CN114122509A - Ceramic oxide solid electrolyte and preparation method thereof - Google Patents
Ceramic oxide solid electrolyte and preparation method thereof Download PDFInfo
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 39
- 239000000919 ceramic Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000654 additive Substances 0.000 claims abstract description 42
- 239000002994 raw material Substances 0.000 claims abstract description 42
- 239000000843 powder Substances 0.000 claims abstract description 40
- 230000000996 additive effect Effects 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 35
- 238000005245 sintering Methods 0.000 claims abstract description 27
- 238000001354 calcination Methods 0.000 claims abstract description 20
- 238000000498 ball milling Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 11
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 27
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002228 NASICON Substances 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- ASTWEMOBIXQPPV-UHFFFAOYSA-K trisodium;phosphate;dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[Na+].[O-]P([O-])([O-])=O ASTWEMOBIXQPPV-UHFFFAOYSA-K 0.000 claims description 5
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 4
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 150000004673 fluoride salts Chemical group 0.000 claims description 3
- 239000011698 potassium fluoride Substances 0.000 claims description 3
- 235000003270 potassium fluoride Nutrition 0.000 claims description 3
- 239000011775 sodium fluoride Substances 0.000 claims description 3
- 235000013024 sodium fluoride Nutrition 0.000 claims description 3
- 239000002223 garnet Substances 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 32
- 238000005303 weighing Methods 0.000 abstract description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 4
- 150000002222 fluorine compounds Chemical group 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000047 product Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material 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
- 229910052574 oxide ceramic Inorganic materials 0.000 description 2
- 239000011224 oxide ceramic Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 229910003249 Na3Zr2Si2PO12 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a ceramic oxide solid electrolyte and a preparation method thereof, and relates to the technical field of electrolytes. The preparation method of the ceramic oxide solid electrolyte is prepared by main raw materials and additives, and comprises the following steps: mixing and calcining the main raw materials to obtain intermediate powder, and mixing and sintering the intermediate powder and an additive; wherein the additive is fluoride, and the mass ratio of the additive to the intermediate powder is 0.1-10: 100. By introducing the additive for sintering after the main raw materials are calcined, the precision requirement on raw material weighing and the process cost of ball milling are reduced, and more importantly: by selecting the types of the additives and adjusting the dosage, the aim of obviously improving the ionic conductivity can be achieved on the premise of adding a little proportion of fluoride, and the method is a simple and efficient process.
Description
Technical Field
The invention relates to the technical field of electrolytes, in particular to a ceramic oxide solid electrolyte and a preparation method thereof.
Background
The battery plays a very important role in energy storage and electric vehicles, but as casualties caused by fire and explosion of the traditional battery occur occasionally, the improvement of the safety of the battery becomes one of the most urgent tasks in the field of battery development. The solid-state battery is one of the most important directions of current battery development, the solid-state electrolyte used by the solid-state battery is nonflammable, and the solid-state battery has ultrahigh safety, and can simultaneously enable the battery to have higher energy density and safety by matching with a metal cathode.
The bottleneck of the current development of the solid-state battery is not only the problem of poor interface effective fusion, but also the low ionic conductivity of the electrolyte is one of the important bottlenecks which hinder the performance of the battery, and the high ionic conductivity can greatly reduce the internal resistance of the battery and enhance the multiplying power and the cycle performance of the battery. However, at present, the ionic conductivity of most solid electrolytes still stays at 1 × 10-4On the order of S/cm, the overall resistance of the electrolyte is approximately 200-300 ohms, and even in the kilo-ohm range for electrolytes of the non-mainstream type, electrolytes of this nature are difficult to use as components of commercial batteries.
At present, the process for improving the performance of the solid electrolyte is limited, and most of the processes use a doping method to improve the intrinsic ionic conductivity of the electrolyte. However, the doping has high process requirements, the doping raw material needs to be mixed with the raw material after calculating the accurate mass of the doping raw material before the weighing stage, and part of the processes need to ball mill the doping raw material and the substituted raw material in advance to form solid solution of two phases, which increases the complexity and time cost of the synthesis process.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a ceramic oxide solid electrolyte and a preparation method thereof, aiming at simplifying synthesis and doping processes and obviously reducing the resistance of the electrolyte under the condition of lower additive dosage.
The invention is realized by the following steps:
in a first aspect, the present invention provides a method for preparing a ceramic oxide solid electrolyte, which is prepared from main raw materials and additives, comprising: mixing and calcining the main raw materials to obtain intermediate powder, and mixing and sintering the intermediate powder and an additive;
wherein the additive is fluoride, and the mass ratio of the additive to the intermediate powder is 0.1-10: 100.
