CN114497658A - Solid electrolyte and preparation method thereof, solid electrolyte ceramic chip and preparation method thereof - Google Patents
Solid electrolyte and preparation method thereof, solid electrolyte ceramic chip and preparation method thereof Download PDFInfo
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 107
- 239000000919 ceramic Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000005245 sintering Methods 0.000 claims abstract description 22
- 239000000126 substance Substances 0.000 claims abstract description 7
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 6
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 6
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 6
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 6
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 6
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 51
- 239000011259 mixed solution Substances 0.000 claims description 45
- 238000010438 heat treatment Methods 0.000 claims description 40
- 238000002156 mixing Methods 0.000 claims description 33
- 150000001875 compounds Chemical class 0.000 claims description 27
- 239000011240 wet gel Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 18
- 238000002485 combustion reaction Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000008139 complexing agent Substances 0.000 claims description 11
- 229910021645 metal ion Inorganic materials 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- 229910052797 bismuth Inorganic materials 0.000 claims description 7
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 7
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 6
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 19
- 239000000243 solution Substances 0.000 description 39
- 238000003756 stirring Methods 0.000 description 36
- 238000012360 testing method Methods 0.000 description 18
- 229960001484 edetic acid Drugs 0.000 description 17
- 238000001035 drying Methods 0.000 description 16
- 238000001816 cooling Methods 0.000 description 14
- 230000008569 process Effects 0.000 description 13
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 11
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 9
- 229910017604 nitric acid Inorganic materials 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000000499 gel Substances 0.000 description 8
- 238000000227 grinding Methods 0.000 description 8
- 238000007873 sieving Methods 0.000 description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 7
- 229910002651 NO3 Inorganic materials 0.000 description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- 238000009694 cold isostatic pressing Methods 0.000 description 7
- 239000000446 fuel Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000003292 glue Substances 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229940036348 bismuth carbonate Drugs 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000005323 carbonate salts Chemical class 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- GMZOPRQQINFLPQ-UHFFFAOYSA-H dibismuth;tricarbonate Chemical compound [Bi+3].[Bi+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GMZOPRQQINFLPQ-UHFFFAOYSA-H 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(III) oxide Inorganic materials O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- -1 oxygen ions Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention belongs to the technical field of solid electrolyte materials, and particularly relates to a solid electrolyte and a preparation method thereof, and a solid electrolyte ceramic chip and a preparation method thereof. The chemical formula of the solid electrolyte provided by the invention is Ce0.98‑x‑yRExM0.02BiyO2‑δ(ii) a The RE is one or more of Dy, La, Nd, Pr, Gd, Sm, Y and Yb; the M is Ca and/or Sr; the value range of x is as follows: x is more than or equal to 0 and less than or equal to 0.20, and the value range of y is as follows: y is more than or equal to 0.01 and less than or equal to 0.05; the Ce0.98‑x‑yRExM0.02BiyO2‑δIs zero. The solid electrolyte provided by the invention can reduce the sintering temperature in the preparation process, and does not introduce extra electronic conductance.
Description
Technical Field
The invention belongs to the technical field of solid electrolyte materials, and particularly relates to a solid electrolyte and a preparation method thereof, and a solid electrolyte ceramic chip and a preparation method thereof.
Background
A solid oxide fuel cell is an all-solid-state energy conversion device that can directly convert chemical energy of fuel into electrical energy through an oxidation-reduction reaction. The novel power generation device has the characteristics of high-efficiency power generation, no environmental pollution, suitability for various fuels, capability of recycling high-temperature waste heat and the like, and is widely applied to the fields of household electricity, portable mobile power sources, auxiliary power sources of automobiles, large-scale distributed power stations and the like.
The solid electrolyte is the core of the solid oxide fuel cell, and the performance of the solid oxide fuel cell is directly determined by the performance of the solid oxide fuel cell. The solid electrolyte functions in the solid oxide fuel cell to separate gases at both ends of an anode and a cathode, to conduct oxygen ions between the electrodes, to block electron conduction, to prevent internal short circuits, and the like. Therefore, the solid electrolyte needs to meet the requirements of low electronic conductivity, high ionic conductivity, high chemical compatibility, good stability and the like.
At present, the common solid electrolyte is mainly cerium oxide-based solid electrolyte, but in the preparation process, the sintering temperature needs to be above 1400 ℃, and the energy consumption is high. In the prior art, the sintering temperature can be reduced by doping copper oxide or cobalt oxide in a cerium oxide-based electrolyte, but the addition of the elements can introduce extra electronic conductance into the system, which is easy to cause the reduction of the output performance of the battery.
Disclosure of Invention
The invention aims to provide a solid electrolyte which can reduce the sintering temperature in the preparation process and does not introduce additional electronic conductance.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a solid electrolyte, the chemical formula of which is Ce0.98-x- yRExM0.02BiyO2-δ；
The RE is one or more of Dy, La, Nd, Pr, Gd, Sm, Y and Yb;
the M is Ca and/or Sr;
the value range of x is more than or equal to 0 and less than or equal to 0.20, and the value range of y is more than or equal to 0.01 and less than or equal to 0.05;
the Ce0.98-x-yRExM0.02BiyO2-δIs zero.
