High energy density ionic dielectric materials and devices
AssigneesThe Penn State Research Foundation, Recapping, Inc.
InventorsClive A. Randall, Leslie E. Cross, Aram Yang, Niall J. Donnelly, Ramakrishnan Rajagopalan, Amanda Lou Baker
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Abstract
Dielectric compositions that include compound of the formula [(M′)1−x(A′)x][(M″)1−y−z,(B″)y(C″)z]O3−δ(VO)δ and protonated dielectric compositions that include a protonated dielectric compound within the formula [(M′)1−x(A′)x](M″)1−y−z(B″)y(C″)z]O3−δ+h(Vo)δ(H*)2h are disclosed. Composite materials that employ one or more of these dielectric compounds together with an electrolyte also are disclosed. Composite material that employs one or more of these dielectric compounds together with an electrochemally active material also are disclosed.
Claims36
A dielectric composition comprising a compound of formula
- [(M′)1−x(A′)x][(M″)1−y−zl (B″)y(C″)z]O3−δ(VO)δ where 0.0≦x≦0.4, 0.00≦b≦0.99, 0.00≦y≦0.40, 0.00≦z≦0.40, M′ is Ba, Mg, Ca, Sr, Pb and mixtures thereof, A′ is selected from the group consisting of K, Na, Li, Ag and mixtures thereof, M″ is selected from the group consisting of Ti, Zr, Hf, Ce, Sn, (Mg1/3,Nb2/3), (Zn1/3,Nb2/3), (Sc1/2,Ta1/2) and mixtures thereof, B″ is selected from the group consisting of Sc, Al, Y, La, Fe, Yb, Ho, Tm, Sb, Sm, Nd, Gd, Er, Pr, Mo, Dy and mixtures thereof, C″ is selected from the group consisting of V, Mn, Cr, Fe, Ni, Cu, Zn, Ca, Mg and mixtures thereof, (VO)δ represents oxygen vacancies and δ≦0.5x+0.5y+z.
A protonated dielectric compound within the formula [(M′)1−x(A′)x](M″)1−y−z(B″)y(C″)z]O3−δ+h(Vo)δ(H*)2h where 0.0≦x≦0.4, 0.00≦b≦0.99, 0.00≦y≦0.40, 0.00≦z≦0.40, M′ is selected from the group consisting of Ba, Mg, Ca, Sr, Pb and mixtures thereof, A′ is selected from the group consisting of K, Na, Li, Ag and mixtures thereof, M″ is selected from the group consisting of Ti, Zr, Hf, Ce, Sn, (Mg1/3,Nb2/3), (Zn1/3,Nb2/3), (Sc1/2,Ta1/2) and mixtures thereof, B″ is selected from the group consisting of Sc, Al, Y, La, Fe, Yb, Ho, Tm, Sb, Sm, Nd, Gd, Er, Pr, Mo, Dy and mixtures thereof, C″ is selected from the group consisting of V, Mn, Cr, Fe, Ni, Cu, Zn, Ca, Mg and mixtures thereof, (VO)δ represents oxygen vacancies and 0.00<h≦δ≦0.5x+0.5y+z.
A protonated dielectric compound within the formula (A1−xA′x)(B1−y−zB″yC″z)O3H*(x+y+2z) where 0.00<x<0.40, 0.00<y<0.40 and 0.00<z<0.40, A is selected from the group consisting of Ba, Mg, Ca, Sr, Pb and mixtures thereof, A′ is selected from the group consisting of K, Na, Li, Ag and mixtures thereof, B is selected from the group consisting of Ti, Zr, Hf, Sn, (Mg1/3,Nb2/3), (Zn1/3,Nb2/3), (Sc1/2,Ta1/2) and mixtures thereof, B″ is selected from the group consisting of Sc, Y, La, Fe, Yb, Ho, Tm, Sb, Sm, Nd, Gd, Er, Pr, Mo, Dy and mixtures thereof, C″ is selected from the group consisting of V, Mn, Cr, Fe, Ni, Cu, Ca, Mg and mixtures thereof, and H* is a proton.
