CN107452941B - Battery electrode protection material and preparation method thereof, battery electrode piece and preparation method thereof, and lithium battery - Google Patents
Battery electrode protection material and preparation method thereof, battery electrode piece and preparation method thereof, and lithium battery Download PDFInfo
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- CN107452941B CN107452941B CN201610378334.1A CN201610378334A CN107452941B CN 107452941 B CN107452941 B CN 107452941B CN 201610378334 A CN201610378334 A CN 201610378334A CN 107452941 B CN107452941 B CN 107452941B
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- 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
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- 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
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- 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
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- 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 provides a battery electrode protection material which is of a core-shell structure and comprises an inner core and an outer shell, wherein the inner core is made of a carbon material, and the outer shell is made of an inorganic ceramic material. This battery electrode protection material can effectively prevent the growth of lithium dendrite, improves the security and the cycle life of lithium cell to solve the unable production that limits lithium dendrite of current lithium cell electrolyte, have the corrosive action to lithium metal electrode, and the SEI membrane that forms repeatedly can lose lithium ion, thereby leads to the problem that lithium cell security and cycle life descend. The invention also provides a preparation method of the battery electrode protection material, and a battery electrode piece and a lithium battery containing the battery electrode protection material.
Description
Technical Field
The invention relates to the field of lithium batteries, in particular to a battery electrode protection material and a preparation method thereof, a battery electrode plate and a preparation method thereof, and a lithium battery.
Background
With the popularization of electronic products in recent years, lithium batteries as power sources thereof are receiving more and more attention due to their advantages of light weight, small size, high operating voltage, high energy density, large output power, high charging efficiency, no memory effect, and the like. In addition, in the fields of electric tools, electric vehicles, large-sized energy storage devices, and the like, development of lithium ion batteries with high safety and high energy density is also being advanced.
Currently commercially available lithium batteries generally consist of a positive electrode sheet, a negative electrode sheet, a separator, an electrolyte and a case. The electrolyte mostly adopts liquid electrolyte taking an organic solvent as a solvent and solid electrolyte mainly comprising polymer and inorganic materials, the two electrolytes can not limit the generation of lithium dendrite, and have a corrosion effect on a lithium metal electrode, and a formed SEI film can lose lithium ions. Therefore, in order to improve the safety of the battery and simultaneously improve the battery capacity, in the lithium battery, the research on both the prevention of the growth of lithium dendrites and the protection of the negative electrode of the lithium battery is important.
At present stage of researchIn view of the above problems, the following methods are often adopted, but these methods have disadvantages: 1. with solid electrolytes, the ion mobility of the solid electrolytes can be substantially at the level of the liquid electrolytes (10)-2S/cm), but most of solid electrolyte is not elastic and cannot be in close contact with the negative electrode of the lithium battery, so that ion transmission is hindered, and most of solid electrolyte material is unstable, so that the charge-discharge cycle number of the battery is influenced, and the use of the battery is severely limited; 2. the lost lithium ions are supplemented by means of adding lithium powder and the like, and the method has harsh preparation conditions, cannot be used in a large scale and cannot limit the growth of future lithium dendrites; 3. the surface of lithium metal is passivated to generate a layer of relatively stable protective film, an inorganic oxide film is generated on the surface of the metal, or an organic lithium salt SEI film as an electrolyte component is adjusted to enable the film to have elasticity and not to crack, however, in the charging and discharging process, the protective film is always in the process of cracking and rebuilding, and dendritic crystals are inevitably generated at certain positions, or the lithium metal is exposed in the electrolyte.
Disclosure of Invention
In view of this, the first aspect of the present invention provides a battery electrode protection material, which can effectively prevent the growth of lithium dendrites and improve the safety and cycle life of a lithium battery, so as to solve the problems that the existing lithium battery electrolyte cannot limit the generation of lithium dendrites, has a corrosive effect on a lithium metal electrode, and loses lithium ions due to a repeatedly formed SEI film, thereby reducing the safety and cycle life of the lithium battery.
In a first aspect, the invention provides a battery electrode protection material, which is a core-shell structure and comprises an inner core and an outer shell, wherein the inner core is made of a carbon material, and the outer shell is made of an inorganic ceramic material.
In the first aspect of the present invention, the carbon material includes at least one of graphene, doped graphene, graphene oxide, doped graphene oxide, hard carbon, doped hard carbon, a soft carbon material, a carbon nanotube, and a doped carbon nanotube.
