CN115036646A - Nano composite material battery diaphragm, preparation method thereof and lithium battery - Google Patents
Nano composite material battery diaphragm, preparation method thereof and lithium battery Download PDFInfo
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- ICXAPFWGVRTEKV-UHFFFAOYSA-N 2-[4-(1,3-benzoxazol-2-yl)phenyl]-1,3-benzoxazole Chemical compound C1=CC=C2OC(C3=CC=C(C=C3)C=3OC4=CC=CC=C4N=3)=NC2=C1 ICXAPFWGVRTEKV-UHFFFAOYSA-N 0.000 claims description 3
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- 238000004519 manufacturing process Methods 0.000 claims description 3
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
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Classifications
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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
- H01M50/44—Fibrous material
-
- 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
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
-
- 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
- H01M50/411—Organic 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
- 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
- H01M50/431—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
- 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
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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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
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
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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
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/497—Ionic conductivity
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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
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Abstract
The invention relates to a nano composite material battery diaphragm and a preparation method thereof, and a lithium battery, wherein a required temperature-resistant high polymer material and an organic solution of an inorganic material are fully mixed and stirred to prepare a sol solution with a certain mass fraction, different concentrations, mass fractions and scraper thicknesses of the sol solution are adjusted, the sol is soaked in water for solvent replacement by a sol-gel method, hydrogel is obtained after the required time is reached, and the hydrogel is flattened and dried in vacuum to obtain the nano composite material battery diaphragm. The composite material diaphragm provided by the invention can greatly improve the chemical performance and safety performance of the battery.
Description
Technical Field
The invention relates to the field of battery diaphragms, in particular to a nanocomposite battery diaphragm, a preparation method thereof and a lithium battery.
Background
Over the past several decades, lithium ion batteries have been widely used in many fields. Such as new energy vehicles, energy storage devices, and the like. The digital battery is the main application field of the current lithium battery, and the power battery is the future development trend of the lithium battery field; in addition, the application of the lithium battery in the field of energy storage mainly surrounds the fields of household light storage systems, power supplies, battery energy storage, electric vehicle charging stations, base station standby and the like, the lithium battery has high specific energy and energy density, low self-discharge rate, no memory effect, environmental protection and no pollution, and the performance of the lithium battery is superior to that of other energy storage battery types in all aspects.
Therefore, the development and research of high-energy density and high-safety lithium batteries are urgent. Lithium metal batteries, because of their highest theoretical capacity (3860mAhg-1), most negative electrochemical potential (-3.04 Vvs, standard hydrogen electrode), and extremely low density (0.59gcm-3), can greatly increase energy density as the negative electrode of the battery. However, as the energy density of the battery increases, the stability becomes poor and the potential safety hazard becomes greater. In order to overcome the safety problem, there is a continuous need for improvement of the internal component materials of lithium metal batteries.
The lithium ion battery mainly comprises a positive electrode, a negative electrode and a diaphragm arranged between the positive electrode and the negative electrode. The diaphragm is used as a key component of the inner layer of the lithium battery and is used for separating the positive electrode and the negative electrode of the battery and preventing the short circuit caused by the contact of the positive electrode and the negative electrode. The performance of the diaphragm determines the interface structure, internal resistance and the like of the battery, directly influences the capacity, circulation, service life, safety and other characteristics of the battery, and the diaphragm with excellent performance has important influence on improving the comprehensive performance of the battery. The polyolefin material used as the raw material of the lithium ion battery diaphragm has the advantages of excellent mechanical property, chemical stability, electrical insulation, low price and easy processability, and is suitable for preparing the diaphragm. Currently, the commercially available separator materials are mainly Polyethylene (PE) and polypropylene (PP). Such separators have serious safety problems during charge and discharge cycles of lithium batteries, for example, dendrite problems caused by non-uniform precipitation of lithium ions on the surface of a negative electrode, causing important problems in the following respects:
(1) the lithium dendrite grows continuously and finally pierces the diaphragm, which causes short circuit of the circuit and rapid increase of current, thus causing accidents such as fire accident and even explosion.
(2) The lithium dendrites grow to a certain extent and break into dead lithium, resulting in a decay of the battery capacity until finally failure.
(3) With the increase of the energy density of the lithium battery, a large amount of heat is generated, the occurrence of a thermal runaway event can be accelerated due to low heat conduction, and even the life safety of a person is threatened.
Therefore, the safety performance of the conventional lithium metal battery is not high, and the main reasons include the lack of the performance of the conventional diaphragm in various aspects;
(1) the generation of lithium dendrites cannot be prevented from the mechanism, and the growth of the lithium dendrites cannot be inhibited from the root;
(2) due to poor high temperature resistance and heat conductivity, the diaphragm can be further deformed and melted by huge heat generated by short circuit in the battery, and thermal runaway occurs. Therefore, the safety performance of the diaphragm is improved, safety accidents can be effectively prevented, and the safety performance of the lithium battery is greatly improved.
In recent years, in view of the safety problems caused by the lithium dendrites, research on methods for improving the safety of the lithium metal battery has been focused, such as doping of an electrolyte, surface modification of a negative electrode, modification of a separator, and the like, but methods for improving thermal stability by replacing other separators to inhibit the growth of lithium dendrites are not common. And also has not been applied to a practical battery separator modification technology, there is an urgent need for a more effective method to solve the above-mentioned safety problems.
Disclosure of Invention
It is an object of the present invention to provide a novel lithium battery separator;
still another object of the present invention is to provide a method for preparing the above battery separator;
it is still another object of the present invention to provide a lithium battery manufactured using the above battery separator.
The technical scheme for solving the technical problems is as follows:
the embodiment of the invention discloses a battery diaphragm made of a nano composite material, which is formed by dissolving a nano fiber material and a two-dimensional nano material respectively through the same organic solvent to form dispersion liquid, then mixing and processing the dispersion liquid, wherein the nano fiber material comprises one or 2-4 of aramid nano fiber, cellulose nano fiber, poly-p-phenylene benzobisoxazole nano fiber and bacterial fiber, and the two-dimensional nano material comprises one or 2-7 of boron nitride, clay, aluminum oxide, graphene oxide, a metal organic framework material and molybdenum disulfide or hydroxyapatite.
As a preferable technical scheme of the embodiment of the invention, the organic solvent comprises one or a composition of 2-5 of dimethyl sulfoxide, tetrahydrofuran, N-dimethylformamide, dimethylacetamide and N-methylpyrrolidone.
As a preferable technical solution of the embodiment of the present invention, the metal organic framework material includes MOF.
As a preferable technical scheme of the embodiment of the invention, the mass ratio of the nanofiber material to the two-dimensional nanomaterial is 0.01-1.5.
As a preferable technical scheme of the embodiment of the invention, the diameter of the nanofiber material is 1-50 nm, and the length of the nanofiber material is 1-100 mu m.
As a preferable technical scheme of the embodiment of the invention, the transverse dimension of the two-dimensional nano material is 0.1-20 mu m, and the thickness of the two-dimensional nano material is 0.5-10 nm.
As a preferable technical scheme of the embodiment of the invention, the thickness of the battery diaphragm made of the nano composite material is 1-100 mu m.
The embodiment of the invention also discloses a method for preparing the battery diaphragm made of the nano composite material, which is characterized by comprising the following steps:
s1, mixing the organic solvent and the nanofiber material to prepare a dispersion liquid A;
s2, mixing the organic solvent and the two-dimensional nano material to prepare a dispersion liquid B;
s3, mixing the dispersion liquid A and the dispersion liquid B to prepare a sol solution C;
s4, pouring the sol solution C into a mold, and removing the redundant sol solution C by using a scraper;
s5, soaking the remaining sol in the mold in water to obtain hydrogel;
s6, flattening and drying the hydrogel to obtain the nanocomposite battery diaphragm.
As a preferable technical scheme of the embodiment of the invention, the setting condition in the step S1 is 25-50 ℃, the mechanical stirring is carried out for 1-120 h, the rotating speed is 1-1200 r/min, and the concentration of the dispersion liquid A is 0.1-10 wt%.
As a preferable technical scheme of the embodiment of the invention, the mixing in the step S2 is ultrasonic mixing, the ultrasonic power is 0-600W, and the ultrasonic time is 0.1-20 h.
The embodiment of the invention also discloses a lithium battery which comprises the nano composite material battery diaphragm.
Compared with the prior art, the invention has at least the following beneficial effects;
the invention provides a preparation method of a battery diaphragm made of a nano composite material, which has the advantages of novel preparation process, convenient operation, capability of producing diaphragms in any shapes in a large scale, reduction of damage to the diaphragms, low cost, mass production and wide prospect, and the composite film is directly suitable for the production of the existing lithium battery process, can induce lithium ions to be uniformly deposited, inhibit the generation and growth of lithium dendrites, effectively improve the coulomb efficiency of a lithium ion battery and prolong the cycle life of the battery; meanwhile, the diaphragm is thin and light, and has a positive influence on the energy density of the lithium battery.
The nanofiber material, the two-dimensional nanomaterial and the like used in the invention have very high melting points, and compared with a PP battery diaphragm, the temperature resistance and the thermal conductivity of the battery diaphragm are greatly improved, the battery diaphragm is prevented from being heated and shrunk and damaged when the battery is overheated, and the problem of internal short circuit of the battery is better prevented. Meanwhile, the two-dimensional nano material has a large number of vacant sites and polar groups, and can uniformly distribute lithium ions, so that the lithium ion transmission efficiency is improved. Mechanical stirring and ultrasonic treatment are used in the mixing process, the mechanical stirring is favorable for fully dispersing the temperature-resistant high polymer material, and the ultrasonic treatment is used for better dispersing and mixing the material, so that the material agglomeration phenomenon is prevented.
In conclusion, the nano composite battery diaphragm provided by the invention can effectively improve the electrochemical performance and safety performance of the lithium metal battery.
The technical solution of the present invention is further described in detail by the accompanying drawings and examples.
Drawings
FIG. 1 is a scanning electron microscope photograph of the surface of the nanocomposite battery separator in example 1;
FIG. 2 is a scanning electron microscope photograph of a cross-section of the nanocomposite battery separator of example 1;
FIG. 3 is a graph comparing the thermal stability of the nanocomposite battery separator of example 2 with that of a conventional PP separator, wherein the first column from the left is at room temperature, the second column from the left is at 140 degrees Celsius, and the third column from the left is at 220 degrees Celsius;
FIG. 4 is a comparative scanning electron microscope image of the growth morphology of lithium metal after cycling the same number of cycles for the nanocomposite battery separator and a conventional PP separator assembled half cell of example 3 under the same cycling conditions;
FIG. 5 is a graph comparing the impedance tests performed in examples 4 to 8;
FIG. 6 is a comparative graph of mechanical property tests conducted on examples 4 to 8.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it is to be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The specific embodiment of the invention discloses a novel lithium battery diaphragm, a preparation method thereof and a lithium battery manufactured by using the battery diaphragm.
The battery diaphragm is 1-100 mu m thick and is prepared by dissolving a nanofiber material and a two-dimensional nano material in an organic solvent to form a dispersion liquid, mixing and processing the dispersion liquid, wherein the nanofiber material comprises one or 2-4 of aramid nanofiber, cellulose nanofiber, poly-p-phenylene benzobisoxazole nanofiber and bacterial fiber, and the two-dimensional nano material comprises one or 2-7 of boron nitride, clay, aluminum oxide, graphene oxide, a metal organic framework material and molybdenum disulfide or hydroxyapatite.
In the above embodiments, the ratio of the mass of the nanofiber material to the mass of the two-dimensional nanomaterial is 0.01 to 1.5, i.e., the nanofiber material is not more than 1.5 times the mass of the two-dimensional nanomaterial at the maximum.
In the above embodiment, the nanofiber material has a diameter of 1 to 50nm and a length of 1 to 100 μm.
In the above embodiment, the two-dimensional nanomaterial has a lateral dimension of 0.1 to 20 μm and a thickness of 0.5 to 10 nm.
In the above embodiments, the metal organic framework material comprises MOF. Metal organic framework material: is a compound composed of metal ions or clusters, and the clusters are coordinated with organic ligands to form a one-dimensional, two-dimensional or three-dimensional structure. They are a subclass of coordination polymers, which are characterized by their generally porous nature. The organic ligands involved are sometimes referred to as "pillars," and more formally, the metal-organic framework is a coordination network with organic ligands containing potential voids. A coordinating network is a coordinating compound that extends through a one-dimensional repeating coordinating entity but has cross-links between two or more individual chains, loops or helical links, or a coordinating compound that extends through two or three repeating coordinating entities. Size; finally, a coordination polymer is a coordination compound in which the repeating coordination entities extend in one, two or three dimensions. In some cases, the pores are stable during the elimination of the guest molecule (usually a solvent) and may be refilled by other compounds. Due to this property, MOFs can serve as excellent frameworks in this embodiment, leading to a significant improvement in the final membrane performance.
The embodiment of the invention also discloses a preparation method of the battery diaphragm made of the nano composite material, which comprises the following steps: the method specifically comprises the following steps:
s1, mixing the organic solvent and the nanofiber material to prepare a dispersion liquid A, wherein the setting condition is that the temperature is 25-50 ℃, the mechanical stirring is carried out for 1-120 h, the rotating speed is 1-1200 r/min, and the concentration of the dispersion liquid A is finally 0.1-10 wt%;
s2, mixing the organic solvent and the two-dimensional nano material to prepare a dispersion liquid B, wherein the mixing is ultrasonic mixing, the ultrasonic power is 0-600W, and the ultrasonic time is 0.1-20 h;
s3, mixing the dispersion liquid A and the dispersion liquid B to prepare a sol solution C;
s4, pouring the sol solution C into a mold, and removing the redundant sol solution C by using a scraper;
s5, soaking the sol left in the mold in water for 1-24 hours to obtain hydrogel;
s6, flattening and vacuum drying the hydrogel, wherein the vacuum drying temperature is 25-120 ℃, and the vacuum drying time is 1-96 h, and the nano composite material battery diaphragm is obtained.
To further verify the advantageous effects of the present invention, experiments of a plurality of examples were conducted by a controlled variable method, and a prior art general PP battery separator was introduced as a comparative example for performance comparison. The method comprises the following specific steps:
example 1
Firstly, preparing a dispersion liquid A of aramid nano-fibers with the mass fraction of 2%, and weighing commercial aramid fiber materials, organic solvents of dimethyl sulfoxide and potassium hydroxide with required mass according to a ratio; the proportioning mass is 2: 98: 6, heating and stirring for 59 hours at the temperature of 35 ℃ and the rotating speed of 1200 r/min.
Preparing a boron nitride dispersion liquid B with the mass fraction of 3%, and weighing the boron nitride two-dimensional nano material and the organic solvent dimethyl sulfoxide with required mass according to the mixture ratio; the proportioning mass is 0.9: 29.1, and carrying out 300W ultrasound for 5 hours at room temperature.
And mechanically stirring and mixing the 2 wt% aramid fiber nano-fiber dispersion liquid A and the 3 wt% boron nitride nano-material dispersion liquid B to prepare a sol solution C, wherein the boron nitride nano-material accounts for 10 wt% of the composite nano-material.
Pouring the sol solution C into a mold, and removing the redundant sol solution C by using a scraper;
soaking the sol solution C left in the mold into water for 12 hours to obtain the required hydrogel;
flattening the hydrogel, putting the hydrogel into a vacuum drying oven, and carrying out vacuum drying treatment at the temperature of 45 ℃ for 12 hours to obtain the boron nitride nanocomposite battery diaphragm.
Scanning electron microscope analysis is carried out on the obtained boron nitride nano composite material battery diaphragm, as shown in figures 1 and 2, the nano composite material structure is an obvious ordered layered structure, and aramid nano fibers are tightly adhered to the surface of a boron nitride sheet. The thickness of the nano composite material diaphragm is about 25 mu m.
Example 2
Firstly, the aramid nano-fiber dispersion liquid A with the mass fraction of 2% is prepared, and the preparation process is the same as that of the example 1.
Preparing a boron nitride dispersion liquid B with the mass fraction of 3%, and weighing the boron nitride nano material and the organic solvent dimethyl sulfoxide with required mass according to the mixture ratio; the proportioning mass is 0.9: 29.1, and carrying out 600W ultrasonic treatment for 10 hours at room temperature.
And mechanically stirring and mixing the 2 wt% aramid fiber nano-fiber dispersion liquid A and the 3 wt% boron nitride nano-material dispersion liquid B to prepare a sol solution C, wherein the boron nitride nano-material accounts for 20 wt% of the composite nano-material.
Pouring the sol solution C into a mold, and removing redundant sol solution by using a scraper;
soaking the remaining sol in the mold into water for 15h to obtain the required hydrogel;
flattening the hydrogel, putting the hydrogel into a vacuum drying oven, and carrying out vacuum drying treatment at 40 ℃ for 12 hours to obtain the Boron Nitride (BN) nano composite material battery diaphragm.
The obtained boron nitride nanocomposite battery diaphragm was subjected to a thermal stability test, as shown in fig. 3, the boron nitride nanocomposite battery diaphragm and the polypropylene diaphragm were heated at 140 ℃ and 220 ℃ to show that the polypropylene diaphragm was significantly wrinkled and damaged at 140 ℃ until finally disappeared, while the boron nitride nanocomposite battery diaphragm maintained good shape at 140 ℃ and also changed significantly at 220 ℃ to show that the boron nitride nanocomposite battery diaphragm had excellent thermal stability.
Example 3
Firstly, preparing 1% of Aramid Nano Fiber (ANF) dispersion liquid by mass fraction, and weighing commercial aramid fiber materials, organic solvents dimethyl sulfoxide (DMSO) and potassium hydroxide (KOH) by mass according to the mixture ratio; the proportioning mass is 1: 99: 3, heating and stirring for 59 hours at the temperature of 35 ℃ and the rotating speed of 1200 r/min.
A boron nitride dispersion B having a mass fraction of 3% was prepared in the same manner as in example 2.
And mechanically stirring and mixing the 1 wt% aramid fiber nano-fiber dispersion liquid A and the 3 wt% boron nitride nano-material dispersion liquid B to prepare a sol solution C, wherein the boron nitride nano-material accounts for 20 wt% of the composite nano-material.
Pouring the sol solution into a mold, and removing the redundant sol solution C by using a scraper;
soaking the sol solution C left in the mold into water for 12h to obtain the required hydrogel;
flattening the hydrogel, putting the hydrogel into a vacuum drying oven, and carrying out vacuum drying treatment at the temperature of 45 ℃ for 12 hours to obtain the boron nitride nanocomposite battery diaphragm.
The method comprises the steps of assembling a half battery by using a boron nitride nanocomposite battery diaphragm and a common polypropylene diaphragm, wherein n-hexyl is a copper foil current collector, a negative electrode is a lithium sheet, disassembling the battery after two assembled half batteries are subjected to charge-discharge cycles with the same number of turns under the same cycle condition, and observing and comparing the growth morphology of lithium metal on the copper foil current collector.
Referring to fig. 4(a) - (b), lithium metal on a copper foil current collector of a conventional polypropylene battery grows into an obvious dendritic morphology, which is easy to pierce a diaphragm to cause internal short circuit, and the deposition of lithium metal is very loose, which causes large volume morphology change in a cycle process, affects interface stability, and causes dead lithium to reduce coulomb efficiency.