Manufacture of a protonated compound within the formula [(M′)1−x(A′)x](M″)1−y−z(B″)y(C″)z]O3−δ+h(Vo)δ(H*)2h where 0.0≦x≦0.4, 0.00≦b≦0.99, 0.00≦y≦0.40, 0.00≦z≦0.40, M′ is selected from the group consisting of Ba, Mg, Ca, Sr, Pb and mixtures thereof, A′ is selected from the group consisting of K, Na, Li, Ag and mixtures thereof, M″ is selected from the group consisting of Ti, Zr, Hf, Ce, Sn, (Mg1/3,Nb2/3), (Zn1/3,Nb2/3), (Sc1/2,Ta1/2) and mixtures thereof B″ is selected from the group consisting of Sc, Al, Y, La, Fe, Yb, Ho, Tm, Sb, Sm, Nd, Gd, Er, Pr, Mo, Dy and mixtures thereof and C″ is selected from the group consisting of V, Mn, Cr, Fe, Ni, Cu, Zn, Ca, Mg and mixtures thereof, (VO)δ represents oxygen vacancies, δ≦0.5x+0.5y+z, H* is a proton and 0.00<h≦δ≦0.5x+0.5y+z comprising,
- forming a mixture of including oxides or precursors of oxides of Ba, Ti and dopant oxide,
- combining the mixture with a liquid to form a slurry,
- calcining the slurry to form a calcined product,
- milling the calcined product to produce a milled powder,
- compressing the milled powder to form a preform,
- sintering the preform at a temperature of about 1000° C. to about 1500° C. to produce a sintered product,
- exposing the sintered product to steam at about 20° C. to about 700° C. at about 0.1 PSI to about 100 PSI for about 1 hr to about 24 hrs.
A composite material comprising a dielectric material for generating an IBBL effect and an electrolyte wherein the electrolyte is selected from the group consisting of ionomeric electrolytes, solid-state protonic electrolytes and mixtures thereof.
A composite material comprising a dielectric material for generating an IBBL effect and an electrochemally active material disposed at grain boundaries of the dielectric material wherein the dielectric material is an ionically conducting dielectric material selected from the group consisting of lithium ion conducting dielectric materials, silver ion conducting dielectric materials, sodium ion conducting dielectric materials, oxygen ion conducting dielectric materials and mixtures thereof.
A composite material comprising a dielectric material for generating an IBBL effect and an electrochemally active material disposed at grain boundaries of the dielectric material wherein the dielectric material is a Ag+ conducting dielectric material selected from the group consisting of AgI, Ag2Te, Ag2Se, AgSBr, Ag3SI, RbAg4I5, KAg4I5, NH4Ag4I5, K1−xCsXAg4I5 where 0<x<1, Rb1−xCsxAg4I5 where 0<x<1;
- CsAg4ClBr2I2, CsAg4Br1−xI2+x where 0<x<1, Ag6I4WO4 and mixtures thereof.
A composite material comprising a dielectric material for generating an IBBL effect and an electrochemally active material disposed at grain boundaries of the dielectric material wherein the dielectric material is a Na+ conducting dielectric material selected from the group consisting of NaCl, Na2S, Na β-alumina, and mixtures thereof.
A composite material comprising a dielectric material for generating an IBBL effect and an electrochemally active material disposed at grain boundaries of the dielectric material wherein the dielectric material is a O2− conducting dielectric material selected from the group consisting of Bi2(MeyV1−y)O6−x where Me is selected from the group consisting of Cu, Co, Zn, Ge, Ca, Sr, Ni, Fe, Mn, Mg or combinations thereof, Bi2(Cu0.1V0.9)O6−x, (1−x)CaO-xAO2 where A is selected from the group consisting of Zr, Hf, Th, Ce or combinations thereof where 0<x<1, 0.2CaO-0.8ZrO2, 0.04Y2O3-0.92ZrO2, (1−x)B2O3-xZrO2 where B is selected from the group consisting of La, Sm, Y, Yb, Sc, Ga, or combinations thereof where 0<x<1.
A composite material comprising a protonated dielectric for generating a PBBL effect and an electrochemically active material disposed at grain boundaries of the protonated dielectric wherein the electrochemally active material is selected from the group consisting of layered double hydroxides of the formula [M2+1−xM3+x(OH)2]x+]Az−x/z.nH2O]x− where 0.1≦x≦0.5, 1<z<3, M2+ is selected from the group consisting of Mg, Ni, Zn, Co, Fe, Ca, Mn and combinations thereof, M3+ is selected from the group consisting of Al, Fe, Cr, Mn and combinations thereof, A is selected from the group consisting of CO32−, SO42−, OH−, Cl− and combinations thereof and 2≦n≦4, and layered double hydroxides of formula [M+1−xM3+x(OH)2](2x−1)+[Az−(2x−1)/z.nH2O]x−, where A is selected from the group consisting of CO32−, SO42−, OH−, Cl− and combinations thereof, 2≦x≦4, 0.2≦x≦0.4, 1<z<3, M+ is selected from the group consisting of Li, Na, K, Ag, and combinations thereof, and M3+ is selected from the group consisting of Al, Fe, Cr, Mn and combinations thereof.
Dependencies are inferred from the claim text.