CN109361014B - Solid electrolyte composite material of lithium secondary battery, preparation method and lithium secondary battery - Google Patents
Solid electrolyte composite material of lithium secondary battery, preparation method and lithium secondary battery Download PDFInfo
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- 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
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M2300/0068—Solid electrolytes inorganic
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Abstract
The invention relates to a solid electrolyte composite material of a lithium secondary battery, a preparation method and the lithium secondary battery, belonging to the field of material chemistry, wherein the material is of a double-layer or three-layer structure, and one layer is L i in the double-layer structure7La3Zr2O12The other layer is CsPbBr3The middle layer is L i in the three-layer structure7La3Zr2O12The upper and lower intermediate layers are respectively provided with a CsPbBr layer3. The material is prepared by a spin-coating method, and is applied to a lithium secondary battery as a solid electrolyte, so that the interface contact between the solid electrolyte and a metal lithium cathode can be improved, the interface resistance is reduced, the battery capacity is improved, and the battery cycle performance is improved.
Description
Technical Field
The invention relates to a solid electrolyte composite material of a lithium secondary battery, a preparation method and the lithium secondary battery, belonging to the field of material chemistry.
Background
Garnet type solid electrolyte L i7La3Zr2O12Due to higher ionic conductivity (1 × 10 at normal temperature)- 3mS·cm-1) Has good chemical stability and wide electrochemical window, and is widely used as the electrolyte material of solid secondary lithium ion battery, but the garnet solid electrolyte L i7La3Zr2O12Recently, a group of people led by the Proc-section California university of Maryland California, employed atomic layer deposition to successfully improve garnet-type solid electrolyte L i by depositing an aluminum oxide layer on the surface of the solid electrolyte7La2.75Ca0.25Zr1.75Nb0.25O12And wettability and chemical stability of lithium metal so that interface resistance of garnet and lithium metal is from 1710 Ω/cm2Down to 1 omega/cm2. On the basis, zinc oxide is successfully deposited on the surface of the solid electrolyte, and the zinc oxide and the metal lithium have good reaction activityThe interface contact between garnet-type solid electrolyte and lithium metal is improved, so that the interface resistance between garnet and lithium metal is reduced to 20 omega/cm2However, the above method has the problems of complicated preparation process and high energy consumption, so a new composite material is needed to solve the problem of garnet-type solid electrolyte L i7La3Zr2O12The electrolyte has the problem of interface contact with electrodes when being used as the electrolyte of a solid secondary lithium ion battery.
Disclosure of Invention
In view of the above, it is an object of the present invention to provide a solid electrolyte composite material for a lithium secondary battery, which has high ionic conductivity and a wide electrochemical window; the invention also aims to provide a preparation method of the solid electrolyte composite material of the lithium secondary battery, which comprises the steps of firstly preparing CsPbBr3Spin coating of precursor solution with garnet-type electrolyte L i7La3Zr2O12The surface is obtained by annealing treatment, and the method is simple and easy to implement; the material is applied to a lithium secondary battery as a solid electrolyte, so that the interface contact between the solid electrolyte and a metal lithium cathode is improved, the interface resistance is reduced, the battery capacity is improved, and the battery cycle performance is improved.
In order to achieve the above object, the technical solution of the present invention is as follows.
A solid electrolyte composite material for lithium secondary battery, the material has a double-layer or three-layer structure, wherein one layer is L i7La3Zr2O12The other layer is CsPbBr3The middle layer is L i in the three-layer structure7La3Zr2O12The upper and lower intermediate layers are respectively provided with a CsPbBr layer3。
Preferably, when the material is a double-layer structure, L i7La3Zr2O12And CsPbBr3Has a mass ratio of 10000:1, and when the material has a three-layer structure, L i7La3Zr2O12And each layer CsPbBr3The mass ratio of (A) to (B) is 10000:1: 1.
