment, all of the components of the electrochemical device 500 that
typically come in contact with the electrolyte (i.e., the anode 104, cathode
106, separator 108,
current collectors 110, buses 122, tabs 120, and the housing 116) are made of
non-metallic
materials. In an embodiment, the current collectors 110, the buses 122 and
tabs 120 may be
made of any suitable electrically conductive form of carbon. The buses and
tabs may be
made of graphite, carbon fiber, or a carbon based conducting composite (e.g.,
polymer matrix
containing carbon fiber or filler material). The housing 116 may be made of,
but is not
limited to, an electrochemically inert and electrically insulating polymer. In
this manner, the
electrochemical device 500 is resistant to corrosion. If the buses 122 do not
contact the
electrolyte (i.e., the tabs extend through a seal material to external buses),
then the buses may
be made of metal. The external electrical contacts 124 may be made of a
metallic material.
In the embodiment illustrated in Figure 7, the buses 122 are surrounded by a
hermetic seal
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CA 02829224 2015-11-26
114 located between the top of the buses 122 and the top of the prismatic
stack 100P of
electrochemical cells 102 and the contacts 124. The seal may comprise a
polymer or epoxy
material which is impervious to electrolyte and oxygen, such as poly-based
epoxy, glue, calk
or melt sealed polymer. The buses 122 may be connected to the contacts 124 by
soldering,
bolts, clamps, and/or pressure provided by the seal material. In this manner,
the external
electrical contacts 124 can be isolated from the electrolyte, thereby allowing
the external
electrical contacts 124 to be made of a metallic material, such as copper.
This way, only the
metal contacts or interconnects 124 protrude from the seal 114 area of the
housing 116.
[0046] Figure 8 is a plot of cell potential versus cell capacity of an
embodiment of an
electrochemical device 500. As can be seen in the plot, a high cell capacity,
such as greater
than 1200 mAh for voltage of 0.5V and below can be achieved.
[0047] Figure 9 illustrates an embodiment of an electrochemical cell 102.
The
electrochemical cell 102 includes an anode electrode 104, a cathode electrode
106 and a
separator 108 between the anode electrode 104 and the cathode electrode 106.
The
electrochemical cell 102 also includes an electrolyte located between the
anode electrode 104
and the cathode electrode 106. In an embodiment, the separator 108 may be
porous with
electrolyte located in the pores. The electrolyte may be aqueous or non-
aqueous. The
electrochemical cell 102 may also include a graphite sheet 110 that acts as a
current collector
for the electrochemical cell 102. Preferably, the graphite sheet 110 is
densified. In an
embodiment, the density of the graphite sheet 110 is greater than 0.6 g/cm3.
The graphite
sheet 110 may be made from, for example, exfoliated graphite. In an
embodiment, the
graphite sheet 110 may include one or more foil layers. Suitable materials for
the anode
electrode 104, the cathode electrode 106, the separator 108 and the
electrolyte are discussed
in more detail below.
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[0048] The anode electrode 104, the cathode electrode 106, the separator
108 and the
graphite sheet current collector 110 may be mounted in a frame 112 which seals
each
individual cell. The frame 112 is preferably made of an electrically
insulating material, for
example, an electrically insulating plastic or epoxy. The frame 112 may be
made from
preformed rings, poured epoxy or a combination of the two. In an embodiment,
the frame
112 may comprise separate anode and cathode frames. In an embodiment, the
graphite sheet
current collector 110 may be configured to act as a seal 114 with the frame
112. That is, the
graphite sheet current collector 110 may extend into a recess in the frame 112
to act as the
seal 114. In this embodiment, the seal 114 prevents electrolyte from flowing
from one
electrochemical cell 102 to an adjacent electrochemical cell 102. In
alternative embodiments,
a separate seal 114, such as a washer or gasket, may be provided such that the
graphite sheet
current collector does not perform as a seal.
