(19) United States
`(12) Patent Application Publication (10) Pub. No.: US 2013/0260225 A1
`Doe et al.
`
`(43) Pub. Date: Oct. 3, 2013
`
`US 20130260225A1
`
`(54) LAYERED MATERIALS WITH IMPROVED
`MAGNESIUM INTERCALATION FOR
`RECHARGEABLE MAGNESIUM ION CELLS
`
`(71) ApplicantszRobert Ellis Doe, Norwood, MA (US);
`Craig Michael Downie, Waltham, MA
`(US); Christopher Fischer, SomerVille,
`MA (US); George Hamilton Lane, St.
`Helens (AU); Dane Morgan, Middleton,
`WI (US); Josh Nevin, Belmont, MA
`(US); Gerbrand Ceder, Wellesley, MA
`(US); Kristin Aslaug Persson, Orinda,
`CA (US); David Eaglesham, Lexington,
`MA (US)
`
`(72)
`
`Inventors: Robert Ellis Doe, Norwood, MA (US);
`Craig Michael Downie, Waltham, MA
`(US); Christopher Fischer, SomerVille,
`MA (US); George Hamilton Lane, St.
`Helens (AU); Dane Morgan, Middleton,
`WI (US); Josh Nevin, Belmont, MA
`(US); Gerbrand Ceder, Wellesley, MA
`(US); Kristin Aslaug Persson, Orinda,
`CA (US); David Eaglesham, Lexington,
`MA (US)
`
`(73) Assignee: Pellion Technologies, Inc., Cambridge,
`MA (US)
`
`(21) Appl.No.: 13/794,508
`
`(22)
`
`Filed:
`
`Mar. 11, 2013
`
`Related US. Application Data
`
`(60) Provisional application No. 61/617,512, filed on Mar.
`29, 2012.
`
`Publication Classification
`
`(51)
`
`Int. Cl.
`H01M 4/38
`(52) US. Cl.
`CPC ..................................... HOIM 4/381 (2013.01)
`USPC ........ 429/188; 429/209; 429/231.6; 429/219;
`429/220; 429/231.5; 429/221; 429/217
`
`(2006.01)
`
`(57)
`
`ABSTRACT
`
`Electrochemical devices which incorporate cathode materials
`that include layered crystalline compounds for which a struc-
`tural modification has been achieved which increases the
`diffusion rate of multi-Valent ions into and out of the cathode
`
`materials. Examples in which the layer spacing of the layered
`electrode materials is modified to have a specific spacing
`range such that the spacing is optimal for diffusion of mag-
`nesium ions are presented. An electrochemical cell com-
`prised of a positive intercalation electrode, a negative metal
`electrode, and a separator impregnated with a nonaqueous
`electrolyte
`solution containing multi-Valent
`ions
`and
`arranged between the positive electrode and the negative elec-
`trode active material is described.
`
`anode terminal
`
`\ anode collector
`
`
`
`insulating package
`
`insulating
`plate
`
`separator
`
`cathode
`
`anode
`
`
`WWW
`
`insulating plate
`
`
`
`cathode can
`
`uw Exhibit 1018, pg. 1
`
`UW Exhibit 1018, pg. 1
`
`

`

`Patent Application Publication
`
`Oct. 3, 2013 Sheet 1 0f 20
`
`US 2013/0260225 A1
`
`centier d
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`FIG. 1A
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`FIG. 2
`
`uw Exhibit 1018, pg. 2
`
`UW Exhibit 1018, pg. 2
`
`

`

`Patent Application Publication
`
`Oct. 3, 2013 Sheet 2 0f 20
`
`US 2013/0260225 A1
`
`6110
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`uw Exhibit 1018, pg. 3
`
`UW Exhibit 1018, pg. 3
`
`

`

`Patent Application Publication
`
`Oct. 3, 2013 Sheet 3 0f 20
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`UW Exhibit 1018, pg. 4
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`

`

`Patent Application Publication
`
`Oct. 3, 2013 Sheet 4 0f 20
`
`US 2013/0260225 A1
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`UW Exhibit 1018, pg. 5
`
`

