CN114497714A - Preparation method of garnet type solid electrolyte with high ionic conductivity - Google Patents

Preparation method of garnet type solid electrolyte with high ionic conductivity Download PDF

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CN114497714A
CN114497714A CN202210158203.8A CN202210158203A CN114497714A CN 114497714 A CN114497714 A CN 114497714A CN 202210158203 A CN202210158203 A CN 202210158203A CN 114497714 A CN114497714 A CN 114497714A
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徐友龙
马晓宁
王景平
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Xian Jiaotong University
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Abstract

The invention discloses a preparation method of garnet type solid electrolyte with high ionic conductivity, which is prepared according to the chemical formula Li7La3Zr2‑ xMxO12Performing ball milling on powder of a lithium source, a lanthanum source, a zirconium source and an M source, then presintering, pressing into a circular biscuit blank, and preserving heat of the biscuit blank for 0.5-3 h at a low temperature section; then continuously heating to a high-temperature section and then cooling to obtain the garnet-type solid electrolyte with high ionic conductivity, wherein the temperature of the high-temperature section is at least 50 ℃ higher than that of the low-temperature section; x is more than or equal to 0.2 and less than or equal to 0.75. The garnet type solid electrolyte with high ionic conductivity prepared by the invention promotes the nucleation speed of crystals, refines primary crystal grains, homogenizes the crystal grain size in the solid electrolyte and reduces the crystal boundary in the crystals, thereby improving the material density and greatly improving the electricityIonic conductivity of the electrolyte.

Description

Preparation method of garnet type solid electrolyte with high ionic conductivity
Technical Field
The invention belongs to the technical field of oxide solid electrolyte preparation, and particularly relates to a method for preparing a garnet type solid electrolyte with high ionic conductivity.
Background
Currently available commercial batteries (e.g., lead-acid, nickel metal hydride, lithium ion, and flow batteries) cannot meet the stringent or ever increasing energy density requirements of portable electronic devices, electric vehicles, and grid energy storage systems. Although liquid electrolytes have the advantages of high conductivity and good wettability of the electrode surfaces, current commercial suppliersWhen industrial batteries are used for energy storage devices with high power and large energy density, problems of insufficient electrochemical and thermal stability, low ion selectivity and poor safety of liquid electrolytes are revealed. After frequent self-ignition events of the electric automobile, higher requirements are put on the safety of the energy storage equipment with large energy density. Therefore, it is urgent to develop a battery having higher energy density, longer cycle life, and higher safety level. Since lithium metal has the highest theoretical specific capacity (3860mAh g)-1) Lowest electrochemical potential (-3.04V vs. standard hydrogen electrode) and light weight (ρ ═ 0.53g cm)-3) Therefore, the lithium metal negative electrode is used for replacing other negative electrodes, so that the energy density of the battery can be effectively improved, and importantly, the growth of lithium dendrite in the liquid organic electrolyte and the easy volatilization, flammability and leakage of organic solvent have potential safety hazards, so that the direct application of lithium metal in the actual production is hindered. Therefore, the research and development of the solid electrolyte to replace flammable and explosive organic liquid electrolyte has the possibility of solving the safety problems, thereby having extremely high research and commercial values.
Among the numerous electrolytes, Li having a cubic phase garnet structure7La3Zr2O12The (LLZO) solid electrolyte has the following advantages: (1) the ionic conductivity can reach 10 at room temperature-4S cm-1(2) the thermal stability is good, and the device can work in a wide temperature range; (3) the material can replace a diaphragm, and has good mechanical property and processability; (4) the safety is good and the fuel is not burnt. Garnet-type solid electrolytes are therefore the current popular materials for electrolytes of lithium metal solid-state batteries.
Currently, the main method for preparing the LLZO solid electrolyte is the conventional solid phase sintering method, and in numerous patents (for example, CN 109935901 a, CN 113363562A and CN 109888374 a), the LLZO solid electrolyte is prepared by keeping the temperature at a fixed temperature for a certain period of time. However, the preparation of LLZO by such a method of maintaining the temperature at a fixed temperature for a certain period of time has certain problems. If sintering is continued at a low temperature, an ionic conductivity of only 10 may occur-6S cm-1Even if the fired LLZO has an ionic conductivity of aboutIs 10-4S cm-1The cubic phase of (2) but also results in smaller grain size and larger grain boundary concentration and voids, resulting in a severe reduction in the ionic conductivity of the material. If the sintering is continuously carried out under the high-temperature condition, not only is the energy consumption large, but also the grain size can overgrow, the abnormal growth condition of the grains is generated, and the serious transgranular phenomenon is generated, so that the relative density and the mechanical strength of the material are reduced, even cracks are generated at the grain boundary, and the ionic conductivity of the material is seriously reduced.
Disclosure of Invention
In view of the problems of the prior art, it is an object of the present invention to provide a method for preparing a garnet-type solid electrolyte having a high ionic conductivity by sintering, the garnet-type solid electrolyte having a lithium ion structure Li7La3Zr2-xMxO12The method has the advantages of high lithium ion conductivity, stability for a lithium metal cathode, capability of obviously homogenizing garnet type solid electrolyte grains, improvement of the compactness of the material, simple preparation method and capability of large-scale production.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a garnet-type solid electrolyte with high ionic conductivity comprises the following steps:
according to the formula Li7La3Zr2-xMxO12Ball-milling powder of a lithium source, a lanthanum source, a zirconium source and an M source, and then pre-sintering at 800-950 ℃ for 8-10.5 h to obtain a primary sintered powder; pressing the primary sintering powder into a circular biscuit sheet, and preserving the heat of the biscuit sheet at a low temperature section for 0.5-3 h; then continuously heating to a high-temperature section and cooling to obtain the garnet-type solid electrolyte with high ionic conductivity, wherein the temperature of the low-temperature section is 950-1200 ℃, the temperature of the high-temperature section is 1000-1350 ℃, and the temperature of the high-temperature section is at least 50 ℃ higher than that of the low-temperature section; the M source is an Al source, a Ga source, a Y source, an In source, a Ti source, an Hf source, an Nb source, a Ta source, a Cr source, a Mo source or a W source, and x is more than or equal to 0.2 and less than or equal to 0.75.
Furthermore, x is more than or equal to 0.2 and less than or equal to 0.5.
Further, the lithium source is one of lithium carbonate, lithium hydroxide, lithium acetate and lithium nitrate.
Further, the lanthanum source is one of lanthanum oxide, lanthanum hydroxide and lanthanum nitrate.
Further, the zirconium source is one of zirconium oxide, zirconium hydroxide and zirconium nitrate.
Further, the M source is an oxide of Al, Ga, Y, In, Ti, Hf, Nb, Ta, Cr, Mo or W.
Further, pressing the primary sintering powder under the pressure of 300-500 MPa to form a circular biscuit sheet.
Further, the biscuit piece is placed in a muffle furnace and heated to a high-temperature section at a heating rate of 1-20 ℃/min.
Further, furnace cooling is adopted for cooling.
Compared with the prior art, the invention has the following beneficial technical effects:
the garnet solid electrolyte is prepared by a dynamic sintering method, the temperature is kept for a period of time at a low temperature section to promote the nucleation of crystal grains, and then the temperature is raised to a high temperature section by a dynamic heating method, the crystal grains can slowly grow in the heating process, and the crystal grains are immediately cooled along with a furnace after reaching the high temperature section to prevent the excessive growth of the crystal grains and the crystal crossing phenomenon caused by the abnormal growth condition of the crystal grains, so that the size of the crystal grains in the solid electrolyte is homogenized, the integrity of the crystal grains is improved, and the aim of improving the ionic conductivity of the crystal grains is finally fulfilled. The invention adopts staged heating, can promote the nucleation speed of the crystal, refines primary crystal grains, homogenizes the crystal grain size in the solid electrolyte and reduces the crystal boundary in the crystal, thereby improving the density of the material and greatly improving the ionic conductivity of the electrolyte. The invention adopts the traditional simple solid phase sintering preparation process, and the method is simple and easy to operate, has lower cost and can be used for large-scale production. Compared with the garnet type solid electrolyte material which is not modified, the method can obviously homogenize the grain size in the solid electrolyte and reduce the grain boundary in the crystal, and the garnet type Li prepared by sintering by the method7La3Zr2-xMxO12The solid electrolyte has homogenized crystal grains, increased density, greatly increased ionic conductivity and 5.7-8.2 times higher lithium ion conductivity at 25 ℃.
Drawings
FIG. 1 shows Li of comparative example 1 of the present invention sintered at a low temperature at a constant temperature7La3Zr1.5Ta0.5O12A micro-topography of the solid electrolyte;
FIG. 2 shows Li of comparative example 2 sintered at a high temperature at a constant temperature7La3Zr1.5Ta0.5O12A micro-topography of the solid electrolyte;
FIG. 3 shows Li prepared by the over-dynamic sintering method of example 37La3Zr1.75Ta0.25O12A micro-topography of the solid electrolyte;
FIG. 4 is an electrochemical impedance spectrum at 25 ℃ of the electrolyte material prepared in comparative example 1;
FIG. 5 is an electrochemical impedance spectrum at 25 ℃ of the electrolyte material prepared in comparative example 2;
FIG. 6 is an electrochemical impedance spectrum at 25 ℃ of an electrolyte material prepared in example 3;
FIG. 7 is an electrochemical impedance spectrum at 25 ℃ of an electrolyte material prepared in example 4;
FIG. 8 is an electrochemical impedance spectrum at 25 ℃ of an electrolyte material prepared in example 5;
FIG. 9 shows Li | Au/Li in example 3 of the present invention7La3Zr1.75Ta0.25O12a/Au | Li symmetrical cell performance diagram.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments, and the embodiments of the present invention are not limited thereto. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
The invention relates to a preparation method of garnet type solid electrolyte with high ionic conductivity, and the structural expression is Li7La3Zr2-xMxO12(M is Al, Ga, Y, In, Ti, Hf, Nb, Ta, Cr, Mo and W; x is more than or equal to 0.2 and less than or equal to 0.75), a dynamic temperature rise sintering method is adopted to promote the nucleation speed of crystals In the solid electrolyte, refine primary crystal grains, homogenize the size of the crystal grains, reduce the crystal boundary In the crystals, improve the compactness of the material, improve the ionic conductivity of the electrolyte, improve the inhibition capacity of the electrolyte on lithium dendrites and further improve the cycle stability of the lithium metal battery.
Specifically, the preparation method of the garnet-type solid electrolyte with high ionic conductivity comprises the following steps:
(1) according to the formula Li7La3Zr2-xMxO12Performing ball milling on powder of a lithium source, a lanthanum source, a zirconium source and an M source to obtain raw powder;
(2) pre-sintering the raw powder at 800-950 ℃ for 8-10.5 h to obtain a primary sintered powder body;
(3) pressing the primary sintering powder into a circular biscuit sheet under the pressure of 300-500 MPa;
(4) heating the biscuit sheet in a muffle furnace to a low temperature section of 950-1200 ℃, and preserving heat for 0.5-3 h;
(5) placing the biscuit sheet in a muffle furnace, heating to a high temperature of 1000-1350 ℃ at a heating rate of 1-20 ℃/min, immediately cooling along with the furnace body without setting the heat preservation time, wherein the temperature of the high temperature section is at least 50 ℃ higher than that of the low temperature section, and finally obtaining Li7La3Zr2-xMxO12A solid electrolyte. Wherein M is one of Al source, Ga source, Y source, In source, Ti source, Hf source, Nb source, Ta source, Cr source, Mo source and W source, x is more than or equal to 0.2 and less than or equal to 0.75, preferably, x is more than or equal to 0.2 and less than or equal to 0.5.
The lithium source is one of lithium carbonate, lithium hydroxide, lithium acetate and lithium nitrate.
The lanthanum source is one of lanthanum oxide, lanthanum hydroxide and lanthanum nitrate.
The zirconium source is one of zirconium oxide, zirconium hydroxide and zirconium nitrate.
The tantalum source is one of tantalum oxide, tantalum oxalate and tantalum hydroxide.
The lithium source needs to be excessive, and the mass of the excessive lithium source is 10-15% of the mass of the lithium source calculated according to the chemical formula.
The garnet-type solid electrolyte with high ionic conductivity prepared by the method has uniform grain size, and the lithium ion conductivity is improved by 5.7-8.2 times at 25 ℃.
The following examples are for the preparation of high ionic conductivity garnet solid electrolytes:
example 1
According to Li7La3Zr1.75Nb0.25O12In a stoichiometric ratio of (A), 0.15mol of La is weighed2O3，0.7mol LiOH·H2O,0.175mol ZrO2And 0.0125mol of Nb2O5In order to compensate for the volatilization of Li element at high temperature in the crystal structure, LiOH. H in the raw material2The O excess is 15% by mass calculated on the stoichiometric ratio. The raw materials are mixed and ball-milled in isopropanol ball-milling medium at the rotating speed of 380r/min for 20h, and then dried in an oven at 80 ℃ for 24h to obtain powder. The obtained powder is ground to be uniform by a mortar, and calcined at 800 ℃ for 10.5h to obtain the mother powder of the presintering product. Weighing a certain mass of mother powder, placing the mother powder in a mold with the diameter of 15mm, placing the mold on a workbench of a tabletting machine, applying the pressure of 350MPa, maintaining the pressure for 5min, demoulding, and taking out the biscuit piece which is completely molded. Embedding the biscuit sheet with mother powder, placing in an alumina crucible, keeping the temperature in a muffle furnace to 1150 ℃ for 2h, sintering while raising the temperature at a rate of 2 ℃/min, cooling along with the furnace after the temperature is raised to 1250 ℃ to obtain Li7La3Zr1.75Nb0.25O12A solid electrolyte.
Example 2
According to Li7La3Zr1.60Hf0.40O12In a stoichiometric ratio of (A), 0.15mol of La is weighed2O3，0.7mol LiOH·H2O,0.16mol ZrO2And 0.02mol of HfO2In order to compensate for the volatilization of Li element at high temperature in the crystal structure,LiOH. H in the starting Material2The O excess is 15% by mass calculated on the stoichiometric ratio. The raw materials are mixed and ball-milled in isopropanol ball-milling medium at the rotating speed of 380r/min for 20h, and then dried in an oven at 80 ℃ for 24h to obtain powder. The obtained powder is ground to be uniform by a mortar, and calcined for 8.5 hours at 950 ℃ to obtain the mother powder of the presintering product. Weighing a certain mass of mother powder, placing the mother powder in a mold with the diameter of 15mm, placing the mold on a workbench of a tabletting machine, applying the pressure of 350MPa, maintaining the pressure for 5min, demoulding, and taking out the biscuit piece which is completely molded. Embedding the biscuit sheet with mother powder, placing in an alumina crucible, keeping the temperature in a muffle furnace to 1200 ℃ for 1h, sintering at the temperature rise rate of 2.5 ℃/min, cooling along with the furnace after the temperature rises to 1250 ℃ to obtain Li7La3Zr1.60Hf0.40O12A solid electrolyte.
Example 3
According to Li7La3Zr1.75Ta0.25O12In a stoichiometric ratio of (A), 0.15mol of La is weighed2O3，0.7mol LiOH·H2O,0.175mol ZrO2And 0.0125mol of Ta2O5In order to compensate for the volatilization of Li element at high temperature in the crystal structure, LiOH. H in the raw material2O is in excess of 15% of the total mass. The raw materials are mixed and ball-milled in an isopropanol ball-milling medium at the rotating speed of 380r/min for 20 hours and then dried in an oven at the temperature of 80 ℃ for 24 hours. Grinding the obtained powder uniformly by using a mortar, calcining at 900 ℃ for 9h to obtain pre-sintered product mother powder, weighing a certain mass of the mother powder, placing the mother powder into a mold with the diameter of 15mm, placing the mold on a workbench of a tabletting machine, applying pressure of 400MPa, maintaining the pressure for 5min, demoulding, and taking out the biscuit piece which is completely molded. Embedding the biscuit sheet with mother powder, placing in an alumina crucible, keeping the temperature in a muffle furnace to 950 ℃ for 3h, sintering at the temperature rise rate of 2 ℃/min, cooling along with the furnace after the temperature rises to 1150 ℃ to obtain Li7La3Zr1.75Ta0.25O12A solid electrolyte.
Example 4
According to Li7La3Zr1.5Ta0.5O12In a stoichiometric ratio of (A), 0.15 is weighedmol La2O3，0.7mol LiOH·H2O,0.150mol ZrO2And 0.0125mol of Ta2O5In order to compensate for the volatilization of Li element at high temperature in the crystal structure, LiOH. H in the raw material2O is in excess of 15% of the total mass. The raw materials are mixed and ball-milled in an isopropanol ball-milling medium at the rotating speed of 380r/min for 20 hours and then dried in an oven at the temperature of 80 ℃ for 24 hours. Grinding the obtained powder uniformly by using a mortar, calcining at 900 ℃ for 9h to obtain pre-sintered product mother powder, weighing a certain mass of the mother powder, placing the mother powder into a mold with the diameter of 15mm, placing the mold on a workbench of a tabletting machine, applying pressure of 400MPa, maintaining the pressure for 5min, demoulding, and taking out the biscuit piece which is completely molded. Embedding the biscuit sheet with mother powder, placing in an alumina crucible, keeping the temperature in a muffle furnace to 1100 ℃ for 1h, sintering at the temperature rise rate of 2 ℃/min, cooling along with the furnace after the temperature rises to 1200 ℃ to obtain Li7La3Zr1.75Ta0.25O12A solid electrolyte.
Example 5
According to Li7La3Zr1.80Y0.20O12In a stoichiometric ratio of (A), 0.15mol of La is weighed2O3，0.7mol LiOH·H2O,0.18mol ZrO2And 0.01mol of Y2O3In order to compensate for the volatilization of Li element at high temperature in the crystal structure, LiOH. H in the raw material2O is in excess of 10% of the total mass. The raw materials are mixed and ball-milled in an isopropanol ball-milling medium at the rotating speed of 380r/min for 20 hours and then dried in an oven at the temperature of 80 ℃ for 24 hours. Grinding the obtained powder uniformly by using a mortar, calcining at 900 ℃ for 10.5h to obtain pre-sintered product mother powder, weighing a certain mass of the mother powder, placing the mother powder into a mold with the diameter of 15mm, placing the mold on a worktable of a tabletting machine, applying pressure of 400MPa, maintaining the pressure for 5min, demoulding and taking out the biscuit piece which is completely molded. Embedding the biscuit sheet with mother powder, placing in an alumina crucible, keeping the temperature in a muffle furnace to 990 ℃ for 4h, sintering at a heating rate of 4 ℃/min, cooling along with the furnace after the temperature is raised to 1250 ℃ to obtain Li7La3Zr1.80Y0.20O12A solid electrolyte.
Example 6
According to Li7La3Zr1.70Nb0.30O12In a stoichiometric ratio of (2), 0.15mol of La is weighed2O3，0.7mol LiOH·H2O,0.17mol ZrO2And 0.015mol of Nb2O5In order to compensate for the volatilization of Li element at high temperature in the crystal structure, LiOH. H in the raw material2The O excess is 15% by mass calculated on the stoichiometric ratio. The raw materials are mixed and ball-milled in isopropanol ball-milling medium at the rotating speed of 380r/min for 20h, and then dried in an oven at 80 ℃ for 24h to obtain powder. The obtained powder is ground to be uniform by a mortar, and calcined at 800 ℃ for 10.5h to obtain the mother powder of the presintering product. Weighing a certain mass of mother powder, placing the mother powder in a mold with the diameter of 15mm, placing the mold on a workbench of a tabletting machine, applying the pressure of 350MPa, maintaining the pressure for 5min, demoulding, and taking out the biscuit piece which is completely molded. Embedding the biscuit sheet with mother powder, placing in an alumina crucible, keeping the temperature in a muffle furnace to 1050 ℃ for 1.5h, sintering at the temperature rise rate of 5 ℃/min, cooling along with the furnace after the temperature rises to 1250 ℃ to obtain Li7La3Zr1.70Nb0.30O12A solid electrolyte.
Example 7
The same as example 1, except that the green sheet was embedded with the mother powder, placed in an alumina crucible, and after heat-retaining for 0.5h at 1200 ℃ in a muffle furnace, sintered at a heating rate of 7.5 ℃/min, and the process was completed after the temperature was raised to 1350 ℃.
Example 8
The difference from example 3 is that the green sheet was embedded with the mother powder, placed in an alumina crucible, and after heat preservation in a muffle furnace to 1050 ℃ for 1.75 hours, sintered at a temperature rise rate of 5 ℃/min, and the process was completed after the temperature was raised to 1300 ℃.
Example 9
The same as example 3, except that the green sheet was embedded with the mother powder, placed in an alumina crucible, and after maintaining the temperature in a muffle furnace to 1150 ℃ for 45mins, sintered at a heating rate of 13 ℃/min, and the process was completed after the temperature was raised to 1280 ℃.