The invention also provides a preparation method of the solid electrolyte, which comprises the following steps:
according to the Ce: RE: m: bi ═ (0.98-x-y): x: 0.02: y, carrying out first mixing on a cerium-containing compound, a RE-containing compound, an M-containing compound, a bismuth-containing compound and water to obtain a first mixed solution; wherein x is greater than or equal to 0 and less than or equal to 0.20, and y is greater than or equal to 0.01 and less than or equal to 0.05;
secondly, mixing the first mixed solution and a complexing agent, adjusting the pH value, and heating to obtain wet gel;
and sequentially carrying out combustion treatment and roasting treatment on the wet gel to obtain the solid electrolyte.
Preferably, the complexing agent comprises citric acid and/or ethylenediaminetetraacetic acid.
Preferably, the concentration of the metal ions in the first mixed solution is 0.20-0.50 mol/L.
Preferably, the molar ratio of the complexing agent to the total amount of metal ions in the first mixed solution is 2.2-2.5: 1.
preferably, the temperature of the combustion treatment is 250-300 ℃, and the time is 1-2 h;
the roasting treatment temperature is 700-800 ℃, and the roasting treatment time is 4-5 h.
The invention also provides a solid electrolyte ceramic chip, wherein the preparation raw material of the solid electrolyte ceramic chip comprises solid electrolyte;
the solid electrolyte is the solid electrolyte described in the above technical scheme or the solid electrolyte prepared by the preparation method described in the above technical scheme.
Preferably, the raw materials for preparing the solid electrolyte ceramic sheet further comprise a binder;
the binder comprises polyvinyl alcohol and/or polyvinyl butyral;
the binder comprises 5 wt% of the solid electrolyte.
The invention also provides a preparation method of the solid electrolyte ceramic chip, which comprises the following steps:
and sequentially tabletting and sintering the preparation raw materials of the solid electrolyte ceramic chip to obtain the solid electrolyte ceramic chip.
Preferably, the sintering temperature is 1250-1300 ℃, and the time is 4-6 h.
The invention provides a solid electrolyte, the chemical formula of which is Ce0.98-x- yRExM0.02BiyO2-δ(ii) a The RE is one or more of Dy, La, Nd, Pr, Gd, Sm, Y and Yb; the M is Ca and/or Sr; the value range of x is more than or equal to 0 and less than or equal to 0.20, and the value range of y is more than or equal to 0.01 and less than or equal to 0.05; the Ce0.98-x- yRExM0.02BiyO2-δIs zero. According to the invention, through the synergistic effect of the elements, the sintering temperature of the electrolyte can be reduced, and no additional electronic conductance is introduced.
Drawings
FIG. 1 is an XRD pattern of a solid electrolyte obtained in examples 1 to 5;
FIG. 2 is an AC impedance diagram of the solid electrolyte ceramic sheets obtained in examples 1 to 5 at 500 ℃;
FIG. 3 is an AC impedance diagram of the solid electrolyte ceramic sheets obtained in examples 1 to 5 at 550 ℃;
FIG. 4 is an AC impedance chart of the solid electrolyte ceramic sheets obtained in examples 1 to 5 at 600 ℃;
FIG. 5 is an AC impedance diagram of the solid electrolyte ceramic sheets obtained in examples 1 to 5 at 650 ℃;
FIG. 6 is an AC impedance chart of the solid electrolyte ceramic sheets obtained in examples 1 to 5 at 700 ℃;
fig. 7 is a conductivity test chart of the solid electrolyte ceramic sheets obtained in examples 1 to 5.
Detailed Description
The invention provides a solid electrolyte, the chemical formula of which is Ce0.98-x- yRExM0.02BiyO2-δ；
The RE is one or more of Dy, La, Nd, Pr, Gd, Sm, Y and Yb;
the M is Ca and/or Sr;
the value range of x is more than or equal to 0 and less than or equal to 0.20, and the value range of y is more than or equal to 0.01 and less than or equal to 0.05;
the Ce0.98-x-yRExM0.02BiyO2-δIs zero.
In the invention, the RE is one or more of Dy, La, Nd, Pr, Gd, Sm, Y and Yb, and when the RE is more than two of the above choices, the proportion of the specific elements is not specially limited in the invention, and the elements can be mixed according to any proportion.
In the present invention, M is Ca and/or Sr, and when M is Ca and Sr, the ratio of the two is not particularly required, and any ratio may be used in the present invention.
In the invention, the value range of x is 0-0.20, more preferably 0.02-0.18, and still more preferably 0.05-0.15. In the invention, the value range of y is more than or equal to 0.01 and less than or equal to 0.05, more preferably more than or equal to 0.02 and less than or equal to 0.04, and even more preferably more than or equal to 0.02 and less than or equal to 0.03. In the present invention, the Ce is0.98-x-yRExM0.02BiyO2-δIs zero.