In an alternative embodiment, the additive is selected from at least one of magnesium fluoride, calcium fluoride, sodium fluoride, and potassium fluoride; preferably magnesium fluoride.
In an optional embodiment, the mass ratio of the additive to the intermediate powder is 1-3: 100; preferably 1-2: 100.
In an alternative embodiment, the intermediate powder and the additive are mixed and ball-milled, and then are sintered after being compression molded.
In an optional embodiment, the sintering temperature is 1100-1300 ℃, and the sintering time is 10-15 h;
preferably, the sintering temperature is 1150-1250 ℃ and the sintering time is 11-13 h.
In an alternative embodiment, the process for preparing the intermediate powder comprises: mixing, ball-milling and calcining the main raw materials, and then carrying out ball-milling again;
preferably, the particle size of the intermediate powder is 2-20 microns.
In an optional embodiment, the calcination temperature is 1000-;
preferably, the calcination temperature is 1050-.
In an alternative embodiment, the main raw materials are mixed by ball milling for 0.5-2 h.
In an alternative embodiment, the main raw material is selected according to the kind of the ceramic oxide solid electrolyte to be prepared;
preferably, the type of the ceramic oxide solid electrolyte is at least one of NASICON type solid electrolyte and garnet type LLZO;
more preferably, the main raw materials comprise, by mass, 31.5-33.1 parts of sodium phosphate dodecahydrate, 18.0-20.0 parts of silicon dioxide, 33.6-34.1 parts of zirconium dioxide and 11.6-12.8 parts of sodium carbonate.
In a second aspect, the present invention provides a ceramic oxide solid electrolyte prepared by the method of any one of the preceding embodiments.
The invention has the following beneficial effects: by introducing the additive for sintering after the main raw materials are calcined, the requirements on the weighing accuracy of the raw materials and the process cost of ball milling are reduced, and more importantly: by selecting the types of the additives and adjusting the dosage, the aim of obviously reducing the total impedance can be achieved on the premise of adding a little proportion of fluoride, and the method is a simple and efficient process.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a graph comparing EIS test results for NASICON electrolyte with magnesium fluoride added and commercial NASICON;
FIG. 2 is a scanning electron micrograph of a NASICON sample with magnesium fluoride added;
FIG. 3 is a scanning electron micrograph of a commercially available electrolyte.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In the prior art, the doping raw materials are generally mixed and calcined together with the main raw materials, the mass of the doping raw materials needs to be accurately calculated before a weighing stage, and a multi-step ball milling process exists in the process, so that the synthesis process is complicated and the time cost is high. Aiming at the problems in the prior art, the inventor changes the adding time of the additive, optimizes the type and the adding amount of the additive and provides a simple and efficient preparation process.
The embodiment of the invention provides a preparation method of a ceramic oxide solid electrolyte, which is prepared from main raw materials and additives and comprises the following steps:
s1 calcination
Mixing and calcining the main raw materials to obtain intermediate powder, and decomposing the raw materials by calcining to obtain corresponding oxides. In the actual operation process, the preparation process of the intermediate powder comprises the following steps: mixing and calcining the main raw materials, and performing ball milling to obtain powder with the particle size meeting the requirement, wherein the particle size of the intermediate powder can be 2-20 microns.
The main raw materials are selected according to the types of the prepared ceramic oxide solid electrolytes, the main raw materials corresponding to different types of ceramic oxide solid electrolytes are different, and the preparation process of the general type of ceramic oxide solid electrolytes is suitable for the preparation method provided by the embodiment of the invention. The composition of the main raw materials of the different types of ceramic oxide solid electrolytes is prior art and is not limited herein.
In some embodiments, the type of ceramic oxide solid state electrolyte may be a NASICON type solid state electrolyte; the main raw materials comprise, by mass, 31.5-33.1 parts of sodium phosphate dodecahydrate, 18.0-20.0 parts of silicon dioxide, 33.6-34.1 parts of zirconium dioxide and 11.6-12.8 parts of sodium carbonate. The NASICON type solid electrolyte is prepared from the main raw materials, the performance of the obtained electrolyte product is very excellent, and the total impedance can be remarkably reduced.
In some embodiments, the calcination temperature is 1000-; preferably, the calcination temperature is 1050-. By controlling the calcination temperature and the calcination time, the raw materials can be sufficiently decomposed to obtain the corresponding oxides.
Specifically, the calcination temperature may be 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃, or the like, or may be any value between the above adjacent temperature values; the calcination time may be 10h, 11h, 12h, 13h, 14h, 15h, or the like, or may be any value between the above adjacent time values.
