CN112436192A - Air-stable garnet solid electrolyte of lithium battery and preparation method thereof - Google Patents

Air-stable garnet solid electrolyte of lithium battery and preparation method thereof Download PDF

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CN112436192A
CN112436192A CN202011284595.XA CN202011284595A CN112436192A CN 112436192 A CN112436192 A CN 112436192A CN 202011284595 A CN202011284595 A CN 202011284595A CN 112436192 A CN112436192 A CN 112436192A
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solid electrolyte
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陈庆
廖健淞
白涛
司文彬
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Chengdu New Keli Chemical Science Co Ltd
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    • H01M10/00—Secondary cells; Manufacture thereof
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Abstract

The invention relates to the field of lithium batteries, and particularly provides an air-stable garnet solid electrolyte of a lithium battery and a preparation method thereof. Mixing powdered Li2CO3、La2O3、ZrO2Mixing, grinding and drying to obtain powder A, then preparing a porous solid material loaded with tungsten trioxide and tantalum pentoxide, marking as solid B, then adding slurry C prepared by high-speed ball milling of the powder A and isopropanol, fully soaking, sintering at high temperature, and annealing to prepare the air-stable garnet solid electrolyte of the lithium battery. According to the method, the ceramic matrix with the porous structure is formed, the doped LLZO electrolyte can be loaded and uniformly dispersed in the calcium oxide ceramic, a lithium ion transmission channel is provided, and the obtained garnet type solid electrolyte has high conductivity and good air stability.

Description

Air-stable garnet solid electrolyte of lithium battery and preparation method thereof
Technical Field
The invention relates to the field of lithium batteries, in particular to preparation of a solid electrolyte, and particularly relates to an air-stable garnet solid electrolyte of a lithium battery and a preparation method thereof.
Background
The lithium ion battery has high energy density, strong stability, no memory effect and long cycle life, and is widely applied as a commercial high-efficiency energy storage device. The electrolyte used in the traditional lithium ion battery is liquid lithium hexafluorophosphate, and the electrolyte is extremely unstable, is easy to decompose to cause battery flatulence, and is extremely easy to combust and explode at high temperature, short circuit, overcharge or physical collision. Despite the protection mechanism added by the external encapsulation, it still has a large safety hazard.
The solid lithium ion battery uses the solid electrolyte to replace the liquid electrolyte, and can fundamentally solve the safety problem and the temperature use region problem of the liquid lithium ion battery. The chemical general formula of the garnet-type compound is A3B2(XO4)3And when the element A is lithium, the conductive material has lithium ion conductivity. Most of the substances as electrolytes are Li7La3Zr2O12(LLZO), which is very stable after being compounded with lithium metal and hardly causes side reactions, is a popular material for solid-state battery electrolytes currently using lithium metal negative electrodes. However, the lithium ion conductor of the conventional garnet structure generally has low ionic conductivity and is sensitive to moisture and carbon dioxide in the air, so that the stability of the material is relatively poor. Therefore, the method has very important practical significance for improving the ionic conductivity and stability of the garnet lithium ion conductor serving as the solid electrolyte.
The chinese patent application No. 201710797774.5 discloses a method for preparing a nano garnet-type solid electrolyte material, which comprises the following steps: (1) dissolving garnet metal ion soluble salt in deionized water or mixed solvent; (2) adding a certain amount of graphene oxide or graphene template material into the step (1); (3) adsorbing garnet metal ions on the graphene oxide or graphene sheet layer; (4) adjusting the pH value, performing hydrolysis reaction, and obtaining a garnet-type solid electrolyte precursor on the graphene oxide or graphene sheet layer; (5) adding a soluble salt solution of lithium; (6) and (4) carrying out heat treatment to obtain the nano garnet type solid electrolyte material.
Chinese invention patent application number 201710874832.X discloses a garnet-structure solid electrolyte material and a preparation method thereof, and specifically comprises the steps of mixing a compound containing five elements of lithium, lanthanum, calcium, zirconium and tantalum in an acidic solution, drying to obtain precursor powder, and sequentially adding the precursor powderCalcining, tabletting and sintering to obtain the garnet-structure solid electrolyte material with the chemical composition of Li7+x-yCaxLa3-xTayZr2-yO12Wherein x is more than 0 and less than or equal to 1, and y is more than 0 and less than or equal to 2.
The chinese patent application No. 201710243637.7 discloses a preparation method of a garnet-type solid electrolyte material, which comprises the following steps: mixing garnet type electrolyte powder, a binder and a solvent to obtain electrolyte slurry; coating the electrolyte slurry on a PET film, and drying at a set drying temperature to evaporate part of the solvent to obtain an electrolyte film; taking the electrolyte film from the PET film, and cutting the electrolyte film according to a certain specification; and discharging the binder and the residual solvent in the cut electrolyte film to obtain a compact garnet-type lithium ion conductor electrolyte sheet.
