CN114976490A - Laminated titanium dioxide modified diaphragm and preparation method and application thereof - Google Patents
Laminated titanium dioxide modified diaphragm and preparation method and application thereof Download PDFInfo
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- CN114976490A CN114976490A CN202210736892.6A CN202210736892A CN114976490A CN 114976490 A CN114976490 A CN 114976490A CN 202210736892 A CN202210736892 A CN 202210736892A CN 114976490 A CN114976490 A CN 114976490A
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- 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
Abstract
The invention discloses a laminated titanium dioxide modified diaphragm and a preparation method and application thereof. The modified separator was used in a lithium metal battery with the modified side of the separator facing the lithium metal negative electrode. According to the invention, a stable interface protection layer is formed in situ on the lithium cathode interface by utilizing the reaction of titanium dioxide and lithium metal, so that the side reaction of the lithium metal cathode and an electrolyte is eliminated, the growth of lithium dendrite is finally inhibited, uniform lithium deposition is realized, the coulombic efficiency of the battery is finally obviously improved, the cycle life of the battery is prolonged, and the possibility of safety problems caused by the continuous growth of uncontrollable lithium dendrite is reduced.
Description
Technical Field
The invention belongs to the technical field of lithium batteries, and relates to a laminated titanium dioxide modified diaphragm and a preparation method and application thereof.
Background
The information disclosed in this background of the invention is only for enhancement of understanding of the general background of the invention and is not necessarily to be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Lithium metal is an ideal negative electrode of the next generation of energy storage equipment due to the advantages of high theoretical specific capacity (3860mAh/g), lowest electrochemical potential (-3.040V/vs. standard hydrogen electrode) and the like. However, uncontrolled dendrite growth during lithium deposition, stripping, can lead to low coulombic efficiency and cycle life, and even puncture of the separator causing short circuits, which can cause serious safety problems. The separator, as a critical part of lithium batteries, can directly affect the performance and safety of the battery. At present, commercial Polyethylene (PE) and polypropylene (PP) diaphragms have poor wettability to electrolyte, and pores are not uniformly distributed, so that local concentration of lithium ion flow is easily caused, uneven lithium deposition is caused, and lithium dendritic crystals grow continuously. And they are also poor in thermal stability and easily shrink at high temperatures, also causing safety problems. Researchers often coat inorganic nano ceramic particles, such as nano silica, alumina, etc., on the surface of the separator to improve the thermal stability of the separator and the wettability of the electrolyte, but these methods cannot inhibit the growth of dendrites in the lithium metal battery, and even solve the safety problem of the lithium metal battery caused by the continuous growth of lithium dendrites.
Disclosure of Invention
The invention aims to provide a laminated titanium dioxide modified diaphragm, a preparation method and application thereof. The method has low cost and simple steps, and can be used for large-scale production.
In order to achieve the purpose, the technical scheme of the invention is as follows:
in a first aspect of the present invention, there is provided a laminated titanium dioxide-modified separator comprising a separator layer and a modified coating layer on a surface of the separator layer. The components of the modified coating are polyacrylic acid and laminated titanium dioxide; the mass ratio of the laminated titanium dioxide to the polyacrylic acid is 2-4: 1.
Further, the average molecular weight of polyacrylic acid is not less than 300000.
Further, the membrane layer is a commercial membrane, including but not limited to: any one of a single-layer PE film, a single-layer PP diaphragm, a double-layer PP film, a double-layer PE film, a double-layer PP/PE film, a three-layer PP/PE/PP film, a Polyester (PEI) film and the like.
Further, one side of the membrane layer is coated with the modified coating, or both sides of the membrane layer are coated with the modified coating.
Further, the thickness of the modified coating is 0.1-50 microns.
In a second aspect of the present invention, there is provided a method for preparing a laminated titanium dioxide modified separator, comprising the steps of: and uniformly mixing the polyacrylic acid binder and the laminated titanium dioxide particles to prepare slurry, coating the slurry on the surface of the diaphragm layer, and drying to obtain the laminated titanium dioxide modified diaphragm.
