CN114725495A - Easy-to-sinter garnet type solid electrolyte and preparation method thereof - Google Patents
Easy-to-sinter garnet type solid electrolyte and preparation method thereof Download PDFInfo
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 38
- 239000002223 garnet Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000005245 sintering Methods 0.000 claims abstract description 26
- 239000003792 electrolyte Substances 0.000 claims abstract description 14
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 18
- 239000000919 ceramic Substances 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 239000010955 niobium Substances 0.000 claims description 9
- 238000000498 ball milling Methods 0.000 claims description 6
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000007605 air drying Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 3
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 3
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 8
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 8
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 3
- 238000004146 energy storage Methods 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 17
- 230000008569 process Effects 0.000 description 9
- 238000000280 densification Methods 0.000 description 3
- 239000002001 electrolyte material Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000001272 pressureless sintering Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000002490 spark plasma sintering Methods 0.000 description 1
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- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
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Abstract
The invention discloses a garnet type solid electrolyte easy to sinter and a preparation method thereof. The chemical general formula of the garnet type solid electrolyte is Li7‑yLa3Zr2‑yTay−xNbxO12Wherein x is more than or equal to 0.35 and less than or equal to 0.5, y is more than or equal to 0.4 and less than or equal to 0.65, and y is more than or equal to 1.3x and more than or equal to y>x. The garnet-type solid electrolyte has the characteristic of easy sintering, can obtain a ceramic material with dense sintering (the density is not less than 93%) under the condition of normal-pressure sintering, and has excellent lithium ion conductivity (more than or equal to 1 mS/cm) at room temperature. The easy-to-sinter garnet electrodeThe electrolyte and the preparation method thereof are suitable for preparing large-area high-ionic conductivity garnet electrolyte sheets and are applied to the field of solid lithium battery energy storage.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to a garnet solid electrolyte easy to sinter and a preparation method thereof.
Background
Lithium ion batteries are an important chemical energy storage battery and are widely applied to the fields of electronic equipment, power batteries and large-scale energy storage. The conventional organic electrolyte has the factors of narrow electrochemical window, flammability, easy leakage and the like, and restricts the further development of the high-safety and high-energy-density lithium battery. Lithium metal has the advantages of high specific energy, low electrochemical potential and the like, is an ideal negative electrode material of a high-performance lithium battery, and has gained attention and development in recent years. The solid electrolyte is expected to replace the traditional liquid electrolyte due to excellent mechanical properties, so that the working voltage is improved, the growth of lithium dendrites in the charging and discharging process of the lithium battery is inhibited, and the safety problems of short circuit, fire burning and the like of the lithium battery are prevented.
The garnet-type oxide solid electrolyte has the advantages of excellent room-temperature ionic conductivity, wide electrochemical window, higher mechanical strength and incombustibility, is an oxide solid electrolyte with very potential application, and has attracted much attention in recent years. To obtain a performance close to the intrinsic ionic conductivity, the density of the solid electrolyte is usually not less than 93%.
However, the garnet-type solid electrolyte in the prior art is difficult to achieve densification under atmospheric pressure sintering conditions. The density of the garnet electrolyte ceramic chip prepared by adopting the normal pressure sintering process is usually below 90%, the porosity in the material is higher, and the room temperature lithium ion conductivity of the garnet electrolyte ceramic chip is obviously reduced. In order to realize the densification sintering of garnet ceramic materials, high-temperature pressure sintering technologies such as hot-pressing sintering, spark plasma sintering and the like are generally adopted, but the technologies have high requirements on equipment and high cost, are not beneficial to large-scale production and application, and limit the large-scale preparation and application of large-size electrolyte ceramic sheets and thin film materials thereof.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a garnet-type solid electrolyte easy to sinter and a preparation method thereof. The preparation method is simple, low in equipment cost, low in energy consumption, green and environment-friendly, and the obtained garnet type solid electrolyte is high in density and ionic conductivity and is suitable for the field of electrochemical energy storage of solid lithium batteries.
