CN112226064B - Negative electrode protective film, preparation method and application thereof, and alkali metal-air battery - Google Patents
Negative electrode protective film, preparation method and application thereof, and alkali metal-air battery Download PDFInfo
- Publication number
- CN112226064B CN112226064B CN202011083900.9A CN202011083900A CN112226064B CN 112226064 B CN112226064 B CN 112226064B CN 202011083900 A CN202011083900 A CN 202011083900A CN 112226064 B CN112226064 B CN 112226064B
- Authority
- CN
- China
- Prior art keywords
- negative electrode
- protective film
- alkali metal
- lithium
- electrode protective
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2333/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/02—Polyalkylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2244—Oxides; Hydroxides of metals of zirconium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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 belongs to the technical field of batteries, and particularly relates to a negative electrode protective film, a preparation method and application thereof, and an alkali metal-air battery. The negative electrode protective film provided by the invention comprises a polymer film and inorganic particles uniformly dispersed in the polymer film; the polymer film is made of one or more of polyvinylidene fluoride-hexafluoropropylene, polyethylene oxide and polymethyl methacrylate; the inorganic particles comprise one or more of lithium fluoride, silica, alumina, zirconia, and zinc oxide. The invention combines the polymer and the inorganic particles, can effectively stabilize the interface of alkali metal and electrolyte in the alkali metal-air battery, homogenizes the deposition of alkali metal ions, reduces the uncontrollable growth of dendrite of an alkali metal cathode, and slows down the corrosion of air, water or a strong oxidizing intermediate product on the alkali metal cathode.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a negative electrode protective film, a preparation method and application thereof, and an alkali metal-air battery.
Background
The alkali metal-air battery is a battery system in which an alkali metal having a negative electrode potential is used as a negative electrode, oxygen or pure oxygen in the air is used as a positive electrode active material, and an alkaline electrolyte aqueous solution is generally used as an electrolyte solution. The negative electrode is very important for realizing the high energy density of the alkali metal-air battery, but the situation of uncontrollable dendritic crystal growth can occur in the deposition process of the alkali metal, so that the dendritic crystal penetrates through a diaphragm of the alkali metal-air battery, short circuit occurs, and further safety accidents such as fire disaster are caused; meanwhile, in a semi-open system of the alkali metal-air battery, air, water, a strong-oxidizing intermediate product and the like can react with the active alkali metal cathode violently until the alkali metal cathode is completely consumed, so that the battery is disabled. Therefore, the uncontrolled dendrite growth and severe corrosion of the alkali metal negative electrode seriously affect the application of the alkali metal-air battery in practical industrialization.
At present, a Solid Electrolyte Interface (SEI) film is generally formed on the surface of an alkali metal negative electrode in the field to protect the alkali metal negative electrode, but the SEI film is not uniform and is easy to crack, and can not avoid the irregular growth of dendrites and the occurrence of severe corrosion, and the alkali metal negative electrode cannot guarantee the use requirements of an alkali metal-air battery.
Disclosure of Invention
Accordingly, the present invention is directed to a negative electrode protective film, which can effectively stabilize the interface between the alkali metal and the electrolyte in the alkali metal-air battery, uniformly deposit the alkali metal ions, reduce the uncontrolled growth of dendrites of the alkali metal negative electrode, and prevent the corrosion of the alkali metal negative electrode by air, water or a strongly oxidizing intermediate product.
In order to achieve the purpose of the invention, the invention provides the following technical scheme:
the invention provides a negative electrode protective film, which comprises a polymer film and inorganic particles uniformly dispersed in the polymer film;
the polymer film is made of one or more of polyvinylidene fluoride-hexafluoropropylene, polyethylene oxide and polymethyl methacrylate;
the inorganic particles comprise one or more of lithium fluoride, silica, alumina, zirconia, and zinc oxide.
Preferably, the mass ratio of the polymer film to the inorganic particles is 50: (1-2500).
Preferably, the thickness of the negative electrode protective film is 50 to 500 μm.
Preferably, the inorganic particles have a particle size of 5 to 50000nm.
The invention also provides a preparation method of the cathode protective film in the technical scheme, which comprises the following steps:
mixing a polymer, inorganic particles and an organic solvent to obtain slurry;
and coating the slurry on the surface of the substrate, and peeling off the substrate after the solvent is evaporated to obtain the cathode protective film.
