as) United States
`a2) Patent Application Publication 0) Pub. No.: US 2017/0250449 Al
` ADAMSetal. (43) Pub. Date: Aug.31, 2017
`
`
`
`US 20170250449A1
`
`(54) ELECTRODE MATERIALS FOR
`RECHARGEABLE ZINC CELLS AND
`BATTERIES PRODUCED THEREFROM
`
`(71) Applicant: UNIVERSITY OF WATERLOO,
`Waterloo (CA)
`
`(72)
`
`.
`Inventors: Brian D. ADAMS,Mitchell (CA);
`Dipan KUNDU,Kitchener (CA);
`Linda Fk. NAZAR, Waterloo (CA)
` 15/513,914
`
`(21) Appl. No.
`
`May 31, 2016
`PCT/CA2016/050613
`
`(22) PCT Filed:
`(86) PCT No.:
`§ 371 (c)(1),
`(2) Date:
`Mar. 23, 2017
`.
`oe
`Related U.S. Application Data
`(60) Provisional application No. 62/230,502,filed on Jun.
`8, 2015.
`
`Publication Classification
`
`(51)
`
`Int. CL
`HOIM 10/36
`HOIM 4/485
`
`(2006.01)
`(2006.01)
`
`tration range from 0.01 to 10 molar.
`
`(2006.01)
`(2006.01)
`
`HOIM 4/62
`HOIM 438
`(52) U.S. CL
`CPC wee HOIM 10/36 (2013.01), HOIM 438
`(2013.01); HOIM 4/485 (2013.01); HOIM
`4/625 (2013.01); HOIM 4/622 (2013.01);
`HOIM 2300/0002 (2013.01); HOIM 2004/021
`(2013.01)
`
`67)
`
`ABSTRACT
`
`The present disclosure discloses a rechargeable Zn battery
`based on layered/tunnelled structure vanadium/molybde-
`num oxides,with/without the presence of neutral/cationie/
`anionic species and/or water molecules inserted into the
`interlayers/tunnels, of nano/microparticle morphology as
`robust materials for high rate and long term reversible Zn?*
`ion intercalation storage at the positive electrode, that are
`coupled with a metallic Zn negative electrode, and an
`aqueous electrolyte. The positive electrode may include
`electronically conducting additives and one or more binders
`along with the Zn** intercalation material;
`the negative
`electrode is Zn metal in any form; the aqueouselectrolyte is
`of pH 1 to 9 and contains a soluble zinc salt in a concen-
`
`UW Exhibit 1012, pg. 1
`
`UW Exhibit 1012, pg. 1
`
`

`

`Patent Application Publication Aug. 31,2017 Sheet 1 of 14
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`US 2017/0250449 Al
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`Discharge
`
`Figure 1A
`
`UW Exhibit 1012, pg. 2
`
`UW Exhibit 1012, pg. 2
`
`

`

`Patent Application Publication Aug. 31,2017 Sheet 2 of 14
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`US 2017/0250449 Al
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`
`
`Figure 1B
`
`UW Exhibit 1012, pg. 3
`
`UW Exhibit 1012, pg. 3
`
`

`

`Patent Application Publication
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`Aug. 31, 2017 Sheet 3 of 14
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`US 2017/0250449 Al
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`UW Exhibit 1012, pg. 4
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`UW Exhibit 1012, pg. 4
`
`

`

`Patent Application Publication
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`Aug. 31, 2017 Sheet 4 of 14
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`US 2017/0250449 Al
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`UW Exhibit 1012, pg. 5
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`UW Exhibit 1012, pg. 5
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`

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`Patent Application Publication
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`Aug. 31, 2017 Sheet 5 of 14
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`UW Exhibit 1012, pg. 6
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`
`

`

`Patent Application Publication
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`Aug. 31, 2017 Sheet 6 of 14
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`US 2017/0250449 Al
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`UW Exhibit 1012, pg. 7
`
`UW Exhibit 1012, pg. 7
`
`

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`Patent Application Publication Aug. 31,2017 Sheet 7 of 14
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`US 2017/0250449 Al
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`UW Exhibit 1012, pg. 8
`
`UW Exhibit 1012, pg. 8
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`