In the first aspect of the present invention, the inorganic ceramic material includes at least one of titanium dioxide, aluminum oxide, zirconium oxide, lithium fluoride, silicon oxide, calcium oxide, magnesium oxide, tantalum oxide, silicon nitride, cubic boron nitride, aluminum nitride, chromium nitride, titanium nitride, silicon carbide, boron carbide, titanium carbide, and chromium carbide.
In the first aspect of the present invention, the mass of the carbon material accounts for 1 to 50% of the total mass of the electrode protection material.
In a first aspect of the invention, the thickness of the shell is 1-10 nm.
In the first aspect of the invention, the electrode protection material is a spherical core-shell structure, and the diameter is 0.01-2 microns.
In a first aspect of the invention, the outer shell is coated directly onto the surface of the inner core.
In the first aspect of the invention, the core and the shell have a gap therebetween, the gap being less than 500 nm.
According to the battery electrode protection material provided by the first aspect of the invention, the carbon material is used as the inner core, the inorganic ceramic material is used as the outer shell, and the carbon material has high electron mobility and high potential, so that the growth of lithium dendrites towards the direction of an electrolyte can be effectively prevented by utilizing the potential difference between the carbon material and an electrode material (such as lithium metal, negative electrode graphite and the like), and therefore, the problems that the generation of the lithium dendrites cannot be limited by a lithium battery electrolyte, the lithium metal electrode is corroded, and lithium ions are lost by an SEI film formed repeatedly in the prior art are solved, and the safety and the cycle life of a lithium battery are improved.
In a second aspect, the present invention provides a method for preparing a battery electrode protection material, comprising the steps of:
taking a carbon material, dispersing the carbon material in a polymer monomer, and obtaining a polymer microsphere containing the carbon material in an emulsion polymerization manner, wherein the microsphere comprises the carbon material and a polymer outer layer coating the carbon material;
and coating an inorganic ceramic material on the outer polymer layer, and removing the outer polymer layer by adopting a dissolving or sintering mode to obtain the battery electrode protection material, wherein the electrode protection material is of a core-shell structure and comprises an inner core and an outer shell, the inner core is made of a carbon material, and the outer shell is made of an inorganic ceramic material.
In a second aspect of the invention, the polymer monomer comprises styrene, methyl methacrylate, an acrylate, vinyl acetate, vinyl chloride, or ethylene oxide.
In the second aspect of the present invention, the polymer microspheres comprising carbon materials obtained by emulsion polymerization specifically include: dispersing the carbon material in a polymer monomer, adding a solvent, a surfactant and an initiator, reacting at 50-150 ℃ for 10-48 hours to obtain a polymer microsphere emulsion containing the carbon material, demulsifying, separating, washing and drying to obtain the polymer microsphere containing the carbon material.
The preparation method provided by the second aspect of the invention has simple process and is suitable for large-scale preparation.
In a third aspect, the invention provides a battery electrode plate, wherein an electrode protection layer is arranged on one surface of the battery electrode plate, which is in contact with an electrolyte, and the material of the electrode protection layer comprises the battery electrode protection material according to the first aspect of the invention.
In the third aspect of the present invention, the thickness of the electrode protection layer is 0.1 to 20 μm.
In the third aspect of the present invention, the material of the electrode protection layer further includes one or more of polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, polyvinylidene chloride, polyvinyl sulfone, polyethylene glycol diacrylate, polyvinylpyrrolidone, and polyvinylidene fluoride.
The electrode plate of the battery provided by the third aspect of the invention can be a positive electrode plate or a negative electrode plate of the lithium battery, and the electrode plate can effectively prevent the generation of lithium dendrites, improve the battery capacity and the safety of the lithium battery and prolong the cycle life of the lithium battery.
In a fourth aspect, the invention provides a preparation method of a battery electrode plate, which comprises the following steps:
the battery electrode protection material of the first aspect of the invention is dispersed in an inert solvent to obtain a slurry, and the slurry is coated on one surface of an electrode plate, which is in contact with an electrolyte, to form an electrode protection layer, so as to obtain the battery electrode plate with the electrode protection layer.
In a fourth aspect of the invention, the inert solvent comprises one or more of hexane, heptane, benzene, diethyl ether, tetrahydrofuran, 1, 2-dimethoxyethane, dibutyl ether and N-methylpyrrolidone.
In a fifth aspect, the invention provides a lithium battery, which comprises the battery electrode plate of the third aspect.
Advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of embodiments of the invention.
Drawings
Fig. 1 is a schematic structural diagram of a battery electrode protection material prepared according to a first embodiment of the present invention.
Detailed Description
While the following is a description of the preferred embodiments of the present invention, it should be noted that those skilled in the art can make various modifications and improvements without departing from the principle of the embodiments of the present invention, and such modifications and improvements are considered to be within the scope of the embodiments of the present invention.