Preferably, the organic solvent includes one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, acetone, acetonitrile, and N-methylpyrrolidone.
Preferably, the mass ratio of the total mass of the polymer and the inorganic particles to the organic solvent is 2: (1-10).
Preferably, the temperature for solvent evaporation is 70-150 ℃ and the time is 4-168 h.
The invention also provides application of the cathode protective film in the technical scheme or the cathode protective film prepared by the preparation method in the technical scheme in an alkali metal-air battery.
The invention also provides an alkali metal-air battery which comprises a positive electrode, a positive electrode catalyst, a negative electrode and electrolyte, wherein the surface of the negative electrode is coated with a negative electrode protective film, and the negative electrode protective film is the negative electrode protective film prepared by the preparation method in the technical scheme or the negative electrode protective film prepared by the preparation method in the technical scheme.
The invention provides a negative electrode protective film, which comprises a polymer film and inorganic particles uniformly dispersed in the polymer film; the polymer film is made of one or more of polyvinylidene fluoride-hexafluoropropylene, polyethylene oxide and polymethyl methacrylate; the inorganic particles comprise one or more of lithium fluoride, silica, alumina, zirconia, and zinc oxide. In the present invention, the polymer is a substantially film-forming material; the inorganic particles are used as the filler, so that the Young modulus of the negative electrode protective film is increased; the polymer and the inorganic particles are combined, so that the interface of alkali metal and electrolyte in the alkali metal-air battery can be effectively stabilized, the deposition of alkali metal ions is uniform, the uncontrollable growth of dendrite of an alkali metal cathode is reduced, and the corrosion of air, water or a strong-oxidizing intermediate product to the alkali metal cathode is slowed down.
The test results of the embodiment show that the negative electrode protective film provided by the invention is used as the protective film on the surface of the alkali metal negative electrode, and the obtained alkali metal-air battery has lower overpotential and long cycle life, which shows that the negative electrode protective film provided by the invention can effectively inhibit the uncontrolled growth of dendrites during the deposition of alkali metal negative electrode ions, prevent the dendrites from puncturing the battery diaphragm, and well slow down the corrosion of the alkali metal negative electrode.
Drawings
FIG. 1 is an SEM photograph of a negative electrode protective film obtained in example 1;
FIG. 2 is an XRD pattern of the negative electrode protective film obtained in example 1;
FIG. 3 is a thermogravimetric graph of the anode protective film obtained in example 1;
FIG. 4 is a graph showing tensile properties of the negative electrode protective film obtained in example 1;
FIG. 5 is an SEM image of ion deposition in a lithium/lithium symmetric cell of example 1;
FIG. 6 is a cycle plot of the lithium/lithium symmetric cell of example 1;
FIG. 7 is an SEM photograph of corrosion of a negative electrode in a lithium-air battery obtained in application example 1;
fig. 8 is a graph showing a cycle curve of a lithium-air battery obtained by applying example 1;
FIG. 9 is an SEM photograph of ion deposition in a lithium/lithium symmetric cell of comparative example 1;
FIG. 10 is a cycle plot of a lithium/lithium symmetric cell of comparative example 1;
FIG. 11 is an SEM photograph showing corrosion of a negative electrode in a lithium-air battery obtained in comparative application example 1;
fig. 12 is a graph showing the cycle characteristics of the lithium-air battery obtained in comparative application example 1.
Detailed Description
The invention provides a negative electrode protective film, which comprises a polymer film and inorganic particles uniformly dispersed in the polymer film;
the polymer film is made of one or more of polyvinylidene fluoride-hexafluoropropylene, polyethylene oxide and polymethyl methacrylate;
the inorganic particles comprise one or more of lithium fluoride, silica, alumina, zirconia, and zinc oxide.
In the present invention, the components are commercially available products well known to those skilled in the art unless otherwise specified.
The negative electrode protective film provided by the invention comprises a polymer film and inorganic particles uniformly dispersed in the polymer film.
In the invention, the material of the polymer film comprises one or more of polyvinylidene fluoride-hexafluoropropylene, polyethylene oxide and polymethyl methacrylate.
