CN111740078A - Manufacturing method of lithium ion battery cathode structure and lithium ion battery cathode structure - Google Patents

Manufacturing method of lithium ion battery cathode structure and lithium ion battery cathode structure Download PDF

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Publication number
CN111740078A
CN111740078A CN201911000230.7A CN201911000230A CN111740078A CN 111740078 A CN111740078 A CN 111740078A CN 201911000230 A CN201911000230 A CN 201911000230A CN 111740078 A CN111740078 A CN 111740078A
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nano
foil
template
lithium ion
current collector
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钟高阔
訾孟飞
任传来
安峰
李江宇
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Shenzhen Institute of Advanced Technology of CAS
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Shenzhen Institute of Advanced Technology of CAS
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/02—Oxides; Hydroxides
    • C01G49/08—Ferroso-ferric oxide (Fe3O4)
    • 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
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0421—Methods of deposition of the material involving vapour deposition
    • H01M4/0423—Physical vapour deposition
    • 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
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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 relates to the technical field of battery cathode structures, in particular to a manufacturing method of a lithium ion battery cathode structure and the lithium ion battery cathode structure. The method comprises the following steps: providing a current collector plate; attaching a porous nano template on the current collector plate; forming a plurality of nano array columns in the holes of the porous nano template in a pulsed laser deposition mode; and removing the porous nano template, and fixing the nano array columns on the current collector plate in a protruding array mode after the removal, wherein the diameter of the nano array columns is between 90 and 300nm, the height of the nano array columns is between 50 and 400nm, and the distance between the nano array columns is between 65 and 125 nm. The method has the advantages of reliable preparation process, high repeatability, simple raw materials and good crystallinity of the sample, and can well avoid the introduction of impurities. The nano-array columns on the negative electrode of the battery are highly ordered and are tightly combined with the current collector plate, so that excellent conductivity and ultralow ion diffusion resistance can be provided.

Description

Manufacturing method of lithium ion battery cathode structure and lithium ion battery cathode structure
Technical Field
The invention relates to the technical field of battery cathode structures, in particular to a manufacturing method of a lithium ion battery cathode structure and the lithium ion battery cathode structure.
Background
With the continuous consumption of fossil energy and the pursuit of clean and pollution-free energy, the development of new energy is one of the current and eternal subjects. Rechargeable batteries are widely applied to the field of electrochemical energy storage, wherein lithium ion batteries have a market leading position in the fields of consumer electronics, electric automobiles and the like due to the characteristics of high energy density, small volume, light weight, long service life and the like. At present, carbon materials are generally adopted for the negative electrode of the lithium ion battery, wherein graphite is already applied to the negative electrode material of the commercial lithium ion battery. However, the theoretical specific capacity of the carbon material is low, such as graphite, the theoretical capacity is only 372mAh/g, and the continuous large-current discharge capacity required by a large-scale power battery cannot be met. It is therefore necessary to find a high specific capacity negative electrode material.
According to a great deal of scientific research work, transition metal oxide (M) is shown as a conversion materialxOyM = Mn, Fe, Co, Ni, etc.) has an extremely high theoretical specific capacity. Such as Fe3O4The theoretical specific capacity is 924mAh/g, and the lithium ion battery cathode material has the advantages of stable structure, low price, wide source and the like, is popular with researchers, and is one of the candidates which are very likely to become the lithium ion battery cathode material. But due to Fe3O4The large volume change rate and the randomness of the electron transmission path in the charging and discharging process result in large capacity attenuation and low rate performance. Mixing Fe3O4The method for combining the nano material with the construction of a special structure is to improve Fe at present3O4One of the main methods for the electrochemical performance of materials is when Fe3O4The size of (A) is in the nanometer level, so that Fe is generated3O4The contact between the material and the electrode and the electrolyte is enhanced, and meanwhile, the transmission distance of lithium ions and electrons is shortened and the large volume change is relieved; and special structures such as hollow, fiber, core-shell, nano-array structures and the like also relieve Fe to a certain extent in the charging and discharging process3O4The volume of (c) is changed.
