TW201120917A - High energy density ionic dielectric materials and devices - Google Patents

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.

Description

201120917 VI. Description of the invention: [Technical field to which the invention pertains] [0001] This application claims US Provisional Application No. 61/278867 filed on October 13, 2009 and US Provisional Application filed on February 11, 2010 The priority of the PCT Patent No. 61/303,644, the entire disclosure of which is incorporated herein by reference. [Prior Art] In a conventional barrier layer, a polycrystalline dielectric, an electron is a mobile type, and the use of electrons as a mobile species allows these dielectrics to achieve a relatively high frequency response. However, the operating voltage of these dielectrics is limited by the electric field drop across the grain boundaries and by electron tunneling across the grain boundaries, which in turn limits the achievable capacitance energy density. Typical barrier dielectrics provide an efficiency-dependent dielectric constant of between about 20,000 and 100,000. However, the energy storage capacity of these dielectrics is limited by electron tunneling at grain boundaries at high electric fields. Also, a typical barrier dielectric can only withstand a low voltage of approximately 3 volts. Commercial barrier layer dielectrics are based on semiconductor grain dies with resistant grain boundaries and heterogeneously distributed resistivity. These dielectrics exploit the space charge under electric field bias to develop a split charge distribution. Polarized dielectric. Commercial dielectric dies, polycrystalline barrier dielectrics, have high conductivity and are typically n-type. However, the grain boundaries in these dielectrics are more resistant than grains and have a double Schottky barrier (Lu (:11〇1:-tky barrier) potential. This is through the polycrystalline dielectric. Limiting DC conduction until tunneling across the grain boundaries occurs under high electric field bias. Conventional techniques attempt to increase the phase resistance to 099134645 at the edge of the grain of the dielectric, for example, sulphur dioxide , or oxidation, and reduce the electron through form number A0101 Page 3 / 66 pages 1003059622-0 201120917 • The possibility of damage is controlled by electrical conduction across the grain boundaries. [0003] Therefore 'existence There is a need to deal with these new materials. Further, the need for I to place some new materials, for example, in high energy density storage applications. [Invention] [0004] In - In an aspect, the present invention relates to an ion-conducting dielectric material that can have a heterogeneous distribution conductivity that produces a barrier layer effect. The ion-conducting dielectric material can employ an ion species such as 'but Not limited to, H+ ' Li+, N a+, Ag+, and 〇2_, and their combination 'as the primary charge carrier, the conductive dielectric material advantageously has the potential to reduce the ionic species, and the increase in crystallites associated with the electrochemically conductive barrier layer The breakdown voltage of a capacitor, when Li + 'Na+, Ag ' and Ο 2 are used as ion-conducting charge carrier species, 'these species may accumulate in the grain boundary region when applied-voltage, resulting in an ion-based Barrier layer (I〇nic_Based_

Barrier-Layer) (IBBL) effect. The IBBL effect can produce an effective barrier capacitance, such as Li +, Na+, Ag+, and 〇2, which can be distributed unevenly within the sheath region of the ion-conducting grains within the grain range. Or heterogeneously distributed in the grain, when Η+ is used as the ion species, Η+ can accumulate at the grain boundary to produce a type of IBBL effect, which is then called a proton-based barrier. Layer (pBBL) effect. In a second aspect, the invention relates to a composite material wherein the grain boundary of the ion-conducting dielectric material is capable of with a dielectric die 099134645 Form No. A0101 Page 4 / Total 66 Page 1003059622-0 201120917 One or more electrochemically active materials in which one or more ion charge carrier species interact. Therefore, the synthetic material can generate a pseudo-capacitance at the interface between the crystal grains and the electrochemically active material to achieve an increase in energy storage capacity. Ion-conducting dielectric materials exhibiting an IBBL effect (eg, pbbl effect) may include ion-conducting grains, eg, single protonated dielectric grains' or with one or more electrochemically active grain boundary compounds or The complex combines with 'when ion-conducting grains, for example, protonated grains, which are used to combine with one or more electrochemically active grain boundary compounds or compositions H' Both static electricity and electrochemical electricity storage mechanism. Electrochemically active grain boundary compounds appearing at the crystal boundaries, for example, metal hydroxides, for example, Α1(〇Η)3, can cause electrochemical reactions and the generation of pseudocapacitors. The ion-conducting dielectric material, for example, those that produce a 1BBL effect (e.g., PBBL effect), can achieve a high charge «ion axis concentration of about 1G18ChT3 to about 10 〇 21 cm-3. When Ή+ is an ionic group, it is possible to achieve a carrier concentration of about 1018 cm-3 to about 1 () 21 、 η + in the case of little or no protonated dielectric to metal transition. Ion-conducting dielectric materials, for example, those that produce IBBL effects (eg, 'PBBL effects), can advantageously have an electrical I of about 5 volts per grain boundary, and/or less than about 〇.! to about 2 Mv. In the case of /_tar^ 'minimizes the crossing of grain boundaries, ion-conducting dielectric materials, such as 'these that produce IBBL effects (eg, pBBL effect), compared to dielectrics that use electrons for charge transport It can also achieve higher voltage operation. Ion-conducting dielectric materials', for example, those that produce IBBL effects (eg, 099134645 Form No. A0101, page 5/site, such as guest bb * 1003059622-0 201120917 'PBBL effect) can also be achieved with approximately ιχι〇4 to approximately 5χι The interface polarization of the effective relevant dielectric constant of 〇5 and the relaxation time of about 1 〇 to about 5 ms, and the low frequency operation of about 10 〇 3 Hz to about 1 〇〇, ion-conducting dielectric materials, for example Those who produce IBBL effects (for example, the PBBL effect) can also avoid degradation under electric field bias that may occur in BaTi03-based dielectrics when electrons are the main carrier species. Ion-conducting dielectric materials, such as those that produce IBBL effects (e.g., PBBL effects), can be used as low frequency, high field dielectrics. Ion-conducting dielectric materials, for example, those that produce iBBL effects (eg, PBBL effects), such as, for example, protonated / ΉοιΖ% 15) 〇 &) 〇3 of Example 2. may also exhibit improved energy storage characteristics. . Ion-conducting dielectric materials, such as those that produce IBBL effects (e.g., PBBL effects), can also be insensitive to voltage and can achieve energy densities of about 100 J/cc or more. Ion-conducting dielectric materials, such as those that produce IBBL effect birds (e.g., pBBL effect), can use protonated dielectrics, for example, real tree 2 rhyme has been protonated

Ba(Sco.i(Tl0.85Zr〇 15)〇 9)〇3, for application of an electric field of about 1 MV, or more per meter, for special energy storage applications, such as ultracapacitors. In a third aspect, the present invention relates to devices that use ion conducting dielectric materials that exhibit ibbl effects (e.g., PBBL effects), such as 'capacitors and electrochemical cells. & is advantageously an ionically conducting dielectric material, for example, those that produce an IBBL effect (e.g., a pbbl effect), e.g., protonated of Example 2 099134645

Ba(Sco.i(Ti〇85Zr〇.i5)Q 9)〇3 ' can be used in, for example, hybrid form number A0101 Page 6 of 66 page 1003059622-0 201120917 ❹ 电动 Electric vehicle 'brake, electronic device ( For example, computers, caches, cameras, military and aerospace applications, and underground oil and gas exploration technology. In the concept of the fourth aspect, the present invention relates to a synthetic material using an ion-conducting dielectric material, for example, a composition of an ion-conducting dielectric material and an insulating material. The present invention is further related to a dielectric composition comprising: -, in the molecular formula or ) χ Α (Α,) χ] [(Μ") ((Β,,) α) 2] 〇 3-/¥〇)5, where 0.0 = x = 0.4, y 〇.〇〇=b=0.99 > 〇. 〇〇=y^.4〇v〇. 00 = z^^ , r , Mg, Ca, Sr, Pb ' and mixtures thereof, A. is any one of K, Na, u, Ag and a mixture thereof, m, zr, ^, ce, Sn > (Mg1/3.Nb2/3) ' (Znl/3, Nb2/3). (Sci/2, Tai/2) and any of its mixtures, B· is Sc, Al, Y, La, Fe, Yb, H〇, Tm, Sb, Sra Any of Nd, Gd, Er, Pr, Mo, Dy, and mixtures thereof, · G" is any one of v, Mn, Cr, Fe, Ni, Cu 'Zn, Ca, Mg, and mixtures thereof, (vo 5 represents oxygen vacancies, and δ = 0.5 χ + 〇 · 5y + z. The present invention is further related to a protonated dielectric compound, under the definition of the formula [(M, Vx(A') χΚΜ") i y_z(B" yen + h(Vo)/H· ) 2h, wherein 0.0 ^χ^4,Λ〇SbS0.99'〇.〇〇SyS0.40,〇.〇〇z〇.4〇, M,4 Ba, Mg, Ca, Sr, Pb, and any mixture thereof, a , which is any of K, Na, Li, Ag, and a mixture thereof, continued, 099134645 is Ti, Zr, Hi, Ce, Sn, (Mg1/3, Nb2/3), (Zn1/3, Nb2/ 3), (Sc1/2'Ta1/2) and the mixture thereof, the form number A〇m, page 7 / total 66 pages touch _·0 201120917 Any one, B' is Sc, A1, Υ, La, Fe , Yb, Ho, Tm,

Any one of Sb, Sm, Nd, Gd, Er, Pr, Mo, Dy, and a mixture thereof, C, of which V, Μη, Cr, Fe, Ni, Cu, Zn, Ca, Mg, and a mixture thereof Any one, representing oxygen vacancies' and 0. 〇〇 <hS (5 SO. 5x + 〇. 5y + z. The protonated dielectric compound may be protonated Ba (ScQ i(Ti.a 9)〇) 3, protonated Ba (Sc. Ji. 9) 〇 3, protonated protonated

Pb(Sc〇iCTio.ssZro 15)〇9)〇3 and the protonated Ba(Zr.8Y〇.2)〇3 of which #何一佣》 The present invention is also related to a kind of quality. An electric compound, in the formula CAA) (BB C" * ) 0 H * aa m -T- 卜 lyz y 3n (x + y+2z), where 0. 00<x<0. 40, 0. 〇〇<y<〇. 40, and 0. 00<z<0. 40, A is any of Ba, Mg 'Ca, Sr, Pb, and a mixture thereof 'A' is K, Na, Li Any one of Ag, Ag, and a mixture thereof, B is Ti, Zr, Hf, Sn, (Mg mk λ

Sl/3' between 2/3', (Zni/3'Nb2/3), (Valley Cl/2, Tai/2) A and any mixture thereof, B' ' is Sc, Y, La, ' Fe, Yb, Ho, Tm, Sb,

Any one of Sm, Nd, Gd, Er, Pr, Mo, Dy, and a mixture thereof, C"' is any one of V, Μη, Cr, Fe, Ni, Cu, Ca, Mg, and a mixture thereof, and The present invention is further related to a method for producing a protonated compound which is subjected to the molecular formula [(Μ')1χ(Α')χ](Μ") ι (Β)y(c")z ]〇3-5+h(Vo) (5 (H ) 2h definition, where 0. 0 ^x^0.4 5 0.00^b^0.99 * 〇.〇〇^y^〇.4〇> 〇〇 〇<zSO. 40, M' is Ba, Mg, Ca, Sr, Pb, and a mixture thereof, 099134645 Form No. A0101 Page 8 / Total 66 Page 1003059622-0 201120917, \' is Κ, Na, Any of Li, Ag, and a mixture thereof, Μ' ' is Ti, Zr, Hf, Ce, Sn, (Mg, , Nb Ί "3 2/3>, (Zni/3, Nb2/3), ( Sci/2, Tai/2) and any of its mixtures, P)' ' is Sc, A1, Y, La, Fe, Yb, Ho, Tm, Ο

Any one of Sb, Sm, Nd, Gd, Er, Pr, Mo, Dy, and a mixture thereof, and Γ is any one of V, Μη, Cr, Fe, Ni, Cu, Zn, Ca, Mg, and a mixture thereof , (v〇) s represents oxygen vacancies, (5 SO. 5x + 0. 5y + z, H* is a proton, and 0 〇〇 <h$ δ SO. 5χ + 〇 · 5y + z, the method needs Forming a mixture comprising Ba, Ti oxide or emulsion impregnation and a conversion of a quality oxide, combining the mixture with a liquid to form a slurry, and calcining the slurry to form a calcined product, grinding the calcined product to produce a ground powder 'compressing the ground powder to form a preform, sintering the preform at a temperature of from about 1 000 C to about 1 500 C To produce a sintered product, and to expose the sintered product to a steam of from about 0.1 PSI to about 100 PSI' from about 250 ° C to about 70 (TC)