In some embodiments, the main raw materials are mixed by ball milling, the ball milling time is 0.5-2h, such as 0.5h, 1h, 1.5h, 2h, etc., or any value between the above adjacent time values, and the ball milling can be performed by using large balls, and the amplitude is controlled to be about 0.1 mm.
S2, sintering
Mixing and sintering the intermediate powder and the additive; wherein the additive is fluoride, and the mass ratio of the additive to the intermediate powder is 0.1-10: 100. The performance of the oxide ceramic electrolyte can be further improved by selecting specific types of additives and controlling the amount.
Specifically, the mass ratio of the additive to the intermediate powder may be 0.1:100, 0.5:100, 1.0:100, 2.0:100, 3.0:100, 4.0:100, 5.0:100, 6.0:100, 7.0:100, 8.0:100, 9.0:100, 10:100, or the like, or may be any value between the above adjacent ratios.
In a preferred embodiment, the mass ratio of the additive to the intermediate powder is 1-3: 100; more preferably 1-2: 100.
The additive can be general fluoride, and the performance of the electrolyte can be greatly improved. In some embodiments, the additive is selected from at least one of magnesium fluoride, calcium fluoride, sodium fluoride, and potassium fluoride; preferably magnesium fluoride. The magnesium fluoride is adopted as the additive, so that the performance of the electrolyte can be obviously improved under the condition of extremely small using amount.
In the actual operation process, the intermediate powder and the additive are mixed and ball-milled, and then are sintered after being pressed and formed, so that the electrolytic sheet with the density meeting the requirement and a specific shape is obtained.
Further, the sintering temperature is 1100-1300 ℃, and the sintering time is 10-15 h; in a preferred embodiment, the sintering temperature is 1150-1250 ℃ and the sintering time is 11-13 h. Specifically, the sintering temperature may be 1100 ℃, 1150 ℃, 1200 ℃, 1250 ℃, 1300 ℃ and the like, and the sintering time may be 10h, 11h, 12h, 13h, 14h, 15h and the like.
The magnesium fluoride is a fluxing agent for manufacturing ceramics, metals and glass, has a melting point of 1261 ℃, is close to a sintering temperature range of a ceramic solid electrolyte, and can play a role in liquid-phase auxiliary sintering in the sintering process, so that the compactness of the ceramics is enhanced, and the grain boundary resistance is reduced. Meanwhile, magnesium ions diffuse in electrolyte lattices to play a certain aliovalent doping effect. The inventor researches show that the above two aspects are main reasons that magnesium fluoride can enhance the performance of the oxide ceramic electrolyte.
The embodiment of the invention provides a ceramic oxide solid electrolyte which is prepared by the preparation method and has the advantages of low cost, low total impedance and the like.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a preparation method of a ceramic oxide solid electrolyte, which is prepared from a main raw material of a NASICON solid electrolyte and a magnesium fluoride additive, and comprises the following steps:
3.5570g of sodium phosphate dodecahydrate, 2.1418g of silicon dioxide, 3.6605g of zirconium dioxide and 1.3853g of sodium carbonate are weighed, the main raw materials are mixed and ground for 1 hour by using a large ball mill with the amplitude of 0.1mm, the uniformly ground powder is put into an alumina crucible and calcined at 1100 ℃ for 12 hours, the obtained product is ground by using the large ball mill with the same amplitude for 30 minutes, and white mother powder with uniform particles is obtained.
Weighing a certain mass of white mother powder, adding magnesium fluoride powder according to the proportion of 1 wt%, ball-milling for 30 minutes, pressing the uniformly mixed mother powder into a disc shape by using a mold under the axial pressure of 700MPa, putting the disc shape into a crucible, and sintering for 12 hours at 1200 ℃ to obtain the electrolyte sheet of the white ceramic oxide.
Example 2
This example provides a method for preparing a ceramic oxide solid electrolyte,with Na3Zr2Si2PO12The preparation method of the main raw material and the magnesium fluoride additive of the solid electrolyte comprises the following steps:
8.2393g of sodium phosphate dodecahydrate, 4.64508g of zirconium dioxide and 2.2649g of silicon dioxide are weighed, the main raw materials are mixed and ground by a large ball mill with the amplitude of 0.1mm for 1 hour, the uniformly ground powder is put into an alumina crucible and calcined at 1100 ℃ for 12 hours, the obtained product is ground by the large ball mill with the same amplitude for 30 minutes, and white mother powder with uniform particles is obtained.
Weighing a certain mass of white mother powder, adding magnesium fluoride powder according to the proportion of 1 wt%, ball-milling for 30 minutes, pressing the uniformly mixed mother powder into a disc shape by using a mold under the axial pressure of 700MPa, putting the disc shape into a crucible, and sintering for 12 hours at 1200 ℃ to obtain the electrolyte sheet of the white ceramic oxide.
Example 3
This example provides a method for preparing a ceramic oxide solid electrolyte, which differs from example 1 only in that: magnesium fluoride is replaced by calcium fluoride.
Example 4
This example provides a method for preparing a ceramic oxide solid electrolyte, which differs from example 1 only in that: magnesium fluoride was added in a mass ratio of 1 wt%.
Example 5
This example provides a method for preparing a ceramic oxide solid electrolyte, which differs from example 1 only in that: magnesium fluoride was added in a mass ratio of 3 wt%.
Example 6
This example provides a method for preparing a ceramic oxide solid electrolyte, which differs from example 1 only in that: magnesium fluoride was added in a mass ratio of 0.1 wt%.
Comparative example 1
This comparative example provides a method of preparing a ceramic oxide solid electrolyte, differing from example 1 only in that: magnesium fluoride was not added.
Comparative example 2
This comparative example provides a method of preparing a ceramic oxide solid electrolyte, differing from example 1 only in that: magnesium fluoride was replaced with sodium silicate.
Comparative example 3
This comparative example provides a method of preparing a ceramic oxide solid electrolyte, differing from example 1 only in that: magnesium fluoride was added in a mass ratio of 5 wt%.
Comparative example 4
This comparative example provides a method of preparing a ceramic oxide solid electrolyte, differing from example 1 only in that: magnesium fluoride was added in a mass ratio of 20 wt%.
Test example 1
The two sides of the electrolyte sheet prepared in example 1 were vacuum evaporated with silver electrodes, and the impedance curve of the electrolyte was measured by Electrochemical Impedance Spectroscopy (EIS) technique at a frequency of 1Hz to 1 MHz. The data obtained were fitted using Zview software and compared with commercially available powder electrolyte. The results are shown in FIG. 1.
As can be seen from fig. 1, the addition of 1 wt% magnesium fluoride reduced the grain resistance of the sample to 33.49 ohms, the grain boundary resistance to 20.04 ohms, and the total resistance to 53.53 ohms. The total resistance of the commercially available powder electrolyte was tested in the same test procedure and was 256.64 ohms, with the added magnesium fluoride sample having a resistance of only 20.85% of that of the common commercial powder.
It should be added that the commercially available powder electrolyte contains Na as a component3Zr2Si2PO12。
Test example 2
The cross section of the electrolyte sample obtained in the example 1 is observed through a scanning electron microscope, the fracture surface is a cleavage surface, and fig. 2 shows that the sample added with magnesium fluoride has large particles, the particles are in close contact with each other, no obvious holes exist, and relatively small grain boundary resistance is provided for the material; the fracture surface has dimple fracture, which shows that the material has good plasticity and higher mechanical strength.
FIG. 3 shows a scanning electron micrograph of a sample of a commercially available electrolyte in test example 1. It can be seen that: the grain size of the commercial product is small, the contact between the grains is insufficient, and more holes exist, so the grain boundary resistance is large, and the ionic conductivity is low. The fracture surface has no obvious dimple fracture, has poor toughness and is easy to be broken when being processed into a battery.
The ionic conductivity of the electrolyte added with magnesium fluoride in example 1 can reach 1.8 × 10 by calculating the ionic conductivity formula, wherein σ is (1/R) × (L/S)-3S/cm, and the conductivity of the electrolyte which is generally commercially available at present is only 3X 10-4S/cm, performance six times that of the commercially available electrolyte.
Test example 3
The performance of the electrolyte products obtained in examples 2 to 6 and comparative examples 1 to 3 was tested, and the impedance data obtained in examples 4 to 6 were 61.69 ohm, 79.67 ohm, and 92.82 ohm, respectively. Comparative examples 1-4 gave impedance data of 460.9 ohms, 392 ohms, 275.3 ohms, 1185 ohms, respectively.
In summary, the invention provides a ceramic oxide solid electrolyte and a preparation method thereof, which changes the adding time of the additive, improves the types of the additive and the dosage of the additive in the preparation process of the solid electrolyte, reduces the requirements on the weighing accuracy of the raw materials and the process cost of ball milling by introducing the additive for sintering after the main raw materials are calcined, and more importantly: by selecting the types and the dosage of the additives, the aim of remarkably reducing the total impedance can be achieved on the premise of adding a little proportion of fluoride.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a ceramic oxide solid electrolyte is characterized by comprising the following steps of: mixing and calcining main raw materials to obtain intermediate powder, and mixing and sintering the intermediate powder and the additive;
wherein the additive is fluoride, and the mass ratio of the additive to the intermediate powder is 0.1-10: 100.
2. The production method according to claim 1, wherein the additive is selected from at least one of magnesium fluoride, calcium fluoride, sodium fluoride, and potassium fluoride; preferably magnesium fluoride.
3. The preparation method according to claim 2, wherein the mass ratio of the additive to the intermediate powder is 1-3: 100; preferably 1-2: 100.
4. The method according to any one of claims 1 to 3, wherein the intermediate powder and the additive are mixed, ball-milled, and then compression-molded and then sintered.
5. The method as claimed in claim 4, wherein the sintering temperature is 1100-1300 ℃, and the sintering time is 10-15 h;
preferably, the sintering temperature is 1150-1250 ℃ and the sintering time is 11-13 h.
6. The preparation method according to claim 1, wherein the preparation process of the intermediate powder comprises: mixing, ball-milling and calcining the main raw materials, and then carrying out ball-milling again; preferably, the particle size of the intermediate powder is 2-20 microns.
7. The method as claimed in claim 6, wherein the calcination temperature is 1000-1200 ℃, and the calcination time is 10-15 h;
preferably, the calcination temperature is 1050-.
8. The preparation method of claim 6, wherein the main raw materials are mixed by ball milling for 0.5-2 h.
9. The production method according to claim 7, wherein the main raw material is selected according to the kind of the ceramic oxide solid electrolyte to be produced;
preferably, the type of the ceramic oxide solid electrolyte is at least one of NASICON type and garnet type LLZO;
more preferably, the main raw materials comprise, by mass, 31.5-33.1 parts of sodium phosphate dodecahydrate, 18.0-20.0 parts of silicon dioxide, 33.6-34.1 parts of zirconium dioxide and 11.6-12.8 parts of sodium carbonate.
10. A ceramic oxide solid electrolyte prepared by the production method according to any one of claims 1 to 9.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
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| CN202111421365.8A CN114122509A (en) | 2021-11-26 | 2021-11-26 | Ceramic oxide solid electrolyte and preparation method thereof |
| PCT/CN2022/072698 WO2023092844A1 (en) | 2021-11-26 | 2022-01-19 | Ceramic oxide solid-state electrolyte and preparation method therefor |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104591231A (en) * | 2013-10-31 | 2015-05-06 | 中国科学院上海硅酸盐研究所 | Fluorine-containing garnet-structure lithium ion oxide ceramic |
| CN107732295A (en) * | 2017-10-12 | 2018-02-23 | 燕山大学 | A kind of solid oxide electrolyte and its low-temperature sintering method based on halogenation lithium doping |
| CN110247105A (en) * | 2018-03-07 | 2019-09-17 | 重庆市科学技术研究院 | A kind of preparation method improving solid electrolyte consistency |
| CN110581312A (en) * | 2019-08-07 | 2019-12-17 | 广东工业大学 | High-ionic-conductivity solid electrolyte with NASICON structure, and preparation and application thereof |
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| WO2013128759A1 (en) * | 2012-03-02 | 2013-09-06 | 日本碍子株式会社 | Solid electrolyte ceramic material and production method therefor |
| CN108727025A (en) * | 2017-04-17 | 2018-11-02 | 中国科学院上海硅酸盐研究所 | Lithium garnet composite ceramics, Its Preparation Method And Use |
| CN112320849A (en) * | 2020-10-13 | 2021-02-05 | 冯云龙 | Solid electrolyte powder and preparation method thereof |
| CN113224379A (en) * | 2021-04-27 | 2021-08-06 | 西南交通大学 | Fluorine-doped F-LLTO composite solid electrolyte, preparation method and application |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104591231A (en) * | 2013-10-31 | 2015-05-06 | 中国科学院上海硅酸盐研究所 | Fluorine-containing garnet-structure lithium ion oxide ceramic |
| CN107732295A (en) * | 2017-10-12 | 2018-02-23 | 燕山大学 | A kind of solid oxide electrolyte and its low-temperature sintering method based on halogenation lithium doping |
| CN110247105A (en) * | 2018-03-07 | 2019-09-17 | 重庆市科学技术研究院 | A kind of preparation method improving solid electrolyte consistency |
| CN110581312A (en) * | 2019-08-07 | 2019-12-17 | 广东工业大学 | High-ionic-conductivity solid electrolyte with NASICON structure, and preparation and application thereof |
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