CN116120060A - Preparation method of LLZTO ceramic coated with aluminum-containing compound - Google Patents
Preparation method of LLZTO ceramic coated with aluminum-containing compound Download PDFInfo
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- CN116120060A CN116120060A CN202211708963.8A CN202211708963A CN116120060A CN 116120060 A CN116120060 A CN 116120060A CN 202211708963 A CN202211708963 A CN 202211708963A CN 116120060 A CN116120060 A CN 116120060A
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 36
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000000919 ceramic Substances 0.000 title claims abstract description 33
- 150000001875 compounds Chemical class 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 46
- 238000000498 ball milling Methods 0.000 claims abstract description 29
- 238000005245 sintering Methods 0.000 claims abstract description 28
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 18
- 235000015895 biscuits Nutrition 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000003825 pressing Methods 0.000 claims abstract description 8
- 238000001238 wet grinding Methods 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 239000011324 bead Substances 0.000 claims description 6
- 238000000227 grinding Methods 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
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000004570 mortar (masonry) Substances 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 239000011812 mixed powder Substances 0.000 claims description 2
- 239000007784 solid electrolyte Substances 0.000 abstract description 5
- 239000011247 coating layer Substances 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 229910052744 lithium Inorganic materials 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 210000001787 dendrite Anatomy 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
- C04B35/49—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates containing also titanium oxides or titanates
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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Abstract
The invention provides a preparation method of LLZTO ceramic coated with aluminum-containing compound, which comprises the steps of adding LiOH into LLZTO powder; and in ZrO 2 Ball milling in a ball milling tank; drying by using a vacuum oven, pressing into a block by using a die, and roasting the block to form an LLZTO phase; the phase-formed block was ground and ZrO was used again 2 Wet milling in a ball milling tank and drying to obtain LLZTO powder coated with aluminum; and (5) preparing a biscuit by using a die and sintering to obtain the LLZTO ceramic plate coated by the aluminum-containing compound. According to the invention, an aluminum-containing compound is introduced, a uniform coating layer is formed after roasting, and a corresponding sintering strategy is matched, so that the high-performance LLZTO solid electrolyte is obtained by sintering under normal pressure; the sintering aid of the grain boundary in the LLZTO ceramic plate sintering is achieved by using a method of generating a coating layer in situ; by a sintering strategy matched with the coating of the aluminum-containing compound, the method canAnd sintering the LLZTO ceramic plate with excellent performance under normal pressure.
Description
Technical Field
The invention relates to the technical field of solid electrolyte, in particular to a preparation method of LLZTO ceramic coated with an aluminum-containing compound.
Background
With the rapid development of electronic products, the demand for batteries is also increasing; thus, battery energy density and battery safety are also a challenge.
For example, a lithium metal solid-state battery employs metallic lithium having the lowest electrochemical formula (-3.04V) as a negative electrode, but since growth and exfoliation of metallic lithium during charge and discharge generate dendrites penetrating through a separator, the safety thereof is still not satisfactory even though the battery has higher energy in this case.
Therefore, pure Solid State Batteries (SSBs) using solid state electrolytes have been developed, which are considered as the most likely candidates for next generation batteries due to their high strength against lithium dendrite penetration and their incombustibility and non-explosiveness compared to conventional organic liquid electrolytes. Oxide solid state electrolytes have a broader electrochemical window and chemical stability than sulfide electrolytes and polymer electrolytes.
However, the battery has high preparation requirements, a large-sized hot press is needed, but the hot press has large energy consumption and large space occupation; secondly, it adopts a method of pressing and sintering at normal pressure, since the sintering is performed under normal pressure, the sintering must be performed at a temperature higher than 1100 ℃, which causes a series of problems such as volatilization of lithium, loosening of biscuit structure, and the like. The ceramic wafer under the normal pressure sintering condition is not compact, the yield is low, the fluctuation of the produced performance is large, and the ceramic wafer which can be used for experiments is difficult to stably produce; furthermore, doping with the sintering aid adversely affects the intrinsic properties of the solid electrolyte.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of LLZTO ceramic coated with aluminum-containing compounds.
The technical scheme of the invention is as follows: a preparation method of LLZTO ceramic coated with aluminum-containing compound comprises the following steps:
s1), adding 10-20wt% of LiOH into LLZTO powder in a glove box;
s2) putting the powder mixed in the step S1) into ZrO 2 Ball milling tank, adding alumina ball milling beads and ethanol, and ball milling for 0-24 h by using a planetary ball mill to obtain viscous slurry;
s3) continuously drying for 5 hours at 85 ℃ by using a vacuum oven, crushing the dried and hardened powder at the moment, pressing the powder into a block by using a mould with the diameter of 25mm under the pressure of 2MPa, and roasting the block in a muffle furnace at 800 ℃ for 10 hours to form a LLZTO phase from the mixture powder;
s4), grinding the phase-formed block in an agate mortar, and reusing ZrO 2 Wet milling in a ball milling tank, and drying at 85 ℃ for 5 hours to obtain aluminum-coated LLZTO powder;
s5), manufacturing a biscuit by using a die with phi of 12mm under the pressure of 9 MPa;
s6), selecting a magnesium oxide crucible, and sintering the biscuit in a muffle furnace under the condition of embedding the mother powder; and obtaining the LLZTO ceramic plate coated with the aluminum-containing compound.