Steam down for 1 hour to about 24 hours. The invention is also related to a synthetic material comprising a dielectric material for producing a bismuth BBL effect, and an electrolyte, wherein the electrolyte is any one of an ionomer electrolyte, a solid proton electrolyte, and a mixture thereof. The ionomer electrolyte is tetrafluoroethylene·perfluoro_3 6 —dioxa-4-methyl-7-octene sulfate copolymer, poly(ethylene conjugated acrylic acid, polyethylene oxide, polyvinylidene fluoride) And any one of the mixtures thereof. The solid ionomer electrolyte is any one of a layered double hydroxide, an ion conductive glass, a conductive ceramic, and a mixture thereof, and the dielectric material is a lithium ion conductive dielectric material, silver Ion Conductive Dielectric Material, 099134645 Form No. A0101 Page 9 / Total 66 Page 1003059622-0 201120917 Sodium ion conducting dielectric (IV), oxygen conducting dielectric material _ and any combination thereof. The lithium ion conducting dielectric material It may have a molecular formula (., Μ) Τι〇3, wherein μ is any one of La, Ce, Pr, Nd, and a combination thereof. The lithium ion conductive dielectric material may also have a molecular formula of 1^04, wherein 1 is selected a transient metal from a group consisting of: 〇, heart, 1^11, (^, ^1, or a combination thereof. The dielectric material may include (1) Li conducting beta-alumina 银 the silver ion conducting dielectric Material can be her 1, "2Te, AgSBr, Ling 3, RbAg4I5, KAg4I5, NH4Ag4l5, Ki xCsX Ag4I5(^tO<x<l) ^

CsAg4ClBr2I2 (wherein 〇&lt;χ&lt;ι), Ag6I4WG4£&lt;&gt; The sleeve ion-conducting dielectric material can be any of Nan, Na2S, N&quot;_oxidation and mixtures thereof. The oxygen ion conductive dielectric material may be B2(MeyVh)〇6_x (where Me is Cu, Co, Zn, Ge, Ca, Sr, Ni, Fe, Mn, Mg*, and any combination thereof), Bl2 (Cu0·^〇. 9)〇6.x ' (lx)CaO-xA〇2(^ t A4Zr . Hf , Th, Ce or any combination thereof), ostrich 〇〇 〇, u4V3-o .mrV (dipole) βΛ_, ν where, Sm'Υ, Yb, Sc, Ga or any combination thereof, wherein any of 0 < χ <1) _ 099134645 The present invention is further related to - The composite material includes a dielectric material for generating a leg effect, and an electrochemical dopant 4 at a grain boundary of the dielectric material, wherein the dielectric material is an ion conductive dielectric material, such as a hetero-substrate (4) Material, silk material dielectric material, sodium ion material dielectric material, oxygen ion conduction medium riding material and straight form number deletion 1 Page 10 / 66 pages ', 1003059622-0 201120917

mixture. The lithium ion conductive dielectric material may be (Li M)Ti〇 (wherein M 3 is any one of La, Ce, Pr, Nd, and combinations thereof),

LiM〇4 (wherein Μ is any one of Co, Mn, Fe, Ni'Cu, Cr, V or a combination thereof), Li-conducting beta-type alumina (U con

Ducting beta-alumina), and a mixture of (Li, M)Ti〇3, UMO and Li-conducting beta-oxidized. The Ag+ conductive dielectric material is

Agl, Ag2Te, Ag2Se, AgSBr, Ag SI, RbAg I, KAg4I5, NH4Ag4I5, Kl xCsxAg4I5 (where 00&lt;x&lt;;1),

RblxCsxAg4I5 (where 〇&lt;x<i), CsAg4clB i , 2 2

Any one of CsAg4Br^xI2+x (where 00&lt;x&lt;1) v Ag614W〇4 and a mixture thereof, the Na+ conductive dielectric material is any one of NaC1, Na/, Na Lu-Oxide, and a mixture thereof, 〇2-conductive dielectric material is Bi2(Mey'-y)06-x (where Me is cu, Co, Zn, Ge,

Any of Ca, Sr, Ni, Fe, Μη, Mg, or a combination thereof,

Bl2(CViV〇.9)06-x, (b x)ca〇_xA〇2 (where A is any one of Zr, Hf, Th, Ce or a combination thereof),

0. 2CaO-0. 8Zr〇2, 〇. 04Υ2〇Γ〇. 92Zr〇2, (1_χ)Β 〇_ xZr〇2 (wherein Β is La, Sm, Υ, Yb, St; Ga or a combination thereof Any one of them, where 0 &lt;X&lt;1). The electrochemically active material is AU〇H)3, Mg(0H)2, Ca(〇H)2, Sr(0H)2, Ba(0H)2Ni(0H)2, Co(〇H)2, Li/ , Ν~〇,: 2〇, molecular formula [Μ 1χΜ χ(0Η)2]χ+[Αζ—χ/ζ·ηΗ2〇]Χ-layered double hydroxide (0. 1 SxSO. 5,1&lt;;ζ&lt;3, and 2$η$4, M2 + is Mg, Ni, Zn, Co, Fe, Ca, Mn, and combinations thereof, and M3 + is any one of A, Fe, Cr, Mn, and combinations thereof, A Is any of c〇2_, S〇4, 〇H, Cl, and combinations thereof) and numerator 099134645 Form No. A0101 Page/Total 66 Page 1003059622-0 201120917 Type [Μ' Μ3+ (0Η) + Zhuang Miscellaneous X 2 [A (2χ-1)/ζ.ηΗ2〇Γ- layered and 虱 emulsion (where A4C0 wide, gas 2' 〇h-, C factory and its combination of any one, heart 4, 0.29 Guest 0.4; Kz&lt;3^ is L!, Na, K'Ag, and any combination of them, and is A1, Fe, rr, M,

Any of Cr Mn and its combination). The invention is also related to a synthetic material, including a protonated dielectric for producing (10), and an electrochemical material at the boundary of the protonated dielectric (4), wherein Material: a layered emulsion of the formula [M2+ M3+ (OH) 1χ+Γλζ~ v 1-χ χ_2]χ/ζ·ηΗ20]χ- (where G. 1 , 1 &lt; ζ &lt; 3, M, Mg, Ni Any one of Zn, Co, Fe, Ca, Mn, and combinations thereof, = 'Μη and any combination thereof, and eight are any of C〇3 S〇4, 〇H, C1, and combinations thereof, And 2 η 4), and a layer of the formula (2 x -1 ) + j - z W - (2x_1) / z · nH2 〇] x -, Cl - and its - x ^ 〇 · 4 &gt; 1 &lt;z&lt;3 [M + i-xM3+x (〇H\ double hydroxide (where AACO plant, SO combined any of them, ^ xt yz 〇- 〇+h δ , where H is incorporated _ oxygen a proton of position and the number Afnm ^ 10 ^ page 12 / page 66 3 + is any of Li Na, κ, Ag, and combinations thereof, and any of Fe Cr, Μη, and combinations thereof - The protonated The electric quantity is bismuth-doped ilmenite, unpush- ilmenite has been doped n undoped tungsten bronze, doped pyrochlore, undoped pyrochlore, layered catenary, and has large or more Any of the oxides of the dielectric coefficient, the contact is in the formula [(『 &gt;1-X(A )X](M ), _y_z(B^ )y(c» )2]〇3_δ+Η(ν 〇)δ(Η 099134645^2h Form number A0101 201120917 0. 00&lt;hS (5 SO. 5x + 0. 5y + z, where 0. 0SxS0.4, 0.00^b^0.99 » 0.00^y^0.40 » O .OO^z 0.40, M' is any one of Ba, Mg, Ca, Sr, Pb and a mixture thereof, A, any of K, Na, Li, Ag, and a mixture thereof, Μ ' is Ti, Zr Any one of Hf, Ce, Sn, (Mg1/3, Nb2/3), (Zn1/3, Nb2/3), (Sc1/2, Ta1/2), and a mixture thereof, B is Sc, A1 Any of Y, La 'Fe, Yb ' Ho ' Tm ' Sb , Sm, Nd, Gd, Er, Pr, Mo, Dy, and mixtures thereof, and C' is V, Μη, Cr, Fe, Ni, Cu Any of Zn, Ca, Mg, and mixtures thereof, and (VO)e represents oxygen vacancies. The invention further relates to an energy storage device employing the dielectric material disclosed herein, such as a capacitor and a battery, the capacitor including a dielectric material for generating an IBBL effect, and a metal when the storage device is a capacitor An electrode using a metal such as Cu, Al, Au, Ag, Ni, Co, Fe, Cr, Pt^Pd and alloys thereof, and a mixture thereof, at least one metal electrode having an ion in the dielectric material The electrochemical activity of the species together is such that pseudo-capacitance can be generated. The invention is also related to an energy generating device employing a dielectric material of any of the ones disclosed herein, which may be a fuel cell. [Embodiment] [0005] Ceramic dielectric materials that can be used to fabricate ion-conducting dielectrics Materials for the fabrication of ion-conducting dielectric materials that exhibit IBBL effects include, but are not limited to, proton-conducting dielectric materials, lithium ions Conductive dielectric material, silver ion conductive dielectric material, sodium ion conductive dielectric material 099134645 Form No. A0101 Page 13 of 66 1003059622-0 201120917, and oxygen ion conductive dielectric materials and combinations thereof. The lithium ion conductive dielectric material may include, but is not limited to, a lanthanide doped LiTi〇3 having a molecular formula of (Li,M)Ti〇3, wherein lanthanum is any one of La, Ce, Pr, Nd, and combinations thereof. . Li transition metal oxide of the formula LiM〇4, wherein M is a transition metal such as Co ' Mn, Fe, Ni, Cu, Cr, V and a combination thereof, and Li conducting beta-alumina. Silver ion conductive dielectric materials that can be used include, but are not limited to, 'such as Agl, Ag2Te, Ag2Se, AgSBr, Ag3SI, and sulfides (chalgogenides), compounds in the form of silver iodide, such as 'Ms, where 0 &lt; χ &lt;;1), Rbl xCsxAg4I5 (where 〇<χ&lt;1),

CsAg4ClBr2I2, (:SAg4Brl xI2+x (where 00&lt;χ&lt;1), silver iodide tungstate Ag6I4W〇4, and mixtures thereof. Sodium ion conductive dielectric materials that can be used include, but are not limited to, NaCl, Na2S, beta-alumina, aluminum oxide (beta aluminas Na-Alumiria), and mixtures thereof, halides and sulfides, which can be used to include, but are not limited to, 'having a general formula Bi2 (MeyU~^BiMeV〇x family (where Me is a metal cation such as Cu, c〇, Zn, Ge, ", , Ni, Fe, Mn, Mg or a combination thereof, and 〇&lt;y&lt;〇5, E.g,

Bi2(Cu〇9)〇6 x), defect-filled fluorites (eg, (b x)Ca〇_xA〇2, where A is 099134645

Zr, Hf 'Th, Ce or a combination thereof' and 〇 &lt; χ < 卜, for example, 0.2CaO-0.8Zr 〇 2), and the doped oxidization error of the formula (dip) ΒΛ Zr ( (where B is La , Sm, γ, Yb, Sc, GXa, 』 combinations thereof, and 0 &lt;x&lt;l, for example, 〇.04Y2〇3_〇92Zr()p. Table early number A0101 Page 14 of 66 '1003059622- 0 201120917 (4) Dielectrics that can be used to fabricate H+ conductive dielectrics (4)

Sintered ceramic dielectrics, for example, acceptor-doped shattering dielectric materials, can be used to fabricate PBBL-effect (tetra) dielectric materials. Sintered ceramic dielectric materials 'eg, when used alone in electrochemically active grain boundary materials, can act as capacitors, and energy densities up to about 100 J/CC or more' can be used to create exhibits. The receptor-doped dielectric material of the dielectric material includes, but is not limited to, any one having a smectite type structure, a crane bronze type structure, a pyrochlore type structure, a striking layer type structure, and a mixture thereof. Examples of ceramic materials having a perovskite structure that can be used include, but are not limited to, BaTiO3, doped BaTi〇3, BaZr〇3, doped BaZr〇3, PbTi〇3, doped PbTi〇3 , mr〇3, doped PbZr〇3 'SrTi〇3, doped (5)^, SrZr〇3, doped SrZr〇3, CaZr〇3, doped CaZr〇3, BiSc〇3, doped Heterobi BiSc〇3 and mixtures thereof.