In the fields of electronic products, electric tools, electric automobiles, large-scale energy storage equipment and the like, lithium batteries with high safety and high energy density are pursued by people all the time. At present, commercially available lithium batteries generally comprise a positive plate, a negative plate, a diaphragm, an electrolyte and a shell, wherein the electrolyte mostly adopts a liquid electrolyte using an organic solvent as a solvent and a solid electrolyte mainly comprising a polymer and an inorganic material, but both the electrolytes cannot limit the generation of lithium dendrites and have a corrosion effect on lithium metal electrodes, and lithium ions are lost by a repeatedly formed SEI film, so that the safety and the battery capacity of the lithium battery are greatly reduced. In order to effectively solve the problem, embodiments of the present invention provide a battery electrode protection material, which is disposed between an electrode and an electrolyte, and can effectively prevent a lithium dendrite from growing toward the electrolyte, thereby improving the safety and cycle life of a lithium battery.
Specifically, the embodiment of the invention provides a battery electrode protection material which is of a core-shell structure and comprises an inner core and an outer shell, wherein the inner core is made of a carbon material, and the outer shell is made of an inorganic ceramic material.
The battery electrode protection material provided by the embodiment of the invention adopts a carbon material with high mobility and relatively high potential compared with negative graphite, lithium metal and the like as a core material, and when the battery electrode protection material is placed between an electrode and an electrolyte to form an electrode protection layer, the potential difference between the electrode protection layer and the electrode material can be used for preventing lithium dendrite from growing towards the direction of electrolyte. Optionally, in an embodiment of the present invention, the carbon material includes at least one of graphene, doped graphene, graphene oxide, doped graphene oxide, hard carbon, doped hard carbon, a soft carbon material, a carbon nanotube, and a doped carbon nanotube. Wherein, the doping element can be one or more of N, P, B, O, S, F, Cl and H. The graphene, doped graphene, graphene oxide, doped graphene oxide may be a single-layer or multi-layer structure.
Because the shapes of the carbon materials such as graphene are relatively irregular, a uniform and flat film is not easy to form on the surface of the electrode, and the protrusions on the surfaces of the carbon materials such as graphene can influence the contact of each interface layer in a battery system and finally influence ion transmission, the embodiment of the invention adopts the inorganic ceramic material as the shell to wrap the carbon materials to obtain a uniform and flat compact shell layer, thereby avoiding the contact of the inner core of the carbon material with electrolyte because of being exposed outside. Meanwhile, the inorganic ceramic material shell also improves the strength of the battery electrode protection material. In an embodiment of the present invention, the inorganic ceramic material includes, but is not limited to, at least one of titanium dioxide, aluminum oxide, zirconium oxide, lithium fluoride, silicon oxide, calcium oxide, magnesium oxide, tantalum oxide, silicon nitride, cubic boron nitride, aluminum nitride, chromium nitride, titanium nitride, silicon carbide, boron carbide, titanium carbide, and chromium carbide.
In an embodiment of the present invention, the mass of the carbon material accounts for 1 to 50% of the total mass of the electrode protection material. Optionally, the mass of the carbon material accounts for 1-10%, 12-30%, 35-50% of the total mass of the electrode protection material.
In order to prevent the conductivity of the electrode protection material from being affected, but to form a spherical structure well, in the embodiment of the present invention, the thickness of the outer shell may be set to 1 to 10nm, or to 3 to 7 nm.
In the embodiment of the invention, the electrode protection material is in a spherical core-shell structure, and the diameter of the electrode protection material can be 0.01-2 micrometers or 0.1-1 micrometer. The electrode protection material is regular in shape and easy to arrange to form a film, and is dispersed by a solvent to form a coating layer for lithium battery assembly.
In the embodiment of the invention, the electrode protection material can be formed by directly coating the shell on the surface of the core, or a gap is formed between the core and the shell, and the gap is less than 500 nm. These two specific structures can be obtained by using different preparation methods.
According to the battery electrode protection material provided by the embodiment of the invention, the carbon material is used as the inner core, the inorganic ceramic material is used as the outer shell, the growth of lithium dendrites towards the direction of an electrolyte can be effectively prevented, the safety of a lithium battery is improved, the cycle life of the lithium battery is prolonged, and the problems that the generation of the lithium dendrites cannot be limited by the lithium battery electrolyte in the prior art, the lithium dendrites have a corrosion effect on a lithium metal electrode, and lithium ions are lost by a repeatedly formed SEI film are solved.