In the present invention, the inorganic particles include one or more of lithium fluoride, silica, alumina, zirconia, and zinc oxide. In the present invention, the particle diameter of the inorganic particles is preferably 5 to 50000nm, more preferably 100 to 40000nm.
In the present invention, the mass ratio of the polymer film to the inorganic particles is preferably 50: (1 to 2500), more preferably 50: (5-500).
In the present invention, the thickness of the negative electrode protective film is preferably 50 to 500 μm, and more preferably 100 to 400 μm.
The invention also provides a preparation method of the cathode protective film in the technical scheme, which comprises the following steps:
mixing a polymer, inorganic particles and an organic solvent to obtain slurry;
and coating the slurry on the surface of the substrate, and peeling off the substrate after the solvent is evaporated to obtain the cathode protective film.
The invention mixes polymer, inorganic particles and organic solvent to obtain slurry.
In the present invention, the polymer and the inorganic particles are the same as those in the above technical solution of the negative electrode protective film, and are not described herein again.
In the present invention, the organic solvent preferably includes one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, acetone, acetonitrile, and N-methylpyrrolidone.
In the present invention, the mass ratio of the total mass of the polymer and the inorganic particles to the organic solvent is preferably 2: (1 to 10), more preferably 2: (2 to 9). The mixing is not particularly limited in the present invention, and is based on the fact that the polymer, the inorganic particles and the organic solvent are fully and uniformly mixed, specifically, stirring.
After the slurry is obtained, the slurry is coated on the surface of the substrate, and the substrate is peeled after the solvent is evaporated, so that the cathode protective film is obtained.
In the present invention, the substrate is preferably glass. In the invention, the coating amount of the slurry on the surface of the substrate is based on the thickness of the cathode protective film after the solvent is evaporated. In the present invention, the manner of coating is preferably a solution casting method.
In the present invention, the temperature at which the solvent is evaporated is preferably 70 to 150 ℃, more preferably 80 to 140 ℃; the time is preferably from 4 to 168 hours, more preferably from 12 to 120 hours. In the present invention, the apparatus for evaporating the solvent is preferably an oven, a vacuum oven or a hot plate. The present invention is not particularly limited to the separation so that the substrate and the negative electrode protective film can be separated from each other.
The invention also provides application of the cathode protective film in the technical scheme or the cathode protective film prepared by the preparation method in the technical scheme in an alkali metal-air battery.
In the invention, the application is to coat the surface of the negative electrode in the alkali metal-air battery with the negative electrode protective film, preferably, slurry obtained by mixing a polymer, inorganic particles and an organic solvent is directly coated on the surface of the negative electrode, and the negative electrode with the surface firmly coated with the negative electrode protective film is obtained by solvent evaporation.
The invention also provides an alkali metal-air battery which comprises a positive electrode, a positive electrode catalyst, a negative electrode and electrolyte, wherein the surface of the negative electrode is coated with a negative electrode protective film, and the negative electrode protective film is the negative electrode protective film prepared by the preparation method in the technical scheme or the negative electrode protective film prepared by the preparation method in the technical scheme.
In the present invention, the alkali metal-air battery includes a positive electrode, a positive electrode catalyst, a negative electrode, and an electrolyte.
In the present invention, the positive electrode includes a binder, a conductive filler, and a positive electrode gas.
In the present invention, the cathode gas is preferably one or more of oxygen, nitrogen, carbon dioxide, air and water vapor.
In the present invention, the binder is preferably one or more of polyvinylidene fluoride, polytetrafluoroethylene, sodium alginate, alkali-metallized nafion, and carboxymethyl cellulose. In the present invention, the conductive filler is preferably one or more of supp carbon, acetylene black, ketjen black, graphite, graphene, carbon nanotubes, amorphous carbon, nanoporous carbon, and the like. The amount of the binder and the conductive filler used in the present invention is not particularly limited, and those known to those skilled in the art may be used.
