GB2249786A - Superconducting oxide materials - Google Patents
Superconducting oxide materials Download PDFInfo
- Publication number
- GB2249786A GB2249786A GB9122495A GB9122495A GB2249786A GB 2249786 A GB2249786 A GB 2249786A GB 9122495 A GB9122495 A GB 9122495A GB 9122495 A GB9122495 A GB 9122495A GB 2249786 A GB2249786 A GB 2249786A
- Authority
- GB
- United Kingdom
- Prior art keywords
- ceramic oxide
- addition
- lithium
- oxide material
- intercalation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000000463 material Substances 0.000 title claims description 39
- 239000000919 ceramic Substances 0.000 claims abstract description 26
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 23
- 238000009830 intercalation Methods 0.000 claims abstract description 18
- 230000002687 intercalation Effects 0.000 claims abstract description 17
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 11
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 9
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 9
- 239000011734 sodium Substances 0.000 claims abstract description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 7
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 239000010949 copper Substances 0.000 claims abstract description 7
- 230000007704 transition Effects 0.000 claims abstract description 7
- 230000000737 periodic effect Effects 0.000 claims abstract description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 5
- 239000011591 potassium Substances 0.000 claims abstract description 5
- 239000003792 electrolyte Substances 0.000 claims description 8
- 229910052738 indium Inorganic materials 0.000 claims description 8
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- -1 hydronium ions Chemical class 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- 229910052712 strontium Inorganic materials 0.000 claims description 5
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052785 arsenic Inorganic materials 0.000 claims description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 239000008240 homogeneous mixture Substances 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 2
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 claims 1
- 239000011224 oxide ceramic Substances 0.000 abstract 1
- 229910052574 oxide ceramic Inorganic materials 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-O oxonium Chemical compound [OH3+] XLYOFNOQVPJJNP-UHFFFAOYSA-O 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 8
- 238000007792 addition Methods 0.000 description 7
- 238000006138 lithiation reaction Methods 0.000 description 6
- 239000008188 pellet Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000002887 superconductor Substances 0.000 description 2
- 229910052716 thallium Inorganic materials 0.000 description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 2
- 229910013462 LiC104 Inorganic materials 0.000 description 1
- 229910020939 NaC104 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000012078 proton-conducting electrolyte Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000013214 routine measurement Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N60/00—Superconducting devices
- H10N60/80—Constructional details
- H10N60/85—Superconducting active materials
- H10N60/855—Ceramic superconductors
- H10N60/857—Ceramic superconductors comprising copper oxide
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N60/00—Superconducting devices
- H10N60/01—Manufacture or treatment
- H10N60/0268—Manufacture or treatment of devices comprising copper oxide
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The superconducting transition temperature (Tc) of a mixed oxide ceramic containing bismuth together with copper and one or more elements of Group 2 of the Periodic Table can be increased by electrochemical intercalation into the ceramic oxide of an alkali metal such as lithium, sodium, potassium, or of a proton (H<+>) or hydronium ion (H3O<+>).
Description
Oxide Materials
This invention relates to ceramic oxide materials having a superconducting transition temperature above 10 K.
Since early 1986, certain families of ceramic oxide materials have been found to be superconductive at temperatures above the highest superconducting transition temperatures (Tc) known for metal alloys. One such family comprises material formulations based on ABxCuyOz and derivatives, where A is a metal in the oxidation state Ill and B is a metal in the oxidation state II. In an example of a member of such a family, A is bismuth and B is one or more elements of Group 2 of the Periodic Table such as strontium and calcium. Examples of such materials are given in International Patent Publication No. W089/07087.
It is also known that such materials may be doped with lead and further doping with small amounts of antimony can enhance the superconducting properties.
Our patent specification No. 2 232 664 describes the use of additions of one or more of indium, gallium and possibly arsenic in place of all or part of the lead or antimony or both in such materials.
Recent published reports have indicated that electrochemical intercalation of silver into the superconductor Bi2Sr2CaCu2O8+x enhanced Tc by about 15 K (G.A.