Example 10
According to Li7La3Zr1.25Al0.75O12In a stoichiometric ratio of (A), 0.15mol of La is weighed2O3，0.7mol LiOH·H2O,0.125mol ZrO2And 0.0375mol of Al2O3In order to compensate for the volatilization of Li element at high temperature in the crystal structure, LiOH. H in the raw material2The O excess is 15% by mass calculated on the stoichiometric ratio. The raw materials are mixed and ball-milled in isopropanol ball-milling medium at the rotating speed of 380r/min for 20h, and then dried in an oven at 80 ℃ for 24h to obtain powder. The obtained powder is ground to be uniform by a mortar, and calcined for 8 hours at 850 ℃ to obtain the mother powder of the presintering product. Weighing a certain mass of mother powder, placing the mother powder in a mold with the diameter of 15mm, placing the mold on a workbench of a tabletting machine, applying the pressure of 300MPa, maintaining the pressure for 5min, demoulding, and taking out the biscuit piece which is completely molded. Embedding the biscuit sheet with mother powder, placing in an alumina crucible, keeping the temperature in a muffle furnace to 950 ℃ for 0.5h, sintering at the heating rate of 1 ℃/min, cooling along with the furnace after the temperature is raised to 1000 ℃ to obtain Li7La3Zr1.25Al0.75O12A solid electrolyte.
Example 11
According to Li7La3Zr1.40Ga0.60O12In a stoichiometric ratio of (A), 0.15mol of La is weighed2O3，0.7mol LiOH·H2O,0.140mol ZrO2And 0.03mol of Ga2O3In order to compensate for the volatilization of Li element at high temperature in the crystal structure, LiOH. H in the raw material2The O excess is 15% by mass calculated on the stoichiometric ratio. The raw materials are mixed and ball-milled in isopropanol ball-milling medium at the rotating speed of 380r/min for 20h, and then dried in an oven at 80 ℃ for 24h to obtain powder. The obtained powder is ground to be uniform by a mortar, and calcined at 870 ℃ for 9.5h to obtain the mother powder of the presintering product. Weighing a certain mass of mother powder, placing the mother powder in a mold with the diameter of 15mm, placing the mold on a workbench of a tabletting machine, applying the pressure of 500MPa, maintaining the pressure for 5min, demoulding, and taking out the biscuit piece which is completely molded. Embedding the biscuit sheet with the mother powder, placing the biscuit sheet in an alumina crucible, keeping the temperature in a muffle furnace to 1050 ℃ for 3h, sintering at the heating rate of 20 ℃/min, and waiting for the temperatureAfter the temperature is raised to 1350 ℃, the Li can be obtained after furnace cooling7La3Zr1.40Ga0.60O12A solid electrolyte.
Example 12
According to Li7La3Zr1.70Cr0.30O12In a stoichiometric ratio of (A), 0.15mol of La is weighed2O3，0.7mol LiOH·H2O,0.17mol ZrO2And 0.015mol of Cr2O3In order to compensate for the volatilization of Li element at high temperature in the crystal structure, LiOH. H in the raw material2The O excess is 15% of the mass calculated according to the stoichiometric ratio. The raw materials are mixed and ball-milled in isopropanol ball-milling medium at the rotating speed of 380r/min for 20h, and then dried in an oven at 80 ℃ for 24h to obtain powder. The obtained powder is ground to be uniform by a mortar, and calcined at 920 ℃ for 10h to obtain the mother powder of the presintering product. Weighing a certain mass of mother powder, placing the mother powder in a mold with the diameter of 15mm, placing the mold on a workbench of a tabletting machine, applying the pressure of 450MPa, maintaining the pressure for 5min, demoulding, and taking out the biscuit piece which is completely molded. Embedding the biscuit sheet with the mother powder, placing the biscuit sheet in an alumina crucible, preserving heat for 2.5h in a muffle furnace to 1050 ℃, sintering at the heating rate of 10 ℃/min, finishing when the temperature is raised to 1250 ℃, and cooling along with the furnace to obtain Li7La3Zr1.70Cr0.30O12A solid electrolyte.
Example 13
The difference from example 12 is that Cr In example 12 is replaced with In.
Example 14
The difference from example 12 is that Cr in example 12 is replaced with Ti.
Example 15
The difference from example 12 is that Cr in example 12 was replaced with Mo.
Example 16
The difference from example 12 is that Cr in example 12 is replaced with W.
Example 17
Different from the embodiment 1 in that La in the embodiment 12O3Replacement by hydrogenLanthanum oxide.
Example 18
Different from the embodiment 1 in that La in the embodiment 12O3And replaced by lanthanum nitrate.
Example 19
Unlike example 1, the difference is that LiOH. H in example 12O is replaced with lithium carbonate.
Example 20
Unlike example 1, the difference is that LiOH. H in example 12O is replaced with lithium acetate.
Example 21
Unlike example 1, the difference is that LiOH. H in example 12O was replaced with lithium nitrate.
Example 22
Unlike example 1, ZrO in example 1 was used2And replaced with zirconium hydroxide.
Example 23
Unlike example 1, ZrO in example 1 was used2And replaced by zirconium nitrate.
Comparative example 1
Comparative example 1 constant temperature sintering of Li at Low temperature7La3Zr1.5Ta0.5O12Preparation of solid electrolyte:
according to Li7La3Zr1.5Ta0.5O12Weighing 0.15mol of La2O3，0.7mol LiOH·H2O,0.15mol ZrO2And 0.025mol Ta2O5In order to compensate for the volatilization of Li element at high temperature in the crystal structure, LiOH. H in the raw material2O is in excess of 15% of the total mass. The raw materials are mixed and ball-milled in an isopropanol ball-milling medium at the rotating speed of 380r/min for 20 hours and then dried in an oven at the temperature of 80 ℃ for 24 hours. Grinding the obtained powder uniformly by using a mortar, calcining at 900 ℃ for 10h to obtain pre-sintered product mother powder, weighing a certain mass of the mother powder, placing the mother powder into a mold with the diameter of 15mm, placing the mold on a workbench of a tabletting machine, applying pressure of 400MPa, maintaining the pressure for 5min, demoulding, and taking out the biscuit piece which is completely molded. Embedding the biscuit sheet with the mother powder, and placing inSintering in a muffle furnace at 1000 ℃ for 12h in an alumina crucible, and cooling along with the furnace to obtain Li after low-temperature sintering7La3Zr1.5Ta0.5O12A solid electrolyte.
Comparative example 2
Comparative example 2 constant temperature sintering of Li at high temperature7La3Zr1.5Ta0.5O12Preparation of solid electrolyte:
according to Li7La3Zr1.5Ta0.5O12Weighing 0.15mol of La2O3，0.7mol LiOH·H2O,0.15mol ZrO2And 0.025mol Ta2O5In order to compensate for the volatilization of Li element at high temperature in the crystal structure, LiOH. H in the raw material2O is in excess of 10% of the total mass. The raw materials are mixed and ball-milled in an isopropanol ball-milling medium at the rotating speed of 380r/min for 20 hours and then dried in an oven at the temperature of 80 ℃ for 24 hours. Grinding the obtained powder uniformly by using a mortar, calcining at 900 ℃ for 10h to obtain pre-sintered product mother powder, weighing a certain mass of the mother powder, placing the mother powder into a mold with the diameter of 15mm, placing the mold on a workbench of a tabletting machine, applying pressure of 400MPa, maintaining the pressure for 5min, demoulding, and taking out the biscuit piece which is completely molded. Embedding the biscuit sheet with mother powder, placing in an alumina crucible, sintering in a muffle furnace at 1200 ℃ for 6h, and cooling with the furnace to obtain high-temperature sintered Li7La3Zr1.5Ta0.5O12A solid electrolyte.
The prepared solid electrolyte sample was subjected to microstructure analysis using a TM 3000 Scanning Electron Microscope (SEM), as shown in fig. 1, 2, and 3.
FIG. 1 shows comparative example 1, i.e., Li sintered at a constant temperature at a low temperature7La3Zr1.5Ta0.5O12The microstructure of the solid electrolyte shows that the crystal grain size of the electrolyte is fine and uneven, crystals do not grow, a plurality of irregular and obvious holes are formed among the crystal grains, a plurality of crystal boundaries are formed among the crystal grains, and a plurality of defects are formed in the material body.
FIG. 2 shows Li of comparative example 2 sintered at a high temperature7La3Zr1.5Ta0.5O12As can be seen from the figure, the solid electrolyte has non-uniform grain size, and a part of the grains excessively grow, showing abnormal grain growth. Both the sintering methods of comparative example 1 and comparative example 2 result in the case where the prepared electrolyte material has low ionic conductivity and low relative density.
FIG. 3 is example 3, Li prepared by the dynamic sintering method7La3Zr1.75Ta0.25O12A solid electrolyte. As can be seen from the figure, the grains are uniform in size, closely arranged, reduced in grain boundary concentration and free of obvious pores.
The electrolyte materials prepared in comparative examples 1 and 2, example 3, example 4 and example 5 were subjected to an ion conductivity analysis test at 25 c by an electrochemical workstation, and the ac impedance spectra thereof are shown in fig. 4, fig. 5, fig. 6, fig. 7 and fig. 8, and it can be seen that all the samples prepared showed a clear semicircular shape in the high frequency region and a tail in the low frequency region, indicating that the materials belong to ion conductors. It was found by calculation that the ionic conductivities of the electrolytes prepared in comparative example 1 and comparative example 2, example 3, example 4 and example 5 were 1.01 × 10 in this order, respectively-4,1.36×10-4，7.73×10-4，8.31×10-4And 7.56X 10-4S cm-1. The comparison shows that the solid electrolyte prepared by the dynamic sintering method has the highest ionic conductivity, and the conductivity is improved by 5.7-8.2 times. The sintering method is shown to be capable of effectively improving the ionic conductivity of the garnet-type solid electrolyte.
To verify the stability of the solid electrolyte material prepared in example 3 to lithium metal, Li | Au/Li was assembled7La3Zr1.75Ta0.25O12the/Au | Li symmetric cells were tested as shown in fig. 9. From the cycle chart, it can be seen that Li prepared by the dynamic sintering method7La3Zr1.75Ta0.25O12Can be at 0.2mA cm-2And stable circulation is carried out for 200h at 25 ℃. Indicating the Li prepared7La3Zr1.75Ta0.25O12The solid electrolyte has a certain effect on the inhibition of lithium dendrites, and also shows excellent stability to lithium metal.
The above-mentioned embodiments are only preferred embodiments of the present invention, and are not intended to limit the embodiments of the present invention, and those skilled in the art can easily understand that the features of the present invention should be included in the scope of the present invention by any modifications, variations, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention, and therefore the scope of the present invention is subject to the protection scope of the following claims.

Claims (9)

1. The preparation method of the garnet-type solid electrolyte with high ionic conductivity is characterized by comprising the following steps of:
according to the formula Li7La3Zr2-xMxO12Ball-milling powder of a lithium source, a lanthanum source, a zirconium source and an M source, and then pre-sintering at 800-950 ℃ for 8-10.5 h to obtain a primary sintered powder; pressing the primary sintering powder into a circular biscuit sheet, and preserving the heat of the biscuit sheet at a low temperature section for 0.5-3 h; then continuously heating to a high-temperature section and cooling to obtain the garnet-type solid electrolyte with high ionic conductivity, wherein the temperature of the low-temperature section is 950-1200 ℃, the temperature of the high-temperature section is 1000-1350 ℃, and the temperature of the high-temperature section is at least 50 ℃ higher than that of the low-temperature section; the M source is an Al source, a Ga source, a Y source, an In source, a Ti source, an Hf source, an Nb source, a Ta source, a Cr source, a Mo source or a W source, and x is more than or equal to 0.2 and less than or equal to 0.75.
2. The method of claim 1, wherein x is 0.2. ltoreq. x.ltoreq.0.5.
3. The method of claim 1, wherein the lithium source is one of lithium carbonate, lithium hydroxide, lithium acetate and lithium nitrate.
4. The method of claim 1, wherein the lanthanum source is one of lanthanum oxide, lanthanum hydroxide and lanthanum nitrate.
5. The method of claim 1, wherein the zirconium source is one of zirconia, zirconium hydroxide and zirconium nitrate.
6. The method of claim 1, wherein the M source is an oxide of Al, Ga, Y, In, Ti, Hf, Nb, Ta, Cr, Mo or W.
7. The method of claim 1, wherein the green powder is pressed under a pressure of 300 to 500MPa to form a circular green sheet.
8. The method for preparing the garnet-type solid electrolyte with high ionic conductivity according to claim 1, wherein the biscuit sheet is placed in a muffle furnace and heated to a high temperature section at a heating rate of 1-20 ℃/min.
9. The method of claim 1, wherein the cooling is furnace cooling.
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