CN114551989A - Garnet type solid electrolyte and preparation method thereof - Google Patents

Garnet type solid electrolyte and preparation method thereof Download PDF

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CN114551989A
CN114551989A CN202210122452.1A CN202210122452A CN114551989A CN 114551989 A CN114551989 A CN 114551989A CN 202210122452 A CN202210122452 A CN 202210122452A CN 114551989 A CN114551989 A CN 114551989A
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solid electrolyte
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garnet
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CN114551989B (en
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陈步天
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Shandong Chuanglu Advanced Battery Technology Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • Y02E60/10—Energy storage using batteries
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Abstract

The invention discloses a garnet type solid electrolyte, belonging to the technical field of lithium ion batteries. The solid electrolyte is prepared by forming Li7La3Zr2O12Lithium, lanthanum and zirconium sources, and LiF and MoSi2(ii) a LiF and MoSi2The total mass percentage of (A) is 0.5-15%. The preparation method comprises the following steps: calcining lanthanum source, weighing lithium source, calcined lanthanum source and zirconium source, mixing, adding MoSi2Ball milling the LiF, the ball milling agent and the ball milling beads to obtain uniformly mixed slurry; drying to obtain mixed powder; sintering to obtain LLZO solid electrolyte precursor powder; pressing into tablets, and sintering for the second time to obtain the finished product. The invention introduces LiF and MoSi into LLZO solid electrolyte2Thereby forming an ion-electron mixed interface layer with excellent lithium affinity on the surface of the LLZO, and effectively improving the interface performance of the LLZO solid electrolyte and lithium metal.

Description

Garnet type solid electrolyte and preparation method thereof
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a garnet-type solid electrolyte and a preparation method thereof.
Background
The lithium ion battery has the advantages of high energy density, large output power, long service life, wide working temperature range, no memory effect, environmental friendliness and the like, and is widely applied to the fields of electric vehicles, rail transit, large-scale energy storage, aerospace and the like. At present, the commercial lithium ion battery adopts an organic liquid electrolyte, and the electrolyte and an electrode material are easy to generate side reactions in the charging and discharging processes, so that the battery capacity is irreversibly attenuated, and the service life of the battery is influenced; and lithium dendrite is easily formed on the surface of the electrode material in the charging and discharging process. Therefore, the use of solid electrolytes instead of liquid electrolytes is the fundamental approach to obtain all-solid-state lithium batteries with high energy density, safety and long cycle life.
Among solid electrolytes that have been developed so far, garnet solid electrolytes (LLZO-based) have received much attention due to their high ionic conductivity. However, compared to other types of solid electrolytes, the existing LLZO garnet solid electrolyte is unstable in air and easily reacts with moisture and carbon dioxide in air, thereby generating a large amount of Li on the LLZO surface2CO3And LiOH, thereby causing the interface contact resistance to be too large; meanwhile, the interface contact of the LLZO solid electrolyte with lithium metal is too poor, and a large amount of lithium dendrites are easily formed. It becomes very important how to improve the interfacial properties of the garnet-type solid electrolyte to reduce its interfacial resistance.
Disclosure of Invention
In order to overcome the disadvantages of the prior art, it is an object of the present invention to provide a garnet-type solid electrolyte by introducing LiF and MoSi2Thereby forming an ion-electron mixed interface layer with excellent lithium affinity on the surface of the LLZTO, and effectively improving the interface performance of the LLZTO solid electrolyte and lithium metal.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a garnet-type solid electrolyte prepared by forming Li7La3Zr2O12Lithium source powder, lanthanum source powder and zirconium source powder of (1), and LiF and MoSi2(ii) a Wherein the LiF and MoSi2The total mass percentage of (B) is 0.5-15%, preferably 1-5%.