Preparation of Nano Fe at present3O4The method of the material is mostly a hydrothermal method, a thermal decomposition method, a coprecipitation method and the like, the coprecipitation method is simple, convenient and easy to implement, but most of generated precipitates are in a colloidal state, are difficult to filter and wash and are easy to introduce impurities, and the nano material has larger surface energy and is easy to aggregate together, and the ferroferric oxide is a ferromagnetic material, and magnetic attraction exists among particles, so the particles are easy to aggregate together. Therefore, the agglomeration phenomenon of the product obtained by the coprecipitation method is very obvious, and the product used as the negative electrode of the battery can seriously affect the performance of the battery. Although the agglomeration phenomenon is relieved, the hydrothermal method still obviously exists, and the performance of the battery is influenced when the hydrothermal method is used as a battery cathode. The thermal decomposition method firstly needs to synthesize iron oleate as a thermal decomposition precursor; the synthesis of the iron oleate has great influence on subsequent results, the system is complex, impurities are easy to introduce, and the performance of the battery can be influenced when the iron oleate is used as a battery cathode.
Disclosure of Invention
The invention aims to provide a manufacturing method of a lithium ion battery cathode structure, which can well avoid the introduction of impurities and limit the agglomeration of products.
The purpose of the invention is realized by the following technical scheme: the manufacturing method of the lithium ion battery cathode structure comprises the following steps:
providing a current collector plate;
attaching a porous nano template on the current collector plate;
forming a plurality of nano array columns in the holes of the porous nano template in a pulsed laser deposition mode;
and removing the porous nano template, and fixing the nano array columns on the current collector plate in a protruding array mode after the porous nano template is removed, wherein the diameter of the nano array columns is between 90 and 300nm, the height of the nano array columns is between 50 and 400nm, and the distance between the nano array columns is between 65 and 125 nm.
The lithium ion battery cathode material nano array columns are deposited on the current collector plate by adopting a pulse laser deposition technology, namely, the highly ordered nano array columns are directly deposited on the current collector plate, so that each nano column has a current collector and is tightly combined with the current collector, and excellent conductivity and ultralow ion diffusion resistance can be provided due to the excellent geometrical characteristics; meanwhile, the spacing space exists between the nano columns, the protective effect of the structural buffer zone can be achieved, the damage caused by volume expansion and contraction is reduced, agglomeration and pulverization are prevented, the expansion of the nano columns cannot interfere with each other in the charging and discharging process of the battery, the phenomenon of branch knots and bulge of the battery is not easy to occur, and the performance and the service life of the battery are greatly improved. In addition, the method has the advantages of reliable preparation process, high repeatability, simple raw materials and good crystallinity of the sample, can well avoid the introduction of impurities, and simultaneously, because the nano-columns grow in the holes, the agglomeration of products in the preparation process is not needed to be worried about. Tests show that the battery performance can be better ensured by controlling the nano array columns according to the size and the distance between the adjacent nano array columns, and meanwhile, the production efficiency is higher.
The invention is further configured to: the height error of the nano array column is within 10%.
The nano array columns are more orderly arranged, and the formed cathode material has better performance.
The invention is further configured to: the height of the nano array column is less than the depth of the holes in the porous nano template.
By adopting the technical scheme, the rear removal of the porous nano template is more convenient, and the nano array column is not easily influenced.
Hair brushThe method is further arranged to evacuate the background in the growth chamber to 5 × 10 before pulsed laser deposition-7Below Torr and maintaining a flowing oxygen partial pressure of less than 5 × 10 during deposition-5Torr
By adopting the technical scheme, the iron ions in the ferroferric oxide are not easy to change valence.
The invention is further configured to: and the porous nano template is attached to the current collector plate, the current collector plate is heated before pulse laser deposition, and the heating rate is controlled to be 10-30 ℃/min.
Through adopting above-mentioned technical scheme, can enough make the fine laminating of porous nanometer template and current collector board, also be convenient for the better porous nanometer template of removing in later stage of later stage. The tight fit of the porous nano template and the current collector plate can be better kept by controlling the heating rate, and the situation that the porous nano template and the current collector plate are peeled off due to thermal stress or the separation of the current collector plate and the porous nano template with different temperature expansion coefficients is avoided as much as possible.
The invention is further configured to: the deposition time of the pulse laser is 30-90 min.
Tests show that the basic requirements of the cathode can be met after deposition lasts for 30min, the content of ferroferric oxide can be increased after the time is prolonged, and the performance of the battery is improved; the cost is increased after the time is too long, which is not beneficial to the actual production.
The invention is further configured to: the current collector plate is made of copper foil, and the nano array column is made of Fe3O4A nano-array column; before the pulse laser deposition, the copper foil is heated to the temperature of 300-500 ℃, the laser energy is 250-350mJ, and the laser frequency is 5-10 Hz.