The invention relates to a preparation method of a solid electrolyte composite material of a lithium secondary battery, which comprises the following steps:
when the material is a double-layer structure:
1M of PbBr2Is spin-coated at L i in N, N-Dimethylformamide (DMF) solution7La3Zr2O12Annealing one side of the tablet at 80 deg.C for 30 min, soaking in excessive 0.07M CsBr in methanol for 10min, cleaning with isopropanol, drying, and annealing at 250 deg.C for 5 min to obtain L i solid electrolyte composite material for lithium secondary battery7La3Zr2O12/CsPbBr3A composite material;
or the method comprises the following steps:
to 0.48M CsPbBr3HBr with the mass fraction of 57 percent is added into the DMF solution to obtain CsPbBr3Mixing the precursor with the solution, and mixing CsPbBr3The precursor mixed solution is coated on L i in a rotating way7La3Zr2O12Annealing one surface of the pressed sheet at 100-120 ℃ for 5-10 min to obtain L i solid electrolyte composite material of the lithium secondary battery7La3Zr2O12/CsPbBr3A composite material;
when the material is a three-layer structure:
1M of PbBr2Is uniformly spin-coated on L i7La3Zr2O12Annealing the two sides of the pressed sheet at 80 ℃ for 30 minutes, soaking the two sides in excessive 0.07M CsBr methanol solution for 10min, cleaning the pressed sheet with isopropanol, drying, and finally annealing at 250 ℃ for 5 minutes to obtain the solid electrolyte composite material of the lithium secondary battery, namely CsPbBr3/Li7La3Zr2O12/CsPbBr3A composite material;
or the method comprises the following steps:
CsPbBr to 0.48M concentration3HBr with the mass fraction of 57 percent is added into the DMF solution to obtain CsPbBr3Mixing the precursor with the solution, and mixing CsPbBr3The precursor mixed solution is uniformly spun at 500mg L i7La3Zr2O12Annealing the two surfaces of the pressed sheet at 100-120 ℃ for 5-10 min to obtain a solid electrolyte composite material of the lithium secondary battery, namely CsPbBr3/Li7La3Zr2O12/CsPbBr3A composite material.
Preferably, when the material is a double-layer structure, PbBr is adopted2With L i7La3Zr2O12The dosage ratio of the components is 40 mu L: 500mg, or CsPbBr3The volume ratio of the DMF solution to HBr is 1m L: 33 mu L, CsPbBr3Precursor mixed solution and L i7La3Zr2O12The dosage ratio of the PbBr is 30 mu L: 500mg, and when the material is of a three-layer structure, PbBr is added2With L i7La3Zr2O12The dosage ratio of the components is 80 mu L: 500mg, or CsPbBr3The volume ratio of the DMF solution to HBr is 1m L: 33 mu L, CsPbBr3Precursor mixed solution and L i7La3Zr2O12The dosage ratio of the components is 60 mu L: 500 mg.
Preferably, the L i7La3Zr2O12The preparation method comprises the following steps:
(1) mixing lithium hydroxide powder, lanthanum oxide powder and zirconium oxide powder according to a molar ratio of 14:3:4, then ball-milling for 9-12 hours at a speed of 400-600 r/min by using isopropanol as a ball-milling solvent, and drying to obtain uniformly mixed raw materials;
(2) calcining the uniformly mixed raw materials for 12 hours at 800 ℃ in air, and cooling to obtain an intermediate product;
(3) taking out the intermediate product, tabletting, calcining the tabletted intermediate product at 1200 ℃ for 36 hours in air, and cooling to obtain L i7La3Zr2O12。
Preferably, the ball milling medium in step (1) is zirconia balls.
The electrolyte of the lithium ion secondary battery is the solid state battery of the lithium ion secondary batteryA composite electrolyte material, CsPbBr when the material is of a double-layer structure3The layer is in contact with a lithium negative electrode.
Has the advantages that:
in the composite material, CsPbBr is on the surface3Has an orthorhombic crystal structure, and the material has high ionic conductivity.
In the method, CsPbBr is added by a spin coating method3Spin coating on L i7La3Zr2O12Surface, simple preparation process, cheap and easily obtained raw materials, prepared L i7La3Zr2O12/CsPbBr3The composite material has the advantages of higher ionic conductivity, wide electrochemical window, good capability of inhibiting dendritic crystal lithium, good wettability with metal lithium and the like.
