CN112186174A - Conductive additive and preparation method and application thereof - Google Patents
Conductive additive and preparation method and application thereof Download PDFInfo
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- CN112186174A CN112186174A CN201910585193.4A CN201910585193A CN112186174A CN 112186174 A CN112186174 A CN 112186174A CN 201910585193 A CN201910585193 A CN 201910585193A CN 112186174 A CN112186174 A CN 112186174A
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- conductive additive
- conductive
- positive electrode
- coating layer
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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
- H01M4/624—Electric conductive fillers
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a conductive additive, a preparation method and an application thereof. After the conductive additive is coated by the oxide, the reactivity between the conductive agent and the electrolyte before coating is reduced, and the interface of the conductive agent is stabilized, so that the capacity retention rate and the charging and discharging coulombic efficiency of the anode in the circulating process are improved.
Description
Technical Field
The invention relates to a conductive additive with an oxide coating layer for a lithium ion battery, and a preparation method and application thereof.
Background
Compared with other rechargeable battery systems, the lithium ion secondary battery has the advantages of high working voltage, light weight, small volume, no memory effect, low self-discharge rate, long cycle life, high energy density and the like, and is widely applied to mobile terminal products such as mobile phones, notebook computers, tablet computers and the like.
In recent years, electric vehicles have been rapidly developed under the push of governments and automobile manufacturers in various countries from the viewpoint of environmental protection, and lithium ion secondary batteries have become an ideal power source for a new generation of electric vehicles by virtue of their excellent performance. Currently, positive electrode materials of lithium ion secondary batteries that are of interest can be roughly classified into three types: with lithium cobaltate (LiCoO)2) A layered material represented by lithium iron phosphate (LiFePO)4) Olivine-type material typified by lithium manganate (LiMn)2O4) Is a typical spinel structure material.
Although lithium batteries have been successfully commercialized as early as 1991, further improvements in energy density are required for the currently available materials. One way to increase the energy density is to increase the voltage. However, as the voltage increases, the side reaction of the positive electrode with the electrolyte is also increased. Not only the positive electrode active material, the conductive additive, the binder, and the aluminum foil may undergo side reactions with the electrolyte. Heretofore, methods for improving the stability of a high-voltage battery system have mainly focused on improvements of a positive electrode active material, a binder, and an aluminum foil. In fact, under high pressure, both anion intercalation and oxidative decomposition of organic molecules affect the structural stability of the conductive additive and the high pressure stability of the electrolyte. Conductive additives occupy 80-98% of the surface area of the overall composite positive electrode, but little attention has been paid to their modification and promotion.
Therefore, providing a surface-stable conductive additive and a preparation method thereof are important for improving the stability of a high-voltage battery system.
Disclosure of Invention
Therefore, an object of the present invention is to provide a conductive additive having an oxide coating layer for a lithium ion battery, and a preparation method and application thereof, thereby improving stability of the conductive additive.
The invention provides a conductive additive, which comprises conductive agent particles and an oxide coating layer coated on the surfaces of the conductive agent particles.
According to the invention provideWherein the oxide coating layer is represented by the formula MxOyWherein M is selected from one or more of Al, Mg, Zn, Ti, Y, Sc, La, Ge, W, Zr, Ta, Nb, Ca, P, Si and Sr, x is more than or equal to 1 and less than or equal to 3, and Y is more than or equal to 1 and less than or equal to 5. Preferably, the oxide constituting the oxide coating layer is Al2O3、ZnO、TiO2、Ta2O5、Nb2O5One or more of (a).
According to the conductive additive provided by the invention, the thickness of the oxide coating layer can be 0.1-10nm, and preferably 3-5 nm.
According to the conductive additive provided by the invention, the mass ratio of the oxide coating layer to the conductive additive particles can be 0.01-5: 100, and preferably 0.1-1: 100.
According to the conductive additive provided by the invention, the particle size of the conductive agent particles can be 1-10000 nm, and preferably 10-100 nm.
