‘US009890048B2 2) United States Patent Goodenough et al US 9,890,048 B2 Feb. 13, 2018 (10) Patent No.: (4s) Date of Patent: (54) WATER SOLVATED GLASS/AMORPHOUS ——(52)_US. C1 SOLID IONIC CONDUCTORS ce Co1B 3332 (201301), CO1B 11/0 (201301); COMB 25/306 (2015 (71). Applicans:Board of Regents, The University of ee “Teaas System, Atuin, TX (US); (Continved) Universidade Do Porto, Pora (PL) (58) Field of Classification Search ABORATORIO NACIONAL cre THOIM 4/364; HOIM 1010862 8 (Continved) Mamede lnfesta (PT) (72) Inventors: John B. Goodenough, Austin, TX om) References Cited (OS), Maria Helena Sousa Soares De US. PATENT DOCUMENTS Oliveira Braga, Porto (PT): owe Forge Do Amaral Ferreira, S. Mamede 430710 A 121981 Joa eta lafesta (PT); Prestam Singh, Austin, 20070003833 AL 12007 Ltt al Tx (US) (Continved) (3) Assignees: BOARD OF REGENTS, THE FOREIGN PATENT DOCUMENTS UNIVERSITY OF TEXAS SYSTEM. Austin, TX (US); UNIVERSIDADE CA raows 9201s DO PORTO, Pon (PT) ee Snes 2017 ZLABORATORIO NACIONAL (Continved) EGA E GEOLOGIA, 8. Mamede Infesta (PT) OTHER PUBLICATIONS (©) Notice: Subject to any disclaimer, the term of this ptr Sere Rept and Witen Opinion ecived for PCT patent is extended or adjusted under 35 page Appiation No, NTIUS20 16036661, dated Now 80 2016 USC. 154) by 0 days, aaa (21) Appl. No. 18/178,228 (Continved) (22) Filed: Jun, 9, 2016 Primary Bvaminer — Khanh ‘Tuan Nguyen (4) Auornes, Agent, or Firm — Baker Botts LLP. 6) Prior Publication Data US 201610368777 AI Dee. 22, 2016 7) ABSTRACT ae The disclosure provides a wateraolvatedglessfamorphous eee solid that i an tonic eonductor-an electron insulator, and (60) Provisional application No. 62/181,606, fled on Jn. dielectric as well as electrochemical devices and processes 18, 2015, provisional application No. 62/189,865, that use this material, such as baeries, including techarge- fied on Jul 8, 2015. le hateie, fel cell, capacitors, electolysis cell, and clectronie devives. The electrochemical devices and prod- 6) Imch ‘vets use a combination ofonie and cleetonic conduction a8 Hig 92 (200601) wel as intemal lectie dipoles corn 3982 006.01), (Continved) 16 Claims, 5 Drawing Sheets icin acoA, TROLYTE MPF EPC e050 a8) +PYOFMEP TOW) =" | | 00US 9,890,048 B2 Page 2 (1) nec. ‘HOIG 186 (201301) HOLM 8/124 (201601) ‘HOIM 100862 (201001) coe 100 (2006.01) coun 25/30 (2006.01) corp 25732 (2008.01) corB 33724 (2006.01), cop saz (2005.01) COE 1146 (2006.01) ‘HOIG 1/62 (201301), OIG 1184 (201301) ‘HUIS 8/1016 (201601) ‘HOIM 1036 (201001) csc 190 (2006.01) cose 4718 (200501), (2) Us. cee (CO1B 28822 (2013.01); COIB 33/24 2013.01); Corb $02 2013.01): COUP T1462 (2013.01); C03 1006 2013.01); CRC 4/18 (013.01): HOIG 1156 (2013.01), HIG 1/82 (201301); HOG HAS (2013.01): ‘HOIM 8/1016 (2013.01), HOLM 8/124 (2013.01); HOLM 10/0562 (2013.01); HOLM 10236 (2013.01); HOIM 2300008 (3013.01): HOLM 23000071 (2013.01); YO2P 70°36 2015.11) (58) Field of Classitication Search spc’ '252/62.2; 429/211, 323 Se application file for complete search history. 66) References Cited USS. 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High pressure high temperature syabess of lthiunsich Li 3.0 (Cl By) and Li 3x Ca x2 OCI ante Perot alides” Inorganic Chemistry Communications 48 (Gots): Ho-t4s * cited by examinerU.S. Patent Feb. 13, 2018 Sheet 1 of 5 US 9,890,048 B2 = LICI+ 1 99L(0H) + 0.0068a(0H), + H0 GEL ELECTROLYTE 1 MLIPF EC-PC (50:50 vol.