Correspondingly, the embodiment of the invention provides a preparation method of a battery electrode protection material, which comprises the following steps:
taking a carbon material, dispersing the carbon material in a polymer monomer, and obtaining a polymer microsphere containing the carbon material in an emulsion polymerization manner, wherein the microsphere comprises the carbon material and a polymer outer layer coating the carbon material;
and coating an inorganic ceramic material on the outer polymer layer, and removing the outer polymer layer by adopting a dissolving or sintering mode to obtain the battery electrode protection material, wherein the electrode protection material is of a core-shell structure and comprises an inner core and an outer shell, the inner core is made of a carbon material, and the outer shell is made of an inorganic ceramic material.
According to the embodiment of the invention, the polymer microspheres are formed by carbon materials such as graphene in an emulsion polymerization mode, and then the inorganic ceramic material is coated, so that the battery electrode protection material with a spherical core-shell structure with a regular shape can be obtained.
Optionally, in an embodiment of the present invention, the carbon material includes at least one of graphene, doped graphene, graphene oxide, doped graphene oxide, hard carbon, doped hard carbon, a soft carbon material, a carbon nanotube, and a doped carbon nanotube. Wherein, the doping element can be one or more of N, P, B, O, S, F, Cl and H. The graphene, doped graphene, graphene oxide, doped graphene oxide may be a single-layer or multi-layer structure.
In an embodiment of the present invention, the polymer monomer includes styrene, methyl methacrylate, acrylate, vinyl acetate, vinyl chloride, or ethylene oxide.
In an embodiment of the present invention, the polymer microspheres containing carbon materials obtained by emulsion polymerization specifically include: dispersing the carbon material in a polymer monomer, adding a solvent, a surfactant and an initiator, reacting at 50-150 ℃ for 10-48 hours to obtain a polymer microsphere emulsion containing the carbon material, demulsifying, separating, washing and drying to obtain the polymer microsphere containing the carbon material.
In the embodiment of the present invention, the solvent, the surfactant, the initiator, and the like are determined depending on the reaction system. For example, the solvent may be water, the surfactant may be sodium dodecylbenzene sulfonate, and the initiator may be potassium persulfate, ammonium persulfate. In the embodiment of the invention, a PH regulator and other auxiliary agents can be added in the emulsion polymerization reaction process, and the PH regulator can be aluminum oxide, sodium hydroxide, potassium hydroxide, ammonia water and hydrochloric acid. The demulsification can be realized by adding 50% of lithium chloride solution by mass fraction.
In an embodiment of the present invention, the inorganic ceramic material includes, but is not limited to, at least one of titanium dioxide, aluminum oxide, zirconium oxide, lithium fluoride, silicon oxide, calcium oxide, magnesium oxide, tantalum oxide, silicon nitride, cubic boron nitride, aluminum nitride, chromium nitride, titanium nitride, silicon carbide, boron carbide, titanium carbide, and chromium carbide. In the embodiment of the present invention, the specific coating method of the inorganic ceramic material is determined according to the kind of the selected inorganic ceramic material, and the examples of the present invention are not particularly limited.
In the embodiment of the invention, the polymer outer layer can be removed by dissolving with an organic solvent or by sintering. Wherein, the selection of the organic solvent is determined by the specific polymer type, and the sintering temperature can be 450-700 ℃.
In an embodiment of the present invention, the mass of the carbon material accounts for 1 to 50% of the total mass of the electrode protection material. Optionally, the mass of the carbon material accounts for 1-10%, 12-30%, 35-50% of the total mass of the electrode protection material.
In order to prevent the conductivity of the electrode protection material from being affected, but to form a spherical structure well, in the embodiment of the present invention, the thickness of the outer shell may be set to 1 to 10nm, or to 3 to 7 nm.
In the embodiment of the invention, the electrode protection material is in a spherical core-shell structure, and the diameter of the electrode protection material can be 0.01-2 micrometers or 0.1-1 micrometer.
The preparation method of the battery electrode protection material provided by the embodiment of the invention is simple in process and suitable for large-scale preparation.
In addition, the embodiment of the invention provides a battery electrode plate, wherein an electrode protection layer is arranged on one surface of the electrode plate, which is in contact with electrolyte, and the material of the electrode protection layer comprises the battery electrode protection material disclosed by the embodiment of the invention.
In the embodiment of the present invention, the thickness of the electrode protection layer may be set to 0.1 to 20 micrometers, or may be set to 1 to 2 micrometers.
In an embodiment of the present invention, the material of the electrode protection layer may further include one or more of polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, polyvinylidene chloride, polyvinyl sulfone, polyethylene glycol diacrylate, polyvinylpyrrolidone, and polyvinylidene fluoride. The polymers are added into the material of the electrode protection layer, so that a dispersion medium can be provided for the battery electrode protection material, and the electrode protection material can be better and more uniformly dispersed in the electrode protection layer.