The invention is through the use of CeO2The electrolyte is doped with multiple elements, so that the sintering temperature is reduced, crystal boundary impurities are removed, the oxygen vacancy concentration is increased, the ionic conductivity of the solid electrolyte is improved, and no extra electronic conductance is introduced.
The invention also provides a preparation method of the solid electrolyte, which comprises the following steps:
according to the Ce: RE: m: bi ═ (0.98-x-y): x: 0.02: y, carrying out first mixing on a cerium-containing compound, a RE-containing compound, an M-containing compound, a bismuth-containing compound and water to obtain a first mixed solution; wherein x is greater than or equal to 0 and less than or equal to 0.20, and y is greater than or equal to 0.01 and less than or equal to 0.05;
secondly, mixing the first mixed solution and a complexing agent, adjusting the pH value, and heating to obtain wet gel;
and sequentially carrying out combustion treatment and roasting treatment on the wet gel to obtain the solid electrolyte.
In the present invention, all the starting materials for the preparation are commercially available products known to those skilled in the art unless otherwise specified.
The invention is characterized in that according to Ce: RE: m: bi ═ (0.98-x-y): x: 0.02: y, carrying out first mixing on a cerium-containing compound, a RE-containing compound, an M-containing compound, a bismuth-containing compound and water to obtain a first mixed solution; wherein x is greater than or equal to 0 and less than or equal to 0.20, and y is greater than or equal to 0.01 and less than or equal to 0.05.
In the present invention, the value ranges of x and y are the same as those of the above technical solution, and are not described herein again. In the present invention, the RE element in the RE-containing compound is identical to the above technical scheme, and is not described herein again. In the present invention, the element M in the M-containing compound is identical to the above technical scheme, and is not described herein again.
In the present invention, the cerium-containing compound preferably includes cerium nitrate or carbonate; the RE-containing compound preferably comprises a RE-containing nitrate or carbonate; the M-containing compound is preferably a nitrate or carbonate salt containing M. In the present invention, when the cerium-containing compound, the RE-containing compound and the M-containing compound are carbonates, it is further preferable to mix and dissolve the carbonates and nitric acid to obtain corresponding soluble nitrates. The process of dissolution is not particularly critical to the present invention and may be carried out using procedures well known to those skilled in the art.
In the present invention, the bismuth-containing compound preferably includes bismuth nitrate or bismuth carbonate. The present invention also preferably includes mixing the bismuth-containing compound and the nitric acid solution for dissolution prior to the first mixing. In the present invention, the concentration of the nitric acid solution is preferably 2 mol/L. In the invention, the dosage ratio of the bismuth-containing compound to the nitric acid solution is preferably 2.4-2.6 g: 10mL, more preferably 2.5 g: 10 mL.
In the present invention, the first mixing is preferably performed under stirring, and the rotation speed of the stirring is preferably 300r/min, and the time is preferably 60 min. In the present invention, the molar concentration of the metal ions in the first mixed solution is preferably 0.20 to 0.50mol/L, more preferably 0.25 to 0.45mol/L, and still more preferably 0.30 to 0.40 mol/L.
After the first mixed solution is obtained, the first mixed solution and the complexing agent are subjected to second mixing, and the wet gel is obtained by heating after the pH value is adjusted.
In the invention, the complexing agent preferably comprises citric acid and/or ethylene diamine tetraacetic acid, and when the complexing agent is citric acid and ethylene diamine tetraacetic acid, the molar ratio of the citric acid to the ethylene diamine tetraacetic acid is preferably 1.2-1.5: 1, more preferably 1.3 to 1.4: 1. in a particular embodiment of the invention, the citric acid is preferably added in the form of a citric acid solution, the concentration of which is preferably 1.5 mol/L; the ethylene diamine tetraacetic acid is preferably added in the form of an ethylene diamine tetraacetic acid solution, and the concentration of the ethylene diamine tetraacetic acid solution is preferably 1 mol/L.
In the present invention, the molar ratio of the complexing agent to the total amount of metal ions in the first mixed solution is preferably 2.2 to 2.5: 1, more preferably 2.3 to 2.4: 1.
in the present invention, the second mixing is preferably performed under stirring, and the rotation speed of the stirring is preferably 300r/min, and the time is preferably 150 min.
In the invention, the reagent used for adjusting the pH value is preferably an ammonia water solution, and the concentration of the ammonia water solution is preferably 1 mol/L. In the invention, the pH value after the pH value adjustment is preferably 5-6. In the above pH range, precipitation during the second mixing can be prevented.
In the invention, the heating temperature is preferably 80-85 ℃, more preferably 82-88 ℃, and more preferably 83-87 ℃; the time is preferably 1300 min. In the present invention, the heating is preferably performed under stirring; the stirring speed is preferably 300 r/min. In the present invention, the heating can evaporate water to obtain a wet gel. In the present invention, the heating treatment is preferably performed in a constant temperature magnetic water bath.
After the wet gel is obtained, the wet gel is sequentially subjected to combustion treatment and roasting treatment to obtain the solid electrolyte.
The present invention also preferably includes drying the wet gel prior to the burning treatment. In the invention, the temperature of the drying treatment is preferably 100-150 ℃, more preferably 110-140 ℃, and more preferably 120-130 ℃; the time is preferably 12 to 15 hours, and more preferably 13 to 14 hours. The present invention does not require any particular drying process, and can be performed as is well known to those skilled in the art. In the present invention, the drying treatment is preferably performed in a constant temperature drying oven.
In the invention, the temperature of the combustion treatment is preferably 250-300 ℃, more preferably 260-290 ℃, and more preferably 270-280 ℃; the time is preferably 1-2 h. In the present invention, the rate of temperature increase to the combustion treatment temperature is preferably 1 ℃/min. In the present invention, the combustion treatment is preferably performed in a muffle furnace or an electric resistance furnace. In the present invention, the combustion treatment is preferably performed in air. In the present invention, the burning treatment is preferably performed by placing the dried gel into a crucible, and then placing the crucible in a muffle furnace or a resistance furnace for burning treatment. In the present invention, the combustion treatment can melt and combust the dried gel obtained by the drying treatment to release gas, so that the nitrate and the complex in the dried gel are decomposed to form oxide, and light yellow fluffy powder is obtained.
In the invention, the roasting treatment temperature is preferably 700-800 ℃, more preferably 720-780 ℃, and more preferably 740-760 ℃; the time is preferably 4 to 5 hours, more preferably 4.2 to 4.8 hours, and even more preferably 4.4 to 4.6 hours. In the present invention, the rate of temperature increase to the baking treatment temperature is preferably 5 ℃/min. In the present invention, the baking treatment is preferably performed in a muffle furnace. In the present invention, the calcination treatment is preferably carried out in air. In the present invention, the firing treatment enables the oxides formed during the combustion treatment to form a solid solution having a cubic fluorite structure.
After the roasting treatment is finished, the invention also preferably comprises the steps of cooling, grinding and sieving the material obtained by the roasting treatment. In the present invention, the temperature after the cooling is preferably room temperature. In the present invention, the grinding is preferably performed in an agate mortar. In the present invention, the mesh number of the sieve used for the sieving treatment is preferably 80 mesh. The cooling, grinding and sieving processes are not particularly limited in the present invention and may be those well known to those skilled in the art.
In the invention, the solid electrolyte prepared by the preparation method has the advantages of uniform components, high purity, small particle size, large specific surface area and high sintering activity, thereby further improving the conductivity of the solid electrolyte.
The invention also provides a solid electrolyte ceramic chip, wherein the preparation raw material of the solid electrolyte ceramic chip comprises solid electrolyte; the solid electrolyte is the solid electrolyte described in the above technical scheme or the solid electrolyte prepared by the preparation method described in the above technical scheme.
In the present invention, the raw material for preparing the solid electrolyte ceramic sheet preferably further includes a binder. In the present invention, the binder is preferably polyvinyl alcohol and/or polyvinyl butyral. In the present invention, the binder preferably accounts for 5 wt% of the solid electrolyte.
The invention also provides a preparation method of the solid electrolyte ceramic chip, which comprises the following steps:
and sequentially tabletting and sintering the preparation raw materials of the solid electrolyte ceramic chip to obtain the solid electrolyte ceramic chip.
Before the tabletting, the invention also preferably comprises the steps of premixing the preparation raw materials of the solid electrolyte ceramic chip and then granulating. In the present invention, the process of premixing preferably comprises: and premixing the solid electrolyte and the adhesive to obtain the electrolyte premix.
The process of premixing and granulating in the present invention has no special requirement, and the method is well known to those skilled in the art.
In the invention, the pressure of the tabletting is preferably 6-8 MPa, and more preferably 6-7 MPa; the time is preferably 1 min. In the present invention, the diameter of the circular thin piece obtained after the tabletting is preferably 15mm, and the thickness thereof is preferably 0.6 mm. In the present invention, the tableting is preferably carried out in a tableting machine. The tabletting process is not particularly limited in the present invention and may be any known process known to those skilled in the art.
After the tabletting is finished, the invention also preferably comprises the steps of sequentially carrying out cold isostatic pressing, glue discharging and heat preservation treatment on the round slices obtained by the tabletting. The present invention does not require any particular process for the cold isostatic pressing, and may be performed as is well known to those skilled in the art. In the invention, the temperature of the binder removal is preferably 30-550 ℃, more preferably 40-540 ℃, and more preferably 50-530 ℃; the time is preferably 600 min. In the present invention, the temperature of the heat-preserving treatment is preferably 550 ℃ and the time is preferably 5 hours.
In the invention, the sintering temperature is preferably 1250-1300 ℃, more preferably 1260-1290 ℃, and more preferably 1270-1280 ℃; the time is preferably 4 to 6 hours, and more preferably 5 hours. In the present invention, the heating rate for heating to the sintering temperature is preferably 2 to 5 ℃/min, and more preferably 3 to 4 ℃/min. After the sintering is finished, the invention also preferably comprises the step of cooling the ceramic wafer obtained by sintering to room temperature.