In the application of the invention, the interface contact performance of the electrolyte and the metallic lithium cathode is greatly improved while the high ionic conductivity is ensured, the interface resistance is greatly reduced, and the attenuation of the battery capacity is prevented, so that the lithium ion secondary battery electrolyte material has wide application prospect. In the composite material, the perovskite layer CsPbBr3On one hand, the lithium is more uniformly contacted with the solid electrolyte, so that the ion transmission area is effectively increased; perovskite layer CsPbBr on the other hand3Can prevent the generation of impurities, such as L i2CO3And L iOH.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of the composite material prepared in example 1;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the composite material prepared in example 1;
FIG. 3 is a graph showing the impedance properties of the assembled battery of example 1;
FIG. 4 is a graph showing the cycle performance test of the assembled battery of example 1;
FIG. 5 is an XRD pattern of the composite material prepared in example 2;
FIG. 6 is an SEM image of a composite material prepared in example 2;
FIG. 7 is a graph of impedance testing of the assembled cell of example 2;
fig. 8 is a cycle performance test chart of the assembled battery of example 2.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
In the following examples:
(1) x-ray diffraction test the instrument is Rigaku D/Max 2200 with Cu K α radiation at a test speed of 5 ℃ per minute.
(2) And (3) testing by a scanning electron microscope: the instrument is Hitachi S-4800, the test voltage is 5KV, and the current is 10 muA.
(3) Battery Assembly L i/L i7La3Zr2O12(LL ZO)/L i lithium ion non-blocking symmetrical cell assembly in which lithium sheets 8mm in diameter were placed on both sides of a polished LL ZO sheet and then sealed with a sealing machine.
Li/CsPbBr3/LLZO/CsPbBr3Assembly of/L i lithium ion non-blocking symmetrical Battery CsPbBr prepared in example3/LLZO/CsPbBr3Lithium pieces with a diameter of 8mm were placed on both sides of the sheet, and then sealed with a sealer.
Assembling of lithium iron phosphate (L FP)/LL ZO/L i battery is carried out in a glove box, L PF or lithium sheet is used as a positive electrode, and 500mg of L i7La3Zr2O12As a solid electrolyte, a button cell is assembled by taking a lithium sheet as a negative electrode. 10 microliters of electrolyte (ethylene carbonate (EC): methyl ethyl carbonate (EMC): dimethyl carbonate (DMC): 1:1:1) was added between the positive electrode and the solid electrolyte.
LFP/LLZO/CsPbBr3Assembly of/L i cell L PF was used as the positive electrode, 500mg of LL ZO/CsPbBr3The composite material is used as a solid electrolyte, and the lithium sheet is used as a negative electrode to assemble the button cell. 10 microliters of electrolyte (ethylene carbonate (EC): methyl ethyl carbonate (EMC): dimethyl carbonate (DMC): 1:1:1) was added between the positive electrode and the solid electrolyte.
LFP/CsPbBr3/LLZO/CsPbBr3Assembly of/L i cell L PF as cathode, 500mg CsPbBr3/LLZO/CsPbBr3The composite material is used as a solid electrolyte, and the lithium sheet is used as a negative electrode to assemble the button cell. 10 microliters of electrolyte (ethylene carbonate (EC): methyl ethyl carbonate (EMC): dimethyl carbonate (DMC): 1:1:1) was added between the positive electrode and the solid electrolyte.
(4) The performance test of the battery is that the Wayne Kerr 6500B electrochemical workstation for impedance test is carried out in the frequency range of 20MHz to 0.1Hz at room temperature, the electrochemical discharge/charge test of the battery with the deviation amplitude of 10 mV. and the frequency range of 20MHz to 1 Hz. is carried out on a L and BTS test system (Wuhan, China), the voltage limit is 4.2-2.5V, and is relative to L i/L i+(standard electrode potential for lithium).
