as) United States
`a2) Patent Application Publication 10) Pub. No.: US 2013/0260225 Al
`
`(43) Pub. Date: Oct. 3, 2013
`Doe et al.
`
`US 20130260225A1
`
`(54) LAYERED MATERIALS WITH IMPROVED
`MAGNESIUM INTERCALATION FOR
`RECHARGEABLE MAGNESIUM ION CELLS
`
`(71) Applicants: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)
`
`(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 U.S. Application Data
`
`(60) Provisional application No. 61/617,512, filed on Mar.
`29, 2012.
`
`Publication Classification
`
`(51)
`
`Int. Cl.
`HOIM 438
`(52) U.S.CL
`CPC viceecccecsececssccesecerteeeseeees HOIM 4/381 (2013.01)
`USPC ou... 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 ofthe 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 betweenthe positive electrode and the negative elec-
`trode active material is described.
`
`anode terminal
`
`\ anodecollectar
`
`insulating package
`
` insulating plateee,ne,
`
`
`insulating
`plate
`
`separator
`
`cathode
`
`anode
`
`UW Exhibit 1018, pg. 1
`
`cathode cali
`
`UW Exhibit 1018, pg. 1
`
`

`

`Patent Application Publication
`
`Oct. 3, 2013 Sheet 1 of 20
`
`US 2013/0260225 Al
`
`
` 1G rate
`
`
`CalguiaiedselfdiffusionD
`
`FIG. 1A
`
`FIG. 2
`
`UW Exhibit 1018, pg. 2
`
`UW Exhibit 1018, pg. 2
`
`

`

`Patent Application Publication
`
`Oct. 3, 2013 Sheet 2 of 20
`
`US 2013/0260225 Al
`
`<=110
`
`Inorganic
`
`105’ &110!
`
`Layers
`
`FIG.1B io
`
`oO
`—
`
`Organic Units
`
`UW Exhibit 1018, pg. 3
`
`UW Exhibit 1018, pg. 3
`
`

`

`Patent Application Publication
`
`Oct. 3, 2013 Sheet 3 of 20
`
`US 2013/0260225 Al
`
`Lailice (Sie) Spacing “)
`
`on
`ow
`eaywens
`
`qo
`
`= 22o
`
`S =&E
`
`r|
`
`1G rate
`
`LE-14
`
`1f-16
`
`g=a
`
`eé
`
`FIG. 3
`
`“8.BOOT
`
`Lattice(Sia)Spacing“
`
`OOOO1
`
`UW Exhibit 1018, pg. 4
`
`UW Exhibit 1018, pg. 4
`
`

`

`Patent Application Publication
`
`Oct. 3, 2013 Sheet 4 of 20
`
`US 2013/0260225 Al
`
`R!
`vaan,
`Ro \ OR
`
`R
`
`FIG. 5
`
`
`
`Peg
`
`oo
`PARES ES
`
`
`
`ARBREREE
`
`FIG. 21
`
`UW Exhibit 1018, pg. 5
`
`UW Exhibit 1018, pg. 5
`
`

`

`Patent Application Publication
`
`Oct. 3, 2013 Sheet 5 of 20
`
`US 2013/0260225 Al
`
`
`lecccesscrececeeessccecscrressccecscerececcecscttesscrecssecesserecscecesscnecececesieteeeeeeboon
`
`
`
`
`
`VYUOleDayAjos}Ia]3|
`
`wee
`
`ii|4Sa
`——
`
`eo
`vw
`
`,
`
`Z°9ls
`
`BruywAoedea
`
`oF
`
`A aBeyoan
`
`UW Exhibit 1018, pg. 6
`
`UW Exhibit 1018, pg. 6
`
`
`
`
`
`

`

`Patent Application Publication
`
`Oct. 3, 2013 Sheet 6 of 20
`
`US 2013/0260225 Al
`
` ayeys
`ulspoyyey
`
`
`SBELSaseys
`
`-Pee
`
`ULSpoyle)
`
`adueyasip
`
`{Spusisecyhk pep
`
`UW Exhibit 1018, pg. 7
`
`UW Exhibit 1018, pg. 7
`
`