In order to further illustrate the present invention, the solid electrolyte and the method for preparing the same, the solid electrolyte ceramic sheet and the method for preparing the same according to the present invention will be described in detail with reference to the accompanying drawings and examples, which should not be construed as limiting the scope of the present invention.
Example 1
2.484g of Bi (NO)3)3·5H2Adding 10mL of 2mol/L nitric acid solution into the O, and mixing and dissolving to obtain a bismuth nitrate solution; according to the Ce: ca: and Bi is 0.95: 0.02: 0.03 mol ratio, 68.374g Ce (NO)3)3·6H2O、0.806g Ca(NO3)2·4H2Stirring and mixing O, bismuth nitrate solution and deionized water for 60min at the stirring speed of 300r/min to obtain first mixed solution with the concentration of 0.25 mol/L;
stirring and mixing 400mL of first mixed solution, 100mL of 1.5mol/L citric acid solution and 100mL of 1mol/L ethylene diamine tetraacetic acid solution at the stirring speed of 300r/min for 150min to obtain second mixed solution (the total amount of metal ions in the second mixed solution and the molar ratio of citric acid to ethylene diamine tetraacetic acid is 1: 1.5: 1), adjusting the pH value of the mixed solution to 6 by using 1mol/L ammonia water solution, transferring the mixed solution to a constant-temperature water bath, and stirring at 80 ℃ and the stirring speed of 300r/min for 1300min to obtain wet gel;
putting the wet gel into a drying box, drying at 150 ℃, putting the dry gel into a crucible, putting the crucible on a resistance furnace, heating to 250 ℃ at a heating rate of 1 ℃/min, and heating for 60min for combustion treatment; then the crucible is transferred to a muffle furnace, the temperature is raised to 800 ℃ at the temperature rise speed of 5 ℃/min, and the crucible is heated for 5 hours for roasting treatment. And after the roasting treatment is finished, naturally cooling the obtained material to room temperature. Then grinding the materials in an agate mortar, and sieving the ground materials through a 80-mesh sieve to obtain a solid electrolyte;
mixing 0.6g of solid electrolyte and 0.03g of polyvinyl alcohol, granulating, putting into a tablet machine, and tabletting under 6MPa to obtain a round sheet with the diameter of 15mm and the thickness of 0.6 mm; carrying out cold isostatic pressing treatment on the obtained round slice, heating at 550 ℃ for 600min for carrying out glue discharging treatment, preserving heat at 550 ℃ for 5h, and cooling to room temperature; and then heating the obtained round slice to 1250 ℃ at the heating rate of 2 ℃/min in a muffle furnace, and preserving heat for 5 hours at 1250 ℃ for sintering treatment to obtain the solid electrolyte ceramic chip.
Example 2
2.557g of Bi (NO)3)3·5H2Adding 10mL of 2mol/L nitric acid solution into the O, and mixing and dissolving to obtain a bismuth nitrate solution; according to the Ce: dy: ca: and Bi is 0.9: 0.05: 0.02: 0.03 mol ratio, 66.992g Ce (NO)3)3·6H2O、0.83g Ca(NO3)2·4H2O、3.979g Dy(NO3)3·6H2Stirring and mixing O, bismuth nitrate solution and deionized water for 60min at the stirring speed of 300r/min to obtain first mixed solution with the concentration of 0.25 mol/L;
stirring and mixing 400mL of first mixed solution, 100mL of 1.5mol/L citric acid solution and 100mL of 1mol/L ethylene diamine tetraacetic acid solution at the stirring speed of 300r/min for 150min to obtain second mixed solution (the total amount of metal ions in the second mixed solution and the molar ratio of citric acid to ethylene diamine tetraacetic acid is 1: 1.5: 1), adjusting the pH value of the mixed solution to 6 by using 1mol/L ammonia water solution, transferring the mixed solution to a constant-temperature water bath, and stirring at the stirring speed of 300r/min at 80 ℃ for 1300min to obtain wet gel;
putting the wet gel into a drying box, drying at 150 ℃, putting the dry gel into a crucible, putting the crucible on a resistance furnace, heating to 250 ℃ at a heating rate of 1 ℃/min, and heating for 60min for combustion treatment; then the crucible is transferred to a muffle furnace, the temperature is raised to 800 ℃ at the temperature rise speed of 5 ℃/min, and the crucible is heated for 5 hours for roasting treatment. And after the roasting treatment is finished, naturally cooling the obtained material to room temperature. Then grinding the materials in an agate mortar, and sieving the ground materials through a 80-mesh sieve to obtain a solid electrolyte;
mixing 0.6g of solid electrolyte and 0.03g of polyvinyl alcohol, granulating, putting into a tablet press, tabletting under 6MPa to obtain a round sheet with the diameter of 15mm and the thickness of 0.6mm, carrying out cold isostatic pressing treatment on the round sheet, heating at 550 ℃ for 600min for carrying out glue removal treatment, keeping the temperature at 550 ℃ for 5h, and cooling to room temperature; and then heating the obtained round slice to 1250 ℃ at the heating rate of 5 ℃/min in a muffle furnace, and preserving heat for 5 hours at 1250 ℃ for sintering treatment to obtain the solid electrolyte ceramic chip.
Example 3
2.519g of Bi (NO)3)3·5H2Adding 10mL of 2mol/L nitric acid solution into the O, and mixing and dissolving to obtain a bismuth nitrate solution; according to the Ce: dy: ca: and Bi is 0.85: 0.10: 0.02: 0.03 mol ratio, 62.819g Ce (NO)3)3·6H2O、0.825g Ca(NO3)2·4H2O、8.399g Dy(NO3)3·6H2O, bismuth nitrate solution and deionized water, then adding a proper amount of deionized water, stirring and mixing for 60min at the stirring speed of 300r/min to obtain first mixed solution with the concentration of 0.25 mol/L;
stirring and mixing 400mL of first mixed solution, 100mL of 1.5mol/L citric acid solution and 100mL of 1mol/L ethylene diamine tetraacetic acid solution at the stirring speed of 300r/min for 150min to obtain second mixed solution (the total amount of metal ions in the second mixed solution and the molar ratio of citric acid to ethylene diamine tetraacetic acid is 1: 1.5: 1), adjusting the pH value of the mixed solution to 6 by using 1mol/L ammonia water solution, transferring the mixed solution to a constant-temperature water bath, and stirring at the stirring speed of 300r/min at 80 ℃ for 1300min to obtain wet gel;
putting the wet gel into a drying box, drying at 150 ℃, putting the dry gel into a crucible, putting the crucible on a resistance furnace, heating to 250 ℃ at a heating rate of 1 ℃/min, and heating for 60min for combustion treatment; then the crucible is transferred to a muffle furnace, the temperature is raised to 800 ℃ at the temperature rise speed of 5 ℃/min, and the crucible is heated for 5 hours for roasting treatment. And after the roasting treatment is finished, naturally cooling the obtained material to room temperature. Then grinding the materials in an agate mortar, and sieving the ground materials through a 80-mesh sieve to obtain a solid electrolyte;
mixing 0.6g of solid electrolyte and 0.03g of polyvinyl alcohol, granulating, putting into a tablet press, tabletting under 6MPa to obtain a round sheet with the diameter of 15mm and the thickness of 0.6mm, carrying out cold isostatic pressing treatment on the round sheet, heating at 550 ℃ for 600min for carrying out glue removal treatment, keeping the temperature at 550 ℃ for 5h, and cooling to room temperature; and then heating the obtained round slice to 1250 ℃ at the heating rate of 5 ℃/min in a muffle furnace, and preserving heat for 5 hours at 1250 ℃ for sintering treatment to obtain the solid electrolyte ceramic chip.
Example 4
2.484g of Bi (NO)3)3·5H2Adding 10mL of 2mol/L nitric acid solution into the O, and mixing and dissolving to obtain a bismuth nitrate solution; according to Ce: dy: ca: bi ═ 0.8: 0.15: 0.02: 0.03 mol ratio, 58.802g Ce (NO)3)3·6H2O、0.821g Ca(NO3)2·4H2O、11.792g Dy(NO3)3·6H2Stirring and mixing O, bismuth nitrate solution and deionized water for 60min at the stirring speed of 300r/min to obtain first mixed solution with the concentration of 0.25 mol/L;
stirring and mixing 400mL of first mixed solution, 100mL of 1.5mol/L citric acid solution and 100mL of 1mol/L ethylene diamine tetraacetic acid solution at the stirring speed of 300r/min for 150min to obtain second mixed solution (the total amount of metal ions in the second mixed solution and the molar ratio of citric acid to ethylene diamine tetraacetic acid is 1: 1.5: 1), adjusting the pH value of the mixed solution to 6 by using 1mol/L ammonia water solution, transferring the mixed solution to a constant-temperature water bath, and stirring at the stirring speed of 300r/min at 80 ℃ for 1300min to obtain wet gel;
putting the wet gel into a drying box, drying at 150 ℃, putting the dry gel into a crucible, putting the crucible on a resistance furnace, heating to 250 ℃ at a heating rate of 1 ℃/min, and heating for 60min for combustion treatment; then the crucible is transferred to a muffle furnace, the temperature is raised to 800 ℃ at the temperature rise speed of 5 ℃/min, and the crucible is heated for 5 hours for roasting treatment. And after the roasting treatment is finished, naturally cooling the obtained material to room temperature. Then grinding the materials in an agate mortar, and sieving the ground materials through a 80-mesh sieve to obtain a solid electrolyte;
mixing 0.6g of solid electrolyte and 0.03g of polyvinyl alcohol, granulating, putting into a tablet press, tabletting under 6MPa to obtain a round sheet with the diameter of 15mm and the thickness of 0.6mm, carrying out cold isostatic pressing treatment on the round sheet, heating at 550 ℃ for 600min for carrying out glue removal treatment, keeping the temperature at 550 ℃ for 5h, and cooling to room temperature; and then heating the obtained round slice to 1250 ℃ at the heating rate of 5 ℃/min in a muffle furnace, and preserving heat for 5 hours at 1250 ℃ for sintering treatment to obtain the solid electrolyte ceramic chip.
Example 5
2.484g of Bi (NO)3)3·5H2Adding 10mL of 2mol/L nitric acid solution into the O, and mixing and dissolving to obtain a bismuth nitrate solution; according to the Ce: dy: ca: and Bi is 0.75: 0.20: 0.02: 0.03 mol ratio, 55.127g Ce (NO)3)3·6H2O、0.821g Ca(NO3)2·4H2O、15.707g Dy(NO3)3·6H2Stirring and mixing O, bismuth nitrate solution and deionized water for 60min at the stirring speed of 300r/min to obtain first mixed solution with the concentration of 0.25 mol/L;
stirring and mixing 400mL of first mixed solution, 100mL of 1.5mol/L citric acid solution and 100mL of 1mol/L ethylene diamine tetraacetic acid solution at a stirring speed of 300r.min for 150min to obtain second mixed solution (the total amount of metal ions in the second mixed solution and the molar ratio of citric acid to ethylene diamine tetraacetic acid is 1: 1.5: 1), adjusting the pH value of the mixed solution to 6 by using 1mol/L ammonia water solution, transferring the mixed solution to a constant-temperature water bath, and stirring at a stirring speed of 300r/min at 80 ℃ for 1300min to obtain wet gel;
putting the wet gel into a drying box, drying at 150 ℃, putting the dry gel into a crucible, putting the crucible on a resistance furnace, heating to 250 ℃ at a heating rate of 1 ℃/min, and heating for 60min for combustion treatment; then the crucible is transferred to a muffle furnace, the temperature is raised to 800 ℃ at the temperature rise speed of 5 ℃/min, and the crucible is heated for 5 hours for roasting treatment. And after the roasting treatment is finished, naturally cooling the obtained material to room temperature. Then grinding the materials in an agate mortar, and sieving the ground materials through a 80-mesh sieve to obtain a solid electrolyte;
mixing 0.6g of solid electrolyte and 0.03g of polyvinyl alcohol, granulating, putting into a tablet press, tabletting under 6MPa to obtain a round sheet with the diameter of 15mm and the thickness of 0.6mm, carrying out cold isostatic pressing treatment on the round sheet, heating at 550 ℃ for 600min for carrying out glue removal treatment, keeping the temperature at 550 ℃ for 5h, and cooling to room temperature; and then heating the obtained round slice to 1250 ℃ at the heating rate of 5 ℃/min in a muffle furnace, and preserving heat for 5 hours at 1250 ℃ for sintering treatment to obtain the solid electrolyte ceramic chip.
Performance testing
Test example 1
XRD (X-ray diffraction) tests are carried out on the solid electrolytes obtained in the embodiments 1-5, the test results are shown in figure 1, and as can be seen from figure 1, the solid electrolyte provided by the invention is of a cubic fluorite structure and is of a pure-phase structure without impurity phase generation, which shows that CaO and Bi2O3And Dy2O3Has been solid-solubilized to CeO2In the crystal lattice of (1).
Test example 2
The solid electrolyte ceramic sheets obtained in examples 1 to 5 were subjected to an ac impedance test, and the test method was: silver wires are led out from two sides of the solid electrolyte ceramic sheet and are connected with an IM6 electrochemical workstation, the alternating current impedance spectrum of the electrolyte sheet is tested at 500-700 ℃ under the air atmosphere, the test interval is 50 ℃, and the test frequency range is 0.01-106Hz, AC amplitude 10 mV. The test results are shown in FIGS. 2 to 6 and Table 1;
table 1 results of ac impedance test of solid electrolyte ceramic sheets obtained in examples 1 to 5
As can be seen from fig. 2 to 6 and table 1, as the test temperature increases, the resistance value of the solid electrolyte ceramic sheet provided by the present invention gradually decreases, and the ionic conductivity increases, because as the test temperature increases, the energy of the carriers in the solid electrolyte ceramic sheet increases, so that the probability of the carriers migrating across the potential barrier increases, and the ionic conductivity increases. And in a low-temperature area, a semicircle and a ray appear in the alternating-current impedance test chart, wherein the semicircle represents the grain boundary process of the electrolyte, and the ray corresponds to the interface process of the electrode/the electrolyte. The semicircle corresponding to the crystal boundary process is gradually reduced along with the rise of the test temperature, and the ray corresponding to the electrode/electrolyte interface process is gradually bent downwards to be shown as a sunken semicircle, which indicates that the electric conduction process of the system is gradually controlled by the electrode/electrolyte interface process after the temperature rises.
Test example 3
The electric conductivity was calculated for the solid electrolyte ceramic sheets obtained in examples 1 to 5 by the formula σ ═ L/RS, where L is the thickness of the solid electrolyte ceramic sheet, S is the electrode area, and R is the sum of the crystal grain and grain boundary resistance. The calculation results are shown in fig. 7 and table 2.