Scholz and F.W. Boswell, Solid State Communications, 74,959(1990)). A recent report has also referred to lithium doping by a high temperature reaction treatment of flexible whiskers of a superconducting oxide of bismuth, strontium, calcium and copper. This doping treatment was reported to be effective in raising Tc in both Bi2Sr2CaCu2O8+x and Bi2Sr2Ca2Cu3Ol0.
We have now found that Tc for superconducting oxide phases of bismuth, strontium, calcium and copper, including such phases with indium doping or lead doping, can be increased by the electrochemical intercalation of lithium or sodium into the materials. On theoretical grounds, it is anticipated that a similar result may be achieved by electrochemical intercalation of potassium, or protons (H+) or hydronium ions (H30+), but this has not yet been established by experiment.
In view of the similarity to these bismuth based materials in the structure of the thallium-based superconducting materials, such as, for example Tl2Ba2CaCu2Oy, it is to be expected that Tc of such thallium-based superconducting materials can also be increased by electrochemical intercalation of lithium.
However, no such effect has been positively demonstrated by experiments so far carried out.
The invention provides, in one of its aspects, a ceramic oxide material having a superconducting transition temperature above 10 K comprising a mixed oxide of bismuth, together with copper and one or more elements of Group 2 of the Periodic Table, and having an intercalation addition which has been electrochemically introduced into the ceramic oxide, and which addition comprises at least one of the alkali metals lithium, sodium, potassium, or protons (H+) or hydronium ions (H30+). Preferably, the one or more elements of Group 2 are strontium and calcium.
Preferably the bismuth based ceramic oxide contains an addition of an oxide or oxides of one or more of indium, gallium, arsenic, scandium, lead and antimony.
The invention provides, in another of its aspects, a method of manufacturing a ceramic oxide material having a superconducting transition temperature above 10 K which method comprises forming a homogeneous mixture by mixing together powders of oxides, or precursors of oxides, of bismuth, copper and one or more elements of Group 2 of the
Periodic Table in relative proportions appropriate for those desired in the product mixed oxide phase, firing the mixture to form the said product, and electrochemically introducing into the said product an addition comprising at least one of the alkali metals lithium, sodium, potassium, or protons (H+) or hydronium ions (H30+).
Preferably the intercalation addition comprises lithium or sodium, and of these, lithium is the more preferable.
The electrochemical intercalation is conveniently carried out by galvanostatic discharge of an electrochemical cell having the said product as working electrode, a counter-electrode of the addition material and an electrolyte capable of conducting lithium ions.
Specific examples of materials and methods for their manufacture embodying the invention will now be described with reference to the drawings filed herewith in which:
Figure 1 is a diagrammatic illustration of an electro-chemical cell,
Figure 2 is a graph illustrating discharge curves for electrochemical cells as shown in Fig. 1 and containing respectively three superconducting ceramic oxide material samples.
Figures 3 - 5 are graphs showing the inductance against temperature for these three superconducting ceramic oxide material samples, and
Figure 6 is a graph showing inductance against temperature for a further example of superconducting ceramic oxide material sample.
The three examples of superconducting ceramic oxide material identified in Figures 2 to 5 will first be described. In each case the homogeneous mixture was prepared from stoichiometric quantities of powdered Bi203, CuO, SrCO3 and CaCO3. For the second example including indium doping, powdered In203 was incorporated in the mix. Similarly for the third example incorporating lead, powdered PbO was incorporated in the mix. The mixture was then pressed into pellets for each example and sintered at 8600C for seventy hours. The sintering was carried out in air for the undoped example and for that containing indium, but was carried out in an atmosphere of argon and oxygen for the material doped with lead.
At this stage, measurements were made on the product materials and these are discussed more fully below.
Intercalation of lithium into the superconducting ceramic oxide materials prepared as described above was carried out by galvanostatic discharge of electrochemical cells containing the superconductor material as working electrode 11, a lithium counter electrode 12 and a lithium ion conducting electrolyte. These components are shown in
Fig. 1 which is a teflon cell 13 having two terminals 14, 15 configuration in which the working electrode 11 and counter electrode 12 are separated by pads 16 of Whatman filter paper soaked in electrolyte. The electrolyte comprised a 1M LiC104 solution in propylene carbonate.
In each case, the cell was assembled in a dry room held at a temperature of 20 C, the dew point temperature being -30 C.