In the present invention, the negative electrode includes a negative electrode sheet, a negative electrode protective film, and a current collector. The present invention does not specifically limit the positional relationship between the negative electrode sheet, the negative electrode protective film and the current collector, and may adopt a positional relationship known to those skilled in the art, specifically, the current collector, the negative electrode sheet and the negative electrode protective film are sequentially stacked, wherein the negative electrode protective film wraps the negative electrode sheet. In this aspect, the negative electrode tab is preferably supported on the current collector by deposition or melting. In the present invention, the material of the negative electrode sheet is preferably lithium, sodium, or potassium. In the present invention, the material of the current collector is preferably one or more of carbon, copper, silver, gold, zinc, and aluminum. In the present invention, the negative electrode protective film is the negative electrode protective film described in the above-described embodiment.
In the present invention, the electrolytic solution includes an organic dispersant and an electrolyte salt. In the present invention, the organic dispersant includes tetraethylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol dimethyl ether, N dimethylacetamide, or dimethylsulfoxide. In the present invention, the electrolyte salt is preferably a lithium salt, a sodium salt, or a potassium salt. In the present invention, the lithium salt is preferably one or more of lithium trifluoromethanesulfonate, lithium bistrifluoromethylsulfonimide, lithium nitrate, lithium tetrafluoroborate, lithium perchlorate and lithium difluorooxalato borate; the sodium salt is preferably one or more of sodium trifluoromethanesulfonate, sodium bistrifluoromethylsulfonyl imide, sodium nitrate, sodium tetrafluoroborate, sodium perchlorate and sodium difluorooxalate; the potassium salt is preferably one or more of potassium triflate, potassium bis-trifluoromethylsulphonylimide, potassium nitrate, potassium tetrafluoroborate, potassium perchlorate and potassium difluorooxalatoborate. In the present invention, the concentration of the electrolytic solution is preferably 0.1mol/L to a saturated concentration. In the present invention, the electrolyte salt corresponds to a negative electrode material, such as a lithium salt when the negative electrode material is lithium metal; when the cathode material is sodium metal, the electrolyte salt is sodium salt; when the negative electrode material is potassium metal, the electrolyte salt is a potassium salt.
In the present invention, the positive electrode catalyst is preferably RuO 2 Ru, au, ag, pt and MnOOH.
The present invention is not particularly limited to the assembly of each component in the alkali metal-air battery, and the assembly of the alkali metal-air battery known to those skilled in the art may be used.
In order to further illustrate the present invention, the following describes a negative electrode protective film, a method for preparing the same, an application thereof, and an alkali metal-air battery in detail with reference to examples, but they should not be construed as limiting the scope of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. 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.
Example 1
Mixing 3g of polyvinylidene fluoride-hexafluoropropylene, 1.5g of lithium fluoride and 4mL of N, N-dimethylformamide, and stirring for 4 hours to obtain slurry; the resulting slurry was poured onto glassOn the plate, formed to be about 100cm 2 Drying the wet film at 80 ℃ for 72 hours, and then peeling off the glass plate to obtain the cathode protective film with the thickness of 100 mu m.
The following tests were performed on the negative electrode protective film obtained in example 1:
1. the negative electrode protective film obtained in example 1 was subjected to scanning electron microscope test, and the SEM image thereof is shown in fig. 1. As can be seen from fig. 1, liF in the negative electrode protective film was uniformly distributed on the PVDF-HFP film.
2. The negative electrode protective film obtained in example 1 was subjected to an X-ray diffraction test, and the obtained XRD pattern is shown in fig. 2. As can be seen from fig. 2, the negative electrode protective film includes a PVDF-HFP peak and a LiF peak, and no other impurity phase exists.
3. Thermogravimetric analysis was performed on the anode protective film obtained in example 1, and the obtained thermogravimetric graph is shown in fig. 3. As can be seen from FIG. 3, the negative protective film can be decomposed only when the temperature reaches 450 ℃, has very good thermal stability, and has potential application in high-temperature batteries.
4. The tensile property test was performed on the negative electrode protective film obtained in example 1, and the tensile property graph is shown in fig. 4. As can be seen from fig. 4, the negative electrode protection film obtained in the present embodiment has good flexibility and a high young modulus (up to 4.83 GPa), and the high young modulus is beneficial to stopping the growth of lithium dendrites and preventing safety accidents such as fire disasters caused by the uncontrollable growth of lithium dendrites penetrating through the membrane.
5. A negative electrode was coated with the negative electrode protective film obtained in example 1 to prepare a lithium/lithium symmetric battery.
At a current density of 0.4mA cm -2 After 5 hours of charging and discharging under the conditions, the ion deposition condition of the negative electrode is tested by a scanning electron microscope, and the obtained SEM image is shown in figure 5. As can be seen from FIG. 5, the deposition morphology of the lithium metal is relatively flat and blocky, which is beneficial to uniform deposition of the lithium metal.
The cycling performance of the lithium/lithium symmetric cell was measured simultaneously and the resulting cycling profile is shown in fig. 6. As can be seen from fig. 6, the lithium/lithium symmetric cell exhibited a lower overpotential of 0.0248V and a longer cycle life, indicating that the resultant negative electrode protection film of the present example can provide a more stable electrode/electrolyte interface.
Application example 1
Preparing a Ru/CNTs positive electrode: according to the mass ratio of 1:1:5 reacting RuCl 3 ·xH 2 O, CNTs and poloxamer (Pluronic F127) were mixed in water and stirred continuously for 12H, the mixture was placed in a tube furnace in H containing 5% hydrogen 2 Calcining for 3 hours at 300 ℃ in an Ar atmosphere, and sequentially washing and drying the calcined product with ethanol to obtain a Ru/CNTs material; and mixing the obtained Ru/CNTs material with a binder PVDF according to the mass ratio of 8:1, uniformly dispersing in NMP, coating on clean carbon paper, cutting into the size of an electrode sheet after primary drying, and finally drying in a vacuum oven at 80 ℃ for 24 hours to obtain a Ru/CNTs anode;
coating the surface of a metal lithium sheet with the diameter of 14mm with the cathode protective film obtained in the example 1 to obtain a cathode;
and (2) assembling the positive electrode and the negative electrode of the Ru/CNTs by taking 1mol/L of tetraethylene glycol dimethyl ether solution of lithium trifluoromethanesulfonate as an electrolyte, and introducing oxygen to obtain the lithium-air battery.
At a current density of 500mA g -1 Lower limit capacity of 1000mAh g -1 And performing 25 times of charge and discharge cycles, and performing scanning electron microscope test on the corrosion condition of the negative electrode of the obtained lithium-air battery, wherein the obtained SEM image is shown in figure 7. As can be seen from fig. 7, after 25 times of charging and discharging, the metal lithium of the negative electrode still maintains a relatively flat shape, which indicates that the negative electrode protective film provided by the invention has a good effect of preventing the metal lithium negative electrode from being corroded.
At a current density of 500mA g -1 Lower limit capacity of 1000mAh g -1 The cycle performance of the resulting lithium-air battery was tested, and the resulting cycle performance graph is shown in fig. 8. As can be seen from fig. 8, the cycle life of the lithium-air battery can be as high as 150 cycles, indicating that the cycle life of the lithium-air battery using the negative electrode protective film provided by the present invention is also high.
Comparative example 1
A commercial PP film, which was purchased from Celgard and has a thickness of 30 μm, was used as the negative electrode protective film.
And (3) coating the negative electrode by taking the PP film in the comparative example 1 as a negative electrode protective film to prepare the lithium/lithium symmetrical battery.
At a current density of 0.4mA cm -2 After 5 hours of charging and discharging under the conditions, the ion deposition condition of the negative electrode is tested by a scanning electron microscope, and the obtained SEM image is shown in figure 9. As can be seen from fig. 9, the deposition morphology of the negative electrode metal lithium exhibits a distinct dendritic morphology, and if the irregular growth occurs for a long time, the lithium penetrates the separator to cause a short-circuit accident, and further causes a fire and the like.
The cycling performance of the lithium/lithium symmetric cell was measured simultaneously and the resulting cycling profile is shown in figure 10. As can be seen from fig. 10, the lithium/lithium symmetric battery has a sharp increase in the overpotential in as short as 100 hours to fail, indicating that the PP film-coated negative electrode in the comparative example has a very unstable metal lithium/electrolyte interface.
Comparative application example 1
The PP film provided in comparative example 1 was used in place of the negative electrode protective film in application example 1, and the remaining technical means were the same as in application example 1, to obtain a lithium-air battery.
At a current density of 500mA g -1 Lower limit capacity of 1000mAh g -1 And performing 25 times of charge and discharge cycles, and performing scanning electron microscope test on the corrosion condition of the negative electrode of the obtained lithium-air battery, wherein the obtained SEM image is shown in figure 11. As can be seen from fig. 11, after 25 times of charge and discharge, the negative electrode metallic lithium has exhibited remarkable unevenness, indicating that the surface of the negative electrode metallic lithium has been severely corroded.
At a current density of 500mA g -1 Lower limit capacity of 1000mAh g -1 The cycling performance of the resulting lithium-air battery was tested and the resulting cycling performance graph is shown in fig. 12. As can be seen from fig. 12, the cycle life of the lithium-air battery is only 70 cycles, which indicates that the cycle life of the lithium-air battery obtained by using the PP film as the negative electrode protective film is low, and laterally indicates that the negative electrode lithium metal is severely corroded and uncontrollable dendritic crystal growth occurs.
Example 2
Mixing 6g of polyethylene oxide, 3g of silicon dioxide and 20mL of acetonitrile, and stirring for 12 hours to obtain slurry; the resulting slurry was poured onto a glass plate to form 300cm 2 Drying the wet film at 80 ℃ for 24h, and stripping the glass to obtain the thicknessThe negative electrode protective film was 100 μm.
Application example 2
Coating the surface of the metal lithium sheet with the negative electrode protective film obtained in the example 2 to obtain a negative electrode;
taking 1mol/L of lithium trifluoromethanesulfonate tetraethylene glycol dimethyl ether solution as electrolyte, and adding RuO 2 And assembling the positive electrode (comprising CNTs and PVDF) and the negative electrode, and introducing air to obtain the lithium-air battery.
Example 3
Mixing 10g of polymethyl methacrylate, 5g of alumina and 50mL of acetone, and stirring for 10 hours to obtain slurry; the resulting slurry was poured onto a glass plate to form a 500cm thick film 2 Drying the wet film at 80 ℃ for 24h, and then stripping the glass to obtain the negative electrode protective film with the thickness of 100 mu m.
Application example 3
Coating the surface of the metal lithium sheet with the negative electrode protective film obtained in the example 3 to obtain a negative electrode;
and (2) assembling a MnOOH positive electrode (comprising SuperP carbon and PVDF) and a negative electrode by taking a 1mol/L tetraethylene glycol dimethyl ether solution of lithium trifluoromethanesulfonate as an electrolyte, and introducing carbon dioxide gas to obtain the lithium-air battery.
Example 4
Mixing 2g of polyvinylidene fluoride, 1g of zinc oxide and 3mL of N-methyl pyrrolidone, and stirring for 8 hours to obtain slurry; the resulting slurry was poured onto a glass plate to form 100cm 2 Drying the wet film at 80 ℃ for 24h, and then stripping the glass to obtain the negative electrode protective film with the thickness of 100 mu m.
Application example 4
Coating the surface of the metal lithium sheet with the negative electrode protective film obtained in the example 4 to obtain a negative electrode;
and (2) assembling a Pt positive electrode (comprising CNTs and PVDF) and a negative electrode by taking a 1mol/L tetraethylene glycol dimethyl ether solution of lithium trifluoromethanesulfonate as an electrolyte, and introducing air to obtain the lithium-air battery.
Example 5
Mixing 8g of polyvinylidene fluoride-hexafluoropropylene, 4g of zirconium oxide and 15mL of dimethyl sulfoxide, and stirring for 8 hours to obtain slurry; mixing the obtained slurryThe batch was poured onto a glass plate to form 400cm 2 Drying the wet film at 80 ℃ for 24h, and then stripping the glass to obtain the negative electrode protective film with the thickness of 100 mu m.
Application example 5
Coating the surface of the lithium metal sheet with the cathode protective film obtained in the example 5 to obtain a cathode;
and (2) assembling a carbon anode (comprising Super carbon and PVDF) and a carbon cathode by taking a 1mol/L tetraethylene glycol dimethyl ether solution of lithium trifluoromethyl sulfonate as an electrolyte, and introducing oxygen to obtain the lithium-air battery.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Claims (8)
1. A negative electrode protective film composed of a polymer film and inorganic particles uniformly dispersed in the polymer film;
the polymer film is made of one or more of polyvinylidene fluoride-hexafluoropropylene, polyethylene oxide and polymethyl methacrylate;
the inorganic particles comprise one or more of lithium fluoride, silica, alumina, zirconia and zinc oxide;
the thickness of the negative electrode protective film is 100-400 mu m.
2. The negative electrode protective film according to claim 1, wherein a mass ratio of the polymer film to the inorganic particles is 50: (1-2500).
3. The negative electrode protective film according to claim 1 or 2, wherein the inorganic particles have a particle diameter of 5 to 50000nm.
4. The method for producing the anode protective film according to any one of claims 1 to 3, comprising the steps of:
mixing a polymer, inorganic particles and an organic solvent to obtain slurry;
and coating the slurry on the surface of the substrate, and peeling off the substrate after the solvent is evaporated to obtain the cathode protective film.
5. The method according to claim 4, wherein the organic solvent comprises one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, acetone, acetonitrile, and N-methylpyrrolidone.
6. The production method according to claim 4, wherein the mass ratio of the total mass of the polymer and the inorganic particles to the organic solvent is 2: (1-10).
7. The method according to claim 4, wherein the solvent is evaporated at a temperature of 70 to 150 ℃ for 4 to 168 hours.
8. Use of the negative electrode protective film according to any one of claims 1 to 3 or the negative electrode protective film produced by the production method according to any one of claims 4 to 7 in an alkali metal-air battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011083900.9A CN112226064B (en) | 2020-10-12 | 2020-10-12 | Negative electrode protective film, preparation method and application thereof, and alkali metal-air battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011083900.9A CN112226064B (en) | 2020-10-12 | 2020-10-12 | Negative electrode protective film, preparation method and application thereof, and alkali metal-air battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112226064A CN112226064A (en) | 2021-01-15 |
| CN112226064B true CN112226064B (en) | 2023-02-10 |
Family
ID=74113350
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011083900.9A Active CN112226064B (en) | 2020-10-12 | 2020-10-12 | Negative electrode protective film, preparation method and application thereof, and alkali metal-air battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112226064B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114242959A (en) * | 2021-12-17 | 2022-03-25 | 华南农业大学 | Alkali metal protective layer, preparation method thereof and application thereof in alkali metal secondary battery |
| CN114709369A (en) * | 2022-03-16 | 2022-07-05 | 南京工业大学 | Zinc cathode, preparation method and water system zinc-based battery based on zinc cathode |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104177738A (en) * | 2013-05-24 | 2014-12-03 | 苏州宝时得电动工具有限公司 | Polymer membrane, preparation method thereof, electrolyte possessing polymer membrane and cell |
| CN109103517A (en) * | 2017-06-20 | 2018-12-28 | 中国科学院化学研究所 | A kind of method and its application of polymer protection metal secondary batteries cathode |
| CN110459823A (en) * | 2019-08-16 | 2019-11-15 | 北京理工大学 | A kind of method that polymer-modified diaphragm is used for the protection of metal battery cathode |
| CN111180673A (en) * | 2020-01-21 | 2020-05-19 | 天齐锂业股份有限公司 | Preparation process of metal lithium cathode with surface protection layer |
| CN111430668A (en) * | 2019-12-31 | 2020-07-17 | 蜂巢能源科技有限公司 | Negative electrode protection layer, preparation method, negative electrode and lithium ion battery |
| CN111463403A (en) * | 2020-04-13 | 2020-07-28 | 武汉大学 | Negative electrode material modified by composite artificial solid electrolyte interface film and battery application thereof |
| CN111525181A (en) * | 2020-05-08 | 2020-08-11 | 上海空间电源研究所 | All-solid-state battery with low interface resistance and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102568794B1 (en) * | 2017-12-12 | 2023-08-22 | 삼성전자주식회사 | Composite electrolyte, Protecting film comprising composite electrolyte, and Protected anode and Lithium battery comprising proting film |
-
2020
- 2020-10-12 CN CN202011083900.9A patent/CN112226064B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104177738A (en) * | 2013-05-24 | 2014-12-03 | 苏州宝时得电动工具有限公司 | Polymer membrane, preparation method thereof, electrolyte possessing polymer membrane and cell |
| CN109103517A (en) * | 2017-06-20 | 2018-12-28 | 中国科学院化学研究所 | A kind of method and its application of polymer protection metal secondary batteries cathode |