%6) + PYDF-HFP (10 WT%) | tog(o, {Som es ‘ & 30) a2 FIG. 2 25°C oo ne | -2— HEATING, FIRST MEASUREMENT 45°) | 0 AT25°G VS, TIME, FIRST MEASUREMENT 8.0 ha ararmeneenpel 22 24 26 28 30 32 34 40007, aU.S. Patent Feb. 13, 2018 Sheet 2 of 5 US 9,890,048 B2 4 LIC! + 2.991i(0H) + 0.005Ba(0H) 9 + HO FIG. 3 me t= 1000 Fe exto® | sx108 | axt0® 6 ee q oe end tmee— t “ee axi08 ; + 1 24 28 28 30 32 34 36 00077) FIG. 6 METAL GLASS ELECTROLYTEU.S. Patent Feb. 13, 2018 Sheet 3 of 5 US 9,890,048 B2 BaKPO , (PROTON CONDUCTIVITY) FIG, 4A saxPo, atgr°o,20 FIG. 4B 2% 3 3 4 4 50 55 60 (0)US 9,890,048 B2 Sheet 4 of 5 Feb. 13, 2018 U.S. Patent 3 & z Z AL Na*-glass / Al —— FIFTH CYCLE jag 3& a 123 1 | I 4 8 2 = | i 3 3 z Fa 4g & z e q i i 3 g = g ~ SIXTH CYCLE 8 3 = § g ANI HRO}A 30 25 20 15 th)U.S. Patent Feb. 13, 2018 Sheet 5 of 5 US 9,890,048 B2 FIG. 7 LEGLASS CELL (© CHARGE (0.05 ¢) X DISCHARGE (0.05 C) TTIME(min) Na-GLASS CELL 0 5 10 8 2 6 TIME (hrs)US 9,890,048 B2 1 WATER SOLVATED GLASS/AMORPHOUS SOLID IONIC CONDUCTORS. PRIORITY CLAIM ‘The present application claims priority under 38 US. $119 10 US. Provisional Patent Application Ser. No.62/18], 606 filed Jun. 18, 2015 and US. Provisional Patent Appli- ‘ation Ser. No. 62/189,865 filed Jul. 8, 2015, the contents of which are incorporated by reference herein in their entirely. ‘TECHNICAL FIELD ‘The disclosure provides a dried, water-salvated glass! amorphous solid that is an alkali-ion conductor and an ‘electronic insulator with a large dielectric constant. The ‘disclosure also provides electrochemical devices and pro> ‘cesses that use this material, such as batteries, including rechargeable batteries, fuel cells, capacitors, eleetolstic eneration of chemical products. inching hydrogen gas (H,), from water, and electronic devices. The electrochemi- ‘eal devices and predicts use « combination of ionie and ‘electronic eondaction. The disclosure alsa provides a water- solvated glass‘amorphous solid that is a proton (HT) cone ‘ductor and an electronic insulator. BACKGROUND Tonic conductors that are also electronic insulators are called electrolytes: they may bea liquid ora solid, Electro Iytes are used in a varity of electrochemical devices ‘nchiding not only those that store electric power as chemic ‘eal energy in a rechargeable battery or those that release ‘chemical energy a electric power in fuel cel, but also those that store electric power as state electric energy in an clectric-double-ayer capacitor. Plectrie power that is released from an elecie-energy stone, whether from ‘chemical or an electrostatic stor, is clean energy. Chemical ‘energy stored in a fel that is released as the heat of ‘combustion is less ellicient process, and combustion is also accompanied by te release of gases that pollute the air and ‘contribute to global warming, ‘An electrochemical cell coatsins an electrolyte beoveen ‘vo electrodes, an anode and a cathode. A Higuid electrolyte requires use of a separator of the two electrodes that is permecuble by the liquid electrolyte; the separator prevents ‘electronic contact between the 0 elected within thecal, AA solid electolyte may serve as both an electrolyte and a ‘separator. Ina rechargeable battery, the anode isa reductant; jn a fuel cell, the anode catalyzes the separation of 3 reactant fel ino its electronic and ionic components. 