Chinese patent application No. 201810563060.2 discloses a doped Bi5+The tin-based garnet solid electrolyte material and the preparation method thereof. The chemical composition of the material is Li7-xLa3Sn2-xBixO12Wherein x is more than 0 and less than 2. Respectively weighing lithium compounds, lanthanum compounds, tin compounds and bismuth compounds, and carrying out mixing ball milling; pre-burning the ball-milled material; grinding the pre-sintered material into powder, sieving, tabletting and preparing a sample; and sintering the prepared sample again to obtain the electrolyte material with the cubic phase garnet type structure.
According to the above, the garnet solid electrolyte used in the lithium battery in the prior art has a weak ion conductivity, a generally low ion conductivity, and is sensitive to moisture and carbon dioxide in the air, resulting in relatively poor stability of the material.
Disclosure of Invention
Aiming at the problems of lower ionic conductivity and poorer air stability of the garnet solid-state battery electrolyte of the lithium battery which is widely applied at present, the invention provides the air stable garnet solid electrolyte of the lithium battery and the preparation method thereof, thereby effectively realizing the improvement of the specific surface area and the photocatalytic effect of cadmium selenide and having good degradation effect on pollutants in the air.
The invention relates to a specific technical scheme as follows:
a preparation method of an air-stable garnet solid electrolyte of a lithium battery comprises the following steps:
(1) mixing powdered Li2CO3、La2O3、ZrO2Mixing and grinding the mixture until the powder is uniformly mixed to obtain ground mixed powder;
(2) putting the ground powder obtained in the step (1) into a corundum crucible, and heating to remove residual moisture to obtain dry powder, which is marked as powder A;
(3) uniformly mixing powder of calcium hydroxide, sodium hydroxide, tungsten trioxide and tantalum pentoxide, a plastic agent, a binder, a pore-forming agent and a solvent to prepare a pug, then extruding the pug to form a blank, placing the blank in a closed container for curing, and cooling to room temperature after the curing to prepare a porous solid material loaded with tungsten trioxide and tantalum pentoxide, which is marked as solid B;
(4) putting the powder A prepared in the step (2) into a ball mill with a polytetrafluoroethylene inner wall, adding an isopropanol medium, and carrying out high-speed ball milling to prepare slurry C;
(5) and (4) soaking the solid B prepared in the step (3) in the slurry C prepared in the step (4), removing the solid B after sufficient adsorption, and then sintering at high temperature and annealing to prepare the air stable garnet solid electrolyte of the lithium battery.
The calcium oxide ceramic matrix prepared by the invention can absorb moisture and carbon dioxide in the air so as to protect the LLZO electrolyte inside. The preparation method comprises the steps of obtaining a ceramic matrix with a porous structure through calcium hydroxide, sodium hydroxide, tungsten trioxide and tantalum pentoxide, adsorbing LLZO precursor slurry and sintering to form a calcium oxide-based ceramic matrix loaded with LLZO electrolyte, and doping the LLZO with the tungsten trioxide and the tantalum pentoxide in the sintering process to uniformly disperse the doped solid electrolyte in the calcium oxide ceramic to provide a lithium ion transmission channel.
Preferably, in step (1), Li is in the form of powder2CO3、La2O3、ZrO2The molar ratio of (A) to (B) is 1: 0.4-0.6: 0.5-0.7.
Preferably, the heating temperature in the step (2) is 110-130 ℃, and the time is 12-13 h.
Preferably, the plasticizer in the step (3) is a mixed solution of phenolic resin and ethanol mixed according to a mass ratio of 1: 3. The adhesive is a jelly formed by mixing sodium tripolyphosphate and epoxy resin according to the mass ratio of 1:1, the pore-forming agent is at least one of sodium bicarbonate and ammonium bicarbonate, and the solvent is a liquid formed by mixing deionized water and absolute ethyl alcohol according to the mass ratio of 1: 1.
Preferably, the temperature of the curing treatment in the step (3) is 500-600 ℃, and the time is 2-3 h.
Preferably, in the step (3), 79-92 parts by weight of calcium hydroxide, 5-8 parts by weight of sodium hydroxide, 8-12 parts by weight of tungsten trioxide, 7-10 parts by weight of tantalum pentoxide, 3-5 parts by weight of a plasticizer, 3-5 parts by weight of a binder, 5-10 parts by weight of a pore-forming agent and 40-60 parts by weight of a solvent.
Preferably, the grinding balls of the high-speed ball milling in the step (4) are zirconia balls, the rotating speed is 800-1000 r/min, and the time is 50-60 min.
Preferably, in the step (4), 40 to 50 parts by weight of the powder A and 50 to 60 parts by weight of isopropanol.
Preferably, the soaking time in the step (5) is 8-12 h; the high-temperature sintering temperature is 800-1000 ℃, and the sintering time is 3-8 h; the annealing temperature is 200-300 ℃, and the annealing time is 10-12 h.
The invention also provides the air stable garnet solid electrolyte of the lithium battery prepared by the preparation method. Mixing powdered Li2CO3、La2O3、ZrO2Mixing and grinding according to a stoichiometric ratio until the powder is uniformly mixed, placing the ground powder into a corundum crucible, heating to remove residual water, marking as powder A, mixing calcium hydroxide powder, sodium hydroxide powder, tungsten trioxide powder and tantalum pentoxide powder uniformly, preparing into pug, and then preparing into pugAnd extruding the pug into a blank, carrying out heat treatment in a closed container at 500-600 ℃ for 2h, and cooling to room temperature to obtain the porous solid material loaded with tungsten trioxide and tantalum pentoxide, which is marked as solid B. And (3) placing the powder A in a ball mill on the inner wall of polytetrafluoroethylene, carrying out high-speed ball milling in an isopropanol medium by using zirconia balls to obtain slurry C, soaking the solid B in the slurry C, fully adsorbing, sintering at high temperature, and annealing to obtain the required solid electrolyte to obtain the product.
The invention provides an air stable garnet solid electrolyte of a lithium battery and a preparation method thereof, compared with the prior art, the air stable garnet solid electrolyte has the outstanding characteristics and excellent effects that:
1. a method for preparing an air stable garnet solid electrolyte for a lithium battery from the formed calcium oxide ceramic matrix is provided.
2. By forming the ceramic matrix with the porous structure, the doped LLZO electrolyte can be loaded and uniformly dispersed in the calcium oxide ceramic, a lithium ion transmission channel is provided, and the obtained garnet-type solid electrolyte has high conductivity and good air stability.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
The preparation process comprises the following steps:
(1) mixing powdered Li2CO3、La2O3、ZrO2Mixing and grinding the mixture until the powder is uniformly mixed to obtain ground mixed powder; wherein Li2CO3、La2O3、ZrO2In a molar ratio of 1:0.4: 0.5;
(2) putting the ground powder obtained in the step (1) into a corundum crucible, and heating to remove residual moisture to obtain dry powder, which is marked as powder A; the heating temperature is 115 ℃, and the time is 13 h;
(3) uniformly mixing powder of calcium hydroxide, sodium hydroxide, tungsten trioxide and tantalum pentoxide, a plastic agent, a binder, a pore-forming agent and a solvent to prepare a pug, then extruding the pug to form a blank, placing the blank in a closed container for curing, and cooling to room temperature after the curing to prepare a porous solid material loaded with tungsten trioxide and tantalum pentoxide, which is marked as solid B; the plasticizer is a mixed solution of phenolic resin and ethanol which are mixed according to the mass ratio of 1: 3. The adhesive is a jelly formed by mixing sodium tripolyphosphate and epoxy resin according to the mass ratio of 1:1, the pore-forming agent is sodium bicarbonate, and the solvent is a liquid formed by mixing deionized water and absolute ethyl alcohol according to the mass ratio of 1: 1; the temperature of the curing treatment is 520 ℃, and the time is 3 h; 82 parts of calcium hydroxide, 5 parts of sodium hydroxide, 9 parts of tungsten trioxide, 8 parts of tantalum pentoxide, 4 parts of a plastic agent, 4 parts of a binder, 8 parts of a pore-forming agent and 46 parts of a solvent;
(4) putting the powder A prepared in the step (2) into a ball mill with a polytetrafluoroethylene inner wall, adding an isopropanol medium, and carrying out high-speed ball milling to prepare slurry C; the grinding balls of the high-speed ball milling are zirconia balls, the rotating speed is 850r/min, and the time is 58 min; wherein, the powder A is 42 weight parts, and the isopropanol is 58 weight parts;
(5) soaking the solid B prepared in the step (3) in the slurry C prepared in the step (4), removing the solid B after full adsorption, and then sintering at a high temperature of 900 ℃ for 5 hours and annealing; the annealing temperature is 250 ℃, the annealing time is 11 hours, and the air stable garnet solid electrolyte of the lithium battery is prepared; the immersion time was 9 h.
The test method comprises the following steps:
taking the solid electrolyte prepared in any embodiment 1, and performing an alternating current impedance test by adopting a Princeton PARSTAT227 type electrochemical workstation, wherein the frequency range is 1 Hz-1 MHz, the amplitude is 10mV, so as to obtain an alternating current impedance map and further obtain the ionic conductivity; the solid electrolyte was then placed in an air environment with a relative humidity of 80% at 20 ℃ and 60 ℃, respectively, and the ionic conductivity was tested, respectively.
The ionic conductivity in the air stability test of the garnet solid electrolyte of example 1 measured by the above method is shown in table 1.
Example 2
The preparation process comprises the following steps:
(1) mixing powdered Li2CO3、La2O3、ZrO2Mixing and grinding the mixture until the powder is uniformly mixed to obtain ground mixed powder; wherein Li2CO3、La2O3、ZrO2In a molar ratio of 1: 0.6: 0.7;
(2) putting the ground powder obtained in the step (1) into a corundum crucible, and heating to remove residual moisture to obtain dry powder, which is marked as powder A; the heating temperature is 125 ℃, and the time is 12 h;
(3) uniformly mixing powder of calcium hydroxide, sodium hydroxide, tungsten trioxide and tantalum pentoxide, a plastic agent, a binder, a pore-forming agent and a solvent to prepare a pug, then extruding the pug to form a blank, placing the blank in a closed container for curing, and cooling to room temperature after the curing to prepare a porous solid material loaded with tungsten trioxide and tantalum pentoxide, which is marked as solid B; the plasticizer is a mixed solution of phenolic resin and ethanol which are mixed according to the mass ratio of 1: 3. The adhesive is a jelly formed by mixing sodium tripolyphosphate and epoxy resin according to the mass ratio of 1:1, the pore-forming agent is ammonium bicarbonate, and the solvent is a liquid formed by mixing deionized water and absolute ethyl alcohol according to the mass ratio of 1: 1; the temperature of the curing treatment is 580 ℃, and the time is 2 hours; 92 parts of calcium hydroxide, 8 parts of sodium hydroxide, 11 parts of tungsten trioxide, 9 parts of tantalum pentoxide, 5 parts of a plastic agent, 5 parts of a binder, 10 parts of a pore-forming agent and 60 parts of a solvent;
(4) putting the powder A prepared in the step (2) into a ball mill with a polytetrafluoroethylene inner wall, adding an isopropanol medium, and carrying out high-speed ball milling to prepare slurry C; the grinding balls of the high-speed ball milling are zirconia balls, the rotating speed is 960r/min, and the time is 52 min; wherein, 48 parts of powder A and 52 parts of isopropanol;
(5) soaking the solid B prepared in the step (3) in the slurry C prepared in the step (4), fully adsorbing and removing, and then sintering at a high temperature of 800 ℃ and annealing for 8 hours; the annealing temperature is 200 ℃, the annealing time is 12 hours, and the air-stable garnet solid electrolyte of the lithium battery is prepared; the immersion time was 11 h.
The test method comprises the following steps:
taking the solid electrolyte prepared in any embodiment 2, and carrying out alternating current impedance test by adopting a Princeton PARSTAT227 type electrochemical workstation, wherein the frequency range is 1 Hz-1 MHz, the amplitude is 10mV, and an alternating current impedance map is obtained, so that the ionic conductivity is obtained; the solid electrolyte was then placed in an air environment with a relative humidity of 80% at 20 ℃ and 60 ℃, respectively, and the ionic conductivity was tested, respectively.
The ionic conductivity in the air stability test of the garnet solid electrolyte of example 2 measured by the above method is shown in table 1.
Example 3
The preparation process comprises the following steps:
(1) mixing powdered Li2CO3、La2O3、ZrO2Mixing and grinding the mixture until the powder is uniformly mixed to obtain ground mixed powder; wherein Li2CO3、La2O3、ZrO2In a molar ratio of 1:0.5: 0.6;
(2) putting the ground powder obtained in the step (1) into a corundum crucible, and heating to remove residual moisture to obtain dry powder, which is marked as powder A; the heating temperature is 118 ℃, and the time is 12.5 h;
(3) uniformly mixing powder of calcium hydroxide, sodium hydroxide, tungsten trioxide and tantalum pentoxide, a plastic agent, a binder, a pore-forming agent and a solvent to prepare a pug, then extruding the pug to form a blank, placing the blank in a closed container for curing, and cooling to room temperature after the curing to prepare a porous solid material loaded with tungsten trioxide and tantalum pentoxide, which is marked as solid B; the plasticizer is a mixed solution of phenolic resin and ethanol according to the mass ratio of 1: 3. The adhesive is a jelly formed by mixing sodium tripolyphosphate and epoxy resin according to the mass ratio of 1:1, the pore-forming agent is sodium bicarbonate, and the solvent is a liquid formed by mixing deionized water and absolute ethyl alcohol according to the mass ratio of 1: 1; the temperature of the curing treatment is 560 ℃, and the time is 2.5 h; 85 parts of calcium hydroxide, 7 parts of sodium hydroxide, 9 parts of tungsten trioxide, 9 parts of tantalum pentoxide, 4 parts of a plastic agent, 4 parts of a binder, 8 parts of a pore-forming agent and 52 parts of a solvent;
(4) putting the powder A prepared in the step (2) into a ball mill with a polytetrafluoroethylene inner wall, adding an isopropanol medium, and carrying out high-speed ball milling to prepare slurry C; the grinding balls of the high-speed ball milling are zirconia balls, the rotating speed is 880r/min, and the time is 56 min; wherein, the powder A is 46 weight parts, and the isopropanol is 54 weight parts;
(5) soaking the solid B prepared in the step (3) in the slurry C prepared in the step (4), fully adsorbing and removing, and then sintering at a high temperature of 1000 ℃ for 3h and annealing; the annealing temperature is 300 ℃, the annealing time is 10 hours, and the air stable garnet solid electrolyte of the lithium battery is prepared; the immersion time was 11 h.