Examples of the ceramic material having a crane bronze type structure which can be used include, but are not limited to, (Si^Ba^x)Nb2〇6 (wherein 〇&lt;χ&lt;1), (SrxBai-x)Ta206 (where 〇&lt;Χ&lt;1), PbNb206, PbTa206,

LiBa2Nb50i5, Ba2Na3YNb1〇〇3〇, Na3Ba3ff3Nb9〇3◦ and mixtures thereof. Examples of ceramic materials having a tungsten bronze type structure that can be used include, but are not limited to, La2Zr2〇7, Bi2(Zn1/3Nb2/3)207,

Cd2Nb2〇7, Bi2(Zn4/3Ta2/3)〇6 and mixtures thereof. Examples of ceramic materials having a tungsten bronze type structure which can be used include, but are not limited to, Bi4Ti3〇i2'Sr2Bi4Ti5〇18, Bi2SrTa2〇9, Bi2Cu〇9〇6 χ (where χ~5.35) and mixtures thereof. 099134645 Form No. Α0101 Page 15 of 66 1003059622-0 201120917 When a doped perovskite material is used as an electric material that exhibits a PBBL effect, the protonated perovskite material may include protonated Ba ( Zr〇8Y〇.2)〇3, protonation

Ba((Zr Τί , 〇 , λ

HsiS.sPo./Co.pOg, and mixtures thereof. When the doped perovskite is used to produce a protonated perovskite, the already-doped state has the general formula (1), [(M,)h(A,)x][(M,, VC")ζ ]03-δ(ν〇νΐ), where 〇.0'x' °·4 5 〇.〇〇^b^0.99 &gt; 0.00^y^0.40 . 0.〇〇^z^ 〇· 4〇,M As Ba, Mg, Ca, Sr, Pb and mixtures thereof, A· is κ, Na, Li, Ag and mixtures thereof, M, is Ti, Zf, Hf, Ce, %, (Mgi/3, Nb2/3 ), (Zn1/3, Nb2/3), (Sc1/2, Tai/2) and mixtures thereof, B, are Sc, A, Y, La, Fe, Yb', Ho, Tm,

Sb, Sm, Nd, Gd, Er, Pr, Mo, Dy and mixtures thereof. And (&quot;V, Μη 'Cr 'Fe 'Ni 'Cu, Zn ' Ca, Mg, and mixtures thereof, the amount of 氡 vacancy (¥ 〇) 5 in the doped dielectric would cause &lt;5 SO. 5x + 0. 5y + z, the doped dielectric of the formula (I) will have the general formula (ΙΑ) (Ιϋ)[(Μ,(A,)](M") 卜z after protonation (B") y(C") 2h, wherein the symbol has the same meaning as in the formula (I), Η* is a proton bound to the oxy__gen site, and 〇. 〇〇&lt;h$ 6 SO 5x + 0. 5y + z, 0.0^x^0.4 » 0.00^b^0.99 &gt; O.OO^y^O.40, 0. OOSzSO. 40. IBBL effect IBBL effect, for example, PBBL effect, can be borrowed This is due to the fact that ions such as protons are transported under an electric field to accumulate at the boundaries of the resistant grains, resulting in an effective capacitance, as shown in Figure 1. At 099134645, Form No. A0101, page 16 / A total of 66 pages 1003059622-0 201120917 1 The program shown in the figure is related to the accumulation of protons at the grain boundaries by proton transport under bias. Relatively 'using electrons and holes as the main charge carriers Polycrystalline The effective capacitance in ceramics is usually expressed by a higher frequency relaxation of about 1 〇 5 Hz in a BaTi 〇 3 based material and about 1 〇 6 以 in a SrTi 〇 based material. The IBBL effect such as the PBBL effect. Measurements can be made by known techniques, such as impedance spectroscopy, cyclic voltammetry, constant current charge/discharge, polarization field (charge and discharge) 'leakage current measurements, and above about -5 (TC to about

The dielectric breakdown strength of the 65 C Xuan* temperature. The energy storage potential of an energy storage device using an ion conducting material that exhibits a 1BBL chain (eg, PBBL effect) can be controlled by varying the grain composition, grain boundary pattern, and grain size of the dielectric grains. . The grain composition can be varied by varying the concentration of the acceptor dopant, and/or combining one or more minor dopants (eg, 'electron acceptor species', such as, but not limited to, Mn, Cr, Fe, Ni, and The type of donor, such as, but not limited to, Nb, La, Y, Dy, and Nd) is controlled.

When the ion conductive material is a u + type conductive material (for example, any one or more of (Li, La) Ti〇3, LiCo〇4, and LiMn2〇4), the grain composition can be changed by changing the receptor (eg, electron acceptor species such as, but not limited to, Torr, Cr, Mn, Fe, Ca, Ni, Cu, Zn, and donor species at the B position, such as, but not limited to, at the A position The upper Mg, Ca, Sr, or the concentration of !^, Ta, Mo, W, Re, Sb at the B position is controlled. When the ion conduction material is a compound type material in the form of an Ag+ type conductive material moth silver, the grain composition can be changed by changing the acceptor (for example, the type of electron acceptor that replaces I (for example, but not limited to, 〇,§e,§, 099134645 Form No. A0101 Page/Total 66 Page 1003059622-0 201120917

Te and its combination), as well as the substitution of the lion and its combined type of donor (for example, but not limited to, Be, Mg, (: a, Sr, Ba, Sc)) g degree. When the cerium ion conducting material is a Na+ type material (for example, Na s), the grain composition can be changed by changing the acceptor dopant (for example, the electron acceptor 2 species 'such as, but not limited to, N, P, As, The concentrations of Sb, C, Si, and combinations thereof, as well as the type of donor, such as, but not limited to, Be, Mg, Ca, and combinations thereof, are controlled. When the ion conducting material is a 〇_2 type material (for example,

When Bl2(CU〇.lV〇.9)〇5.35), the grain composition can be changed by the accepting receptor (for example, 'electron acceptor species, such as, but not limited to, Mn, Η, Zn, Sc, Τι , V, Cr, La, Nd, Dy, Ho and combinations thereof, and the type of donor, such as, but not limited to, Nb, Ta, w, M〇, and combinations thereof, are controlled by agronomy. The grain boundary pattern can be changed by incorporating the dopant, and the incorporated dopant can correct the bulk grain characteristics and correct the grain boundary defect state. The transport characteristics of the grain interface. Examples of such dopants include, but are not limited to, Bi, pb, Zn, Si, B, Nb, Ta, W, Li, Ca, Mg, Cr, Ni, Tn, A1, P, and oxides thereof, Carbonates, sulfates, nitrates, and hydroxides. The transport characteristics across the protonated grain-grains can be controlled by varying the grain size, which can be increased by using higher sintering temperatures and longer sintering times. Sintering assistance (eg, ZnO in an amount from about 1% mol to about 8% m〇i) can be added to the ceramic powder during the post-calcining grinding stage to reduce the sintering temperature by about 1 〇{rc to about Form No. A0101 099134645 Page 18 of 66 201120917 200 C, which in turn promotes grain growth at lower temperatures. Fabrication of IBBL materials using electrochemically active grain boundary materials can exhibit dielectrics of IBBL effects (eg, PBBL effects) with one or more electrochemically active grain boundary materials (eg, electrochemically active grain boundaries) The compound, or electrochemically active grain boundary composition) may be mixed 'either or may be coated with one or more electrochemically active grain boundary materials. The ionically conductive dielectric (e.g., &apos;protonated dielectric) may be present in the mixture in an amount from about 1% to about 99.999%, with the remainder being an electrochemically active grain boundary material.

When an ion-conducting dielectric (eg, a protonated dielectric) is coated with one or more electrochemically active grain boundary compounds, or compositions, for ionically conductive dielectrics (eg, protonated dielectrics) The coating can be achieved by immersing the dielectric in a metal salt precursor solution and then air drying the solution to precipitate a salt on the dielectric. Next, the resulting salt-coated dielectric is exposed to a hydrogen-oxygen solution to convert the metal salt into a layered double hydroxide (Uyered d(kble hy_ 〇dr〇Xlde). The thickness of the coating can be It is from about 0.1 nm to about 500 nm, preferably from about 1 nm to about 15 〇 nm, more preferably from about 50 nm to about i5 〇 nm. Layered dihydrogen on the surface of the &quot;electrical substance The coprecipitation of the oxide can be carried out in a supersaturated solution of cerium and lanthanum, supersaturation can be achieved by ρΗ control, and the reaction vessel can be heated to about 100. (:, and/or supersaturated at high temperatures and high pressures Ammonia-based hydrolysis is achieved under hot water conditions. For example, the thermal decomposition of urea can be used to control the sinking by the control of Qiu, so that the layered double hydroxide can be uniformly coated on the dielectric. Because hydrolysis and pH can be controlled by heating a solution containing a suitable ratio of metal form number, A0101, page 19/66, salt before 1003059622-0 201120917, to 80-10 (TC) , the decomposition of urea will release ammonia, and increase the pH, into Precipitation of metal hydroxides. Electrochemical charge transfer reaction Electrochemically active materials and charge transfer reactions between protonated dielectrics can produce pseudo-electric valleys (PSeUd〇CapacitanCe). 2C and 6 The figure schematically shows the function of the electrochemical mechanism in the case of a dielectric exhibiting a PBBL effect with an eight 1 (〇11) 3 grain boundary phase. Using an ion exhibiting an IBBL effect (pour, effect) An electrochemically active grain boundary compound of a conductive dielectric material that forms hydrides, hydroxides, hydrated oxides, or mixtures thereof at grain boundaries and produces pseudocapacitors at grain boundaries. Examples of boundary materials (eg, electrochemically active grain boundary compounds that may be used) include, but are not limited to, hydroxides (eg, A1 (〇H), 3

Mg (OH) 2 ' Ca(0H)2 ' Sr(〇H〇i.:' Ba(0H)|Ni (OH) ' L 2 2

Co(0H)2 and mixtures thereof), alkali metal oxides (such as Li 〇, N 〇L·L· , K 2 〇 and mixtures thereof) and mixtures of hydroxides and alkali metal oxides, other useful electrochemical The active grain boundary compound includes a layered double hydroxide having a hydrotalcite-like structure and having the molecular formula CM2 + 1_xM3+x(〇H)2]x+[Az-x/z.nH2〇]x-^t0. 1^x^ 〇· 5 ; 1&lt;ζ&lt;3 ; Μ is Mg, Ni, Zn, Co, Fe, Ca, Μη and their combination; M3 + is A1, Fe, Cr, Μη and their combination, A is C0q2 -, S〇42-, OH, Cl and combinations thereof, and 2 η 4. The molecular formula of the layered double hydroxide may also be [Μ'_χΜ3+χ(ΟΗ)2](2χ-ι)+[ΑΖ-(2χ_1)/ζ·ηΗ2〇]Χ-, its form number Α0101 099134645 1003059622 -0 Page 20 of 66 201120917 Α is an anion, for example, C〇32-, S〇42—, 〇Η—, CT and its combination, 2$nS4, 0.2 χ 0. 4 ; 1&lt;ζ&lt;3 Wherein M+ comprises Li, Na, K, Ag, and combinations thereof, and M3+ is A1, Fe, Cr, Μη, and combinations thereof. Preferably, the layered double hydroxide is LiAl(〇Η)7·ηΗ2〇. Manufacture of ion-conducting dielectrics exhibiting IBBL effect Li-conducting ionic materials exhibiting IBBL effect (for example, Ο(Li, La)Ti〇3) can be fabricated from conventional mixed oxide pathways as 'initial chemical compound powders LiJO, La, yttrium, and Ti 〇 2 may be included, and these powders may be ball-milled by a suitable molar ratio in ethanol (for example, Li:La:Ti::0.33:0.57:1, for example) The phases were mixed, and then (the dried powder was calcined at 1150 ° C for 1 hour), again ground by ball milling, pressed into pellets, and sintered at 13 ° C for 4 hours. Ag conduction exhibiting IBBL effect Ionic materials (such as 'RbAg4I5) can be melted by stoichiometric Agl and ribs in a white gold crucible.

And then rapidly cooled to room temperature, and then the solidified melt is ground into a powder which can be carried out in a steel mold at a pressure of about 1 Torr, 〇〇〇PSI for about 20 hours. Cold pressed to form dense globules. A Na-conductive ion material exhibiting an IBBL effect (for example, Na-beta aluminum oxide) can be produced by a conventional solid state reaction method by a method of

The NaCO is mixed, and, at a high temperature (for example, about 1600 ° C 〇 2 3 ), the powder is calcined, followed by ball milling to reduce the particle size, and then the powder can be formed into a small spherical shape and sintered. a 〇2 conducting ionic material exhibiting an IBBL effect (for example,

Bi2(Cu〇 9)〇6 χ, where 0 &lt;x&lt;0. 65) can be manufactured by the conventional 099134645 Form No. A0101 No. 21 Buy/Total 66 Page 1003059622-0 201120917 Core Reaction Method. Stoichiometric (4) starting material _5 mixed in ethanol by ball milling, dry release of Erqiguang, (four) pin, in the following calcination (four) hours, ·: emulsified ethanol in the (four) 'to make the agglomeration read, then The material = tempered at the age of (4) became a small spherical shape, and sintered at a side to = c for about 4 hours to form a dense sintered body. approximately_. Manufacture of ion-conducting dielectrics exhibiting PBBL effect

The fabrication of ion-conducting dielectric materials exhibiting effects of doped or undoped dielectrics (eg, doped or undoped = shelled 'doped or undoped blue steel' has been doped or miscellaneous a boulder, a thief ore, and an oxide having a dielectric constant of about 5 G or more, preferably 'molecular gas' has been or has not been, for example, barium titanate, undoped titanic acid钡 and its mixture).