[0049] In an embodiment, the electrochemical cell is a hybrid
electrochemical cell. That
is, the cathode electrode 106 in operation reversibly intercalates alkali
metal cations and the
anode electrode 104 comprises a capacitive electrode which stores charge
through either (1) a
reversible nonfaradiac reaction of alkali metal cations on a surface of the
anode electrode or
(2) a pseudocapacitive electrode which undergoes a partial charge transfer
surface interaction
with alkali metal cations on a surface of the anode electrode.
[0050] Figure 11 illustrates a bipolar stack 100B of electrochemical cells
102 according
to another embodiment. In contrast to conventional stacks of electrochemical
cells which
include separate anode side and cathode side current collectors, the bipolar
stack 100B
operates with a single graphite sheet current collector 110 located between
the cathode
electrode 106 of one electrochemical cell 102 and the anode electrode 104 of
an adjacent
electrochemical cell 102. Thus, bipolar stack 100B only uses half as many
current collectors
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as the conventional stack of electrochemical cells.
[0051] In an embodiment, the bipolar stack 100B is enclosed in an outer
housing 116 and
provided with conducting headers 118 on the top and bottom of the bipolar
stack 100B. The
headers 118 preferably comprise a corrosion resistant current collector metal,
including but
not limited to, aluminum, nickel, titanium and stainless steel. Preferably,
pressure is applied
to the bipolar stack 100B when assembled. The pressure aids in providing good
seals to
prevent leakage of electrolyte.
[0052] In an embodiment, the electrochemical cell 102 is a secondary hybrid
aqueous
energy storage device. In this embodiment, the anode electrode 104 and cathode
electrode
106 may be between 0.05 and 1 cm thick, such as between 0.05 and 0.15 cm
thick.
[0053] Figure 10 illustrates another embodiment of the invention. In this
embodiment,
the anode electrode 104 may include discrete anode electrode members 104a
separated by
anode boundary areas 104b. Further, the cathode electrode 106 may include
discrete cathode
electrode members 106a separated by cathode boundary areas 106b. As
illustrated, the anode
electrode 104 includes two discrete anode electrode members 104a and the
cathode electrode
106 includes three discrete cathode electrode members 106a. However, this is
for illustration
only. The anode electrode 104 and the cathode electrode 106 may include any
number of
discrete anode electrode members 104a and discrete cathode electrode members
106a,
respectively. Additionally, in an embodiment, the anode boundary areas 104b
and the
cathode boundary areas 106b may comprise electrolyte filled voids.
[0054] Further, Figure 10 only illustrates a cross section in one
dimension. A cross
sectional view in an orthogonal direction may also illustrate the anode
electrode 104 and the
cathode electrode 106 having discrete anode electrode members 104a and
discrete cathode
electrode members 106a. That is, the anode electrode 104 and the cathode
electrode 106 may
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CA 02829224 2015-11-26
comprise a two dimensional checkerboard pattern. In other words, the discrete
anode
electrode members 104a and discrete cathode electrode members 106a may be
arranged in an
array of rows and columns. The individual discrete anode electrode members
104a and
discrete cathode electrode members 106a may, for example, be square or
rectangular in
shape. In an embodiment, the inventors have found that providing the anode
electrode 104
and the cathode electrode 106 with a different number of discrete anode
electrode members
104a and discrete cathode electrode members 106a improves the structural
integrity of
electrochemical cells 102. In this embodiment, the anode rows and columns are
offset from
the cathode rows and columns. In an embodiment, at least 50%, such as 50-100%,
including
75-95% of the anode boundary areas 104b are not aligned with a respective
cathode boundary
areas 106b across the separator 108. Alternatively, the anode electrode 104
and the cathode
electrode 106 may include the same number of discrete anode electrode members
104a and
discrete cathode electrode members 106a. In an alternative embodiment, either
the anode
electrode 104 or the cathode electrode 106 may comprise a single unitary sheet
while the
other electrode comprises a checkerboard pattern of discrete members.