1a both types of cells, the ionic component of the chemical reaction between two electrodes is transported to the cathode inside the cell inthe electrolyte, but the electrolyte forees the ‘electronic component to go to the cathode via an extemal circuit as an electric creat Tata voltage V to provide ‘electric power P=IV for performance of work. Since the jonie conductivity in the electrolyte is much smaller than the ‘electronic conductivity in good metal, battery cells and Jue ells are fabricated with large-area electrodes and a thin ‘electrolyte: the active electrode materials ae fabricated t0| ‘make electronie cantact with a metalic cureentcaleetoe for fast transport of electrons hetween the active electrode particles and the externa circuits wells ionic contact with the cloctmlyte that transports ions between the electrodes inside the cell. 0 o 2 Solid electrolytes with lange dielectric eoustant may also be used in electronic devices as separators of liquid or gaseous reactants as Well as of solid resetans Liquide are generally much better ionic conductors room temperature than most knowa solids, which is why Tiquids are normally used as the electoiyte of @ room- temperature device. However, in some applications a solid clectrolyte may be strongly preferred. For example, the [Liston rechargeable battery uses a flammable onganic lig asthe eleetolyte anda solid electrolyte would be safer and ‘might be capable of improving the density of energy stored ‘without sacrificing the rate of charge and discharge. More- ‘over if the solid eleetolyte also contsins electric dipoles that give ita high dielectric constant, it can store moeh more electric enerzy than a liguid in an electric cpacitanee of an electric double layer of a metabelectolyte interface In an electric-double-layer capacitor, metalic electrodes are fabricated so as to provide a maximum electrode! lectroyte interface, lons in the electrolyte pin electrons or electron hoes of opposite charge inthe electrode across an electric double layer on charge. ‘The separation of the electrons and holes aeross the dauble layer is small (atomic dimension so the capacitance is lage. On discharge pinned tlecions at the anode pass through the extemal cre t0 -eeombine withthe pinned electro holes inthe cathode, and the mobile ions inside the electrolyte return to an equlib- sium positon. Ifthe electrolyte has a large dieleetsic eon- stant ©, the capacitance of the electric douible layer is enhanced, With a solid elestolyte having 2 large delete ‘constant, the enhancement of the expacitance is large, and it ‘becomes possible to construct a cll where the energy stored has Paradaic component as in a battery and a capacitive ‘component as in an electri-double-layer capacitor, SUMMARY, Te present disclosure includes a dried, watersolvated alass‘amorphous solid electrolyte that conducts ether Li" or 1a’, or both, nearly as rapidly aa flammable organic liquid at room temperature and also sa large dielectric constant. ‘Moreover, alkali metals ean be plated and stripped from/to it without dendrite formation, thus avoiding safety issues fand a limited chargeldischarge eyele life, A dried, water solvated glass‘amorphous solid that conducts Li* may be referred to herein at a "Li-glas.” A dried, water-solvated ‘alass‘amomphous solid that eoudhts Na” may be referred to herein as & “Nacglass.” The present disclosure includes a watersolvated glass! amorphous solid eloctolyte that conduets H" and may be referred 10 herein as a “proton electrolyte” BRIEE DESCRIPTION OF THE DRAWINGS A more complete understanding of the present embodi- ‘ments and advantages thereof may be acquired by referring to the following description taken in conjunction with the accompanying drawings, which relate to embodiments of the present disclosure, PIG, 