`

`Patent Application Publication
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`Oct. 3, 2013 Sheet 5 of 20
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`UW Exhibit 1018, pg. 6
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`

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`Patent Application Publication
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`Oct. 3, 2013 Sheet 6 0f 20
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`US 2013/0260225 A1
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`UW Exhibit 1018, pg. 7
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`

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`Patent Application Publication
`
`Oct. 3, 2013 Sheet 7 0f 20
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`US 2013/0260225 A1
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`

`

`Patent Application Publication
`
`Oct. 3, 2013 Sheet 8 0f 20
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`US 2013/0260225 A1
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`UW Exhibit 1018, pg. 9
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`

`

`Patent Application Publication
`
`Oct. 3, 2013 Sheet 9 0f 20
`
`US 2013/0260225 A1
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`UW Exhibit 1018, pg. 10
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`

`

`Patent Application Publication
`
`Oct. 3, 2013 Sheet 10 0f 20
`
`US 2013/0260225 A1
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`UW Exhibit 1018, pg. 11
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`UW Exhibit 1018, pg. 11
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`

`

`Patent Application Publication
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`Oct. 3, 2013 Sheet 11 0f 20
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`US 2013/0260225 A1
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`UW Exhibit 1018, pg. 12
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`UW Exhibit 1018, pg. 12
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`

`

`Patent Application Publication
`
`Oct. 3, 2013 Sheet 12 0f 20
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`US 2013/0260225 A1
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`UW Exhibit 1018, pg. 13
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`

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`Patent Application Publication
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`US 2013/0260225 A1
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`

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`Patent Application Publication
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`Oct. 3, 2013 Sheet 14 0f 20
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`US 2013/0260225 A1
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`Patent Application Publication
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`Patent Application Publication
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`Patent Application Publication
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`Oct. 3, 2013 Sheet 17 of 20
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`US 2013/0260225 A1
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`Patent Application Publication
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`US 2013/0260225 A1
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`

`

`Patent Application Publication
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`Oct. 3, 2013 Sheet 19 0f 20
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`US 2013/0260225 A1
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`UW Exhibit 1018, pg. 20
`
`

`

`Patent Application Publication
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`Oct. 3, 2013 Sheet 20 of 20
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`US 2013/0260225 A1
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`UW Exhibit 1018, pg. 21
`
`

