CN113161605A - Organic-inorganic composite solid electrolyte material and preparation method and application thereof - Google Patents

Organic-inorganic composite solid electrolyte material and preparation method and application thereof Download PDF

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CN113161605A
CN113161605A CN202110454207.6A CN202110454207A CN113161605A CN 113161605 A CN113161605 A CN 113161605A CN 202110454207 A CN202110454207 A CN 202110454207A CN 113161605 A CN113161605 A CN 113161605A
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solid electrolyte
organic
lithium
inorganic composite
composite solid
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廖友好
臧国景
李冠杰
李伟善
洪名瑶
卢亦铿
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South China Normal University
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South China Normal University
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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
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention relates to an organic-inorganic composite solid electrolyte material and a preparation method and application thereof, wherein the organic-inorganic composite solid electrolyte material comprises the following components in parts by mass: 1-30 parts of polyoxyethylene and Li6Zr2O75-30 parts of lithium salt and 1-10 parts of lithium salt; the Li6Zr2O7The mass of (a) is 35 to 140% of the total mass of the polyethylene oxide and the lithium salt. The invention is achieved by using Li6Zr2O7The organic-inorganic composite solid electrolyte material has high ionic conductivity, wide electrochemical window and good mechanical property under the synergistic effect of polyoxyethylene and lithium salt according to a specific proportion.

Description

Organic-inorganic composite solid electrolyte material and preparation method and application thereof
Technical Field
The invention relates to the technical field of batteries, in particular to an organic-inorganic composite solid electrolyte material and a preparation method and application thereof.
Background
Lithium ion batteries are currently the most common commercial secondary batteries, and compared with lead-acid batteries and nickel-metal hydride batteries, lithium ion batteries have the advantages of high energy density, high output voltage, long cycle life, small self-discharge, no memory effect and the like, and are widely applied to the fields of mobile electronic equipment, power batteries and the like.
The main structure of the lithium ion battery comprises three parts of a positive electrode, a negative electrode and electrolyte, and Li is used for dissolving lithium+The charge and discharge are realized by shuttling between the anode and the cathode. Lithium ion batteries currently commercialized deliver Li by using organic electrolytes+Also known as liquid lithium ion batteries. However, the presence of the organic electrolyte solution brings disadvantages such as a narrow operating temperature range, easy generation of a solid electrolyte interface film (SEI film), a narrow electrochemical window, easy leakage, low energy density of a battery, poor safety, easy generation of lithium dendrites, and the like. More importantly, the organic electrolyte in the lithium ion battery is usually flammable and explosive, and when the lithium ion battery is overcharged, collided and short-circuited, the lithium ion battery may cause extreme conditions such as high temperature, and at this time, there is a risk of combustion or explosion. Due to the potential safety hazard, the lithium ion battery is greatly limited when being popularized and applied in the field of large batteries of pure electric vehicles, hybrid electric vehicles and the like.
Compared with a liquid lithium ion battery, the solid electrolyte is used in the all-solid-state battery to replace the electrolyte, and the all-solid-state battery is not easy to burn at high temperature, so that the safety is greatly improved, but the ionic conductivity and the electrochemical window of the solid electrolyte are still further improved.
Disclosure of Invention
Based on the organic-inorganic composite solid electrolyte material, the invention provides an organic-inorganic composite solid electrolyte material with higher ionic conductivity and wider electrochemical window, and a preparation method and application thereof.
The technical scheme of the invention for solving the technical problems is as follows.
An organic-inorganic composite solid electrolyte material comprises the following components in parts by mass:
1-30 parts of polyoxyethylene;
Li6Zr2O75-30 parts of a solvent;
1-10 parts of lithium salt;
the Li6Zr2O7The mass of (a) is 35 to 140% of the total mass of the polyethylene oxide and the lithium salt.
In some of the embodiments, the organic-inorganic composite solid electrolyte material, the Li6Zr2O7The mass of (a) is 40-100% of the total mass of the polyethylene oxide and the lithium salt.
In some embodiments, the mass ratio of the polyethylene oxide to the lithium salt in the organic-inorganic composite solid electrolyte material is (1-8): 1.