Referring to fig. 4(c) - (d), the boron nitride nanocomposite battery lithium metal growth has no obvious dendritic crystal morphology, and is dense, so that the generation of dead lithium can be effectively reduced, high coulombic efficiency is maintained, and it is demonstrated that the two-dimensional raw material has a large number of vacancies and polar groups, so that the lithium ion distribution can be uniform, the growth of lithium dendritic crystals can be inhibited to a certain extent, and the safety performance of the lithium metal battery can be improved.
As can be seen from examples 1 to 3, the performance of the battery separator in the present invention is largely affected by the ratio of each component in the raw materials, and therefore examples 4 to 8 were set by gradient change using the dispersion B as Boron Nitride (BN), as follows:
as shown in fig. 5, the impedance test was performed for examples 4 to 8, example 6: 20 wt% OH-BNNS/ANF has a lower impedance.
Further, as shown in fig. 6, mechanical property tests were performed on examples 4 to 8, example 6: the 20 wt% OH-BNNS/ANF has excellent mechanical properties relative to other films.
In conclusion, in the embodiment of the invention, the most preferable embodiment is the battery separator prepared by combining 80 wt% of aramid nano fiber and 20 wt% of boron nitride.
While the preferred embodiments of the present invention have been illustrated and described, it will be appreciated that the invention may be embodied otherwise than as specifically described and that equivalent alterations and modifications, which may be effected thereto by those skilled in the art without departing from the spirit of the invention, are deemed to be within the scope and spirit of the invention.
Claims (10)
1. A battery diaphragm made of a nano composite material is characterized in that a nano fiber material and a two-dimensional nano material are dissolved by the same organic solvent to form dispersion liquid, and then are mixed and processed, wherein the nano fiber material comprises one or 2-4 of aramid nano fibers, cellulose nano fibers, poly-p-phenylene benzobisoxazole nano fibers and bacterial fibers, and the two-dimensional nano material comprises one or 2-7 of boron nitride, clay, aluminum oxide, graphene oxide, a metal organic framework material and molybdenum disulfide or hydroxyapatite.
2. The nanocomposite battery separator according to claim 1, wherein the organic solvent comprises one or a combination of 2 to 5 of dimethylsulfoxide, tetrahydrofuran, N-dimethylformamide, dimethylacetamide, or N-methylpyrrolidone.
3. The nanocomposite battery separator according to claim 1, wherein the ratio of the mass of the nanofiber material to the mass of the two-dimensional nanomaterial is 0.01 to 1.5.
4. The nanocomposite battery separator according to claim 1, wherein the nanofiber material has a diameter of 1 to 50nm and a length of 1 to 100 μm.
5. The nanocomposite battery separator according to claim 1, wherein the two-dimensional nanomaterial has a lateral dimension of 0.1 to 20 μm and a thickness of 0.5 to 10 nm.
6. The nanocomposite battery separator according to claim 1, wherein the nanocomposite battery separator has a thickness of 1 to 100 μm.
7. A method of making the nanocomposite battery separator of any of claims 1 to 6, comprising the steps of:
s1, mixing the organic solvent and the nanofiber material to prepare a dispersion liquid A;
s2, mixing the organic solvent and the two-dimensional nano material to prepare a dispersion liquid B;
s3, mixing the dispersion liquid A and the dispersion liquid B to prepare a sol solution C;
s4, pouring the sol solution C into a mold, and removing the redundant sol solution C by using a scraper;
s5, soaking the remaining sol in the mold in water to obtain hydrogel;
s6, flattening and drying the hydrogel to obtain the nanocomposite battery diaphragm.
8. The method for preparing the battery separator made of the nano composite material according to claim 7, wherein the setting conditions in the step S1 are 25-50 ℃, the mechanical stirring is carried out for 1-120 h, the rotating speed is 1-1200 r/min, and the concentration of the dispersion liquid A is 0.1-10 wt%.
9. The method for preparing the battery separator made of the nano composite material according to claim 7, wherein the mixing in the step S2 is ultrasonic mixing, the ultrasonic power is 0-600W, and the ultrasonic time is 0.1-20 h.
10. A lithium battery comprising a nanocomposite battery separator as claimed in any one of claims 1 to 6.
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