1 isa graph comparing Arrhenius plots of Lithium. jon (Li*) conductivity (,,) versus temperature of polymer gel with a salt, LPF, and that of a Lilass formed from precursor lithium hydroxides, LiOH, chlorides, LiCl and solvated water (FO); the solid was dried before measure ‘ment. The conductivity of Agl is also shown. FIG. 2 isa graph showing the dependence on temperature closed circles, and time at 25° C., open circles, of the Na* jonduetivity, Oya, oF a NacplassUS 9,890,048 B2 3 FIG, 3 is a graph showing the temperature dependence of the relative permiivity (=<) meesured inn ae eld of frequency £1000 Hz, of a Liglss obtined from 0 precuror composition of nominal Lis BagypC10.€ iste Sisbetie coum IG. 44 isan Ariens plot showing the tempertre Aepenienceo the proton i" eondetvty (o,f peoton evils solid obtained by solating water fn BaKPO, IG, 4B sa groph showing arerescnative Nygust pot taken af 28° Cv ofthe fretncy dependence of Oy ot & proton electrolyte: the impedance is 2-712" IG, $y grph showing the eargidnchargeeyeling of a capacitor formed by a tick, Liglasselecrlyte sande tricked betwen two lui pls. TG. ¢ isa schematic dag of the ordering wih time. pressre, anor emerstre of eet dipoles inane oF {elect fl IG. Tis araph showing chargldscharge cures of 3 {ll lithium cell showing platingstripping of a metalic 2 Tithium anode from a Liglass eleetolyte, FIG. 8is.a prph showing charge'discharge voltages of {ull sodium cell showing plating'stipping of @ metlic- sodium anode from a Ne-glas electrolyte. DETAILED DESCRIPTION ‘The present disclosure relates to a watersolvate glass! monphous solid that conducts monovalent eations such as i", Nat, oF H*, and mixmures thereof, and is an electronic inslator If the walersolvated glassamomhows solid con- ‘duets Lit, Na", or mixtures thereof, it is dried: an H* ‘conductor isnot dried, The Li-glass and Navglats are excel= conductors of Li*, Na" of mixtures thereof, and have high diclctrie constants because of the presence of electric ‘dipoles. They also have a large enough eleetronie-sate ‘energy gap not only to be excellent electronic instlators, but ‘alba to allow plating of alkali-metal nodes and the use of high-voltage cathodes in alkali-metal rechargeable batteries that eontain the died water solvated glass/amorphons solid as the electrolyte or separator, electrochemical capacitors of high elecrical-sorage eapacty ean also be made with the “alse or Navglass os the electrolyte, They are wet by the alkali metal to allow plating and stripping of akalimeta ‘anodes without dendrite formation, a they are capable of high-voltage storage of electrostatic energy ata glassmetal interface. The materials ean be formed as a paste for facile application toa large surface area. They can be used as the ‘lecirolyte andlor separator of a Balter, el cel, of elec teolysis cell andlor as a material ina capacitor of an ‘electron device. The disclosure also includes a method of forming the watersolvated glas/amorphous solid electrolyte from con- stintent precursors containing at lest one alkali metal atom, particularly lithium (Li) andor sodium (Na), with oxygen nd atleast one halide atom, particularly chlorine (C1), bromine (Br), iodine (D, oF mixtures thereof, and. water (H,O) added in an amount less than or equal to te solvation Jimit of the glasvamorphous product. For example, the ‘constituent precursors ofthe glass/amorphous prodt may include A; H,OX, AX+A,0, of 2AOH+AX (HO) with el where A is an alkali metal suchas Li andor sodium Ne ‘oF