In the present invention, MoSi2And the addition of LiF is beneficial to the protection of the crystal grains and the grain boundaries of the LLZO: f to Li with high electronegativity+Has strong binding effect and can effectively avoid H in the air2O and CO2Attack to amorphous phase of crystal boundary, so as to effectively avoid H+Ions enter the LLZO structure, thereby effectively avoiding Li+Ions with H+The exchange is carried out, and the generation of lithium carbonate on the surface of the LLZO is effectively inhibited. Second, LiF is a very good ionic conductor, while MoSi2Has very high conductivity, and can be used for preparing LiF and MoSi2And simultaneously added into the LLZO, so that an ion-electron mixed interface can be formed on the surface of the LLZO, and the interface performance of the lithium metal and the LLZO solid electrolyte can be greatly improved.
As a preferred embodiment of the present invention, the solid electrolyte further includes a compound containing a doping element; the doping element comprises one or more elements of Ta, Nb, Al, Ga, W, Mo, Gd, Ti, Ca, Ba, Y and Re.
As a preferable embodiment of the invention, the solid electrolyte further comprises an additive, wherein the additive is added by the mass percentage of 0-10%; the additive is Li2S、Li2O and/or montmorillonite.
As a preferred embodiment of the present invention, the LiF and MoSi are2The mass ratio of the components is 5: 1-1: 5.
In a preferred embodiment of the present invention, the lithium source powder is lithium hydroxide, the lanthanum source powder is lanthanum oxide, and the zirconium source powder is zirconium oxide.
Further preferably, the lithium hydroxide is in excess of 5% to 40%, preferably 5% to 20%, to supplement the volatilization of lithium at high temperature during synthesis.
Another object of the present invention is to provide a method for preparing the garnet-type solid electrolyte, comprising the steps of:
s1, placing lanthanum source powder in a muffle furnace to be calcined for 4-24 hours at 700-1200 ℃;
s2, according to Li7La3Zr2O12Weighing lithium source powder, lanthanum source powder and zirconium source powder prepared in step S1 according to the stoichiometric ratio, uniformly mixing, and adding MoSi2Performing ball milling on the powder, the LiF powder, the ball milling agent and the ball milling beads to obtain uniformly mixed slurry;
s3, drying the obtained mixed slurry to obtain mixed powder; sintering the mixed powder at 700-1200 ℃ for 4-24 h to obtain LLZO solid electrolyte precursor powder;
s4, pressing the LLZO solid electrolyte precursor powder into a sheet, and sintering at 1050-1500 ℃ for a second time, wherein the sintering time is 0.5-36 h, so as to obtain the garnet solid electrolyte.
As a preferred embodiment of the present invention, the mass ratio of all powders to the ball milling agent and the ball milling beads in step S2 is powder: ball grinding agent: the ratio of ball milling beads to ball milling beads is 1: 1-5: 4 to 20.
The ball milling time in the step S2 is 4 to 48 hours, preferably 8 to 24 hours; the rotation speed is 200 to 1200r/min, preferably 400 to 800 r/min.
In a preferred embodiment of the present invention, the ball milling agent is one of ethanol, isopropanol, acetonitrile, diethyl ether, petroleum ether and acetone; the ball milling beads are one of agate beads, zirconia beads, stainless steel beads and polyurethane beads.
In a preferred embodiment of the present invention, the drying temperature in the step S3 is 50 to 150 ℃, preferably 60 to 120 ℃; the drying time is 4-24 h, preferably 6-16 h.
In a preferred embodiment of the present invention, the LLZO solid electrolyte precursor powder is pressed into a disk having a diameter of 10 to 20mm, preferably 13 to 18mm, in the step S4.
Preferably, the sintering temperature in the step S3 is 850-1050 ℃, and the sintering time is 6-16 h.
Preferably, the sintering temperature of the secondary sintering in the step S4 is 1150-1300 ℃.
Compared with the prior art, the invention has the beneficial effects that:
the invention introduces LiF and MoSi with good conductivity into the LLZO solid electrolyte at the same time2An ion-electron mixed interface layer with excellent lithium affinity can be formed on the surface of the LLZO, so that the interface performance of the LLZO solid electrolyte and lithium metal is improved; simultaneously, LiF and MoSi2Effectively improves the contact performance of the LLZO and the air, and greatly improves the LLZO solid electrolyte in the airThe storage performance of (2). In addition, MoSi2The density of the LLZO solid electrolyte can be effectively improved, so that the room-temperature conductivity of the LLZO solid electrolyte is improved.
Drawings
FIG. 1 is an EIS resistance test chart of a LLZO solid electrolyte sheet obtained in example 1 of the present invention;
FIG. 2 is an XRD test pattern of a LLZO solid electrolyte sheet obtained in example 1 of the present invention;
FIG. 3 is an EIS impedance test chart of LLZTO solid electrolyte sheet obtained in example 2 of the present invention;
FIG. 4 is an XRD test pattern of a LLZTO solid electrolyte sheet obtained in example 2 of the present invention;
FIG. 5 is an EIS impedance test chart of LLZTO solid electrolyte sheet obtained in example 3 of the present invention;
FIG. 6 is an EIS impedance test chart of LLZTO solid electrolyte sheet obtained in example 4 of the present invention;
FIG. 7 is an EIS resistance test chart of the LLZO solid electrolyte sheet obtained in comparative example 1 of the present invention;
FIG. 8 is an XRD test pattern of a LLZO solid electrolyte sheet obtained in comparative example 1 of the present invention;
FIG. 9 is an EIS resistance test chart of the LLZO solid electrolyte sheet obtained in comparative example 2 of the present invention;
FIG. 10 is an EIS impedance test chart of a LLZTO solid electrolyte sheet obtained in comparative example 3 of the present invention;
fig. 11 is a graph showing the results of the interfacial performance test of a lithium symmetrical cell assembled with an electrolyte sheet obtained in example 1 of the present application.
Fig. 12 is a graph showing the results of the interfacial performance test of a lithium symmetrical cell assembled with an electrolyte sheet obtained in comparative example 2 of the application example of the present invention.
Fig. 13 is a graph showing the results of the interfacial performance test of a lithium symmetrical cell assembled with an electrolyte sheet obtained in example 2 of the application of the present invention.
Fig. 14 is a graph showing the results of interfacial performance testing of a lithium symmetrical cell assembled with an electrolyte sheet obtained in comparative example 3 of the application example of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
A garnet-type solid electrolyte prepared by forming Li7La3Zr2O12Lithium source powder, lanthanum source powder and zirconium source powder of (1), and LiF and MoSi2(ii) a Wherein the LiF and MoSi2The total mass percentage of (B) is 0.5-15%, preferably 0.5-5%. Preferably, the lithium source powder is lithium hydroxide, the lanthanum source powder is lanthanum oxide, and the zirconium source powder is zirconium oxide, wherein the lithium hydroxide is in excess of 5% to 40%, preferably 5% to 20%.
The solid electrolyte may further include a compound containing a doping element; the doping element comprises one or more elements of Ta, Nb, Al, Ga, W, Mo, Gd, Ti, Ca, Ba, Y and Re. The solid electrolyte can also comprise an additive, wherein the additive accounts for 0-10% of the mass of the solid electrolyte; the additive is Li2S、Li2O and/or montmorillonite.
The preparation method of the garnet-type solid electrolyte as described above includes the steps of:
s1, placing lanthanum source powder in a muffle furnace to be calcined for 4-24 hours at 700-1200 ℃;
s2, according to Li7La3Zr2O12Weighing and uniformly mixing lithium source powder, lanthanum source powder prepared in step S1 and zirconium source powder according to the stoichiometric ratio, and adding MoSi2Powder, LiF powder, by all powders: ball grinding agent: the ratio of ball milling beads to ball milling beads is 1: 1-5: adding a ball milling agent and ball milling beads in a mass ratio of 4-20, and performing ball milling for 4-48 hours at a rotating speed of 200-1200 r/min to obtain uniformly mixed slurry; wherein the ball milling agent is one of ethanol, isopropanol, acetonitrile, diethyl ether, petroleum ether and acetone; the ball milling beads are one of agate beads, zirconia beads, stainless steel beads and polyurethane beads;
s3, drying the obtained mixed slurry at 50-150 ℃ for 4-24 hours to obtain mixed powder; sintering the mixed powder at 700-1200 ℃ for 4-24 h to obtain LLZO solid electrolyte precursor powder;
s4, pressing LLZO solid electrolyte precursor powder into a wafer with the diameter of 10-20 mm, and sintering for a second time at 1050-1500 ℃ for 0.5-36 h to obtain the garnet solid electrolyte;
s5, the garnet solid electrolyte obtained was polished and then subjected to the test of EIS impedance, XRD, and the like.