The test method comprises the following steps:
taking the solid electrolyte prepared in any embodiment 3, and performing an alternating current impedance test by adopting a Princeton PARSTAT227 type electrochemical workstation, wherein the frequency range is 1 Hz-1 MHz, the amplitude is 10mV, so as to obtain an alternating current impedance map and further obtain the ionic conductivity; the solid electrolyte was then placed in an air environment with a relative humidity of 80% at 20 ℃ and 60 ℃, respectively, and the ionic conductivity was tested, respectively.
The ionic conductivity in the air stability test of the garnet solid electrolyte of example 3 measured by the above method is shown in table 1.
Example 4
The preparation process comprises the following steps:
(1) mixing powdered Li2CO3、La2O3、ZrO2Mixing and grinding until powderUniformly mixing the powder to obtain ground mixed powder; wherein Li2CO3、La2O3、ZrO2In a molar ratio of 1: 0.6: 0.7;
(2) putting the ground powder obtained in the step (1) into a corundum crucible, and heating to remove residual moisture to obtain dry powder, which is marked as powder A; the heating temperature is 130 ℃, and the time is 12 h;
(3) uniformly mixing powder of calcium hydroxide, sodium hydroxide, tungsten trioxide and tantalum pentoxide, a plastic agent, a binder, a pore-forming agent and a solvent to prepare a pug, then extruding the pug to form a blank, placing the blank in a closed container for curing, and cooling to room temperature after the curing to prepare a porous solid material loaded with tungsten trioxide and tantalum pentoxide, which is marked as solid B; the plasticizer is a mixed solution of phenolic resin and ethanol according to the mass ratio of 1: 3. The adhesive is a jelly formed by mixing sodium tripolyphosphate and epoxy resin according to the mass ratio of 1:1, the pore-forming agent is ammonium bicarbonate, and the solvent is a liquid formed by mixing deionized water and absolute ethyl alcohol according to the mass ratio of 1: 1; the temperature of the curing treatment is 600 ℃, and the time is 2 hours; 79 parts of calcium hydroxide, 8 parts of sodium hydroxide, 12 parts of tungsten trioxide, 10 parts of tantalum pentoxide, 5 parts of a plastic agent, 5 parts of a binder, 10 parts of a pore-forming agent and 55 parts of a solvent;
(4) putting the powder A prepared in the step (2) into a ball mill with a polytetrafluoroethylene inner wall, adding an isopropanol medium, and carrying out high-speed ball milling to prepare slurry C; the grinding balls of the high-speed ball milling are zirconia balls, the rotating speed is 1000r/min, and the time is 50 min; wherein, 50 parts of powder A and 50 parts of isopropanol;
(5) soaking the solid B prepared in the step (3) in the slurry C prepared in the step (4), removing the solid B after full adsorption, and then sintering at a high temperature of 850 ℃ and annealing for 6 hours; the annealing temperature is 260 ℃, the annealing time is 10 hours, and the air-stable garnet solid electrolyte of the lithium battery is prepared; the immersion time was 12 h.
The test method comprises the following steps:
taking the solid electrolyte prepared in any embodiment 5, and performing an alternating current impedance test by adopting a Princeton PARSTAT227 type electrochemical workstation, wherein the frequency range is 1 Hz-1 MHz, the amplitude is 10mV, so as to obtain an alternating current impedance map and further obtain the ionic conductivity; the solid electrolyte was then placed in an air environment with a relative humidity of 80% at 20 ℃ and 60 ℃, respectively, and the ionic conductivity was tested, respectively.
The ionic conductivity in the air stability test of the garnet solid electrolyte of example 5 measured by the above method is shown in table 1.