`

`US 2013/0260225 A1
`
`Oct. 3, 2013
`
`LAYERED MATERIALS WITH IMPROVED
`MAGNESIUM INTERCALATION FOR
`RECHARGEABLE MAGNESIUM ION CELLS
`
`CROSS-REFERENCE TO RELATED
`APPLICATIONS
`
`[0001] This application claims priority to and the benefit of
`co-pending US. provisional patent application Ser. No.
`61/617,512, filed Mar. 29, 2012, which application is incor-
`porated herein by reference in its entirety.
`
`STATEMENT REGARDING FEDERALLY
`FUNDED RESEARCH OR DEVELOPMENT
`
`[0002] This invention was made with government support
`under award number DE-AR0000062, awarded by Advanced
`Research Projects Agency-Energy (ARPA-E), U.S. Depart-
`ment of Energy. The government has certain rights in the
`invention.
`
`FIELD OF THE INVENTION
`
`[0003] The invention relates to electrode materials in gen-
`eral and particularly to electrode materials useful in second-
`ary batteries that employ Mg in their electrolytes.
`
`BACKGROUND OF THE INVENTION
`
`[0004] A variety of new secondary electrochemical cells
`that exhibit high energy density have been demonstrated.
`However, commercial systems remain primarily based on
`lithium ion (Li-ion) chemistry. Such cells frequently consist
`of a layered transition metal oxide cathode material, an
`anode-active lithium metal or lithium intercalation or alloy
`compound such as graphitic carbon, tin and silicon, and an
`electrolytic solution containing a dissolved lithium-based salt
`in an aprotic organic or inorganic solvent or polymer. Today
`there is great demand for energy storage devices that exhibit
`higher volumetric and gravimetric energy density when com-
`pared to commercially available lithium ion batteries. Con-
`sequently an increasingly sought after route to meeting this
`demand higher energy density is to replace the monovalent
`cation lithium (Li+) with multi-valent ions, such as divalent
`magnesium cations (Mg2+), because these ions can enable
`many times the charge of Li+ to be transferred per ion.
`[0005]
`Furthermore, alkali metals, and lithium in particu-
`lar, have numerous disadvantages. Alkali metals are expen-
`sive. Alkali metals are highly reactive. Alkali metals are also
`highly flammable, and fire resulting from the reaction of
`alkali metals with oxygen, water or other active materials is
`extremely difficult to extinguish. Lithium is poisonous and
`compounds thereof are known for their severe physiological
`effects, even in minute quantities. As a result, the use of alkali
`metals requires specialized facilities, such as dry rooms, spe-
`cialized equipment and specialized procedures.
`[0006] Gregory et al., “Nonaqueous Electrochemistry of
`Magnesium; Applications to Energy Storage” J. Electro-
`chem. Soc., Vol. 137, No. 3, March 1990 discloses C0304,
`anO3, Mn3O4, MoO3, PbOZ, Pb3O4, Rqu, V205, W03,
`TiSZ, VSZ, ZrSZ, MoBZ, TiBZ, and ZrB2 as positive electrode
`materials for a magnesium battery. However, only the first
`cycle discharge is shown and all materials exhibit significant
`polarization for medium current densities.
`[0007] Novak et al., “Electrochemical Insertion of Magne-
`sium in Metal Oxides and Sulfides from Aprotic Electro-
`lytes,” JECS 140(1) 1993 discloses TiSz, ZrSZ, Rqu, Co3O4
`
`and V205 as positive electrode materials of a magnesium
`battery. However, only layeredVZO5 shows promising capac-
`ity and reversibility. Furthermore, Novak et al. show that
`Mg2+ insertion into this oxide depends on the ratio between
`the amounts of H20 and Mg2+ as well as on the absolute
