US009780412B2
`
`(12) United States Patent
`US 9,780,412 B2
`(10) Patent No.:
`Adams et al.
`(45) Date of Patent:
`Oct. 3, 2017
`
`(54)
`
`ELECTRODE MATERIALS FOR
`RECHARGEABLE ZINC CELLS AND
`BATTERIES PRODUCED THEREFROM
`
`(71)
`
`Applicant: Brian D. Adams, Mitchell (CA)
`
`(72)
`
`Inventors: Brian D. Adams, Mitchell (CA); Dipan
`Kundu, Kitchener (CA)
`
`(56)
`
`References Cited
`U. S. PATENT DOCUMENTS
`
`5,336,572 A
`8,663,844 B2
`2013/0157138 A1
`
`8/1994 Koksbang
`3/2014 Kang et a1.
`6/2013 Mettan et a1.
`
`(Continued)
`
`FOREIGN PATENT DOCUMENTS
`
`(*)
`
`Notice:
`
`Subject to any disclaimer, the term of this
`patent is extended or adjusted under 35
`U.S.C. 154(b) by 0 days.
`
`CN
`WO
`
`102110858
`2013112660
`
`6/2011
`8/2013
`
`(21)
`
`Appl. No.: 15/461,849
`
`(22)
`
`Filed:
`
`Mar. 17, 2017
`
`(65)
`
`(63)
`
`(60)
`
`(51)
`
`(52)
`
`(58)
`
`Prior Publication Data
`
`US 2017/0207492 A1
`
`Jul. 20, 2017
`
`Related US. Application Data
`
`application
`of
`Continuation
`PCT/CA2016/050613, filed on May 31, 2016.
`
`No.
`
`Provisional application No. 62/230,502, filed on Jun.
`8, 2015.
`
`Int. Cl.
`
`H01M 4/66
`H01M 4/62
`H01M 4/485
`H01M 10/36
`US. Cl.
`
`(2006.01)
`(2006.01)
`(2010.01)
`(2010.01)
`
`CPC ........... H01M 10/36 (2013.01); H01M 4/485
`(2013.01); H01M 4/623 (2013.01); H01M
`4/625 (2013.01); H01M 4/661 (2013.01);
`H01M 4/663 (2013.01); H01M 2300/0002
`(2013.01)
`
`Field of Classification Search
`CPC ........ H01M 10/36; H01M 4/50; H01M 4/244;
`H01M 4/485; H01M 4/66; H01M 4/62
`See application file for complete search history.
`
`OTHER PUBLICATIONS
`
`“Manganese vanadium oxides as cathodes for lithium batteries”,
`Heai-Ku Park, Solid State Ionics, 176, p. 307-312, 2005*
`(Continued)
`
`Primary Examiner 7 Kenneth Douyette
`(74) Attorney, Agent, or Firm 7 Bereskin & Parr LLP
`
`(57)
`
`ABSTRACT
`
`The present disclosure discloses a rechargeable Zn battery
`based on layered/tunnelled structure vanadium/molybde-
`num oxides, with/without the presence of neutral/cationic/
`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 Zn2+
`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 Zn2+ intercalation material:
`the negative
`electrode is Zn metal in any form; the aqueous electrolyte is
`of pH 1 to 9 and contains a soluble zinc salt in a concen-
`tration range from 0.01 to 10 molar.
`
`16 Claims, 14 Drawing Sheets
`
`flisaharga <
`
`/
`
`\
`}
`
`f 10
`
`
`
`
`
`uw Exhibit 1001, pg. 1
`
`UW Exhibit 1001, pg. 1
`
`