`

`FIG.9
`
`UW Exhibit 1018, pg. 8
`
`Qs
`=
`:
`é
`g
`8
`e
`8
`
`a o
`
`O w
`
`v
`Cs
`
`
`
`
`
`=
`gs
`ge &
`ar
`vie
`= bo
`oO te
`E
`E
`
`e &po
`
`£
`
`
`
`
`
`
`
`(3/yyui)} Ayisedes ayioads
`
`UW Exhibit 1018, pg. 8
`
`

`

`Patent Application Publication
`
`Oct. 3, 2013 Sheet 8 of 20
`
`US 2013/0260225 Al
`
`PeteerrrnnnennnninnnnnnnnnnEEEEEEEE
`
`arged CellE
`c”\\FE
`
`wed
`
`DischargedDischargedDB CellcMXGWFE
`
`
`
`
`4Capacityderivedfromtransientmagnesium
`
`cell8DischargedDischarged Ce}
`
`detectedinnon-cycledceils
`
`
`ChargedCallChargedCellChargedCell B
`
`
`
`@P13contentexpressedinmAh/g-carrectedforN
`
`cellDB
`
`A
`
`FIG.10
`
`Wy,
`
`Y7)]]
`
`
`
`
`
`
`
`OM
`wt
`Qo
`
`wd
`8
`
`oO
`Q
`
`wo
`a
`
`st
`Q
`
`am
`Q
`
`Q
`
`UW Exhibit 1018, pg. 9
`
`UW Exhibit 1018, pg. 9
`
`

`

`Patent Application Publication
`
`Oct. 3, 2013 Sheet 9 of 20
`
`US 2013/0260225 Al
`
`60
`
`7s
`<<
`
` §.008999
`
`> -
`oe
`°
`
`we
`O
`
`20
`
`A obe}0A
`
`UW Exhibit 1018, pg. 10
`
`UW Exhibit 1018, pg. 10
`
`

`

`Patent Application Publication
`
`Oct. 3, 2013 Sheet 10 of 20
`
`US 2013/0260225 Al
`
`FIG.12
`
`A abelon
`
`UW Exhibit 1018, pg. 11
`
`UW Exhibit 1018, pg. 11
`
`

`

`Patent Application Publication
`
`Oct. 3, 2013 Sheet 11 of 20
`
`US 2013/0260225 Al
`
`FIG.13
`
`UW Exhibit 1018, pg. 12
`
`(uidd) apoyzes ul quazU02 UAasOsIN
`
`UW Exhibit 1018, pg. 12
`
`

`

`Patent Application Publication
`
`Oct. 3, 2013 Sheet 12 of 20
`
`US 2013/0260225 Al
`
`= =
`
`is
`Q
`Q
`ss
`=
`Loss
`LO
`OQ 8
`Oo
`cs A
`=
`= 9
`
`
` FIG.14
`
`
`an
`
`ta
`
`ey
`
`80
`
`= = BD
`= a
`a
`
`UW Exhibit 1018, pg. 13
`
`UW Exhibit 1018, pg. 13
`
`

`

`Patent Application Publication
`
`Oct. 3, 2013 Sheet 13 of 20
`
`US 2013/0260225 Al
`
`ath
`
`as
`
`osiG
`
`a
`
`;2
`
`nevveeeennne|pecn
`
`BryAyoedea
`
`GL“Old
`
`
`
`
`
`
`A abeyon
`
`“o
`
`e.
`
`UW Exhibit 1018, pg. 14
`
`UW Exhibit 1018, pg. 14
`
`
`
`