When using a dielectric oxide that has been doped with an AB〇3 perovskite form, the vapor can be doped with one or more electron acceptor dopants to create vacancies in the gas sub-lattice, thereby compensating for electrons The extra negative charge of the bulk dopant. Preferably, a 氡 vacancy is generated for each of the 2+ shoulder electron dopant acceptor species at position 3, and an oxygen vacancy is generated for every two 丨+ valence electron acceptor dopants at the A position, and An oxygen vacancy is generated for every two 3 + valence electron dopant acceptors at position 6. The electron acceptor dopant concentration can be up to about 50% of the total B position and up to about 5% of the total A position. The a-position cation having a valence 丨+ in the titanium ore of AB03 may include, but is not limited to, K, Na, Li, Ag, and combinations thereof. The a-position cation in the ABO3 perovskite may include a 2 + valence cation such as Ba, Mg, Ca, Sr, Pb, Cd, and combinations thereof. B-position cations having a valence number include, but are not limited to, v, Cr, Μη, ρ r 6, 099134645 Form No. 1010101 Page 22 of 66 1003059622-0 201120917 i Cu, Ζη, Ca, Mg, and combinations thereof. The B-position cations in the ABO^^-qin and having the valence of ^ + include, but are not limited to, Sc, A1, γ, La, Y*b

Ho, Tm ' Sb, Sm ' Nd, Gd, Er, Pr, Mo, Dy and their junctions 13 . The B-position cation in AB〇3 per ton may include 4+ valence cations such as, but not limited to, Ti, Zr, Hf, Sn, Ce, Th, Μη, Ο

Ir and a polycation type with an average valence of 4 +. Examples of polycation species that can be used include, but are not limited to, (Mgi/3, Nb2/3), (2ni/3, Nb2/3), (Sc1/2, Ta1/2), (Mgl/2, W&quot; 2) and its combination. The 钦 菖 菖 菖 A Ba Ba Ba Ba Ba Ba Ba Ba Ba Ba Ba Ba Ba Ba Ba Ba Ba Ba Ba Ba Ba Ba Ba Ba Ba Ba Ba Ba Ba Ba Ba Ba Ba Ba Ba Ba Ba Ba Ba Ba Ba Ba Ba Ba Ba Ba Ba Ba Ba 3 + valence electron acceptor B ”. Examples of dopants include, but are not limited to, Sc, A1, Γ, U, I?e, Yb, Ho, Tm, Sb, Sm, Nd, Gd, Er, Pr, Mo , Dy and combinations thereof; examples of 2 + valence electron acceptor dopants which can be used to replace the B site include, and the values are not limited to V, Cr, Mn, Fe, Ni, Cu, Zn, Ca, Mg, and their junctions.

Hehe. For example, a dielectric of a dielectric oxide, for example, a perovskite oxide (for example, doped barium titanate or undoped barium titanate) can be protonated by subjecting the dielectric to steam heat treatment. For example, at about 3 Torr &lt; ^ to 9 ° C, about 〇1 psi to about 1 psi of steam for about 1 hour to about 24 hours. The dielectric may be protonated to from about 1% to about 4%, preferably from about 0.5% to about 20%, more preferably from about 1% to about 15%, here, all The amount is expressed in terms of the percentage of moles. The degree of protonation can be measured by techniques such as mass increase 'conductivity change, and infrared spectroscopy. 099134645 Form No. A0101 Page 23 of 66 1003059622-0 201120917 When the A position in the AB〇3. titanium ore is doped, the protonated, doped dielectric will have a molecular formula (A A' B0 . ) (Η·), its 〇. 〇&lt;χ&lt;0· 5, and wherein a' and η* are defined as the formula ία, when the β position is doped in the ΑΒ〇3 perovskite, The protonated, doped dielectric has the formula A(B, B" C' , )0 (Η * 1-yz yz 3-y-2zv )y + 2z ' where 〇. 〇〇&lt;y&lt ;〇4〇,〇〇〇&lt;z&lt;〇4〇, and wherein A, Β, Β', C', and H* are defined as in Formula IA. When ΑΒ〇3 perovskite When the position and the 8 positions are each doped, the protonated, doped dielectric has a molecular formula (Αΐ χΑ, x) (Bi-y-zBM yC, J * ^t〇.0&lt;x&lt;lt;;〇.4 ' 〇&lt;y&lt;0. 4 ' and 〇· 〇〇&lt;ζ&lt;〇· 40, and, among them, A, A, B, B', and c', as in the molecular sIA Definition. The formula is (ΙΑ) [(Μ,) (a,)](M")

Vc")z]WV0MH.) 2h fabrication of protonated dielectric exhibiting PBBL effect. Dielectric compound used to fabricate dielectric materials exhibiting PBBL effects, for example, doped ABO3 goodite (eg, beta doping) Hetero BaTi〇, which has been doped with BaZr〇3, has been doped with PbTi〇3, has been pulverized &amp; 〇3, has been SrTi〇3, has been doped with SrZr〇3, has been doped with cazr〇3, and Any one or more of the doped Bisects, which can be obtained by using a starting material (eg, 'BaC〇3, Ti〇2, and Sc2〇3) in a liquid (eg, low-burning alcohol, 099134645 such as ethanol or water-ammonia) The solution is ball milled to form a polymer to form a 'typically' starting material having a purity of about 99.9% or higher and a liquid having a pH of from about 7 to about 14. Starting material. (For example, an oxide starting material having a purity of 99.9% or higher) can be obtained from Aidrich. The crucible is dried, and then at about 8 〇〇^ to form number A0101, page 24 / total 66 Page 1003059622-0 201120917 calcination at about 1 400 ° C, preferably from about 1 000 ° C to about 1 300 ° C, more preferably large 1微米至约10 The particle size is about 0.1 μm to about 10, and the perovskite phase is formed by ball milling to produce a particle size of about 0.1 μm to about 10 The micron milled powder, preferably from about 0.1 micron to about 5 microns, more preferably from about 0.1 micron to about 1 micron. The ground powder forms pellets, for example, produced by uniaxial pressing. The preform, the preform may be further compressed by, for example, iso-static pressing. The preform is sintered in air at a temperature of from about 1000 ° C to about 1500 ° C, It is preferably from about 1050 ° C to about 1 500 ° C, more preferably from about 1 250 ° C to about 1 500 ° C, and lasts from about 1 hour to about 20 hours, preferably from about 2 hours to about 10 hours, more preferably from about 2 hours to about 6 hours. Alternatively, the doped ABOq perovskite (e.g., doped barium titanate) can be chemically (e.g., by precipitation from solution). Prepared. In the already doped AB0Q perovskite (if already doped with barium titanate, already doped 0

BaZr〇3, which has been doped with PbTiOq, which has been doped with PbZrOq, which has been doped Ο 0

During the synthesis of SrTi〇3, SrZrOQ doped, CaZrOQ doped, and any one or more of the doped BiSc〇3, the B-site precursor solution is mixed with the A-site precursor solution to form a precipitate. One of the A position and the B position solution, or both, may be heated from about 20 ° C to about 100 ° C before mixing. The first precursor solution (hereinafter referred to as the B-site precursor solution) may include a liquid containing a perovskite B site species such as, but not limited to, Ti, Zr, Hf, and Sn, and combinations thereof. The B-position precursor solution may include an organometallic B-position species such as, but not limited to, decyloxy 099134645 Form No. A0101 Page 25 of 66 1003059622-0 201120917 Compound, ethyl oxide, propyl oxide, butyl In the form of oxides and mixtures thereof. The organometallic B position species is dissolved in an organic solvent such as, but not limited to, ethanol, isopropanol or a mixture thereof. The 浓度 Μ Μ Μ 在 在 在 在 在 Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ About 0.5 Μ. The second precursor solution (hereinafter referred to as the ruthenium position precursor solution) includes an aqueous alkaline solution containing one or more salts of the A site species, which may include, but are not limited to, Ba(0H)2. Sr(OH)2Mg(OH)2, Pb(OH)2 or a mixture thereof.至至约0. 5 至至约0. 5 至至约0. Hey. The pH of the ruthenium precursor solution can be adjusted to 4 3 4 from about 8 to about 14, preferably about 10 by the addition of a strong base such as, but not limited to, NaOH, hydrazine, hydrazine or (CHjJOH, or a mixture thereof). Up to about 13, more preferably from about 11 to about 12. Mixing of the A and B precursor precursor solutions can be accomplished by rapidly pouring one of the solutions into the other, or by slowly adding one of the solutions. Drip into the other to complete, thereby forming a precipitate. The treatment of the precipitate may be by about 80 ° C to about 100 ° C, preferably about 85 ° C to about 99 ° C, more preferably about 90 °. From C to about 95 ° C, refluxing from 0.5 hours to about 48 hours, preferably from about 1 hour to about 24 hours, more preferably from about 5 hours to about 20 hours, is achieved. Alternatively, the precipitation can be achieved. Treated in a sterilizer or treated with hot water in an oven at a temperature of from about 100 ° C to about 300 ° C, preferably from about 150 ° C to about 2 50 ° C, more preferably about 180 ° C. To approximately 240 ° C, pressure approximately 099134645 Form No. A0101 Page 26 / Total 66 Page 1003059622- 0 201120917 20 PSI to about 500 PSI, preferably from about 100 PSI to about 400 PSI, more preferably from about 200 PSI to about 300 PSI, to produce a powder having a particle size greater than the precipitate and having a crystallinity greater than the precipitate. Washing in deionized water and removing it from the solution by filtration or centrifugation' Next, the powder is dried at a temperature of from about 50 ° C to about 200 ° C, preferably from about 80 ° C to about 150 ° C. More preferably, it is about 1 〇〇 c to about 120 ° C to produce a dried powder. Further, the dried powder can be processed into a sintered body by the above-described calcination-sintering procedure. ABO compounds, for example, sintered BaTi〇\3 and sintered have been pushed B'a T i 0:3 into: protonation. During protonation, the BaTi〇3 compound has been sintered, for example, 'doped already The sintered barium titanate will be exposed to the flowing steam, for example, at about 2 Torr. (: to about 9 Torr. The tubular furnace of C is preferably about 3 Torr (Tc to about 9 Torr). (:, better, about 500 C to about 700 ° C, great power From 1 psi to about 100 PSI, preferably from about 1 psi to about 5 psi, more preferably from about 2 PSI to about 20 PSI, for about 1 hour to 24 hours, preferably about 2 hours to Approximately 15 hours, more preferably from about 5 hours to about 10 hours. Energy storage and production devices are manufactured using energy storage devices of ion conducting dielectric materials, such as those known to be used in vehicles, for example, electric Cars, hybrid electric vehicles (such as 'hybrid electric cars'). Other applications include, but are not limited to, brakes, electronic devices (such as computers, electronic cache units, video recorders, and the like). These dielectrics and the devices in which they are used have particular utility in military and aerospace applications, as well as in underground oil and gas exploration technologies. 1003059622-0 099134645 Form No. A0101 Page 27 of 66 201120917 Multilayer capacitors Multilayer capacitors using a dielectric exhibiting an IBBL effect (for example, PBBL effect) can be fabricated by known methods, for example, in the manufacture of components. The layer of tape casting and thick film screen printing technology. A similar tradition can be utilized by using a metal paste (eg, including A1, Ni, Cu, Fe, Pt, Pd, Ag, Au, and alloys thereof) to deposit electrical connections on multiple layers of deposited dielectric. The edges of each layer are formed in a manner used in a multilayer capacitor, or piezoelectric actuator structure. It is also possible to use an electrode connection by being connected to each other. Thin strip casting or screen printing can be used to produce a single layer of protonated dielectric exhibiting a PBBL effect, a plurality of single layers can have a thickness of up to about 100 microns, and from about 25 mm2 to about 4 cm2, or more A large surface area is used as a dielectric layer in a multilayer capacitor, and then the plurality of single layers are subjected to heat treatment to cause densification, and after the heat treatment, the plurality of single layers are again protonated by steam treatment And capable of achieving a millifarad capacitance across a layer of 10 microns to about 20 microns at a voltage of about 500V to about 800V. As used herein, the term "thick film" is understood to mean a film having a minimum single layer thickness of about 0.5 microns and a maximum single layer thickness of about 500 microns. A dielectric exhibiting an IBBL effect (eg, a PBBL effect) using a synthetic composition of an ion-conducting dielectric can be used with an ionomeric electrolyte, a solid proton electrolyte, and mixtures thereof to provide an energizable dielectric. A synthetic material consisting of a reversible reaction between any one or more ionomers and a proton electrolyte. These synthetic material compositions can be used in rechargeable energy storage 099134645 Form No. A0101 Page 28 of 66 1003059622-0 201120917 Storage devices, such as batteries, capacitors, cameras, caches, portable power tools, Laptops, portable video devices, and military hardware. Examples of ionomer electrolytes that may be used include, but are not limited to, tetrafluoroethylene-perfluoro-3. 6-dioxa-4-methyl-7-octene sulfate copolymer ("Nafion"), poly(ethylene) Co-methyl acrylate, polyethylene oxide, polyvinylidene fluoride, and mixtures thereof. Solid ionomer electrolytes that can be used include, but are not limited to, layered double hydroxides (such as those described above), ions Conductive glass, conductive ceramics, and mixtures thereof. The composite composition can be made by mixing one or more of the above electrolytes with one or more ion-conducting dielectric phases exhibiting an IBBL effect (eg, PBBL effect). The amount of the composition may be from about 0.1% to about 99. 99%, preferably from 1% to about 50%, more preferably from 5% to about 35%, the remainder being dielectric, Herein, all amounts are based on the total volume of the synthetic composition. The invention is described in more detail below by reference to the following non-limiting examples. Examples 1A-1D and 2 illustrate protons. Production Example 1A: Protonated BaCSc Manufacture of O.lTiODOq 〇197. 3 g BaCOq, 71. 88 g Ti09 and 6.896 g Sc90q are 〇LL &lt; 5 starting materials (here, the purity of the starting material from Sigma-A1 dr i ch 99.9%, or higher, in a Teflon-lined ball mill, stable oxidation of the wrong ball by yttrium oxide, and ball milling in ethanol for 24 hours to form a slurry The slurry was dried at 80 ° C for 24 hours to produce a dry powder, and the dried powder was successively calcined at 1 050 ° C for 10 hours at 1150 099134645 Form No. A0101 Page 29 / Total 66 Page 1003059622 -0 201120917 calcination for 10 hours at °C for 1 hour at rc (for 1 hour at rc, forging for 1 hour at 1400 °C, and then forging for 10 hours at 15 〇 (rc) In order to form Ba(Sc Ti )〇(v), V〇 is a vacancy in the oxygen position. The Ba(Scn , Ti )〇 (V, 0.1 0.1〇. 9川2·95, Vo. 05 is utilized in the oxidation of ethanol. The stabilized oxidized pellets were ball milled for 24 hours to form a slurry of milled powder having a particle size of 1 micron' or less. The ground powder was drilled at 8 (TC) The rows were dried, followed by uniaxial pressing at 15,000 PSI to produce a preform. The preforms were then subjected to pressure equalization at 30,000 PSI to yield a preform which was sintered at 1550 C. After 〇 hours, the sintered Ba(Sc〇iTi〇9)〇 2.95(V〇)〇〇5〇 is sintered to form the sintered Ba(Sc〇π,9)02 95(V〇)〇〇5 to form Thin disk, and exposed to steam in 0·005 CFM for 2 hours in a 560 PSI tubular furnace, followed by slow cooling from 900 °C to 1〇0 °C at a rate of 0.5 °C/min. Example 1 AT ··. 15 was manufactured at a rate of 0.5 ° C / min from 1 〇 (TC cooled to 20 (the period of TC 'Example 1A of sintered Ba (ScQ) TiQ 9 ) 02 95 (V〇) 〇〇 5 5°C。 Manufactured at 0. 5 ° C. 5% (5) 制造 55 55 55 55 560 560 560 560 560 560 560 560 560 560 560 560 560 560 560 560 560 560 560 560 560 560 560 560 560 560 560 560 560 560 560 560 560 560 560 560 560 560 560 560 560 The sintered Ba(ScQ9)〇2 μ disk of Example 1A was exposed to steam flowing at 0.001 CFM in a 560 PSI tubular furnace during the cooling of the temperature from 900 ° C to 300 ° C. 099134645 Form Number A0101 Page 30 of 66 1003059622-0 201120917 Example IB: The protonated Ba(Scn)〇 manufacture follows the procedure of Example 1A except that 197.3 grams of 6&amp;(^〇3, 47.92 g of 14 is used) 5°C。 〇2 and 27.584 g of 8. 0. 2 3 Example 1BT: Ba(Scn"Tin e)0n (Vo) (Η*) 0.4 〇.6y 2.83, Vl7, V〇6 is manufactured at 0. 5 ° C At a rate of /min, the sintered disk produced in Example IB was exposed to 0.001 CFM of steam in a 560 PSI tubular furnace from 90 (TC cooled to 200 °C).

I8(H*&gt;o.〇4 Example lBU: Ba(SCfwTiG s)〇2 82(Vo) was fabricated at a rate of 0.5 ° €/min from 9 ° 0 ° C to 300 ° C. During this time, the sintered disk produced in Example 1B was exposed to steam flowing in 0.001 CFM in a 560 PSI tubular furnace. Example 1C: Manufacture of protonated Ca(SC()jTi.9)§3

The procedure of Example 1A was followed except that BaCOQUl00.08 grams of CaCO33 was substituted.

Example 1CT: ^(^.^^.9)02:9575(70)0.(^5^)0. 015 Manufactured following the procedure of Example 1C except at 900 ° at a rate of 0.9 rc/min During the cooling of C to 200 °C, the sintered disk produced as in Example ic was exposed to steam flowing in o.ooi CFM in a 1 000 PSI tubular furnace. Example 101:

Ca(SC0. , 0.9)02.955^0)0.045(^)0. The manufacture of 〇1〇 follows the procedure of Example 1C except that it is slowly cooled from 300 ° C to 300 ° at a rate of 〇. rc/min. During the period of C, as burned in Example 1C, 099134645, Executor No. A0101, Page 31/66, 1003059622-0, 201120917, the magnetic disk was exposed to 0.001 CFM of steam flowing in a 1 000 PSI tubular furnace. Example 1D: Manufacture of protonated Pb(Scn Q)Oq Follow the procedure of Example 1A, except for Bac〇 with 267.2 grams? 1&gt;(:0, u 0 is substituted. Example 1DT: Ρΐ3(δε〇.1Τί〇.9)〇2.9575 (ν〇)〇.〇425 (Η*)〇·015^^^ Follow the procedure of the instance ID, except During the slow cooling from 900 ° C to 200 ° C at a rate of 5 5 ° C / min, the burnt as produced in Example 1D

The junction disk was exposed to a flow of 0.001 CFM in a 100 PSI tubular furnace. s,. Example 1DU: ? Follow the procedure of Example 1D, except that during the slow cooling from 900 °C to 300 °C at a rate of 55 ° C / min, the sintered disk produced as in Example 1D was exposed. It is classified in 0.001 CFM steam in a 100 PSI tubular furnace. Example 1E: 巳Protonated Ba(ZrQ 8YQ 2)〇3 was produced from 8丨舀1113-人1 (11'丨(:11, purity of 99.9% or higher starting material 197·3 g BaCO, 98. 576 g of ZrOQ and 22.581 g of Y 〇' were mixed by ball milling in ethanol for 24 hours, and dried, and the obtained dry powder was successively calcined at 105 (TC for 10 hours at 115 (TC). The calcination was carried out for 10 hours, calcination at 125 CTC for 10 hours, calcination at 1400 ° C for 1 hour, and then calcination at 15 ° C for 10 hours to form Ba (Zr〇). 8Y. 2) 〇 2 9(V〇)〇”' where V〇 is the oxygen position vacancy. 099134645 Form No. A0101 Page 32 of 66 1003059622-0 201120917 2) 02.9(^)(^ and 2%wt ZnO (Based on Ββ(ΖΓ0·8Υ0.2)〇2.9 (,)〇.1 by weight), ball milling was carried out in ethanol using oxidized-stabilized zirconia balls for 24 hours to form a particle size of 1 μm or smaller. Slurry of ground powder. The ground powder was dried at 8 ° C. Then uniaxially pressed at 15,0 〇 0 PSI to produce a preform. Then, the preform was at 30, 0 The preform formed by pressure equalization at 00 PSI was obtained at 155 Torr. (Sintering was carried out for 1 Torr to produce sintered Ba(Zr〇Λ 2)〇2 9(V〇)〇丨. Sintered Ba(Zr〇8Y〇2)〇2 9(V〇).” Polished to form a thin disk 'and at a rate from 90 ITC to 20 ° C while being exposed to the tube at 15 PSI The inside of the crucible flows in 0.01 CFM of steam to produce protonated ga(z,2)〇3 Example 1ET : Ba(Zr Y )〇(v〇) (Η木) 0-8 0.2y 2.925^ ^ 0.0 75 ^ ;0.〇5 Manufacturing ' Ί

Following the procedure of Example 1E, except for the cooling from 900 ° C to 400 ° C at a rate of 0.5-C/min, the disk produced by the example ιέ is in! 5 PSI is exposed to the steam in the tube crucible flowing in the steam of the 〇i CFM. Example 1EU: Ba(Zr.8Y.2) 〇2 93 (ν〇)η _(H*) 0.07 Manufactured in accordance with the procedure of Example 1E except at a rate of 0.5-c/min from 900 °C While cooling to 300 °C, as in Example 1; the resulting disk was exposed to steam flowing from the 〇〇1 CFM in a tubular furnace at 15 PSI. ) 02.94(V〇)〇.〇6(10))〇. Example 1EV: Ba(Zrn δΥη U. ο 〇 Manufacture 099134645 Follow the procedure of Example 1Ε, except at the rate of 〇5°c/min Form No. A0101 Page 33 / Total 66 pages and 1003059622-0 201120917 While cooling from 900 °C to 200 °C, the disk produced as in Example 1E was exposed to steam flowing from the 〇· 01 CFM in a tubular furnace at 15 PSI. Example 1EW : Ba(Zrn cYn )〇(Vo) (Η*) 0.8 0.2y 2.97ν y0.03v ^0.14^ Manufacture follows the procedure of Example IE except at 900 °C at a rate of 〇5 °c/min While cooling to 100 ° C, the disk produced as in Example 1E was exposed to steam in a tubular furnace at 15 PSI flowing in a steam of 〇.〇1 CFM. Example 2: Protonated Ba (Sc„ (Ti Zr ) 0. 1, 0·85 0·15y 0· 9 Chuan 309 Manufactured from Sigma-Aldrich, pure; degree of f 9·9% or higher starting material 197. 3 g BaC〇3 ' 61 10' g TiO?, 1.6.· 635 g ZrO and 6. 869 g Sc2〇3 ' in a spheroidal grinder lined with Teflon. (Tefi..on) And ball milling in ethanol 24 small The slurry is dried at 80 ° C for 24 hours to produce a dry powder, and the dried powder is continuously calcined at 10 ° C for 1 hour at 115 ° C. The calcination was carried out for 1 hour, and calcined for 10 hours at 12507, calcined at 140 (TC for 1 hour, and then calcined at 15 〇〇»c for 10 hours to form

Ba (Sc. ^ Ti. 85Zr. 15). 9) 〇 2 95 (v.). . The

Ba(Sco.i(Ti〇 g5Zr〇 i5)〇 9)〇2 95 (V〇)〇 〇5^2% wt

ZnO—from ethanol in a cerium oxide stabilized zirconia ball for 24 hours to a particle size of 1 micron, the ground powder is dried at 8 ° C, followed by uniaxial pressing at 15,000 PSI. To produce a pre-form, then the preform is further pressure-compressed at 30,000 PSI and the resulting preform is sintered at 155 (TC for 1 hour to produce 099134645).

Form No. A0101 Page 34 / Total 66 I 1003059622-0 201120917 Sintered BaCS% / Ti, the sintered 〇.85Zr〇. 15^. 9^2.95^^ 0 0.05

Ba (SC0. I (TV 85Zr0. 15).· 9). 2. 95(VQ)G·°5 is exposed to a 15 PSI tubular furnace flowing in 0. 〇〇5 CFM of steam, and 〇. The rate of C/min is from 90 (TC is cooled to 2 (TC, resulting in protonated Ba (Sc〇JT, 85Zr. 丨5). 9) 〇 3. Has been protonated #5 titanium oxide form oxide, for example , 钦 钡 form dielectric (eg, protonated)

Ba(Scx(Ti(K85Zr〇ΐ5)ΐ χ)〇(3_0 5χ), where 0.00&lt;x&lt;0.40 (eg 'X-read'1))' can exhibit about 1 with respect to unprotonated dielectric 0000:; The low frequency effective dielectric constant has been enhanced. When the proton is a charge carrier species, as in a protonated _ already doped ferroelectric (for example, Ba(Sc(Ti Zr ) ) 0 ), °· 1 ο. 85 0. 1 5 ^0. 9yu3} The τ 徕 relaxation response may occur at a low frequency of approximately 1 Hz.

Figure 2 shows the effective dielectric constant (£ r) across the 〇.〇1 Hz-100 kHz frequency range for the unprotonated and protonated BVSCo./TiuJro.BWOs of Example 2. Before protonation (Fig. 2A), unprotonated

Ba(Scn ,(Ti 85ΖΓ〇·15)〇·9)〇2·95(ν〇)〇.〇5 Effective dielectric constant &lt;1000, after protonation (Fig. 2) At 1 Hz, The protonated Ba of Example 2 (Sc.i(Ti〇"zr.15).9) has an effective dielectric constant of 10,000 Å in the protonated form of Example 2

Ba(Sc〇 /T, 85Zro.i5)Q 9)〇3 has unprotonated as shown in Fig. 2A and Fig. 2B.

Ba(SC.·l(Ti.·85Zr.·15)〇. 9) 〇2·95^)0. 5 has a strong low frequency response. Low Frequency Response Using Solartron SI 1287 Electrochemical 099134645 Form No. A0101 Page 35 of 66 1003059622-0 201120917 Learning Interface / 125_ Rate Response Analyzer, in the frequency range spanning 1〇-&amp; _i〇6hz, and at l_mV The measurement is performed under the oscillating voltage. Figure 3 shows the measurement of the activation energy of the grain and grain boundaries. Measurements were made using an S〇iartron SI 1287 Electrochemical Interface / 1255B Frequency Response Analyzer with IV oscillating voltage, which was measured for protonation of Example 2.

The protonated grain activation energy ("EA") of Ba(Sco.i(Tlo.85Zr0.15)0 9)〇3 at 0·45 eV, and the protonated of measurement example 2

Ba(Sco_i(Ti0.85Zr0.15)0 9)〇3于〇. 59 eV protonated grain activation energy EA. .. Figure 3A(a) shows cyclic voltammetry for exhibiting a reversible capacitive response at the solid interface of A1(〇H)3/Naf i〇n, and Fig. 3A(b) shows at Α1(ΟΗ)3/ Protonated dielectric (curve A) and protonated of A1(0H)3/case 2

Cyclic voltammetry for exhibiting a reversible capacitive response at the solid interface of Ba(Sc〇 /T, 85Zr〇. 15)〇 9)〇3 (curve β). Curve B shows a significant reduction in leakage current compared to unprotonated BaU%. (Ti0. 85Zr0. 15) 〇·9) 〇2·95(ν〇)〇.05 Figure 4 shows the protonated grain boundary capacitance (low frequency) and grain capacitance (high frequency) due to Example 2. The temperature stability of the effective dielectric constant is based on impedance measurements made using the Solartron SI1287 Electrochemical Interface / 1255B Frequency Response Analyzer. Figure 5 shows the protonation

Ba(SCx(Ti〇0.85Zr0.15)lx)〇(3-°-5x)(*t 099134645 Form No. A0101 Page 36/Total 66 Page 1003059622-0 201120917 0.00&lt;χ&lt;0.40, specifically Example 2 Protonated

Ba (Sco. ΙΟ10·85?% 15) 〇 9) 〇 3) Polarization vs. electric field The measurement was performed using a computer controlled Trek 609C-6 high voltage amplifier connected to a modified Sawyer-Tower circuit. The protonated of Example 2

The dielectric constant of Ba(Sco. 15)〇9)〇3 is a linear function of the electric field strength to 2 MV/m, which is a dielectric of commercial BaTi〇3 dielectric exhibiting a loss of dielectric coefficient as the electric field strength increases. The coefficients are opposite. Fabrication of dielectric materials exhibiting PBBL using electrochemically active cladding

Example 3-3E illustrates the fabrication of a dielectric material exhibiting a pBBL effect in combination with an electrochemically active coating. Example 3 t絵: heart

10 g of Example with 1 μm average grain size 1. Protonated Ba(Sco.iTi〇9)〇3, dispersed by ball milling in deionized water for 24 hours, the coating solution was prepared by克的八1(仰3)3.9112〇 is dissolved in 100|111 of deionized water to form a solution, and then 5 grams of urea is added to the solution to achieve, then, the protonated Ba (Sc〇[Til ^) 〇3 was added to the coating solution, and the resulting mixture was placed on a hot plate and heated to 90 ° C for 2 hours under vigorous stirring to be protonated at the same time.

Ba(ScQ.lTiU) 〇3 kills A1(〇H)3. After 2 hours, the mixture is rapidly cooled in cold water, and the coated, protonated Ba(SC()9 is removed by centrifugation. ) 〇 3, then, the powder is at 12 〇. Dry overnight.

Example 3A follows the procedure of Example 3 except that the protonated Ba(Sco.iTi〇.9)03 of the example π replaces the protonated of Example 1A.

Ba (Sc〇 Jio, 9) 〇 3. 099134645 Form No. A0101 Page 37 of 66 1003059622-0 201120917

Example 3B follows the procedure of Example 3 except that the protonated Ca(Sco.4Ti〇.6)03 of the example ic replaces the protonated of Example 1A.

Ba(Sc〇 Jio. 9)0 实例 Example 3C follows the procedure of Example 3, except that the protonated Pb(ScO.lTi〇 9)〇3 of the instance ID replaces the protonated of the example ^

Ba(Sc〇 Jio. 9)〇3.

Example 3D followed the procedure of Example 3 except that Example 1B^C〇(N〇)H Α replaced Α1(Ν〇3)3 9Η20 on the basis of 〇 0.9 2 1:1. Example 3 遵循 Follow the procedure of Example 3, except for the example) Η 取代 Replace A1(N0 ) HO with a basis of 3 3.9 2 1:1. 3 3.9 2 Manufacture of capacitors using electrochemically active coated ion-conducting dielectrics Ion-conductive dielectric powders (eg, proton-transporting dielectric powders) utilize polymer binders (eg, poly(butyral)) Grinding is carried out in an organic solvent (for example, ethanol) to produce a slurry which is cast into a carrier material (for example, 'Mylar) in a thin strip and dried, and then the 'dried strands are cut into Small squares 'and use conductive electrodes to carry ink (eg, aluminum, silver, copper, gold, platinum, handle, nickel, or a mixture thereof) for screen printing 'to form electrodes, and then, the printed ribbons are stacked' A plurality of layers are formed and joined together by gentle pressing to form a pressed wafer, and then the pressed wafer is electrically connected by removing the edges to expose the electrodes by conducting the metallic ink and 099134645 Form No. A0101 No. 38 Page / Total 66 pages 1003059622-0 201120917 Manufacture of dielectric capacitors using iBBL effects (eg, pBBL effect) for the fabrication of η pseudocapacitor layers (eg 'Co(0H)2) Long in an anode (e.g., Ni bismuth square), means to produce an anode. A sol-gel hybrid dielectric exhibiting a PBBL effect is coated on the anode assembly and then heated to about ι〇〇田至U〇『C, and then the heated anode assembly is cooled to the chamber' Apply-cathode layer' and, if necessary, re-anneal Ο The resulting structure is protonated by 1Q (TC to about cc.). Ion-conducting dielectric-insulation material synthesis*

In another aspect, an ion-conducting dielectric material, for example, exhibiting a proton barrier effect, can be used with - or a plurality of electrochemically active grain boundary materials = and insulating materials to produce ion-conducting dielectrics. Insulating materials, these synthetic materials can be used in capacitors, or energy storage. 'Encourage' poetry money hybrid electric vehicle materials, energy storage, laptop money, fast _ disc, portable power Tools, military hardware, surface mount capacitors, remote energy harvesting devices, grid scale energy storage. In this regard, an insulating material of glass, metal oxide 'polymer, or a mixture thereof can be applied to the dielectric to achieve the desired thickness of the insulating material. The insulating material acts to limit protons and electron transport to the electrochemically active grain boundaries - protonated dielectric grain units (eg, A1_protonated dielectric grain units), and the insulating material can have about 1 Ηιπ to a thickness of about 50 (10). Glass that can be used as an insulating material includes, but is not limited to, Shi Xi 099134645 Form No. Surface Page 39 / Total 66 Page 1003059622-0 201120917 , Shao Shi Xi Yan Salt, "Salt, Qing Acid, Surface Forming Oxide Mixture ( For example, boron oxide, cerium oxide), and other metal oxides (such as oxidized, oxidized, oxidized, zinc oxide, oxidized, copper oxide, magnesium oxide, and mixtures thereof). Metal oxides that can be used as insulating materials include, but are not limited to, oxidized, oxidized, oxidized, zinc oxide, oxygenated brain, oxidized steel, magnesium oxide, and mixtures thereof. ---------- π & 孖 的 bamboo common composition including, but not limited to, polyethyl ethoxylate, polyethylene butyl, polyethylene terephthalate, poly (diethylene ), polyimine and mixtures thereof. Insulation can be applied to the dielectric by ball milling together with the insulating material. The resulting abrasive material is dried and shrinked to form a pressure-resistant, heated Producing the embryo to produce a higher degree of pressure, the heating can be carried out under a pressure of from (10) m to about 30 PSI to help when the polymerization: as an insulator, the degree of application is about 80 to About 3〇〇〇c, &quot; When the m-breaking or metal oxide mixture is incorporated as an insulating phase, the typical heating temperature is about 5〇〇C to about 140. (TC. The manufacture of synthetic materials using insulating materials is generally:: The synthetic materials using insulating materials are made by grinding the embryos together with the protonated dielectric, and the edges are dried, To form: the end "two to form a poly ^ ^ π attack 鮝 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Or hydrogen gas is used during firing and junction. Alternatively, ^ Airflow 099134645 Form No. (4) A total of 66 pages of sintered sample can be carried out in a humid air stream of air 'or 201120917 nitrogen, or hydrogen, or a mixture thereof at a temperature of about 10 ° C to about 1 20 0 ° C. Annealing from 0.1 to about 10 days, and slowly cooling for several days, then the sintered body is formed into a capacitor by applying an appropriate electrode as described above. Example 4 illustrates a synthetic material using glass insulating material Manufactured. Example 4: 100 grams of protonated Ba(SC{) 9) 〇3 of Example 1A was milled with 7.5% wt of zinc borate glass in ethanol for 24 hours to produce a slurry which was dried Overnight, to form a powder, which is then compressed into a green compact, which is heated at 4 ° C / min to a sintering temperature of 1100 ° C and maintained at 1100 ° C for 2 hours. The composite dielectric - insulating material can be used to electrode The material is applied to the composite material to form a capacitor* electrode material (eg, *conducting electrode ink) may be applied by, for example, painting, or one or more conductive metals may be used by sputtering or evaporation. , Au, Al, Ag, Pt, Ni, Fe Pd, Sn or a combination thereof, and alloys thereof are applied to the electrode material, and the applied electrode can provide an electrochemical capacitance contribution. A device using a synthetic dielectric-insulation material can be used in a vehicle in a hybrid electric vehicle. Energy storage, energy storage in portable devices (eg, laptops, mobile phones, military applications, and satellites) Manufacturing single-layer IBBL devices for single-layer IBBL devices, for example, single-layer PBBL devices, can be as follows The way to construct: a layered double hydroxide with a high surface area (for example, about 1 m2/gin to about 1 000 m2/gm) (for example, C〇, A1(OH)) by applying 099134645 Form No. A0101 41 pages/total 66 pages 1003059622-0 201120917 are formed on a metal current collector such as a low voltage of about 1.5 V to deposit a layer on an anode having a surface area of from about 1 m2/gm to about 1 000 m2/gm. Layered double hydroxide material. Next, the anode having a layered double hydroxide cover is circulated in an ionic solution (for example, KOH) to produce a hydroxide surface, and then the layered double hydroxide material is made of a metal such as Au, Sn, Pb , or a combination thereof or alloy coating, or coated with a metal oxide such as yttria, titanium oxide, or a combination thereof to improve capacitance and reversibility. The hydroxide surface-supporting anode is then coated with a sol-gel precursor coated with a solid electrolyte to provide a collection which can be annealed at a temperature of up to 1 500 ° C. Reprotonation is carried out via steam treatment, wet gas flow, pressure vessel, or electrochemical cycling. The high surface area cathode can be coated by coating a solution of cobalt, Mn 〇 2, nickel, magnesium, and the like, which can also be coprecipitated by aluminum and transition metals (Co, Ni, Ζη, Μη). The resulting high surface area dendritic growth wherein the conductive electrode is formed by a coprecipitation from (Α100Η + Α100Η + XCoO, or XNiO ' or ΧΜηΟ, X &lt; = 0.85). Fabrication of devices employing synthetic dielectric-insulating materials using synthetic materials of ion-conducting dielectric materials, such as proton barrier materials, and/or dielectrically insulating synthetic materials, may be formed by cementitious reactions To be a dense body suitable for use in a capacitor, in this aspect, the cementitious material is mixed with an ion conducting dielectric (eg, a proton conducting dielectric). The cementing material that can be used includes, but is not limited to, CaO, Si〇2, Al2〇3, CaS〇4, or a mixture thereof, and the amount of the cementing material and the dielectric in the mixture can be about 0.11 099134645 Form No. A0101 42 pages / total 66 pages 1003059622-0 201120917 (d) a wide range of dielectrics to about 5 〇 wt% dielectric (based on the total weight of the mixture) 'Next, the fart in the sword (such as water, ethanol Acetone, or a compound thereof, is subjected to ball milling for a period of time (for example, about 24 hours) to produce a slurry, which is then formed into a sheet shape by, for example, thin strip casting, whereby the cement is formed. The material can cause the slurry to be SJ into a strong sheet. The electrode is then applied to the sheet to create a capacitor. The attachable electrode can include Νι, or Ag-Pd on the sintered dielectric, and PBBL. Ag, or A1 composition of dielectric and polymer. Manufacture of capacitors using electrochemically active dielectrics exhibiting IBBL effects During the fabrication of capacitors using dielectrics exhibiting IBBL effects (eg, PBBL effects), "N" electrolytically active grain boundary-dielectric cells (For example, the protonated BaTi03/Al(0H)^B grain boundary-dielectric unit can be used in series. The battery voltage of the capacitor is distributed along the cell according to V = Vcell / N. Ο When a protonated electrolytically active grain boundary-dielectric unit (eg, 'BaTi〇3/Al(OH)^B grain boundary-dielectric unit) is used, the effective charge stored in the electrolytically active grain boundary interface may be

Qeff = QpBBL + QAl(〇H)3/AlH3redox represents the charge of Q in the PBBL effect, and QA1(0H)3/AlH3redox ugly 4(d) is the charge associated with the electrochemically active phase. The result ^^eff^cel 1 ^/^^) = ^pbblVPBBL + CPSEUDO η OVERPOTENTIAL ^ and the effective capacitance of the capacitor using the ion-conducting dielectric exhibiting the IBBL effect (for example, PBBL effect) can be expressed as 099134645 Form No. A0101 43 pages/total 66 pages 1003059622-0 201120917 [0006] ΒΒ^ΓρΒΒΖ + C PSSUD(^ OVSRPOTSmAl

KeU where CPBBL is the capacitance associated with the PBBL effect, VDBBT is the voltage associated with the DDL. The PBBL effect, CpsEu(10) is the capacitance associated with the electrochemical phase, and ?OVERPOTENTIAL is the voltage associated with the electrochemical phase. PBBL CpSEUDO... and 〇VERJPG: TENTIAL· can control the degree of protonation of the dielectric (eg, BaTi〇3) and the electrolytically active grain boundary material at the grain boundaries (eg, A1(〇h)) The thickness of the layer is managed. The $degree of the electrolytically active grain boundary material layer is dependent on the intrinsic value of the CPSEUD0 and ^OVERPOTENTIAL of the grain boundary material. 电解The electrolytic capacitance of the dielectric grain boundary-dielectric unit is the overall capacitance 曰ίέ jL · P — 疋a OVERALL CEFF (#PARALLEL/#SERIES) and 疋, where #PARALLEL represents the number of electrolytically active grain boundaries _ dielectric units in the parallel architecture, and #seriesr table electrolytically active grain boundaries - mustard The number of units in the tandem architecture. Electrolytic active grain boundaries in series configuration - the number of dielectric cells and the number of electrolytically active grain boundaries in a parallel configuration - the number of dielectric cells can be controlled by grain size, layer area, and layer thickness. The number of series configurations is defined as a function of layer thickness and grain size, i.e., the number of 'series configurations is defined as the layer thickness divided by the grain size. Similarly, the number of parallel configurations is defined as the layer area divided by the square of the grain size. 099134645 Form No. A0101 Page 44 of 66 1003059622-0 201120917 The overall capacitance of a capacitor using a dielectric material exhibiting an IBBL effect (eg, pBBL effect) can be varied by varying length, width, thickness, and number of layers in the capacitor. Managed, it is located in a multi-layer device for approximately 〇丨 micron grain size, with approximately! An energy density of approximately (1 〇〇〇 J/cc) can be achieved in the overall capacitance of the mF and in a capacitor operating at approximately 500 V of battery voltage. The ion conduction mediator that exhibits the IBBL effect (eg, the pBBL effect) can have a large (four), _ high effective dielectric constant, which is constant for field strengths up to 2 MV/m. Demonstrating IBBL effects (eg, PBBL effects), using any one or more electrochemically active grain boundary materials (eg, electrochemically active grain boundary metal hydroxides at grain boundaries (eg, ι eg:; , A ((h)3)) of the ion-conducting dielectric can produce an electrochemical reaction between the electrochemically active boundary of the material composition and the grain to generate pseudo-capacitance, which can increase the output Capacitance, capture of electronic carriers, and operation at higher voltages. An ion-conducting dielectric exhibiting an IBBL effect (eg, a PBBL effect) can increase the effective dielectric constant by a factor of three, which can be achieved by combining the IBBL effect of an ion-conducting dielectric (eg, protonated dielectric) ( For example, the PBBL effect) and the electrochemical effect of electrochemically active grain boundary material at the grain boundaries (eg, ai(oh)3) occur. Therefore, when a protonated dielectric having an effective dielectric constant of 10, due to the proton blocking effect, is used to interact with the electrochemically active grain boundary material at the grain boundary (for example, ai(oh) 3) When combined, the effective dielectric constant can be increased to about 30, 在 at a dielectric grain size as small as about 0.1 micron. An overpotential of approximately 2 V to approximately 5 V and a pseudocapacitance of approximately InF at the grain boundary and a special capacitance of approximately 300 F/g are also 099134645 Form No. A0101 Page 45 / Total 66 Page 1003059622-0 201120917 Can be Achieving 'this can result in a breakdown voltage of about 2 volts to about 5 volts, and an electrostatic energy density of about 1 000 J/cc. [Simple description of the diagram] [0007] Fig. 1 is a schematic diagram showing the barrier layer capacitor and impedance data showing the reinforced capacitor in the protonated Ba(zr Y ) 0.8 at low frequencies; Figure 1A: A schematic representation of dielectric relaxation in the frequency domain; 2A and 2B: showing Ba(SC() (Tl〇.85^0.15^. correlation) measured before and after protonation, respectively. "Electrical coefficient £ r and loss tangent (tan.d); Figure 2C: Schematic diagram for example - proton proton electrochemical reaction. Figure 3: shows protonated Ba (Sc) produced by the method of Example 2. 〇.i(Ti〇85Zr〇15)〇9)〇3, the effective impedance of the grain and grain boundary regions associated with the activation energy; Figure 3A: shows the measurement using cyclic voltammetry at 8 1 (01〇3_831^〇3 charge transfer reaction at grain boundaries; Fig. 4: shows protonation produced by the method of Example 2

Ba(Sc〇.i(Tlo.85Zro.i5)o.9)03 'The temperature stability of the effective dielectric constant at low frequencies and high frequencies; Fig. 5: showing the results produced by the method of Example 2 Protonation

Comparison of polarization and electric field of Ba(Sc01(Ti〇85Zr〇15)〇9)〇3; and Fig. 6: when electrochemically active grain boundary material additionally exists with wA1(〇H)3 Schematic representation of the functionality of the electrochemical mechanism in the PBBL effect dielectric. 099134645 Form No. A0101 Page 46 of 66 1003059622-0 201120917 [Description of main component symbols] [0008] No Ο ❹ 099134645 Form No. A0101 Page 47 of 66 1003059622-0

Claims (1)