`amount of H20 in the electrolyte. According to Novak, water
`molecules preferentially solvate Mg2+ ions, which facilitate
`the insertion process by co-intercalation.
`[0008] Novak et al., “Electrochemical Insertion of Magne-
`sium into Hydrated Vanadium Bronzes” Electrochem. Soc.,
`Vol. 142, No. 8, 1995 discloses Mg2+ insertion into layered
`vanadium bronzes, MeV3OS(H2O)y where (Me:Li, Na, K,
`Ca0_5, and Mg0_5). Variations in the content of bound lattice
`water in the bronzes were found to be responsible for a dif-
`ference in the electrochemical properties of the same starting
`material dried at different temperatures. The presence of this
`water was deemed essential but the lattice water is removed
`
`during cycling after which the capacity deteriorates. Further-
`more, attempts to cycle the compounds in dry electrolytes
`failed. The beneficial effect ofwater was speculated to be due
`to its solvation of the Mg2+ ion.
`[0009] Le et al., “Intercalation of Polyvalent Cations into
`V205 Aerogels” Chem. Mater. 1998, 10, 682-684 discloses
`multi-valent ion insertion into V205 areogels where the small
`diffusion distances and high surface area are regarded as
`beneficial for multi-valent intercalation. X-ray diffraction of
`the aerogel shows an interlayer spacing of 12.5 A (due to
`retaining acetone), as compared to the 8.8 A characteristic of
`the V205*0.5H20 xerogel.
`[0010] Amatucci et al., “Investigation ofYttrium and Poly-
`valent
`Ion Intercalation into Nanocrystalline Vanadium
`Oxide,” J Electrochem Soc, 148(8), A940-A950, Jul. 13,
`2001, show reversible intercalation of several multi-valent
`cations (Mg, Ca“, Y3+) into nano-metric layered V205 but
`with significant polarization (e.g., energy loss) and at a low
`rate of 0.04C which signifies the low diffusivity of the Mg
`ions.
`
`[0011] The current, proven state of the art high energy,
`rechargeable Mg cell is described by Aurbach et al., US. Pat.
`No. 6,316,141, issued Nov. 13, 2001, as a cell comprised ofa
`magnesium metal anode, a “Chevrel” phase active material
`cathode, and an electrolyte solution derived from an organo-
`metallic complex containing Mg. Chevrel compounds are a
`series of ternary molybdenum chalcogenide compounds first
`reported by R. Chevrel, M. Sergent, and J. Prigent in J. Solid
`State Chem. 3, 515-519 (1971). The Chevrel compounds have
`the general formula MXMo6X8, where M represents any one
`of a number of metallic elements throughout the periodic
`table; x has values between 1 and 4, depending on the M
`element; and X is a chalcogen (sulfur, selenium or tellurium).
`Furthermore, in E. Levi et al, “New Insight on the Unusually
`High Ionic Mobility in Chevrel Phases,” Chem Mat 21 (7),
`1390-1399, 2009, the Chevrel phases are described as unique
`materials which allow for a fast and reversible insertion of
`
`various cations at room temperature.
`[0012] Michot et al., US. Pat. No. 6,395,367, issued May
`28, 2002, is said to disclose ionic compounds in which the
`anionic load has been delocalized. A compound disclosed by
`the invention includes an anionic portion combined with at
`least one cationic portion M’"+ in sufficient numbers to ensure
`overall electronic neutrality; the compound is further com-
`prised of M as a hydroxonium, a nitrosonium NO+, an ammo-
`nium NH4+, a metallic cation with the valence m, an organic
`cation with the valence m, or an organometallic cation with
`
`UW Exhibit 1018, pg. 22
`
`UW Exhibit 1018, pg. 22
`
`