Further, the preparation method of the laminated titanium dioxide particles comprises the following steps: mixing Ti 3 AlC 2 And (MAX phase) is etched by hydrofluoric acid to obtain MXene powder, then hydrothermal reaction is carried out, and finally heating oxidation is carried out in the air to obtain laminated titanium dioxide particles. Preferably, the hydrothermal reaction temperature is 200 ℃, and the hydrothermal reaction time is 6 h; preferably, the heating oxidation temperature is 300 ℃; the time is 3 h.
Further, the polyacrylic acid binder is an organic solution of polyacrylic acid. The mass fraction of polyacrylic acid in the polyacrylic acid binder is 1-3%.
In a third aspect of the present invention, there is provided a lithium battery comprising a lithium metal negative electrode, a positive electrode, a separator and an electrolyte, wherein the separator is located between the lithium metal negative electrode and the positive electrode, and the electrolyte is filled in the battery; the diaphragm is the laminated titanium dioxide modified diaphragm, and one surface coated with the modified coating faces the lithium metal negative electrode.
The fourth aspect of the invention provides an application of the lithium battery in the field of new energy industry.
The laminated titanium dioxide coating is utilized to improve the lithium affinity and the thermal stability of the commercial diaphragm, and meanwhile, a stable interface protective layer is formed on the surface of the lithium metal negative electrode through the in-situ reaction of the laminated titanium dioxide and the lithium metal, so that uniform lithium deposition is realized, and the growth of lithium dendrites is inhibited. After coating, the laminated titanium dioxide particles can increase the wettability of the commercial separator to the electrolyte, and the laminated structure of the particles can also increase the liquid absorption rate of the separator to the electrolyte and can also improve the thermal stability of the separator. After the coating of the modified diaphragm is contacted with lithium metal, lithiation reaction is carried out, and an artificial interface protection layer is formed on the surface of the lithium metal negative electrode. The direct contact between the electrolyte and lithium metal is isolated, the side reaction is eliminated, the lithium ion flow can be homogenized, and the lithium deposition without dendritic crystal is realized.
Compared with the prior art, the invention has the following beneficial effects:
(1) the laminated titanium dioxide is added, has a laminated structure, can effectively form an interface protective layer, inhibits the growth of lithium dendrites, and can improve the liquid absorption rate of the diaphragm to electrolyte. The titanium dioxide is low in cost, the requirements of diaphragm coating on the process and the environment are low, and industrial preparation is easy to realize.
(2) The method provided by the invention can effectively improve the wettability and the thermal stability of the diaphragm to the electrolyte, is beneficial to the rapid passing of lithium ions in the battery, and simultaneously ensures the stability of the performance of the lithium battery.
(3) The method provided by the invention can form an artificial protective interface layer on the surface of the lithium cathode, protect the lithium cathode from being corroded by electrolyte and realize uniform lithium deposition without dendrites.
(4) The method provided by the invention obviously improves the coulombic efficiency of the battery, prolongs the cycle life of the battery, and avoids the safety problem caused by the continuous growth of the lithium dendrite.
(5) The method provided by the invention can be used for preparing the modified diaphragm through a simple coating process without the protection of special atmosphere, and is very beneficial to large-scale production.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a schematic flow chart of the preparation of a modified separator in examples 1 to 10 of the present invention.
Fig. 2 is a graph of coulombic efficiencies for cells of example 1 of the present invention and comparative example.
Fig. 3 is a long cycle diagram of the cells of example 1 of the present invention and comparative example.
FIG. 4 is a graph of 10mAh/cm of deposition using a commercial PE separator cell in a comparative example of the invention 2 Scanning electron microscope images of the surface of the lithium negative electrode after lithium.
FIG. 5 shows the deposition of 10mAh/cm for a battery using a laminated titanium dioxide modified separator in example 1 of the present invention 2 Scanning electron microscope images of the surface of the lithium negative electrode after lithium.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. 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.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In the operation process of the lithium metal battery, uneven deposition of lithium and side reaction of electrolyte and a lithium cathode can cause growth of lithium dendrite, lower coulombic efficiency and cycle life of the lithium battery are caused, the continuously grown lithium dendrite can pierce through a diaphragm, a battery short circuit is caused, and safety problems such as thermal runaway and even explosion are caused. Therefore, the invention provides a laminated titanium dioxide modified diaphragm and a preparation method and application thereof.