Table 2 conductivity of solid electrolyte ceramic sheets obtained in examples 1 to 5
As can be seen from fig. 7 and table 2: in the test temperature range of 500-700 ℃, the conductivity of the solid electrolyte ceramic chip provided by the invention is in positive correlation with the temperature, and the conductivity is increased when the temperature is increased because the migration capability of oxygen vacancies is enhanced after the temperature is increased on one hand, and the positively charged oxygen vacancies (V') exist in the Dy-doped cerium oxide material on the other handO) And negatively charged dopant ion (Dy'Ce) In the low temperature region, Coulomb attraction is generated between them to form oxygen vacancy cluster (V'O...Dy′Ce) The concentration of oxygen vacancies capable of freely moving is reduced, and only free oxygen vacancies are effective conductive carriers, so the conductivity is low; in the high-temperature region, as the movement of ions is increased, the oxygen vacancy clusters are dissociated and become independent and independent bodies, so that the concentration of free oxygen vacancies is increased, and the conductivity is increased.
Test example 4
The thermal expansion coefficient of the solid electrolyte obtained in examples 1 to 5 was measured by using a thermal expansion meter, in which the electrolyte powder was compressed into a rectangular solid of 5mm × 5mm × 25mm, sintered at 1250 ℃ for 5 hours in a muffle furnace, polished and ultrasonically cleaned, and then measured by using an L75HS1600C thermal expansion meter under the conditions of room temperature rising to 800 ℃, a rising rate of 5 ℃/min, and the measurement results are shown in table 3.
TABLE 3 results of measuring thermal expansion coefficients of solid electrolytes obtained in examples 1 to 5
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Coefficient of thermal expansion/K-1 | 10.95×10-6 | 11.33×10-6 | 11.50×10-6 | 11.42×10-6 | 11.39×10-6 |
As can be seen from Table 3, the coefficient of thermal expansion of the solid electrolyte ceramic sheet provided by the present invention is similar to that of the conventional CeO2The base electrolyte material is similar to the average expansion coefficient of conventional cathode and anode materials.
Although the above embodiments have been described in detail, they are only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and all of the embodiments belong to the protection scope of the present invention.
Claims (10)
1. A solid electrolyte characterized in that the solid electrolyte has a chemical formula of Ce0.98-x-yRExM0.02BiyO2-δ；
The RE is one or more of Dy, La, Nd, Pr, Gd, Sm, Y and Yb;
the M is Ca and/or Sr;
the value range of x is more than or equal to 0 and less than or equal to 0.20, and the value range of y is more than or equal to 0.01 and less than or equal to 0.05;
the Ce0.98-x-yRExM0.02BiyO2-δIs zero.
2. The method for producing a solid electrolyte according to claim 1, comprising the steps of:
according to the Ce: RE: m: bi ═ (0.98-x-y): x: 0.02: y, carrying out first mixing on a cerium-containing compound, a RE-containing compound, an M-containing compound, a bismuth-containing compound and water to obtain a first mixed solution; wherein x is greater than or equal to 0 and less than or equal to 0.20, and y is greater than or equal to 0.01 and less than or equal to 0.05;
secondly, mixing the first mixed solution and a complexing agent, adjusting the pH value, and heating to obtain wet gel;
and sequentially carrying out combustion treatment and roasting treatment on the wet gel to obtain the solid electrolyte.
3. The method of claim 2, wherein the complexing agent comprises citric acid and/or ethylenediaminetetraacetic acid.
4. The method according to claim 2, wherein the concentration of the metal ions in the first mixed solution is 0.20 to 0.50 mol/L.
5. The method according to any one of claims 2 to 4, wherein a molar ratio of the amount of the complexing agent to the total amount of the metal ions in the first mixed solution is 2.2 to 2.5: 1.
6. the preparation method according to claim 2, wherein the temperature of the combustion treatment is 250 to 300 ℃ and the time is 1 to 2 hours;
the roasting treatment temperature is 700-800 ℃, and the roasting treatment time is 4-5 h.
7. The solid electrolyte ceramic chip is characterized in that the preparation raw material of the solid electrolyte ceramic chip comprises a solid electrolyte;
the solid electrolyte is the solid electrolyte as defined in claim 1 or the solid electrolyte prepared by the preparation method as defined in any one of claims 2 to 6.
8. The solid electrolyte ceramic sheet according to claim 7, wherein the raw material for producing the solid electrolyte ceramic sheet further comprises a binder;
the binder comprises polyvinyl alcohol and/or polyvinyl butyral;
the binder comprises 5 wt% of the solid electrolyte.
9. The method of manufacturing a solid electrolyte ceramic sheet according to claim 7 or 8, comprising the steps of:
and sequentially tabletting and sintering the preparation raw materials of the solid electrolyte ceramic chip to obtain the solid electrolyte ceramic chip.
10. The preparation method according to claim 9, wherein the sintering temperature is 1250-1300 ℃ and the sintering time is 4-6 h.
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