Fe3O4The nano array column can greatly increase the specific capacity of the battery, has a stable structure and can greatly improve the performance of the battery. Tests show that the nano array column crystal phase obtained by selecting the technical parameters is good and the arrangement is more regular.
The invention is further configured to: before pulse laser deposition, the copper foil is bonded to the heat conducting sheet by silver paste and then deposition is carried out.
The heat conducting sheet has a good heat conducting effect, can uniformly conduct heat to the copper foil, and has better quality and better performance of the negative electrode after deposition. The silver paste can well bond the heat-conducting strip and the copper foil, is high-temperature resistant, and can play a certain shaping role in the copper foil after being dried; the silver paste has good thermal conductivity, so that the copper foil is heated more uniformly, and the quality of the formed nano array column is better.
The invention is further configured to: in the step of attaching the porous nano template to the current collector plate, the porous nano template is a PMMA/AAO template, the PMMA/AAO template is soaked in an organic solvent to separate a PMMA support layer, and then the AAO template is attached to the Cu foil.
The AAO template holes are of a bi-pass AAO structure, the barrier layers of the single-pass AAO template are removed, the thickness of the single-pass AAO template is only dozens to hundreds of nanometers, the AAO template holes are uniform in diameter, the hole arrangement is short-range and ordered, and the method is very suitable for preparing the nano array column in the application; the surface of the AAO template is coated with a layer of PMMA for supporting, so that the AAO template can be very conveniently taken, put, cut and transferred onto any target substrate, and the AAO template is more flexible to use. The template is soaked in the organic solvent to separate the PMMA supporting layer, the method is simple, the AAO template is not easily polluted, the surface of the AAO template can be kept smooth, and the quality of the anode material prepared in the later stage is better.
The invention also aims to provide a lithium ion battery cathode structure, the nano array columns are highly ordered, are tightly combined with the current collector plate, have excellent geometric characteristics, and can provide excellent conductivity and ultralow ion diffusion resistance.
The second purpose of the invention is realized by the following technical scheme: a lithium ion battery negative electrode structure comprising:
a current collector plate;
a plurality of nano-array pillars;
wherein the nanometer array columns are convexly array-fixed on the current collector plate, the diameter of the nanometer array columns is between 90nm and 300nm, the height of the protrusions of the nanometer array columns is between 50nm and 400nm, and the distance between the nanometer array columns is between 65 nm and 125 nm.
By adopting the technical scheme, the nano array columns on the battery cathode are highly ordered, are tightly combined with the current collector plate, have excellent geometric characteristics, and can provide excellent conductivity and ultralow ion diffusion resistance.
The invention is further configured to: the height error of the nano array column is within 10%.
The nano array columns are more orderly arranged, and the formed cathode material has better performance.
In conclusion, the beneficial technical effects of the invention are as follows:
1. the lithium ion battery cathode material nano array columns are deposited on the current collector plate by adopting a pulse laser deposition technology, namely, the highly ordered nano array columns are directly deposited on the current collector of the current collector plate, so that each nano column has a current collector and is tightly combined with the current collector, and excellent conductivity and ultralow ion diffusion resistance can be provided due to the excellent geometrical characteristics; meanwhile, the spacing space exists between the nano columns, the protective effect of the structural buffer zone can be achieved, the damage caused by volume expansion and contraction is reduced, agglomeration and pulverization are prevented, the expansion of the nano columns cannot interfere with each other in the charging and discharging process of the battery, the phenomenon of branch knots and bulge of the battery is not easy to occur, and the performance and the service life of the battery are greatly improved.
2. The method has the advantages of reliable preparation process, high repeatability, simple raw materials and good crystallinity of the sample, can well avoid the introduction of impurities, and simultaneously, because the nano-columns grow in the holes, the agglomeration of products in the preparation process is not needed to be worried about.
3. The height of the nano array column is less than that of the hole in the porous nano template. The porous nano template is more convenient to remove at the back, and the nano array column is not easy to be influenced.
4. The porous nano template is attached to the current collector plate, so that the porous nano template can be well attached to the current collector plate, and the porous nano template can be removed better in the later period. The collector plate is heated before the pulsed laser deposition, the heating rate is controlled to be 10-30 ℃/min, and the porous nano template can be better kept to be tightly attached to the collector plate by controlling the heating rate. The separation of the porous nano template and the current collector plate due to thermal stress peeling or the difference of the temperature expansion coefficients of the current collector plate and the porous nano template is avoided as much as possible.