a mixture thereof and X a halide atom, The constituent precursor may also contain an oxide or hydroxide promotor Of glass formation such as Ba(OH),, S{OH),, BaO, S10, ‘CaO, MgO, Al,0,, B.O,, oF SiO. anda promoter in which sulfr replaces the oxygen, An altemative is to press ata o 4 appropriate temperature the precursor oxide, hydroxide, halide, and any other additive, including 1,0, until it fers a pass. In addition, the disclosure includes a method of drying the Water-solvated glassamorphous product. The method makes use of two chemical reactions. First, the reaction H.O#X"-(COHY+HXt, whore HX evaporates asa gas, e-8 HCI during heating te form the glass/amorphous product. Second, the reaction 2)OH)-OF +H1,Of exhausts steam (gaseous 11,0) below the decomposition temperature ofthe alas. Excess alkali fons (A*) can form three types of dipole to sive a large dielectric constant: OH", OA", and A" in an ‘asymmetric glass anion site. Orientation of the dipoles at higher temperatures, eg. S0, CalOH)., Mg(OH)., AIOH), oF Bad, Sr0, CaO, MgO, AIO, B.0,, ALO,, 8i0,, 8 andlor LiUS 9,890,048 B2 13 wherein the additive comprises a least two of Ba(OH),, SKOH),, Ca(OH). Mg(OHD., AI(OH),, oF BaO, $20, a0, MgO, A10, B,O,, Aly, Si0,, S andlor Lis. 7. The method of claim 4, wherein the adliive comprises at least two of an oxide, « hydroxide, and/or a sulfide 8. The method claim 4, wherwin the dried, wate-solvated tlass‘smogphous solid comprises less than 2 mole pereent of the glass-forming ative. 9, The method of claim 4, where lass tansition temperature T, of amorphous solid, 10. The method of claim 1, wherein the at last one halide ‘comprises chlorine (Cl, bromine (Br) andor iodine (D. 1, The method of elaim 1, wherein atleast a portion of the at least one halide exits the water-solvated glass/amor- phous sold as a hydrogen halide gas 12, The method of claim 1, wherein the hydroxide reacts ‘o form 11,0 that exits the water-solvated glass/amorphous solid as gaseous 10. the additive adjusts the e water-solvated glass! \watersolvated glass’amorphous Na* or Li” ion-conducting solid to dey the water-solvated glassfamogphous Na* of Liv fon-condvcting solid. prior 40 heating the water-solvated alasslamomphous Na" or Li ion-conducting solid in an lllemating current (2c) ora direct current (de) electric eld 14, The method of claim 13, wherein beating the water solvated glassamorphous Na" or Li ion-conductng solid t0 dry the Watersolvated glasvamorphous Na" or Lit ion- teonducting solid comprises heating to @ temperature of at Teast 230° C 15, The metho of claim 4, wherein heating the water solvated glass!amorphous Na” or Li" ion-conucting solid ‘comprises heating a temperature Between 50°C, and 110° ©. 16, The method of claim 1, wherein the watersolvated alasslamomphous Na* or Li* ion-conducting. solid has 2 aber cation conductivity. at room temperature than an therwise identical material that is not heated ia an aller- ‘ting current (ae) or a direet current (de) elect Held.UNITED STATES PATENT AND TRADEMARK OFFICE, CERTIFICATE OF CORRECTION PATENT NO. 9,890,048 B2 Page 1 of I APPLICATION NO. 15/178228 DATED February 13, 2018 INVENTOR(S) John B. Goodenough etal Itis certified that error appears in the above-identified patent and that said Letters Patent is hereby corrected as shown below: On the Title Page Under (72) Inventors: Delete “Preetam Singh, Austin, TX (US)” Signed and Sealed this Fourth Day of December, 2018 pokes bre Andre anew Director ofthe Untied Sates Patent and Trademark: Ofce