In some embodiments, the organic-inorganic composite solid electrolyte material comprises the following components in parts by mass:
15-20 parts of polyoxyethylene;
Li6Zr2O710-20 parts;
5 parts of lithium salt.
In some of the examples, the viscosity average molecular weight Mv of the polyethylene oxide in the organic-inorganic composite solid electrolyte material is 3 × 105～5×106。
In some of the embodiments, the organic-inorganic composite solid electrolyte material, wherein the lithium salt is selected from at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium perchlorate, lithium bistrifluoromethanesulfonylimide (LiTFSI), lithium difluoroborate, lithium dioxalate borate, lithium difluorooxalato borate, lithium difluorophosphate, and lithium oxalato phosphate.
The invention also provides a preparation method of the organic-inorganic composite solid electrolyte material, which comprises the following steps:
mixing the polyethylene oxide and the Li6Zr2O7And mixing and stirring the lithium salt and the organic solvent, casting and drying.
In some of the embodiments, in the method for producing an organic-inorganic composite solid electrolyte material, the organic solvent is at least one selected from acetonitrile, acetone, N-dimethylformamide, and N-methylpyrrolidone.
In some embodiments, in the preparation method of the organic-inorganic composite solid electrolyte material, the stirring temperature is 20 ℃ to 60 ℃, and the stirring time is 6h to 24 h; the drying temperature is 50-90 ℃, and the drying time is 12-48 h.
The invention provides an application of an organic-inorganic composite solid electrolyte material in the preparation of batteries.
The invention provides an electrolyte comprising the organic-inorganic composite solid electrolyte material as described above.
The invention provides a battery, which comprises a positive electrode, a negative electrode and a solid electrolyte arranged between the positive electrode and the negative electrode, wherein the solid electrolyte comprises the organic-inorganic composite solid electrolyte material.
Compared with the prior art, the organic-inorganic composite solid electrolyte material has the following beneficial effects:
the organic-inorganic composite solid electrolyte material adopts Li6Zr2O7Mixing with polyethylene oxide (PEO) and lithium salt, by controlling Li6Zr2O7The mass of the organic-inorganic composite solid electrolyte material is 35-140% of the total mass of the polyoxyethylene and the lithium salt, and the organic-inorganic composite solid electrolyte material has high ionic conductivity, wide electrochemical window and good mechanical property under the synergistic effect of a specific proportion. And the organic-inorganic composite solid electrolyte material also contains Li as an inorganic ceramic material6Zr2O7And polyethylene oxide as the matrix of the organic polymer, so the advantages of the flexibility of the organic polymer and the rigid structure of the framework of the inorganic ceramic material are also considered. Meanwhile, the safety performance of the all-solid-state battery prepared by adopting the organic-inorganic composite solid electrolyte material is greatly improvedAnd the cycle performance is greatly improved.
The preparation method of the organic-inorganic composite solid electrolyte material has simple process and mild conditions, and can be used for large-scale production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a diagram showing an organic-inorganic composite solid electrolyte material obtained in example 1;
FIG. 2 is a SEM image of the micro-morphology of an organic-inorganic composite solid-state electrolyte material prepared in example 1;
FIG. 3 is a linear sweep voltammogram of the organic-inorganic composite solid electrolyte prepared in example 1 and example 2;
fig. 4 is a graph of cycle performance at 60 ℃ at 0.1C rate of all-solid batteries of the organic-inorganic composite solid electrolyte assemblies prepared in examples 1 and 2;
fig. 5 is a microscopic morphology SEM image of the organic-inorganic composite solid electrolyte material prepared in example 2.
Detailed Description
The organic-inorganic composite solid electrolyte of the present invention, the method for producing the same, and the use thereof will be described in further detail with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
The weight of the related components mentioned in the description of the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present invention as long as it is in accordance with the description of the embodiments of the present invention. Specifically, the weight described in the description of the embodiment of the present invention may be a unit of mass known in the chemical industry field, such as μ g, mg, g, and kg.
The invention provides an organic-inorganic composite solid electrolyte material, which comprises the following components in parts by mass:
1-30 parts of polyoxyethylene;
Li6Zr2O75-30 parts of a solvent;
1-10 parts of lithium salt;
the Li6Zr2O7The mass of (a) is 35 to 140% of the total mass of the polyethylene oxide and the lithium salt.
With Li6Zr2O7The organic-inorganic composite solid electrolyte material has high ionic conductivity, wide electrochemical window and good mechanical property under the synergistic effect of polyoxyethylene and lithium salt according to a specific proportion.
In some of these examples, in the organic-inorganic composite solid electrolyte material, Li6Zr2O7The mass of the lithium salt is 40 to 100 percent of the total mass of the polyoxyethylene and the lithium salt.
In some specific examples thereof, in the organic-inorganic composite solid electrolyte material, Li6Zr2O7The mass of the lithium salt is 50 to 100 percent of the total mass of the polyoxyethylene and the lithium salt.
In some specific examples thereof, in the organic-inorganic composite solid electrolyte material, Li6Zr2O7The mass of the lithium salt is 50 to 75 percent of the total mass of the polyoxyethylene and the lithium salt.
Preferably, Li6Zr2O7The mass of (b) is 50% of the total mass of the polyoxyethylene and lithium salt.
In some examples, the mass ratio of the polyoxyethylene to the lithium salt in the organic-inorganic composite solid electrolyte material is (1-8): 1.
In some examples, the mass ratio of the polyoxyethylene to the lithium salt in the organic-inorganic composite solid electrolyte material is (2-6): 1.
In some specific examples, the mass ratio of the polyoxyethylene to the lithium salt in the organic-inorganic composite solid electrolyte material is (3-4): 1.
In some examples, the organic-inorganic composite solid electrolyte material includes the following components in parts by mass:
15-20 parts of polyoxyethylene;
Li6Zr2O710-20 parts;
5 parts of lithium salt.
It can be understood that the mass ratio of the polyoxyethylene to the lithium salt is (3-4): 1, and Li is satisfied6Zr2O7The mass of the lithium salt is 40 to 100 percent of the total mass of the polyoxyethylene and the lithium salt.
In some of the preferred examples, the organic-inorganic composite solid electrolyte material contains Li6Zr2O7The mass of (a) is 50% of the total mass of the polyoxyethylene and the lithium salt, and the mass ratio of the polyoxyethylene to the lithium salt is 3:1。
In some of these examples, the viscosity average molecular weight Mv of the polyethylene oxide in the organic-inorganic composite solid electrolyte material is 3 × 105～5×106。
In some preferred examples thereof, the viscosity average molecular weight Mv of the polyethylene oxide in the organic-inorganic composite solid electrolyte material is 6 × 105。
In some of these examples, the lithium salt in the organic-inorganic composite solid electrolyte material is selected from at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium perchlorate, lithium bistrifluoromethanesulfonylimide, lithium difluoroborate, lithium dioxalate borate, lithium difluorooxalate borate, lithium difluorophosphate, and lithium oxalato phosphate.
In some of these examples, the lithium salt in the organic-inorganic composite solid electrolyte material is selected from at least one of lithium bistrifluoromethanesulfonylimide and lithium difluorooxalatoborate.
In some preferred examples thereof, the lithium salt in the organic-inorganic composite solid electrolyte material is selected from lithium bistrifluoromethanesulfonylimide.
One embodiment of the present invention provides a method for preparing an organic-inorganic composite solid electrolyte material, comprising the steps of:
mixing polyethylene oxide, inorganic ceramic material, lithium salt and organic solvent, stirring, casting and drying.
It is understood that the slurry is obtained by mixing and stirring the polyethylene oxide, the inorganic ceramic material, the lithium salt and the organic solvent.
In some examples, in the method for producing the organic-inorganic composite solid electrolyte material, a slurry obtained by mixing and stirring polyethylene oxide, an inorganic ceramic material, a lithium salt, and an organic solvent is placed on a template, and then, casting and drying are performed.
In some examples, the organic-inorganic composite solid electrolyte material is prepared by placing the slurry on a template by casting, knife coating, spray coating, and roll coating. It is to be understood that the manner in which the slurry is placed on the form is not limited, and other conventional manners of placing slurry on the form may be implemented.
In some examples, in the preparation method of the organic-inorganic composite solid electrolyte material, the slurry is placed on the template in a pouring manner.
In some of the examples, in the method of producing the organic-inorganic composite solid electrolyte material, the template is a Polytetrafluoroethylene (PTFE), stainless steel, or silica gel plate. It is to be understood that the choice of template is not limiting.
In some of the examples, in the method of producing an organic-inorganic composite solid electrolyte material, the template is polytetrafluoroethylene.
In some of the examples, in the method of producing an organic-inorganic composite solid electrolyte material, the organic solvent is selected from at least one of acetonitrile, acetone, N-Dimethylformamide (DMF), and N-methylpyrrolidone (NMP).
In some preferred examples thereof, the organic solvent in the organic-inorganic composite solid electrolyte material is acetonitrile.
In some examples, in the preparation method of the organic-inorganic composite solid electrolyte material, the stirring temperature is 20-60 ℃, and the stirring time is 6-24 hours; the drying temperature is 50-90 ℃, and the drying time is 12-48 h.
In some specific examples, in the preparation method of the organic-inorganic composite solid electrolyte material, the stirring temperature is 20-40 ℃, and the stirring time is 16-24 hours; the drying temperature is 50-70 ℃, and the drying time is 18-30 h.
In some preferred examples thereof, in the method for producing an organic-inorganic composite solid electrolyte material, the temperature of stirring is 30 ℃ and the time of stirring is 18 hours; the drying temperature is 60 ℃ and the drying time is 24 h.
In some examples, in the preparation method of the organic-inorganic composite solid electrolyte material, the slurry is dried for 6 to 24 hours at room temperature after being cast, and then is heated and dried. It is understood that the inorganic composite solid electrolyte material can be obtained by drying and peeling, and the obtained inorganic composite solid electrolyte material can be cut into a desired size as required.
An embodiment of the present invention provides an application of the organic-inorganic composite solid electrolyte material in battery preparation.
One embodiment of the present invention provides an electrolyte, which includes the above organic-inorganic composite solid electrolyte material.
One embodiment of the invention provides a battery, which comprises a positive electrode, a negative electrode and a solid electrolyte arranged between the positive electrode and the negative electrode, wherein the solid electrolyte comprises the organic-inorganic composite solid electrolyte material.
In some of these examples, the positive electrode contains a positive electrode active material and the negative electrode contains a negative electrode active material.
In one specific example, the composite electrolyte material is cut into round pieces, and the round pieces, the positive electrode and the negative electrode are stacked together, pressed and sealed in a button battery case, and assembled into an all-solid battery.
Compared with the traditional electrolyte material, the invention adopts polyethylene oxide (PEO) as the matrix of the solid electrolyte (the viscosity-average molecular weight Mv is 3 multiplied by 10)5～5×106) From an inorganic ceramic material Li6Zr2O7As inorganic filler, further in conjunction with lithium salt, and defining Li6Zr2O7The mass of the organic-inorganic composite solid electrolyte material is 35 to 140 percent of the total mass of the polyoxyethylene and the lithium salt, and the organic-inorganic composite solid electrolyte material is blended according to a specific proportion, so that the lithium ion conductivity of the organic-inorganic composite solid electrolyte material can reach 6.97 multiplied by 10 at a high temperature of 60 DEG C-4S cm-1(ii) a Meanwhile, the electrochemical window of the composite solid electrolyte material reaches 5.32V, and the mechanical property is effectively improved. Due to Li6Zr2O7The organic-inorganic composite solid electrolyte material is an inorganic ceramic material, polyethylene oxide is an organic polymer matrix, and the organic-inorganic composite solid electrolyte material also has the advantages of both the flexibility of an organic polymer and the rigid structure of the framework of the inorganic ceramic material. The safety performance of the all-solid-state battery prepared by the organic-inorganic composite solid electrolyte material is greatly improved, and the cycle performance is also greatly improved.
The raw materials used in the invention have wide sources and simple preparation process, and the prepared composite solid electrolyte has strong chemical stability, high ionic conductivity at high temperature and easy realization of industrialization, and can be widely used in all-solid-state lithium ion secondary batteries.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Hereinafter, the organic-inorganic composite solid electrolyte material, the method for producing the same, and the use thereof according to the present invention will be exemplified, and it will be understood that the organic-inorganic composite solid electrolyte material, the method for producing the same, and the use thereof are not limited to the following examples.
Example 1
Preparing raw materials: lithium bistrifluoromethanesulfonimide (LiTFSI)0.50g, polyethylene oxide (PEO, viscosity average molecular weight Mv 6X 10)5)1.50g、Li6Zr2O7(LZO)1.00g and acetonitrile 40 mL;
the preparation method comprises the following steps: li to be weighed6Zr2O7Polyethylene oxide and lithium bistrifluoromethanesulfonylimide were dispersed in 40mL of acetonitrile, an organic solvent, and mechanically stirred at 30 ℃ for 18h to form a uniform slurry. And after uniformly mixing the slurry, pouring the slurry into a Polytetrafluoroethylene (PTFE) template for tape casting, drying the template for 12 hours at room temperature, then drying the template for 24 hours at 60 ℃, and then stripping the template to obtain an organic-inorganic composite solid electrolyte membrane (SPE) with the thickness L of 100 mu m. Fig. 1 is a physical diagram of an organic-inorganic composite solid electrolyte membrane in example 1, and fig. 2 is a microscopic morphology diagram of an organic-inorganic composite solid electrolyte material in example 1, and it can be seen from fig. 1 to 2 that the organic-inorganic composite solid electrolyte material prepared in example 1 has a uniform and dense structure.
Cutting the prepared composite solid electrolyte material into 18mm round sheets, respectively overlapping the round sheets with a lithium sheet and a steel sheet in a glove box, tightly pressing and sealing the round sheets to assemble a lithium sheet/SPE/steel sheet (Li/SPE/SS) battery, testing an electrochemical window of the battery, and measuring a potential window to be 5.32V by a linear sweep voltammetry curve as shown in figure 3.
A composite solid electrolyte membrane and positive lithium iron phosphate (LiFePO) are arranged in a glove box4) And the negative electrode lithium metal (Li) are overlapped together, compressed and sealed to form an all-solid-state battery which is charged at 60 ℃ and 0.1C multiplying powerThe charging and discharging circulation is carried out, the result is shown in figure 4, and the specific capacity is kept 80mAh/g after 100 times of circulation, and the good circulation performance is shown.
And (3) respectively superposing the composite solid electrolyte diaphragm and two steel sheets (with the diameter of 16mm) together in a glove box, compacting and sealing to assemble a steel sheet/SPE/steel sheet (SS/SPE/SS) battery. The resistance R of the composite solid electrolyte material was measured to be 7.14 Ω at 60 ℃, and the ionic conductivity was calculated to be 6.97 × 10-4Scm-1。
The ionic conductivity is calculated by the formula:
Figure BDA0003039202260000111
where R is the internal resistance of SPE, L is the thickness of SPE, S is the contact area between SPE and steel sheet, and the diameter of the contact area of example 1 is 16 mm.
Example 2
The embodiment 2 is basically the same as the embodiment 1, and is different from the embodiment 1 in the following specific points:
preparing raw materials: lithium bistrifluoromethanesulfonimide (LiTFSI)0.50g, polyethylene oxide (PEO, viscosity average molecular weight Mv 6X 10)5)1.50g、Li6Zr2O7(LZO)2.00g and acetonitrile 40 mL;
the preparation method comprises the following steps: li to be weighed6Zr2O7Polyethylene oxide and lithium bistrifluoromethanesulfonylimide were dispersed in 40mL of acetonitrile, an organic solvent, and mechanically stirred at 30 ℃ for 18h to form a uniform slurry. And after the slurry is uniformly mixed, pouring the mixture into a Polytetrafluoroethylene (PTFE) template for tape casting, drying the mixture at room temperature for 12 hours, then drying the mixture at 60 ℃ for 24 hours, and then stripping the dried mixture to obtain the organic-inorganic composite solid electrolyte membrane. Fig. 5 is a microscopic morphology view of the organic-inorganic composite solid electrolyte material of example 1.
Cutting the prepared composite solid electrolyte material into 18mm round sheets, respectively overlapping the round sheets with a lithium sheet and a steel sheet in a glove box, compacting and sealing the round sheets to assemble a lithium sheet/SPE/steel sheet (Li/SPE/SS) batteryThe electrochemical window was tested, and the linear sweep voltammogram was as shown in FIG. 3, and the potential window was measured to be 5.15V. A composite solid electrolyte membrane and positive lithium iron phosphate (LiFePO) are arranged in a glove box4) The negative electrode lithium metal (Li) was stacked, pressed, sealed, and assembled into an all-solid battery, and subjected to charge-discharge cycles at 60 ℃ and 0.1C magnification, and the results are shown in fig. 4. Ionic conductivity at 60 ℃ of 5.39X 10-4S cm-1。
Example 3
The embodiment 3 is basically the same as the embodiment 1, but different in the following parts:
preparing raw materials: lithium bistrifluoromethanesulfonimide (LiTFSI)0.50g, polyethylene oxide (PEO, viscosity average molecular weight Mv 6X 10)5)2.00g、Li6Zr2O7(LZO)1.00g and acetonitrile 40 mL;
the preparation method comprises the following steps: li to be weighed6Zr2O7Polyethylene oxide and lithium bistrifluoromethanesulfonylimide were dispersed in 40mL of acetonitrile, an organic solvent, and mechanically stirred at 30 ℃ for 18h to form a uniform slurry. And after the slurry is uniformly mixed, pouring the mixture into a Polytetrafluoroethylene (PTFE) template for tape casting, drying the mixture at room temperature for 12 hours, then drying the mixture at 60 ℃ for 24 hours, and then stripping the dried mixture to obtain the organic-inorganic composite solid electrolyte membrane. The composite solid electrolyte membrane obtained by the above preparation was cut into 18mm round pieces, and was mixed with lithium iron phosphate (LiFePO) as the positive electrode in a glove box4) And the negative electrode lithium metal (Li) is overlapped together, compressed and sealed to assemble the all-solid-state battery.
Example 4
The embodiment 4 is basically the same as the embodiment 1, but different in the following points:
preparing raw materials: lithium bistrifluoromethanesulfonimide (LiTFSI)0.50g, polyethylene oxide (PEO, viscosity average molecular weight Mv 6X 10)5)1.50g、Li6Zr2O7(LZO)1.50g and acetonitrile 40 mL;
the preparation method comprises the following steps: li to be weighed6Zr2O7Polyethylene oxide and lithium bis (trifluoromethanesulfonylimide) dispersed in 40mL of organic solventContinuously mechanically stirring the mixture for 18 hours at 30 ℃ in acetonitrile to form uniform slurry. And after the slurry is uniformly mixed, pouring the mixture into a Polytetrafluoroethylene (PTFE) template for tape casting, drying the mixture at room temperature for 12 hours, then drying the mixture at 60 ℃ for 24 hours, and then stripping the dried mixture to obtain the organic-inorganic composite solid electrolyte membrane. The composite solid electrolyte membrane obtained by the above preparation was cut into 18mm round pieces, and was mixed with lithium iron phosphate (LiFePO) as the positive electrode in a glove box4) And the negative electrode lithium metal (Li) is overlapped together, compressed and sealed to assemble the all-solid-state battery.
Comparative example 1
The comparative example 1 is basically the same as the example 1, and is different from the example 1 in the following specific points in parts by mass:
preparing raw materials: lithium bistrifluoromethanesulfonimide (LiTFSI)0.50g, polyethylene oxide (PEO, viscosity average molecular weight Mv 6X 10)5)1.50g、Li6Zr2O7(LZO)0.20g and acetonitrile 40 mL;
the preparation method comprises the following steps: li to be weighed6Zr2O7Polyethylene oxide and lithium bistrifluoromethanesulfonylimide were dispersed in 40mL of acetonitrile, an organic solvent, and mechanically stirred at 30 ℃ for 18h to form a uniform slurry. And after the slurry is uniformly mixed, pouring the mixture into a Polytetrafluoroethylene (PTFE) template for tape casting, drying the mixture at room temperature for 12 hours, then drying the mixture at 60 ℃ for 24 hours, and then stripping the dried mixture to obtain the organic-inorganic composite solid electrolyte membrane. The composite solid electrolyte membrane obtained by the above preparation was cut into 18mm round pieces, and was mixed with lithium iron phosphate (LiFePO) as the positive electrode in a glove box4) And the negative electrode lithium metal (Li) is overlapped together, compressed and sealed to assemble the all-solid-state battery.
The composite solid electrolyte membrane prepared in comparative example 1 and lithium iron phosphate (LiFePO) as a positive electrode were placed in a glove box4) And the negative electrode lithium metal (Li) is overlapped together, compressed and sealed to form an all-solid-state battery, and the all-solid-state battery is subjected to charge-discharge circulation at 60 ℃ and 0.1C multiplying power, short circuit occurs, and the circulation performance test cannot be carried out.
Comparative example 2
The comparative example 2 is basically the same as the example 1, but different in parts by mass, specifically as follows:
preparing raw materials: lithium bistrifluoromethanesulfonimide (LiTFSI)0.50g, polyethylene oxide (PEO, viscosity average molecular weight Mv 6X 10)5)1.50g、Li6Zr2O7(LZO)0.60g and acetonitrile 40 mL;
the preparation method comprises the following steps: li to be weighed6Zr2O7Polyethylene oxide and lithium bistrifluoromethanesulfonylimide were dispersed in 40mL of acetonitrile, an organic solvent, and mechanically stirred at 30 ℃ for 18h to form a uniform slurry. And after the slurry is uniformly mixed, pouring the mixture into a Polytetrafluoroethylene (PTFE) template for tape casting, drying the mixture at room temperature for 12 hours, then drying the mixture at 60 ℃ for 24 hours, and then stripping the dried mixture to obtain the organic-inorganic composite solid electrolyte membrane. The composite solid electrolyte membrane obtained by the above preparation was cut into 18mm round pieces, and was mixed with lithium iron phosphate (LiFePO) as the positive electrode in a glove box4) And the negative electrode lithium metal (Li) is overlapped together, compressed and sealed to assemble the all-solid-state battery.
The composite solid electrolyte membrane prepared in comparative example 2 and lithium iron phosphate (LiFePO) as the positive electrode were placed in a glove box4) And the negative electrode lithium metal (Li) is overlapped together, compressed and sealed to form an all-solid-state battery, and the all-solid-state battery is subjected to charge-discharge circulation at 60 ℃ and 0.1C multiplying power, short circuit occurs, and the circulation performance test cannot be carried out.
Comparative example 3
The comparative example 3 is basically the same as the example 1, but different in parts by mass, specifically as follows:
preparing raw materials: lithium bistrifluoromethanesulfonimide (LiTFSI)0.50g, polyethylene oxide (PEO, viscosity average molecular weight Mv 6X 10)5)1.50g、Li6Zr2O7(LZO)3.00g and acetonitrile 40 mL;
the preparation method comprises the following steps: li to be weighed6Zr2O7Polyethylene oxide and lithium bistrifluoromethanesulfonylimide were dispersed in 40mL of acetonitrile, an organic solvent, and mechanically stirred at 30 ℃ for 18h to form a uniform slurry. And after the slurry is uniformly mixed, pouring the mixture into a Polytetrafluoroethylene (PTFE) template for tape casting, drying the mixture at room temperature for 12 hours, then drying the mixture at 60 ℃ for 24 hours, and then stripping the dried mixture to obtain the organic-inorganic composite solid electrolyte membrane. Will be provided withThe composite solid electrolyte membrane prepared above was cut into 18mm round pieces, and was mixed with lithium iron phosphate (LiFePO) as the positive electrode in a glove box4) And the negative electrode lithium metal (Li) is overlapped together, compressed and sealed to assemble the all-solid-state battery.
The composite solid electrolyte membrane prepared in comparative example 3 and lithium iron phosphate (LiFePO) as the positive electrode were placed in a glove box4) And the negative electrode lithium metal (Li) is overlapped together, compressed and sealed to form an all-solid-state battery, and the all-solid-state battery is subjected to charge-discharge circulation at 60 ℃ and 0.1C multiplying power, short circuit occurs, and the circulation performance test cannot be carried out.
The parts of the components added in examples 1 to 4 and comparative examples 1 to 3 are shown in Table 1.
TABLE 1
Figure BDA0003039202260000141
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. The organic-inorganic composite solid electrolyte material is characterized by comprising the following components in parts by mass:
1-30 parts of polyoxyethylene;
Li6Zr2O75-30 parts of a solvent;
1-10 parts of lithium salt;
the Li6Zr2O7The mass of (a) is 35 to 140% of the total mass of the polyethylene oxide and the lithium salt.
2. The organic-inorganic composite solid electrolyte material according to claim 1, wherein the mass ratio of the polyethylene oxide to the lithium salt is (1-8): 1.
3. The organic-inorganic composite solid electrolyte material according to claim 1, comprising the following components in parts by mass:
15-20 parts of polyoxyethylene;
Li6Zr2O710-20 parts;
5 parts of lithium salt.
4. The organic-inorganic composite solid electrolyte material according to claim 1, wherein the lithium salt is selected from at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium perchlorate, lithium bistrifluoromethanesulfonylimide, lithium difluoroborate, lithium dioxalate borate, lithium difluorooxalato borate, lithium difluorophosphate, and lithium oxalato phosphate.
5. The method for producing an organic-inorganic composite solid electrolyte material according to any one of claims 1 to 4, characterized by comprising the steps of:
mixing the polyethylene oxide and the Li6Zr2O7And mixing and stirring the lithium salt and the organic solvent, casting and drying.
6. The method for producing an organic-inorganic composite solid electrolyte material according to claim 5, wherein the organic solvent is at least one selected from the group consisting of acetonitrile, acetone, N-dimethylformamide, and N-methylpyrrolidone.
7. The method for producing an organic-inorganic composite solid electrolyte material according to claim 5, wherein the stirring temperature is 20 ℃ to 60 ℃ and the stirring time is 6 hours to 24 hours; the drying temperature is 50-90 ℃, and the drying time is 12-48 h.
8. Use of the organic-inorganic composite solid electrolyte material according to any one of claims 1 to 4 for producing a battery.
9. An electrolyte comprising the organic-inorganic composite solid electrolyte material according to any one of claims 1 to 4.
10. A battery comprising a positive electrode, a negative electrode, and a solid electrolyte provided between the positive electrode and the negative electrode, wherein the solid electrolyte comprises the organic-inorganic composite solid electrolyte material according to any one of claims 1 to 4.
CN202110454207.6A 2021-04-26 2021-04-26 Organic-inorganic composite solid electrolyte material and preparation method and application thereof Pending CN113161605A (en)

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EP3258532A1 (en) * 2015-02-13 2017-12-20 Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences All-solid-state polymer electrolyte, and preparation and application thereof
CN108365203A (en) * 2018-02-27 2018-08-03 山东大学 A kind of compound lithium zirconate is modified the technology of preparing of two-phase lithium titanate/titanium dioxide cathode material
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CN108963332A (en) * 2017-05-18 2018-12-07 珠海市赛纬电子材料股份有限公司 A kind of composite solid electrolyte material and preparation method and all-solid-state battery
CN109378521A (en) * 2018-10-19 2019-02-22 中国电子科技集团公司第十八研究所 Inorganic-organic composite solid electrolyte, preparation method thereof and assembled all-solid-state lithium battery

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3258532A1 (en) * 2015-02-13 2017-12-20 Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences All-solid-state polymer electrolyte, and preparation and application thereof
CN108963327A (en) * 2017-05-18 2018-12-07 珠海市赛纬电子材料股份有限公司 A kind of compound PEO solid electrolyte material of inorganic filler and preparation method and all-solid-state battery
CN108963332A (en) * 2017-05-18 2018-12-07 珠海市赛纬电子材料股份有限公司 A kind of composite solid electrolyte material and preparation method and all-solid-state battery
CN108365203A (en) * 2018-02-27 2018-08-03 山东大学 A kind of compound lithium zirconate is modified the technology of preparing of two-phase lithium titanate/titanium dioxide cathode material
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