`

`US 9,780,412 B2
`
`Page 2
`
`(56)
`
`References Cited
`U.S. PATENT DOCUMENTS
`
`2014/0050970 A1*
`
`2/2014 Li
`
`........................... H01M4/26
`429/163
`
`OTHER PUBLICATIONS
`
`“Structure and properties of layered manganese-vanadium oxide as
`a cathode material for lithium secondary batteries”, Lu et al.,
`Electrochemistry Communications 6, p. 672-677, 2004*
`Le et al., “Intercalation of Polyvalent Cations into V205 Aerogels”,
`Chemistry of Materials, 1998, pp. 682-684, vol. 10 (3).
`Jiahong et al., “AC Impedance Study of the Aqueous Zn/V205
`Secondary Battery”, Acta Physicochimica Sinica, 2000, pp. 454-
`458; vol. 16, No. 5.
`Giorgetti et al., “Identification of an unconventional zinc coordina-
`tion site in anhydrous anV205 aerogels from x-ray absorption”,
`1999, pp. 2257-2264, vol. 11(8).
`Zhang et al., “Hydrothermal synthesis and characterization of a
`series of novel zinc vanadium oxides as cathode materials”, Mate-
`rials Research Society Symposium Proceedings, Materials for Elec-
`trochemical Energy Storage and Conversion IIiBatteries, Capaci-
`tors and Fuel Cells, 1998, pp. 367-372, vol. 496.
`
`Xu et al., “Reversible Insertion Properties of Zinc Ion into Man-
`ganese Dioxide and Its Application for Energy Storage”, Electro-
`chemical and Solid-State Letters, 2009, pp. A61-A65, vol. 12(4).
`International Search Report and Written Opinion for PCT/CA2016/
`050613 dated Sep. 21, 2016.
`Joint Center for Energy Storage Research, downloaded from:
`https://Www.jcesr.org/research/multivalent-intercalation/, Retrieved
`on Jul. 19, 2017.
`Levi et al., “A review on the problems of the solid state ions
`diffusion in cathodes for rechargeable mg batteries.” Journal of
`Electroceramics, 2009, 22(1-3), 13-19.
`Rong et al., “Materials Design Rules for Multivalent Ion Mobility
`in Intercalation Structures” Chemistry of Materials, 2015, 27(17),
`6016-6021.
`Xu et al., Supporting Information for “Energetic Zinc Ion Chem-
`istry: The Rechargeable Zinc Ion Battery” Angewandte Chemie,
`2012, 51, 933-935.
`Paulsen et al., “Layered LiiMn-Oxide with the 02 Structure: A
`Cathode Material for Li-Ion Cells Which Does not Convert to
`Spinel” Journal of The Electrochemical Society, 1999, 146(10),
`3560-3565.
`
`* cited by examiner
`
`uw Exhibit 1001, pg. 2
`
`UW Exhibit 1001, pg. 2
`
`

`

`U.S. Patent
`
`Oct. 3, 2017
`
`Sheet 1 0f 14
`
`US 9,780,412 B2
`
`fiischm‘ge
`
`
`
`Figure 1A
`
`uw Exhibit 1001, pg. 3
`
`UW Exhibit 1001, pg. 3
`
`

`

`U.S. Patent
`
`Oct. 3, 2017
`
`Sheet 2 of 14
`
`US 9,780,412 B2
`
`
`
`figure 18
`
`uw Exhibit 1001, pg. 4
`
`UW Exhibit 1001, pg. 4
`
`

`

`U.S. Patent
`
`Oct. 3, 2017
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`Oct. 3, 2017
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`U S. Patent
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`Oct. 3, 2017
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`Oct. 3, 2017
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`Oct. 3, 2017
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`

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`U.S. Patent
`
`Oct. 3, 2017
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`