In each example, the cell was discharged at room temperature to a voltage of 1.OV, using a microprocessor controlled multi-channel galvanostat. The current densities were typically of the order of 0.1 mA cm~2. The mole fraction of the intercalated lithium in the superconducting phase was calculated from the capacity obtained on the discharge together with the weight of the pellet. After discharge, each cell was dismantled and the electrolyte removed from the pellet surface.
The respective electrochemical cell discharge curves for each of the sample pellets of superconducting ceramic oxide are shown in Fig. 2. The code is as follows:
2212 for Bi2Sr2CaCu2O8+x In-2212 for Bi1 .91n0 .1Sr2CaCu2O8+x Pb-2223 for Bi1#84Pb0#34Sr2Ca2Cu3O10 Although the open circuit voltages on assembly of the electrochemical cells were in the region 3.43V to 3.53V there is no significant capacity at these high voltages and the discharge voltage rapidly falls below 2V in each case. The discharge curves for the indium and lead doped samples decrease monotonously with lithium insertion, this being indicative of a single phase reaction. The discharge curve for the Bi2Sr2CaCu2O8+x material has a short step at about 1.4 volts that may be associated with a two- phase region in the intercalation process. The final compositions based on the quantity of charge passed were as follows: Li0 .l6Bi2Sr2CaCu2O8+x Lio . 23bit 91n0 lSr2Cacu2og+x Lio . 19Bi1 . 84PbO . 34Sr2Ca2Cu30l0 The lattice parameters for the tetragonal host oxide materials and the corresponding lithiated phases were derived from X-ray diffraction patterns using a Siemens D500 diffractometer and the results are given as follows in Table 1::
TABLE 1 Bi2Sr2CaCuO8+x a=3.824(2), c=30.724(25) Li0.16Bi2Sr2CaCu2O8+x a=3.835(11), c=30.911(94) Bi1,9In0.1Sr2CaCu208+x a=5.439(5),c=30.818(43) Li0.23Bil.9In0.1Sr2CaCU-2 s+x a=5.453(12) , c=30.867(97) Bi1.84Pb0.34Sr2Ca2Cu3O10 a=5.437(8), c=37.292(85) Li0.19Bi1.84PS0.34Sr2Ca2Cu3010 a=5.439(13), c=37.373(134)
In each case it can be seen that the introduction of lithium results in an expansion in the c lattice parameter.
However, lithiation results in line broadening in the X-ray diffraction pattern that makes the determination of accurate lattice parameters difficult. This is reflected in the greater standard deviations (indicated in parenthesis) for the lithiated phases. The standard deviations are largest in the lithiated super-conducting ceramic oxide phases that contain the additional dopant ion (indium or lead). This type of anisotropic lattice expansion on intercalation is a feature of. layered materials, and is consistent with the lithium ions occupying the space between the segregated copper-oxygen layers in the perovskite structure.
Inductance measurements were made on the sample pellets by measuring the self-inductance of a transversely wound coil adjacent to the sample, using a Hewlett Packard 4274A LCR meter. The sample probe was lowered down the temperature gradient set up above the surface of liquid helium. The temperature gradient was approximately 10K per mm depending on the level of liquid in the dewar. For these routine measurements, the magnetic flux density produced by the coil was less than 10-4 Tesla.
The results of these measurements of inductance against temperature are shown in Figs. 3, 4, 5. The measurements were made on each sample both before (curves (a)) and after (curves (b)) lithiation. The respective curves are readily distinguishable in that the curves (a) for the material before lithiation exhibit a sharp downturn in inductance at the critical temperature whereas the curves (b) for the lithiated material show a more gradual decrease in inductance with decreasing temperature.The data shown in the figures relates to the materials in each case before and after lithiation as follows:
Fig. 3 - Bi2Sr2CaCu2O8+x Fig. 4 - Bi1.9In0.1Sr2CaCu2OB+x Fig. 5 - Bil#84Pb0#34Sr2Ca2Cu3010 It will be noted that in Fig. 4 the intercalation of lithium has resulted in a significant increase of about 150K in the temperature at which onset of superconductivity is evident. It was noted that in all the samples there appeared to be a decrease in the volume of the superconducting phase as a result of intercalating lithium.
This may be because the method used to introduce lithium into the starting material was not producing a homogeneous modification. For example it is possible that grain surfaces might accept more lithium than the bulk material.
In a modification of the method above described, a lithium polymer solid electrolyte based on a modified polyethylene oxide electrolyte was used in the electrochemical cell. The sample before lithiation had the composition: Bi1,7In0.3Sr2CaCu208+, A lower level of lithiation (about 4%) was achieved, yielding: Li0 .O4Bil .71n0 .3Sr2CaCu208+x The increase in Tc was about 5 K, and with a much smaller reduction in the superconducting volume, as is apparent from Figure 6.
In an example for the electrochemical intercalation of sodium, instead of lithium, into a bismuth based superconducting ceramic material, the apparatus and procedures were as described with reference to Figure 1, except that the electrolyte comprised a 1 molar solution of NaC104 in propylene carbonate, and the counter-electrode was sodium metal. After passage of 5 mole % of sodium into the superconducting ceramic material, the Tc had increased from 100 K to 105 K.
For intercalation of hydrogen into such superconducting ceramic oxide starting material, it is envisaged that the electrochemical cell would comprise the ceramic oxide as working electrode, a hydrogen or hydride counter electrode 12 and a proton conducting electrolyte such as 1M HC104 solution in propylene carbonate.
The invention is not restricted to the details of the foregoing examples. For instance the selected alkali metal need not necessarily be introduced electrochemically on its own into the ceramic oxide, but may be introduced in combination with one or more other alkali metals.
Claims (9)
1. A ceramic oxide material having a superconducting transition temperature above 10 K comprising a mixed oxide of bismuth, together with copper and one or more elements of Group 2 of the Periodic Table, and having an intercalation addition which has been electrochemically introduced into the ceramic oxide, and which addition comprises at least one of the alkali metals lithium, sodium potassium, or protons (H+) or hydronium ions (H30+).
2. A ceramic oxide material as claimed in Claim 1, wherein the said one or more elements of Group 2 are strontium and calcium.
3. A ceramic oxide material as claimed in Claim 1 or
Claim 2, containing an addition of an oxide or oxides of one or more of indium, gallium, arsenic, scandium, lead and antimony.
4. A ceramic oxide material as claimed in any of Claims 1 to 3, wherein the addition comprises lithium and/or sodium.
5. A ceramic oxide material as claimed in any of Claims. l to 3, wherein the intercalation addition comprises lithium.
6. A method of manufacturing a ceramic oxide material having a superconducting transition temperature above 10 K which method comprises forming a homogeneous mixture by mixing together powders of oxides, or precursors of oxides, of bismuth, copper and one or more elements of
Group 2 of the Periodic Table in relative proportions appropriate for those desired in the product mixed oxide phase, firing the mixture to form the said product, and electrochemically introducing into the said product an addition comprising at least one of the alkali metals lithium, sodium, potassium, or protons (H+) or hydronium ions (H30+).
7. A method as claimed in Claim 4, wherein the electrochemical intercalation is conveniently carried out by galvanostatic discharge of an electrochemical cell having the said product as working electrode, a counter-electrode of the addition material and an electrolyte capable of conducting ions of the addition material.