The battery electrode plate provided by the embodiment of the invention can be used as a positive electrode plate or a negative electrode plate of a lithium battery, can effectively prevent lithium dendrites from being generated, and improves the battery capacity, safety and cycle life of the lithium battery.
Correspondingly, the embodiment of the invention provides a preparation method of a battery electrode plate, which comprises the following steps:
the battery electrode protection material provided by the embodiment of the invention is dispersed in an inert solvent to obtain slurry, and the slurry is coated on one surface of an electrode pole piece, which is in contact with an electrolyte, to form an electrode protection layer, so that the battery electrode pole piece is obtained.
In an embodiment of the present invention, the inert solvent comprises one or more of hexane, heptane, benzene, diethyl ether, tetrahydrofuran, 1, 2-dimethoxyethane, dibutyl ether and N-methylpyrrolidone.
In the embodiment of the invention, after the slurry is coated on the electrode plate, the electrode plate is dried for 10-24 hours at room temperature in an inert gas atmosphere. Further drying the mixture in a vacuum oven at 60-100 ℃ for 12-48 h.
In the embodiment of the present invention, the thickness of the electrode protection layer may be set to 0.1 to 20 micrometers, or may be set to 1 to 2 micrometers.
In an embodiment of the present invention, the slurry further includes one or more polymer materials selected from polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, polyvinylidene chloride, polyvinyl sulfone, polyethylene glycol diacrylate, polyvinylpyrrolidone, and polyvinylidene fluoride.
In addition, the embodiment of the invention also provides a lithium battery which comprises the battery electrode pole piece disclosed by the embodiment of the invention.
The following examples are intended to illustrate the invention in more detail. The embodiments of the present invention are not limited to the following specific embodiments. The present invention can be modified and implemented as appropriate within the scope of the main claim.
Example one
A preparation method of a battery electrode protection material comprises the following steps:
(1) preparing a styrene-coated graphene microsphere: dispersing 1g of nano-graphene in 20mL of styrene liquid to obtain a first dispersion liquid; dissolving 0.9g of sodium dodecyl benzene sulfonate and 10g of aluminum oxide in 250mL of deionized water to obtain a mixed solution; adding the obtained first dispersion liquid into the vigorously stirred mixed solution, stirring and emulsifying, then adding 0.5g of potassium persulfate, heating to 70 ℃, stirring and reacting for 14 hours, stopping the reaction to obtain polystyrene nano microsphere emulsion containing graphene, adding a small amount of lithium chloride solution with the mass fraction of 50% into the emulsion for demulsification, filtering, washing and drying to obtain 6.5g of graphene-polystyrene microspheres for later use.
(2) Coating titanium dioxide: 3g of the prepared graphene-polystyrene microsphere is dispersed in 30mL of ethanol, then 0.6gKH550 coupling agent is added and uniformly stirred to obtain a second dispersion solution, 6mL of ethanol solution in which 0.6mL of tetrabutyl titanate is dispersed is slowly added into the second dispersion solution, and the mixture is vigorously stirred for 2 hours and then filtered to obtain the graphene-polystyrene microsphere mixed solution coated with the compact titanium dioxide.
(3) Dissolving to remove polystyrene: and adding 10mL of the prepared graphene-polystyrene microsphere mixed solution coated with the compact titanium dioxide into 20mL of tetrahydrofuran, magnetically stirring for 2h to dissolve and remove the polystyrene, and filtering to obtain the graphene nano particles coated with the titanium dioxide, thereby obtaining the battery electrode protection material. As shown in fig. 1, the battery electrode protection material obtained in this embodiment is a spherical core-shell structure, and includes a core 1 and a shell 2, where the core 1 is graphene, the shell 2 is titanium dioxide, a gap 3 is formed between the graphene core 1 and the shell 2, and a particle diameter of the battery electrode protection material is 0.01 to 2 micrometers.
Preparation of electrode plate of lithium ion battery
Mixing graphite, conductive carbon black and polyvinylidene fluoride in N-methyl pyrrolidone at a ratio of 85: 10: 5, uniformly coating the mixture on a copper foil current collector, and drying the copper foil current collector in vacuum at 120 ℃ to obtain the electrode plate. 2g of the titanium dioxide-coated graphene nanoparticles prepared in the embodiment are added into 20mL of hexane and uniformly stirred and dispersed to obtain slurry, the slurry is coated on one surface provided with an active material, the active material is dried for 16 hours at room temperature under argon atmosphere, and then the active material is dried for 36 hours at 90 ℃ in a vacuum oven to form an electrode protection layer, so that a lithium ion battery negative electrode piece is finally obtained.