`

`US 2013/0260225 Al
`
`Oct. 3, 2013
`
`the valence m. The anionic load is carried by a pentacyclical
`nucleus of tetrazapentalene derivative bearing electroattrac-
`tive substituents. The compounds can be used notably for
`ionic conducting materials, electronic conducting materials,
`colorant, and the catalysis of various chemical reactions.
`[0013] US. Pat. No. 6,426,164 B1 toYamaura et al., issued
`Jul. 30, 2002, is said to disclose a non-aqueous electrolyte
`battery capable of quickly diffusing magnesium ions and
`improving cycle operation resistance, incorporating a posi-
`tive electrode containing LiXMO2 (where M is an element
`containing at least Ni or Co) as a positive-electrode active
`material thereof; a negative electrode disposed opposite to the
`positive electrode and containing a negative-electrode active
`material which permits doping/dedoping magnesium ions:
`and a non-aqueous electrolyte disposed between the positive
`electrode and the negative electrode and containing non-
`aqueous solvent and an electrolyte constituted by magnesium
`salt, wherein the value of x of LiXMO2 satisfies a range
`0.1sx50.5. It is also said that for Li concentrations st.1, the
`host material becomes unstable and for higher Li concentra-
`tions x205, there are not enough available Mg lattice sites
`available. Specifically, there is no mention of interlayer dis-
`tance.
`
`[0014] Michot et al., US. Pat. No. 6,841,304, issued Jan.
`1 1, 2005, is said to disclose novel ionic compounds with low
`melting point whereof the onium type cation having at least a
`heteroatom such as N, O, S or P bearing the positive charge
`and whereofthe anion includes, wholly orpartially, at least an
`ion imidide such as (FXIO)N'(OX2F) wherein X1 and X2 are
`identical or different and comprise S0 or PF, and their use as
`solvent in electrochemical devices. Said composition com-
`prises a salt wherein the anionic charge is delocalised, and can
`be used, inter alia, as electrolyte.
`Publication No.
`[0015] US.
`Patent Application
`20090068568 A1 (Yamamoto et al. inventors), published on
`Mar. 12, 2009, is said to disclose a magnesium ion containing
`non-aqueous electrolyte in which magnesium ions and alu-
`minum ions are dissolved in an organic etheric solvent, and
`which is formed by: adding metal magnesium, a halogenated
`hydrocarbon RX, an aluminum halide AlY3, and a quaternary
`ammonium salt R1R2R3R4N+Z' to an organic etheric solvent;
`and applying a heating treatment while stirring them (in the
`general formula RX representing the halogenated hydrocar-
`bon, R is an alkyl group or an aryl group, X is chlorine,
`bromine, or iodine, in the general formula AlY3 representing
`the aluminum halide, Y is chlorine, bromine, or iodine, in the
`general formula R1R2R3R4N+Z' representing the quaternary
`ammonium salt, R1, R2, R3, and R4 represent each an alkyl
`group or an aryl group, and Z represents chloride ion, bromide
`ion, iodide ion, acetate ion, perchlorate ion, tetrafluoro borate
`ion, hexafluoro phosphate ion, hexafluoro arsenate ion, per-
`fluoroalkyl sulfonate ion, or perfluoroalkyl sulfonylimide
`ion. These additives are aimed at increasing the stability ofthe
`electrolyte in atmospheric air and facilitate the production
`process for said electrolytes.
`Publication No.
`[0016] US.
`Patent Application
`20100136438 Al (Nakayama et al. inventors), published Jun.
`3, 2010, is said to disclose a magnesium battery that is con-
`stituted of a negative electrode, a positive electrode and an
`electrolyte. The negative electrode is formed ofmetallic mag-
`nesium and can also be formed of an alloy. The positive
`electrode is composed of a positive electrode active material,
`for example, a metal oxide, graphite fluoride ((CF)n) or the
`like, etc. The electrolytic solution is, for example, a magne-
`
`sium ion containing nonaqueous electrolytic solution pre-
`pared by dissolving magnesium(ll) chloride (MgClz) and
`dimethylaluminum chloride ((CH3)2AlCl) in tetrahydrofuran
`(THF). In the case of dissolving and depositing magnesium
`by using this electrolytic solution, they indicate that the fol-
`lowing reaction proceeds in the normal direction or reverse
`direction.
`
`2Mg2+ +
`
`2
`
`C1
`
`CH3
`\ /
`/Al
`CH3
`\Cl
`
`+ 6THF —>
`
`C1
`THF
`\ / \ /
`Mg
`Mg
`/ \ / \
`C1
`
`THF
`
`THF 2+
`
`THF
`
`+
`
`2
`
`CH
`
`3\ /
`Al
`/ \
`CH3
`
`C1
`
`THF
`
`According to this, there are provided a magnesium ion-con-
`taining nonaqueous electrolytic solution having a high oxi-
`dation potential and capable of sufficiently bringing out
`excellent characteristics of metallic magnesium as a negative
`electrode active material and a method for manufacturing the
`same, and an electrochemical device with high performances
`using this electrolytic solution.
`Publication No.
`[0017] US.
`Patent Application
`20110111286 A1 (Yamamoto et al. inventors), published on
`May 12, 2011, is said to disclose a nonaqueous electrolytic
`solution containing magnesium ions which shows excellent
`electrochemical characteristics and which can be manufac-
`
`tured in a general manufacturing environment such as a dry
`room, and an electrochemical device using the same are pro-
`vided. A Mg battery has a positive-electrode can, a positive-
`electrode pellet made of a positive-electrode active material
`or the like, a positive electrode composed of a metallic net
`supporting body, a negative-electrode cup, a negative elec-
`trode made of a negative-electrode active material, and a
`separator impregnated with an electrolytic solution and dis-
`posed between the positive-electrode pellet and the negative-
`electrode active material. Metal Mg, an alkyl
`trifluo-
`romethanesulfonate, a quaternary ammonium salt or/and a
`1,3-alkylmethylimidazolium salt, more preferably, an alumi-
`num halide are added to an ether system organic solvent and
`are then heated, and thereafter, more preferably, a trifluorobo-
`raneether complex salt is added thereto, thereby preparing the
`electrolytic solution. By adopting a structure that copper con-
`tacts the positive-electrode active material, the electrochemi-
`cal device can be given a large discharge capacity.
`[0018] Nazar et al, “Insertion of Poly(p-phenylenevi-
`nylene) in Layered M003”, J. Am. Chem. Soc. 1992, 114,
`6239-6240 discloses insertion of high molecular weight PPV
`into a layered oxide by intercalating the PPV precursor poly-
`mer between the layers of M003, by ion exchange. The layer
`spacing was reported to increase from 6.9 A to 13.3 A. No
`electrochemical investigations of the host material were per-
`formed.
`
`[0019] Nazar et al, “Hydrothermal Synthesis and Crystal
`Structure ofa Novel Layered Vanadate with 1 ,4-Diazabicyclo
`[2.2.2]octane as the Structure-Directing Agent: C6H14N27
`V6014.HZO” Chem. Mater. 1996, 8, 327 discloses Li inser-
`tion into organic cation (C6H12N2 or ‘DABCO’)-templated
`vanadium oxide resulting from hydrothermal synthesis. The
`host crystal structure possesses a structure composed ofa new
`arrangement of edge-shared VO5 square pyramids that are
`
`UW Exhibit 1018, pg. 23
`
`UW Exhibit 1018, pg. 23
`
`