`

`Patent Application Publication
`
`Oct. 3, 2013 Sheet 14 of 20
`
`US 2013/0260225 Al
`
`enhsape
`
`-
`
`OOcecgnben
`
`are
`
`
`
`
`
` eee%,tin3Weeltnttieapar,
`
`
`
`a
`
`My
`
`
`
`sthststinasennasencasersaresMiensueasensesenssscarunsgusentusenteressacesensessasssestusessusestatentesesssceseatessasssestessegsentatestucesiucesentessasssestusestasentesestcessatesessssesssessesesigsin SN oeXs ewcnncensacencesensncescncesensaseastbptt
`
`
`
`
`
`7)UOTTeDayAjo4I913
`
`3=e
`
`BjuywAyioedes
`
`91“OlA
`
`oe
`
`UW Exhibit 1018, pg. 15
`
`UW Exhibit 1018, pg. 15
`
`
`
`
`
`
`
`
`

`

`Patent Application Publication
`
`Oct. 3, 2013 Sheet 15 of 20
`
`US 2013/0260225 Al
`
`GLEOctGOLObi
`
`
`
`BruyuwAyoredea
`
`ZLOIA
`
`Weaenwoetiins
`
`
`
`Wecervecesentaritiaddivetasuseestpés12s
`
`ecttpnente,
`
`ue
`endgannnnnnnnninnngan
`ay
`
`-W
`
`thetpping,Metisse
`
`SPOON SAA
`
`aeceegsnenee
`SARAANURKNNNNERENEE
`
`Bo
`
`GOD
`
`UW Exhibit 1018, pg. 16
`
`
`
`PSpencerenersccccenmecesecerseccsuntncrsorericesdeomcrsenerscecensserscerscecensasercrsereeicedensescrsencesccomuusorsecerstcomuniercesereecudbeasenceseneescesuapesceseseestatescaiestieeteslbdtnitilitetbnbtnitdeTibteTSenbbnbebeTétbbEtid,boonZée)
`
`
`
`
`
`UW Exhibit 1018, pg. 16
`
`
`
`
`

`

`Patent Application Publication
`
`Oct. 3, 2013 Sheet 16 of 20
`
`US 2013/0260225 Al
`
`
`
`
`
`CSEELIEELISULIEEEESELESILILESIDEEESIIILLSISIEEESSSEESLLIELESUSEESILLLLRSEEEEE
`
`
`
`ADDLsacBEEPalPREPtalebeeELEEPheePEEEAALSceeddLLebbhttebensitbe
`
`‘
`
`
`
`ET-OTSajdAD
`
`peel
`
`:t
`
`9)9A9
`
`4
`
`See
`
`Booman
`
`SRE
`Seige
`
`coomnenaeroths
`
`
`
`4p£oASs
`See*RDAANAARNFES
`
`SSaa
`SSAIOEUNSINNARAANS
`SoeESSccncenees
`SEEeentneSeeeRnOOSSSSS
`sse
`
`Pan
`
`Yay
`
`3
`
`g
`
`UW Exhibit 1018, pg. 17
`
`UW Exhibit 1018, pg. 17
`
`
`
`
`
`
`
`
`
`
`

`

`Patent Application Publication
`
`Oct. 3, 2013 Sheet 17 of 20
`
`US 2013/0260225 Al
`
`
`
`GLa
`
`oO
`oF
`A aBbeyon
`
`0
`
`Gei
`
`UW Exhibit 1018, pg. 18
`
`UW Exhibit 1018, pg. 18
`
`

`

`Patent Application Publication
`
`Oct. 3, 2013 Sheet 18 of 20
`
`US 2013/0260225 Al
`
` [e}oWBY
`uoopour
`
`J0499[[09JWoLMS
`
`
`
`
`
`
`
`Joyay[oo
`
`
`
`JUALINUOspoyyespopls-ajqnog
`
`-prlees[aDporeasospejoyonog
`
`JoyeredasgqadAy
`
`0c‘DIA
`
`UW Exhibit 1018, pg. 19
`
`UW Exhibit 1018, pg. 19
`
`

`

`Patent Application Publication
`
`Oct. 3, 2013 Sheet 19 of 20
`
`US 2013/0260225 Al
`
`—
`£ a
`q
`S
`8
`™
`faa] £
`oO Oo
`QD
`7
`c
`th
`Oo
`mo
`
`bo
`=
`aw
`2 gy
`3.4
`“wn aL
`£a
`
`
`
`FIG.22
`
`insulatingpackage
`
`
`anodecollector
`
`
`athodecan
`
`insulatingplate
`
` anodeterminal
`
`
`
`—c
`
`
`
`UW Exhibit 1018, pg. 20
`
`UW Exhibit 1018, pg. 20
`
`

`

`Patent Application Publication
`
`Oct. 3, 2013 Sheet 20 of 20
`
`US 2013/0260225 Al
`
`
`
`
`
`uedapoyjyed——
`
`J0}93]]09
`
`UOIe|NSUl
`
`
`
`apoue
`
`apoyyes
`
`Joyesedas
`
`ecOld
`
`UW Exhibit 1018, pg. 21
`
`UW Exhibit 1018, pg. 21
`
`
`

`

`US 2013/0260225 Al
`
`Oct. 3, 2013
`
`LAYERED MATERIALS WITH IMPROVED
`MAGNESIUM INTERCALATION FOR
`RECHARGEABLE MAGNESIUM ION CELLS
`
`CROSS-REFERENCE TO RELATED
`APPLICATIONS
`
`[0001] This application claimspriority to and the benefit of
`co-pending U.S. provisional patent application Ser. No.
`61/617,512, filed Mar. 29, 2012, which application is incor-
`porated herein by referencein its entirety.
`
`STATEMENT REGARDING FEDERALLY
`FUNDED RESEARCH OR DEVELOPMENT
`
`[0002] This invention was made with governmentsupport
`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 Mgin theirelectrolytes.
`
`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 dissolvedlithium-basedsalt
`in an aprotic organic or inorganic solvent or polymer. Today
`there is great demandfor 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 (Mg?*), because these ions can enable
`many timesthe 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 knownfor 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 equipmentand 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 Co;0,,
`Mn,0,;, Mn,0,, MoO;, PbO,, Pb,0,, RuO,, V,0;, WO;,
`TiS,, VS,, ZrS,, MoB,, TiB,, and ZrB, as positive electrode
`materials for a magnesium battery. However, only the first
`cycle discharge is shown andall materials exhibit significant
`polarization for medium current densities.
`[0007] Novak etal., “Electrochemical Insertion of Magne-
`sium in Metal Oxides and Sulfides from Aprotic Electro-
`lytes,” JECS 140 (1) 1993 discloses TiS,, ZrS,, RuO,, Co,0,
`
`and VO, as positive electrode materials of a magnesium
`battery. However, only layered V,0, shows promising capac-
`ity and reversibility. Furthermore, Novak et al. show that
`Mg?*insertion into this oxide depends on the ratio between
`the amounts of H,O and Mg”* as well as on the absolute
`amount of H,O in the electrolyte. According to Novak, water
`molecules preferentially solvate Mg** 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 Mg”* insertion into layered
`vanadium bronzes, MeV,0,(H2O),, where (Me=Li, Na,K,
`Cay5, and Mg,;). Variations in the content of boundlattice
`water in the bronzes were foundto be responsible for a dif-
`ference in the electrochemical properties of the samestarting
`material dried at different temperatures. The presenceofthis
`water was deemed essential but the lattice water is removed
`
`during cycling after which the capacity deteriorates. Further-
`more, attempts to cycle the compoundsin dry electrolytes
`failed. The beneficial effect ofwater was speculated to be due
`to its solvation of the Mg** ion.
`[0009]
`Leet al., “Intercalation of Polyvalent Cations into
`V0, Aerogels” Chem. Mater. 1998, 10, 682-684 discloses
`multi-valent ion insertion into VO, 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 comparedto the 8.8 A characteristic of
`the V,0,;*0.5H,O xerogel.
`[0010] Amatucci etal., “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?*, Y**) into nano-metric layered VO, but
`with significant polarization (e.g., energy loss) and at a low
`rate of 0.04C whichsignifies the low diffusivity of the Mg
`ions.
`
`[0011] The current, proven state of the art high energy,
`rechargeable Mgcell is described by Aurbachet al., U.S. Pat.
`No. 6,316,141, issued Nov. 13, 2001, as a cell comprised of a
`magnesium metal anode, a “Chevrel” phase active material
`cathode, and an electrolyte solution derived from an organo-
`metallic complex containing Mg. Chevrel compoundsare a
`series of ternary molybdenum chalcogenide compoundsfirst
`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 M,Mo,Xg, 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 ortellurtum).
`Furthermore, in E. Levietal, “New Insight on the Unusually
`High Ionic Mobility in Chevrel Phases,’ Chem Mat 21 (7),
`1390-1399, 2009, the Chevrel phasesare described as unique
`materials which allow for a fast and reversible insertion of
`various cations at room temperature.
`[0012] Michotet al., U.S. Pat. No. 6,395,367, issued May
`28, 2002, is said to disclose ionic compounds in which the