`

`US 9,780,412 B2
`
`1
`ELECTRODE MATERIALS FOR
`RECHARGEABLE ZINC CELLS AND
`BATTERIES PRODUCED THEREFROM
`
`FIELD
`
`This disclosure relates generally to batteries, and, more
`specifically to zinc ion batteries involving zinc intercalation
`positive electrode materials, zinc metal based negative elec-
`trodes in any form, and an aqueous electrolyte containing
`zinc salt and batteries using these positive electrode mate-
`rials.
`
`BACKGROUND
`
`Given the looming concerns of climate change, sustain-
`able energy resources such as solar and wind have entered
`the global spotlight, triggering the search for reliable, low
`cost electrochemical energy storage. Among the various
`options, lithium ion batteries are currently the most attrac-
`tive 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 applications, and
`dictate against their use in stationary grid storage where low
`cost and durability are more of a concern than weight. What
`is needed is a high energy density battery that is recharge-
`able, cheap, safe, and easy to manufacture and dispose of or
`recycle. Aqueous batteries (water based electrolytes) are
`therefore attracting tremendous attention. Their high con-
`ductivity (up to 1 Siemens (S) cm'l) compared to the
`non-aqueous electrolytes (0.001 to 0.01 S cm‘l) also favour
`high rate capabilities suitable for emerging applications.
`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-olf between the reduc-
`tion potential of a metal, E°, (low values give higher cell
`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
`
`negative electrode in primary aqueous battery systems.
`Moreover, zinc has (a) high abundance and large production
`which makes it 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.
`Vanadium and molybdenum are low cost metals possess-
`ing a range of oxidation states (V: +2 to +5; Mo: +2 to +6),
`which allows for multiple redox and hence large specific
`capacities for vanadium or molybdenum based electrode
`materials. Layered VnOm (vanadium oxides: V205, V308,
`V4011) and MoOy (molybdenum oxides) that are made of
`two dimensional sheet structures were the subject of much
`past investigation for non-aqueous and aqueous alkali (Li
`and Na) ion batteries. The additional presence of interlayer
`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.
`
`SUMMARY
`
`The present disclosure discloses a rechargeable Zn battery
`based on layered/tunnelled structure vanadium/molybde-
`num oxides, with/without the presence of neutral/cationic/
`
`10
`
`15
`
`20
`
`25
`
`30
`
`35
`
`40
`
`45
`
`50
`
`55
`
`60
`
`65
`
`2
`
`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 Zn2+
`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 Zn2+ intercalation material;
`the negative
`electrode is Zn metal in any form; the aqueous electrolyte is
`may have a pH in a range of 1 to 9 and contains a soluble
`zinc salt which may be in a concentration range from 0.01
`to 10 molar.
`
`Thus, disclosed herein is a zinc ion battery, comprising:
`a positive electrode compartment having enclosed therein
`an intercalation layered positive electrode material
`MXVzOSnHZO, wherein x is in a range from 0.05 to 1,
`n is in a 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 V205 is a layered
`crystal structure having the metal
`ions M pillared
`between the layers, and waters of hydration coordi-
`nated to the metal ions M;
`a negative electrode compartment having enclosed therein
`a negative electrode for storing Zinc;
`a separator electrically insulating and permeable to zinc
`ions separating the positive and negative compart-
`ments; and
`an electrolyte comprising water and having a salt of zinc
`dissolved therein.
`
`There is also disclosed herein a zinc ion battery, compris-
`ing:
`a positive electrode compartment having enclosed therein
`and intercalated layered positive electrode material
`MXV3O7.nHZO, 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 V307 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;
`a negative electrode compartment having enclosed therein
`a negative electrode for storing Zinc;
`a separator electrically insulating and permeable to zinc
`ions separating the positive and negative compart-
`ments; and
`an electrolyte comprising water and having a salt of zinc
`dissolved therein.
`
`There is also disclosed a zinc ion battery; comprising:
`a positive electrode compartment having enclosed therein
`an intercalated layered positive electrode material
`MXMoOynHZO, wherein x is in a range from 0 to 1, y
`is in a range from 2 to 3, n is in a 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 MoOy has a layer or tunnel crystal struc-
`ture, and the metal ions M, if present, pillared between
`the layers, and waters of hydration coordinated to the
`metal ions M pillared between the layers;
`a negative electrode compartment having enclosed therein
`a negative electrode for storing Zinc; a separator elec-
`trically insulating and permeable to zinc ions separating
`the positive and negative compartments; and
`
`UW Exhibit 1001, pg. 17
`
`UW Exhibit 1001, pg. 17
`
`