Drawings
FIG. 1 is a flow chart of the fabrication of a negative electrode structure for a battery;
FIG. 2 is a schematic diagram of the construction of a current collector plate;
FIG. 3 is a schematic diagram of a structure for attaching a porous nanotemplate to a current collector plate;
FIG. 4 is a schematic illustration of a porous nanotemplate after deposition of nanoarray columns within the pores thereof;
FIG. 5 is a schematic diagram of a negative electrode structure of a lithium ion battery;
FIG. 6a is an SEM image of copper foil in example 1 before the AAO template is removed;
FIG. 6b is an SEM image of a partially removed AAO template on copper foil according to specific application example 1;
FIG. 6c shows Fe after removing AAO template from copper foil in practical example 13O4SEM images of the nano-array columns;
FIG. 6d shows the negative electrode material Fe of lithium ion battery3O4SEM picture when the average grain diameter of the nano array column is 90 nm;
FIG. 6e shows the negative electrode material Fe of lithium ion battery3O4SEM picture when the average grain diameter of the nano array column is 260 nm;
FIG. 6f shows the negative electrode material Fe of lithium ion battery3O4SEM picture when the average grain diameter of the nano array column is 350 nm;
FIG. 7 shows the negative electrode material Fe of lithium ion battery3O4TEM images of the nano-array columns;
FIG. 8 shows the negative electrode material Fe of lithium ion battery3O4XPS plot of nano-array columns;
fig. 9 is a diagram of lithium ion battery cycle performance.
Reference numerals: 1. a current collector plate; 2. a porous nano-template; 21. a hole; 3. a nano-array column; 4. silver paste; 5. a heat conductive sheet; 6. and depositing a layer.
Detailed Description
The invention is described in further detail below with reference to the accompanying figures 1-9 and examples.
Example 1
A method for manufacturing a negative electrode structure of a lithium ion battery, as shown in fig. 1, includes the following steps:
providing a current collector plate 1;
attaching a porous nano template 2 on the current collector plate 1;
forming a plurality of nano array columns 3 in the holes 21 of the porous nano template 2 in a pulse laser deposition mode;
and removing the porous nano template 2, and convexly array and fixing the nano array columns 3 on the current collector plate 1 to obtain the lithium ion battery cathode structure.
The lithium ion battery cathode structure prepared by the invention comprises a current collector plate 1 and a plurality of nano array columns 3 which are convexly arrayed and fixed on the current collector plate 1, wherein the diameter of each nano array column 3 is between 90 and 300nm, the height of each nano array column 3 is between 50 and 400nm, and the distance between every two nano array columns 3 is between 65 and 125 nm; the nano array columns 3 on the battery cathode are highly ordered, are tightly combined with the current collector plate 1, have excellent geometric characteristics, and can provide excellent conductivity and ultralow ion diffusion resistance. The battery cathode has simple structure and is beneficial to manufacture.
In the preferred embodiment, the height error of the nano array columns 3 is within 10%, so that the nano array columns 3 are more orderly arranged, and the performance of the battery cathode is better. The diameter of the nano-array column 3 is between 100 and 200 nm.
In the process of pulse laser deposition, a part of particles can be deposited on the surface of the porous nano template 2 to form a deposition layer 6, and in order to remove the porous nano template 2 more conveniently, as shown in fig. 1, the height of the nano array columns 3 in the embodiment is smaller than the depth of the holes in the porous nano template 2, so that the deposition layer 6 cannot be adhered to the nano array columns in the holes 21 in the porous nano template 2, and in the process of removing the porous nano template 2 through suction or adhesion, direct suction or adhesion cannot be generated on the nano array columns 3, and the stability of the cathode structure can be better maintained.
In this embodiment, a molecular pump is used before pulsed laser depositionThe background vacuum in the long chamber was pulled to 5 × 10-7Below Torr and maintaining a flowing oxygen partial pressure of less than 5 × 10 during deposition-5And (5) Torr. The porous nano template 2 is attached to the current collector plate 1 by surface activation, van der waals attraction, intermolecular adsorption, or adhesive bonding, but not limited thereto. The porous nano template 2 is attached to the current collector plate 1, so that the porous nano template 2 can be well attached to the current collector plate 1, and the porous nano template 2 can be removed better in the later period. The current collector plate 1 is heated before the pulse laser deposition, the heating rate is controlled to be 10-30 ℃/min, and the situation that the porous nano template and the current collector plate are stripped due to thermal stress or the separation of the current collector plate and the porous nano template with different temperature expansion coefficients is avoided as much as possible.