According to the conductive additive provided by the invention, the conductive agent particles can be conductive agent materials commonly used in the field, for example, traditional conductive agents such as carbon black, conductive graphite, carbon fibers and the like can be used, and novel conductive agents such as carbon nanotubes, graphene, mixtures thereof and the like can also be used.
In another aspect, the invention further provides a preparation method of the conductive additive, wherein the preparation method comprises the step of coating the oxide on the surface of the conductive agent particles by adopting a gas phase method and/or a liquid phase method to form an oxide coating layer.
Wherein the vapor phase method may include an atomic layer deposition method and a chemical vapor deposition method; the liquid phase process may include a liquid phase adsorption process and a hydrolysis process. The gas phase method and the liquid phase method have the advantages that the gas phase method can more easily obtain the coating layer with uniform and compact thickness and adjustable thickness, and the liquid phase method has simple operation and low cost.
In yet another aspect, the invention further provides the use of the conductive additive or the conductive additive prepared according to the method of the invention in a lithium ion battery, wherein the conductive additive is used in the positive electrode of the lithium ion battery.
In another aspect, the invention further provides a lithium ion battery positive electrode, which includes a current collector, a positive active material, a binder and a conductive additive, wherein the conductive additive is the conductive additive provided by the invention or the conductive additive prepared by the method provided by the invention.
According to the positive electrode for a lithium ion battery provided by the present invention, the positive electrode active material may be a positive electrode active material commonly used in the art, and the present invention is not particularly limited thereto.
According to the positive electrode for a lithium ion battery provided by the present invention, the binder may be a binder commonly used in the art, and the present invention is not particularly limited thereto.
The invention further provides a lithium ion battery which comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the positive electrode is the positive electrode provided by the invention.
According to the present invention, there is provided a lithium ion secondary battery, wherein the battery further comprises a case, and wherein a positive electrode, a negative electrode, a separator (collectively referred to as an electrode group), and an electrolyte are sealed in the case.
According to the lithium metal secondary battery provided by the present invention, the anode, the separator and the electrolyte may employ anode, separator and electrolyte materials that are conventional in the art, and the present invention is not particularly limited thereto. In some embodiments, the negative electrode is metallic lithium; in some embodiments, the separator is a three layer film of PP/PE/PP coated on both sides with alumina; and in some embodiments, the electrolyte is LiPF6The non-aqueous electrolyte of Ethylene Carbonate (EC)/dimethyl carbonate (DMC) with the concentration of 1mol/L, wherein the volume ratio of EC to DMC is 1: 1.
According to the conductive additive containing the oxide coating layer, the coated conductive additive reduces the reactivity between the conductive additive and electrolyte, and stabilizes the interface of the conductive additive, so that the capacity retention rate and the charge-discharge coulombic efficiency of the anode in the circulation process are improved.
The conductive additive containing the oxide coating layer can be used as a positive electrode conductive additive of a lithium ion battery, and the battery made of the material has excellent cycle performance.
The conductive additive containing the oxide coating layer provided by the invention obviously improves the cycle stability and the coulombic efficiency of the anode. Without wishing to be bound by theory, it is believed that by the method provided by the present invention, a uniform and dense oxide coating is formed on the surface of the conductive additive. The coating can inhibit the decomposition of the electrolyte on the surface of the conductive additive, thereby increasing the stability of the battery system. Lithium ion batteries comprising the conductive additives of the present invention are useful as energy sources for electric tools, electric bicycles, hybrid electric vehicles, and pure electric vehicles, among other applications.
Drawings
Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:
FIG. 1 is an XPS scan of Al element from coated acetylene black prepared in example 1;
FIG. 2 is an XPS scan of Ti for coated conductive graphite prepared in example 3;
FIG. 3 shows XPS scans of Nb for coated carbon nanotubes prepared in example 4;
FIG. 4 is an XPS scan of Ta element for coated conductive graphite prepared in example 8;
FIG. 5 is a graph showing the use of virgin acetylene black and the coated acetylene black obtained in example 1 for high pressure LiNi0.5Mn1.5O4High temperature charge-discharge cycle curves in the material;
FIG. 6 shows the use of virgin acetylene black and the coated acetylene black obtained in example 1 for high-pressure LiNi0.5Mn1.5O4High temperature coulombic efficiency curve in the material.
Detailed Description
The present invention is described in further detail below with reference to specific embodiments, which are given for the purpose of illustration only and are not intended to limit the scope of the invention.
Example 1
The conductive additive is prepared by adopting an atomic deposition method, and the method comprises the following specific operations:
putting 2g of acetylene black into a stainless steel screen mesh mold, then integrally putting the stainless steel screen mesh mold into an atomic layer deposition cavity, vacuumizing, keeping the temperature of the cavity at about 250 ℃, introducing trimethylaluminum vapor at room temperature into the cavity for 0.02s, vacuumizing the cavity, standing for 6s, introducing water vapor at room temperature into the cavity for 0.02s, vacuumizing the cavity, and introducing trimethylaluminum vapor again for 8s to finish one cycle of deposition. Depositing according to the steps for 10 times in a circulating way to obtain Al2O3A coated acetylene black material.
Example 2
The conductive additive is prepared by adopting an atomic deposition method, and the method comprises the following specific operations:
putting 2g of acetylene black into a stainless steel screen mesh mold, then integrally putting the stainless steel screen mesh mold into an atomic layer deposition cavity, vacuumizing the atomic layer deposition cavity, keeping the temperature of the cavity to be about 220 ℃, introducing dimethylamino tantalum steam heated to 120 ℃ into the cavity for 0.2s, vacuumizing the cavity for 30s, introducing water vapor at room temperature into the cavity for 0.03s, vacuumizing the cavity, and introducing dimethylamino tantalum steam again for 20s to complete the cyclic deposition. Depositing according to the step for 40 times in a circulating way to obtain Ta2O5A coated acetylene black material.
Example 3
The conductive additive is prepared by adopting an atomic deposition method, and the method comprises the following specific operations:
placing 2g of conductive graphite in a stainless steel screen mesh mold, then integrally placing the conductive graphite in an atomic layer deposition cavity, vacuumizing, keeping the temperature of the cavity at about 200 ℃, introducing dimethylamino titanium steam heated to 100 ℃ into the cavity for 0.1s, vacuumizing the cavity for 30s, introducing water vapor at room temperature into the cavity for 0.01s, vacuumizing the cavity, and introducing dimethylamino titanium steam again for 30s to complete the cyclic deposition. The step is repeated for 30 times to obtain TiO2A coated acetylene black material.
Example 4
The conductive additive is prepared by adopting an atomic deposition method, and the method comprises the following specific operations:
putting 2g of conductive graphite into a stainless steel screen mesh mold, then integrally putting the stainless steel screen mesh mold into an atomic layer deposition cavity, keeping the temperature of the cavity at about 220 ℃, introducing ethanol niobium steam heated to 100 ℃ into the cavity for 0.2s, then vacuumizing the cavity for 40s, introducing proper amount of water vapor into the cavity for 0.02s, and then vacuumizing the cavity, thereby completing one cycle of deposition. The deposition is cycled for 10 times according to the steps to obtain Nb2O5A coated conductive graphite material.
Example 5
The conductive additive is prepared by adopting a liquid phase adsorption method, and the preparation method specifically comprises the following operations:
0.25g of magnesium acetate was added to a flask containing 50ml of ethanol, 10g of carbon nanotubes were placed in the flask and subjected to ultrasonic treatment and stirring, the resulting mixture was placed in an oil bath at 100 ℃ to be subjected to volatilization drying for 5 hours, and the resulting dried powder was heated at 200 ℃ in vacuum for 5 hours to finally obtain an MgO-coated carbon nanotube material.
Example 6
The conductive additive is prepared by adopting a liquid phase adsorption method, and the preparation method specifically comprises the following operations:
0.25g of zinc acetate was added to a flask containing 50ml of ethanol, 10g of acetylene black was then placed in the flask and subjected to ultrasonic treatment and stirring, the resulting mixture was placed in an oil bath pan at 100 ℃ to be subjected to volatilization drying for 5 hours, and the resulting dried powder was heated at 200 ℃ in vacuum for 5 hours to finally obtain a ZnO-coated acetylene black material.
Example 7
The conductive additive is prepared by adopting a liquid phase adsorption method, and the preparation method specifically comprises the following operations:
0.25g of titanium ethoxide was charged into a flask containing 50ml of ethanol, and then 10g of acetylene black was charged into the flask and subjected to ultrasonic treatment and stirringVolatilizing and drying the obtained mixture in an oil bath pan at 100 ℃ for 5h, heating the obtained dry powder at 200 ℃ in vacuum for 5h to finally obtain TiO2A coated acetylene black material.
Example 8
The conductive additive is prepared by adopting a liquid phase adsorption method, and the preparation method specifically comprises the following operations:
adding 0.25g of tantalum ethoxide into a flask containing 50ml of ethanol, then adding 10g of conductive graphite into the flask, performing ultrasonic treatment and stirring, putting the obtained mixture into an oil bath kettle at 100 ℃ for volatilization and drying for 5 hours, heating the obtained dry powder at 200 ℃ in vacuum for 5 hours to finally obtain Ta2O5A coated acetylene black material.
Example 9
The conductive additive is prepared by a hydrolysis method, and the preparation method specifically comprises the following operations:
0.25g of titanium ethoxide was charged into a flask containing 50ml of ethanol, 10g of acetylene black was then charged into the flask and subjected to ultrasonic agitation, and deionized water vapor ultrasonically atomized was slowly introduced into the flask and discharged from a gas outlet for 1 hour. After the reaction is finished, acetylene black in the flask is filtered and dried, and then heated for 5 hours at 200 ℃ in vacuum to finally obtain TiO2A coated acetylene black material.
Material characterization
FIG. 1 shows the XPS scan of Al element in the coated acetylene black prepared in example 1, wherein the peak around 74.4eV is Al2O3The 2p orbital electron of the medium Al is excited by X-rays.
FIG. 2 is the XPS scan of Ti element with coated conductive graphite prepared in example 3, wherein the peaks around 459eV and around 464eV are the TiO peaks2The 2p orbital electron of Ti is excited by X-ray.
FIG. 3 is the XPS scan of Nb element for the coated carbon nanotubes prepared in example 4, wherein the peaks at about 210eV and 207eV are Nb2O5Medium Nb 3d orbital electron receiving X-rayA line-excited signal.
FIG. 4 is an XPS scan of Ta element from the coated conductive graphite prepared in example 8, wherein peaks at about 26.5eV and about 28.5eV are the peaks for Ta2O5The 4f orbital electron of medium Ta is excited by X-rays.
Performance testing
The conductive additives prepared in examples 1-6 were assembled into button cells according to the following procedure.
(1) Preparation of Positive electrode sheet
The conductive additive, LiNi, prepared in example0.5Mn1.5O4(LNMO) and polyvinylidene fluoride (PVDF) are used as binders and are dispersed in N-methyl pyrrolidone (NMP) according to the weight ratio of 80:10:10, and the materials are uniformly mixed to prepare uniform positive electrode slurry. Uniformly coating the uniform positive electrode slurry on an aluminum foil current collector with the thickness of 15 mu m, drying at 55 ℃ to form a pole piece with the thickness of 100 mu m, and rolling the pole piece under a roller press (the pressure is about 1MPa multiplied by 1.5 cm)2) Cutting the anode plate into round pieces with the diameter of 14mm, then placing the round pieces in a vacuum oven to be dried for 6 hours at the temperature of 120 ℃, naturally cooling the round pieces, taking out the round pieces and placing the round pieces in a glove box to be used as anode pieces.
(2) Assembling lithium ion secondary battery
In a glove box filled with inert atmosphere, metal lithium is taken as the negative electrode of the battery, a PP/PE/PP three-layer film with two sides coated with alumina is taken as a diaphragm and is placed between the positive electrode and the negative electrode, and 1M LiPF is dripped6And (2) dissolving the nonaqueous electrolyte in EC/DMC (volume ratio of 1:1), and assembling the button cell with the model number of CR2032 by using the positive pole piece prepared in the step (1) as a positive pole and using metal lithium as a negative pole.
And (3) standing the prepared button cell for 10 hours at room temperature (25 ℃), activating the cell, namely controlling the charging and discharging voltage range to be 3.5V-4.9V at room temperature for 5 weeks, then transferring the cell to a high-temperature environment at 55 ℃, continuously circulating the cell for 50 weeks at the multiplying power of 0.2C, and similarly controlling the charging and discharging voltage range of the cell to be 3.5V-4.9V.
The measured electrochemical performance data is set forth in table 1, in comparison to the conductive agent itself prior to coating using the inventive examples.
TABLE 1
In particular, fig. 5 and 6 show that the raw acetylene black and the coated acetylene black prepared in example 1 are used for high-pressure LiNi0.5Mn1.5O4Charge-discharge cycles and efficiency profiles of the cells at high temperatures in the material. The result shows that the capacity of a battery assembled by the original acetylene black material after 50 weeks is 128.8mAh/g, the coulombic efficiency is 98.81%, the capacity attenuation is rapid, and the coulombic efficiency is low under the high-temperature test environment at 55 ℃, because the electrolyte is decomposed on the surface of the conductive additive under the high-temperature test environment, the electrolyte is unstable; the capacity of the coated acetylene black is 130.4mAh/g after 50 weeks in a high-temperature test environment at 55 ℃, and the coulombic efficiency is 99.3%, because the coated acetylene black relieves the harmful side reaction between the conductive additive and the electrolyte, inhibits the decomposition of the electrolyte, and thus improves the cycling stability of the battery.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (11)
1. The conductive additive comprises conductive agent particles and an oxide coating layer coated on the surfaces of the conductive agent particles.
2. The conductive additive of claim 1, wherein the oxide packageThe coating is represented by the chemical formula MxOyWherein M is one or more selected from the group consisting of Al, Mg, Zn, Ti, Y, Sc, La, Ge, W, Zr, Ta, Nb, Ca, P, Si and Sr, x is 1. ltoreq. x.ltoreq.3, and Y is 1. ltoreq. y.ltoreq.5, preferably, the oxide constituting the oxide coating layer is Al2O3、ZnO、TiO2、Ta2O5、Nb2O5One or more of (a).
3. The conductive additive according to claim 1 or 2, wherein the oxide coating layer has a thickness of 0.1-10nm, preferably 3-5 nm.
4. The conductive additive according to any one of claims 1 to 3, wherein the mass ratio of the oxide coating layer to the conductive additive particles is 0.01 to 5:100, preferably 0.1 to 1: 100.
5. The conductive additive according to any one of claims 1 to 4, wherein the particle size of the conductive agent particles is 1 to 10000nm, preferably 10 to 100 nm.
6. The conductive additive of any one of claims 1-5, wherein the conductive agent particles are one or more of carbon black, conductive graphite, carbon fibers, carbon nanotubes, and graphene.
7. A method for producing the conductive additive as claimed in any one of claims 1 to 6, which comprises coating an oxide on the surface of a conductive agent particle by a vapor phase method and/or a liquid phase method to form an oxide coating layer.
8. The production method according to claim 7, wherein the vapor phase method is an atomic layer deposition method or a chemical vapor deposition method; the liquid phase method is a liquid phase adsorption method or a hydrolysis method.
9. Use of the conductive additive of any one of claims 1 to 6 or the conductive additive prepared according to the preparation method of claim 7 or 8 in a lithium ion battery, wherein the conductive additive is used in a positive electrode of the lithium ion battery.
10. A positive electrode of a lithium ion battery, comprising a current collector, a positive active material, a binder and a conductive additive, wherein the conductive additive is the conductive additive of any one of claims 1 to 6 or the conductive additive prepared by the preparation method of claim 7 or 8.
11. A lithium ion battery comprising a positive electrode, a negative electrode, a separator, and an electrolyte, wherein the positive electrode is the positive electrode of claim 10.
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