100551 In an
embodiment, the anode electrode members 104a and the cathode electrode
members 106a are made from rolled sheet or pressed pellets of activated carbon
and
manganese oxide, respectively. Another embodiment is drawn to a method of
making an
electrochemical device of Figure 10, which includes the steps of (1) stacking
an anode
electrode 104 that includes a plurality of discrete anode electrode members
104a separated by
anode boundary areas 104b, (2) stacking a separator 108 on the anode electrode
104 and (3)
stacking a cathode electrode 106 comprising a plurality of discrete cathode
electrode
members 106a separated by cathode boundary areas 106b on the separator 108. In
one
aspect, at least 50% of the anode boundary areas 104b are not aligned with a
respective
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cathode boundary areas 106b across the separator 108. The method may also
include a step
of stacking a graphite sheet current collector 110 on the cathode electrode
106. The anode
electrode members 104a and/or the cathode electrode members 106b may be formed
by
cutting the members 104a, 106a from a rolled sheet of anode or cathode
material, or by
pressing a pellet of anode or cathode material.
[0056] Another embodiment of the invention is drawn to a method of making a
stack
100B, 100P of electrochemical cells 102. The method may include the steps of
forming a
stack electrochemical cells and pouring an electrically insulating polymer
around the stack
100B,P of electrochemical cells 102. The method may also include the step of
solidifying the
polymer to form a solid insulating shell or frame 112. Alternatively, the
method may include
the step of providing a preformed solid insulating shell 112 around the stack
of
electrochemical cells 102. The polymer may be, but is not limited to, an epoxy
or an acrylic.
[0057] The method may also include affixing conducting end plate headers
118 shown in
Figure 11, to the top and bottom of the stack 110. The stack 110 and the solid
insulating shell
or frame 112 may then be placed in a hollow cylindrical shell or outer housing
116. The
method also includes placing a graphite sheet current collector 110 between
adjacent
electrochemical cells 102 in the stack 100B,P of electrochemical cells 102. In
an
embodiment, each electrochemical cell 102 in the stack 100B,P of
electrochemical cells 102
comprises an anode electrode 104 having an active anode area and a cathode
electrode 106
having an active cathode area. The graphite sheet current collector 110 may
have an area
larger than the active anode area and the active cathode area to act as a seal
as shown in
Figure 9.
Device Components
Cathode
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[0058] Several materials comprising a transition metal oxide, sulfide,
phosphate, or
fluoride can be used as active cathode materials capable of reversible Na-ion
intercalation /
deintercalation. Materials suitable for use as active cathode materials in
embodiments of the
present invention preferably contain alkali atoms, such as sodium, lithium, or
both, prior to
use as active cathode materials. It is not necessary for an active cathode
material to contain
Na and/or Li in the as-formed state (that is, prior to use in an energy
storage device).
However, Na cations from the electrolyte must be able to incorporate into the
active cathode
material by intercalation during operation of the energy storage device. Thus,
materials that
may be used as cathodes in the present invention comprise materials that do
not necessarily
contain Na in an as-formed state, but are capable of reversible intercalation
/ deintercalation
of Na-ions during discharging / charging cycles of the energy storage device
without a large
overpotential loss.
[0059] In embodiments where the active cathode material contains alkali-
atoms
(preferably Na or Li) prior to use, some or all of these atoms are
deintercalated during the
first cell charging cycle. Alkali cations from the electrolyte (overwhelmingly
Na cations) are
re-intercalated during cell discharge. This is different than nearly all of
the hybrid capacitor
systems that call out an intercalation electrode opposite activated carbon. In
most systems,
cations from the electrolyte are adsorbed on the anode during a charging
cycle. At the same
time, the counter-anions, such as hydrogen ions, in the electrolyte
intercalate into the active
cathode material, thus preserving charge balance, but depleting ionic
concentration, in the
electrolyte solution. During discharge, cations are released from the anode
and anions are
released from the cathode, thus preserving charge balance, but increasing
ionic concentration,
in the electrolyte solution. This is a different operational mode from devices
in embodiments
of the present invention, where hydrogen ions or other anions are preferably
not intercalated
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into the cathode active material.