Example 1
A method for preparing a garnet-type solid electrolyte comprises the following steps:
s1, mixing La2O3Drying the powder at 900 ℃ for 12h to obtain dry La2O3And (3) powder.
S2, Li in stoichiometric ratio7La3Zr2O12(LLZO), 3.234g of lithium hydroxide, 4.887g of lanthanum oxide and 2.464g of zirconium oxide are weighed out respectively and placed in an agate jar, 2% LiF and 1% MoSi are added2And 15g of ball milling agent isopropanol, and performing ball milling for 24 hours at the rotating speed of 350r/min to obtain uniformly mixed slurry.
S3, drying the mixed slurry in an oven at 60 ℃ for 15h to obtain dry mixed powder; and sintering the mixed powder at 850 ℃ for 16h to obtain the LLZO solid electrolyte precursor powder.
S4, pressing the LLZO solid electrolyte precursor powder into a wafer with the diameter of phi 15mm, and sintering at 1230 ℃ for 18h to obtain the LLZO solid electrolyte sheet.
S5, and testing the ac impedance and XRD after grinding and polishing, the results are shown in fig. 1 and 2.
As can be seen from fig. 1, XRD diffraction peaks of the prepared LLZO solid electrolyte sheet were sharp, indicating that the prepared LLZTO solid electrolyte sheet was good in crystallinity, and no impurity peak was observed, so that the diffraction peaks all belonged to LLZTO, demonstrating that the solid electrolyte prepared in this example is a pure-phase LLZO.
As can be seen from FIG. 2, the lithium ion conductivity of the LLZO solid electrolyte sheet calculated was 2.2X10-4S/cm。
Example 2
A method for preparing a garnet-type solid electrolyte comprises the following steps:
s1, mixing La2O3Drying the powder at 1000 ℃ for 12h to obtain dry La2O3And (3) powder.
S2, Li in stoichiometric ratio6.5La3Zr1.5Ta0.5O12(LLZTO), 4.5045g of lithium hydroxide, 7.3305g of lanthanum oxide, 2.772g of zirconium oxide and 1.6575g of tantalum oxide were weighed respectively into an agate jar, 1% LiF and 2% MoSi were added2And 20g of ball grinding agent isopropanol, and performing ball milling for 24 hours at the rotating speed of 450r/min to obtain uniformly mixed slurry.
S3, drying the mixed slurry in an oven at 80 ℃ for 10 hours to obtain dry mixed powder; sintering the mixed powder at 950 ℃ for 8h to obtain the LLZTO solid electrolyte precursor powder.
S4, pressing the LLZTO solid electrolyte precursor powder into a wafer with the diameter of phi 15mm, and sintering at 1250 ℃ for 6h to obtain the LLZTO solid electrolyte wafer.
S5, and testing the ac impedance and XRD after grinding and polishing, the results are shown in fig. 3 and 4.
As can be seen from fig. 3, the XRD diffraction peak of the prepared LLZTO solid electrolyte sheet is sharp, which indicates that the prepared LLZTO solid electrolyte sheet has good crystallinity, and no impurity peak is observed, so that the diffraction peaks all belong to LLZTO, indicating that the solid electrolyte prepared in this example is pure-phase LLZTO.
As can be seen from FIG. 4, the lithium ion conductivity of the LLZTO solid electrolyte sheet obtained by calculation was 6.59X10-4S/cm。
Example 3
A method for preparing a garnet-type solid electrolyte comprises the following steps:
s1, mixing La2O3Drying the powder at 900 ℃ for 12h to obtain dry La2O3And (3) powder.