Example 1
Weighing lithium hydroxide, lanthanum oxide and zirconium oxide according to a stoichiometric ratio of chemical mol (14:3:4), then using isopropanol as a ball milling solvent, using zirconium oxide balls as a ball milling medium, carrying out ball milling for 12 hours, drying to obtain a uniformly mixed raw material, then placing the ball-milled raw material into a tubular atmosphere furnace, calcining for 12 hours at 800 ℃, naturally cooling, taking out the calcined sample, pressing the sample into a wafer with the diameter of 13.5mm by using a manual dry pressing forming machine, using the pressure of 2-4 MPa, keeping the pressure for 2-3 minutes, placing the wafer into a ceramic boat, calcining for 36 hours at 1200 ℃ in the tubular atmosphere furnace, naturally cooling, and preparing the garnet L i7La3Zr2O12。
Preparation of 1M PbBr2Of N, N-Dimethylformamide (DMF) and 0.07M CsBr in methanol, 40. mu.l of PbBr2The solution was spin-coated onto a 500mg piece of L i at 2000rpm/30s7La3Zr2O12One side of the tablet was pressed and then 40. mu.l of PbBr was added2The solution was spin coated at 2000rpm/30s on the L i7La3Zr2O12And (3) annealing the other surface of the pressed sheet at 80 ℃ for 30 minutes, soaking the sheet in 10m of methanol solution of L CsBr for 10 minutes, cleaning the sheet with isopropanol, drying the sheet in air, and finally annealing the sheet at 250 ℃ for 5 minutes to obtain the solid electrolyte composite material of the lithium secondary battery, namely CsPbBr3/Li7La3Zr2O12/CsPbBr3A composite material.
The XRD results of the composite material are shown in FIG. 1, wherein L i is shown5La3Nb2O12(since there are no L i in the existing database7La3Zr2O12Standard card of (2), so L i is commonly used5La3Nb2O12L i7La3Zr2O12Phase analysis of) and CsPbBr3The presence of a phase, indicating that the material consists of L i7La3Zr2O12And CsPbBr3And (4) forming.
The SEM result of the composite material is shown in FIG. 2, in which the granular perovskite CsPbBr is3Grains, indicating CsPbBr3Was successfully deposited at L i7La3Zr2O12Of (2) is provided.
Assembled L i/CsPbBr3/LLZO/CsPbBr3The impedance performance results of the/L i lithium ion non-blocking symmetrical battery and the L i/LL ZO/L i lithium ion non-blocking symmetrical battery are shown in figure 3, and it can be seen from the figure that the interface resistance of the composite material prepared by the embodiment as a solid electrolyte is greatly reduced, and the interface resistance is 17 × 105Omega drops to 8 × 105Ω。
Assembled L FP/CsPbBr3/LLZO/CsPbBr3The cycle performance results of the cell of/L i and the cell of L FP/LL ZO/L i are shown in FIG. 4, from which it can be seen that the composite material prepared in this example as a solid electrolyte increases the capacity of the solid cell from 141mA h g-1Increased to 161mA h g-1。
Example 2
According to the chemical molar ratio of lithium hydroxide to lanthanum oxide to zirconium oxide (14:3:4), isopropanol is used as a ball milling solvent, zirconium oxide balls are used as a ball milling medium, ball milling is carried out for 12 hours, and drying is carried out to obtain the uniformly mixed raw material. Then putting the ball-milled raw materials into a tubular atmosphere furnace, calcining for 12 hours at 800 ℃ in air, and naturally cooling; the calcined sample was taken out by handPressing the sample into a wafer with the diameter of 13.5mm by a dynamic dry pressing forming machine, wherein the used pressure is 2-4 MPa, the pressure maintaining time is 2-3 minutes, putting the wafer into a porcelain boat, calcining for 36 hours at 1200 ℃ in the air, and then naturally cooling to prepare the garnet L i7La3Zr2O12。
Weighing PbBr of the same molar weight2And CsBr powder in DMF to give 0.48M CsPbBr3Then, to 1m L CsPbBr333 μ L HBr (57% by mass) was added to the DMF solution to obtain CsPbBr3Precursor mixed solution, 30 mu L CsPbBr3The precursor mixed solution was spin-coated at 2000rpm/30s with 500mg of L i7La3Zr2O12Compressing one side of the tablet, and adding 30 μ L CsPbBr3The precursor mixed solution is coated on the L i in a spinning way at 2000rpm/30s7La3Zr2O12The other side of the tablet is annealed for 10 minutes at 120 ℃, and the precursor solution becomes CsPbBr of an orthorhombic system3To obtain a solid electrolyte composite material CsPbBr of the lithium secondary battery3/Li7La3Zr2O12/CsPbBr3A composite material.
The XRD results of the composite are shown in FIG. 5, in which L i is shown5La3Nb2O12(since there are no L i in the existing database7La3Zr2O12Standard card of (2), so L i is commonly used5La3Nb2O12L i7La3Zr2O12Phase analysis of) and CsPbBr3The presence of a phase, indicating that the material consists of L i7La3Zr2O12And CsPbBr3And (4) forming.
The SEM result of the composite material is shown in FIG. 6, in which the granular perovskite CsPbBr is3Grains, indicating CsPbBr3Was successfully deposited at L i7La3Zr2O12Of (2) is provided.
Assembled L i/CsPbBr3/LLZO/CsPbBr3The impedance performance results of the/L i lithium ion non-blocking symmetrical battery and the L i/LL ZO/L i lithium ion non-blocking symmetrical battery are shown in FIG. 7, and it can be seen that the interface resistance of the composite material prepared by the embodiment as a solid electrolyte is greatly reduced, and the interface resistance is 17 × 105Omega drops to 8 × 105Ω。
Assembled L FP/CsPbBr3/LLZO/CsPbBr3The cycle performance results of the cell of/L i and the cell of L FP/LL ZO/L i are shown in FIG. 8, from which it can be seen that the composite material prepared in this example as a solid electrolyte increases the capacity of the solid cell from 141mA h g-1Increased to 161mA h g-1。
Example 3
Weighing lithium hydroxide, lanthanum oxide and zirconium oxide according to a stoichiometric ratio of chemical mol (14:3:4), then using isopropanol as a ball milling solvent, using zirconium oxide balls as a ball milling medium, carrying out ball milling for 12 hours, drying to obtain a uniformly mixed raw material, then placing the ball-milled raw material into a tubular atmosphere furnace, calcining for 12 hours at 800 ℃, naturally cooling, taking out the calcined sample, pressing the sample into a wafer with the diameter of 13.5mm by using a manual dry pressing forming machine, using the pressure of 2-4 MPa, keeping the pressure for 2-3 minutes, placing the wafer into a ceramic boat, calcining for 36 hours at 1200 ℃ in the tubular atmosphere furnace, naturally cooling, and preparing the garnet L i7La3Zr2O12。
Preparation of 1M PbBr2Of N, N-Dimethylformamide (DMF) and 0.07M CsBr in methanol, 40. mu.l of PbBr2The solution was spin-coated onto a 500mg piece of L i at 2000rpm/30s7La3Zr2O12One surface of the tablet is annealed at 80 ℃ for 30 minutes, then soaked in 5m methanol solution of L CsBr for 10 minutes, washed by isopropanol and dried in air, and finally annealed at 250 ℃ for 5 minutes to obtain the solid electrolyte composite material of the lithium secondary battery, namely L i7La3Zr2O12/CsPbBr3A composite material.
Said compoundingThe XRD result of the material is L i5La3Nb2O12(since there are no L i in the existing database7La3Zr2O12Standard card of (2), so L i is commonly used5La3Nb2O12L i7La3Zr2O12Phase analysis of) and CsPbBr3The presence of a phase, indicating that the material consists of L i7La3Zr2O12And CsPbBr3And (4) forming.
In SEM result of the composite material, the particle is perovskite CsPbBr3Grains, indicating CsPbBr3Was successfully deposited at L i7La3Zr2O12Of (2) is provided.
Assembled L i/LL ZO/CsPbBr3Impedance performance results of a/L i lithium ion non-blocking symmetrical battery and a L i/LL ZO/L i lithium ion non-blocking symmetrical battery show that the composite material prepared by the example is used as a solid electrolyte to greatly reduce the interface resistance, and the interface resistance is 18 × 105Omega is reduced to 14 × 105Ω。
Assembled L FP/LL ZO/CsPbBr3The cycle performance results of the/L i battery and the L FP/LL ZO/L i battery show that the capacity of the solid-state battery is improved by using the composite material prepared by the embodiment as the solid-state electrolyte, and the battery capacity is increased from 141mA h g-1Increased to 153mA h g-1。
Example 4
According to the chemical molar ratio (14:3:4), using isopropanol as a ball milling solvent, using zirconia balls as a ball milling medium, performing ball milling for 12 hours, drying to obtain a uniformly mixed raw material, putting the ball-milled raw material into a tubular atmosphere furnace, calcining for 12 hours at 800 ℃ in air, naturally cooling, taking out the calcined sample, pressing the sample into a wafer with the diameter of 13.5mm by using a manual dry pressing forming machine, using the pressure of 2-4 MPa, maintaining the pressure for 2-3 minutes, putting the wafer into a ceramic boat, calcining for 36 hours at 1200 ℃ in air, naturally cooling, and preparing the garnet L i7La3Zr2O12。
Weighing PbBr of the same molar weight2And CsBr powder in DMF to give 0.48M CsPbBr3Then, to 1m L CsPbBr333 μ L HBr (57% by mass) was added to the DMF solution to obtain CsPbBr3Precursor mixed solution, 30 mu L CsPbBr3The precursor mixed solution was spin-coated at 2000rpm/30s with 500mg of L i7La3Zr2O12One surface of the tablet is annealed for 10 minutes at the temperature of 120 ℃, and the precursor solution becomes CsPbBr of an orthorhombic system3To obtain a solid electrolyte composite material for lithium secondary battery, i.e. L i7La3Zr2O12/CsPbBr3A composite material.
The XRD result of the composite material is L i5La3Nb2O12(since there are no L i in the existing database7La3Zr2O12Standard card of (2), so L i is commonly used5La3Nb2O12L i7La3Zr2O12Phase analysis of) and CsPbBr3The presence of a phase, indicating that the material consists of L i7La3Zr2O12And CsPbBr3And (4) forming.
In SEM result of the composite material, the particle is perovskite CsPbBr3Grains, indicating CsPbBr3Was successfully deposited at L i7La3Zr2O12Of (2) is provided.
Assembled L i/LL ZO/CsPbBr3Impedance performance results of a/L i lithium ion non-blocking symmetrical battery and a L i/LL ZO/L i lithium ion non-blocking symmetrical battery show that the composite material prepared by the example is used as a solid electrolyte to greatly reduce the interface resistance, and the interface resistance is 18 × 105Omega is dropped to 11 × 105Ω。
Assembled L FP/LL ZO/CsPbBr3The cycle performance results of the/L i battery and the L FP/LL ZO/L i battery show that the capacity of the solid-state battery is improved by using the composite material prepared by the embodiment as the solid-state electrolyte, and the battery capacity is increased from 141mA h g-1Increased to 165mA h g-1。
The invention includes, but is not limited to, the above embodiments, and any equivalent substitutions or partial modifications made under the spirit and principle of the invention are deemed to be within the scope of the invention.
Claims (6)
1. A solid electrolyte composite material for lithium secondary battery is characterized in that the material has a double-layer or three-layer structure, wherein one layer is L i7La3Zr2O12The other layer is CsPbBr3The middle layer is L i in the three-layer structure7La3Zr2O12The upper and lower intermediate layers are respectively provided with a CsPbBr layer3(ii) a The negative electrode of the lithium secondary battery is metal lithium; when the material is a double-layer structure, CsPbBr3The layer is in contact with a metallic lithium negative electrode.
2. The solid electrolyte composite material for lithium secondary battery according to claim 1, wherein L i is defined as a double-layer structure7La3Zr2O12And CsPbBr3Has a mass ratio of 10000:1, and when the material has a three-layer structure, L i7La3Zr2O12And each layer CsPbBr3The mass ratio of (A) to (B) is 10000:1: 1.
3. A method for preparing a solid electrolyte composite material for a lithium secondary battery according to claim 1 or 2, characterized in that: the method comprises the following steps:
when the material is a double-layer structure:
1M of PbBr2Spin-coating DMF solution at L i7La3Zr2O12Annealing one side of the tablet at 80 deg.C for 30 min, soaking in excessive 0.07M CsBr in methanol for 10min, cleaning with isopropanol, drying, and annealing at 250 deg.C for 5 min to obtain L i solid electrolyte composite material for lithium secondary battery7La3Zr2O12/CsPbBr3A composite material;
or the method comprises the following steps:
to 0.48M CsPbBr3HBr with the mass fraction of 57 percent is added into the DMF solution to obtain CsPbBr3Mixing the precursor with the solution, and mixing CsPbBr3The precursor mixed solution is coated on L i in a rotating way7La3Zr2O12Annealing one surface of the pressed sheet at 100-120 ℃ for 5-10 min to obtain L i solid electrolyte composite material of the lithium secondary battery7La3Zr2O12/CsPbBr3A composite material;
when the material is a three-layer structure:
1M of PbBr2Is uniformly spin-coated in a DMF solution at L i7La3Zr2O12Annealing the two sides of the pressed sheet at 80 ℃ for 30 minutes, soaking the two sides in excessive 0.07M CsBr methanol solution for 10min, cleaning the pressed sheet with isopropanol, drying, and finally annealing at 250 ℃ for 5 minutes to obtain the solid electrolyte composite material of the lithium secondary battery, namely CsPbBr3/Li7La3Zr2O12/CsPbBr3A composite material;
or the method comprises the following steps:
CsPbBr to 0.48M concentration3HBr with the mass fraction of 57 percent is added into the DMF solution to obtain CsPbBr3Mixing the precursor with the solution, and mixing CsPbBr3The precursor mixed solution is uniformly spun at 500mg L i7La3Zr2O12Annealing the two surfaces of the pressed sheet at 100-120 ℃ for 5-10 min to obtain a solid electrolyte composite material of the lithium secondary battery, namely CsPbBr3/Li7La3Zr2O12/CsPbBr3A composite material.
4. A method for preparing a solid electrolyte composite material for a lithium secondary battery according to claim 3, wherein: when the material is of a double-layer structure, PbBr2With L i7La3Zr2O12In the ratio of500mg of 40 mu L, or CsPbBr3The volume ratio of the DMF solution to HBr is 1m L: 33 mu L, CsPbBr3Precursor mixed solution and L i7La3Zr2O12The dosage ratio of the PbBr is 30 mu L: 500mg, and when the material is of a three-layer structure, PbBr is added2With L i7La3Zr2O12The dosage ratio of the components is 80 mu L: 500mg, or CsPbBr3The volume ratio of the DMF solution to HBr is 1m L: 33 mu L, CsPbBr3Precursor mixed solution and L i7La3Zr2O12The dosage ratio of the components is 60 mu L: 500 mg.
5. The method for preparing a solid electrolyte composite material for a lithium secondary battery according to claim 3, wherein L i is defined as7La3Zr2O12The preparation method comprises the following steps:
(1) mixing lithium hydroxide powder, lanthanum oxide powder and zirconium oxide powder according to a molar ratio of 14:3:4, then ball-milling for 9-12 hours at a speed of 400-600 r/min by using isopropanol as a ball-milling solvent, and drying to obtain uniformly mixed raw materials;
(2) calcining the uniformly mixed raw materials for 12 hours at 800 ℃ in air, and cooling to obtain an intermediate product;
(3) taking out the intermediate product, tabletting, calcining the tabletted intermediate product at 1200 ℃ for 36 hours in air, and cooling to obtain L i7La3Zr2O12。
6. The method of preparing a solid electrolyte composite material for a lithium secondary battery according to claim 5, wherein: in the step (1), the ball milling medium is zirconia balls.
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