`

`Patent Application Publication Aug. 31,2017 Sheet 8 of 14
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`US 2017/0250449 Al
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`Figure7B
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`UW Exhibit 1012, pg. 9
`
`UW Exhibit 1012, pg. 9
`
`

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`Patent Application Publication Aug. 31,2017 Sheet 9 of 14
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`UW Exhibit 1012, pg. 10
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`UW Exhibit 1012, pg. 10
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`

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`Patent Application Publication Aug. 31,2017 Sheet 10 of 14
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`US 2017/0250449 Al
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`

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`Patent Application Publication
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`Aug. 31, 2017 Sheet 11 of 14
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`UW Exhibit 1012, pg. 12
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`Patent Application Publication Aug. 31,2017 Sheet 12 of 14
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`Patent Application Publication Aug. 31,2017 Sheet 13 of 14
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`UW Exhibit 1012, pg. 14
`
`UW Exhibit 1012, pg. 14
`
`

`

`Patent Application Publication Aug. 31,2017 Sheet 14 of 14
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`US 2017/0250449 Al
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`
`
`
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`UW Exhibit 1012, pg. 15
`
`UW Exhibit 1012, pg. 15
`
`

`

`US 2017/0250449 Al
`
`Aug. 31, 2017
`
`SUMMARY
`
`ELECTRODE MATERIALS FOR
`RECHARGEABLE ZINC CELLS AND
`BATTERIES PRODUCED THEREFROM
`
`FIELD
`
`[0001] This disclosure relates generally to batteries, and,
`more specifically to zinc ion batteries involving zinc inter-
`calation positive electrode materials, zinc metal based nega-
`tive electrodes in any form, and an aqueous electrolyte
`containing zinc salt and batteries using these positive elec-
`trode materials.
`
`[0005] The present disclosure discloses a rechargeable Zn
`battery based on layered/tunnelled structure vanadium/mo-
`lybdenum oxides, with/without
`the presence of neutral/
`cationic/anionic species and/or water molecules inserted
`into the interlayers/tunnels, of nano/microparticle morphol-
`ogy as robust materials for high rate and long term reversible
`Zn** ion intercalation storage at the positive electrode, that
`are coupled with a metallic Zn negative electrode, and an
`aqueous electrolyte. The positive electrode may include
`electronically conducting additives and one or more binders
`along with the Zn** intercalation material;
`the negative
`electrode is Zn metal in any form; the aqueouselectrolyte is
`BACKGROUND
`may have a pH inarange of 1 to 9 and contains a soluble
`zinc salt which may be in a concentration range from 0.01
`to 10 molar.
`
`[0002] Given the looming concerns of climate change,
`sustainable energy resources such as solar and wind have
`entered the global spotlight, triggering the search for reli-
`able, low cost electrochemical energy storage. Among the
`various options, lithium ion batteries are currently the most
`attractive candidates due to their high energy density, and
`foothold in the marketplace. However, many factors (cost,
`safety, and lifetime) will likely limit their large scale appli-
`cations, and dictate against
`their use in stationary grid
`storage where low cost and durability are more of a concern
`than weight. Whatis neededis a high energy density battery
`that is rechargeable, cheap, safe, and easy to manufacture
`and dispose of or recycle. Aqueous batteries (water based
`electrolytes) are therefore attracting tremendous attention.
`Their high conductivity (up to 1 Siemens (S) cm7') com-
`paredto the non-aqueouselectrolytes (0.001 to 0.01 S em™')
`also favour high rate capabilities suitable for emerging
`applications.
`[0010] anelectrolyte comprising water and havingasalt of