In order to solve the problems of the prior art, the invention adopts the technical scheme that:
the easy-to-sinter garnet solid electrolyte has the chemical general formula of Li7-yLa3Zr2-yTay-xNbxO12Wherein x is more than or equal to 0.35 and less than or equal to 0.5, y is more than or equal to 0.4 and less than or equal to 0.65, and y>x。
As an improved scheme, the optimized values of x and y conform to the relation that x is more than or equal to y and is 1.3.
The preparation method of the garnet-type solid electrolyte comprises the following steps:
and 3, weighing the garnet powder prepared in the step 2, putting the garnet powder into a stainless steel mold, performing mechanical pressing under the pressure of 20-30MPa, putting the green body into a magnesium oxide crucible, using the powder prepared in the step 2 as mother powder to cover and protect the green body, sintering the green body in a high-temperature furnace at the sintering temperature of 1050 plus materials and 1200 ℃, and preserving heat for 4-12 hours to prepare the garnet electrolyte ceramic sheet with high compactness and high ionic conductivity.
As a modification, in the step 1, the lithium-containing compound is Li2CO3Or LiOH. H2One or two of O are mixed.
The improvement is that the calcining temperature in the step 2 is 900 ℃, and the calcining time is 4-6 hours.
As an improvement, the sintering temperature in the step 3 is 1100-1150 ℃, and the heat preservation time is 6-8 hours.
Has the advantages that:
compared with the prior art, the garnet-type solid electrolyte easy to sinter and the preparation method thereof have the following advantages:
1. the garnet type solid electrolyte has excellent sintering activity, can be sintered by adopting a pressureless sintering process to obtain a high-density electrolyte ceramic material, has the density of 94-96 percent, does not need to adopt high-temperature pressurized sintering technologies such as hot-pressing sintering, discharge plasma sintering and the like, reduces the defects of high requirements on production equipment, high cost, difficulty in large-scale production and application and the like, and limits the large-scale preparation and application of large-size electrolyte ceramic sheets and thin film materials thereof;
2. after the easy-to-sinter garnet solid electrolyte is sintered and compacted by a pressureless sintering process, the easy-to-sinter garnet solid electrolyte shows excellent lithium ion conductivity at room temperature, and the lithium ion conductivity is not lower than 1mS/cm at 22 ℃.
Drawings
FIG. 1 is an X-ray diffraction pattern of the easy-to-sinter garnet-type solid electrolytes of example 1 and comparative examples 1 to 5;
FIG. 2 is a scanning electron micrograph of a cross-section of the easy-to-sinter garnet-type solid electrolyte ceramic of example 1 and comparative examples 1 to 5, in which (a) comparative example 1, (b) comparative example 2, (c) comparative example 3, (d) comparative example 4, (e) example 1, (e) comparative example 5;
fig. 3 is a graph showing the change of ion conductivity with temperature of the easy-to-sinter garnet-type solid electrolyte described in example 1 and comparative examples 1 to 5.
Detailed Description
The present invention will be described in more detail below with reference to specific examples. These examples are only for facilitating the easy understanding of the present invention, and the present invention is not limited to these examples.
Example 1
Using lithium carbonate (Li)2CO3) Lanthanum oxide (La)2O3) Zirconium oxide (ZrO)2) Tantalum pentoxide (Ta)2O5) Niobium pentoxide (Nb)2O5) As raw material, according to the chemical formula Li7-yLa3Zr2-yTay-xNbxO12Wherein, the stoichiometric ratio of y is 0.5 and x is 0.4, the raw materials are calculated and weighed, the raw materials are put into an agate ball milling pot, grinding balls and industrial alcohol are added, and the raw materials are put into a planetary ball mill for wet ball milling for 5 hours to be fully and uniformly mixed;
putting the raw material mixture into a forced air drying oven, keeping the temperature at 75 ℃ for 24 hours, drying, transferring into a magnesium oxide crucible, putting into a muffle furnace for calcining, wherein the calcining temperature is 900 ℃, the calcining time is 6 hours, and cooling to obtain high-purity garnet powder;
and (2) forming the garnet powder under the pressure of 30MPa by adopting a machine pressing forming method, putting the formed green body into a magnesium oxide crucible, covering and protecting the green body by adopting the mother powder, sintering in a high-temperature furnace at the sintering temperature of 1150 ℃, and preserving heat for 6 hours to prepare the garnet electrolyte ceramic wafer.