`

`US 2013/0260225 A1
`
`Oct. 3, 2013
`
`corner-shared with VO4 tetrahedra to form highly puckered
`layers, between which the DABCO cations are sandwiched.
`The results show that Li insertion is hindered in the DABCO-
`
`filled host and improved performance is obtained when the
`DABCO ion is removed.
`
`electrical connection on an external surface of the energy-
`storage apparatus and having at least one cathode surface
`within the energy- storage apparatus, and an electrolyte bear-
`ing the multi-valent positive ion in contact with the at least
`one anode surface and the at least one cathode surface.
`
`[0020] Goward et al, “Poly(pyrrole) and poly(thiophene)/
`vanadium oxide interleaved nanocomposites: positive elec-
`trodes for lithium batteries”, Electrochimica Acta, 43, 10-11,
`pp. 1307, 1998 reports on synthesis and electrochemical
`investigation of conductive polymer-V205 nanocomposites
`that have a structure comprised of layers of polymer chains
`interleaved with inorganic oxide lamellae. It was found that
`for modified [PANI] -VZOS, polymer incorporation resulted in
`better reversibility, and increased Li capacity in the nanocom-
`posite compared to the original V205 xerogel. For PPY and
`PTH nanocomposites,
`the electrochemical response was
`highly dependent on the preparation method, nature of the
`polymer, and its location. In conclusion, Goward et al note
`that the results, though promising, were still short of theoreti-
`cal expectations.
`[0021] Chirayil et al, ‘Synthesis and characterization of a
`new vanadium oxide, TMA-V8020’ J. Mater. Chem., 1997,
`7(11), 2193-2195 discloses synthesis ofa layered vanadium
`oxide with a new monoclinic structure in which the tetram-
`
`ethylammonium ions reside between the vanadium oxide lay-
`ers. The powder X-ray diffraction pattern indicate that this
`new vanadium oxide has an interlayer spacing of 11.5 Ang-
`strom. Electrochemical investigation of the compound indi-
`cates that Li insertion is hindered due to the TMA ions
`
`between the layers.
`[0022] Lutta et al, “Solvothermal synthesis and character-
`ization of a layered pyridinium vanadate, C5H6N7V3O7” J.
`Mater. Chem., 2003, 13, 1424-1428 reports on synthesis and
`properties of a layered vanadate which has an aromatic inter-
`calate (pyridinium ion) between the vanadium oxide layers:
`pyHiV3O7. Chemical lithiation show some reactivity with
`Li but better performance was obtained when the pyridinium
`was removed from the vanadate. Indeed, Lutta et al concludes
`with saying that none of the aromatic V3O7 based structures
`(TMA-V307, MA-V3O7, pyH-V3O7) or their decomposition
`products lead to electrochemically interesting materials.
`[0023] The results described above show that slow diffu-
`sion of multi-valent ions in layered cathode materials is a
`limiting factor in rechargeable multi-valent electrochemical
`cells.
`
`Furthermore, the results above also show that it is
`[0024]
`commonly believed that organic -inorganic hybrid host mate-
`rials do not improve intercalation performance, specifically
`for lithium ions.
`
`[0025] There is a need for systems and methods for making
`improved positive electrode layered materials with high
`energy density as well as facile Mg ion diffusion.
`
`SUMMARY OF THE INVENTION
`
`[0026] According to one aspect, the invention features a
`multi-valent ion battery. The multi-valent ion battery com-
`prises an anode configured to accept and release a multi-
`valent positive ion, the anode having at least one electrical
`connection on an external surface ofthe energy-storage appa-
`ratus, and having at least one anode surface within the energy-
`storage apparatus; a cathode containing a layered compound
`comprising a first plurality of layers of inorganic material
`separated by a second plurality of units of an organic species
`situated on intervening planes, the cathode having at least one
`
`In one embodiment, the multi-valent positive ion is
`[0027]
`a Mg2+ ion.
`[0028]
`In another embodiment, the electrolyte is a magne-
`sium-bearing electrolyte comprising a magnesium salt and an
`onium ion.
`
`In yet another embodiment, the cathode comprising
`[0029]
`a layered compound comprises a compound having the
`chemical formula MgaMbe, wherein M is a metal cation or
`a mixture of metal cations, X is an anion or a mixture of
`anions, a is in the range of0 to about 2, b is in the range of
`about 1 to about 2, and ys9.
`[003 0]
`In still another embodiment, the anode configured to
`accept and release the Mg2+ ion comprises a material selected
`from the group consisting of Mg, Mg alloys AZ31, AZ61,
`AZ63, AZ80, AZ81, AZ91, AM50, AM60, Elektron 675,
`ZK51, ZK60, ZK61, ZC63, M1A, ZC71, Elektron 21, Elek-
`tron 675, Elektron, Magnox, and Mg alloys containing Mg
`alloys containing at least one of the elements Al, Ca, Bi, Sb,
`Sn, Ag, Cu, and Si.
`[0031]
`In a further embodiment, the anode configured to
`accept and release the multi-valent positive ion comprises
`insertion materials including Anatase TiOZ, rutile TiOZ,
`M0688, FeSz, TiSZ, and M082 and combinations thereof.
`[0032]
`In yet a further embodiment, the anode configured to
`accept and release the multi-valent positive ion comprises an
`electronically conductive additive.
`[0033]
`In an additional embodiment, the anode configured
`to accept the multi-valent positive ion comprises a polymer
`binder.
`
`In one more embodiment, the energy-storage appa-
`[0034]
`ratus is a secondary battery
`[0035]
`In still a further embodiment, the plurality ofunits of
`the organic species comprises an organic neutral molecule.
`[0036]
`In one embodiment, the plurality of units of the
`organic species comprises an organic anion.
`[0037]
`In another embodiment, the plurality of units of the
`organic species comprises an organic cation.
`[0038]
`In yet another embodiment, the plurality of units of
`the organic species comprises an onium cation.
`[0039]
`In still another embodiment, the cathode further
`comprises an electronically conductive additive.
`[0040]
`In a further embodiment, the cathode further com-
`prises a polymer binder.
`[0041]
`In yet a further embodiment, wherein a selected one
`ofthe cathode and the anode comprises a carbonaceous mate-
`rial.
`
`[0042] The foregoing and other objects, aspects, features,
`and advantages of the invention will become more apparent
`from the following description and from the claims.
`
`BRIEF DESCRIPTION OF THE DRAWINGS
`
`[0043] The objects and features of the invention can be
`better understood with reference to the drawings described
`below, and the claims. The drawings are not necessarily to
`scale, emphasis instead generally being placed upon illustrat-
`ing the principles of the invention. In the drawings, like
`numerals are used to indicate like parts throughout the various
`v1ews.
`
`UW Exhibit 1018, pg. 24
`
`UW Exhibit 1018, pg. 24
`
`

`

`US 2013/0260225 A1
`
`Oct. 3, 2013
`
`FIG. 1A is a schematic diagram of a layered material
`[0044]
`with Mg ions situated in the layer and the shortest metal-metal
`inter-layer center distance indicated.
`[0045]
`FIG. 1B is a schematic diagram ofa layered material
`having a first plurality of layers of inorganic material sepa-
`rated by a second plurality of units of an organic species
`situated on intervening planes.
`[0046]
`FIG. 2 is a graph of calculated diffusivity by first
`principles nudged elastic band calculations for a single Mg
`ion in layered V205 as a function of the metal-metal center
`layer distance. The equilibrium un—modified materials layer
`distance is specified as well as the estimated 1C rate perfor-
`mance for a representative 100 nm radius electrode particle.
`[0047]
`FIG. 3 is a graph of calculated diffusivity by first
`principles nudged elastic band calculations for a single Mg
`ion in layered MnO2 as a function of the metal-metal center
`layer distance. The equilibrium un—modified materials layer
`distance is specified as well as the estimated 1C rate perfor-
`mance for a representative 100 nm radius electrode particle.
`[0048]
`FIG. 4 is a graph of calculated diffusivity by first
`principles nudged elastic band calculations for a single Li ion
`in layered V205 as a function of the metal-metal center layer
`distance. The equilibrium un-modified materials slab layer
`distance is specified as well as the estimated 1C rate perfor-
`mance for a representative 100 nm radius particle.
`[0049]
`FIG. 5 is a schematic diagram of an example onium
`ion. The moieties R1, R2, R3 , and R4 each represent an alkyl,
`aryl, alkenyl, alkynyl group, or mixture thereof, and N+ can
`be substituted for other cation centers including, but not lim-
`ited, to P, As, Sb, Bi, F, and S.
`[0050]
`FIG. 6 is a diagram of a pyrrolidinium ion.
`[0051]
`FIG. 7 is a graph of the behavior of a three electrode
`pouch cell containing a increased-layer spacing modified
`V205 material incorporated into a working electrode and
`displaying nucleation of a new “scaffolded” phase due to P13
`onium cation co-intercalation during discharge one as com-
`pared to subsequent voltage profiles demonstrating facile Mg
`intercalation. The cell was cycled between —1.2 and 0.7 V
`versus the Ag/Ag+ quasi-reference at 80° C.
`[0052]
`FIG. 8 is a diagram showing the X-ray diffraction
`(XRD) spectra of increased-layer spacing V205 cathodes
`cycled in P13-TFSI/Mg-TFSI electrolyte indicating the struc-
`tural changes corresponding to the modification of the mate-
`rial. For reference, a representative XRD pattern of an elec-
`trode containing the un-modified V205 material is shown in
`comparison to the intercalated (discharged) and de-interca-
`lated (charged) cathode. The cathodes containing the modi-
`fied materials show a new peak at 18° corresponding to the
`spreading of the layers within this cathode host structure.
`[0053]
`FIG. 9 is a graph that shows the comparison of
`capacity of discharged cells containing modified layered
`cathode material to the transient magnesium quantified by
`elemental analysis.
`[0054]
`FIG. 10 is a graph that shows the comparison of the
`scaffolding P13 ion content and the transient magnesium
`content in charge and discharged cells.
`[0055]
`FIG. 11 is a graph that demonstrates the voltage
`profile of a cell with a V205 layered cathode material in an
`electrolyte containing only the scaffolding ion P13 in TFSI,
`and no magnesium salt. The voltage is measured versus the
`Ag/Ag+ quasi-reference.
`[0056]
`FIG. 12 is a graph that shows the voltage profile for
`the first discharge and subsequent charge ofa cell with aV205
`layered cathode material in an electrolyte containing P13-
`
`TFSI in the electrolyte, but no magnesium salt. The voltage is
`measure