Example 5
The preparation process comprises the following steps:
(1) mixing powdered Li2CO3、La2O3、ZrO2Mixing and grinding the mixture until the powder is uniformly mixed to obtain ground mixed powder; wherein Li2CO3、La2O3、ZrO2In a molar ratio of 1:0.4: 0.5;
(2) putting the ground powder obtained in the step (1) into a corundum crucible, and heating to remove residual moisture to obtain dry powder, which is marked as powder A; the heating temperature is 110 ℃, and the time is 13 h;
(3) uniformly mixing powder of calcium hydroxide, sodium hydroxide, tungsten trioxide and tantalum pentoxide, a plastic agent, a binder, a pore-forming agent and a solvent to prepare a pug, then extruding the pug to form a blank, placing the blank in a closed container for curing, and cooling to room temperature after the curing to prepare a porous solid material loaded with tungsten trioxide and tantalum pentoxide, which is marked as solid B; the plasticizer is a mixed solution of phenolic resin and ethanol according to the mass ratio of 1: 3. The adhesive is a jelly formed by mixing sodium tripolyphosphate and epoxy resin according to the mass ratio of 1:1, the pore-forming agent is sodium bicarbonate, and the solvent is a liquid formed by mixing deionized water and absolute ethyl alcohol according to the mass ratio of 1: 1; the temperature of the curing treatment is 500 ℃, and the time is 3 h; wherein, 84 parts by weight of calcium hydroxide, 8 parts by weight of sodium hydroxide, 8 parts by weight of tungsten trioxide, 7 parts by weight of tantalum pentoxide, 3 parts by weight of plastic agent, 3 parts by weight of binder, 5 parts by weight of pore-forming agent and 48 parts by weight of solvent;
(4) putting the powder A prepared in the step (2) into a ball mill with a polytetrafluoroethylene inner wall, adding an isopropanol medium, and carrying out high-speed ball milling to prepare slurry C; the grinding balls of the high-speed ball milling are zirconia balls, the rotating speed is 800r/min, and the time is 60 min; wherein, the powder A accounts for 40 parts by weight, and the isopropanol accounts for 60 parts by weight;
(5) soaking the solid B prepared in the step (3) in the slurry C prepared in the step (4), fully adsorbing and removing, and then sintering at a high temperature of 950 ℃ for 4h and annealing; the annealing temperature is 220 ℃, the annealing time is 12 hours, and the air-stable garnet solid electrolyte of the lithium battery is prepared; the immersion time was 8 h.
The test method comprises the following steps:
taking the solid electrolyte prepared in any embodiment 5, and performing an alternating current impedance test by adopting a Princeton PARSTAT227 type electrochemical workstation, wherein the frequency range is 1 Hz-1 MHz, the amplitude is 10mV, so as to obtain an alternating current impedance map and further obtain the ionic conductivity; the solid electrolyte was then placed in an air environment with a relative humidity of 80% at 20 ℃ and 60 ℃, respectively, and the ionic conductivity was tested, respectively.
The ionic conductivity in the air stability test of the garnet solid electrolyte of example 5 measured by the above method is shown in table 1.
Example 6
The preparation process comprises the following steps:
(1) mixing powdered Li2CO3、La2O3、ZrO2Mixing and grinding the mixture until the powder is uniformly mixed to obtain ground mixed powder; wherein Li2CO3、La2O3、ZrO2In a molar ratio of 1:0.5: 0.6;
(2) putting the ground powder obtained in the step (1) into a corundum crucible, and heating to remove residual moisture to obtain dry powder, which is marked as powder A; the heating temperature is 120 ℃, and the time is 12.5 h;
(3) uniformly mixing powder of calcium hydroxide, sodium hydroxide, tungsten trioxide and tantalum pentoxide, a plastic agent, a binder, a pore-forming agent and a solvent to prepare a pug, then extruding the pug to form a blank, placing the blank in a closed container for curing, and cooling to room temperature after the curing to prepare a porous solid material loaded with tungsten trioxide and tantalum pentoxide, which is marked as solid B; the plasticizer is a mixed solution of phenolic resin and ethanol according to the mass ratio of 1: 3. The adhesive is a jelly formed by mixing sodium tripolyphosphate and epoxy resin according to the mass ratio of 1:1, the pore-forming agent is ammonium bicarbonate, and the solvent is a liquid formed by mixing deionized water and absolute ethyl alcohol according to the mass ratio of 1: 1; the temperature of the curing treatment is 550 ℃, and the time is 2.5 h; the coating comprises, by weight, 83 parts of calcium hydroxide, 8 parts of sodium hydroxide, 10 parts of tungsten trioxide, 8 parts of tantalum pentoxide, 4 parts of a plastic agent, 4 parts of a binder, 7 parts of a pore-forming agent and 50 parts of a solvent.
(4) Putting the powder A prepared in the step (2) into a ball mill with a polytetrafluoroethylene inner wall, adding an isopropanol medium, and carrying out high-speed ball milling to prepare slurry C; the grinding balls of the high-speed ball milling are zirconia balls, the rotating speed is 900r/min, and the time is 55 min; wherein, the powder A comprises 45 weight parts and 55 weight parts of isopropanol;
(5) soaking the solid B prepared in the step (3) in the slurry C prepared in the step (4), removing the solid B after full adsorption, and then sintering at a high temperature of 880 ℃ and for 7 hours; the annealing temperature is 24 ℃, the annealing time is 11 hours, and the air stable garnet solid electrolyte of the lithium battery is prepared; the immersion time was 10 h.
The test method comprises the following steps:
taking the solid electrolyte prepared in any embodiment 6, and performing an alternating current impedance test by adopting a Princeton PARSTAT227 type electrochemical workstation, wherein the frequency range is 1 Hz-1 MHz, the amplitude is 10mV, so as to obtain an alternating current impedance map and further obtain the ionic conductivity; the solid electrolyte was then placed in an air environment with a relative humidity of 80% at 20 ℃ and 60 ℃, respectively, and the ionic conductivity was tested, respectively.
The ionic conductivity in the air stability test of the garnet solid electrolyte of example 6 measured by the above method is shown in table 1.
Comparative example 1
The preparation process comprises the following steps:
(1) mixing powdered Li2CO3、La2O3、ZrO2Mixing and grinding the mixture until the powder is uniformly mixed to obtain ground mixed powder; wherein Li2CO3、La2O3、ZrO2In a molar ratio of 1:0.5: 0.6;
(2) putting the ground powder obtained in the step (1) into a corundum crucible, and heating to remove residual moisture to obtain dry powder, which is marked as powder A; the heating temperature is 120 ℃, and the time is 12.5 h;
(3) uniformly mixing calcium hydroxide, sodium hydroxide powder, a plastic agent, a binder, a pore-forming agent and a solvent to prepare a pug, then extruding and forming the pug into a blank, placing the blank into a closed container for solidification, and cooling to room temperature after solidification to prepare a porous solid material, which is marked as solid B; the plasticizer is a mixed solution of phenolic resin and ethanol according to the mass ratio of 1: 3. The adhesive is a jelly formed by mixing sodium tripolyphosphate and epoxy resin according to the mass ratio of 1:1, the pore-forming agent is ammonium bicarbonate, and the solvent is a liquid formed by mixing deionized water and absolute ethyl alcohol according to the mass ratio of 1: 1; the temperature of the curing treatment is 550 ℃, and the time is 2.5 h; the composite material comprises, by weight, 83 parts of calcium hydroxide, 8 parts of sodium hydroxide, 4 parts of a plastic agent, 4 parts of a binder, 7 parts of a pore-forming agent and 50 parts of a solvent.
(4) Putting the powder A prepared in the step (2) into a ball mill with a polytetrafluoroethylene inner wall, adding an isopropanol medium, and carrying out high-speed ball milling to prepare slurry C; the grinding balls of the high-speed ball milling are zirconia balls, the rotating speed is 900r/min, and the time is 55 min; wherein, the powder A comprises 45 weight parts and 55 weight parts of isopropanol;
(5) soaking the solid B prepared in the step (3) in the slurry C prepared in the step (4), removing the solid B after full adsorption, and then sintering at a high temperature of 880 ℃ and for 7 hours; the annealing temperature is 24 ℃, the annealing time is 11 hours, and the air stable garnet solid electrolyte of the lithium battery is prepared; the immersion time was 10 h.
Comparative example 2
The preparation process comprises the following steps:
(1) mixing powdered Li2CO3、La2O3、ZrO2Mixing and grinding the mixture until the powder is uniformly mixed to obtain ground mixed powder; wherein Li2CO3、La2O3、ZrO2In a molar ratio of 1:0.5: 0.6;
(2) putting the ground powder obtained in the step (1) into a corundum crucible, and heating to remove residual moisture to obtain dry powder, which is marked as powder A; the heating temperature is 120 ℃, and the time is 12.5 h;
(3) mixing the powder A prepared in the step (2) with tungsten trioxide and tantalum pentoxide powder, and then sintering at a high temperature and annealing, wherein the powder A comprises 45 parts by weight of tungsten trioxide 10 parts by weight of tungsten trioxide and 8 parts by weight of tantalum pentoxide; the high-temperature sintering temperature is 900 ℃, and the sintering time is 5 h; the annealing temperature is 250 ℃, the annealing time is 11 hours, and the air stable garnet solid electrolyte of the lithium battery is prepared.
The test method comprises the following steps:
taking the solid electrolyte prepared in any comparative example 1, and carrying out alternating current impedance test by adopting a Princeton PARSTAT227 type electrochemical workstation, wherein the frequency range is 1 Hz-1 MHz, the amplitude is 10mV, and an alternating current impedance map is obtained, so that the ionic conductivity is obtained; the solid electrolyte was then placed in an air environment with a relative humidity of 80% at 20 ℃ and 60 ℃, respectively, and the ionic conductivity was tested, respectively.
The ionic conductivities of the garnet solid electrolyte of comparative example 1 measured by the above-described methods in the air stability test are shown in table 1.
Table 1:
Figure DEST_PATH_IMAGE001
the ionic conductivities of examples 1 to 6 in table 1 at 20 ℃ and 60 ℃ are much higher than those of comparative example 1 and comparative example 2, because the calcium oxide ceramic is used as a solid electrolyte substrate to load the LLZO electrolyte in examples 1 to 6, the calcium oxide ceramic adsorbs water and carbon dioxide in the air in a high-humidity air environment, the influence of the LLZO electrolyte is relieved, meanwhile, the water and carbon dioxide tolerance of the electrolyte is also improved by W, Ta doping, comparative example 1 is protected by only the calcium oxide ceramic and is not subjected to W, Ta doping treatment, and still can be influenced by the water and carbon dioxide, and comparative example 2 is not protected by adding the calcium oxide ceramic, and the LLZO is modified by only W, Ta doping, so that the water and carbon dioxide tolerance is relatively poor.