201120917 VII. Patent application scope: 1 · A dielectric composition comprising a compound of the formula (M,) (A 1 -χ ,)χ][(Μ" )y(C" , where 0.0 SxS0.4 ' 〇.〇〇sbS0.99, 0.00SyS0.40, O.OOg z S 0. 40 ' M is Ba, Mg, Ca, Sr, Pb and mixtures thereof, A' is K, Na ' Li, Ag and mixtures thereof , μ· ' is selected from the group consisting of Ti ' Zr, Hf, Ce, Sn, (Mg1/3, Nb2/3), (Zn1/3, Nb2/3), (Sci/2, Ta1/ 2) and its mixture 'B,' is selected from the group consisting of Sc, A1, Y, La, Fe, Yb, Ho, Tm, Sb, Sm, Nd, Gd, Er, Pr, Mo, Dy and mixtures thereof , (:" selected from the group consisting of v, Μη 'Cr, Fe, Ni, Cu, Zn, Ca, Mg, and mixtures thereof, '(V0)5 represents oxygen vacancies, and d s0. 5x + 0. 5y + z. 2 . A protonated dielectric compound, defined by the following formula [(M, )ι-χ(α')χ](Μ")...(B")y(c")z]wv〇 VH • )2h, where O.OSxSO.4 ' 0.00SbS0.99, O.OOgyg .0. 40,0. 00 $ z S 〇. 40,,;' from 'B'a, _Mg, Ca, Sr , Pb a group consisting of a mixture selected from the group consisting of K, Na, Li, Ag, and mixtures thereof, selected from the group consisting of Ti, Zr, Hf, Ce, Sn, (Mg1/3, Nb2/ 3), (, /3 genus 2/3), (SCi/2, Tai/2) and a mixture thereof, B', selected from Sc, A1, Y, La, Fe, Yb, Ho, a group consisting of Tm, Sb, Sm, Nd, Gd, Er, Pr, Mo, Dy, and mixtures thereof, and C. selected from V ' Μ η 'Cr 'Fe, Ni, Cu, Zn, Ca, Mg, and The group consisting of the mixture, (v〇) ^ represents oxygen vacancies, and 0· 00&lt;hS 6 SO. 5x+0. 5y + z. 3 · Protons defined by the formula as described in claim 2 Dielectric 099134645 Form No. A0101 Page 48 of 66 1003059622-0 201120917 Compound 'where the compound is protonated Ba(SC〇-l(Ti〇.85Zr〇-15)〇.9)〇3° The protonated dielectric compound defined by the formula of claim 2, wherein the compound is protonated tBa(s Ti ) 〇 0.1 0.9 3 , as defined in the formula of claim 2 Protonated dielectric compound, , The protonated compounds as Ca (SC〇.l (Ti〇.85Zr〇15) 〇.9) 〇3 ° The protonated dielectric compound defined by the formula of claim 2, wherein the compound is protonated Pb (5ScO , (Tift Zr ) ) 0 » •1 0.85 0.1 5 ^0. 9; Υ3 The protonated dielectric compound as defined in the formula of claim 2, wherein the compound is protonated tBa(Zr γ )〇. 0.8 0.2 3 A protonated dielectric compound, defined by the following formula (8a' 1 -X χ)(Β,_ Β' ' c' ' )*, loaded with Φ 1 yzy ζ 3 (x + y + 2z) with 0.00&lt;x&lt;0.40 ' 〇.〇〇&lt;y&lt;〇.4〇' and 〇, 〇〇i&lt;z&lt;〇. 40,A selection from Ba 'Mg, Ca, Sr, A group consisting of Pb and a mixture thereof, A' is selected from the group consisting of K, Na, Li, Ag, and mixtures thereof, and b is selected from the group consisting of Ti, Zr, Hf, Sn, (Mgi/3, Nb2/3) , (Zni/3, Nb2/3), (Sci/2, Ta1/2) and a mixture thereof, b, 'selected from Sc, Y, La, Fe, Yb, Ho, Tm, Sb, a group consisting of Sm, Nd, Gd, Er, Pr, Mo, Dy, and mixtures thereof, c", selected from the group consisting of v, Mn, Cr 'Fe 'Ni, Cu, Ca, Mg, and mixtures thereof And Η* is a proton. • A method for producing a protonated compound, which is defined by the following formula [(M,) (A,)] (M") (B,,) (C,,)] 〇, 1 χ χ 1 -y~zy ζ 3- Form No. 1010101 Page 49/Total 66 Page 1003059622-0 201120917 5+h(V〇) &lt;5 (H · )2h ' where 〇. 00$Χ$〇· 40 ' 0· 00$b$ 0.99, 0.00SyS0.40, 0.0〇SzS〇.4〇, M is selected from Ba, Mg, Ca, a group consisting of Sr, Pb, and a mixture thereof, a• selected from the group consisting of κ, Na, Li, Ag, and a mixture thereof, μ... selected from Ti, Zr, Hf, Ce, Sn, (Mgl/3) , Nb2/3), ..., ~), (SCl/2, Tai/2), and a group 'B' composed of a mixture thereof, selected from Sc, A1, Y, La, Fe, Yb, Ho' a group consisting of Tm ' Sb, Sm, Nd, Gd, Er, Pr, Mo, Dy and mixtures thereof, selected from the group consisting of v, Μη, Cr, Fe, Ni, Cu, Zn, Ca, Mg and mixtures thereof In the group, (V0)5 represents oxygen vacancies, 6 g x+〇. 5y + z, H* is a proton ' and 0. 00&lt;hS δ S 0· 5x + 0. 5y+z, the method includes: forming Including a salt of Ba, Ti or an oxide precursor and a mixture of dopant oxides; combining the mixture with a liquid to form a slurry; calcining the slurry to form a calcined product a product; grinding the calcined product to produce a ground powder; compressing the ground Finally, forming a pre-form; sintering the preform at a temperature of about 100 (TC to about 1500 ° C to produce a sintered product; and exposing the sintered product to about 0.1 pSI to about 1 〇〇PSI, about 20 C to about 70 (TC steam for 1 hour to about 24 hours. A composite material comprising a dielectric material for producing an IBBL effect and an electrolyte, wherein the electrolyte is selected from the group consisting of an ionomer electrolyte, a solid proton electrolyte, and mixtures thereof. The synthetic material according to claim 10, wherein the ionomer electrolyte is selected from the group consisting of tetrafluoroethylene-perfluoro-3. 6-dioxa-4-methyl-7-simly 099134645 No. A0101 Page 50 of 66 1003059622-0 201120917 Group of sulphuric acid copolymer, poly(ethylene methionine, polyethylene oxide, polyvinylidene fluoride and mixtures thereof. The synthetic material of claim 1, wherein the solid ionomer electrolyte is selected from the group consisting of layered double hydroxide, ion conductive glass, conductive ceramics, and mixtures thereof. The composite material according to the first aspect of the invention, wherein the dielectric material is selected from the group consisting of a lithium ion conductive dielectric material, a silver ion conductive dielectric material, a sodium ion conductive dielectric material, an oxygen ion conductive dielectric material, and a combination thereof. The composition of the composition according to the first aspect of the invention, wherein the molecular formula of the dielectric material comprises one ion conduction of (Li,.:jQT.i..〇3. Dielectric material 'where Μ is selected from La, Ce, Pr, Nd, The composite material according to the first aspect of the invention, wherein the dielectric material comprises a lithium ion conductive dielectric material of the formula um〇4, wherein Μ is selected A synthetic metal t-spoon from the following group of groups: c〇, g Fe, Ni, Cu, Cr, V, or a combination thereof. 16. The synthetic material according to claim 10, wherein The dielectric material includes Li conducting beta-alumina. The composite material according to claim 10, wherein the dielectric material is selected from the group consisting of Agl, Ag2Te, Ag2Se, AgSBr, Ag3SI, RbAg4I5, KAg4I5, NH4Ag4I5, KbxCsX Ag4I5 (where 00&lt;x&lt;1), Rln-xCsX Ag4I5 (where 〇&lt;x&lt;i), CsAg4ClBr2I2, (where 〇&lt;x&lt;l), Ag6I4W〇4 And a mixture of the same. 099134645 Form No. A0101 Page 51 of 66 1003059622-0 201120917 18 19 . 20 . 21 . 22 . 23 . 099134645 The synthetic material as described in the scope of the patent application, Wherein the dielectric tree material is selected from the group consisting of NaC1 A group consisting of Na2S, Na ^ 氡化铭, and mixtures thereof. Apply for a full-time (4) synthetic material as described in 1Q, wherein the dielectric material is selected from the group consisting of Bi2(MeyVw)〇6x (where Me is selected from Cu, c〇, a group consisting of Zn, ^, ,, or a combination thereof, 2 (CV 1V0.9) 06-x, (1-x)Ca〇xA〇2 (wherein A is selected from Zr, Lee or a combination thereof) Group of groups), 〇 Z Zr〇 '〇.〇4Y2〇3-〇.92Zr〇2^ (lx)B2〇3_xZr〇2(^〇tU^ La Sm, Y, Yb, Sc, Ga, or a combination thereof, where 〇&lt;; χ &lt;1) group. - a synthetic material 'includes a dielectric material for generating a ship effect and an electrochemically active material at a grain boundary of the dielectric material, wherein the dielectric material is selected from the group consisting of The ion-conducting dielectric material includes: a rotor conductive dielectric material, a silver ion conductive dielectric material, a sodium ion conductive dielectric material, an oxygen ion conductive dielectric, and combinations thereof. The composite material wheel according to claim 19, wherein the dielectric material The knife type includes a group of ion-conducting dielectric materials of the formula (Li,M)Ti〇3, wherein the lanthanum is selected from the group consisting of La, Ce, Pr, Nd, and combinations thereof. The synthetic material according to claim 19, wherein the dielectric material comprises a lithium ion conductive dielectric material of the formula LiM〇4, wherein the germanium is a transition metal selected from the group consisting of: C〇, Fe 'Ni, Cu, Cr, V, or a combination thereof. The synthetic material of claim 19, wherein the dielectric material comprises Li-conducting beta-type oxidation. 1003059622-0 Form No. A0101 Page 52 of 66 201120917 24 includes a dielectric material for generating an IBBL effect, a synthetic material, and an electrochemically active material at the grain boundary of the dielectric material, wherein The dielectric material is an Ag+ conductive dielectric material selected from the group consisting of: Agl, Ag2Te, Ag2Se, AgSBr 'Ag3SI, RbAg4l5, NW5, \, &quot;^15(3 wherein 〇&lt;^&lt;1 ), ribs 1-5 ((: with eight £415 (where 〇 &lt; 乂 &lt; 1), CsAg4CiBr2I2, CsAg4Br 卜 (where 〇 &lt; χ &lt; 1), Ag6I / 〇 4 and mixtures thereof. a composite material comprising a dielectric material for generating an IBBL effect, and a &quot;. lean chemically active material located at the crystal material of the &quot;electric material, wherein the dielectric material is selected from the group consisting of a group of Na+ conductive dielectric materials, including .NaCl, Na2S, Na-alumina, and mixtures thereof 26. A synthetic material comprising a dielectric material for generating an IBBL effect and located in the dielectric An electrochemically active material at the grain boundary of the electrical material, wherein The dielectric material is a 〇2-electroconductive dielectric material selected from the group consisting of Bi2(MeyVl y)0 χ (wherein Me is selected from Cu, C., Zn 'Ge, Ca, Sr, a group consisting of Ni, Fe, Μη, Mg, or a combination thereof, Βί2((:ινΛ·9)〇6_χ, (Bu x)Ca0_xA02 (wherein A is selected from the group consisting of Zr 'Hf 'Th, Ce, or a combination thereof) Group), 〇.2CaO_〇8Zr〇2, 0.〇4Υ2〇3-0·92Zr〇2, (1_x)B203-xZr02 (wherein B is selected from La, Sm, Y, Yb, Sc, Ga, or And a composite material according to any one of the preceding claims, wherein the electrochemically inert material is selected from the group consisting of: 099134645 A1(0H)3 , Mg(OH)2 , Ca(OH)2 , Sr(OH)2 , Form No. A0101 Page 53 of 66 1003059622-0 201120917 Ni(〇H)2, c〇(0H 2, Li2〇, Na2〇, K2〇, layered double hydroxide of the formula [M2 + i-xm3+x(〇H)2]x+[Az-x/z · πΗ20]χ_ (where 0.1$ χ$〇.5,1&lt;ζ&lt;3, and 2SnS4, Μ2 + is Mg, Ni, Zn, Co, Fe ' Ca, Μη and their combination, M3 + It is selected from the group consisting of A, Fe 2- , Cr, Μη and combinations thereof, A is selected from the group consisting of C0q2_, SO 〇 〇Η - 'C factory and its combination group), and the molecular formula - χΜ3 + χ (10) 2] ( 2X-1) + [AZ-(2x-1)/z [1T double hydroxide (where A is selected from the group consisting of C0Q2_, SO A j .nH2〇]x^) - i or, cr and their combination Group, 2$11$4, 0.2^$0.4; 1&lt;2&lt;3, wherein M+ is selected from the group consisting of Li, Na, K, Ag, and combinations thereof, and Μ is selected from the group consisting of Al, Fe, Cr, Μη and Combine the group of groups). 28 29 099134645 A synthetic material comprising an aprotonated dielectric for generating an IBBL effect and an electrochemically active material at a grain boundary of the protonated dielectric, wherein the electrochemically active material The group consisting of the following group [Αζ-χ/ζ.ηΜ] includes: a layered double hydroxide of the formula [M2' M3+ (OH) 1Χ+ 1-xxy 2 (where 0.1$χ$0.5,1&lt;z&lt;3 M2 + is selected from the group consisting of Mg ' Νι, Zn, Co, Fe, Ca, Μη and combinations thereof, and Μ3 + is selected from the group consisting of Al, Fe, Cr, Μη and combinations thereof, and is selected from C032, S042-, 〇『, C" and its combination group and nS4), and the formula [M i-xm3+x(oh)2](2x-1)+[Az_(2X-i)/z · ηΗ2层]χ-layered double hydroxide (wherein Α is selected from the group consisting of C〇32—, s〇42—, 0H-, C1- and combinations thereof, 2$η$4, 0.2sd4, 1&lt;z&lt;lt 3, M+ is selected from the group consisting of Li, Na, K, Ag, and combinations thereof, and M3 + is selected from the group consisting of Al, Fe, Cr, Μη, and combinations thereof. Form No. A0101 The synthetic material described in item 28 , wherein the proton has been selected from the group consisting of doped perovskite, undoped perovskite, tungsten-doped steel, undoped tungsten bronze, and doped a synthetic group of a pyrochlore, an undoped pyrochlore, a layered perovskite, and an oxide having a dielectric constant of about 50 or more, such as the synthetic material described in claim 28, wherein The protonated dielectric is a perovskite, and its molecular formula is defined as [(M,) ix(A, )x](M" w, vc" )z]〇...(v〇v:') 2h, Where H* is a proton incorporated into an oxygen position, and 〇〇〇&lt;h$ 占 s. 5x + 〇. 5y + z, where 〇.〇sxs〇.4,00〇sbs〇99, 〇. OOSySO. 40 '〇· ooszgo. 40,Μ' is selected from the group consisting of Ba, Mg, Ca, Sr, Pb and mixtures thereof, A, selected from the group consisting of κ, Na, Li, Ag and mixtures thereof. Select a group consisting of ^Ti, Zr%, Ce, Sn, (Mg1/3, Nb2/3), (Zni/3, Nb2/3), (Sc1/2, Ta1/2) and mixtures thereof, B, 'Selected from Sc, A1, Y, La, Fe, Yb, Ho, Tm, Sb, Sm, Nd, Gd, Er, Pr, Mo, Dy Groups of mixtures thereof, and groups of jt from v, Mn, Cr, Fe, Ni, Cu, Zn, Ca, Mg, and mixtures thereof, and (vo) 5 represents oxygen vacancies. 31. An energy storage device comprising a dielectric material as described in any one of claims 1-7, 9-26, and 28-30. The device of claim 31, wherein the device is any one of a capacitor and a battery. 33. The device of claim 32, wherein the device is a capacitor comprising a dielectric material for generating an IBBL effect and a plurality of metal electrodes, the metal electrodes being selected from the group consisting of Group of metals, including: Cu, Al, Au, Ag, Ni, Co, Fe, Cr, Pt, Pd 099134645 Form No. A0101 Page 55 of 66 (201120917, alloys and mixtures thereof. 34. Application The device of claim 33, wherein the at least one metal electrode device together with an ion species in the dielectric material enables electrochemical activity generated by the pseudo capacitance. 35. An energy generating device comprising, as claimed in the patent application The device of any one of the preceding claims, wherein the device is a fuel, the device of claim 33, wherein the device is a fuel. Battery 099134645 Form No. A0101 Page 56 / Total 66 Page 1003059622-0