[0060] Suitable active cathode materials may have the following general
formula during
use: AxMy0z, where A is Na or a mixture of Na and one or more of Li, K, Be,
Mg, and Ca,
where x is within the range of 0 to 1, inclusive, before use and within the
range of 0 to 10,
inclusive, during use; M comprises any one or more transition metal, where y
is within the
range of 1 to 3, inclusive; preferably within the range of 1.5 and 2.5,
inclusive; and 0 is
oxygen, where z is within the range of 2 to 7, inclusive; preferably within
the range of 3.5 to
4.5, inclusive.
[0061] In some active cathode materials with the general formula AxMy0z, Na-
ions
reversibly intercalate / deintercalate during the discharge / charge cycle of
the energy storage
device. Thus, the quantity x in the active cathode material formula changes
while the device
is in use.
[0062] In some active cathode materials with the general formula AxMy0z, A
comprises
at least 50 at% of at least one or more of Na, K, Be, Mg, or Ca, optionally in
combination
with Li; M comprises any one or more transition metal; 0 is oxygen; x ranges
from 3.5 to 4.5
before use and from 1 to 10 during use; y ranges from 8.5 to 9.5 and z ranges
from 17.5 to
18.5. In these embodiments, A preferably comprises at least 51 at% Na, such as
at least 75
at% Na, and 0 to 49 at%, such as 0 to 25 at%, Li, K, Be, Mg, or Ca; M
comprises one or more
of Mn, Ti, Fe, Co, Ni, Cu, V, or Sc; x is about 4 before use and ranges from 0
to 10 during
use; y is about 9; and z is about 18.
[0063] In some active cathode materials with the general formula AxMy0z, A
comprises
Na or a mix of at least 80 atomic percent Na and one or more of Li, K, Be, Mg,
and Ca. In
these embodiments, x is preferably about 1 before use and ranges from 0 to
about 1.5 during
use. In some preferred active cathode materials, M comprises one or more of
Mn, Ti, Fe, Co,
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Ni, Cu, and V, and may be doped (less than 20 at%, such as 0.1 to 10 at%; for
example, 3 to 6
at%) with one or more of Al, Mg, Ga, In, Cu, Zn, and Ni.
[0064] General classes of suitable active cathode materials include (but
are not limited to)
the layered/orthorhombic NaM02 (birnessite), the cubic spinel based manganate
(e.g., M02,
such as k-Mn02 based material where M is Mn, e.g., LixM204 (where 1 < x < 1.1)
before use
and NayMn204 in use), the Na2M307 system, the NaMPO4 system, the NaM2(PO4)3
system,
the Na2MPO4F system, and the tunnel-structured Nao 44M02, where M in all
formula
comprises at least one transition metal. Typical transition metals may be Mn
or Fe (for cost
and environmental reasons), although Co, Ni, Cr, V, Ti, Cu, Zr, Nb, W, Mo
(among others),
or combinations thereof, may be used to wholly or partially replace Mn, Fe, or
a combination
thereof. In embodiments of the present invention, Mn is a preferred transition
metal. In
some embodiments, cathode electrodes may comprise multiple active cathode
materials,
either in a homogenous or near homogenous mixture or layered within the
cathode electrode.
[0065] In some embodiments, the initial active cathode material comprises
NaMn02
(birnassite structure) optionally doped with one or more metals, such as Li or
Al.
[0066] In some embodiments, the initial active cathode material comprises -
Mn02 (i.e.,
the cubic isomorph of manganese oxide) based material, optionally doped with
one or more
metals, such as Li or Al.
[0067] In these embodiments, cubic spinel -Mn02 may be formed by first
forming a
lithium containing manganese oxide, such as lithium manganate (e.g., cubic
spinel LiMn204
or non- stoichiometric variants thereof). In embodiments which utilize a cubic
spinel -
Mn02 active cathode material, most or all of the Li may be extracted
electrochemically or
chemically from the cubic spinel LiMn204 to form cubic spinel -Mn02 type
material (i.e.,
material which has a 1:2 Mn to 0 ratio, and/or in which the Mn may be
substituted by
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CA 02829224 2015-11-26
another metal, and/or which also contains an alkali metal, and/or in which the
Mn to 0 ratio
is not exactly 1:2). This extraction may take place as part of the initial
device charging cycle.
In such instances, Li-ions are deintercalated from the as-formed cubic spinel
LiMn204 during
the first charging cycle. Upon discharge, Na-ions from the electrolyte
intercalate into the
cubic spinel -1 -Mn02. As such, the formula for the active cathode material
during
operation is NayLiõMn204 (optionally doped with one or more additional metal
as described
above, preferably Al), with 0 < x < 1, 0 < y < 1, and x + y < 1.1. Preferably,
the quantity x +
y changes through the charge / discharge cycle from about 0 (fully charged) to
about 1 (fully
discharged). However, values above 1 during full discharge may be used.
Furthermore, any
other suitable formation method may be used. Non-stoichiometric LixMn204
materials with
more than 1 Li for every 2 Mn and 4 0 atoms may be used as initial materials
from which
cubic spinel -Mn02 may be formed (where 1 < x < 1.1 for example). Thus, the
cubic spinel
-manganate may have a formula A1zLiMn2_z04 where 1 < x < 1.1 and 0 < z < 0.1
before
use, and A1zLi,NayMn204 where 0 < x < 1.1, 0 < y < 1, 0 < x+y < 1.1, and 0 < z
< 0.1 in use
(and where Al may be substituted by another dopant).
[0068] In some embodiments, the initial cathode material comprises
Na2M11307,
optionally doped with one or more metals, such as Li or Al.
[0069] In some embodiments, the initial cathode material comprises
Na2FePO4F,
optionally doped with one or more metals, such as Li or Al.
[0070] In some embodiments, the cathode material comprises Na0.44Mn02,
optionally
doped with one or more metals, such as Li or Al. This active cathode material
may be made
by thoroughly mixing Na2CO3 and Mn203 to proper molar ratios and firing, for
example at
about 800 C. The degree of Na content incorporated into this material during
firing
determines the oxidation state of the Mn and how it bonds with 02 locally.
This material has
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CA 02829224 2015-11-26
been demonstrated to cycle between 0.33 < x < 0.66 for NaxMn02 in a non-
aqueous
electrolyte.
[0071] Optionally, the cathode electrode may be in the form of a composite
cathode
comprising one or more active cathode materials (e.g., 1-49%, such as 2-10% by
weight of
the minor component, such as the orthorhombic tunnel structured material), a
high surface
area conductive diluent (such as conducting grade graphite, carbon blacks,
such as acetylene
black, non-reactive metals, and/or conductive polymers), a binder, a
plasticizer, and/or a
filler. Exemplary binders may comprise polytetrafluoroethylene (PTFE), a
polyvinylchloride
(PVC)-based composite (including a PVC-Si02 composite), cellulose-based
materials,
polyvinylidene fluoride (PVDF), hydrated birnassite (when the active cathode
material
comprises another material), other non-reactive non-corroding polymer
materials, or a
combination thereof A composite cathode may be formed by mixing a portion of
one or
more preferred active cathode materials with a conductive diluent, and/or a
polymeric binder,
and pressing the mixture into a pellet. In some embodiments, a composite
cathode electrode
may be formed from a mixture of about 50 to 90 wt% active cathode material,
with the
remainder of the mixture comprising a combination of one or more of diluent,
binder,
plasticizer, and/or filler. For example, in some embodiments, a composite
cathode electrode
may be formed from about 80 wt% active cathode material, about 10 to 15 wt%
diluent, such
as carbon black, and about 5 to 10 wt% binder, such as PTFE.
[0072] One or more additional functional materials may optionally be added
to a
composite cathode to increase capacity and replace the polymeric binder. These
optional
materials include but are not limited to Zn, Pb, hydrated NaMn02 (birnassite),
and hydrated
Na0.44Mn02 (orthorhombic tunnel structure). In instances where hydrated NaMn02

(birnassite) and/or hydrated Na0.44Mn02 (orthorhombic tunnel structure) is
added to a
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CA 02829224 2015-11-26
composite cathode, the resulting device has a dual functional material
composite cathode.