S2, Li in stoichiometric ratio6.5La3Zr1.5Te0.25O123.1395g of lithium hydroxide, 4.887g of lanthanum oxide and,2.156g of zirconia and 0.399g of tellurium oxide were placed in an agate jar and 2% LiF and 1% MoSi were added2And 0.5% Li2And S and 30g of ball milling agent isopropanol are subjected to ball milling for 8 hours at the rotating speed of 500r/min to obtain uniformly mixed slurry.
S3, drying the mixed slurry in a 90 ℃ oven for 6 hours to obtain dry mixed powder; sintering the mixed powder at 850 ℃ for 24h to obtain the LLZTO solid electrolyte precursor powder.
S4, pressing the LLZTO solid electrolyte precursor powder to form a wafer with the diameter of phi 15mm, and sintering at 11500 ℃ for 20h to obtain the LLZTO solid electrolyte wafer.
S5, testing the alternating current impedance after grinding and polishing, and calculating the conductivity, wherein the result is shown in figure 5.
As can be seen from FIG. 5, the lithium ion conductivity of the LLZTO solid electrolyte was calculated to be 5.5X10-4S/cm。
Example 4
A method for preparing a garnet-type solid electrolyte comprises the following steps:
s1, mixing La2O3Drying the powder at 950 ℃ for 12h to obtain dry La2O3And (3) powder.
S2, Li in stoichiometric ratio6.5La3Zr1.5Ta0.5O124.5045g of lithium hydroxide, 7.3305g of lanthanum oxide, 2.772g of zirconium oxide and 1.6575g of tantalum oxide are respectively weighed and placed in an agate ball milling pot, and 2.5 percent of LiF and 0.5 percent of MoSi are added2And 1% of Li2O and 15g of ball milling agent isopropanol are subjected to ball milling for 48 hours at the rotating speed of 250r/min to obtain uniformly mixed slurry.
S3, drying the mixed slurry in a 60 ℃ oven for 12 hours to obtain dry mixed powder; sintering the mixed powder at 950 ℃ for 8h to obtain the LLZTO solid electrolyte precursor powder.
S4, pressing the LLZTO solid electrolyte precursor powder into a wafer with the diameter of phi 15mm, and sintering at 1350 ℃ for 0.5h to obtain the LLZTO solid electrolyte sheet.
S5, conductivity was calculated after grinding and polishing, and the result is shown in fig. 6.
As can be seen from FIG. 6, the lithium ion conductivity of the LLZTO solid electrolyte was calculated to be 5.9X10-4S/cm。
Comparative example 1
A method for preparing a garnet-type solid electrolyte comprises the following steps:
s1, mixing La2O3Drying the powder at 900 ℃ for 12h to obtain dry La2O3And (3) powder.
S2, Li in stoichiometric ratio7La3Zr2O12Respectively weighing 3.234g of lithium hydroxide, 4.887g of lanthanum oxide and 2.464g of zirconium oxide, placing the materials in an agate ball milling tank, adding 15g of ball milling agent isopropanol, and carrying out ball milling for 24 hours at the rotating speed of 350r/min to obtain uniformly mixed slurry.
S3, drying the mixed slurry in an oven at 60 ℃ for 15h to obtain dry mixed powder; and sintering the mixed powder at 850 ℃ for 16h to obtain the LLZO solid electrolyte precursor powder.
S4, pressing the LLZO solid electrolyte precursor powder into a wafer with the diameter of phi 15mm, and sintering at 1230 ℃ for 18h to obtain the LLZO solid electrolyte sheet.
S5, testing ac impedance and XRD after grinding and polishing, calculating the conductivity, and the results are shown in fig. 7 and 8.
As can be seen from fig. 8, XRD diffraction peaks of the prepared LLZTO solid electrolyte sheet were sharp, indicating that the prepared LLZTO solid electrolyte sheet was good in crystallinity, while no impurity peak was observed, so the diffraction peaks all belonged to LLZTO, indicating that the solid electrolyte prepared in this comparative example was a pure-phase LLZO.