As shown in fig. 4, in the present embodiment, it is preferable to perform deposition by bonding a copper foil to a thermally conductive sheet 5 with a silver paste 4 before the pulsed laser deposition. The heat conducting sheet 5 is preferably a SiC sheet, the SiC sheet has a good heat conducting effect, heat can be uniformly conducted to the copper foil, the quality of the deposited product is better, and the performance of the negative electrode is better. The silver paste 4 can well bond the heat conducting strip 5 and the copper foil, is high-temperature resistant, and can play a certain shaping role in the copper foil after being dried; the silver paste 4 has good thermal conductivity, so that the copper foil is heated more uniformly, and the quality of the formed nano array column 3 is better.
Example 2
A manufacturing method of a lithium ion battery cathode structure comprises the following steps: as shown in fig. 1, a current collector plate 1 is provided; the current collector plate 1 is a copper foil.
Attaching a porous nano template 2 on the current collector plate 1;
forming a plurality of nano array columns 3 in the holes 21 of the porous nano template 2 in a pulse laser deposition mode; the nano array column 3 is Fe3O4A nano array column 3; before the pulse laser deposition, the copper foil is heated to the temperature of 300-500 ℃, the laser energy is 250-350mJ, and the laser frequency is 5-10 Hz.
Removing the porous nano template 2, and convexly arraying and fixing the nano array columns 3 on the current collector plate 1 after removal, wherein the diameter of the nano array columns 3 is between 90 and 300nm, the height of the nano array columns 3 is between 50 and 400nm, and the distance between the nano array columns 3 is between 65 and 125 nm.
Fe3O4The nano array column 3 can greatly increase the specific capacity of the battery, has stable structure and can greatly improve the performance of the battery. Tests show that the obtained nano array columns 3 have good crystal phase and more regular arrangement by selecting the technical parameters, and the height error of the nano array columns 3 is within 5 percent.
In this embodiment, in the step of attaching the porous nano template 2 to the current collector plate 1, the porous nano template 2 is a PMMA/AAO template, the PMMA/AAO template is immersed in an organic solvent to separate the PMMA supporting layer, and then the AAO template is attached to the Cu foil.
Example 3
A method for manufacturing a negative electrode structure of a lithium ion battery, as shown in fig. 1, includes the following steps:
(1) cutting the metal foil, and performing cleaning pretreatment on the metal foil;
(2) soaking the PMMA/AAO template in an organic solvent to separate a PMMA supporting layer, and then attaching the PMMA supporting layer to a metal foil subjected to cleaning pretreatment to prepare the metal foil attached with the AAO template;
(3) preparing highly ordered Fe on the metal foil attached with the AAO template obtained in the step (2) by adopting a pulse laser deposition system3O4A nano-array;
(4) for the Fe prepared in the step (3)3O4And cooling the nano array sample, and then removing the AAO template by adhesion.
Wherein the organic solvent is preferably acetone.
In this embodiment, preferably, the metal foil is a copper foil, and the step (1) specifically includes the following steps:
a. soaking the Cu foil in acetone, and ultrasonically cleaning for 5-20 min;
b. soaking the Cu foil in absolute ethyl alcohol, and ultrasonically cleaning for 5-20 min;
c. then soaking the Cu foil in deionized water, and ultrasonically cleaning for 5-20 min;
d. then drying the Cu foil in a nitrogen atmosphere or an inert gas atmosphere;
e. and finally, cleaning the surface of the Cu foil for 150-250 seconds by using a plasma cleaning machine.
The cleaning in the steps a-c can clean the surface of the Cu foil, and the performance of the battery cathode can be better ensured. The drying in step d can avoid oxidation of the Cu foil surface. E, bombarding the surface of the Cu foil by the plasma in the step e, so that the surface of the Cu foil is cleaner, and the copper foil and Fe in the later period can be improved3O4Adhesion between the nano-array columns 3. Therefore, the method can ensure the cleanness of the surface of the Cu foil and increase the hydrophilicity of the Cu foil through the cleaning pretreatment step, thereby being beneficial to the close fit with the AAO template and the Fe3O4The nano-array grows uniformly.
After the AAO template is adhered by the adhesive tape, the AAO template is continuously adhered to the Fe by the adhesive tape3O4Removing the nano-array column 3 again, repeating the above steps for more than 5 times without Fe3O4The nano-array column 3 is stuck off.
Preferably, the step (2) specifically comprises the following steps:
(a) shearing a PMMA/AAO template into a shape and a size which are the same as those of the Cu foil, placing the PMMA/AAO template into a beaker filled with acetone, standing for 3-10min, and then slowly dragging the PMMA/AAO template in the acetone by using tweezers until the PMMA supporting layer is separated;
(b) aligning and tightly attaching the cleaned and pretreated Cu foil to an AAO template in acetone, and taking out;
(c) and finally, standing and drying the AAO/Cu foil in air.
According to the invention, the AAO template and the Cu foil are tightly bonded through the bonding treatment of the AAO template and the Cu foil, so that Fe is favorably bonded3O4And the growth uniformity of the nano array on the surface of the Cu foil.
Preferably, the temperature of the Cu foil is set to be 300-500 ℃, the heating rate is 10-30 ℃/min, the laser energy is 250-350mJ, the frequency is 5-20Hz, and the flowing oxygen partial pressure is 1 × 10-6-5×10-5mTorr. For pulse laserDeposition system for producing Fe3O4The temperature, the heating rate, the laser energy, the laser frequency, the dynamic oxygen partial pressure and the like of the Cu foil are optimized in the nano-array process, and highly ordered and tightly combined Fe is prepared3O4And (4) nano arrays.
Preferably, the step (3) specifically comprises the following steps:
A. mixing Fe3O4The target material is arranged in a pulse laser deposition rotating target position;
B. bonding the AAO/Cu foil obtained in the step (2);
C. placing the AAO/Cu foil after bonding treatment on a laser heating table in a growth cavity of a pulse laser deposition system, and vacuumizing the background in the cavity to 5 × 10-7Below Torr, setting the temperature of Cu foil at 300-500 deg.C, the heating rate at 10-30 deg.C/min, the laser energy at 250-350mJ, the laser frequency at 5-10Hz, and the flowing oxygen partial pressure at 1 × 10-6-5×10-5Torr, turn on the laser to bombard Fe3O4Target material of Fe3O4Deposited on an AAO/Cu foil;
D. the deposition time of the step C is 30-90min, and highly ordered Fe is prepared3O4And (4) nano arrays.
The invention utilizes a pulsed laser deposition system to deposit Fe on an AAO/Cu foil3O4The array, since AAO template has a thickness of 600nm, can prepare Fe with different heights according to different conditions in the deposition process3O4And (4) nano arrays.
Preferably, the treatment of the AAO/Cu foil in step B specifically comprises the steps of:
(A) uniformly coating high-temperature silver paste 4 on a SiC sheet;
(B) then pasting the AAO/Cu foil on an undried SiC sheet coated with high-temperature silver paste 4;
(C) finally, the SiC piece stuck with the AAO/Cu foil is placed on a heating table at the temperature of 110-140 ℃ and baked for 5-20 min.
According to the invention, the AAO/Cu foil is bonded with the SiC sheet by using the high-temperature silver paste 4, and the drying of the silver paste 4 can be ensured by setting reasonable heating temperature and time, so that the AAO/Cu foil is more firmly bonded on the SiC sheet; as SiC has the characteristic of good heat conductivity, the AAO/Cu foil is bonded with the SiC sheet, so that the aim of uniformly heating the AAO/Cu foil is fulfilled.
The step (4) is specifically that the sample is at the high temperature of 300-500 ℃ and the temperature of 1 × 10-6-5×10-5Placing the sample under the oxygen partial pressure of Torr for 5-30min, then slowly cooling to room temperature at the cooling speed of 10-20 ℃/min under the same oxygen partial pressure, taking out the sample, and then adhering the AAO template on the sample by using a polyimide high-temperature adhesive tape.
In the invention, Fe3O4The nanoarrays are placed at high temperature and partial pressure of oxygen for a period of time to facilitate better crystallization.
Specific examples of applications obtained by the production method of example 1 are as follows.
Specific application example 1
(1) As shown in fig. 2, a Cu foil with a size of 5 × 5mm is cut and subjected to a cleaning pretreatment, which specifically includes the following steps:
a. placing the Cu foil in a beaker filled with acetone, then placing the beaker in an ultrasonic cleaner filled with a certain amount of water, and carrying out ultrasonic cleaning for 10 min;
b. soaking the Cu foil in absolute ethyl alcohol, and ultrasonically cleaning for 10 min;
c. then soaking the Cu foil in deionized water, and ultrasonically cleaning for 10 min;
d. then, drying the Cu foil in a nitrogen atmosphere with the purity of 99.999 percent;
e. and finally, cleaning the surface of the Cu foil for 180s by using a plasma cleaning machine.
(2) The specific steps for preparing the AAO/Cu foil comprise the following steps:
(a) shearing a PMMA/AAO template into a shape and a size which are the same as those of the Cu foil, placing the PMMA/AAO template into a beaker filled with acetone, standing for 5min, and then slowly swaying the PMMA/AAO template in the acetone by using tweezers until the PMMA supporting layer is separated;
(b) aligning and tightly attaching the cleaned and pretreated Cu foil to an AAO template in acetone, and taking out the Cu foil after the clean and pretreated Cu foil is tightly attached to the AAO template, and referring to fig. 3;
(c) and finally, standing and drying the AAO/Cu foil in air.
(3) Preparation of Fe on AAO/Cu foil by pulsed laser deposition system3O4Nano array, KrF (lambda =248nm) excimer laser as the laser, and during deposition, the temperature of Cu foil is set at 400 deg.C, the heating rate is 20 deg.C/min, the laser energy is 300mJ, the frequency is 10Hz, and the flowing oxygen partial pressure is 3 × 10-6Torr specifically comprises the following steps:
A. mixing Fe3O4The target material is arranged in a pulse laser deposition rotating target position;
B. as shown in fig. 4, the back surface of the AAO/Cu foil obtained in step (2) is attached to a SiC sheet coated with uniform and undried high-temperature silver paste 4, and then the SiC sheet attached with the AAO/Cu foil is placed on a heating table at 120 ℃ and baked for 10min to ensure that the silver paste 4 is dried so that the Cu foil is more firmly adhered to the SiC sheet;
C. placing the bonded SiC piece adhered with the AAO/Cu foil on a laser heating table in a growth cavity of a pulse laser deposition system, and vacuumizing the background in the cavity to 5 × 10-7Torr below, the temperature of Cu foil is set at 400 deg.C, the heating rate is 20 deg.C/min, the laser energy is 300mJ, the frequency is 10Hz, and the flowing oxygen partial pressure is 3 × 10-6Torr, turn on the laser to bombard Fe3O4Target material of Fe3O4Deposited on an AAO/Cu foil;
D. the deposition time of the step C is 60min, and highly ordered Fe is prepared3O4And (4) nano arrays.
(4) After the deposition was completed, the sample was heated at 400 ℃ to 3 × 10-6Placing the mixture for 10min under an oxygen pressure atmosphere of Torr, and then slowly cooling the mixture to room temperature at a cooling speed of 10 ℃/min under the same oxygen partial pressure to obtain a sample.
Lithium ion battery cathode material Fe prepared in specific application example 13O4The nano-array column 3 is taken as an SEM picture, as shown in FIG. 6a, which is the SEM picture before the AAO template is removed from the copper foil in the specific application example 1, and Fe can be clearly seen3O4Deposited in the AAO template pores 21; then using polyimide high-temperature adhesive tapeThe AAO template on the sample was taped off. FIG. 6b is an SEM image of a partially removed AAO template on a copper foil, and FIG. 6c is Fe after removing the AAO template on the copper foil in example 13O4SEM image of the nano-array column 3, it can be clearly seen that Fe is generated during the process of adhering the AAO template by the polyimide high-temperature adhesive tape3O4The nano-array columns 3 are not affected at all and still adhere tightly to the copper foil.
Concrete application example 2
(1) As shown in fig. 2, a Cu foil with a size of 5 × 5mm is cut and subjected to a cleaning pretreatment, which specifically includes the following steps:
a. placing the Cu foil in a beaker filled with acetone, then placing the beaker in an ultrasonic cleaner filled with a certain amount of water, and carrying out ultrasonic cleaning for 10 min;
b. soaking the Cu foil in absolute ethyl alcohol, and ultrasonically cleaning for 10 min;
c. then soaking the Cu foil in deionized water, and ultrasonically cleaning for 10 min;
d. then, drying the Cu foil in a nitrogen atmosphere with the purity of 99.999 percent;
e. and finally, cleaning the surface of the Cu foil for 180s by using a plasma cleaning machine.