Preparation of lithium ion battery
The positive electrode of the battery, the negative electrode plate of the lithium ion battery prepared in the embodiment and the electrolyte membrane are assembled into an all-solid-state secondary lithium battery cell, and then the cell is packaged by an aluminum plastic film and formed to obtain the lithium ion battery.
Example two
A preparation method of a battery electrode protection material comprises the following steps:
(1) preparing a styrene-coated graphene microsphere: dispersing 1g of nano nitrogen-doped graphene in 20mL of styrene liquid to obtain a first dispersion liquid; dissolving 0.9g of sodium dodecyl benzene sulfonate and 3g of sodium hydroxide in 250mL of deionized water to obtain a mixed solution; and adding the obtained first dispersion liquid into the vigorously stirred mixed solution, stirring and emulsifying, then adding 0.5g of ammonium persulfate, heating to 80 ℃, stirring and reacting for 24 hours, stopping the reaction to obtain the polystyrene nano-scale microsphere emulsion containing the nitrogen-doped graphene, adding a small amount of lithium chloride solution with the mass fraction of 50% into the emulsion to perform demulsification, filtering, washing and drying to obtain 6.8g of the nitrogen-doped graphene-polystyrene microsphere for later use.
(2) Coating titanium dioxide: 3g of the prepared nitrogen-doped graphene-polystyrene microsphere is dispersed in 30mL of ethanol, then 0.6gKH550 coupling agent is added and uniformly stirred to obtain a second dispersion solution, 6mL of ethanol solution in which 0.6mL of tetrabutyl titanate is dispersed is slowly added into the second dispersion solution, and the mixture is vigorously stirred for 2 hours and then filtered to obtain the nitrogen-doped graphene-polystyrene microsphere mixed solution coated with compact titanium dioxide.
(3) Dissolving to remove polystyrene: and adding 10mL of the prepared nitrogen-doped graphene-polystyrene microsphere mixed solution coated with the compact titanium dioxide into 20mL of tetrahydrofuran, magnetically stirring for 2h to dissolve and remove the polystyrene, and filtering to obtain the nitrogen-doped graphene nanoparticles coated with the titanium dioxide, thereby obtaining the battery electrode protection material. The battery electrode protection material obtained in the embodiment is of a spherical core-shell structure, and the diameter of the battery electrode protection material is 0.01-2 microns.
Preparation of negative pole piece of lithium battery
Taking 2g of the titanium dioxide-coated nitrogen-doped graphene nanoparticles prepared in the embodiment, adding the titanium dioxide-coated nitrogen-doped graphene nanoparticles into 20mL of benzene, uniformly stirring and dispersing to obtain slurry, coating the slurry on a lithium sheet, and then placing the lithium sheet in an argon atmosphere to dry at room temperature for 16 hours to form an electrode protection layer, thereby finally obtaining a lithium battery negative electrode piece.
Preparation of lithium batteries
The positive electrode of the battery, the negative electrode plate of the lithium battery prepared in the embodiment and the electrolyte membrane are assembled into an all-solid-state secondary lithium battery core, and then the battery is packaged into a battery by using an aluminum plastic film and formed into the lithium battery.
EXAMPLE III
A preparation method of a battery electrode protection material, which is also the second embodiment.
Preparing a lithium battery electrode piece: taking 2g of the titanium dioxide-coated nitrogen-doped graphene nanoparticles prepared in the embodiment and 0.2g of polyvinylidene fluoride, adding the mixture into 20mL of tetrahydrofuran, stirring and dispersing uniformly to obtain slurry, coating the slurry on a lithium sheet, and then placing the lithium sheet in an argon atmosphere to dry at room temperature for 16 hours to form an electrode protection layer, thereby finally obtaining the lithium battery electrode piece.
Preparation of lithium batteries
The battery positive electrode, the lithium battery electrode plate prepared in the embodiment and the electrolyte membrane are assembled into an all-solid-state secondary lithium battery cell, and then the cell is packaged into a battery by using an aluminum plastic film and formed.