| CN110459823A (en) * | 2019-08-16 | 2019-11-15 | 北京理工大学 | A kind of method that polymer-modified diaphragm is used for the protection of metal battery cathode |
| CN111430668A (en) * | 2019-12-31 | 2020-07-17 | 蜂巢能源科技有限公司 | Negative electrode protection layer, preparation method, negative electrode and lithium ion battery |
| CN111180673A (en) * | 2020-01-21 | 2020-05-19 | 天齐锂业股份有限公司 | Preparation process of metal lithium cathode with surface protection layer |
| CN111463403A (en) * | 2020-04-13 | 2020-07-28 | 武汉大学 | Negative electrode material modified by composite artificial solid electrolyte interface film and battery application thereof |
| CN111525181A (en) * | 2020-05-08 | 2020-08-11 | 上海空间电源研究所 | All-solid-state battery with low interface resistance and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112226064A (en) | 2021-01-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4211865B2 (en) | Li-Ni composite oxide particle powder for non-aqueous electrolyte secondary battery, method for producing the same, and non-aqueous electrolyte secondary battery | |
| CN109244546B (en) | Solid composite electrolyte film, preparation method thereof and all-solid-state battery | |
| CN112133918B (en) | Application of metal-organic framework material as negative electrode protection material of alkali metal air battery and alkali metal air battery | |
| US11380897B2 (en) | Preparation method of graphene flower and use of graphene flower in lithium sulfur battery | |
| KR20220092556A (en) | Anode active material for battery and manufacturing method thereof, battery negative electrode, battery | |
| CN104157909B (en) | A kind of preparation method of lithium-sulfur cell membrane electrode | |
| CN110600695B (en) | Yolk-eggshell structure tin@hollow mesoporous carbon sphere material and preparation method thereof | |
| KR20070056765A (en) | Active material for rechargeable lithium battery and rechargeable lithium battery comprising same | |
| CN114464909B (en) | Nano composite anode lithium supplement slurry and anode | |
| CN112226064B (en) | Negative electrode protective film, preparation method and application thereof, and alkali metal-air battery | |
| CN112467200B (en) | Lithium fluoride/lithium lanthanum titanate nanofiber solid electrolyte interface material and preparation method and application thereof | |
| CN111916716A (en) | PVDF-TiO2Preparation method of composite membrane and application of composite membrane in inhibiting growth of lithium dendrite | |
| CN113451566A (en) | Composite coated positive electrode material and preparation method and application thereof | |
| JP2017526145A (en) | Anode materials for lithium-ion batteries | |
| CN112349894B (en) | Preparation method of lithium battery electrode material and construction method of rapid lithium ion conduction interface | |
| Ikeda et al. | Lithium-tin alloy/sulfur battery with a solvate ionic liquid electrolyte | |
| Sharma et al. | LiMn2O4-rGO/PANI Nanocomposite as a Cathode Material for Li-Ion Batteries | |
| JP2016192341A (en) | Titanium-based material for sodium ion secondary battery, manufacturing method thereof, electrode active material using titanium-based material, electrode active material layer, electrode, and sodium ion secondary battery | |
| CN109461897B (en) | Preparation method of spindle-shaped carbon-coated vanadium-based positive electrode material | |
| CN113328096A (en) | Preparation method of silicon-carbon composite material, silicon-based negative electrode material and lithium ion battery | |
| CN109950484A (en) | Prepare method, the anode, battery of rich lithium composite positive pole | |
| CN112397771B (en) | Solid electrolyte membrane, preparation method thereof and application thereof in solid lithium-sulfur battery | |
| EP4369436A1 (en) | Composition for electrode formation | |
| CN111106339B (en) | Octahedral CuO lithium battery anode material and application thereof | |
| CN109768229B (en) | Electrode for lithium ion secondary battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20210914 Address after: Room 1002, financial building, No. 1577, Jinhui Road, China South Korea (Changchun) International Cooperation Demonstration Zone, Changchun, Jilin 130102 Applicant after: Jilin Dongchi New Energy Technology Co.,Ltd. Address before: 130024 No. 5268 Renmin Street, Jilin, Changchun Applicant before: Northeast Normal University |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |