(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)
`(19) World Intellectual Property
`CANORAACTA
`Organization
`International Bureau
`
`
`
`(43) International Publication Date
`15 December 2016 (15.12.2016) WIPO! PCT
`
`(51) International Patent Classification:
`HOIM 10/36 (2010.01)
`HOIM 4/485 (2010.01)
`HOIM 4/42 (2006.01)
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`(81)
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`(21)
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`International Application Number:
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`PCT/CA2016/050613
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`(22)
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`International Filing Date:
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`31 May 2016 (31.05.2016)
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`(10) International Publication Number
`WO2016/197236 Al
`
`
`Designated States (unless otherwise indicated, for every
`kind of national protection available): AE, AG, AL, AM,
`AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY,
`BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM,
`DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT,
`HN, HR, HU,ID,IL,IN,IR, IS, JP, KE, KG, KN, KP, KR,
`KZ, LA, LC, LK, LR, LS, LU, LY, MA, MD, ME, MG,
`MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ, OM,
`PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SA, SC,
`SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN,
`TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW.
`
`Designated States (unless otherwise indicated, for every
`kind of regional protection available): ARIPO (BW, GH,
`GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, ST, SZ,
`TZ, UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU,
`TJ, TM), European (AL, AT, BE, BG, CH, CY, CZ, DE,
`DK,EE, ES, FI, FR, GB, GR, HR, HU,IE,IS, IT, LT, LU,
`LV, MC, MK, MT, NL, NO,PL, PT, RO, RS, SE, SL, SK,
`SM, TR), OAPI (BF, BJ, CF, CG, CL CM, GA, GN, GQ,
`GW, KM, ML, MR, NE, SN, TD, TG).
`
`English
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`English
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`(84)
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`Filing Language:
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`Publication Language:
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`Priority Data:
`62/230,502
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`8 June 2015 (08.06.2015)
`
`US
`
`Inventors; and
`Applicants : ADAMS, Brian D. [CA/CA]; 228 Morenz
`Drive, Mitchell, Ontario NOK 1NO (CA). KUNDU, Dipan
`[IN/CA]; Apartment 914, 11 Overlea Drive, Kitchener,
`Ontario N2M 5C8 (CA). NAZAR,Linda F. [CA/CA]; 504
`Fox Cove Place, Waterloo, Ontario N2K 4A7 (CA).
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`(25)
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`(26)
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`(30)
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`(72)
`(71)
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`(74)
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`Agent: HILL & SCHUMACHER; 264 Avenue Road, Published:
`Toronto, Ontario M4V 2G7 (CA).
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`with international search report (Art. 21(3))
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`(54) Title: ELECTRODE MATERIALS FOR RECHARGEABLE ZINC CELLS AND BATTERIES PRODUCED THEREFROM
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`12
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` Discharge
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`tonne Gee
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`@t--- E <f--
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`46 % Charge
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`Figure 1A
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`(57) Abstract: The present disclosure discloses
`a rechargeable Zn battery based on layered/tun-
`nelled structure vanadium/molybdenum oxides,
`with/without the presence of neutral/cationic/an -
`ionic species and/or water molecules inserted
`into the
`interlayers/tunnels, of nano/micro-
`particle morphology as robust materials for high
`rate and long term reversible Zn?* ion intercala-
`tion storage at the positive electrode,
`that are
`coupled with a metallic Zn negative electrode,
`and an aqueous electrolyte. The positive elec-
`trode mayinclude electronically conducting ad-
`ditives and one or more binders along with the
`Zn* intercalation material;
`the negative elec-
`trode is Zn metal in any form; the aqueous elec-
`trolyte is of pH 1
`to 9 and contains a soluble
`zinc salt in a concentration range from 0.01 to
`10 molar.
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`UW Exhibit 1004, pg. 1
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`WoO2016/197236AJ[IIITTIMNAINITNIANTIINUAITATAAUIM
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`UW Exhibit 1004, pg. 1
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`WO 2016/197236
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`ELECTRODE MATERIALS FOR RECHARGEABLE ZINC CELLS AND
`BATTERIES PRODUCED THEREFROM
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`FIELD
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`This disclosure relates generally to batteries, and, more specifically to
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`zinc ion batteries involving zinc intercalation positive electrode materials, zinc
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`metal based negative electrodes in any form, and an aqueous electrolyte
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`containing zinc salt and batteries using these positive electrode materials.