Example four
A preparation method of a battery electrode protection material comprises the following steps:
(1) preparing styrene-coated graphene oxide microspheres: dispersing 1g of nano-scale carbon nano-tube in 20mL of styrene liquid to obtain a first dispersion liquid; dissolving 0.9g of sodium dodecyl benzene sulfonate and 10g of aluminum oxide in 250mL of deionized water to obtain a mixed solution; adding the obtained first dispersion liquid into the vigorously stirred mixed solution, stirring and emulsifying, then adding 0.5g of potassium persulfate, heating to 70 ℃, stirring and reacting for 14 hours, stopping the reaction to obtain the polystyrene nano-scale microsphere emulsion containing the carbon nano-tube, adding a small amount of lithium chloride solution with the mass fraction of 50% into the emulsion for demulsification, filtering, washing and drying to obtain 7.5g of the carbon nano-tube-polystyrene microsphere for later use.
(2) Coating aluminum oxide and removing polystyrene: 5g of Al (OOC)8H15)2(OC3H7)2Dissolving in 50ml isopropanol, adding 1g carbon nanotube-polystyrene microsphere, stirring for 20 hr, evaporating solvent at 130 deg.C to obtain 20ml concentrated solution, cooling the concentrated solution, dropping 500ml n-hexane under stirring, and filtering to obtain Al-coated (OOC)8H15)2(OC3H7)2And then sintering the carbon nano tube-polystyrene microspheres at 700 ℃ for 4h to obtain a core-shell structure material with an outer shell of aluminum oxide and an inner core of the carbon nano tube, thus obtaining the battery electrode protection material.
Preparation of lithium battery electrode pole piece
2g of the carbon nanotube nanoparticles coated with alumina prepared in the embodiment is added into 20mL of benzene and uniformly stirred and dispersed to obtain slurry, the slurry is coated on a lithium sheet, and then the lithium sheet is placed in an argon atmosphere to be dried for 16 hours at room temperature to form an electrode protection layer, so that a lithium battery electrode piece is finally obtained.
Preparation of lithium batteries
The battery positive electrode, the lithium battery electrode plate prepared in the embodiment and the electrolyte membrane are assembled into an all-solid-state secondary lithium battery cell, and then the cell is packaged into a battery by using an aluminum plastic film and formed.
Claims (15)
1. An electrode protection material is applied to a lithium battery and is characterized in that the electrode protection material is of a core-shell structure and comprises an inner core and an outer shell, wherein the inner core is made of a carbon material, and the outer shell is made of an inorganic ceramic material; wherein the shell is directly coated on the surface of the inner core, or a gap is formed between the shell and the inner core, and the gap is less than 500 nm.
2. The electrode protection material of claim 1, wherein the carbon material comprises at least one of graphene, doped graphene, graphene oxide, doped graphene oxide, hard carbon, doped hard carbon, soft carbon material, carbon nanotubes, and doped carbon nanotubes.
3. The electrode protection material of claim 1 or 2, wherein the inorganic ceramic material comprises at least one of titanium dioxide, aluminum oxide, zirconium oxide, lithium fluoride, silicon oxide, calcium oxide, magnesium oxide, tantalum oxide, silicon nitride, cubic boron nitride, aluminum nitride, chromium nitride, titanium nitride, silicon carbide, boron carbide, titanium carbide, and chromium carbide.
4. The electrode protection material according to claim 1 or 2, wherein the mass of the carbon material is 1 to 50% of the total mass of the electrode protection material.
5. The electrode protection material according to claim 1 or 2, wherein the thickness of the outer shell is 1 to 10 nm.
6. The electrode protection material according to claim 1 or 2, wherein the electrode protection material is a spherical core-shell structure, and the diameter of the electrode protection material is 0.01 to 2 micrometers.
7. A method for preparing an electrode protection material for a lithium battery, comprising the steps of:
taking a carbon material, dispersing the carbon material in a polymer monomer, and obtaining a polymer microsphere containing the carbon material in an emulsion polymerization manner, wherein the microsphere comprises the carbon material and a polymer outer layer coating the carbon material;
and coating an inorganic ceramic material on the outer polymer layer, and removing the outer polymer layer by adopting a dissolving or sintering mode to obtain the battery electrode protection material, wherein the electrode protection material is of a core-shell structure and comprises an inner core and an outer shell, the inner core is made of a carbon material, and the outer shell is made of an inorganic ceramic material.
8. The method of claim 7, wherein the polymer monomer comprises styrene, methyl methacrylate, acrylate, vinyl acetate, vinyl chloride, or ethylene oxide.
9. The method according to claim 7 or 8, wherein the polymer microspheres comprising carbon materials obtained by emulsion polymerization are specifically: dispersing the carbon material in a polymer monomer, adding a solvent, a surfactant and an initiator, reacting at 50-150 ℃ for 10-48 hours to obtain a polymer microsphere emulsion containing the carbon material, demulsifying, separating, washing and drying to obtain the polymer microsphere containing the carbon material.