`
`zinc dissolved therein.
`[0003] The use of metallic negative electrodes is a means
`to achieve high energy density and ease of battery assembly
`(hence lower cost). There is a trade-off between the reduc-
`tion potential of a metal, E°, (low values give highercell
`voltages) and safety. Metals with low reduction potentials
`(e.g., lithium, potassium, calcium, sodium, and magnesium)
`react with water to produce hydrogen. However, zinc is
`stable in water and for that reason it has been used as the
`
`[0006] Thus, disclosed herein is a zine ion battery, com-
`prising:
`a positive electrode compartment having enclosed
`[0007]
`therein an intercalation layered positive electrode material
`M,.V,0;.nH,O, wherein x is in a range from 0.05 to 1, n is
`in arange from 0 to 2, wherein M is any one or combination
`of a d-block metal ion, f-block metal ion and alkaline earth
`ion, the metal M ion being in a +2 to +4 valence state, and
`wherein said V,O, is a layered crystal structure having the
`metal ions M pillared between the layers, and waters of
`hydration coordinated to the metal ions M;
`[0008]
`a negative electrode compartment having enclosed
`therein a negative electrode for storing zinc;
`[0009]
`a separator electrically insulating and permeable to
`zinc ions separating the positive and negative compartments;
`and
`
`[0011] There is also disclosed herein a zinc ion battery,
`comprising:
`[0012]
`a positive electrode compartment having enclosed
`therein and intercalated layered positive electrode material
`M,.V3;0,.nH,O, wherein x is in a range from 0.05 to 1, n is
`greater than 0 and less than 2, wherein M is any one or
`combination of a d-block metal ion, f-block metal ion and
`alkaline earth ion, the metal M ion being in a +2 to +4
`valence state, and wherein said V,O, is a layered crystal
`structure having the metal
`ions M pillared between the
`layers, and waters of hydration coordinated to the metal ions
`M and/or hydrogen bonded to the layers;
`[0013]
`a negative electrode compartment having enclosed
`therein a negative electrode for storing zinc;
`[0014]
`a separator electrically insulating and permeable to
`zinc ions separating the positive and negative compartments;
`and
`
`negative electrode in primary aqueous battery systems.
`Moreover, zinc has (a) high abundanceandlarge production
`which makesit inexpensive; (b) non-toxicity; (c) low redox
`potential (-0.76 V vs. standard hydrogen electrode (SHE))
`compared to other negative electrode materials used in
`aqueous batteries; and (d) stability in water due to a high
`overpotential for hydrogen evolution. The latter renders a
`large voltage window (~2 V) for aqueous zinc-ion batteries
`(AZIBs) employing a metallic Zn negative electrode.
`
`[0004] Vanadium and molybdenum are low cost metals
`[0015] anelectrolyte comprising water and havingasalt of
`
`possessing a range of oxidation states (V: +2 to +5; Mo: +2
`zinc dissolved therein.
`to +6), which allows for multiple redox and hence large
`specific capacities for vanadium or molybdenum based
`electrode materials. Layered V,,O,, (vanadium oxides: V,0.,
`V30s, V4O,,) and MoO, (molybdenum oxides) that are
`madeof two dimensional sheetstructures were the subject of
`muchpast investigation for non-aqueous and aqueousalkali
`(Li and Na) ion batteries. The additional presence of inter-
`layer neutral molecules, ions, metal ions and/or water of
`hydration in such layered oxides act as pillars, providing
`structural
`stability during long term charge discharge
`cycling.
`
`[0016] There is also disclosed a zinc ion battery; compris-
`ing:
`a positive electrode compartment having enclosed
`[0017]
`therein an intercalated layered positive electrode material
`M,Mo0O,,.nH,O, wherein x is in a range from 0 to 1, y is in
`a range from 2 to 3, nis ina range from 0 to 2, wherein M
`is any one or combination of a d-block metal ion, f-block
`metal ion and alkaline earth ion, the metal M ion being in a
`+2 to +4 valence state, and wherein said MoO,, has a layer
`or tunnel crystal structure, and the metal ions M,if present,
`
`UW Exhibit 1012, pg. 16
`
`UW Exhibit 1012, pg. 16
`
`