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`BACKGROUND
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`Given the looming concernsof climate change, sustainable energy
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`resources such as solar and wind have entered the global spotlight, triggering
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`the searchforreliable, low cost electrochemical energy storage. Among the
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`various options,lithium ion batteries are currently the most attractive candidates
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`due to their high energy density, and foothold in the marketplace. However,
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`manyfactors (cost, safety, andlifetime) will likely limit their large scale
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`applications, and dictate against their use in stationary grid storage where low
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`cost and durability are more of a concern than weight. What is needed is a high
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`energy density battery that is rechargeable, cheap, safe, and easy to
`manufacture and dispose of or recycle. Aqueous batteries (water based
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`electrolytes) are therefore attracting tremendousattention. Their high
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`conductivity (up to 1 Siemens (S) cm") compared to the non-aqueous
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`electrolytes (0.001 to 0.01 S cm’’) also favour high rate capabilities suitable for
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`emerging applications.
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`The use of metallic negative electrodes is a means to achieve high
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`energy density and ease of battery assembly (hence lowercost). There is a
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`UW Exhibit 1004, pg. 2
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`UW Exhibit 1004, pg. 2
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`trade-off between the reduction potential of a metal, E°, (low values give higher
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`cell voltages) and safety. Metals with low reduction potentials (e.g., lithium,
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`potassium, calcium, sodium, and magnesium) react with water to produce
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`hydrogen. However, zinc is stable in water and for that reason it has been used
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`as the negative electrode in primary aqueous battery systems. Moreover, zinc
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`has (a) high abundance and large production which makesit inexpensive; (b)
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`non-toxicity; (c) low redox potential (-0.76 V vs. standard hydrogen electrode
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`(SHE)) compared to other negative electrode materials used in aqueous
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`batteries; and (d) stability in water due to a high overpotential for hydrogen
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`evolution. The latter renders a large voltage window (~2 V) for aqueous zinc-ion
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`batteries (AZIBs) employing a metallic Zn negative electrode.
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`Vanadium and molybdenum are low cost metals possessing a range of
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`oxidation states (V: +2 to +5; Mo: +2 to +6), which allows for multiple redox and
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`hence large specific capacities for vanadium or molyodenum based electrode
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`materials. Layered VnOm (vanadium oxides: V2Os, V3O8, V4O14) and MoOy
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`(molyodenum oxides) that are made of two dimensional sheet structures were
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`the subject of much past investigation for non-aqueous and aqueousalkali (Li
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`and Na) ion batteries. The additional presence of interlayer neutral molecules,
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`ions, metal ions and/or water of hydration in such layered oxides act aspillars,
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`providing structural stability during long term charge discharge cycling.
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`SUMMARY
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`The present disclosure discloses a rechargeable Zn battery based on
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`layered/tunnelled structure vanadium/molybdenum oxides, with/without the
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`presenceof neutral/cationic/anionic species and/or water molecules inserted
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`UW Exhibit 1004, pg. 3
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`UW Exhibit 1004, pg. 3
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`into the interlayers/Aunnels, of nano/microparticle morphology as robust
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`materials for high rate and long term reversible Zn** ion intercalation storage at
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`the positive electrode, that are coupled with a metallic Zn negative electrode,
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`and an aqueouselectrolyte. The positive electrode mayinclude electronically
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`conducting additives and one or more binders along with the Zn**intercalation
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`material; the negative electrode is Zn metal in any form; the aqueouselectrolyte
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`is may have a pHin a range of 1 to 9 and contains a soluble zinc salt which
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`may be in a concentration range from 0.01 to 10 molar.
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`Thus, disclosed herein is a zinc ion battery, comprising:
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`a positive electrode compartment having enclosed therein an
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`intercalation layered positive electrode material MyV205.nH2O, wherein x is ina
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`range from 0.05 to 1, nis in a range from 0 to 2, wherein M is any one or
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`combination of a d-block metalion, f-block metal ion and alkaline earth ion, the
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`metal M ion being in a +2 to +4 valence state, and wherein said V2Os is a
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`layered crystal structure having the metal ions M pillared betweenthe layers,
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`and waters of hydration coordinated to the metal ions M;
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`a negative electrode compartment having enclosed therein a negative
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`electrode for storing zinc;
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`a separator electrically insulating and permeable to zinc ions separating
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`the positive and negative compartments; and
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`an electrolyte comprising water and having a salt of zinc dissolved
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`therein.
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`Thereis also disclosed herein a zinc ion battery, comprising:
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`a positive electrode compartment having enclosed therein and
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`intercalated layered positive electrode material MxV3O7.nH20, wherein x is ina
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`UW Exhibit 1004, pg. 4
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`UW Exhibit 1004, pg. 4
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`range from 0.05 to 1, nis greater than 0 and less than 2, wherein M is any one
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`or combination of a d-block metal ion, f-block metal ion and alkaline earth ion,
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`the metal M ion being in a +2 to +4 valence state, and wherein said V30;7is a
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`layered crystal structure having the metal ions M pillared betweenthelayers,
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`and waters of hydration coordinated to the metal ions M and/or hydrogen
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`bondedto the layers;
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`a negative electrode compartment having enclosed therein a negative
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`elecirodefor storing zinc;
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`a separatorelectrically insulating and permeable to zinc ions separating
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`the positive and negative compartments; and
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`an electrolyte comprising water and having a salt of zinc dissolved
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`therein.
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`There is also disclosed a zinc ion battery; comprising:
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`a positive electrode compartment having enclosed therein an
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`intercalated layered positive electrode material M,MoOy.nH2O, wherein x is ina
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`range from 0 to 1, y is in a range from 2 to 3, nis in a range from0to 2,
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`wherein M is any one or combination of a d-block metalion, f-block metal ion
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`and alkaline earth ion, the metal M ion being in a +2 to +4 valence state, and
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`wherein said MoOy hasa layer or tunnel crystal structure, and the metal ions M,
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`if present, pillared between the layers, and waters of hydration coordinated to
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`the metal ions M pillared between the layers;
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`a negative electrode compartment having enclosed therein a negative
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`electrode for storing zinc; a separatorelectrically insulating and permeable to
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`zinc ions separating the positive and negative compartments; and
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`UW Exhibit 1004, pg. 5
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`UW Exhibit 1004, pg. 5
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`an electrolyte comprising water and having a salt of zinc dissolved
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`therein.
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`A further understanding of the functional and advantageous aspects of
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`the disclosure can be realized by reference to the following detailed description
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`and drawings.
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`BRIEF DESCRIPTION OF THE DRAWINGS
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`Embodiments of the disclosure will now be described, by way of example
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`only, with reference to the drawings, in which:
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`Figure 1A shows a conceptual scheme of a zinc-ion battery constructed
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`in accordancewith the present disclosure.
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`Figure 1B is a cross section of a zinc-ion battery.
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`Figure 2 showslinear sweep voltammograms at 1 mV/s on Pt, Ti, and
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`Zn in 1 M NaeSO, showing the onset of the hydrogen evolution reaction.
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`Figure 3 showslinear sweep voltammograms at 1 mV/s in 1 M NazSO,
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`showing the hydrogen evolution reaction. The dotted voltammogram in (a)
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`shows zinc deposition on a zinc disk electrode in 1 M ZnSQ, for comparison.
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`Figure 4A showscyclic voltammograms at 5 mV/s on a Ti disk
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`electrode.
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`Figure 4B showscyclic voltammograms at 5 mV/s on stainless steel rod
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`ind M ZnSQ,.
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`Figure 5 showslinear sweep voltammograms on a zinc disk electrode
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`(cathodic sweep) and a stainless steel disk electrode (anodic sweep) at 1 mV/s
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`in 1 M ZnSOx,. The cathodic sweep on zinc shows zinc deposition and the
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`anodic sweep on thestainless steel shows the oxygen evolution reaction.
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`UW Exhibit 1004, pg. 6
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`UW Exhibit 1004, pg. 6
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`Figures 7A, 7B, 7C and 7D showatypical SEM image of the H2V3O¢
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`These two electrochemical reactions dictate the potential operating window for
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`aqueous zinc-ion batteries using this electrolyte.
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`Figure 6A showsRietveld refinement of H2V3O,. Data points (circles);
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`calculated profile (line); difference profile (dotted line); Bragg positions (vertical
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`lines) are as indicated. Refined lattice parameters are a = 16.87 A, b = 9.332
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`(3) A, c = 3.63 A, and a = B = y = 90°Inset shows the layered structure
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`projected in the ac plane. VOx polyhedra are shownin black.
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`Figure 6B showsthe Rietveld refinement of Zno.25V20s5,.nH2O.Data
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`points (circles); calculated profile (blackline); difference profile (blue line) are as
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`indicated. Refined parameters are a= 10.75 A, b=7.77 A, c= 10.42 A, a=
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`91.26°, B = 90.31°, and y = 88.66° The VO, and ZnO, polyhedra are shownin
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`black and grey, respectively.
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`(7A and 7B) and Zno.25V20s5.nH2O (7C and 7D) nanofibers.
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`Figures 8A and 8B show galvanostatic polarization curves for the (8A)
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`HeV30¢ and (8B) Zno.25V20s.nH2O electrodes at various current rates. Here, 1C
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`is defined as 350 mA g’ for HsV3Ox3 and 300 mA g"for Zno.25V20s.nH2O.
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`Figures 9A. 9B, 9C and 9D show specific capacity and coulombic
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`efficiency of the HeV3Ox. (9A and 9B) and Zno.25V20s5,nH2O0 (9C and 9D) as a
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`function of cycling at 4C (9A and 9C) and 8C (9B and 9D) currentrates.
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`Figures 10A and 10B show rate capability of the (9A) H2V3Os3 and (9B)
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`ZNo.25V20s5.nH20 cells studied undervariable current loading as a function of
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`cycling. The corresponding coulombic efficiencies are also shown.
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`UW Exhibit 1004, pg. 7
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`UW Exhibit 1004, pg. 7
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`Figure 11 showsthe tradeoff between energy and power density
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`(Ragoneplot) for reversible Zn** storage in Zno.25V20s.nH2O, H2V3Os, MnOz,
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`and Zns[Fe(CN)s>.
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`DETAILED DESCRIPTION
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`Various embodiments and aspects of the disclosure will be described
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`with reference to details discussed below. The following description and
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`drawingsare illustrative of the disclosure and are not to be construedaslimiting
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`the disclosure. Numerous specific details are described to provide a thorough
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`understanding of various embodiments of the present disclosure. However,in
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`certain instances, well-known or conventional details are not described in order
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`to provide a concise discussion of embodiments of the present disclosure.
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`The Figures are not to scale and some features may be exaggerated or
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`minimized to show details of particular elements while related elements may
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`have been eliminated to prevent obscuring novel aspects. Therefore, specific
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`structural and functional details disclosed herein are not to be interpreted as
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`limiting but merely as a basis for the claims and as a representative basis for
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`teaching one skilled in the art to variously employ the present disclosure.
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`As used herein, the term “about”, when used in conjunction with ranges
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`of dimensions, temperatures, concentrations or other physical properties or
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`characteristics is meant to coverslight variations that may exist in the upper
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`and lowerlimits of the ranges of dimensions so as to not exclude embodiments
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`where on average most of the dimensionsare satisfied but wherestatistically
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`dimensions mayexist outside this region.
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`UW Exhibit 1004, pg. 8
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`UW Exhibit 1004, pg. 8
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`As used herein, the phrase “a negative electrode for storing zinc” means
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`that the negative electrode can incorporate and release zinc reversibly by
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`electrodeposition/dissolution (plating/stripping) of elemental zinc from/to the
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`electrolyte, by alloying/dealloying reaction, or the negative electrode comprises
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`a material that can store zinc by any one or combination of intercalation,
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`conversion, and capacitive storage (adsorption/deadsorption of Zn** ions).
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`Figure 1A shows a conceptual schemeof a zinc-ion battery shown
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`generally at 10, which includes an anode 12, and an intercalated layered
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`positive electrode material 14 separated by an electrolyte 16, with Figure 1A
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`showing diagrammatically the operation of the battery 10, namely during the
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`charging cycle Zn ions are attracted io the negative electrode 12, and during
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`the discharge cycle Zn ions are attracted to the intercalated positive electrode
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`material 14 into which they intercalate. Electrons flow through the external
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`circuit connecting the negative and positive electrodes which are used to do
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`work.
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`Figure 1B is a cross section of an actual zinc-ion battery showing the
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`positive electrode 14 contained in a positive electrode compartment 20, the
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`negative electrode 12 contained in a negative electrode compartment 22, and
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`the electrolyte 16 contained in an electrolyte compartment 24 in which a
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`separator 28 whichis electrically insulating and permeable to zinc ions
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`separating the positive and negative compartments is located. Non-limiting
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`examples of separator 28 include organic polymers (polyethylene (PE),
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`polypropylene (PP), poly(tetrafluorcethylene) (PTFE), poly(vinyl chloride)
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`(PVC)), polyvinylidene fluoride (PVDF), nylon, organic polymer-inorganic oxide,
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`UW Exhibit 1004, pg. 9
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`UW Exhibit 1004, pg. 9
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`silica glass fiber, poroussilica or alumina ceramic membranes,cellulose,
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`cellulose-ceramic oxide, wood, or any combination of these.
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`The present disclosure provides several embodimentsof the intercalated
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`layered positive electrode material 14. In an embodiment the intercalation
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`layered positive electrode material 14 may be M,V2O0s.nH20, where x is ina
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`range from 0.05 to 1, nis in a range from 0 to 2, and M is any one or
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`combination of a d-block metal ion, f-block metal ion and alkaline earth ion with
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`the metal M ion being in a +2 to +4 valence state. The V2Os has a layered
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`crystal structure having the metal ions M pillared between the layers, and
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`waters of hydration coordinated to the metal ions M. The number of waters of
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`hydration n in some embodiments may be greater than 0 and less than 1.
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`Some of the waters of hydration may be hydrogen bondedto the layers.
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`In a preferred embodiment x = 0.25, andn= 1.
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`In another embodiment, the intercalated layered positive electrode
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`material 14 may be MyV307.nH20, wherein x is in a range from 0.05 to 1, nis
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`greater than 0 and less than 2. M is any one or combination of a d-block metal
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`ion, f-block metal ion and alkaline earth ion, with the metal M ion being in a +2
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`to +4 valence state. The V3O0;is a layered crystal structure having the metal
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`ions M pillared between the layers, and waters of hydration coordinated to the
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`greater than 0 and less than 1.
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`In a preferred embodiment x = 0.05, andn = 1.
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`In another embodiment, the intercalated layered positive electrode
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`material 14 may be M,xMoO,.nH20, in which x is in a range from 0 to 1, yis ina
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`range from 2 to 3, and nis in a range from 0 to 2. M is any one or combination
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`metal ions M and/or hydrogen bondedto the layers. In an embodimentnis
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`UW Exhibit 1004, pg. 10
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`UW Exhibit 1004, pg. 10
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`In a preferred embodimentx = 0.25, y = 3 andn=0.
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`of a d-block metal ion, f-block metal ion and alkaline earth ion, with the metal M
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`ion being in a +2 to +4 valence state. The MoO,hasa layer or tunnel crystal
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`structure, and the metalions M, if present, are pillared between the layers, and
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`waters of hydration are coordinated to the metal ions M pillared between the
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`layers.
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`In some embodiments n is greater than 0 and less than 2. In some
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`embodiments the waters of hydration are hydrogen bondedto the layers.
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`The electrolyte 16 is an aqueous based electrolyte and contains a salt of
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`zinc dissolved therein. Non-limiting examples of the zinc salt comprises any one
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`or combination of zinc sulfate, zinc acetate, zinc citrate, zinc iodide, zinc
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`chloride, zinc perchlorate, zinc nitrate, zinc phosphate, zinctriflate, zinc
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`bis(trifluoromethanesulfonyl)imide, zinc tetrafluoroborate, and zinc bromide to
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`mention a few.
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`The dissolved zinc is present in an amountin the liquid in a range from
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`about 0.01 to about 10 molar (M), and preferably is present in a range from
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`about 0.1 to about 4 M.
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`The electrolyte may have a pH in a range between 1 and about 8 but
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`preferably between 4 and about 8 and more preferably 4 to 7. The electrolyte is
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`an aqueous based electrolyte and may be just water containing the dissolved
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`salt of zinc, or additional solvents may be included, for example alcohols,
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`nitriles, carbonates, ethers, sulfoxides, glycols, esters, and amines. Typically,
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`the zinc salt may comprise anyoneor combination of zinc sulfate, zinc acetate,
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`zinc citrate, zinc iodide, zinc chloride, zinc perchlorate, zinc nitrate, zinc
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`phosphate, zinctriflate, zinc bis(trifluoromethanesulfonylimide, zinc
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`UW Exhibit 1004, pg. 11
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`UW Exhibit 1004, pg. 11
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`tetrafluoroborate, and zinc bromidein 0.1 to 4 M concentration of Zn** with or
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`without the nonaqueous componentand with or without additionalionically-
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`conductive salts such as quaternary ammonium salts or alkali metal salts.
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`The negative electrode may be madeof a solid sheet, mesh, or rod of
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`zinc, or it may be comprised of a zinc layer formed on a current collector. When
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`the battery is assembled with metallic zinc contained in the negative electrode,
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`ihe battery is typically referred to as a zinc battery. This is opposed to a zinc ion
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`battery in which the negative electrodein its initial state does not contain any
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`zinc. The zinc layer may be a thin sheetof zinc or an alloy, or powder zinc
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`bonded adhered to the surface of the negative electrode facing into the
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`negative electrode compartment. The zinc may be a constituent of a formulation
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`which is adhered to the surface of the current collector. Non-limiting examples
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`of zinc alloys that may be used include alloys of zinc with lead, vanadium,
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`chromium, manganese,iron, cobalt, nickel, cadmium, tungsten, bismuth, tin,
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`indium, antimony, copper, and titanium.
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`The negative current collector is an electrically conductive support for
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`active zinc which may be comprised of any one or combination of carbon,
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`boron, lead, vanadium, chromium, manganese, iron, cobalt, nickel, cadmium,
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`tungsten, bismuth, tin, indium, antimony, copper, titanium, and zinc metal. A
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`feature of the negative electrodeis that it comprises a material that can store
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`elemental zinc by any one or combination of intercalation, conversion, and
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`capacitive storage. In a conversion process, the electrochemical reaction of the
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`negative electrode material with zinc leads to its decomposition into two or
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`more products. In capacitive storage the Zn** ions are stored at the surface of
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`the negative electrode material by a non-faradic process.
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`11
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`UW Exhibit 1004, pg. 12
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`The intercalated layered positive electrode material may havedifferent
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`morphologies. The intercalation layered positive electrode material 14 has a
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`nanostructured morphology. Preferably the average particle size is less than
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`1000 nm in a direction of Zn ion transport through the particle, and more
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`preferably less than 500 nm in a direction of Zn ion transport through the
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`particle. Non-limiting morphologies include nanowires, fibers, wires, cubes,
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`platelets, spheres, and uneven morphology. They maybe simple particles. The
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`particles may have a meansize in a range from about 5 nm to about 50 pm.
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`The particles may be coated with electrically conducting material, in
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`which
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`the electrically conducting material is any one or combination of carbon powder
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`and conducting polymer. The particles may be embeddedin anelectrically
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`conducting matrix and the electrically conducting matrix may comprise any one
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`or combination of carbon and conducting polymer, and including a binder. The
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`binder may be any one or combination of styrene butadiene rubber (SBR),
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`sodium carboxymethylcellulose (CMC), polyvinyl acetate (PVAc), polyethylene
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`glycol (PEG), polybutyl acrylate (PBA), polyurethane, acrylonitrile, polypyrrole,
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`polyaniline, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF),
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`perfluorosulfonic acid (PFSA), and poly(3,4-ethylenedioxythiophene) (PEDOT).
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`The zinc ion battery materials disclosed herein will now beillustrated by
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`the following non-limiting examples.
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`Examples
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`Two vanadium oxide based compoundswith layered crystal structures
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`andin ultralong one-dimensional morphology exhibiting as robust host
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`materials for high rate and long term reversible Zn** ion storage in aqueous
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`UW Exhibit 1004, pg. 13
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`electrolyte were produced. Vanadium is a cheap and environmentally benign
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`metal possessing a range of oxidation states (+2 to +5), which allowsfor
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`multiple redox and hencelarge specific capacities for vanadium based
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`electrode materials. Particularly, oxides of vanadium e.g., V2Os which is non-
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`toxic and producedin large quantities, displays numerous crystal and
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`compositional chemistries for reversible metal ion storage. Layered M,V,Om
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`oxides (M = metal ion) of compositions such as V2O0s, V3Os, V4O11 that are
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`made of two dimensional sheet structures have been the subject of intense
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`investigation for both non-aqueous and aqueousalkali (Li and Na) ion batteries.
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`The presenceof interlayer metal ions and/or water of hydration actaspillars,
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`providing structural stability during long term charge discharge cycling.
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`Embodying such qualities are H2VsOg and ZnxV20s.nH2O, which we
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`have synthesized in nanofiber morphology by a simple and rapid microwave
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`hydrothermal treatment of V2Os, without using any toxic or corrosive chemicals,
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`and converted to freestandingfilm electrodes by adopting a cheaper and
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`greener water based electrode fabrication process. Nanomorphology and
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`compactfilm structure allowsfor facile release of strain resulting upon Zn**
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`cycling, shorter ion diffusion paths, better interaction of carbon additives with
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`the active material and robust conductive wiring - facilitating high specific
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`capacities of ~300 mAh g' and long term cyclabilities up to 1000 cycles at high
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`coulombic efficiency using fast current rates.
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`Experimental Methods
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`Synthesis of H2V30, and Zn,V20s
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`UW Exhibit 1004, pg. 14
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`Microwave solvothermal method developed overlast two decades are
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`now often used to prepare positive electrode materials for lithium ion batteries.
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`In this work, we have modified a time consuming and energy expensive
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`hydrothermal approach usedin the synthesis of single crystalline H2V3Os
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`nanobelt to a rapid and scalable microwave hydrothermal methodfor the
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`synthesis of highly homogeneous H2V3Og and Zn,V205.nH20 nanofibers. Ina
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`typical procedure, 3 to 4 millimoles (mmol) V2Os was dispersed in 15:1
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`water/ethanol (v) mixture with or without stoichiometric amountof zinc acetate
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`(for Zn,V20s.nNH2O) and transferred to a sealed Teflon™ vessel. The vessels
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`werefitted to a rotor equipped with temperature and pressure sensors. The
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`rotor containing the vessels was then placedin a rotating platform for uniform
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`heating in an Anton Parr microwave synthesis system (Synthos 3000). The
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`system temperature was raised to 180°C in 10 minutes and maintained for 60
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`to 90 minutes. The preset temperature was maintained automatically by
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`continuous adjustment of the applied power(limited to 800 Watts). The as-
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`synthesized product was thoroughly washed with distilled water followed by a
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`small amount of iso-propanol and dried at 60°C for 24 h.
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`Characterization Methods
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`Powder X-ray diffraction was performed on a Bruker D8-Advance
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`powderdiffractometer equipped with Vantec-1 detector, using Cu-Ka radiation
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`(A= 1.5405A)in the range from 5° to 80° (26) at a stepsize of 0.025° using
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`Bragg-Brentano geometry. X-ray data refinement was carried out by
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`conventional Rietveld refinement method using the Bruker-AXS TOPAS 4.2
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`software (Bruker-AXS, 2008). The background, scale factor, zero point, lattice
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`parameters, atomic positions and coefficients for the peak shape function were
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`iteratively refined until convergence was achieved. The morphologies of the
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`samples were examined byfield-emission scanning electron microscopy (FE-
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`SEM, LEO 1530) equipped with an energy dispersive X-ray spectroscopy
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`(EDX) attachment.
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`Battery Cycling
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`For electrochemical performance evaluation, a freestandingfilm type
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`nanofibers were mixed with conducting nanocarbon Super P® and water based
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`composite binder carboxymethylcellulose (CMC) and styrene-butadiene
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`rubber(SBR) (CMC/SBR= 2:1) in 70:27:3 weight ratio. The mixture was
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`dispersed in small amount of water by using an ultrasonic mixerto obtain a
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`stable homogeneousink which wasfiltered through Durapore® DVPP 0.65 um
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`filtration membrane. The water soluble CMC facilitates the dispersion of
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`hydrophobic carbon particles into water and enablesits intimate mixing with the
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`nanofibers. Whereas SBR with high binding abilities for a small amount
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`provides adhesion andelectrode flexibility. The binder molecules not involvedin
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`this anchoring and adhesion get washed awayduringfiltration and that way
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`electrodefilms with very small binder content is achieved. After drying at 60°C
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`the compositefilm automatically came off which was then punchedinto 1 cm?
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`electrode coins. The electrodes were further dried at 180°C for 1 h (H2V3Og) or
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`60°C for 12 h (for Zn,V205.nH20). The electrochemical properties were
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`investigated in PFA based Swagelok® type cell using 1 M ZnSO,in water as the
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`electrolyte and titanium or stainless steel rods as the current collector. The
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`H2V3O¢ or ZN,V205.nH2O and zinc foil served as the positive and negative
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`electrode wasfabricated by a facile green approach. Inatypical process,
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`UW Exhibit 1004, pg. 16
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`electrodes, respectively. Galvanostatic cycling studies were performed using
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`multichannel biologic VMP3 potentiostat/galvanostat.
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`Three-Electrode Electrochemical Measurements
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`The voltammetric electrochemical experiments were performed with a
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`three-electrodecell consisting of the working electrode, Pt mesh (1 cm?) as the
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`counter electrode, and an Ag/AgCl (3 M KCI) reference electrode. The working
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`electrodes examined were a Zn disk (p = 2 mm), a Ti disk (¢ = 2 mm), a
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`stainless steel rod (316 grade, » = 12 mm), and the H2V30g composite
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`electrode. Cyclic voltammetry was performed ata scan rate of 5 mV/s and
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`linear sweep voltammograms were acquired at 1 mV/s. These techniques were
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`controlled with a CHI700E potentiostat (CH Instruments, Inc.). The electrolytes
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`used were 1 M NaeSO,jfor the hydrogen evolution reaction and 1 M ZnSO,for
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`zinc plating/stripping and the oxygen evolution reaction. All experiments were
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`performed at room temperature (23 + 2°C).
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`Results and Discussion
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`The operating voltage of all secondary aqueousbatteriesis limited by
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`the potentials for hydrogen evolution and oxygen evolution from water
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`electrolysis. Since both the hydrogen and oxygen evolution reactions (HER and
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`OER,respectively) are pH dependent(see reactions 2 to 5) and catalytic in
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`nature, the precise potential at which they occur is sensitive to the electrolyte
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`composition and electrode material. HER and OER occur during charge at the
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`negative and positive electrodes, respectively, and are displayed below in
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`reactions 2 to 5, while the zinc deposition reaction is shownin reaction 1:
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`Cathodic Reactions:
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`Zinc Deposition:
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`UW Exhibit 1004, pg. 17
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`(1)
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`Zn** +26 — Zn
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`E°= -0.76 V vs. SHE
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`Hydrogen Evolution Reaction (HER):
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`(2)
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`(3)
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` 2H2O + 2e — He + 20H
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`E°= -0.83 V vs. SHE
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`2H*+2e— Hp
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`E°= 0.00 V vs. SHE
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`Anodic Reactions:
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`Oxygen Evolution Reaction (OER):
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`(4)
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`(5)
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`40H — O02 + 2H20+ 4e
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`E°= 0.40 V vs. SHE
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` 2H2O > Oo + 4H* + 4e
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`E% 1.23 V vs. SHE
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`To examinethe suitability of a metallic zinc negative electrode for
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`secondaryzinc-ion batteries, linear sweep voltammetry was usedto probe the
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`HER. In Figure 2, a zinc-ion-free (1 M NazSOx) electrolyte was used which
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`contained the same concentration of the sulfate anion and similar pH value (4-
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`5) as the 1 M ZnSO,electrolyte usedfor all other studies. Here,it can be seen
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`that the hydrogen evolution reaction has an overpotential of ~0.4 V with respect
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`to Pt on both zinc metal and titanium metal. Titanium was found to be an
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`excellent current collector for the negative, comparable to Znitself, as evident
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`from Figure 3A, which also showsthat zinc deposition on a zinc electrodein 1
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`M ZnSO, occurs at a higher potential than the HER. Stainless steel was
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`deemedto be unsuitable