10. A battery electrode piece, characterized in that an electrode protection layer is arranged on one side of the battery electrode piece, which is in contact with an electrolyte, and the material of the electrode protection layer comprises the electrode protection material according to any one of claims 1 to 6.
11. The battery electrode tab of claim 10 wherein the electrode protective layer has a thickness of 0.1 to 20 microns.
12. The battery electrode sheet of claim 10 or 11, wherein the material of the electrode protection layer further comprises one or more of polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, polyvinylidene chloride, polyvinyl sulfone, polyethylene glycol diacrylate, polyvinyl pyrrolidone, and polyvinylidene fluoride.
13. A preparation method of a battery electrode plate is characterized by comprising the following steps:
dispersing the electrode protection material according to any one of claims 1 to 6 in an inert solvent to obtain a slurry, and coating the slurry on one surface of an electrode sheet, which is in contact with an electrolyte, to form an electrode protection layer, thereby obtaining the battery electrode sheet with the electrode protection layer.
14. The method of preparing a battery electrode tab of claim 13, wherein the inert solvent comprises one or more of hexane, heptane, benzene, diethyl ether, tetrahydrofuran, 1, 2-dimethoxyethane, butyl ether, and N-methylpyrrolidone.
15. A lithium battery comprising the battery electrode sheet according to any one of claims 10 to 12.
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| CN107516744B (en) * | 2016-06-16 | 2020-03-10 | 华为技术有限公司 | Solid electrolyte material, electrolyte, lithium battery and preparation method thereof |
| CN108134060A (en) * | 2017-12-20 | 2018-06-08 | 深圳市贝特瑞新能源材料股份有限公司 | Solid electrolyte interface film coats composite material, the preparation method and the usage of negative material |
| CN108987684B (en) * | 2018-06-05 | 2021-07-16 | 燕山大学 | Preparation method of metal lithium capable of being stably placed in air |
| CN109346692B (en) * | 2018-10-10 | 2021-06-04 | 青岛泰达华润新能源科技有限公司 | Lithium ion battery cathode material and preparation method thereof |
| CN110085852A (en) * | 2019-05-28 | 2019-08-02 | 中国科学院重庆绿色智能技术研究院 | Conductive structure and electrode |
| CN110492084B (en) * | 2019-09-06 | 2021-01-08 | 中南大学 | Spherical negative electrode composite material Si @ MXene with core-shell structure and preparation method thereof |
| CN111613790B (en) * | 2020-06-10 | 2021-09-07 | 新疆星力电气有限公司 | Efficient attenuation-resistant graphene power lithium battery material and preparation method thereof |
| CN114436675A (en) * | 2020-11-02 | 2022-05-06 | 恒大新能源技术(深圳)有限公司 | Composite material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005089352A2 (en) * | 2004-03-16 | 2005-09-29 | Toyota Technical Canter Usa, Inc. | Battery with molten salt electrolyte and protected lithium-based negative electrode material |
| CN102201565A (en) * | 2011-04-14 | 2011-09-28 | 杭州万好万家动力电池有限公司 | High-capacity metal lithium powder composite cathode and preparation method thereof, and multi-layer composite electrode |
| CN103022423A (en) * | 2012-11-28 | 2013-04-03 | 上海锦众信息科技有限公司 | Method for preparing lithium-ion safe negative pole |
| CN103022414A (en) * | 2012-12-30 | 2013-04-03 | 无锡富洪科技有限公司 | Lithium ion battery and negative pole piece thereof |
| CN103299459A (en) * | 2011-01-11 | 2013-09-11 | 株式会社Lg化学 | Method for preparing a negative electrode active material |
-
2016
- 2016-05-31 CN CN201610378334.1A patent/CN107452941B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005089352A2 (en) * | 2004-03-16 | 2005-09-29 | Toyota Technical Canter Usa, Inc. | Battery with molten salt electrolyte and protected lithium-based negative electrode material |
| CN103299459A (en) * | 2011-01-11 | 2013-09-11 | 株式会社Lg化学 | Method for preparing a negative electrode active material |
| CN102201565A (en) * | 2011-04-14 | 2011-09-28 | 杭州万好万家动力电池有限公司 | High-capacity metal lithium powder composite cathode and preparation method thereof, and multi-layer composite electrode |
| CN103022423A (en) * | 2012-11-28 | 2013-04-03 | 上海锦众信息科技有限公司 | Method for preparing lithium-ion safe negative pole |
| CN103022414A (en) * | 2012-12-30 | 2013-04-03 | 无锡富洪科技有限公司 | Lithium ion battery and negative pole piece thereof |
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