In an exemplary embodiment of the present invention, a laminated titanium dioxide modified separator is provided. The laminated titanium dioxide particles can increase the wettability of a commercial diaphragm to electrolyte, and the laminated structure of the particles can also increase the liquid absorption rate of the diaphragm to the electrolyte and can also improve the thermal stability of the diaphragm; the coating of the modified diaphragm is lithiated to form an interface protection layer after contacting with lithium metal, so that direct contact of electrolyte and the lithium metal is isolated while rapid and uniform passing of lithium ions is ensured, corrosion of side reaction to a lithium cathode is eliminated, lithium ion flow is homogenized, and dendrite-free lithium deposition is realized.
One side of the membrane layer is connected with the modified coating, or both sides of the membrane layer are connected with the modified coating.
In some examples of this embodiment, the membrane layer is a commercial membrane, including but not limited to: any one of a single-layer PE film, a single-layer PP diaphragm, a double-layer PP film, a double-layer PE film, a double-layer PP/PE film, a three-layer PP/PE/PP film, a Polyester (PEI) film and the like.
In some examples of this embodiment, the polyacrylic acid has an average molecular weight of 300000 or more.
In some examples of this embodiment, the mass ratio of titanium dioxide to polyacrylic acid is 2 to 4: 1.
The invention also provides a preparation method of the laminated titanium dioxide modified diaphragm, which comprises the steps of uniformly mixing a polyacrylic acid binder and laminated titanium dioxide particles to prepare slurry, coating the slurry on the surface of the diaphragm, and drying to obtain the laminated titanium dioxide modified diaphragm; the polyacrylic acid binder is an organic solution of polyacrylic acid.
In some examples of this embodiment, the method of making the layered titanium dioxide particles comprises: mixing Ti 3 AlC 2 And (MAX phase) is etched by hydrofluoric acid to obtain MXene powder, then hydrothermal reaction is carried out, and finally heating oxidation is carried out in the air to obtain laminated titanium dioxide particles. Preferably, the hydrothermal reaction temperature is 200 ℃, and the hydrothermal reaction time is 6 h; preferably, the heating oxidation temperature is 300 ℃; the time is 3 h.
In some examples of this embodiment, the polyacrylic acid has an average molecular weight of 300000 or more.
In some examples of this embodiment, the mass ratio of titanium dioxide to polyacrylic acid is 2 to 4: 1.
In some examples of this embodiment, the polyacrylic acid binder has a polyacrylic acid content of 1 to 3% by weight.
In some embodiments of this embodiment, the organic solvent in the polyacrylic acid binder is ethanol. The ethanol has good volatility and lower toxicity than other organic solvents, is easy to recover, and is beneficial to modification and environmental protection of the diaphragm.
In some examples of this embodiment, the coating is spray coating, knife coating, spin coating, or roll coating.
In a third embodiment of the present invention, there is provided a use of the above-described laminated titanium dioxide-modified separator in a lithium metal battery.
In a fourth embodiment of the present invention, there is provided a lithium metal battery including a lithium metal negative electrode, a positive electrode, a separator and an electrolyte, wherein the separator is located between the lithium metal negative electrode and the positive electrode, and the electrolyte is filled in the battery; the diaphragm is the laminated titanium dioxide modified diaphragm, and the modified side of the diaphragm faces to the lithium metal negative electrode.
In some examples of this embodiment, the lithium metal negative electrode includes, but is not limited to: lithium sheet, lithium foil, lithium block, lithium ribbon, lithium powder, lithium alloy.
In some examples of this embodiment, the electrolyte is an ester electrolyte or an ether electrolyte.
In some examples of this embodiment, assembling the lithium metal battery is performed under an inert atmosphere. The inert atmosphere comprises any one of argon, helium, hydrogen-argon mixed gas and the like, and the moisture content of the inert atmosphere is less than 1ppm, and the oxygen content of the inert atmosphere is less than 1 ppm.
In some examples of this embodiment, the lithium metal battery is a symmetrical battery or a full battery.
The fifth embodiment of the invention provides an application of the lithium battery in the field of new energy industry.
In particular to the application in unmanned aerial vehicles, electric vehicles or energy storage devices.
In order to make the technical solution of the present invention more clearly understood by those skilled in the art, the technical solution of the present invention will be described in detail below with reference to specific examples and comparative examples.
Example 1
A method of making a lithium metal battery utilizing a laminated titanium dioxide modified separator to inhibit lithium dendrite growth, comprising the steps of:
(1) polyacrylic acid with the average molecular weight of 1250000 is dissolved in ethanol to prepare the adhesive with the polyacrylic acid mass fraction of 2%.
(2) Mixing Ti 3 AlC 2 (MAX phase) is etched by hydrofluoric acid to obtain MXene powder, then the MXene powder is placed at 200 ℃ for hydrothermal reaction for 6h, finally the powder is heated in air at 300 ℃ for 3h for further oxidation to obtain laminated anatase TiO 2 。
(3) Subjecting the layered TiO of step (2) 2 Uniformly mixing the particles with the binder in the step (1) to prepare slurry, wherein the mass ratio of titanium dioxide to polyacrylic acid is 4: 1.
(4) and (4) spraying the slurry mixed in the step (3) on a commercial single-layer PE diaphragm, and drying to obtain the modified diaphragm, as shown in figure 1.
(5) Cutting the modified diaphragm obtained in the step (4) into a circular sheet with the diameter of 16mm, then taking a lithium sheet with the diameter of 1cm as a counter electrode, adopting lipid liquid electrolyte 1MLiPF6+ EC/DEC (volume ratio of 1: 1)/10% FEC, and assembling into a 2032 type button cell under the argon atmosphere, wherein the button cell comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a lithium sheet, electrolyte and the modified diaphragm.
Example 2
A method for preparing a lithium metal battery using a laminated titanium dioxide modified separator to inhibit the growth of lithium dendrites, comprising the steps of:
(1) polyacrylic acid with the average molecular weight of 1250000 was dissolved in ethanol to prepare a binder with a polyacrylic acid mass fraction of 1%.
(2) Mixing Ti 3 AlC 2 Etching (MAX phase) with hydrofluoric acid to obtain MXene powder, hydrothermal reacting at 200 deg.C for 6 hr, and heating at 300 deg.C in air for 3 hrOxidizing to obtain laminated anatase type TiO 2 。
(3) Subjecting the layered TiO of step (2) 2 Uniformly mixing the particles with the binder in the step (1) to prepare slurry, wherein the mass ratio of titanium dioxide to polyacrylic acid is 4: 1.
(4) and (4) spraying the slurry mixed in the step (3) on a commercial single-layer PE diaphragm, and drying to obtain the modified diaphragm, as shown in figure 1.
(5) Cutting the modified diaphragm obtained in the step (4) into a circular sheet with the diameter of 16mm, then using a lithium sheet with the diameter of 1cm as a counter electrode, adopting lipid liquid electrolyte 1MLiPF6+ EC/DEC (volume ratio 1: 1)/10% FEC, and assembling the modified diaphragm of the embodiment into the 2032 type button cell described in the embodiment 1 under the argon atmosphere.
Example 3
A method of making a lithium metal battery utilizing a laminated titanium dioxide modified separator to inhibit lithium dendrite growth, comprising the steps of:
(1) polyacrylic acid with average molecular weight of 450000 was dissolved in ethanol to prepare a binder with polyacrylic acid mass fraction of 2%.
(2) Mixing Ti 3 AlC 2 (MAX phase) is etched by hydrofluoric acid to obtain MXene powder, then the MXene powder is placed at 200 ℃ for hydrothermal reaction for 6h, finally the powder is heated in air at 300 ℃ for 3h for further oxidation to obtain laminated anatase TiO 2 。
(3) Subjecting the layered TiO of step (2) 2 Uniformly mixing the particles with the binder in the step (1) to prepare slurry, wherein the mass ratio of titanium dioxide to polyacrylic acid is 4: 1.
(4) and (4) spraying the slurry mixed in the step (3) on a commercial single-layer PE diaphragm, and drying to obtain the modified diaphragm, as shown in figure 1.
(5) Cutting the modified diaphragm obtained in the step (4) into a circular sheet with the diameter of 16mm, then using a lithium sheet with the diameter of 1cm as a counter electrode, adopting lipid liquid electrolyte 1MLiPF6+ EC/DEC (volume ratio 1: 1)/10% FEC, and assembling the modified diaphragm of the embodiment into the 2032 type button cell described in the embodiment 1 under the argon atmosphere.
Example 4
A method of making a lithium metal battery utilizing a laminated titanium dioxide modified separator to inhibit lithium dendrite growth, comprising the steps of:
(1) polyacrylic acid having an average molecular weight of 450000 was dissolved in ethanol to prepare a binder having a polyacrylic acid mass fraction of 1%.
(2) Mixing Ti 3 AlC 2 (MAX phase) is etched by hydrofluoric acid to obtain MXene powder, then the MXene powder is placed at 200 ℃ for hydrothermal reaction for 6h, finally the powder is heated in air at 300 ℃ for 3h for further oxidation to obtain laminated anatase TiO 2 。
(3) Subjecting the layered TiO of step (2) 2 Uniformly mixing the particles and the binder in the step (1) to prepare slurry, wherein the mass ratio of titanium dioxide to polyacrylic acid is 4: 1.
(4) and (4) spraying the slurry mixed in the step (3) on a commercial single-layer PE diaphragm, and drying to obtain the modified diaphragm, as shown in figure 1.
(5) Cutting the modified diaphragm obtained in the step (4) into a circular sheet with the diameter of 16mm, then using a lithium sheet with the diameter of 1cm as a counter electrode, adopting lipid liquid electrolyte 1MLiPF6+ EC/DEC (volume ratio 1: 1)/10% FEC, and assembling the modified diaphragm of the embodiment into the 2032 type button cell described in the embodiment 1 under the argon atmosphere.
Example 5
A method of making a lithium metal battery utilizing a laminated titanium dioxide modified separator to inhibit lithium dendrite growth, comprising the steps of:
(1) polyacrylic acid with the average molecular weight of 1250000 is dissolved in ethanol to prepare the adhesive with the polyacrylic acid mass fraction of 2%.
(2) Mixing Ti 3 AlC 2 (MAX phase) is etched by hydrofluoric acid to obtain MXene powder, then the MXene powder is placed at 200 ℃ for hydrothermal reaction for 6h, finally the powder is heated in air at 300 ℃ for 3h for further oxidation to obtain laminated anatase TiO 2 。
(3)Subjecting the layered TiO of step (2) 2 Uniformly mixing the particles with the binder in the step (1) to prepare slurry, wherein the mass ratio of titanium dioxide to polyacrylic acid is 2: 1.
(4) and (4) spraying the slurry mixed in the step (3) on a commercial single-layer PE diaphragm, and drying to obtain the modified diaphragm, as shown in figure 1.
(5) Cutting the modified diaphragm obtained in the step (4) into a circular sheet with the diameter of 16mm, then using a lithium sheet with the diameter of 1cm as a counter electrode, adopting lipid liquid electrolyte 1MLiPF6+ EC/DEC (volume ratio 1: 1)/10% FEC, and assembling the modified diaphragm of the embodiment into the 2032 type button cell described in the embodiment 1 under the argon atmosphere.
Example 6
A method of making a lithium metal battery utilizing a laminated titanium dioxide modified separator to inhibit lithium dendrite growth, comprising the steps of:
(1) polyacrylic acid with the average molecular weight of 1250000 is dissolved in ethanol to prepare the adhesive with the polyacrylic acid mass fraction of 2%.
(2) Mixing Ti 3 AlC 2 (MAX phase) is etched by hydrofluoric acid to obtain MXene powder, then the MXene powder is placed at 200 ℃ for hydrothermal reaction for 6 hours, finally the powder is heated in air at 300 ℃ for 3 hours for further oxidation to obtain laminated anatase type TiO 2 。
(3) Subjecting the layered TiO of step (2) 2 Uniformly mixing the particles with the binder in the step (1) to prepare slurry, wherein the mass ratio of titanium dioxide to polyacrylic acid is 4: 1.
(4) and (4) coating the slurry mixed in the step (3) on a commercial single-layer PE diaphragm in a scraping manner, and drying to obtain the modified diaphragm, wherein the modified diaphragm is shown in figure 1.
(5) Cutting the modified diaphragm obtained in the step (4) into a circular sheet with the diameter of 16mm, then using a lithium sheet with the diameter of 1cm as a counter electrode, adopting lipid liquid electrolyte 1MLiPF6+ EC/DEC (volume ratio 1: 1)/10% FEC, and assembling the modified diaphragm of the embodiment into the 2032 type button cell described in the embodiment 1 under the argon atmosphere.
Example 7
A method of making a lithium metal battery utilizing a laminated titanium dioxide modified separator to inhibit lithium dendrite growth, comprising the steps of:
(1) polyacrylic acid with the average molecular weight of 1250000 is dissolved in ethanol to prepare the adhesive with the polyacrylic acid mass fraction of 2%.
(2) Mixing Ti 3 AlC 2 (MAX phase) is etched by hydrofluoric acid to obtain MXene powder, then the MXene powder is placed at 200 ℃ for hydrothermal reaction for 6h, finally the powder is heated in air at 300 ℃ for 3h for further oxidation to obtain laminated anatase TiO 2 。
(3) Subjecting the layered TiO of step (2) 2 Uniformly mixing the particles with the binder in the step (1) to prepare slurry, wherein the mass ratio of titanium dioxide to polyacrylic acid is 4: 1.
(4) and (3) rolling and coating the mixed slurry in the step (3) on a commercial single-layer PE diaphragm, and drying to obtain the modified diaphragm, as shown in figure 1.
(5) Cutting the modified diaphragm obtained in the step (4) into a circular sheet with the diameter of 16mm, then using a lithium sheet with the diameter of 1cm as a counter electrode, adopting lipid liquid electrolyte 1MLiPF6+ EC/DEC (volume ratio 1: 1)/10% FEC, and assembling the modified diaphragm of the embodiment into the 2032 type button cell described in the embodiment 1 under the argon atmosphere.
Example 8
A method of making a lithium metal battery utilizing a laminated titanium dioxide modified separator to inhibit lithium dendrite growth, comprising the steps of:
(1) polyacrylic acid with the average molecular weight of 1250000 is dissolved in ethanol to prepare the adhesive with the polyacrylic acid mass fraction of 2%.
(2) Mixing Ti 3 AlC 2 (MAX phase) is etched by hydrofluoric acid to obtain MXene powder, then the MXene powder is placed at 200 ℃ for hydrothermal reaction for 6h, finally the powder is heated in air at 300 ℃ for 3h for further oxidation to obtain laminated anatase TiO 2 。
(3) Subjecting the layered TiO of step (2) 2 Uniformly mixing the particles with the binder in the step (1) to prepare slurryThe material comprises the following components in percentage by mass: 1.
(4) and (4) spin-coating the mixed slurry obtained in the step (3) on a commercial single-layer PE diaphragm, and drying to obtain the modified diaphragm, as shown in figure 1.
(5) Cutting the modified diaphragm obtained in the step (4) into a circular sheet with the diameter of 16mm, then using a lithium sheet with the diameter of 1cm as a counter electrode, adopting lipid liquid electrolyte 1MLiPF6+ EC/DEC (volume ratio 1: 1)/10% FEC, and assembling the modified diaphragm of the embodiment into the 2032 type button cell described in the embodiment 1 under the argon atmosphere.
Example 9
A method of making a lithium metal battery utilizing a laminated titanium dioxide modified separator to inhibit lithium dendrite growth, comprising the steps of:
(1) polyacrylic acid with the average molecular weight of 1250000 is dissolved in ethanol to prepare the adhesive with the polyacrylic acid mass fraction of 2%.
(2) Mixing Ti 3 AlC 2 (MAX phase) is etched by hydrofluoric acid to obtain MXene powder, then the MXene powder is placed at 200 ℃ for hydrothermal reaction for 6h, finally the powder is heated in air at 300 ℃ for 3h for further oxidation to obtain laminated anatase TiO 2 。
(3) Subjecting the layered TiO of step (2) 2 Uniformly mixing the particles with the binder in the step (1) to prepare slurry, wherein the mass ratio of titanium dioxide to polyacrylic acid is 4: 1.
(4) and (4) spraying the slurry mixed in the step (3) on a commercial single-layer PP diaphragm, and drying to obtain the modified diaphragm, as shown in figure 1.
(5) Cutting the modified diaphragm obtained in the step (4) into a circular sheet with the diameter of 16mm, then using a lithium sheet with the diameter of 1cm as a counter electrode, adopting lipid liquid electrolyte 1MLiPF6+ EC/DEC (volume ratio 1: 1)/10% FEC, and assembling the modified diaphragm of the embodiment into the 2032 type button cell described in the embodiment 1 under the argon atmosphere.
Example 10
A preparation method of a lithium battery for inhibiting the growth of lithium dendrites by utilizing a laminated titanium dioxide modified diaphragm comprises the following steps:
(1) polyacrylic acid with the average molecular weight of 1250000 is dissolved in ethanol to prepare the adhesive with the polyacrylic acid mass fraction of 2%.
(2) Mixing Ti 3 AlC 2 (MAX phase) is etched by hydrofluoric acid to obtain MXene powder, then the MXene powder is placed at 200 ℃ for hydrothermal reaction for 6h, finally the powder is heated in air at 300 ℃ for 3h for further oxidation to obtain laminated anatase TiO 2 。
(3) Subjecting the layered TiO of step (2) 2 Uniformly mixing the particles with the binder in the step (1) to prepare slurry, wherein the mass ratio of titanium dioxide to polyacrylic acid is 4: 1.
(4) and (4) spraying the slurry mixed in the step (3) on a commercial double-layer PE/PP diaphragm, and drying to obtain the modified diaphragm, as shown in figure 1.
(5) Cutting the modified diaphragm obtained in the step (4) into a circular sheet with the diameter of 16mm, then using a lithium sheet with the diameter of 1cm as a counter electrode, adopting lipid liquid electrolyte 1MLiPF6+ EC/DEC (volume ratio 1: 1)/10% FEC, and assembling the modified diaphragm of the embodiment into the 2032 type button cell described in the embodiment 1 under the argon atmosphere.
Comparative example
A method for preparing a lithium battery using a commercial separator, comprising the steps of:
the commercial PE separator was cut into 1.6cm circular pieces, and then assembled into a 2032 type button cell as described in example 1 under argon atmosphere using a 1cm diameter lithium sheet as the counter electrode and using a lipid liquid electrolyte of 1MLiPF6+ EC/DEC (1: 1 by volume)/10% FEC.
Performance testing
(1) The 2032 type button cell prepared in example 1 was used as an example, and the coulombic efficiency and the cycle stability of the cell were evaluated by using a charge and discharge device (novacar CT-4008). Meanwhile, as a comparison, the above-described performance of the battery (comparative example) assembled with the uncoated modified commercial PE separator was also tested, and the results are shown in fig. 2 to 4.
First, at a current density of 1.0mA/cm 2 The capacity is 1.0mAh/cm 2 The coulombic efficiency of the two groups of batteries is tested under the condition, the result is shown in figure 2, and it can be seen that the coulombic efficiency is 95.3% after 40 cycles of cycle by using the modified diaphragm, but the comparative example fails, and the improvement is very obvious.
Next, at a current density of 1.0mA/cm 2 The capacity is 1.0mAh/cm 2 The results of testing the cycling stability of the two groups of batteries under the conditions are shown in fig. 3, and it can be seen that the symmetrical batteries can stably cycle for more than 180 hours after the modified diaphragm is adopted, while the batteries using the commercial PE diaphragm have a sudden voltage drop at 70 hours, a local short circuit occurs, and then the batteries fail, and the cycling stability is obviously improved compared with the batteries using the commercial PE diaphragm.