Preferably, in step S1), the mass ratio of LiOH to LLZTO powder is: 3:20.
preferably, in step S2), the mass ratio of the mixed powder to the ethanol is: 1:0.996.
preferably, in step S2), a planetary ball mill is used for a ball milling time of 4-12 hours.
Preferably, in step S6), the sintering conditions in the muffle furnace are as follows: sintering at 1250 deg.c for 1.5 hr at 5 deg.c/min.
The beneficial effects of the invention are as follows:
1. according to the invention, an aluminum-containing compound is introduced in the synthesis process, a uniform coating layer is formed after roasting, and a corresponding sintering strategy is matched, so that a low-cost, simple and reliable process is used, and a high-performance LLZTO solid electrolyte is obtained by sintering under normal pressure;
2. the method for generating the coating layer in situ is used, so that sintering assistance of the grain boundary in LLZTO ceramic chip sintering is achieved;
3. according to the invention, the LLZTO ceramic plate with excellent performance can be sintered under normal pressure by a sintering strategy matched with the coating of the aluminum-containing compound.
Drawings
Fig. 1 is an EDS diagram of an LLZTO ceramic wafer prepared in an embodiment of the present invention.
Fig. 2 is an EIS diagram of an LLZTO ceramic wafer prepared according to an embodiment of the present invention.
Detailed Description
The following is a further description of embodiments of the invention, taken in conjunction with the accompanying drawings:
example 1
The embodiment provides a preparation method of an aluminum-containing compound coated LLZTO ceramic, which comprises the following steps:
s1), adding 5g of LiOH into 100g of LLZTO powder in a glove box;
s2) putting the powder mixed in the step S1) into ZrO 2 Ball milling tank, adding alumina ball milling beads and 100ml ethanol, and ball milling for 4 hours by using a planetary ball mill to obtain viscous slurry;
s3) continuously drying for 5 hours at 85 ℃ by using a vacuum oven, crushing the dried and hardened powder at the moment, pressing the powder into a block by using a mould with the diameter of 25mm under the pressure of 2MPa, and roasting the block in a muffle furnace at 800 ℃ for 10 hours to form a LLZTO phase from the mixture powder;
s4), grinding the phase-formed block in an agate mortar, and reusing ZrO 2 Wet milling in a ball milling tank, and drying at 85 ℃ for 5 hours to obtain aluminum-coated LLZTO powder;
s5), manufacturing a biscuit by using a die with phi of 12mm under the pressure of 9 MPa;
s6), selecting a magnesium oxide crucible, and sintering the biscuit in a muffle furnace under the condition of embedding the mother powder; and obtaining the LLZTO ceramic plate coated with the aluminum-containing compound.
As shown in fig. 1, fig. 1 is a graph showing the characterization of the aluminum coated LLZTO ceramic sheet prepared in this example using dispersive spectroscopy (EDS), and referring specifically to fig. 1a, the elemental distribution can be obtained. Notably, however, in addition to the uniform distribution of the elements La, zr, ta, O, see in particular (fig. 1 b-e), the Al element was also uniformly present on the LLZTO surface (fig. 1 f), each element being uniformly distributed in the sample, which confirmed the successful preparation of aluminum coated LLZTO. Fig. 2 is an Electrochemical Impedance Spectrum (EIS) for characterizing the aluminum-coated LLZTO ceramic sheet prepared in this example, and referring specifically to fig. 2, an impedance of 150Ω can be obtained. The ceramic plate after sintering had a diameter of 8.8mm and a thickness of 0.7mm, and the conductivity was calculated to be 7.67×10 from σ=d/re×s -4 S/cm, is a solid electrolyte with excellent performance.
Example 2
The embodiment provides a preparation method of an aluminum-containing compound coated LLZTO ceramic, which comprises the following steps:
s1), adding 10g of LiOH into 100g of LLZTO powder in a glove box;
s2) putting the powder mixed in the step S1) into ZrO 2 Ball milling tank, adding alumina ball milling beads and 100ml ethanol, ball milling for 8 hours by using planetary ball mill to obtain viscous slurry;
s3) continuously drying for 5 hours at 85 ℃ by using a vacuum oven, crushing the dried and hardened powder at the moment, pressing the powder into a block by using a mould with the diameter of 25mm under the pressure of 2MPa, and roasting the block in a muffle furnace at 800 ℃ for 10 hours to form a LLZTO phase from the mixture powder;
s4), grinding the phase-formed block in an agate mortar, and reusing ZrO 2 Wet milling in a ball milling tank, and drying at 85 ℃ for 5 hours to obtain aluminum-coated LLZTO powder;
s5), manufacturing a biscuit by using a die with phi of 12mm under the pressure of 9 MPa;
s6), selecting a magnesium oxide crucible, and sintering the biscuit in a muffle furnace under the condition of embedding the mother powder; and obtaining the LLZTO ceramic plate coated with the aluminum-containing compound.