8. A ceramic oxide substantially as herein described in any one of the examples.
9. A method of manufacturing a ceramic oxide material as herein described in any one of the examples and with reference to Figure 1 of the drawings filed herewith.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9122495A GB2249786A (en) | 1990-11-01 | 1991-10-23 | Superconducting oxide materials |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB909023799A GB9023799D0 (en) | 1990-11-01 | 1990-11-01 | Oxide materials |
| GB9122495A GB2249786A (en) | 1990-11-01 | 1991-10-23 | Superconducting oxide materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB9122495D0 GB9122495D0 (en) | 1991-12-04 |
| GB2249786A true GB2249786A (en) | 1992-05-20 |
Family
ID=26297884
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB9122495A Withdrawn GB2249786A (en) | 1990-11-01 | 1991-10-23 | Superconducting oxide materials |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2249786A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994020991A1 (en) * | 1993-03-08 | 1994-09-15 | International Business Machines Corporation | Method and apparatus for doping a solid material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2232664A (en) * | 1989-06-17 | 1990-12-19 | Atomic Energy Authority Uk | Oxide materials |
-
1991
- 1991-10-23 GB GB9122495A patent/GB2249786A/en not_active Withdrawn
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2232664A (en) * | 1989-06-17 | 1990-12-19 | Atomic Energy Authority Uk | Oxide materials |
Non-Patent Citations (5)
| Title |
|---|
| J.Electrochem.Soc.Vol.136,No.8,August 1989,pages 2300-2305 * |
| Physica C Vol.172, No.3-4,15 Dec.1990, pages 193-8 * |
| Physica C Vol.173, No.3-4,1 Feb.1991, pages 220-6 * |
| Physica C Vol.180, No.5-6,15 Sept.1991, pages 387-93 * |
| Solid State Communications,Vol.74,No.9,June 1990, pages 959-60 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994020991A1 (en) * | 1993-03-08 | 1994-09-15 | International Business Machines Corporation | Method and apparatus for doping a solid material |
Also Published As
| Publication number | Publication date |
|---|---|
| GB9122495D0 (en) | 1991-12-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Cao et al. | Modeling, preparation, and elemental doping of Li 7 La 3 Zr 2 O 12 garnet-type solid electrolytes: A review | |
| EP2317596B1 (en) | Ceramic material and preparation method therefor | |
| Xie et al. | Consolidating the grain boundary of the garnet electrolyte LLZTO with Li 3 BO 3 for high-performance LiNi 0.8 Co 0.1 Mn 0.1 O 2/LiFePO 4 hybrid solid batteries | |
| KR101935218B1 (en) | Solid electrolyte materials and pre-solid lithium ion secondary batteries | |
| EP0017400B1 (en) | Electrochemical cell and method of making ion conductors for said cell | |
| Najib et al. | Doping strategies to optimise the oxide ion conductivity in apatite-type ionic conductors | |
| EP2302723B1 (en) | Ceramic material and use thereof | |
| Maeda et al. | Synthesis and characterization of the superconducting cuprates (Pb, Cu) Sr 2 (Y, Ca) Cu 2 O z | |
| EP3466888B1 (en) | Lowly symmetric garnet-related structured solid electrolyte and lithium secondary battery | |
| Beaudet-Savignat et al. | Oxide ion conduction in Ba, Ca and Sr doped apatite-type lanthanum silicates | |
| Sharma et al. | Superconducting fluctuation study of the 110 K phase in polycrystalline Bi1. 6Pb0. 4Sr2Ca2Cu3Oγ high-Tc superconductor | |
| Slade et al. | Chemical and electrochemical mixed alkali metal insertion chemistry of the hexagonal tungsten trioxide framework | |
| Mellander et al. | High temperature protonic conduction in phosphate-based salts | |
| Touboul et al. | Electrical conductivity and phase diagram of the system Li2SO4 Li3PO4 | |
| Arashi et al. | Electrical properties in the ZrO2-CeO2-Y2O3 system | |
| GB2249786A (en) | Superconducting oxide materials | |
| Molenda et al. | Influence of lithium on the electronic structure of YBa2Cu3O7− δ | |
| US5665662A (en) | High-temperature superconductor | |
| Sammes et al. | Phase stability and ionic conductivity in bismuth lead (antimony) oxide | |
| Kazakov et al. | Synthesis of alkali-substituted Sr, Cu oxycarbonates superconductivity in Sr2− xKxCuO2CO3 (0.25⩽ x⩽ 0.7) | |
| Le Cras et al. | Low-temperature lithium-manganese oxide cathode materials for polymer batteries | |
| JP7445504B2 (en) | Lithium ion conductor, power storage device, and method for manufacturing lithium ion conductor | |
| JP7442878B2 (en) | A composite oxide with a new crystal structure and an all-solid-state lithium-ion secondary battery using this composite oxide as a solid electrolyte | |
| Scotti et al. | Thermal expansion and electrical conductivity of yttria-substituted lanthanum strontium manganites | |
| Le Cras et al. | Defect Spinels in the System Li—Mn—O. Chemistry and Lithium Insertion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |