CN111509290A - Composite solid electrolyte with high ceramic content and preparation method thereof - Google Patents
Composite solid electrolyte with high ceramic content and preparation method thereof Download PDFInfo
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Abstract
The invention relates TO the field of electrochemical energy storage, in particular TO a high-ceramic-content composite solid electrolyte and a preparation method thereof, wherein the components of the composite solid electrolyte are perovskite type solid electrolyte LL TO, PAN and lithium salt, wherein the mass fraction of LL TO is 60-85%‑1) Good flexibility and simple preparation methodThe method is suitable for the fields of lithium ion batteries, flow batteries and the like.
Description
Technical Field
The invention relates to the field of electrochemical energy storage, in particular to a high-ceramic-content composite solid electrolyte and a preparation method thereof.
Background
In recent years, with the rapid development of portable electronic devices and electric vehicles, a new-generation battery having high energy density and high safety is in urgent need. Lithium metal batteries have recently attracted extensive attention in academia and industry due to their high energy density. Conventional lithium ion batteries generally use liquid electrolyte, and lithium metal reacts with the liquid to form an unstable solid electrolyte interface film, which on one hand continuously consumes the electrolyte, and on the other hand, the growth of lithium metal dendrites can cause short circuit of the battery, which causes safety problems. The use of a solid electrolyte, which is non-flammable and has a high shear modulus, instead of a liquid state is an effective way to realize a lithium metal battery and to solve the safety problem.
Solid electrolytes can be generally classified into three types: inorganic solid electrolytes (ceramics), polymer solid electrolytes, and composite solid electrolytes (composites of ceramics and polymers). The inorganic solid electrolyte generally has a high ionic conductivity (10)-3～10-4Scm-1) But its brittleness severely limits its application. On the contrary, the polymer solid electrolyte has very good flexibility but too low ionic conductivity (10)-6～10-8S cm-1). The composite solid electrolyte has the advantages of both ceramics and polymers, and has wide application prospect. Although potentially possible, the current ionic conductivity of composite solid electrolytes generally fails to meet practical standards ((>10-4S cm-1). More importantly, the ceramic content of the existing composite solid electrolyte is too low (general mass fraction)<50%), a lower shear modulus, and does not achieve the effect of inhibiting lithium metal dendrites.
Therefore, there is a need for improvements in existing composite solid electrolytes and methods of making the same.
Disclosure of Invention
The invention aims to provide a high-ceramic-content composite solid electrolyte and a preparation method thereof. The preparation process is simple and easy to control, and the operability is strong.
The technical scheme of the invention is as follows:
the composite solid electrolyte with high ceramic content comprises ceramic, a polymer and lithium salt, wherein the ceramic content in the composite solid electrolyte is 60-85 wt%.
The ceramic used in the composite solid electrolyte is calcium titaniumOre-type solid electrolyte
The value of x is 0.01-0.6.
The polymer of the high-ceramic-content composite solid electrolyte is Polyacrylonitrile (PAN).
The lithium salt of the high-ceramic-content composite solid electrolyte adopts lithium perchlorate (L iClO)4) Lithium bis (trifluoromethanesulfonyl) imide (L iTFSI), or other lithium salts.
The mass ratio of the polymer to the lithium salt is 1: 0.01-1: 10.
The preparation method of the composite solid electrolyte with high ceramic content comprises the following specific steps:
(1) LL TO powder is prepared by a high-temperature solid-phase method;
(2) mixing the LL TO powder prepared in the step (1) with Polyacrylonitrile (PAN) and lithium salt, adding N, N-Dimethylformamide (DMF) solvent, and performing one or any combination of ball milling, stirring and ultrasound TO obtain precursor slurry of the composite solid electrolyte;
(3) and (3) coating the slurry obtained in the step (2) on a clean glass plate by adopting a tape casting forming method, and placing the glass plate in a vacuum drying oven for heating and drying to obtain the high-ceramic-content composite solid electrolyte.
According TO the preparation method of the high-ceramic-content composite solid electrolyte, when LL TO powder is prepared by a high-temperature solid-phase method, the amount of lithium salt is 0-60 wt% more than the stoichiometric ratio, so that the volatilization loss of the lithium salt at high temperature is compensated.
In the preparation method of the high-ceramic-content composite solid electrolyte, the average particle size of LL TO powder is 0.01-50 mu m.
The preparation method of the composite solid electrolyte with high ceramic content comprises the following steps: the method comprises pouring out the precursor slurry from a container, coating the precursor slurry on a base band by a scraper, drying, curing, peeling to form a film of the green band, and punching or laminating the green band according to the size and shape of the finished product.
According to the preparation method of the high-ceramic-content composite solid electrolyte, the mass ratio of N, N-Dimethylformamide (DMF) to Polyacrylonitrile (PAN) is 1: 1-100: 1.
The design idea of the invention is as follows:
1. the invention relates to polymer PAN and inorganic solid electrolyte perovskite
The composite solid electrolyte with ultrahigh ceramic content (LL TO content is up TO 60-85 wt%) is successfully synthesized, the composite electrolyte has the advantages of high lithium ion conductivity, high shear modulus and the like due TO high ceramic content, and the polymer PAN with strong bonding property enables the composite solid electrolyte TO have excellent flexibility.
2. The invention prepares the precursor slurry of the composite solid electrolyte by ball milling, stirring or ultrasound (one or any combination of the three methods), and then prepares the composite solid electrolyte by a blade coating method. The preparation method is simple and rapid, has high yield, and is suitable for large-scale production.
The invention has the following advantages and beneficial effects:
1. the invention prepares the precursor slurry of the composite solid electrolyte by ball milling, stirring or ultrasound (one or any combination of the three methods), and then prepares the composite solid electrolyte by a blade coating method. The preparation method is simple and rapid, has high yield, and is suitable for large-scale production.
2. The composite solid electrolyte prepared by the invention has high conductivity and good flexibility, and more importantly, the ceramic proportion is as high as 60-85 wt%, so that the composite solid electrolyte has high shear modulus, improves the effect of inhibiting lithium metal dendrites, and can be used in the fields of lithium ion batteries, flow batteries and the like.
Drawings
Fig. 1 is a photograph of a high ceramic content composite solid electrolyte prepared in example 1. Wherein, (a) is a surface view, and (b) is a curved view.
Fig. 2 is a Scanning Electron Microscope (SEM) image of the high ceramic content composite solid electrolyte prepared in example 1. Wherein, (a) is a surface view, and (b) is a cross-sectional view.
FIG. 3 is a thermogravimetric plot (TGA) of the high ceramic content composite solid electrolyte prepared in example 1 under an oxygen atmosphere at a temperature rise rate of 10 deg.C/min.
Fig. 4 is an Electrochemical Impedance Spectrum (EIS) of the high ceramic content composite solid electrolyte prepared in example 1. In the figure, the abscissa Z' represents the real part of impedance (Ω), and the ordinate Z ″ represents the imaginary part of impedance (Ω).
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth 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 specific implementation process, the high-ceramic-content composite solid electrolyte comprises the perovskite type solid electrolyte
Polyacrylonitrile (PAN) and lithium salts (e.g., lithium perchlorate (L iClO)4) Or lithium bistrifluoromethanesulfonylimide (L iTFSI)), wherein the mass fraction of LL TO is controlled TO be 60-85%, the mass ratio of PAN TO lithium salt is 1: 0.01-1: 10 (preferably 1: 0.3-1: 0.5), the preparation method comprises the following steps of preparing LL TO by adopting a high-temperature solid phase method, performing ball milling for 0.5-200 h (preferably 20-60 h) TO reduce the particle size of the LL TO TO obtain LL TO powder with the average particle size of 0.01-50 mu m (preferably 0.01-0.1 mu m), and then performing powder preparation of the LL TOAnd PAN and L iClO4Mixing according to a required mass ratio, adding a certain volume of N, N-Dimethylformamide (DMF) solvent (the mass ratio of N, N-Dimethylformamide (DMF) to Polyacrylonitrile (PAN) is 1: 1-100: 1, preferably 5: 1-30: 1), and performing ball milling or stirring or ultrasonic treatment for 0-200 h (preferably 20-60 h) to obtain slurry; and finally, coating the obtained slurry on a clean glass plate by adopting a tape casting forming method, and then placing the glass plate in a vacuum drying oven to be heated and dried for 0.5-200 h (preferably 6-24 h) at the temperature of 0-200 ℃ (preferably 60-100 ℃), thus obtaining the composite solid electrolyte.
In some of these examples, the process for making LL TO powder was a high temperature solid phase process,
wherein the value of x is 0.01-0.6 (preferably 0.26-0.36), and the product is obtained
The sintering temperature of the solid electrolyte is 1000-1400 ℃,
the sintering time of the solid electrolyte is 1-100 h (preferably 10-30 h). when LL TO powder is prepared by adopting a high-temperature solid phase method, the amount of the lithium salt is 0-60 wt% (preferably 5-30 wt%) more than the stoichiometric ratio, so that the volatilization loss of the lithium salt at high temperature is compensated.
The present invention will be described in further detail below by way of examples and figures.
Example 1:
in this example, the specific preparation process of the high ceramic content composite solid electrolyte is as follows:
3.511g of lithium carbonate (L i) were weighed out2CO3) 21.894g lanthanum oxide (L a)2O3) And 19.168g of titanium oxide (TiO)2) The mixture is placed in a 250ml ball milling tank, 100ml of ethanol is added, and then ball milling is carried out for 48 hours at the rotating speed of 400 rpm. And drying the obtained sample, placing the sample in a corundum crucible, and presintering the sample at 900 ℃ for 12 hours, wherein the heating and cooling speeds are 3 ℃/min. The obtained powder is firstly put into a mortar for hand milling for 30min and then put into a 250ml ball milling tankAdding 120ml ethanol, ball milling at 400rpm for 48h, oven drying, sintering at 1210 deg.C for 16h in high temperature box furnace at 1 deg.C/min to obtain perovskite type solid electrolyte L i0.33La0.557TiO3(LL TO) is firstly milled by hands in a mortar for 30min, then placed in a 250ml ball milling pot, added with 120ml ethanol, ball milled for 96h at the rotating speed of 400rpm TO reduce the particle size, and dried TO obtain the required LL TO powder with the particle size of about 0.15 μm.
3.20g of this LL TO powder, 0.267g of Polyacrylonitrile (PAN) and 0.533g of lithium perchlorate (L iClO) were weighed out4) And putting the mixture into a 250ml ball milling tank, adding 40ml of N, N-Dimethylformamide (DMF), and carrying out ball milling for 12-24 h at the rotating speed of 400rpm to obtain the precursor slurry for preparing the high-ceramic-content composite solid electrolyte. Taking a clean glass plate, placing the glass plate on a flat experiment table, dripping 5ml of slurry on the glass plate, scraping the glass plate by using a scraper, immediately placing the glass plate in a vacuum oven, vacuumizing, and preserving heat at 70 ℃ for 12 hours to obtain the high-ceramic-content composite solid electrolyte, and cutting the composite solid electrolyte into wafers with different sizes by using a punch head according to needs.
The high ceramic content composite solid electrolyte of the present example was characterized in structure and performance as follows:
FIG. 1 shows the resulting high ceramic content composite solid electrolyte, which has a uniform and smooth surface as shown in FIG. 1(a), and which has excellent flexibility as shown in FIG. 1(b), indicating that it is not easily broken during use and has high utility, FIG. 2 shows an SEM image of the high ceramic content composite solid electrolyte, which is shown in FIG. 2(a), and perovskite L i0.33La0.557TiO3(LL TO) particles are dispersed very uniformly fig. 2(b) is a cross-sectional view of the composite solid electrolyte, which is seen TO have a very uniform and dense structure with a thickness of about 80 μm, fig. 3 is a TGA curve of the prepared high ceramic content composite solid electrolyte at a temperature rise rate of 10 ℃/min in an oxygen atmosphere, it is seen that the decomposition starting temperature of the composite solid electrolyte is about 200 ℃,the decomposition process is complete by 600 at which time the PAN is completely oxidatively decomposed to gas, L iClO4Decomposed into lithium chloride (L iCl) and oxygen (O)2) The residue was found TO have LL TO particles as a major component and was found TO have a mass fraction of about 80%. FIG. 4 is an Electrochemical Impedance Spectroscopy (EIS) of the prepared high ceramic content composite solid electrolyte. the test uses a button cell holder having a stainless steel sheet as a lithium ion blocking electrode and the composite solid electrolyte sandwiched between two sheets of stainless steel, pressed into a button cell, and an ESI curve was measured over a frequency range of 1Hz TO 7 MHz. the curve includes two parts, the first part is an incomplete semicircle in the high frequency region and represents the resistance of the composite solid electrolyte, the second part is an upward straight line in the low and medium frequency region and represents the interfacial resistance between the composite solid electrolyte and the stainless steel sheet-1。
Example 2:
in this example, the specific preparation process of the high ceramic content composite solid electrolyte is as follows:
for solid electrolyte
Weighing L i according to stoichiometric ratio when x is 0.052CO3(excess 30%), TiO2And L a2O3Mixing, sintering at 1260 deg.C for 20h, and ball milling for 100h TO obtain LL TO powder with particle size of about 0.07 μm according TO LL TO, PAN and L iClO4Weighing three materials according to the mass ratio of 0.7:0.075:0.15, mixing, adding a DMF solvent (the mass is 30 times of PAN), and carrying out ball milling at the rotating speed of 300rpm for 30 hours to obtain precursor slurry for preparing the high-ceramic-content composite solid electrolyte. Coating the obtained precursor slurry on a clean glass plate by adopting a tape casting method, placing the glass plate in a vacuum drying oven for heating and drying, vacuumizing, and preserving heat at 60 ℃ for 12 hours to obtain the precursor for preparing the high-ceramic-content composite solid electrolyteAnd (3) slurry.
Example 3:
in this example, the specific preparation process of the high ceramic content composite solid electrolyte is as follows:
for solid electrolyte
Taking x as 0.2, weighing L i according to stoichiometric ratio2CO3(excess 5%), TiO2And L a2O3Mixing, sintering at 1180 deg.C for 15h, and ball milling for 60h TO obtain LL TO powder with particle size of about 0.10 μm according TO LL TO, PAN and L iClO4Weighing the three materials according to the mass ratio of 0.85:0.1:0.05, mixing, adding a DMF solvent (the mass is 15 times of PAN), and carrying out ball milling at the rotating speed of 500rpm for 10 hours to obtain precursor slurry for preparing the high-ceramic-content composite solid electrolyte. And coating the obtained precursor slurry on a clean glass plate by adopting a tape casting method, placing the glass plate in a vacuum drying oven for heating and drying, vacuumizing, and preserving heat at 80 ℃ for 12 hours to obtain the precursor slurry for preparing the high-ceramic-content composite solid electrolyte.
Example 4:
in this example, the specific preparation process of the high ceramic content composite solid electrolyte is as follows:
for solid electrolyte
Weighing L i according to stoichiometric ratio when x is 0.112CO3(excess 5%), TiO2And L a2O3Mixing, sintering at 1200 ℃ for 16h, ball-milling for 60h TO obtain LL TO powder with the particle size of about 0.10 mu m, weighing three materials according TO the mass ratio of LL TO TO PAN TO L ITFSI of 0.85:0.075:0.075, mixing, adding DMF solvent (the mass is 5 times of PAN), ball-milling at 600rpm for 2h TO obtain precursor slurry for preparing the high-ceramic-content composite solid electrolyte, coating the precursor slurry on a clean glass plate by adopting a tape casting method, placing the glass plate in a vacuum drying oven for heating and drying, vacuumizing, and preserving heat at 50 ℃ for 24h TO obtain the precursor slurry for preparing the high-ceramic-content composite solid electrolyteAnd (4) driving body slurry.
Example 5:
in this example, the specific preparation process of the high ceramic content composite solid electrolyte is as follows:
for solid electrolyte
Taking x as 0.3, weighing L i according to stoichiometric ratio2CO3(excess 30%), TiO2And L a2O3Mixing, sintering at 1150 ℃ for 10h, ball-milling for 200h TO obtain LL TO powder with the particle size of about 0.06 μm, weighing three materials according TO the mass ratio of LL TO TO PAN TO L ITFSI of 0.75:0.15:0.1, mixing, adding DMF solvent (with the mass being 20 times of PAN), ball-milling at 200rpm for 50h TO obtain precursor slurry for preparing the composite solid electrolyte with high ceramic content, coating the precursor slurry on a clean glass plate by adopting a tape casting method, placing the glass plate in a vacuum drying oven for heating and drying, vacuumizing, and preserving heat at 90 ℃ for 8h TO obtain the precursor slurry for preparing the composite solid electrolyte with high ceramic content.
The embodiment result shows that the composite solid electrolyte has high lithium ion conductivity (0.1-5 mScm)-1) Good flexibility, simple preparation method and the like, and is suitable for the fields of lithium ion batteries, flow batteries and the like.
Claims (10)
1. The composite solid electrolyte with high ceramic content is characterized by comprising ceramic, a polymer and lithium salt, wherein the ceramic content is 60-85 wt%.
2. The high ceramic content composite solid electrolyte according to claim 1, wherein the ceramic used in the composite solid electrolyte is a perovskite type solid electrolyte
The value of x is 0.01-0.6.
3. The high ceramic content composite solid electrolyte according to claim 1, wherein the polymer is Polyacrylonitrile (PAN).
4. The high ceramic content composite solid electrolyte as claimed in claim 1, wherein the lithium salt is lithium perchlorate (L iClO)4) Lithium bis (trifluoromethanesulfonyl) imide (L iTFSI), or other lithium salts.
5. The high-ceramic-content composite solid electrolyte according to claim 1, wherein the mass ratio of the polymer to the lithium salt is 1:0.01 to 1: 10.
6. A method for preparing the high ceramic content composite solid electrolyte according to any one of claims 1 to 5, characterized by comprising the following steps:
(1) LL TO powder is prepared by a high-temperature solid-phase method;
(2) mixing the LL TO powder prepared in the step (1) with Polyacrylonitrile (PAN) and lithium salt, adding N, N-Dimethylformamide (DMF) solvent, and performing one or any combination of ball milling, stirring and ultrasound TO obtain precursor slurry of the composite solid electrolyte;
(3) and (3) coating the slurry obtained in the step (2) on a clean glass plate by adopting a tape casting forming method, and placing the glass plate in a vacuum drying oven for heating and drying to obtain the high-ceramic-content composite solid electrolyte.
7. The method for preparing the composite solid electrolyte with high ceramic content according TO claim 6, wherein when LL TO powder is prepared by a high-temperature solid-phase method, the amount of lithium salt is 0-60 wt% more than the stoichiometric ratio, so as TO compensate the volatilization loss of the lithium salt at high temperature.
8. The method for producing a composite solid electrolyte with a high ceramic content according TO claim 6, wherein the LL TO powder has an average particle size of 0.01 TO 50 μm.
9. The method for producing a composite solid electrolyte with a high ceramic content according to claim 6, wherein the tape casting method is: the method comprises pouring out the precursor slurry from a container, coating the precursor slurry on a base band by a scraper, drying, curing, peeling to form a film of the green band, and punching or laminating the green band according to the size and shape of the finished product.
10. The method for preparing the composite solid electrolyte with high ceramic content according to claim 6, wherein the mass ratio of N, N-Dimethylformamide (DMF) to Polyacrylonitrile (PAN) is 1: 1-100: 1.
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