`

`US 2017/0250449 Al
`
`Aug. 31, 2017
`
`FIGS. 10A and 10B show rate capability of the
`[0034]
`pillared between the layers, and waters of hydration coor-
`(9A) H,V,0, and 9B) Zn, .;V,0;.nH,O cells studied
`dinated to the metal ions M pillared between the layers;
`under variable current loading as a function of cycling. The
`[0018]
`a negative electrode compartment having enclosed
`corresponding coulombicefficiencies are also shown.
`therein a negative electrode for storing zinc; a separator
`[0035]
`FIG. 11 showsthe tradeoff between energy and
`electrically insulating and permeable to zinc ions separating
`power density (Ragone plot) for reversible Zn** storage in
`the positive and negative compartments; and
`
`
`[0019] anelectrolyte comprising water and havingasalt of ZNo.25V20;.nH,O, H,V3;0g, MnO,, and Zn,[Fe(CN)¢]>.
`zinc dissolved therein.
`[0020] A further understanding of the functional and
`advantageous aspects of the disclosure can be realized by
`reference to the following detailed description and drawings.
`
`[0036] Various embodiments and aspects of the disclosure
`will be described with reference to details discussed below.
`
`DETAILED DESCRIPTION
`
`BRIEF DESCRIPTION OF THE DRAWINGS
`
`[0021] Embodiments of the disclosure will now be
`described, by way of example only, with reference to the
`drawings, in which:
`[0022]
`FIG. 1A showsa conceptual schemeof a zinc-ion
`battery constructed in accordance with the present disclo-
`sure.
`
`FIG. 1B is a cross section of a zinc-ion battery.
`[0023]
`1
`FIG. 2 shows linear sweep voltammograms at
`[0024]
`mV/s on Pt, Ti, and Zn in 1 M Na,SO, showing the onset of
`the hydrogen evolution reaction.
`1
`[0025]
`FIG. 3 shows linear sweep voltammograms at
`mV/s in 1 M Na,SO, showing the hydrogen evolution
`reaction. The dotted voltammogram in (a) shows zinc depo-
`sition on a zine disk electrode in 1 M ZnSO, for comparison.
`[0026]
`FIG. 4A showscyclic voltammograms at 5 mV/s
`on a Ti disk electrode.
`
`The following description and drawingsareillustrative of
`the disclosure and are not to be construed as limiting the
`disclosure. Numerous specific details are described to pro-
`vide a thorough understanding of various embodiments of
`the present disclosure. However, in certain instances, well-
`known or conventional details are not described in order to
`
`provide a concise discussion of embodiments of the present
`disclosure.
`[0037] The Figuresare not to scale and some features may
`be exaggerated or minimized to show details of particular
`elements while related elements may have been eliminated
`to prevent obscuring novel aspects. Therefore, specific struc-
`tural and functional details disclosed herein are not to be
`
`interpreted as limiting but merely as a basis for the claims
`and as a representative basis for teaching one skilled in the
`art to variously employ the present disclosure.
`[0038] As used herein, the term “about”, when used in
`conjunction with ranges of dimensions, temperatures, con-
`FIG. 4B showscyclic voltammograms at 5 mV/s
`[0027]
`centrations or other physical properties or characteristics is
`on stainless steel rod in 1 M ZnSO,.
`meant to cover slight variations that may exist in the upper
`[0028]
`FIG. 5 showslinear sweep voltammograms on a
`and lower limits of the ranges of dimensions so as to not
`zinc disk electrode (cathodic sweep) andastainless steel
`exclude embodiments where on average most of the dimen-