`

`US 9,780,412 B2
`
`3
`an electrolyte comprising water and having a salt of zinc
`dissolved therein.
`
`A further understanding of the functional and advanta-
`geous aspects of the disclosure can be realized by reference
`to the following detailed description and drawings.
`
`BRIEF DESCRIPTION OF THE DRAWINGS
`
`Embodiments of the disclosure will now be described, by
`way of example only, with reference to the drawings, in
`which:
`
`FIG. 1A shows a conceptual scheme of a zinc-ion battery
`constructed in accordance with the present disclosure.
`FIG. 1B is a cross section of a zinc-ion battery.
`FIG. 2 shows linear sweep voltammograms at l mV/s on
`Pt, Ti, and Zn in l M NaZSO4 showing the onset of the
`hydrogen evolution reaction.
`FIG. 3A shows a linear sweep voltammogram at l mV/s
`in l M NaZSO4 showing the hydrogen evolution reaction for
`zinc and titanium. The dotted voltammogram shows zinc
`deposition on a zinc disk electrode in l M ZnSO4 for
`comparison.
`FIG. 3B shows a linear sweep voltammogram at l mV/s
`in l M NaZSO4 showing the hydrogen evolution reaction for
`stainless steel and titanium.
`
`FIG. 4A shows cyclic voltammograms at 5 mV/s on a Ti
`disk electrode.
`
`4
`
`FIG. 11 shows the tradeolf between energy and power
`density (Ragone plot)
`for
`reversible Zn2+ storage in
`Zn0_25VzOS.nHZO, H2V3OS, MnOZ, and Zn3[Fe(CN)6]2.
`
`DETAILED DESCRIPTION
`
`Various embodiments and aspects of the disclosure will be
`described with reference to details discussed below. The
`
`following description and drawings are illustrative 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.
`
`The Figures are 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.
`As used herein, the term “about”, when used in conjunc-
`tion with ranges of dimensions, temperatures, concentra-
`tions or other physical properties or characteristics is meant
`to cover slight variations that may exist in the upper and
`lower limits of the ranges of dimensions so as to not exclude
`embodiments where on average most of the dimensions are
`satisfied but where statistically dimensions may exist outside
`this region.
`the phrase “a negative electrode for
`As used herein,
`storing zinc” means that the negative electrode can incor-
`porate and release zinc reversibly by electrodeposition/
`dissolution (plating/stripping) of elemental zinc from/to the
`electrolyte, by alloying/dealloying reaction, or the negative
`electrode comprises a material that can store zinc by any one
`or combination of intercalation, conversion, and capacitive
`storage (adsorption/deadsorption of Zn2+ ions).
`FIG. 1A shows a conceptual scheme of a zinc-ion battery
`shown generally at 10, which includes an anode 12, and an
`intercalated layered positive electrode material 14 separated
`by an electrolyte 16, with FIG. 1A showing diagrammati-
`cally 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.
`
`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 con-
`tained 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 separa-
`tor 28 include organic polymers (polyethylene (PE), poly-
`propylene (PP), poly(tetrafluoroethylene) (PTFE), poly(vi-
`nyl 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 of these.
`The present disclosure provides several embodiments of
`the intercalated layered positive electrode material 14. In an
`
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`UW Exhibit 1001, pg. 18
`
`FIG. 4B shows cyclic voltammograms at 5 mV/s on
`stainless steel rod in l M ZnSO4.
`FIG. 5 shows linear sweep voltammograms on a zinc disk
`electrode (cathodic sweep) and a stainless steel disk elec-
`trode (anodic sweep) at l mV/s in l M ZnSO4. The cathodic
`sweep on zinc shows zinc deposition and the anodic sweep
`on the stainless steel shows the oxygen evolution reaction.
`These two electrochemical reactions dictate the potential
`operating window for aqueous zinc-ion batteries using this
`electrolyte.
`FIG. 6A shows Rietveld refinement of H2V3OS. Data
`points (circles); calculated profile (line); difference profile
`(dotted line); Bragg positions (vertical lines) are as indi-
`cated. Refined lattice parameters are a:l 6.87 A, b:9.332 (3)
`A, c:3.63 A, and G:B:Y:90°. Inset shows the layered
`structure projected in the ac plane. VOx polyhedra are
`shown in black.
`FIG.
`6B
`
`of
`
`shows
`
`the Rietveld
`
`refinement
`
`Zn0_25VZOS.nHZO. 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,
`(x:9l.26°,
`[3:90.31°, and y:88.66°. The VO,C and ZnO,C
`polyhedra are shown in black and grey, respectively.
`FIGS. 7A, 7B, 7C and 7D show a typical SEM image of
`the H2V3O8 (7A and 7B) and Zn0_25VzOs.nHzO (7C and 7D)
`nanofibers.
`
`FIGS. 8A and 8B show galvanostatic polarization curves
`for the (8A) H2V3O8 and (8B) Zn0_25VzOS.nHzO electrodes
`at various current rates. Here, 1C is defined as 350 mA g"1
`for H2V3O8 and 300 mA g'1 for Zn0_25VZOS.nHZO.
`FIGS. 9A, 9B, 9C and 9D show specific capacity and
`coulombic efficiency of the H2V3O8 (9A and 9B) and
`Zn0_25VZOS.nHZO (9C and 9D) as a function of cycling at
`4C (9A and 9C) and 8C (9B and 9D) current rates.
`FIGS. 10A and 10B show rate capability of the (9A)
`H2V3O8 and (9B) Zn0_25VzOS.nHzO cells studied under
`variable current
`loading as a function of cycling. The
`corresponding coulombic efficiencies are also shown.
`
`UW Exhibit 1001, pg. 18
`
`