Testing the density of the prepared garnet type solid electrolyte ceramic chip by adopting an Archimedes drainage method; the ionic conductivity of the sample was analyzed at different temperatures by electrochemical impedance spectroscopy at a temperature range of 22-90 ℃ using a model PARSTAT MC-2000 multifunctional electrochemical workstation manufactured by Aromatk, USA.
As a result, the garnet-type solid electrolyte prepared in example 1 had a density of 95%, and an ionic conductivity of 1.05X 10 at room temperature of 22 deg.C-3S/cm (see Table 1).
Example 2
This example 2 is different from example 1 in that Li in the chemical formula7-yLa3Zr2-yTay-xNbxO12Y is 0.65 and x is 0.5, the calcination temperature is 850 ℃ and held for 10 hours, the sintering temperature is 1000 ℃ and held for 8 hours, and other processes and conditions are the same as in example 1.
The density and ionic conductivity of the garnet-type solid electrolyte ceramic sheet prepared in this example were measured by the same measuring method as in example 1.
The results showed that the density of the prepared garnet-type solid electrolyte was 96%, and the ionic conductivity thereof was 1.12X 10 at room temperature of 22 deg.C-3S/cm (see Table 1).
Example 3
In example 3, the difference from example 1 is that y is 0.45 and x is 0.35 in the chemical formula, and the lithium-containing compound in the raw material is lithium hydroxide (LiOH · H)2O), the calcination temperature is 900 ℃, the heat preservation time in the calcination process is 4 hours, the sintering temperature is 1150 ℃, the heat preservation time is 8 hours, and other processes and conditions are the same as those in the example 1.
The density and ionic conductivity of the garnet-type solid electrolyte ceramic sheet prepared in this example were measured by the same measuring method as in example 1.
As a result, the density of the prepared garnet-type solid electrolyte was 95%, and the ionic conductivity at room temperature of 22 ℃ was 1.08X 10-3S/cm (see Table 1).
Comparative examples 1 to 5
Comparative examples 1, 2, 3, 4 and 5 differ from example 1 in the chemical formula Li7-yLa3Zr2-yTay-xNbxO12Wherein y is 0.5 and x is 0, 0.1, 0.2, 0.3 and 0.5, respectively, and other processes and conditions are the same as in example 1.
The phase of the garnet-type solid electrolytes described in example 1 and comparative examples 1 to 5 was analyzed, and the results are shown in fig. 1, and each material was synthesized to obtain a high-purity cubic structure garnet phase.
The volume density and the compactness of the garnet-type solid electrolytes described in example 1 and comparative examples 1 to 5 were measured by the archimedes' drainage method (table 1). It can be seen that the garnet-type solid electrolyte material has the highest density of 95% when x is 0.4 (i.e., example 1).
FIG. 2 is a microstructure photograph of the garnet-type solid electrolyte ceramics described in example 1 and comparative examples 1 to 5 using Hitachi SU-70 scanning electron microscope. As can be seen from fig. 2, when x is 0.4 (i.e., example 1), the electrolyte ceramic achieves sintering at 1150 ℃ for 6 hours, the fracture exhibits a transgranular fracture mode, and it can be observed that a large number of sintered compact regions favorable for lithium ion conduction are formed in the ceramic.
For comparison, the materials of comparative examples 1-5 have poor sintering densification under the same sintering process conditions, a large number of pores are visible in the fracture, and the granular grains are visually distinguishable.
The material of example 1 was significantly denser than the materials of comparative examples 1-5, the specific sintered densities of which are shown in table 1.