Example 3
The embodiment provides a preparation method of an aluminum-containing compound coated LLZTO ceramic, which comprises the following steps:
s1), adding 15g of LiOH into 100g of LLZTO powder in a glove box;
s2) putting the powder mixed in the step S1) into ZrO 2 Ball milling tank, adding alumina ball milling beads and 100ml ethanol, ball milling for 12 hours by using planetary ball mill to obtain viscous slurry;
s3) continuously drying for 5 hours at 85 ℃ by using a vacuum oven, crushing the dried and hardened powder at the moment, pressing the powder into a block by using a mould with the diameter of 25mm under the pressure of 2MPa, and roasting the block in a muffle furnace at 800 ℃ for 10 hours to form a LLZTO phase from the mixture powder;
s4), grinding the phase-formed block in an agate mortar, and reusing ZrO 2 Wet milling in a ball milling tank, and drying at 85 ℃ for 5 hours to obtain aluminum-coated LLZTO powder;
s5), manufacturing a biscuit by using a die with phi of 12mm under the pressure of 9 MPa;
s6), selecting a magnesium oxide crucible, and sintering the biscuit in a muffle furnace under the condition of embedding the mother powder; and obtaining the LLZTO ceramic plate coated with the aluminum-containing compound.
Example 4
The embodiment provides a preparation method of an aluminum-containing compound coated LLZTO ceramic, which comprises the following steps:
s1), adding 20g of LiOH into 100g of LLZTO powder in a glove box;
s2) putting the powder mixed in the step S1) into ZrO 2 Ball milling tank, adding alumina ball milling beads and 100ml ethanol, ball milling for 24 hours by using planetary ball mill to obtain viscous slurry;
s3) continuously drying for 5 hours at 85 ℃ by using a vacuum oven, crushing the dried and hardened powder at the moment, pressing the powder into a block by using a mould with the diameter of 25mm under the pressure of 2MPa, and roasting the block in a muffle furnace at 800 ℃ for 10 hours to form a LLZTO phase from the mixture powder;
s4), grinding the phase-formed block in an agate mortar, and reusing ZrO 2 Wet milling in a ball milling tank, and drying at 85 ℃ for 5 hours to obtain aluminum-coated LLZTO powder;
s5), manufacturing a biscuit by using a die with phi of 12mm under the pressure of 9 MPa;
s6), selecting a magnesium oxide crucible, and sintering the biscuit in a muffle furnace under the condition of embedding the mother powder; and obtaining the LLZTO ceramic plate coated with the aluminum-containing compound.
The foregoing embodiments and description have been provided merely to illustrate the principles and best modes of carrying out the invention, and various changes and modifications can be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (5)
1. The preparation method of the LLZTO ceramic coated with the aluminum-containing compound is characterized by comprising the following steps:
s1), adding 10-20wt% of LiOH into LLZTO powder in a glove box;
s2) putting the powder mixed in the step S1) into ZrO 2 Ball milling tank, adding alumina ball milling beads and ethanol, and ball milling for 0-24 h by using a planetary ball mill to obtain viscous slurry;
s3) continuously drying for 5 hours at 85 ℃ by using a vacuum oven, crushing the dried and hardened powder at the moment, pressing the powder into a block by using a mould with the diameter of 25mm under the pressure of 2MPa, and roasting the block in a muffle furnace at 800 ℃ for 10 hours to form a LLZTO phase from the mixture powder;
s4), grinding the phase-formed block in an agate mortar, and reusing ZrO 2 Wet milling in a ball milling tank, and drying at 85 ℃ for 5 hours to obtain aluminum-coated LLZTO powder;
s5), manufacturing a biscuit by using a die with phi of 12mm under the pressure of 9 MPa;
s6), selecting a magnesium oxide crucible, and sintering the biscuit in a muffle furnace under the condition of embedding the mother powder; and obtaining the LLZTO ceramic plate coated with the aluminum-containing compound.
2. The method for preparing the aluminum-containing compound coated LLZTO ceramic according to claim 1, wherein the method comprises the following steps: in the step S1), the mass ratio of the LiOH to the LLZTO powder is as follows: 3:20.
3. the method for preparing the aluminum-containing compound coated LLZTO ceramic according to claim 1, wherein the method comprises the following steps: in the step S2), the mass ratio of the mixed powder to the ethanol is as follows: 1:0.996.
4. the method for preparing the aluminum-containing compound coated LLZTO ceramic according to claim 1, wherein the method comprises the following steps: in the step S2), a planetary ball mill is used for ball milling for 4-12 hours.
5. The method for preparing the aluminum-containing compound coated LLZTO ceramic according to claim 1, wherein the method comprises the following steps: in step S6), the sintering conditions in the muffle furnace are as follows: sintering at 1250 deg.c for 1.5 hr at 5 deg.c/min.
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