U.S. patent application number 16/098353 was filed with the patent office on 2020-07-02 for battery electrode with carbon additives in meta-solid-state battery.
This patent application is currently assigned to The Hong Kong University of Science and Technology. The applicant listed for this patent is The Hong Kong University of Science and Technology. Invention is credited to Francesco Ciucci, Stephen Chin-To Kwok, Kan Kan Yeung, Matthew Ming-Fai Yuen.
Application Number | 20200212445 16/098353 |
Document ID | / |
Family ID | 60202655 |
Filed Date | 2020-07-02 |
United States Patent
Application |
20200212445 |
Kind Code |
A9 |
Yuen; Matthew Ming-Fai ; et
al. |
July 2, 2020 |
BATTERY ELECTRODE WITH CARBON ADDITIVES IN META-SOLID-STATE
BATTERY
Abstract
A meta-solid-state battery includes a first layer disposed on a
first current collector, a second layer disposed on a second
current collector, and third layer disposed between the first layer
and the second layer. The first layer and the second layer are the
cathode and anode electrodes. The third layer includes a first
meta-solid-state electrolyte material. Each of the cathode and
anode electrodes contain: an active material in an amount ranging
from approximately 70% to 99.98% by weight, a carbon additive in an
amount ranging from approximately 0.010% to 20% by weight, and a
second meta-solid-state electrolyte material in an amount ranging
from approximately 0.010% to 10% by weight. The first and second
meta-solid-state electrolyte material include a gel polymer.
Inventors: |
Yuen; Matthew Ming-Fai;
(Hong Kong, CN) ; Ciucci; Francesco; (Hong Kong,
CN) ; Kwok; Stephen Chin-To; (Hong Kong, CN) ;
Yeung; Kan Kan; (Hong Kong, CN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
The Hong Kong University of Science and Technology |
Hong Kong |
|
CN |
|
|
Assignee: |
The Hong Kong University of Science
and Technology
Hong Kong
CN
|
Prior
Publication: |
|
Document Identifier |
Publication Date |
|
US 20190165376 A1 |
May 30, 2019 |
|
|
Family ID: |
60202655 |
Appl. No.: |
16/098353 |
Filed: |
May 3, 2016 |
PCT Filed: |
May 3, 2016 |
PCT NO: |
PCT/CN2016/080879 PCKC 00 |
371 Date: |
November 1, 2018 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
H01M 4/485 20130101;
H01M 4/625 20130101; H01M 10/0525 20130101; H01M 4/38 20130101;
H01M 2300/0011 20130101; H01M 10/0565 20130101; H01M 4/56 20130101;
H01M 4/139 20130101; H01M 4/525 20130101; H01M 4/5825 20130101;
H01M 2300/0085 20130101; H01M 10/0585 20130101; H01M 4/0404
20130101; H01M 4/48 20130101; H01M 4/505 20130101; H01M 2300/0091
20130101; H01M 2300/0068 20130101; H01M 4/0471 20130101 |
International
Class: |
H01M 4/62 20060101
H01M004/62; H01M 10/0525 20060101 H01M010/0525; H01M 10/0585
20060101 H01M010/0585; H01M 10/0565 20060101 H01M010/0565; H01M
4/38 20060101 H01M004/38; H01M 4/56 20060101 H01M004/56; H01M 4/04
20060101 H01M004/04; H01M 4/139 20060101 H01M004/139; H01M 4/525
20060101 H01M004/525; H01M 4/485 20060101 H01M004/485; H01M 4/505
20060101 H01M004/505 |
Claims
1. A meta-solid-state battery comprising: a first layer that is a
cathode electrode; a second layer that is an anode electrode; a
third layer comprising a first meta-solid-state electrolyte
material disposed between the first layer and the second layer; a
first current collector and a second current collector, wherein the
first layer is disposed on the first current collector and the
second layer is disposed on the second current collector, wherein
each of the cathode electrode and the anode electrode comprises: an
active material in an amount ranging from approximately 70% to
99.98% by weight; a carbon additive in an amount ranging from
approximately 0.01% to 20% by weight; and a second meta-solid-state
electrolyte material in an amount ranging from approximately 0.01%
to 10% by weight, and wherein the first and second meta-solid-state
electrolyte material comprise a gel polymer.
2. The meta-solid-state battery of claim 1, wherein each of the
cathode electrode and the anode electrode comprises: an active
material in an amount ranging from 90% to 98.9% by weight; a carbon
additive in an amount ranging from 0.1% to 5% by weight; and a
second meta-solid-state electrolyte material in an amount ranging
from 1% to 5% by weight
3. The meta-solid-state battery of claim 1, wherein the
meta-solid-state battery is a rechargeable battery.
4. The meta-solid-state battery of claim 1, wherein the carbon
additive is one selected from a group consisting of carbon black,
carbon fiber, carbon nanotubes, graphite, graphite oxide, graphene,
and graphene oxide with a range of 0.1 nm to 500 .mu.m in size.
5. The meta-solid-state battery of claim 1, the amount of the
carbon additive is approximately 0.2% by weight.
6. The meta-solid-state battery of claim 1, wherein the carbon
additive is produced using chemical vapor deposition, liquid
exfoliation, electrochemical exfoliation, microwave exfoliation, or
chemical carbon additives, and are functionalized with
oxygen-containing groups or conducting polymers.
7. The meta-solid-state battery of claim 1, wherein the first and
second meta-solid-state electrolyte materials have a charge
transfer resistance in a range of approximately 0.1.OMEGA. to
5.31.OMEGA..
8. The meta-solid-state battery of claim 1, wherein the
meta-solid-state electrolyte material is prepared using solution
mixing, hydrothermal colloidal dispersion, or sol-gel and is mixed
with the active material through solution mixing, centrifugation,
pressure infiltration, or vacuum infiltration.
9. The meta-solid-state battery of claim 1, wherein the first and
second meta-solid-state electrolyte materials further comprise
lithium salt and ionic conducting ceramic particles.
10. The meta-solid-state battery of claim 9, wherein the lithium
salt is one selected from a group consisting of LiPF.sub.6,
Li[N(SO.sub.2F).sub.2] and LiN(SO.sub.2CF.sub.3).sub.2 in an amount
ranging from approximately 95% to 98% by weight of the gel
polymer.
11. The meta-solid-state battery of claim 10, wherein the ionic
conducting ceramic particles are lithium garnet selected from a
group consisting of Li.sub.7La.sub.3Zr.sub.2O.sub.12 (LLZO),
Li.sub.3OCl anti-perovskite, NASICON, LiAlTiSiPO (LATP), and
Li.sub.7-xLa.sub.3Zr.sub.2-xTa.sub.xO.sub.12 (LLZTO) in an amount
ranging from approximately 90% to 94% by weight of the
meta-solid-state electrolyte material comprising the gel polymer
and the lithium salt.
12. The meta-solid-state battery of claim 11, wherein the lithium
garnet is fabricated using solid-state reaction or sol-gel
method.
13. The meta-solid-state battery of claim 1, wherein the cathode
and anode electrodes are lead acid battery electrodes.
14. The meta-solid-state battery of claim 13, wherein the active
material is one selected from a group consisting of Pb and
PbO.sub.2, and the gel polymer is one selected from a group
consisting of polyaniline (PANI), Polyvinyl alcohol (PVA), and
polydimethylsiloxane (PDMS).
15. The meta-solid-state battery of claim 14, wherein the first and
second meta-solid-state electrolyte material contains sulfuric acid
(H.sub.2SO.sub.4) in an amount of approximately 20% to 95% by
weight.
16. The meta-solid-state battery of claim 1, wherein the cathode
and anode electrodes are lithium-ion battery electrodes.
17. The meta-solid-state battery of claim 16, wherein the active
material is one selected from a group consisting of lithium iron
phosphate (LFP), lithium titanate oxide (LTO), lithium ruthenium
tin oxide (LRS), lithium nickel cobalt manganese oxide (NMC), and
Lithium nickel manganese oxide (LNM), and the gel polymer is one
selected from a group consisting of polyacrylonitrile (PAN) and
polyacrylicacid (PAA).
18. A method for producing an electrode for a meta-solid-state
battery comprising: obtaining a plurality of materials for the
electrode; mixing the plurality of materials to form a mixture;
disposing the mixture on a current collector; and curing the
mixture disposed on the current collector, wherein the plurality of
materials for the electrode comprises: an active material in an
amount ranging from approximately 70% to 99.98% by weight; a carbon
additive in an amount ranging from approximately 0.01% to 20% by
weight; and a meta-solid-state electrolyte material in an amount
ranging from approximately 0.01% to 10% by weight, and wherein the
meta-solid-state electrolyte material is composed of a gel
polymer.
19. The method for producing an electrode for a meta-solid-state
battery of claim 18, wherein each of the cathode electrode an the
anode electrode comprises: an active material in an amount ranging
from 90% to 98.9% by weight; a carbon additive in an amount ranging
from 0.1% to 5% by weight; and a meta-solid-state electrolyte
material in an amount ranging from 1% to 5% by weight
20. The method for producing an electrode for a meta-solid-state
battery of claim 18, wherein the meta-solid-state battery is a
rechargeable battery.
21. The method for producing an electrode for a meta-solid-state
battery of claim 18, wherein the meta-solid-state electrolyte
material has a charge transfer resistance in a range of
approximately 0.1.OMEGA. to 5.31.OMEGA..
22. The method for producing an electrode for a meta-solid-state
battery of claim 18, wherein the electrode for the solid state
battery is a lead acid battery electrode and the disposing of the
mixture comprises printing the mixture onto the current collector
and the curing of the mixture comprises curing the mixture in a
humidity chamber.
23. The method for producing an electrode for a meta-solid-state
battery of claim 18, wherein the electrode for the solid state
battery is a lithium-ion battery electrode and the disposing of the
mixture comprises spraying the mixture onto the current collector
and the curing of the mixture comprises curing the mixture in an
oven.
24. The method for producing an electrode for a meta-solid-state
battery of claim 22, wherein the active material is one selected
from a group consisting of Pb and PbO.sub.2, and the gel polymer is
one selected from a group consisting of polyaniline (PANI),
Polyvinyl alcohol (PVA), and polydimethylsiloxane (PDMS).
25. The method for producing an electrode for a meta-solid-state
battery of claim 24 wherein the meta-solid-state electrolyte
material contains sulfuric acid (H.sub.2SO.sub.4) in an amount of
approximately 95% by weight.
26. The method for producing an electrode for a meta-solid-state
battery of claim 23, wherein the active material is one selected
from a group consisting of lithium iron phosphate (LFP), lithium
titanate oxide (LTO), lithium ruthenium tin oxide (LRS), lithium
nickel cobalt manganese oxide (NMC) and Lithium nickel manganese
oxide (LNM), and the gel polymer is one selected from a group
consisting of polyacrylonitrile (PAN) and polyacrylicacid
(PAA).
27. The method for producing an electrode for a meta-solid-state
battery of claim 23, wherein the meta-solid-state electrolyte
materials further comprise lithium salt and ionic conducting
ceramic particles.
28. The method for producing an electrode for a meta-solid-state
battery of claim 27, wherein the lithium salt is one selected from
a group consisting of LiPF.sub.6, Li[N(SO.sub.2F).sub.2] and
LiN(SO.sub.2CF.sub.3).sub.2 in an amount ranging from approximately
95% to 98% by weight in the meta-solid-state electrolyte
material.
29. The method for producing an electrode for a meta-solid-state
battery of claim 28, wherein the ionic conducting ceramic particles
are lithium garnet selected from a group consisting of
Li.sub.7La.sub.3Zr.sub.2O.sub.12 (LLZO), Li.sub.3OCl
anti-perovskite, NASICON, LiAlTiSiPO (LATP), and
Li.sub.7-xLa.sub.3Zr.sub.2-xTa.sub.xO.sub.12 (LLZTO) in an amount
ranging from approximately 90% to 94% by weight in the
meta-solid-state electrolyte material comprising the gel polymer
and the lithium salt.
30. The method for producing an electrode for a meta-solid-state
battery of claim 29, wherein the lithium garnet is fabricated using
solid-state reaction or sol-gel method.
Description
FIELD OF INVENTION
[0001] Embodiments of the invention generally relate to a
meta-solid-state battery, and a method for producing an electrode
for a meta-solid-state battery.
BACKGROUND
[0002] A growing need has been determined for energy storage
systems for future unmanned vehicles as well as for portable
electronic devices. Presently, the majority of energy storage
systems used in transportation systems still rely on conventional
batteries that contain liquid electrolytes. However, liquid
electrolytes are highly flammable, corrosive, and decompose easily
under high temperature. As a result, safer alternatives are
constantly being sought after.
[0003] Solid-state batteries contain many advantages over
conventional batteries that contain liquid electrolytes. In fact,
solid-state batteries are non-flammable, non-volatile, and inert.
In addition, solid-state batteries can be fabricated into thin film
structures, which can significantly reduce the battery weight and
size. However, a major hurdle for developing a successful
solid-state battery is the minimization of the resistance between
the electrodes and the solid-state electrolyte. A high interfacial
resistance hinders the ionic transport across interfaces, which
leads to a major challenge in the development of solid-state
batteries.
SUMMARY
[0004] A meta-solid-state battery includes a first layer disposed
on a first current collector, a second layer disposed on a second
current collector, and third layer disposed between the first layer
and the second layer. The first layer and the second layer are the
cathode and anode electrodes. The third layer includes a first
meta-solid-state electrolyte material. Each of the cathode and
anode electrodes contain: an active material in an amount ranging
from approximately 70% to 99.98% by weight, a carbon additive in an
amount ranging from approximately 0.01% to 20% by weight, and a
second meta-solid-state electrolyte material in an amount ranging
from approximately 0.01% to 10% by weight. The first and second
meta-solid-state electrolyte materials include a gel polymer.
[0005] A method for producing an electrode for a meta-solid-state
battery includes steps for obtaining a plurality of materials for
the electrode, mixing the plurality of materials to form a mixture,
disposing the mixture on a current collector, and curing the
mixture disposed on the current collector. The plurality of
materials for the electrode includes an active material in an
amount ranging from approximately 70% to 99.98% by weight, a carbon
additive in an amount ranging from approximately 0.01% to 20% by
weight, and a meta-solid-state electrolyte material in an amount
ranging from approximately 0.01% to 10% by weight. The
meta-solid-state electrolyte material is composed of a gel
polymer.
[0006] Other aspects and advantages of one or more embodiments will
be apparent from the following description and the appended
claims.
BRIEF DESCRIPTION OF DRAWINGS
[0007] FIGS. 1A-D shows a meta-solid-state battery in accordance
with one or more embodiments.
[0008] FIG. 2 shows a graph in accordance with one or more
embodiments.
[0009] FIG. 3 shows a graph in accordance with one or more
embodiments.
[0010] FIG. 4 shows a graph in accordance with one or more
embodiments.
[0011] FIG. 5 shows a graph in accordance with one or more
embodiments.
[0012] FIG. 6 shows a flow chart in accordance with one or more
embodiments.
DETAILED DESCRIPTION
[0013] Specific embodiments will now be described in detail with
reference to the accompanying figures. Like elements in the various
figures are denoted by like reference numerals for consistency.
[0014] In the following detailed description of embodiments,
numerous specific details are set forth in order to provide a more
thorough understanding by one of ordinary skill in the art.
However, it will be apparent to one of ordinary skill in the art
that the embodiments described herein may be practiced without
these specific details. In other instances, well-known features
have not been described in detail to avoid unnecessarily
complicating the description.
[0015] Throughout the application, ordinal numbers (e.g., first,
second, third, etc.) may be used as an adjective for an element
(i.e., any noun in the application). The use of ordinal numbers
does not imply or create a particular ordering of the elements nor
limit any element to being only a single element unless expressly
disclosed, such as by the use of the terms "before," "after,"
"single," and other such terminology. Rather, the use of ordinal
numbers is to distinguish between the elements. By way of an
example, a first element is distinct from a second element, and the
first element may encompass more than one element and succeed (or
precede) the second element in an ordering of elements.
[0016] It is to be understood that the singular forms "a," "an,"
and "the" include plural referents unless the context clearly
dictates otherwise. Thus, for example, reference to "a horizontal
beam" includes reference to one or more of such beams.
[0017] Terms like "approximately," "substantially," etc., mean that
the recited characteristic, parameter, or value need not be
achieved exactly, but that deviations or variations, including for
example, tolerances, measurement error, measurement accuracy
limitations and other factors known to those of skill in the art,
may occur in amounts that do not preclude the effect the
characteristic was intended to provide.
[0018] In general, embodiments described herein relate to the
development of a meta-solid-state battery with low charge transfer
resistance, effective ionic transport, and high electric
conductivity. Specifically, embodiments discussed herein provide a
meta-solid-state battery with a first meta-solid-state electrolyte
material disposed in electrical contact between a cathode and an
anode electrode that each contain an active material, a carbon
additive, and a second meta-solid-state electrolyte material.
Furthermore, in one or more embodiments described herein, the
meta-solid-state battery may be, but is not limited to, a
rechargeable battery.
[0019] In the research area of solid-state electrolytes, the term
"meta" usually refers to a solid-state electrolyte with two or more
ionic conducting phases that coexist together where ions can be
transferred from one phase to the other with high ionic
conductivity. In one or more embodiments, the meta-solid-state
electrolyte includes inorganic ceramic-based particles that are
uniformly dispersed in an organic polymeric-based gel matrix where
ions can be transferred from the organic polymer matrix to the
inorganic ceramic-based particles. For example, to form a more
effective electrode and solid-state electrolyte interface, in one
or more embodiments, a gel polymer is mixed with ionic conducting
ceramic particles to form a meta-solid-state electrolyte.
Alternatively, in one or more embodiments, the gel polymer is mixed
with sulfuric acid (H.sub.2SO.sub.4) to form a meta-solid-state
electrolyte.
[0020] Furthermore, in one or more embodiments, to provide better
contact and ionic transport, the meta-solid-state electrolyte is
mixed with an active material to fill into the gaps between
irregular-shaped particles within the electrode. However, due to
the poor electronic conductivity of the meta-solid-state
electrolyte, the electronic conductivity of the electrode is
sacrificed. In order to improve the electrode's electronic
conductivity carbon additives such as graphene and other carbon
allotropes that have high electronic conductivity may be added into
the electrode.
[0021] In reference to the active material discussed above, the
active material may be any material that is essential for normal
functioning of a device. In one or more embodiments described
herein, the active material may be, but is not limited to,
constituents of a cell that participate in the electrochemical
charge/discharge reaction. Examples of the active material may
include, but is not limited to, lead (Pb), lead oxide (PbO.sub.2),
lithium titanate oxide (LTO), lithium iron phosphate (LFP), lithium
ruthenium tin oxide (LRS), lithium nickel cobalt manganese oxide
(NMC), and lithium nickel manganese oxide (LNM).
[0022] In reference to the electrode discussed above, the electrode
is not limited only to battery applications. In one or more
embodiments described herein, the electrode may be either an anode
electrode carrying a positive charge or a cathode electrode
carrying a negative charge. The electrode can be any type of an
electrical conductor through which electricity enters or leaves an
object, substance, or region. In one or more embodiments described
herein, the electrode may or may not be in contact with either a
metallic or nonmetallic part of a circuit.
[0023] The electrodes manufactured using the methods of one or more
embodiments described herein can be either an anode or a cathode,
depending on the preparation process of the electrode. Opposite
polarities of the electrodes manufactured using the methods of one
or more embodiments can be paired with each other to form a
complete set. A set of a completed meta-solid-state battery cell
consists of electrodes with electrolyte separators sandwiched in
between. Furthermore, the electrodes manufactured using the methods
of one or more embodiments can be paired with readily available
electrodes that can be purchased or obtained by one of ordinary
skill in the art. For example, an electrode manufactured using the
methods of one or more embodiments is able to be paired with an
existing electrode of the opposite polarity that is made of similar
active material.
[0024] The assembled electrodes of one or more embodiments were
subjected to electrochemical impedance spectroscopy (EIS) testing
with a frequency range of 1 Hz to 10 kHz and an amplitude of 0.1V.
The EIS testing was conducted with a electrochemical workstation
that is equipped with AC impedance technique on a lead or
lead-graphene working electrode and an lead oxide counter
electrode. The impedance data obtained were fitted with an
equivalent circuit model to extract the values for charge transfer
resistance (R.sub.CT). The results demonstrated that, in an example
with an electrode modified with graphene, the R.sub.CT of the
electrode is reduced by approximately 21% when compared to a
battery of one or more embodiments without electrodes modified with
a carbon additive.
[0025] The assembled electrodes of one or more embodiments were
also subjected to deep cycle tests at 20 mA charge and discharge.
The discharge curve results show that the discharge time of a
graphene modified electrode of one or more embodiments is longer
than that of an electrode of one or more embodiments without carbon
additives by approximately 6% under the same testing conditions.
Although not confined to a particularly theory as to why the
embodiments described herein has increase in discharge time, it is
possible that the increase in discharge time may be a result of a
reduction in the R.sub.CT, which leads to higher reversibility of
active particles.
[0026] In addition, an addition of graphene and graphene oxide to
the electrodes of a conventional battery containing liquid
electrolytes shows an enhancement in the partial-state-of-charge
(PSoC) cycle life of the electrode. The cycle life of the electrode
of the conventional battery containing liquid electrolytes is
enhanced by more than approximately 200% with the addition of
graphene and graphene oxide.
[0027] FIGS. 1A-D show a meta-solid-state battery (100) in
accordance with one or more embodiments. The meta-solid-state
battery (100), as shown in FIGS. 1A-D, has multiple components
including a first layer (101), a second layer (103), a third layer
(105), a first meta-solid-state electrolyte material (106), a first
current collector (107a), a second current collector (107b), an
external device (108), an active material (109), a carbon additive
(111), a second meta-solid-state electrolyte material (113), a
first meta-solid-state electrolyte interface, a second
meta-solid-state electrolyte interface, lithium salt (115), and
ionic conducting ceramic particles (117). The various components
and structures of the meta-solid-state battery (100) listed above
may interact directly or indirectly with one another. Each of these
components will be described below in more detail.
[0028] FIG. 1A shows a structural illustration of the
meta-solid-state battery (100) according to one or more
embodiments, including all of the components that make up the
complete meta-solid-state battery (100). The meta-solid-state
battery (100) of FIG. 1A includes the first layer (101), the second
layer (103), the third layer (105), the first current collector
(107a), and the second current collector (107b). In one or more
embodiments, the meta-solid-state battery (100) may be, but is not
required to be, a rechargeable battery.
[0029] In one or more embodiments, the first layer (101) is a
cathode electrode of the meta-solid-state battery (100) and the
second layer (103) is an anode electrode of the meta-solid-state
battery (100). In one or more embodiments, the first layer (101)
may be the anode electrode and the second layer (103) may be the
cathode electrode. In one or more embodiments, the first layer
(101) and the second layer (103) have, but are not limited to, the
same shape.
[0030] In one or more embodiments, the shape of the first layer
(101) and the second layer (103) may be, but is not limited to, a
circle, a square, a rectangle, or a polygon. The thickness, from a
measurement taken in the y-axis of the two-dimensional view as
shown in FIG. 1A, of the first layer (101) and the second layer
(103), may be within a range of approximately 1 .mu.m to 1 cm.
[0031] Although certain shapes and thicknesses have been described
above, it will now be apparent to one of ordinary skill in that the
shape and thickness of the first layer (101) and the second layer
(103) may vary depending on the specific battery model.
[0032] In one or more embodiments, the third layer (105) is an
electrolyte layer of a first meta-solid-state electrolyte material.
In one or more embodiments, the thickness, from a measurement taken
in the y-axis of the two-dimensional view as shown in FIG. 1A, of
the third layer (105) may be within a range of approximately 1
.mu.m to 1 cm. In one or more embodiments, the third layer (105) is
the same shape as the first layer (101) and the second layer
(103).
[0033] In one or more embodiments, the first current collector
(107a) and the second current collector (107b) may have, but is not
limited to, the same shape as the first layer (101), the second
layer (103), and the third layer (105). The thickness, from a
measurement taken in the y-axis of the two-dimensional view as
shown in FIG. 1A, of the first current collector (107a) and the
second current collector (107b) may be within a range of
approximately 10 .mu.m to 1 cm.
[0034] In one or more embodiments, the combined thickness, from a
measurement taken in the y-axis of the two-dimensional view as
shown in FIG. 1A, of a current collector and an electrode is
approximately 2 mm. Alternatively, in one or more embodiments, the
combined thickness, from a measurement taken in the y-axis of the
two-dimensional view as shown in FIG. 1A, of a current collector
and an electrode is approximately 80 .mu.m.
[0035] In one or more embodiments, the material of the first
current collector (107a) and the second current collector (107b)
may be, but is not limited to, lead (Pb) alloy, aluminum (Al),
copper (Cu), nickel (Ni), iron-nickel (Fe--Ni), stainless steel, or
carbon (C). In one or more embodiments, the material of the first
current collector (107a) or second current collector (107b),
whichever is used for the anode electrode, is carbon (C).
[0036] As seen in FIG. 1A, one or more embodiments, the first layer
(101) is disposed on either the first current collector (107a) or
the second current collector (107b) and the second layer (103) is
disposed on the alternative current collector. Alternatively, the
first layer (101) and the second layer (103) can be disposed on the
alternative current collector. In one or more embodiments, the
electrons from the external electrical circuit can be transferred
through the current collectors into the respective first and second
layers. In one or more embodiments, the third layer (105) is
disposed between the first layer (101) and the second layer
(103).
[0037] In one or more embodiments, the term "disposed" is defined
as a surface of a first component is "in physical contact with" a
surface of a second component. For example, in terms of the first
layer (101) and the third layer (105), a surface of the first layer
(101) is in physical contact with a surface of the third layer
(105). In a further example, in terms of all three layers, one
surface of the third layer (105) is in physical contact with a
surface of the first layer (101) while an opposite surface of the
third layer (105) is in contact with a surface of the second layer
(103). In one or more embodiments, the term "disposed" is
alternatively or further defined as "in electrical contact with".
For example, it is possible to transport ions and electrical
charges between the surfaces of the two components that are
disposed on each other.
[0038] As seen in FIG. 1B, in one or more embodiments, the
meta-solid-state battery (100) of FIG. 1A may further be connected
to the external device (108). In one or more embodiments, the
meta-solid-state battery (100) may be connected, either directly or
indirectly, to the external device (108). Alternatively, in one or
more embodiments, the meta-solid-state battery (100) may also be
directly inserted into the external device (108).
[0039] The external device (108) as shown in FIG. 1B may be any
electrical device that is able to provide or receive an electrical
charge from the meta-solid-state battery (100). For example, the
external device may be one of, but is not limited to, a battery
charger, an electrical circuit, an electrical device or appliance,
and a mechanical motor.
[0040] In one or more embodiments, the first current collector
(107a) and the second current collector (107b) are configured to
receive electrons from or to provide electrons to the external
device (108). It would be apparent to one of ordinary skill in the
art that the external device (108) may comprise a positive and a
negative terminal. Accordingly, the anode electrode and the cathode
electrode of the meta-solid-state battery (100) must be properly
connected to the respective terminals of the external device (108)
in order for electrical charges to flow between the two
components.
[0041] It would further be apparent to one of ordinary skill in the
art that direct contact between the surface of the meta-solid-state
battery (100) and the surface of the external device (108) is not
required. For example, an indirect connection between the
meta-solid-state battery (100) and the external device (108) may be
achievable through electrical conducting leads or wires.
[0042] 1 FIG. 1C shows the composition of each layer of the
meta-solid-state battery (100) according to one or more
embodiments. As seen in FIG. 1C, in one or more embodiments, the
first layer (101) and the second layer (103) of the
meta-solid-state battery (100) both have a composition that
includes the active material (109), the carbon additive (111), and
the second meta-solid-state electrolyte material (113).
Furthermore, the third layer (105) contains a composition of the
first meta-solid-state electrolyte material (106). In one or more
embodiments, the first meta-solid-state electrolyte material (106)
and the second meta-solid-state electrolyte material (113) may be
composed of, but is not limited to, the same material composition.
Each of the components that make up the composition of the first
layer (101), the second layer (103), and the third layer (105) are
described below in more detail.
[0043] In one or more embodiments, the active material (109) may
be, but is not limited to lead (Pb), lead oxide (PbO.sub.2),
lithium titanate oxide (LTO), lithium iron phosphate (LFP), lithium
ruthenium tin oxide (LRS), lithium nickel cobalt manganese oxide
(NMC), or lithium nickel manganese oxide (LNM). The type of active
material determines whether the meta-solid-state battery (100) is a
lead-acid battery or a lithium-ion battery. In one or more
embodiments, the active material (109) is lead (Pb) or lead oxide
(PbO.sub.2). In such cases, the meta-solid-state battery (100) of
FIG. 1 is a lead-acid battery. Alternatively, in the case that the
active material is one of lithium titanate oxide (LTO), lithium
iron phosphate (LFP), lithium ruthenium tin oxide (LRS), lithium
nickel cobalt manganese oxide (NMC), or lithium nickel manganese
oxide (LNM), the meta-solid-state battery (100) of FIG. 1 is a
lithium-ion battery.
[0044] In one or more embodiments, the carbon additive (111) may be
any carbon allotropes, such as, but is not limited to, carbon
black, carbon fiber, carbon nanotubes, graphite, graphite oxide,
graphene or graphene oxide. In one or more embodiments, the size of
the carbon additive may be, but is not limited to, a size within
the range of approximately 0.1 nm to 500 .mu.m.
[0045] In one or more embodiments, the first meta-solid-state
electrolyte material (106) and the second meta-solid-state
electrolyte material (113) may have, but is not limited to, the
same material composition. In one or more embodiments, the first
meta-solid-state electrolyte material (106) and the second
meta-solid-state electrolyte material (113), may be, but is not
limited to, a gel polymer. In one or more embodiments, the gel
polymer may be, but is not limited to, polyaniline (PANI),
polyvinyl alcohol (PVA), silica gel or polydimethylsiloxane (PDMS),
polyacrylonitrile (PAN) or polyacrylicacid (PAA). The type of gel
polymer determines whether the meta-solid-state battery (100) is a
lead-acid battery or a lithium-ion battery. In one or more
embodiments, in the example of the lead-acid battery, the gel
polymer is polyaniline (PANI), polyvinyl alcohol (PVA), or silica
gel or polydimethylsiloxane (PDMS). In one or more embodiments, the
first meta-solid-state electrolyte material (106) is only ionically
conductive and cannot be electrically conductive. In one or more
embodiments, the first meta-solid-state electrolyte material (106)
is not polyaniline (PANI).
[0046] In one or more embodiments, in the example of the lead-acid
battery, the gel polymer of the first and second meta-solid-state
electrolyte is further mixed with sulfuric acid (H.sub.2SO.sub.4)
in an amount of approximately 20% to 95% by weight of the first and
second meta-solid-state electrolyte material.
[0047] In one or more embodiments, the phrase of "by weight of the
first and second meta-solid state electrolyte material", as used
above, is defined as the total weight percentage of one of the
first or second meta-solid-state electrolyte material. For example,
in one or more embodiments, the first meta-solid-state electrolyte
material (106) has a weight percentage of approximately 100%. The
total weight of the gel polymer and the sulfuric acid
(H.sub.2SO.sub.4) would add up to a total weight percentage of
approximately 100%. Similarly, in one or more embodiments, the
second meta-solid-state electrolyte material (113) also has a
weight percentage of approximately 100%. The total weight of the
gel polymer and the sulfuric acid (H.sub.2SO.sub.4) would add up to
a total weight percentage of approximately 100%. In one or more
embodiments, the first meta-solid-state electrolyte material (106)
contains 80% gel polymer by weight and 20% sulfuric acid
(H.sub.2SO.sub.4) by weight and the second meta-solid-state
electrolyte material (113) contains 5% gel polymer by weight and
95% sulfuric acid (H.sub.2SO.sub.4) by weight.
[0048] Alternatively, in one or more embodiments, in the example of
the lithium-ion battery, the gel polymer is polyacrylonitrile (PAN)
or polyacrylicacid (PAA).
[0049] In one or more embodiments, the first meta-solid-state
electrolyte interface and the second meta-solid-state electrolyte
interface are areas on the surface of either the first or second
meta-solid-state electrolyte material that come into direct contact
with the active material (109). For example, the first
meta-solid-state interface is considered any area of the first
meta-solid-state electrolyte material (106) at the surface of the
third layer (105) that is in contact with the active material (109)
at the surface of the first layer (101) and the second layer (103).
The second meta-solid-state electrolyte interface is considered any
area of the second meta-solid-state electrolyte material (113)
within the first layer (101) and the second layer (103) that is in
contact with the active material (109) within the first layer (101)
and the second layer (103). Although the first and second
meta-solid-state electrolyte interfaces are not shown in the FIGS.
1A-D, it will now be apparent to one of ordinary skill in the art
that the first and second meta-solid-state electrolyte interfaces
exist throughout the meta-solid-battery (100) in areas where the
first and second meta-solid-state electrolyte materials are in
direct contact with the active material (109).
[0050] In one or more embodiments, the first layer (101) is
composed of a material composition that includes the active
material (109) in an amount of approximately 70% to 99.98% by
weight of the first layer (101), the carbon additive (111) in an
amount of approximately 0.01% to 20% by weight of the first layer
(101), and the second meta-solid-state electrolyte material (113)
in an amount of approximately 0.01% to 10% by weight of the first
layer (101). Similarly, in one or more embodiments, the second
layer (103) has, but is not limited to, the same material
composition as the first layer (101). In one or more embodiments,
the material composition of the second layer (103) may be, but is
not limited to, the same amount by weight as described above for
the first layer (101).
[0051] It would be apparent to one of ordinary skill in the art
that the amount of each material by weight may vary depending on
the specific battery model. It would also be apparent to one of
ordinary skill in the art that the amount by weight of each
material described above may vary depending on the type of
electrode being manufactured (cathode or anode).
[0052] In one or more embodiments, the phrase of "by weight of the
first layer (101)", as used above, is defined as the total weight
percentage of the first layer (101). For example, in one or more
embodiments, the first layer (101) has a weight percentage of
approximately 100%. The total amount of the active material (109),
the carbon additive (111), and the second meta-solid-state material
(113) within the first layer (101) would add up to a total weight
percentage of approximately 100%. Similarly, in one or more
embodiments, the second layer (103) also has a weight percentage of
approximately 100%. The total weight of the active material (109),
the carbon additive (111), and the second meta-solid-state material
(113) within the second layer would add up to a total weight
percentage of approximately 100%. Depending on the specific battery
model, the actual weight of the first layer (101) and the second
layer (103) may vary.
[0053] In one or more embodiments, the first meta-solid-state
electrolyte material of the third layer (105) acts as a separator
between the first layer (101) and the second layer (103). In one or
more embodiments, the second meta-solid-state electrolyte material
(113) acts as a filling that fills the gaps between the particles
of the active material (109) within each of the first layer (101)
and the second layer (103).
[0054] The configuration of the first and second meta-solid-state
electrolytes as described above provides better contact and ionic
transport between the active material (109) and the first and
second meta-solid-state electrolyte materials. In addition, the
carbon additives in the first layer (101) and the second layer
(103) can act as the electronic conductive network for electron
transport. In one or more embodiments, the carbon additives in the
first layer (101) and the second layer (103) enhances the
electronic conductivity of the first and second layers.
[0055] FIG. 1D, shows the composition of each layer of the
meta-solid-state battery (100) according to one or more
embodiments. As seen in FIG. 1D, in one or more embodiments, the
first layer (101) and the second layer (103) of the
meta-solid-state battery (100) are both composed of a combination
of the active material (109), the carbon additive (111), and the
second meta-solid-state electrolyte material (113). Furthermore,
the third layer (105) contains a composition of the first
meta-solid-state electrolyte material (106). The active material
(109), the carbon additive (111), the first meta-solid-state
electrolyte material (106), and the second meta-solid-state
electrolyte material (113) have been described above in one or more
embodiments of FIG. 1C. As described in FIG. 1C, in one or more
embodiments, the first meta-solid-state electrolyte material (106)
and the second meta-solid-state electrolyte layer (113) may have,
but is not limited to, the same material composition.
[0056] In one or more embodiments, the meta-solid-state battery
(100) of FIG. 1D is a lithium-ion battery. As seen in FIG. 1D, the
composition of the first layer (101) and the second layer (103)
further comprises the lithium salt (115), and the ionic conducting
ceramic particles (117). The lithium salt (115) and the ionic
conducting ceramic particles (117) are described below in more
detail.
[0057] It would be apparent to one of ordinary skill in the art
that, in one or more embodiments, the active material (109) of the
meta-solid-state battery (100) of FIG. 1D is one of lithium
titanate oxide (LTO), lithium iron phosphate (LFP), lithium
ruthenium tin oxide (LRS), lithium nickel cobalt manganese oxide
(NMC), or lithium nickel manganese oxide (LNM). In one or more
embodiments, the gel polymer of the first and second
meta-solid-state electrolyte material of the meta-solid-state
battery (100) of FIG. 1D is polyacrylonitrile (PAN) or
polyacrylicacid (PAA).
[0058] In one or more embodiments, the lithium salt (115) may be
any type of salt that contains lithium ions such as, but is not
limited to, LiPF.sub.6, Li[N(SO.sub.2F).sub.2] and
LiN(SO.sub.2CF.sub.3).sub.2.
[0059] In one or more embodiments, the ionic ceramic particles
(117) may be, a type of lithium garnet such as, but is not limited
to, Li.sub.7La.sub.3Zr.sub.2O.sub.12, Li.sub.3OCl anti-perovskite,
NASICON, LiAITiSiPO (LATP), and
Li.sub.7-xLa.sub.3Zr.sub.2-xTa.sub.xO.sub.12. Depending on the type
of lithium garnet selected, the shape and size of the lithium
garnet may vary.
[0060] In one or more embodiments, the first meta-solid-state
electrolyte material (106) containing only gel polymer may further
contain lithium salt (115) in an amount of approximately 95% to 98%
by weight of the first meta-solid-state electrolyte material (106).
In one or more embodiments, the first meta-solid-state electrolyte
material (106) containing only the combination of the mixture of
the gel polymer and the lithium salt (115) may further contain
ionic ceramic particles (117) in an amount of approximately 90% to
94% by weight of the first meta-solid-state electrolyte material
(106) containing the combination of the mixture of the gel polymer
and the lithium salt (115).
[0061] In one or more embodiments, the phrase "by weight of the
first meta-solid-state electrolyte material (106)," as used above,
is defined as the total weight percentage of the first
meta-solid-state electrolyte material (106) containing only the gel
polymer and the lithium salt (115). For example, in one or more
embodiments, the total weight of the first meta-solid-state
electrolyte material (106) may contain approximately 95% to 98% of
the lithium salt (115) and approximately 2% to 5% of the gel
polymer, respectively. Depending on the specific battery model, the
actual weight of the first meta-solid-state electrolyte material
(106) may vary.
[0062] Similarly, in one or more embodiments, the phrase "by weight
of the first meta-solid-state electrolyte material (106) containing
the combination of the mixture of the gel polymer and the lithium
salt (115)," as used above, is defined as the total weight
percentage of the first meta-solid-state electrolyte material (106)
containing the combination of the gel polymer, the lithium salt
(115), and the ionic ceramic particles (117). For example, in one
or more embodiments, the total weight of the first meta-solid-state
electrolyte (106) material may contain approximately 90% to 94% of
the ionic ceramic particles (117) and approximately 6% to 10% of
the gel polymer and lithium salt (115) mixture, respectively.
Depending on the specific battery model, the actual weight of the
first meta-solid-state electrolyte material (106) may vary.
[0063] In one or more embodiments, the second meta-solid-state
electrolyte material (113) containing only gel polymer may further
contain lithium salt (115) in an amount of approximately 95% to 98%
by weight of the second meta-solid-state electrolyte material.
(113) In one or more embodiments, the second meta-solid-state
electrolyte material containing the combination of the mixture of
the gel polymer and the lithium salt (115) may further contain
ionic ceramic particles (117) in an amount of approximately 90% to
94% by weight of the second meta-solid-state electrolyte material
(113) containing the combination of the mixture of the gel polymer
and the lithium salt (115).
[0064] In one or more embodiments, the phrase "by weight of the
second meta-solid-state electrolyte material (113)," as used above,
is defined as the total weight percentage of the second
meta-solid-state electrolyte material (113) containing only the gel
polymer and the lithium salt (115). For example, in one or more
embodiments, the total weight of the second meta-solid-state
electrolyte material (113) may contain approximately 95% to 98% of
the lithium salt (115) and approximately 5% to 10% of the gel
polymer, respectively. Depending on the specific battery model, the
actual weight of the second meta-solid-state electrolyte material
(113) may vary.
[0065] Similarly, in one or more embodiments, the phrase "by weight
of the second meta-solid-state electrolyte material (113)
containing the combination of the mixture of the gel polymer and
the lithium salt (115)," as used above, is defined as the total
weight percentage of the second meta-solid-state electrolyte
material (113) containing the combination of the gel polymer, the
lithium salt (115), and the ionic ceramic particles (117). For
example, in one or more embodiments, the total weight of the second
meta-solid-state electrolyte material (113) material may contain
approximately 90% to 94% of the ionic ceramic particles (117) and
approximately 6% to 10% of the gel polymer and lithium salt (115)
mixture, respectively. Depending on the specific battery model, the
actual weight of the second meta-solid-state electrolyte material
(113) may vary.
[0066] In one or more embodiments, in order to increase the ionic
conductivity of the meta-solid-state battery (100), lithium salt
(115) such as LiPF.sub.6, Li[N(SO.sub.2F).sub.2] and
LiN(SO.sub.2CF.sub.3).sub.2 and lithium garnet such as
Li.sub.7La.sub.3Zr.sub.2O.sub.12, Li.sub.3OCl anti-perovskite,
NASICON, LiAITiSiPO (LATP), and
Li.sub.7-xLa.sub.3Zr.sub.2-xTa.sub.xO.sub.2 are added to the first
and second meta-solid-state electrolyte materials. An advantage
achieved by this combination is that the ionic conductivity of the
ceramic-based conductor such as lithium garnet
Li.sub.7La.sub.3Zr.sub.2O.sub.12 can be tuned by doping and
manipulating the stoichiometry ratio of doping elements, for
example, by doping and manipulating
Li.sub.7La.sub.3Zr.sub.2O.sub.12 into
Li.sub.7-xLa.sub.3Zr.sub.2-xTa.sub.xO.sub.2 with a ratio between a
range of approximately X=0.2 to 2.0.
[0067] FIG. 2 is a graph of the electrochemical impedance
spectroscopy (EIS) results for two different batteries. The first
battery (201) is a lead-acid meta-solid-state battery of one or
more embodiments with graphene modified electrodes. The second
battery (203) is a lead-acid meta-solid-state battery of one or
more embodiments without carbon modified electrodes. The data for
both batteries will be taken and fitted with an equivalent circuit
model (205). In one or more embodiments, the data for both
batteries was fitted using Z-fit function of a data analysis
software to fit the experimental results with the equivalent
circuit model (205) using the following equation:
Z ( f ) = R 1 + R 2 R 2 Q 2 ( j 2 .pi. f ) .alpha. 2 + 1 + R 3 R 3
Q 3 ( j 2 .pi. f ) .alpha. 3 + 1 Equation 1 ##EQU00001##
Although graphene was the carbon additive used in this example, it
may be apparent to one of ordinary skill in the art that the carbon
additive is not limited to only graphene. Alternatively, as
discussed above, the carbon additive may be any carbon allotropes
such as, but is not limited to, carbon black, carbon fiber, carbon
nanotubes, graphite, graphite oxide, graphene, and graphene
oxide.
[0068] As seen in FIG. 2, the impedance result of the first battery
(201) is comparable to the impedance result of the second battery
(203). Therefore, the comparable results indicate that the
lead-acid meta-solid-state battery of one or more embodiments with
graphene modified electrodes is superior compared to the lead-acid
meta-solid-state battery of one or more embodiments without carbon
modified electrodes.
[0069] As further seen in FIG. 2, the ohmic resistance, which is
the intercepting point of the curve with the x-axis, of the first
battery (201) is much smaller compared to the second battery (203).
The ohmic resistance of an electrolyte represents the electrolyte's
electrolytic resistance.
[0070] In FIG. 2, the arc of the open loop in the circuit model
(205) signifies the charge transfer resistance in the reaction
layer where the electrochemical reaction processes occur at the
interface of the active material. The value of the charge transfer
resistance for one or more embodiments can be extracted using the
circuit model (205).
[0071] Overall, FIG. 2 demonstrates that the addition of graphene
to the electrode of a meta-solid-state battery is able to not only
achieve comparable impedance results as that of the conventional
battery, but also able to reduce the charge transfer resistance
across the interface of the gel electrolyte and electrode
surface.
[0072] FIG. 3 is a graph showing the charge transfer resistance
results obtained after fitting the results from FIG. 2 into the
circuit model shown in FIG. 2. As demonstrated in FIG. 3, the
charge transfer resistance of the first battery (301), a lead-acid
meta-solid-state battery of one or more embodiments with graphene
modified electrodes, is lower than the charge transfer resistance
of the second battery (303), a lead-acid meta-solid-state battery
of one or more embodiments without carbon modified electrodes. The
lead-acid meta-solid-state battery of one or more embodiments with
graphene modified electrodes and the lead-acid meta-solid-state
battery of one or more embodiments without carbon modified
electrodes have been described above in FIG. 2.
[0073] As demonstrated in FIG. 3, the charge transfer resistance of
the first battery (301) is in a range of approximately 0.1.OMEGA.
to 5.31.OMEGA. whereas the charge transfer resistance of the second
battery (303) is in a range of approximately 0.1.OMEGA. to
6.45.OMEGA.. The results demonstrate that the charge transfer
resistance of the first battery (301) is approximately 21% lower
than the charge transfer resistance of the second battery
(303).
[0074] This indicates that the addition of graphene to the
electrode of the first battery (301) reduces the charge transfer
resistance within the reaction layer. As discussed above, the
reaction layer is where the electrochemical reaction processes
occur at the interface of the active material.
[0075] FIG. 4 is a graph showing discharge time results for the two
batteries described in FIG. 2. In FIG. 4, a discharge time result
for the first battery (401), the lead-acid meta-solid-state battery
of one or more embodiments with graphene modified electrodes, is
compared to a discharge time result for the second battery (403), a
lead-acid meta-solid-state battery of one or more embodiments
without carbon modified electrodes. The lead-acid meta-solid-state
battery of one or more embodiments with graphene modified
electrodes and the lead-acid meta-solid-state battery of one or
more embodiments without carbon modified electrodes have been
described above in FIG. 2.
[0076] As demonstrated in FIG. 4, the discharge time of the first
battery (401) is approximately 6% longer than the discharge time of
the second battery (403). The results demonstrate that the first
battery (401) was not only able to deliver comparable performance
to the second battery (403), but was also able to maintain a
slightly longer overall discharge time.
[0077] The longer discharge time demonstrates that the capacity of
the first battery (401) is larger than the capacity of the second
battery (403). Furthermore, the longer discharge time also
demonstrates that the addition of graphene increased the amount of
energy that the first battery (401) can deliver compared to the
amount of energy deliverable by the second battery (403).
[0078] FIG. 5 is a graph showing the results of
partial-state-of-charge (PSoC) tests conducted for three different
batteries. The first battery is a control battery (501). The
control battery (501) is a battery that is not modified with any
carbon additives. The second battery (503) is a battery with the
anode electrode modified with a carbon additive of graphene. The
third battery (505) is a battery with the anode electrode modified
with a carbon additive of graphene oxide. All three batteries are
conventional lead-acid batteries with liquid electrolytes that do
not contain meta-solid-state electrolytes.
[0079] In one or more embodiments, the anode electrode in the
second battery (503) and the third battery (505) contain carbon
additives of approximately 0.2% by weight (0.2 wt %) of each
electrode.
[0080] In one or more embodiments, the phrase of "by weight of each
electrode", as used above, is defined as the total weight
percentage of a single electrode. For example, in one or more
embodiments, the anode electrode has a total weight percentage of
approximately 100%. The total amount of the carbon additive in the
anode electrode is approximately 0.2% of the anode electrode's
total weight percentage. Depending on the specific battery model,
the actual weight of each electrode may vary.
[0081] Although graphene and graphene oxide were the carbon
additives used in this example, it may be apparent to one of
ordinary skill in the art that the carbon additive is not limited
to only graphene and graphene oxide. Alternatively, as discussed
above, the carbon additive may be any carbon allotropes such as,
but is not limited to, carbon black, carbon fiber, carbon
nanotubes, graphite, graphite oxide, graphene, and graphene
oxide.
[0082] A partial-state-of-charge test is used to assess the cycle
life of a battery. During a partial-state-of-charge test, the
tested battery is partially charged and discharged repeatedly, each
partial charge and discharge being one complete cycle, until a
cut-off voltage is reached. The cut-off voltage is the cell or
battery voltage at which the discharge is terminated and the
battery is no longer able to supply power.
[0083] As demonstrated in FIG. 5, the second battery (503) and the
third battery (505) both show PSoC results of over 20,000 cycles
while the PSoC result of the control battery (501) is only 6,000
cycles. This result indicates that the cycle life of the second
battery (503) and the third battery (505) are each 200% greater
than the cycle life of the control battery (501.) The results also
demonstrate that graphene and graphene oxide additives improve
performance, likely due to their ability to effectively suppress
sulfation, which is the accumulation of non-conductive lead sulfate
(PbSO.sub.4) particles produced during the electrochemical reaction
that occurs during the repeated partial charge and discharge of the
batteries.
[0084] As further demonstrated in FIG. 5, compared to the graphene
additive, it is believed that the graphene oxide additive was more
effective in suppressing sulfation. In fact, as demonstrated in
FIG. 5, the third battery (505) that was modified with graphene
oxide has a larger partial-state-of-charge result with
approximately 2,000 more cycles compared to the
partial-state-of-charge result of the second battery (503) that was
modified with graphene.
[0085] FIG. 6 shows a method for producing an electrode for a
meta-solid-state battery in accordance with one or more
embodiments. Specifically, FIG. 6 shows a method for producing an
electrode for a meta-solid-state battery in accordance to one of
the meta-solid-state batteries described in FIGS. 1A-D. It would be
apparent to one of ordinary skill in the art that the method
described below would be applicable to one or more embodiments of
the meta-solid-state battery described in FIGS. 1A-D.
[0086] In Step 601, at least one of an active material, a carbon
additive, and a meta-solid-state electrolyte material for producing
the electrode for a meta-solid-state battery is obtained. In one or
more embodiments, the composition of the meta-solid-state
electrolyte may vary depending on the specific battery model.
[0087] In one or more embodiments, the carbon additives can be any
carbon allotropes such as, but is not limited to, carbon black,
carbon fiber, carbon nanotubes, graphite, graphite oxide, graphene,
and graphene oxide. The carbon additives can be produced using
chemical vapor deposition, liquid exfoliation, electrochemical
exfoliation, microwave exfoliation, or chemical exfoliation. In one
or more embodiments, the carbon additives can be functionalized
with oxygen-containing groups and/or conducting polymers such as
polyaniline, polyphenylene vinylene, or polyvinylpyrollidone. In
one or more embodiments, the carbon additives can be mixed into the
electrode in the form of dried powder, liquid suspension, gel-like,
or three-dimensional interconnected foam structures.
[0088] In one or more embodiments, the electrode for a
meta-solid-state battery is made up of the active material in an
amount of approximately 70% to 99.98% by weight of the electrode,
the carbon additive in an amount of approximately 0.01% to 20% by
weight of the electrode, and the meta-solid-state electrolyte
material in an amount of approximately 0.01% to 10% by weight of
the electrode.
[0089] In one or more embodiments, the phrase of "by weight of the
electrode", as used above, is defined as the total weight
percentage of the electrode. For example, in one or more
embodiments, the electrode has a total weight percentage of
approximately 100%. The total amount of the active material, the
carbon additive, and the meta-solid-state material within the
electrode should add up to the total weight percentage of
approximately 100%. Depending on the specific battery model, the
actual weight of the electrode may vary.
[0090] In one or more embodiments, in the example of a lead-acid
battery, the active material is lead (Pb) or lead oxide
(PbO.sub.2). In one or more embodiments, the meta-solid-state
electrolyte material is a gel polymer that is polyaniline (PANI),
polyvinyl alcohol (PVA), silica gel or polydimethylsiloxane (PDMS).
In one or more embodiments, the gel polymer of the meta-solid-state
electrolyte is further mixed with sulfuric acid (H.sub.2SO.sub.4)
in an amount of approximately 95% by weight of the meta-solid-state
electrolyte material.
[0091] In one or more embodiments, the phrase of "by weight of the
meta-solid-state electrolyte material", as used above, is defined
as the total weight percentage the meta-solid-state electrolyte
material. For example, in one or more embodiments, the
meta-solid-state electrolyte material has a weight percentage of
approximately 100%. The total weight of the gel polymer and the
sulfuric acid (H.sub.2SO.sub.4) would add up to a total weight
percentage of approximately 100%.
[0092] In one or more embodiments, the meta-solid-state electrolyte
material containing gel polymer and sulfuric acid (H.sub.2SO.sub.4)
is prepared using methods such as solution mixing, hydrothermal, or
colloidal dispersion.
[0093] In one or more embodiments, in the example of a lithium-ion
battery, the active material is lithium titanate oxide (LTO),
lithium iron phosphate (LFP), lithium nickel manganese oxide (LNM),
lithium ruthenium tin oxide (LRS) or lithium nickel cobalt
manganese oxide (NMC). In one or more embodiments, the
meta-solid-state electrolyte material is a gel polymer that is
polyacrylonitrile (PAN) or polyacrylicacid (PAA). The
meta-solid-state electrolyte material may further contain lithium
salt in an amount of approximately 95% to 98% by weight of the
meta-solid-state electrolyte material. In one or more embodiments,
the meta-solid-state electrolyte material containing the
combination of the mixture of the gel polymer and the lithium salt
may further contain ionic ceramic particles in an amount of
approximately 90% to 94% by weight of the meta-solid-state
electrolyte material containing the combination of the mixture of
the gel polymer and the lithium salt.
[0094] In one or more embodiments, the phrase of "by weight of the
meta-solid-state electrolyte material," as used above, is defined
as the total weight percentage the meta-solid-state electrolyte
material containing only the gel polymer and the lithium salt. For
example, in one or more embodiments, the total weight of the
meta-solid-state electrolyte material may contain approximately 95%
to 98% of the lithium salt and approximately 2% to 5% of the gel
polymer, respectively. Depending on the specific battery model, the
actual weight of the meta-solid-state electrolyte material may
vary.
[0095] Similarly, in one or more embodiments, the phrase of "by
weight of the meta-solid-state electrolyte material containing the
combination of the mixture of the gel polymer and the lithium
salt," as used above, is defined as the total weight percentage of
the meta-solid-state electrolyte material containing the gel
polymer, the lithium salt, and the ionic ceramic particles. For
example, in one or more embodiments, the total weight of the
meta-solid-state electrolyte material may contain approximately 90%
to 94% of the ionic ceramic particles and approximately 6% to 10%
of the gel polymer and lithium salt mixture, respectively.
Depending on the specific battery model, the actual weight of the
meta-solid-state electrolyte material may vary.
[0096] In one or more embodiments, the lithium garnet is fabricated
through solid-state reaction or a sol-gel method. In one or more
embodiments, the meta-solid-state electrolyte material containing
the gel polymer, the lithium salt, and the ionic ceramic particles
is prepared using methods such as solution mixing, hydrothermal,
colloidal dispersion, or a sol-gel method.
[0097] In one or more embodiments, the lithium salt is first
dissolved in a mixture of propylene carbonate (PC) and dimethyl
carbonate (DEC) to form a first mixture. The first mixture is then
added to the gel polymer to form a lithium conductive polymer. The
lithium conductive polymer is then mixed with the prepared lithium
garnet to form the meta-solid-state electrolyte material.
[0098] In Step 603, the active material, the carbon additive, and
the meta-solid-state electrolyte material obtained in Step 601 are
mixed together to form an electrode mixture. In one or more
embodiments, the method of mixing the active material, the carbon
additive, and the meta-solid-state electrolyte material may vary
depending on the type of battery being produced.
[0099] In one or more embodiments, in the example of the lead-acid
battery, the active material, the carbon additive, and the
meta-solid-state electrolyte material is mixed together using a
planetary mixer.
[0100] In one or more embodiments, in the example of the
lithium-ion battery, the active material, the carbon additive, and
the meta-solid-state electrolyte material are mixed together using
a motorized dissolver stirrer at 1000 rpm for 1 hour.
[0101] In Step 605, the electrode mixture from Step 603 is disposed
on the surface of a current collector. In one or more embodiments,
the method of disposing the electrode mixture onto the surface of
the current collector may vary depending on the type of battery
being produced.
[0102] In one or more embodiments, the term "disposed" is defined
as a surface of a first component is "in physical contact with" a
surface of a second component. For example, in terms of the
electrode mixture and the current collector, a surface of the
current collector is in physical contact with a surface of the
electrode mixture. In one or more embodiments, the term "disposed"
is alternatively or further defined as "in electrical contact
with". For example, it is possible to transport electrical charges
between the surfaces of the two components that are disposed on
each other.
[0103] In one or more embodiments, in the example of the lead-acid
battery, the electrode mixture is printed onto the surface of the
current collector. In one or more embodiments, the electrode
mixture is mechanically pressed or spread onto the surface of a
current collector. The current collector with the electrode mixture
is then pressed to form an electrode.
[0104] In one or more embodiments, in the example of the
lithium-ion battery, the electrode mixture is printed or sprayed
onto the surface of the current collector. In one or more
embodiments, a screen mesh was pressurized by a rubber squeegee to
coat the electrode mixture onto the current collector. The distance
between the screen mesh and the current collector is approximately
50 .mu.m.
[0105] In Step 607, the current collector with the electrode
mixture from Step 605 is cured. In one or more embodiments, the
method of curing the current collector with the electrode mixture
may vary depending on the type of battery being produced. After the
current collector with the electrode mixture is cured, the carbon
additive and the meta-solid-state material in the resulting
electrode are uniformly distributed within the electrode.
[0106] In one or more embodiments, in the example of the lead-acid
battery, the current collector with the electrode mixture is cured
in a humidity chamber. In one or more embodiments, the current
collector with the electrode mixture is cured in a humidity chamber
at approximately 40.degree. C. to 80.degree. C. with a relative
humidity (RH) of approximately 65% RH to 95% RH for approximately
10-40 hours and then at approximately 40.degree. C. to 80.degree.
C. only for approximately 10-40 hours.
[0107] In one or more embodiments, in the example of the
lithium-ion battery, the current collector with the electrode
mixture is cured in an oven. In one or more embodiments, the
current collector with the electrode mixture is cured in an oven at
a temperature of 40.degree. C. to 80.degree. C. only for
approximately 10-40 hours.
[0108] While the invention has been described with respect to a
limited number of embodiments, those skilled in the art, having
benefit of this disclosure, will appreciate that other embodiments
can be devised which do not depart from the scope of the invention
as disclosed herein. Accordingly, the scope of the invention should
be limited only by the attached claims.
* * * * *