The sintered material was subjected to normal and variable temperature lithium ion conductivity tests using PARSTAT MC-2000 electrochemical impedance analyzer of AMETEK corporation, usa, and the obtained electrochemical impedance spectra were subjected to fitting analysis to obtain ion conductivity data of each electrolyte ceramic sheet at different temperatures (fig. 3). The ionic conductivity of each electrolyte material at room temperature of 22 ℃ is shown in table 1.
TABLE 1 bulk density, theoretical density, compactness, and ion conductivity at room temperature of garnet-type solid electrolyte ceramics described in example 1 and comparative examples 1 to 5
As can be seen from both table 1 and fig. 3, the ionic conductivity of the garnet electrolyte of example 1 was higher than that of the garnet electrolyte materials of comparative examples 1 to 5. The ionic conductivity of the garnet electrolyte material of example 1 was 1.05X 10 at 22 ℃ under room temperature conditions-3S/cm。
As can be seen from examples 1 to 3, the garnet electrolyte according to the present invention has excellent sintering activity and room temperature ionic conductivity.
In light of the foregoing description of the preferred embodiments of the present invention, those skilled in the art can make various modifications, substitutions, changes, etc. without departing from the scope and spirit of the present invention, and all such modifications, substitutions, changes, and alterations are intended to be included within the scope of the present invention.
Claims (6)
1. An easy-to-sinter garnet-type solid electrolyte, characterized in that the chemical formula of the easy-to-sinter garnet-type solid electrolyte is Li7-yLa3Zr2-yTay−xNbxO12Wherein x is more than or equal to 0.35 and less than or equal to 0.5, y is more than or equal to 0.4 and less than or equal to 0.65, and y is more than or equal to 0.35>x。
2. The easy-to-sinter garnet-type solid electrolyte as claimed in claim 1, wherein the optimized values of x and y satisfy the relationship of 1.3x ≧ y.
3. The method for preparing a garnet-type solid electrolyte easy to sinter as claimed in claim 1, comprising the steps of:
step 1, taking a lithium-containing compound, lanthanum oxide, zirconium oxide, tantalum pentoxide and niobium pentoxide as raw materials according to a general formula Li7- yLa3Zr2-yTay−xNbxO12The raw materials are weighed according to the stoichiometric ratio, wherein x is more than or equal to 0.35 and less than or equal to 0.5, y is more than or equal to 0.4 and less than or equal to 0.65, and y>x, putting the mixture into an agate ball milling tank, adding grinding balls and industrial alcohol, and putting the mixture into a planetary ball mill for wet ball milling for 3-10 hours to fully and uniformly mix the mixture;
step 2, placing the mixture obtained in the step 1 into a forced air drying oven, preserving heat for 12-36 hours at 75 ℃, drying, transferring into a magnesium oxide crucible, calcining in air atmosphere at 850-950 ℃ for 2-12 hours, cooling, grinding and sieving to obtain cubic-phase garnet powder;
and 3, weighing the garnet powder prepared in the step 2, putting the garnet powder into a stainless steel mold, performing mechanical pressing under the pressure of 20-30MPa, putting the green body into a magnesium oxide crucible, using the powder prepared in the step 2 as mother powder to cover and protect the green body, sintering the green body in a high-temperature furnace at the sintering temperature of 1050 plus materials and 1200 ℃, and preserving heat for 4-12 hours to prepare the garnet electrolyte ceramic sheet with high compactness and high ionic conductivity.
4. The method of claim 3, wherein the lithium-containing compound in step 1 is Li2CO3Or LiOH. H2One or two of O are mixed.
5. The method of claim 3, wherein the calcining temperature in step 2 is 900 ℃ and the calcining time is 4-6 hours.
6. The method for preparing a garnet-type solid electrolyte easy to sinter as claimed in claim 3, wherein the sintering temperature in step 3 is 1100-1150 ℃ and the holding time is 6-8 hours.
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