`anionic load has been delocalized. A compounddisclosed by
`the invention includes an anionic portion combined with at
`least one cationic portion M”* in sufficient numbers to ensure
`overall electronic neutrality; the compoundis further com-
`prised of Mas a hydroxonium,a nitrosonitum NO*, an ammo-
`nium NH,", 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 loadis 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] U.S. Pat. No. 6,426,164 B1 to Yamauraetal., issued
`Jul. 30, 2002, is said to disclose a non-aqueouselectrolyte
`battery capable of quickly diffusing magnesium ions and
`improving cycle operation resistance, incorporating a posi-
`tive electrode containing Li,MO, (where M is an element
`containing at least Ni or Co) as a positive-electrode active
`materialthereof; 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-aqueouselectrolyte disposed betweenthe positive
`electrode and the negative electrode and containing non-
`aqueoussolvent and an electrolyte constituted by magnesium
`salt, wherein the value of x of Li,MO,satisfies a range
`0.1sxs0.5. It is also said that for Li concentrations xs0.1, the
`host material becomes unstable and for higher Li concentra-
`tions x20.5, there are not enough available Mglattice sites
`available. Specifically, there is no mention of interlayer dis-
`tance.
`
`[0014] Michotet al., U.S. Pat. No. 6,841,304, issued Jan.
`11, 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, whollyor partially, at least an
`ion imidide such as (FX'O)N-(OX?F) wherein X' and X? are
`identical or different and comprise SO or PF, andtheir use as
`solvent in electrochemical devices. Said composition com-
`prises a salt wherein the anionic charge is delocalised, andcan
`be used, inter alia, as electrolyte.
`Publication No.
`[0015] U.S.
`Patent Application
`20090068568 Al (Yamamotoet al. inventors), published on
`Mar. 12, 2009, is said to disclose a magnesium ion containing
`non-aqueouselectrolyte in which magnesium ions andalu-
`minum ions are dissolved in an organic etheric solvent, and
`whichis formed by: adding metal magnesium,a halogenated
`hydrocarbon RX, an aluminum halide AIY,, anda quaternary
`ammonium salt R'R?R*R*N*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 AIY, representing
`the aluminum halide, Y is chlorine, bromine,or iodine,in the
`general formula R'R?R*R*N*Z-representing the quaternary
`ammonium salt, R’, R*, R*, and R* represent each an alkyl
`groupor 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 aimedat increasing thestability ofthe
`electrolyte in atmospheric air and facilitate the production
`process for said electrolytes.
`Publication No.
`[0016] U.S.
`Patent Application
`20100136438 Al (Nakayamaetal. 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 composedofa positive electrode active material,
`for example, a metal oxide, graphite fluoride ((CF),,) or the
`like, etc. The electrolytic solution is, for example, a magne-
`
`sium ion containing nonaqueouselectrolytic solution pre-
`pared by dissolving magnesium(I]) chloride (MgCl,) and
`dimethylaluminum chloride ((CH;),AICI) 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.
`
`2 Mg?*
`
`+
`
`CH;
`Cl
`7
`2 y +
`cH;
`‘cl
`
`6 THF ——»
`
`THE
`N
`
`THE
`
`Mg
`
`cl
`
`cl
`
`Va
`Mg
`XN
`
`THF]
`
`THE
`
`+
`
`2
`
`CH;
`
`\ 7
`Al
`ZN
`CH;
`
`cl
`
`“THE
`
`Accordingto this, there are provided a magnesium ion-con-
`taining nonaqueouselectrolytic 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] U.S.
`Patent Application
`20110111286 Al (Yamamotoet al. inventors), published on
`May 12, 2011, is said to disclose a nonaqueouselectrolytic
`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 sameare pro-
`vided. A Mgbattery 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 betweenthe 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 complexsalt 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 MoO,”, J. Am. Chem. Soc. 1992, 114,
`6239-6240 discloses insertion of high molecular weight PPV
`into a layered oxide by intercalating the PPV precursorpoly-
`mer betweenthe layers of MoO,, 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] Nazaret al, “Hydrothermal Synthesis and Crystal
`Structure ofa Novel Layered Vanadate with 1,4-Diazabicyclo
`[2.2.2]octane as the Structure-Directing Agent: C,H, ,N.—
`V;O,,-H,O” Chem. Mater. 1996, 8, 327 discloses Li inser-
`tion into organic cation (Cs;H,,N, or ‘DABCO’)-templated
`vanadium oxide resulting from hydrothermal synthesis. The
`host crystal structure possessesa structure composed ofa new
`arrangement of edge-shared VO, square pyramids that are
`
`UW Exhibit 1018, pg. 23
`
`UW Exhibit 1018, pg. 23
`
`

`

`US 2013/0260225 Al
`
`Oct. 3, 2013
`
`corner-shared with VO, tetrahedra to form highly puckered
`layers, between which the DABCOcations are sandwiched.
`Theresults show that Li insertion is hindered in the DABCO-
`filled host and improved performance is obtained when the
`DABCOionis removed.
`[0020] Gowardetal, “Poly(pyrrole) and poly(thiophene)/
`vanadium oxide interleaved nanocomposites: positive elec-
`trodesfor lithium batteries”, Electrochimica Acta, 43, 10-11,
`pp. 1307, 1998 reports on synthesis and electrochemical
`investigation of conductive polymer-V,0, nanocomposites
`that have a structure comprised of layers of polymer chains
`interleaved with inorganic oxide lamellae. It was found that
`for modified [PANI]-V,O0,, polymer incorporation resulted in
`better reversibility, and increased Li capacity in the nanocom-
`posite comparedto the original V,O, xerogel. For PPY and
`PTH nanocomposites,
`the electrochemical response was
`highly dependent on the preparation method, nature of the
`polymer, andits location. In conclusion, Gowardet al note
`that the results, though promising, werestill short of theoreti-
`cal expectations.
`[0021] Chirayil et al, “Synthesis and characterization of a
`new vanadium oxide, TMA-V,0,0’ J. Mater. Chem., 1997,
`7(11), 2193-2195 discloses synthesis of a layered vanadium
`oxide with a new monoclinic structure in which the tetram-
`ethylammonium ionsreside 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]
`Luttaet al, “Solvothermal synthesis and character-
`ization of a layered pyridinium vanadate, C;H;N—V,0,”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:
`pyH—V,0.,. Chemicallithiation show somereactivity with
`Li but better performance was obtained whenthe pyridinium
`was removed from the vanadate. Indeed, Lutta et al concludes
`with saying that none of the aromatic VO, based structures
`(TMA-V,0,, MA-V,0., pyH-V;0,) or their decomposition
`products lead to electrochemically interesting materials.
`[0023]
`Theresults 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 isa need for systems and methods for making
`improved positive electrode layered materials with high
`energy density as well as facile Mg ion diffusion.
`
`SUMMARYOF 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 secondplurality of units of an organic species
`situated on intervening planes, the cathode havingat least one
`
`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 andtheat least one cathode surface.
`
`In one embodiment, the multi-valent positive ion is
`[0027]
`a Mg**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 Mg,,M,X,,, wherein M is a metalcation or
`a mixture of metal cations, X is an anion or a mixture of
`anions, a is in the range of 0 to about2, b is in the range of
`about 1 to about 2, and y=9.
`[0030]
`Instill another embodiment, the anode configured to
`accept andrelease the Mg** ion comprisesa 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 Mgalloys containing Mg
`alloys containing at least one of the elements Al, Ca, Bi, Sb,
`Sn, Ag, Cu, and Si.
`[0031]
`Ina further embodiment, the anode configured to
`accept and release the multi-valent positive ion comprises
`insertion materials including Anatase T10,, rutile Ti0,,
`Mo,Sg; FeS,, TiS,, and MoS, and combinations thereof.
`[0032]
`Inyeta further embodiment, the anode configured to
`accept andrelease 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]
`Instilla 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]
`Ina further embodiment, the cathode further com-
`prises a polymerbinder.
`[0041]
`Inyeta 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 uponillustrat-
`ing the principles of the invention. In the drawings, like
`numerals are used to indicate like parts throughoutthe various
`views.
`
`UW Exhibit 1018, pg. 24
`
`UW Exhibit 1018, pg. 24
`
`

`

`US 2013/0260225 Al
`
`Oct. 3, 2013
`
`[0044] FIG.1A is aschematic diagram of a layered material
`with Mgionssituated in the layer and the shortest metal-metal
`inter-layer center distance indicated.
`[0045] FIG.1Bisaschematic 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 V,O, 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-
`mancefor a representative 100 nm radius electrodeparticle.
`[0047]
`FIG. 3 is a graph of calculated diffusivity by first
`principles nudged elastic band calculations for a single Mg
`ion in layered MnO,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-
`mancefor a representative 100 nm radius electrodeparticle.
`[0048]
`FIG. 4 is a graph of calculated diffusivity by first
`principles nudgedelastic band calculations for a single Li ion
`in layered V,O, 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-
`mancefor a representative 100 nm radiusparticle.
`[0049]
`FIG. 5is a schematic diagram of an example onium
`ion. The moieties R’, R?, R*, and R* each representan 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 isa graphof the behaviorofa three electrode
`pouch cell containing a increased-layer spacing modified
`V,O; 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 subsequentvoltage 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 V,O, cathodes
`cycled in P13-TFSI/Mg-TFSlelectrolyte indicating the struc-
`tural changes corresponding to the modification of the mate-
`rial. For reference, a representative XRDpattern of an elec-
`trode containing the un-modified V,O, 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 ofthe
`scaffolding P13 ion content and the transient magnesium
`content in charge and dischargedcells.
`[0055]
`FIG. 11 is a graph that demonstrates the voltage
`profile of a cell with a V,O, 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 showsthe voltageprofile for
`the first discharge and subsequent charge ofa cell witha V,O,
`layered cathode material in an electrolyte containing P13-
`
`TFSIin the electrolyte, but no magnesium salt. The voltage is
`measured vs. an Ag/Ag* quasi-reference electrode. Thecell
`was discharged to -1 V (vs. Ag quasi) and charged to 0.7 V
`(vs. Ag quasi) galvanostatically at 200 mA/g. A discharge
`capacity of approximately 60 mAh/g, and a subsequent
`charge of 20 mAh/g are observed, which are attributed to
`semi-reversible intercalation of the onium cation (P13).
`[0057]
`FIG. 13 is a graph that shows a comparison of the
`nitrogen content in cathodes of cycled cells (ending in both
`discharged and chargedstates) and non-cycledcells (1.e., only
`soaked in electrolyte containing P13-TFSI). Nitrogen content
`is quantified using LECOtime-of-flight mass spectrometry.
`[