As can be seen from FIG. 7, the lithium ion conductivity of the LLZO solid electrolyte was calculated to be 1.5X10-4 S/cm。
Comparative example 2
A method for preparing a garnet-type solid electrolyte comprises the following steps:
s1, mixing La2O3Drying the powder at 900 ℃ for 12h to obtain dry La2O3And (3) powder.
S2, pressStoichiometric ratio of Li7La3Zr2O12Respectively weighing 3.234g of lithium hydroxide, 4.887g of lanthanum oxide and 2.464g of zirconium oxide, placing the materials into an agate ball milling tank, adding 1% of MoSi2And 15g of ball milling agent isopropanol, and performing ball milling for 24 hours at the rotating speed of 350r/min to obtain uniformly mixed slurry.
S3, drying the mixed slurry in a 60 ℃ oven for 15 hours to obtain dry mixed powder; and sintering the mixed powder at 850 ℃ for 16h to obtain the LLZO solid electrolyte precursor powder.
S4, pressing the LLZO solid electrolyte precursor powder into a wafer with the diameter of phi 15mm, and sintering at 1230 ℃ for 18h to obtain the LLZO solid electrolyte sheet.
S5, after grinding and polishing, the conductivity was calculated, and the result is shown in fig. 9.
As can be seen from FIG. 9, the lithium ion conductivity of LLZO calculated was 1.9X10-4 S/cm。
Comparative example 3
A method for preparing a garnet-type solid electrolyte comprises the following steps:
s1, mixing La2O3Drying the powder at 1000 ℃ for 12h to obtain dry La2O3And (3) powder.
S2, Li in stoichiometric ratio6.5La3Zr1.5Ta0.5O124.5045g of lithium hydroxide, 7.3305g of lanthanum oxide, 2.772g of zirconium oxide and 1.6575g of tantalum oxide are respectively weighed and placed in an agate ball milling tank, 20g of isopropanol serving as a ball milling agent is added, and ball milling is carried out for 24 hours at the rotating speed of 450r/min, so as to obtain uniformly mixed slurry.
S3, drying the mixed slurry in an oven at 80 ℃ for 10 hours to obtain dry mixed powder; sintering the mixed powder at 950 ℃ for 8h to obtain the LLZTO solid electrolyte precursor powder.
S4, pressing the LLZTO solid electrolyte precursor powder into a wafer with the diameter of phi 15mm, and sintering at 1250 ℃ for 18h to obtain the LLZTO solid electrolyte wafer.
S5, testing after grinding and polishing, calculating the conductivity, and the result is shown in fig. 10.
As can be seen from FIG. 10, the lithium ion conductivity of the LLZTO solid electrolyte sheet obtained by calculation was 4.8X10-4S/cm。
Application example 1
The LLZTO solid electrolyte sheets obtained in example 1 and comparative example 2 were assembled into lithium symmetrical batteries, respectively, and their interfacial properties were tested, and the results are shown in fig. 11 and 12.
As can be seen from FIG. 11, the lithium symmetric cell assembled with the LLZTO solid electrolyte sheet obtained in example 1 has a current density of 0.1mA cm-2Can stably circulate for more than 125h and shows very good interface performance. While the results of FIG. 12 show that the lithium symmetrical cell assembled with the LLZTO solid electrolyte sheet obtained in comparative example 2 has a current density of 0.1mA cm-2Under the conditions of (1), short circuit occurred after 37 hours of the cycle, and the interface performance was very poor.
Application example 2
The LLZTO solid electrolyte sheets obtained in example 2 and comparative example 3 were assembled into lithium symmetrical batteries, respectively, and their interfacial properties were tested, and the results are shown in fig. 13 and 14.
As can be seen from FIG. 13, the lithium symmetric cell assembled by the LLZTO solid electrolyte sheet obtained in example 2 has a current density of 0.1mA cm-2Can stably circulate for more than 200h and shows very good interface performance. While the results of FIG. 14 show that the lithium symmetric cell assembled with the LLZTO solid electrolyte sheet obtained in comparative example 3 has a current density of 0.1mA cm-2Under the conditions of (1), short circuit occurred after 4 hours of cycling, and the interface properties were very poor.
As can be seen from the above, the present invention is achieved by simultaneously introducing LiF and MoSi having good conductivity to the LLZO solid electrolyte2An ion-electron mixed interface layer having excellent lithium affinity can be formed on the surface of LLZO, thereby improving the interface properties of LLZO solid electrolyte and lithium metal.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.

Claims (10)

1. A garnet-type solid electrolyte characterized in that: the raw material for preparing the solid electrolyte comprises forming Li7La3Zr2O12Lithium source powder, lanthanum source powder and zirconium source powder of (4), and LiF and MoSi2(ii) a The LiF and MoSi2The total mass percentage of (A) is 1-15%.
2. The garnet-type solid electrolyte according to claim 1, characterized in that: also includes a compound containing a doping element; the doping element comprises one or more elements of Ta, Nb, Al, Ga, W, Mo, Gd, Ti, Ca, Ba, Y and Re.
3. The garnet-type solid electrolyte according to claim 1, characterized in that: the additive also comprises an additive, wherein the additive accounts for 0-10% of the total weight of the additive; the additive is Li2S、Li2O and/or montmorillonite.
4. The garnet-type solid electrolyte according to claim 1, characterized in that: the LiF and MoSi2The mass ratio of the components is 5: 1-1: 5.
5. A method for preparing the garnet-type solid electrolyte according to claim 1, wherein: the method comprises the following steps:
s1, placing lanthanum source powder in a muffle furnace to be calcined for 4-24 hours at 700-1200 ℃;
s2, according to Li7La3Zr2O12Weighing and uniformly mixing lithium source powder, lanthanum source powder prepared in step S1 and zirconium source powder according to the stoichiometric ratio, and adding MoSi2Performing ball milling on the powder, the LiF powder, the ball milling agent and the ball milling beads to obtain uniformly mixed slurry;
s3, drying the obtained mixed slurry to obtain mixed powder; sintering the mixed powder at 700-1200 ℃ for 4-24 h to obtain LLZO solid electrolyte precursor powder;
s4, pressing the LLZO solid electrolyte precursor powder into a sheet, and sintering at 1050-1500 ℃ for a second time, wherein the sintering time is 0.5-36 h, so as to obtain the garnet solid electrolyte.
6. The method for producing a garnet-type electrolyte as set forth in claim 5, wherein: the mass ratio of all the powder to the ball milling agent and the ball milling beads in the step S2 is powder: ball grinding agent: the ratio of ball milling beads to ball milling beads is 1: 1-5: 4 to 20.
7. The method for producing a garnet-type electrolyte as set forth in claim 5, wherein: the ball milling time in the step S2 is 4-48 h, and the rotating speed is 200-1200 r/min.
8. The method for producing a garnet-type electrolyte as set forth in claim 5, wherein: the ball grinding agent is one of ethanol, isopropanol, acetonitrile, diethyl ether, petroleum ether and acetone.
9. The method for producing a garnet-type electrolyte as set forth in claim 5, wherein: the drying temperature in the step S3 is 50-150 ℃, and the drying time is 4-24 h.
10. The method for producing a garnet-type electrolyte as set forth in claim 5, wherein: and S4, pressing the LLZO solid electrolyte precursor powder into a wafer with the diameter of 10-20 mm.
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CN113964390A (en) * 2021-09-22 2022-01-21 西安交通大学 Halogen ion doped LLZO solid electrolyte and preparation method thereof

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JPH1143373A (en) * 1997-07-22 1999-02-16 Toyota Central Res & Dev Lab Inc Production of composite material
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116655380A (en) * 2023-05-26 2023-08-29 香河昆仑新能源材料股份有限公司 Garnet type solid electrolyte and preparation method and application thereof

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