[0073] A cathode electrode will generally have a thickness in the range of
about 40 to
800 pm.
Anode:
[0074] The anode may comprise any material capable of reversibly storing Na-
ions
through surface adsorption / desorption (via an electrochemical double layer
reaction and/or a
pseudocapacitive reaction (i.e., a partial charge transfer surface
interaction)) and have
sufficient capacity in the desired voltage range. Exemplary materials meeting
these
requirements include porous activated carbon, graphite, mesoporous carbon,
carbon
nanotubes, disordered carbon, Ti-oxide (such as titania) materials, V-oxide
materials,
phospho-olivine materials, other suitable mesoporous ceramic materials, and a
combinations
thereof. In preferred embodiments, activated carbon is used as the anode
material.
[0075] Optionally, the anode electrode may be in the form of a composite
anode
comprising one or more anode materials, a high surface area conductive diluent
(such as
conducting grade graphite, carbon blacks, such as acetylene black, non-
reactive metals,
and/or conductive polymers), a binder, such as PTFE, a PVC-based composite
(including a
PVC-Si02 composite), cellulose-based materials, PVDF, other non-reactive non-
corroding
polymer materials, or a combination thereof, plasticizer, and/or a filler. A
composite anode
may be formed by mixing a portion of one or more preferred anode materials
with a
conductive diluent, and/or a polymeric binder, and pressing the mixture into a
pellet. In some
embodiments, a composite anode electrode may be formed from a mixture from
about 50 to
90 wt% anode material, with the remainder of the mixture comprising a
combination of one
or more of diluent, binder, plasticizer, and/or filler. For example, in some
embodiments, a
composite anode electrode may be formed from about 80 wt% activated carbon,
about 10 to
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15 wt% diluent, such as carbon black, and about 5 to 10 wt% binder, such as
PTFE.
[0076] One or more additional functional materials may optionally be added
to a
composite anode to increase capacity and replace the polymeric binder. These
optional
materials include but are not limited to Zn, Pb, hydrated NaMn02 (birnassite),
and hydrated
Na04.4Mn02 (orthorhombic tunnel structure).
[0077] An anode electrode will generally have a thickness in the range of
about 80 to
1600 pm.
Electrolyte:
[0078] Electrolytes useful in embodiments of the present invention comprise
a salt
dissolved fully in water. For example, the electrolyte may comprise a 0.1 M to
10 M solution
of at least one anion selected from the group consisting of S042- , NO3-, C104-
, P043-, co32-,
CF, and/or OH-. Thus, Na cation containing salts may include (but are not
limited to)
Na2SO4, NaNO3, NaC104, Na3PO4, Na2CO3, NaC1, and NaOH, or a combination
thereof.
[0079] In some embodiments, the electrolyte solution may be substantially
free of Na. In
these instances, cations in salts of the above listed anions may be an alkali
other than Na
(such as K) or alkaline earth (such as Ca, or Mg) cation. Thus, alkali other
than Na cation
containing salts may include (but are not limited to) K2SO4, KNO3, KC104,
K3PO4, K2CO3,
KC1, and KOH. Exemplary alkaline earth cation containing salts may include
CaSO4,
Ca(NO3)2, Ca(C104)2, CaCO3, and Ca(OH)2, Mg504, Mg(NO3)2, Mg(C104)2, MgCO3,
and
Mg(OH)2. Electrolyte solutions substantially free of Na may be made from any
combination
of such salts. In other embodiments, the electrolyte solution may comprise a
solution of a Na
cation containing salt and one or more non-Na cation containing salt.
[0080] Molar concentrations preferably range from about 0.05 M to 3 M, such
as about
0.1 to 1 M, at 100 C for Na2504 in water depending on the desired performance
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CA 02829224 2013-09-05
WO 2012/122353 PCT/US2012/028228
characteristics of the energy storage device, and the degradation /
performance limiting
mechanisms associated with higher salt concentrations. Similar ranges are
preferred for other
salts.
[0081] A blend of different salts (such as a blend of a sodium containing
salt with one or
more of an alkali, alkaline earth, lanthanide, aluminum and zinc salt) may
result in an
optimized system. Such a blend may provide an electrolyte with sodium cations
and one or
more cations selected from the group consisting of alkali (such as K),
alkaline earth (such as
Mg and Ca), lanthanide, aluminum, and zinc cations.
[0082] Optionally, the pH of the electrolyte may be altered by adding some
additional
OH- ionic species to make the electrolyte solution more basic, for example by
adding NaOH
other OH-containing salts, or by adding some other OH- concentration-affecting
compound
(such as H2SO4 to make the electrolyte solution more acidic). The pH of the
electrolyte
affects the range of voltage stability window (relative to a reference
electrode) of the cell and
also can have an effect on the stability and degradation of the active cathode
material and
may inhibit proton (H ) intercalation, which may play a role in active cathode
material
capacity loss and cell degradation. In some cases, the pH can be increased to
11 to 13,
thereby allowing different active cathode materials to be stable (than were
stable at neutral
pH 7). In some embodiments, the pH may be within the range of about 3 to 13,
such as
between about 3 and 6 or between about 8 and 13.
[0083] Optionally, the electrolyte solution contains an additive for
mitigating degradation
of the active cathode material, such as birnassite material. An exemplary
additive may be,
but is not limited to, Na2HPO4, in quantities sufficient to establish a
concentration ranging
from 0.1 mM to 100 mM.
Separator:
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CA 02829224 2013-09-05
WO 2012/122353 PCT/US2012/028228
[0084] A separator for use in embodiments of the present invention may
comprise a
cotton sheet, PVC (polyvinyl chloride), PE (polyethylene), glass fiber or any
other suitable
material.
Operational Characteristics
[0085] As described above, in embodiments where the active cathode material
contains
alkali-atoms (preferably Na or Li) prior to use, some or all of these atoms
are deintercalated
during the first cell charging cycle. Alkali cations from the electrolyte
(overwhelmingly Na
cations) are re-intercalated during cell discharge. This is different than
nearly all of the
hybrid capacitor systems that call out an intercalation electrode opposite
activated carbon. In
most systems, cations from the electrolyte are adsorbed on the anode during a
charging cycle.
At the same time, the counter-anions in the electrolyte intercalate into the
active cathode
material, thus preserving charge balance, but depleting ionic concentration,
in the electrolyte
solution. During discharge, cations are released from the anode and anions are
released from
the cathode, thus preserving charge balance, but increasing ionic
concentration, in the
electrolyte solution. This is a different operational mode from devices in
embodiments of the
present invention.
Example
[0086] A hybrid energy storage device having the prismatic / parallel
electrical
connection shown in Figure 1A and a physical structure shown in Figs. 5-7 was
assembled.
The device containing were three levels of anode 104 /cathode 106 sets (of 2
each) with an
expanded graphite sheet current collector 110a, 110c structures (500 microns
thick) and non-
woven fibrous separator material 108, as shown in Fig. 5. The cathode
contained a X-Mn02
phase active material as described above, and was made from a compacted
granulate of active
material, carbon black, graphite powder and PTFE. The anode contained
activated carbon
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CA 02829224 2013-09-05
WO 2012/122353 PCT/US2012/028228
mixed with carbon black and PTFE. Pressure was used to contact each graphite
anode and
cathode current collector 110a, 110c with a respective anode and cathode
graphite bus bars
122a, 122c that served as the positive and negative bus bars for the device. A
polypropylene
enclosure 116 was used to house the device and the graphite bus bars 122a,
122c were fed
through properly sized holes in the polypropylene enclosure and were then
sealed against the
polypropylene with a silicone adhesive material. Copper wires were then
connected via
pressure with the external (non-electrolyte touching) bus bars 124 coming out
of the
enclosure and the entire external bus bar was covered with potting epoxy.
[0087] The device was then taken through 15 formation cycles and was then
tested for
energy storage capacity and stability though many cycles. Figure 12 shows the
results of this
testing. Figure 12(a) shows the device potential vs. accumulated capacity
under charge and
discharge conditions over 30 cycles. The cycling was performed at a C/6
current rating, and
the device had a capacity of approximately 1.1 Ah. The data show near perfect
overlap of the
voltage profiles from cycle to cycle, indicative of a system that is extremely
stable and
exhibits no loss in capacity or has any internal corrosion. Figure 12(b) is a
plot of cell charge
and discharge capacity as a function of cycle. There is no loss in capacity as
function of
cycle through at least 60 cycles. Data from other cells indicate that this
should be maintained
though thousands of cycles. Also, the columbic efficiency was found to be 98
to 100% for
these cycles.
[0088] This example shows that a highly stable aqueous electrolyte hybrid
energy storage
device is created without the use of any metal inside the battery casing. The
device exhibits
excellent stability and shows great promise for long-term use in a variety of
energy storage
applications.
[0089] Although the foregoing refers to particular preferred embodiments,
it will be
-29-

CA 02829224 2016-06-07
understood that the invention is not so limited. It will occur to those of
ordinary skill in the
art that various modifications may be made to the disclosed embodiments and
that such
modifications are intended to be within the scope of the invention.
-30-

Representative Drawing
A single figure which represents the drawing illustrating the invention.
Administrative Status

For a clearer understanding of the status of the application/patent presented on this page, the site Disclaimer , as well as the definitions for Patent , Administrative Status , Maintenance Fee  and Payment History  should be consulted.

Administrative Status

Title Date
Forecasted Issue Date 2016-10-04
(86) PCT Filing Date 2012-03-08
(87) PCT Publication Date 2012-09-13
(85) National Entry 2013-09-05
Examination Requested 2015-11-26
(45) Issued 2016-10-04
Deemed Expired 2020-03-09

Abandonment History

There is no abandonment history.

Payment History

Fee Type Anniversary Year Due Date Amount Paid Paid Date
Application Fee $400.00 2013-09-05
Maintenance Fee - Application - New Act 2 2014-03-10 $100.00 2014-02-21
Registration of a document - section 124 $100.00 2014-03-05
Registration of a document - section 124 $100.00 2014-03-05
Maintenance Fee - Application - New Act 3 2015-03-09 $100.00 2015-03-03
Request for Examination $800.00 2015-11-26
Maintenance Fee - Application - New Act 4 2016-03-08 $100.00 2016-02-17
Final Fee $300.00 2016-08-24
Maintenance Fee - Patent - New Act 5 2017-03-08 $200.00 2017-03-06
Maintenance Fee - Patent - New Act 6 2018-03-08 $400.00 2018-03-26
Owners on Record

Note: Records showing the ownership history in alphabetical order.

Current Owners on Record
AQUION ENERGY INC.
Past Owners on Record
None
Past Owners that do not appear in the "Owners on Record" listing will appear in other documentation within the application.
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Document
Description 
Date
(yyyy-mm-dd) 
Number of pages   Size of Image (KB) 
Abstract 2013-09-05 1 75
Claims 2013-09-05 7 234
Drawings 2013-09-05 8 460
Description 2013-09-05 30 1,284
Cover Page 2013-10-29 1 37
Description 2015-11-26 30 1,272
Claims 2015-11-26 3 108
Drawings 2016-06-07 8 366
Claims 2016-06-07 3 109
Abstract 2016-06-07 1 26
Description 2016-06-07 30 1,257
Representative Drawing 2016-07-07 1 59
Cover Page 2016-09-01 1 102
PCT 2013-09-05 13 530
Assignment 2013-09-05 6 167
Fees 2014-02-21 1 33
Assignment 2014-03-05 11 733
Prosecution-Amendment 2014-03-05 1 48
Examiner Requisition 2015-12-07 5 284
Prosecution-Amendment 2015-11-26 19 841
Amendment 2016-06-07 25 964
Final Fee 2016-08-24 1 43