`disk electrode (anodic sweep) at 1 mV/s in 1 M ZnSO,. The
`sions are satisfied but where statistically dimensions may
`cathodic sweep on zinc shows zinc deposition and the
`exist outside this region.
`anodic sweep on the stainless steel shows the oxygen
`[0039] As used herein,the phrase “a negative electrode for
`evolution reaction. These two electrochemical reactions
`storing zinc” means that the negative electrode can incor-
`dictate the potential operating window for aqueous zinc-ion
`porate and release zinc reversibly by electrodeposition/
`batteries using this electrolyte.
`dissolution (plating/stripping) of elemental zinc from/to the
`[0029]
`FIG. 6A shows Rietveld refinement of H,V;O,.
`electrolyte, by alloying/dealloying reaction, or the negative
`Data points (circles); calculated profile (line); difference
`electrode comprises a material that can store zinc by any one
`profile (dotted line); Bragg positions (vertical lines) are as
`or combination of intercalation, conversion, and capacitive
`indicated. Refined lattice parameters are a=16.87 A, b=9.
`storage (adsorption/deadsorption of Zn** ions).
`332 (3) A, c=3.63 A, and a=B=y=90°. Inset shows the
`[0040]
`FIG. 1A showsa conceptual schemeof a zinc-ion
`layered structure projected in the ac plane. VOx polyhedra
`battery shown generally at 10, which includes an anode 12,
`are shownin black.
`and an intercalated layered positive electrode material 14
`separated by an electrolyte 16, with FIG. 1A showing
`diagrammatically the operation of the battery 10, namely
`during the charging cycle Zn ions are attracted to the
`negative electrode 12, and during the discharge cycle Zn
`ions are attracted to the intercalated positive electrode
`material 14 into which they intercalate. Electrons flow
`through the external circuit connecting the negative and
`positive electrodes which are used to do work.
`[0041]
`FIG. 1B is a cross section of an actual zinc-ion
`battery showing the positive electrode 14 contained in a
`positive electrode compartment 20, the negative electrode
`12 contained in a negative electrode compartment 22, and
`the electrolyte 16 contained in an electrolyte compartment
`24 in which a separator 28 which is electrically insulating
`and permeable to zinc ions separating the positive and
`negative compartments is located. Non-limiting examples of
`separator 28 include organic polymers (polyethylene (PE),
`polypropylene (PP), poly(tetrafluoroethylene) (PTFE), poly
`
`FIG. 6B shows the Rietveld refinement of Zng.
`[0030]
`25V,0,.nH,0. Data points
`(circles); calculated profile
`(black line); difference profile (blue line) are as indicated.
`Refined parameters are a=10.75 A, b=7.77 A, c=10.42 A,
`a=91.26°, B=90.31°, and y=88.66°. The VO, and ZnO,
`polyhedra are shown in black and grey, respectively.
`[0031]
`FIGS. 7A, 7B, 7C and 7D show a typical SEM
`image of the H,V,0, (7A and 7B) and Zn, ,;V,0;.nH,O
`(7C and 7D) nanofibers.
`[0032]
`FIGS. 8A and 8B show galvanostatic polarization
`curves for the (8A) H,V,;0, and (8B) Zn,.5V,0;.nH,O
`electrodes at various current rates. Here,
`1 C is defined as
`350 mA g' for H,V3;O, and 300 mA g"! for Zn,.;V,Os.
`nH,O.
`FIGS. 9A. 9B, 9C and 9D show specific capacity
`[0033]
`and coulombic efficiency of the H,V,O, (9A and 9B) and
`ZNg25V>05.0H,0 (9C and 9D)as a function of cycling at 4
`C QA and 9C) and 8C (9B and 9D) currentrates.
`
`UW Exhibit 1012, pg. 17
`
`UW Exhibit 1012, pg. 17
`
`