(2) And (3) characterizing the lithium deposition morphology:
the batteries prepared according to the method of example 1 and comparative example were used at a current density of 1mA/cm 2 Under the condition of (1), depositing 10mA/cm 2 To a lithium metal cathode. And then disassembling the battery under the argon atmosphere to obtain the lithium foil after lithium deposition, and observing the lithium growth morphology on the surface of the lithium foil by using a scanning electron microscope. The results are shown in FIG. 4 (comparative example) and FIG. 5 (example 1). As can be seen in fig. 4, the lithium foil using the commercial PE separator had numerous dendritic lithium dendrites thereon. As can be seen from fig. 5, no dendritic lithium dendrites were found on the lithium foil using the laminated titanium dioxide modified PE separator. The above results indicate that the laminated titanium dioxide modified separator can suppress the generation of lithium dendrites and induce uniform lithium deposition, which contributes to the improvement of coulombic efficiency and cycle stability of the battery and the reduction of the occurrence of safety problems due to the growth of lithium dendrites.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A laminated titanium dioxide modified diaphragm is characterized by comprising a diaphragm layer and a modified coating coated on the surface of the diaphragm layer; the modified coating is formed by compounding polyacrylic acid and laminated titanium dioxide particles; the mass ratio of the laminated titanium dioxide to the polyacrylic acid is 2-4: 1.
2. The laminated titanium dioxide-modified separator according to claim 1, wherein the average molecular weight of polyacrylic acid is not less than 300000.
3. The laminated titanium dioxide-modified separator according to claim 1, wherein the separator layer comprises any one of a single-layer PE film, a single-layer PP separator, a double-layer PP film, a double-layer PE film, a double-layer PP/PE film, a triple-layer PP/PE/PP film, and a Polyester (PEI) film.
4. The laminated titanium dioxide-modified membrane according to claim 1, wherein the membrane layer is coated with the modified coating on one side, or both sides of the membrane layer are coated with the modified coating.
5. The laminated titanium dioxide modified membrane of claim 1, wherein the modified coating layer has a thickness of 0.1 to 50 μm.
6. A method for producing the laminated titanium dioxide-modified membrane according to any one of claims 1 to 5, comprising the steps of:
and uniformly mixing the polyacrylic acid binder and the laminated titanium dioxide particles to prepare slurry, coating the slurry on the surface of the diaphragm layer, and drying to obtain the laminated titanium dioxide modified diaphragm.
7. The production method according to claim 6, wherein the laminated titanium dioxide particles are produced by: mixing Ti 3 AlC 2 Etching (MAX phase) with hydrofluoric acid to obtain MXene powder, hydrothermal reacting, and heating and oxidizing in air to obtain laminated productTitanium dioxide particles; preferably, the hydrothermal reaction temperature is 200 ℃, and the hydrothermal reaction time is 6 h; preferably, the heating oxidation temperature is 300 ℃; the time is 3 h.
8. The method of claim 6, wherein the polyacrylic acid binder is an organic solution of polyacrylic acid; preferably, the polyacrylic acid binder contains polyacrylic acid in an amount of 1 to 3% by mass.
9. A lithium battery is characterized by comprising a lithium metal negative electrode, a positive electrode, a diaphragm and electrolyte, wherein the diaphragm is positioned between the lithium metal negative electrode and the positive electrode, and the electrolyte is filled in the battery; the separator is the laminated titanium dioxide modified separator as defined in any one of claims 1 to 5, wherein the side coated with the modified coating layer faces the lithium metal negative electrode;
preferably, the lithium metal negative electrode is a lithium sheet, a lithium foil, a lithium block, a lithium ribbon, a lithium powder or a lithium alloy;
preferably, the electrolyte is an ester electrolyte or an ether electrolyte;
preferably, the lithium battery is a symmetrical battery or a full battery.
10. The use of a lithium battery as claimed in claim 9 in the field of new energy industry; preferably, in a drone, an electric vehicle or an energy storage device.
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