Claims (10)

1. The preparation method of the air stable garnet solid electrolyte of the lithium battery is characterized by comprising the following steps of:
(1) mixing powdered Li2CO3、La2O3、ZrO2Mixing and grinding the mixture until the powder is uniformly mixed to obtain ground mixed powder;
(2) putting the ground powder obtained in the step (1) into a corundum crucible, and heating to remove residual moisture to obtain dry powder, which is marked as powder A;
(3) uniformly mixing powder of calcium hydroxide, sodium hydroxide, tungsten trioxide and tantalum pentoxide, a plastic agent, a binder, a pore-forming agent and a solvent to prepare a pug, then extruding the pug to form a blank, placing the blank in a closed container for curing, and cooling to room temperature after the curing to prepare a porous solid material loaded with tungsten trioxide and tantalum pentoxide, which is marked as solid B;
(4) putting the powder A prepared in the step (2) into a ball mill with a polytetrafluoroethylene inner wall, adding an isopropanol medium, and carrying out high-speed ball milling to prepare slurry C;
(5) and (4) soaking the solid B prepared in the step (3) in the slurry C prepared in the step (4), removing the solid B after sufficient adsorption, and then sintering at high temperature and annealing to prepare the air stable garnet solid electrolyte of the lithium battery.
2. The method of claim 1A preparation method of an air stable garnet solid electrolyte of a lithium battery is characterized by comprising the following steps: in step (1), powdered Li2CO3、La2O3、ZrO2The molar ratio of (A) to (B) is 1: 0.4-0.6: 0.5-0.7.
3. The method of claim 1, wherein the air-stable garnet solid electrolyte for a lithium battery comprises: and (3) heating at the temperature of 110-130 ℃ for 12-13 h.
4. The method of claim 1, wherein the air-stable garnet solid electrolyte for a lithium battery comprises: the plasticizer in the step (3) is a mixed solution formed by mixing phenolic resin and ethanol according to the mass ratio of 1: 3; the adhesive is a jelly formed by mixing sodium tripolyphosphate and epoxy resin according to the mass ratio of 1:1, the pore-forming agent is at least one of sodium bicarbonate and ammonium bicarbonate, and the solvent is a liquid formed by mixing deionized water and absolute ethyl alcohol according to the mass ratio of 1: 1.
5. The method of claim 1, wherein the air-stable garnet solid electrolyte for a lithium battery comprises: and (4) curing at 500-600 ℃ for 2-3 h.
6. The method of claim 1, wherein the air-stable garnet solid electrolyte for a lithium battery comprises: in the step (3), 79-92 parts by weight of calcium hydroxide, 5-8 parts by weight of sodium hydroxide, 8-12 parts by weight of tungsten trioxide, 7-10 parts by weight of tantalum pentoxide, 3-5 parts by weight of a plastic agent, 3-5 parts by weight of a binder, 5-10 parts by weight of a pore-forming agent and 40-60 parts by weight of a solvent.
7. The method of claim 1, wherein the air-stable garnet solid electrolyte for a lithium battery comprises: and (4) grinding balls of the high-speed ball milling in the step (4) are zirconia balls, the rotating speed is 800-1000 r/min, and the time is 50-60 min.
8. The method of claim 1, wherein the air-stable garnet solid electrolyte for a lithium battery comprises: in the step (4), 40-50 parts by weight of the powder A and 50-60 parts by weight of isopropanol.
9. The method of claim 1, wherein the air-stable garnet solid electrolyte for a lithium battery comprises: the temperature of the high-temperature sintering in the step (5) is 800-1000 ℃, and the sintering time is 3-8 h; the annealing temperature is 200-300 ℃, and the annealing time is 10-12 h.
10. An air-stable garnet solid electrolyte for a lithium battery prepared by the method of any one of claims 1 to 9.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113078350A (en) * 2021-03-26 2021-07-06 光鼎铷业(广州)集团有限公司 Preparation method of rubidium-doped high-conductivity LLZTO/PEO composite solid electrolyte
CN115347232A (en) * 2022-08-12 2022-11-15 广东凯金新能源科技股份有限公司 Garnet type solid electrolyte and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113078350A (en) * 2021-03-26 2021-07-06 光鼎铷业(广州)集团有限公司 Preparation method of rubidium-doped high-conductivity LLZTO/PEO composite solid electrolyte
CN115347232A (en) * 2022-08-12 2022-11-15 广东凯金新能源科技股份有限公司 Garnet type solid electrolyte and preparation method and application thereof

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