`

`US 2017/0250449 Al
`
`Aug. 31, 2017
`
`(vinyl chloride) (PVC)), polyvinylidene fluoride (PVDF),
`nylon, organic polymer-inorganic oxide, silica glass fiber,
`porous silica or alumina ceramic membranes, cellulose,
`cellulose-ceramic oxide, wood, or any combination ofthese.
`[0042] The present disclosure provides several embodi-
`ments of the intercalated layered positive electrode material
`14. In an embodiment the intercalation layered positive
`electrode material 14 may be M,V,O0,.nH,O, where x is in
`a range from 0.05 to 1, n is in a range from 0 to 2, and M
`is any one or combination of a d-block metal ion, f-block
`metal ion and alkaline earth ion with the metal M ion being
`in a +2 to +4 valence state. The V,O, has a layered crystal
`structure having the metal
`ions M pillared between the
`layers, and waters of hydration coordinated to the metal ions
`M. The number of waters of hydration n in some embodi-
`ments may be greater than 0 and less than 1. Some of the
`waters of hydration may be hydrogen bondedto the layers.
`[0043]
`Ina preferred embodiment x=0.25, and n=1.
`[0044]
`In another embodiment,
`the intercalated layered
`positive electrode material 14 may be M,V,0,.nH,O,
`wherein x is in a range from 0.05 to 1, nis greater than 0 and
`less than 2. M is any one or combination of a d-block metal
`ion, f-block metal ion and alkaline earth ion, with the metal
`M ion being in a +2 to +4 valence state. The V,0, is a
`layered crystal structure having the metal ions M pillared
`between the layers, and waters of hydration coordinated to
`the metal ions M and/or hydrogen bondedto the layers. In
`an embodiment n is greater than 0 andless than 1.
`[0045]
`Ina preferred embodiment x=0.05, and n=1.
`[0046]
`In another embodiment,
`the intercalated layered
`positive electrode material 14 may be M,MoO,,.nH,0, in
`which x is in a range from 0 to 1, y is in a range from 2 to
`3, and n is in a range from 0 to 2. M is any one or
`combination of a d-block metal ion, f-block metal ion and
`alkaline earth ion, with the metal M ion being in a +2 to +4
`valence state. The MoO,, has a layer or tunnel crystal
`structure, and the metal
`ions M, if present, are pillared
`between the layers, and waters of hydration are coordinated
`to the metal ions M pillared between the layers.
`[0047]
`In some embodiments n is greater than 0 and less
`than 2. In some embodiments the waters of hydration are
`hydrogen bondedto the layers.
`[0048]
`Ina preferred embodiment x=0.25, y=3 and n=0.
`[0049] The electrolyte 16 is an aqueous based electrolyte
`and contains a salt of zinc dissolved therein. Non-limiting
`examples of the zinc salt comprises any one or combination
`of zinc sulfate, zinc acetate, zinc citrate, zinc iodide, zinc
`chloride, zinc perchlorate, zinc nitrate, zinc phosphate, zinc
`triflate, zinc bis(trifluoromethanesulfonyl)imide, zinc tetra-
`fluoroborate, and zinc bromide to mention a few.
`[0050] The dissolved zinc is present in an amount in the
`liquid in a range from about 0.01 to about 10 molar (M), and
`preferably is present in a range from about 0.1 to about 4 M.
`[0051] The electrolyte may have a pH in a range between
`1 and about 8 but preferably between 4 and about 8 and more
`preferably 4 to 7. The electrolyte is an aqueous based
`electrolyte and may be just water containing the dissolved
`salt of zinc, or additional solvents may be included, for
`example alcohols, nitriles, carbonates, ethers, sulfoxides,
`glycols, esters, and amines. Typically, the zinc salt may
`comprise anyone or combination of zinc sulfate, zinc
`acetate, zinc citrate, zinc iodide, zinc chloride, zinc perchlo-
`rate, zinc nitrate, zinc phosphate, zinc triflate, zinc bis
`(trifluoromethanesulfonyl)imide, zinc tetrafluoroborate, and
`
`zinc bromide in 0.1 to 4 M concentration of Zn?* with or
`without the nonaqueous component and with or without
`additional
`ionically-conductive salts such as quaternary
`ammonium salts or alkali metal salts.
`
`[0052] The negative electrode may be made ofa solid
`sheet, mesh, or rod of zinc, or it may be comprised of a zinc
`layer formed on a current collector. When the battery is
`assembled with metallic zinc contained in the negative
`electrode, the battery is typically referredto as a zinc battery.
`This is opposed to a zinc ion battery in which the negative
`electrode in its initial state does not contain any zinc. The
`zinc layer may be a thin sheetof zinc or an alloy, or powder
`zinc bonded adheredto the surface of the negative electrode
`facing into the negative electrode compartment. The zinc
`maybe a constituent of a formulation whichis adhered to the
`surface of the current collector. Non-limiting examples of
`zincalloys that may be used includealloys of zinc with lead,
`vanadium, chromium, manganese, iron, cobalt, nickel, cad-
`mium, tungsten, bismuth,tin, indium, antimony, copper, and
`titanium.
`
`[0053] The negative current collector is an electrically
`conductive support for active zinc which may be comprised
`of any one or combination of carbon, boron, lead, vanadium,
`chromium, manganese,iron, cobalt, nickel, cadmium, tung-
`sten, bismuth, tin, indium, antimony, copper, titanium, and
`zinc metal. A feature of the negative electrode is that it
`comprises a material that can store elemental zinc by any
`one or combination ofintercalation, conversion, and capaci-
`tive storage. In a conversion process, the electrochemical
`reaction of the negative electrode material with zinc leads to
`its decomposition into two or more products. In capacitive
`storage the Zn°* ionsare stored at the surface of the negative
`electrode material by a non-faradic process.
`
`[0054] The intercalated layered positive electrode material
`may have different morphologies. The intercalation layered
`positive electrode material 14 has a nanostructured morphol-
`ogy. Preferably the averageparticle size is less than 1000 nm
`in a direction of Zn ion transport through the particle, and
`more preferably less than 500 nm in a direction of Zn ion
`transport through the particle. Non-limiting morphologies
`include nanowires, fibers, wires, cubes, platelets, spheres,
`and uneven morphology. They may be simple particles. The
`particles may have a meansize in a range from about 5 nm
`to about 50 um.
`
`[0055] The particles may be coated with electrically con-
`ducting material, in which
`
`the electrically conducting material is any one or combina-
`tion of carbon powder and conducting polymer. The par-
`ticles may be embeddedin an electrically conducting matrix
`and the electrically conducting matrix may comprise any
`one or combination of carbon and conducting polymer, and
`including a binder. The binder may be any one or combi-
`nation of styrene butadiene rubber (SBR), sodium car-
`boxymethylcellulose (CMC), polyvinyl acetate (PVAc),
`polyethylene glycol (PEG), polybutyl acrylate (PBA), poly-
`urethane, acrylonitrile, polypyrrole, polyaniline, polytetra-
`fluoroethylene (PTFE), polyvinylidene fluoride (PVDF),
`perfluorosulfonic acid (PFSA), and poly(3,4-ethylenedioxy-
`thiophene) (PEDOT).
`
`Thezinc ion battery materials disclosed herein will
`[0056]
`now beillustrated by the following non-limiting examples.
`
`UW Exhibit 1012, pg. 18
`
`UW Exhibit 1012, pg. 18
`
`