`

`US 9,780,412 B2
`
`5
`the intercalation layered positive electrode
`embodiment
`material 14 may be MXVzOSnHZO, 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 V205 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 embodiments may
`be greater than 0 and less than 1. Some of the waters of
`hydration may be hydrogen bonded to the layers.
`In a preferred embodiment x:0.25, and n:1.
`In another embodiment, the intercalated layered positive
`electrode material 14 may be MXV3O7.nHZO wherein x is in
`a range from 0.05 to 1, n is 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 V307 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. In an embodiment
`n is greater than 0 and less than 1.
`In a preferred embodiment x:0.05, and n:1.
`In another embodiment, the intercalated layered positive
`electrode material 14 may be MXMoOynHzO, 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
`MoOy 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.
`In some embodiments n is greater than 0 and less than 2.
`In some embodiments the waters of hydration are hydrogen
`bonded to the layers.
`In a preferred embodiment x:0.25, y:3 and n:0.
`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.
`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.
`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 Zn2+ with or
`without the nonaqueous component and with or without
`additional
`ionically-conductive salts such as quaternary
`ammonium salts or alkali metal salts.
`
`The negative electrode may be made of a 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 referred to as a zinc battery. This is
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`6
`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 sheet of zinc or an alloy, or powder zinc
`bonded adhered to the surface of the negative electrode
`facing into the negative electrode compartment. The zinc
`may be a constituent of a formulation which is adhered to the
`surface of the current collector. Non-limiting examples of
`zinc alloys that may be used include alloys of zinc with lead,
`vanadium, chromium, manganese, iron, cobalt, nickel, cad-
`mium, tungsten, bismuth, tin, indium, antimony, copper, and
`titanium.
`
`The negative current collector is an electrically conduc-
`tive support for active zinc which may be comprised of any
`one or combination of carbon, boron, lead, vanadium, chro-
`mium, manganese, iron, cobalt, nickel, cadmium, tungsten,
`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 of intercalation, conversion, and capacitive
`storage. In a conversion process, the electrochemical reac-
`tion of the negative electrode material with zinc leads to its
`decomposition into two or more products. In capacitive
`storage the Zn2+ ions are stored at the surface of the negative
`electrode material by a non-faradic process.
`The intercalated layered positive electrode material may
`have different morphologies. The intercalation layered posi-
`tive electrode material 14 has a nanostructured morphology.
`Preferably the average particle 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 mean size in a range from about 5 nm
`to about 50 um.
`The particles may be coated with electrically conducting
`material, in which
`the electrically conducting material is any one or combina-
`tion of carbon powder and conducting polymer. The par-
`ticles may be embedded in 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).
`The zinc ion battery materials disclosed herein will now
`be illustrated by the following non-limiting examples.
`
`EXAMPLES
`
`Two vanadium oxide based compounds with layered
`crystal structures and in ultralong one-dimensional morphol-
`ogy exhibiting as robust host materials for high rate and long
`term reversible Zn2+ ion storage in aqueous electrolyte were
`produced. Vanadium is a cheap and environmentally benign
`metal possessing a range of oxidation states (+2 to +5),
`which allows for multiple redox and hence large specific
`capacities for vanadium based electrode materials. Particu-
`larly, oxides of vanadium e.g., V205 which is non-toxic and
`produced in large quantities, displays numerous crystal and
`compositional chemistries for reversible metal ion storage.
`Layered MXVnOm oxides (M:metal ion) of compositions
`
`UW Exhibit 1001, pg. 19
`
`UW Exhibit 1001, pg. 19
`
`

`

`US 9,780,412 B2
`
`7
`such as V205, V308, V4011 that are made of two dimen-
`sional 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 act as pillars, providing structural
`stability during long term charge discharge cycling.
`and
`Embodying
`such
`qualities
`are
`H2V3O8
`ZnXVZOSnHzO, which we have synthesized in nanofiber
`morphology by a simple and rapid microwave hydrothermal
`treatment of V205, 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 Zn2+
`cycling, shorter ion diffusion paths, better interaction of
`carbon additives with the active material and robust con-
`
`ductive wiringifacilitating high specific capacities of ~300
`mAh g"1 and long term cyclabilities up to 1000 cycles at
`high coulombic efficiency using fast current rates.
`Experimental Methods
`Synthesis of H2V3O8 and ZnXVZO5
`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 hydro-
`thermal approach used in the synthesis of single crystalline
`H2V3O8 nanobelt to a rapid and scalable microwave hydro-
`thermal method for the synthesis of highly homogeneous
`H2V3O8 and ZnXVZOSnHZO nanofibers. In a typical proce-
`dure, 3 to 4 millimoles (mmol) V205 was dispersed in 15:1
`water/ethanol (v) mixture with or without stoichiometric
`amount of zinc acetate (for ZnXVzOSnHZO) and transferred
`to a sealed Teflon vessel. The vessels were fitted 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 was raised
`to 180° C.
`in 10 minutes and maintained for 60 to 90
`
`minutes. The preset temperature was maintained automati-
`cally 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.
`Characterizatio