`

`US 2017/0250449 Al
`
`Aug. 31, 2017
`
`Examples
`
`[0057] Two vanadium oxide based compounds with lay-
`ered crystal structures and in ultralong one-dimensional
`morphology exhibiting as robust host materials for high rate
`and long term reversible Zn** ion storage in aqueouselec-
`trolyte were produced. Vanadium is a cheap and environ-
`mentally benign metal possessing a range of oxidationstates
`(+2 to +5), which allows for multiple redox and hencelarge
`specific capacities for vanadium based electrode materials.
`Particularly, oxides of vanadium e.g., V,O; which is non-
`toxic and produced in large quantities, displays numerous
`crystal and compositional chemistries for reversible metal
`ion storage. Layered M,V,O,, oxides (M=metal
`ion) of
`compositions such as V,0;, VO, V,O,, that are made of
`two dimensional sheet structures have been the subject of
`intense investigation for both non-aqueous and aqueous
`alkali (Li and Na) ion batteries. The presence of interlayer
`metal ions and/or water of hydration actas pillars, providing
`structural
`stability during long term charge discharge
`cycling.
`and
`are H,V;0,
`[0058] Embodying such qualities
`Zn,,V,0;.nH,O, which we have synthesized in nanofiber
`morphology by a simple and rapid microwave hydrothermal
`treatment of V,O;, without using any toxic or corrosive
`chemicals, and converted to freestanding film electrodes by
`adopting a cheaper and greener water based electrode fab-
`rication process. Nanomorphology and compact film struc-
`ture allows for facile release of strain resulting upon Zn?*
`cycling, shorter ion diffusion paths, better interaction of
`carbon additives with the active material and robust con-
`
`ductive wiring-facilitating high specific capacities of ~300
`mAh g™' and long term cyclabilities up to 1000 cycles at
`high coulombic efficiency using fast current rates.
`
`Experimental Methods
`
`Synthesis of H,V,O, and Zn,V,O0,
`[0059]
`[0060] Microwave solvothermal method developed over
`last two decades are now often used to prepare positive
`electrode materials for lithium ion batteries. In this work, we
`have modified a time consuming and energy expensive
`hydrothermal approach used in the synthesis of single crys-
`talline H,V,O0, nanobelt to a rapid and scalable microwave
`hydrothermal method for the synthesis of highly homoge-
`neous H,V,Og, and Zn,V,0,;.nH,O nanofibers. In a typical
`procedure, 3 to 4 millimoles (mmol) V,O0, was dispersed in
`15:1 water/ethanol (v) mixture with or without stoichiomet-
`ric amount of zinc acetate (for Zn,V,O,.nH,O) and trans-
`ferred to a sealed Teflon™ vessel. The vessels werefitted to
`
`a rotor equipped with temperature and pressure sensors. The
`rotor containing the vessels was then placed in a rotating
`platform for uniform heating in an Anton Parr microwave
`synthesis system (Synthos 3000). The system temperature
`wasraised to 180° C. in 10 minutes and maintained for 60
`
`temperature was maintained
`to 90 minutes. The preset
`automatically by continuous adjustment of the applied
`power (limited to 800 Watts). The as-synthesized product
`was thoroughly washed with distilled water followed by a
`small amount of iso-propanol and dried at 60° C. for 24 h.
`
`Characterization Methods
`
`Powder X-ray diffraction was performed on a
`[0061]
`Bruker D8-Advance powder diffractometer equipped with
`Vantec-1 detector, using Cu-Ka. radiation (A=1.5405 A) in
`
`the range from 5° to 80° (26) at a step size of 0.025° using
`Bragg-Brentano geometry. X-ray data refinement was car-
`ried out by conventional Rietveld refinement method using
`the Bruker-AXS TOPAS4.2 software (Bruker-AXS, 2008).
`The background,scale factor, zero point, lattice parameters,
`atomic positions and coeflicients for the peak shape function
`wereiteratively refined until convergence was achieved. The
`morphologies of the samples were examined byfield-emis-
`sion scanning electron microscopy (FE-SEM, LEO 1530)
`equipped with an energy dispersive X-ray spectroscopy
`(EDX) attachment.
`
`Battery Cycling
`
`For electrochemical performance evaluation, a
`[0062]
`freestanding film type electrode was fabricated by a facile
`green approach.In a typical process, nanofibers were mixed
`with conducting nanocarbon Super P® and water based
`composite binder carboxymethylcellulose (CMC) andsty-
`rene-butadiene rubber (SBR) (CMC/SBR=2:1) in 70:27:3
`weight ratio. The mixture was dispersed in small amount of
`water by using an ultrasonic mixer to obtain a stable
`homogeneous ink which was filtered through Durapore®
`DVPP 0.65 umfiltration membrane. The water soluble CMC
`facilitates the dispersion of hydrophobic carbon particles
`into water and enables its intimate mixing with the nanofi-
`bers. Whereas SBR with high binding abilities for a small
`amount provides adhesion and electrode flexibility. The
`binder molecules not involved in this anchoring and adhe-
`sion get washed away duringfiltration and that way elec-
`trode films with very small binder content is achieved. After
`drying at 60° C. the composite film automatically came off
`which was then punched into 1 cm? electrode coins. The
`electrodes were further dried at 180° C. for 1 h (H,V,0,) or
`60° C. for 12 h (for Zn,V,0,.nH,O). The electrochemical
`properties were investigated in PFA based Swagelok® type
`cell using 1 M ZnSO,in water asthe electrolyte and titanium
`or stainless steel rods as the current collector. The H,V,0,
`or 7n,.V,0,;.nH,O and zinc foil served as the positive and
`negative electrodes,
`respectively. Galvanostatic cycling
`studies were performed using multichannel biologic VMP3
`potentiostat/galvanostat.
`
`Three-Electrode Electrochemical Measurements
`
`[0063] The voltammetric electrochemical experiments
`were performed with a three-electrode cell consisting of the
`working electrode, Pt mesh (1 cm?)as the counterelectrode,
`and an Ag/AgCl (3 M KCl) reference electrode. The work-
`ing electrodes examined were a Zn disk (=2 mm), a Ti disk
`(o=2 mm), a stainless steel rod (316 grade, ¢=12 mm), and
`the H,V,O, composite electrode. Cyclic voltammetry was
`performed at a scan rate of 5 mV/s and linear sweep
`voltammograms were acquired at 1 mV/s. These techniques
`were controlled with a C