(2) The specific steps for preparing the AAO/Cu foil comprise the following steps:
(a) shearing a PMMA/AAO template into a shape and a size which are the same as those of the Cu foil, placing the PMMA/AAO template into a beaker filled with acetone, standing for 5min, and then slowly swaying the PMMA/AAO template in the acetone by using tweezers until the PMMA supporting layer is separated;
(b) aligning and tightly attaching the cleaned and pretreated Cu foil to an AAO template in acetone, and taking out the Cu foil after the clean and pretreated Cu foil is tightly attached to the AAO template, and referring to fig. 3;
(c) and finally, standing and drying the AAO/Cu foil in air.
(3) Preparation of Fe on AAO/Cu foil by pulsed laser deposition system3O4Nano array, KrF (lambda =248nm) excimer laser as the laser, and in the deposition process, the temperature of Cu foil is set to 380 ℃, the heating rate is 20 ℃/min, the laser energy is 300mJ, the frequency is 10Hz, and the flowing oxygen partial pressure is 3×10-6Torr specifically comprises the following steps:
A. mixing Fe3O4The target material is arranged in a pulse laser deposition rotating target position;
B. as shown in fig. 4, the back surface of the AAO/Cu foil obtained in step (2) is attached to a SiC sheet coated with uniform and undried high-temperature silver paste 4, and then the SiC sheet attached with the AAO/Cu foil is placed on a heating table at 120 ℃ and baked for 10min to ensure that the silver paste 4 is dried so that the Cu foil is more firmly adhered to the SiC sheet;
C. placing the bonded SiC piece adhered with the AAO/Cu foil on a laser heating table in a growth cavity of a pulse laser deposition system, and vacuumizing the background in the cavity to 5 × 10-7Below Torr, the temperature of the Cu foil is set at 380 deg.C, the temperature rise rate is 20 deg.C/min, the laser energy is 300mJ, the frequency is 10Hz, and the flowing oxygen partial pressure is 3 × 10-6Torr, turn on the laser to bombard Fe3O4Target material of Fe3O4Deposited on an AAO/Cu foil;
D. the deposition time of the step C is 60min, and highly ordered Fe is prepared3O4And (4) nano arrays.
(4) After deposition, the samples were heated at 380 ℃ to 3 × 10-6Placing the sample under an oxygen pressure atmosphere of Torr for 10min, then slowly cooling to room temperature under the same oxygen partial pressure at a cooling rate of 10 ℃/min, taking out the sample, and then adhering the AAO template on the sample by using a polyimide high-temperature adhesive tape (see figure 5).
Concrete application example 3
(1) As shown in fig. 2, a Cu foil with a size of 5 × 5mm is cut and subjected to a cleaning pretreatment, which specifically includes the following steps:
a. placing the Cu foil in a beaker filled with acetone, then placing the beaker in an ultrasonic cleaner filled with a certain amount of water, and carrying out ultrasonic cleaning for 10 min;
b. soaking the Cu foil in absolute ethyl alcohol, and ultrasonically cleaning for 10 min;
c. then soaking the Cu foil in deionized water, and ultrasonically cleaning for 10 min;
d. then, drying the Cu foil in a nitrogen atmosphere with the purity of 99.999 percent;
e. and finally, cleaning the surface of the Cu foil for 180s by using a plasma cleaning machine.
(2) The specific steps for preparing the AAO/Cu foil comprise the following steps:
(a) shearing a PMMA/AAO template into a shape and a size which are the same as those of the Cu foil, placing the PMMA/AAO template into a beaker filled with acetone, standing for 5min, and then slowly swaying the PMMA/AAO template in the acetone by using tweezers until the PMMA supporting layer is separated;
(b) aligning and tightly attaching the cleaned and pretreated Cu foil to an AAO template in acetone, and taking out the Cu foil after the clean and pretreated Cu foil is tightly attached to the AAO template, and referring to fig. 3;
(c) and finally, standing and drying the AAO/Cu foil in air.
(3) Preparation of Fe on AAO/Cu foil by pulsed laser deposition system3O4Nano array, KrF (lambda =248nm) excimer laser as the laser, and during deposition, the temperature of Cu foil is set at 400 deg.C, the heating rate is 20 deg.C/min, the laser energy is 300mJ, the frequency is 10Hz, and the flowing oxygen partial pressure is 1 × 10-5Torr specifically comprises the following steps:
A. mixing Fe3O4The target material is arranged in a pulse laser deposition rotating target position;
B. as shown in fig. 4, the back surface of the AAO/Cu foil obtained in step (2) is attached to a SiC sheet coated with uniform and undried high-temperature silver paste 4, and then the SiC sheet attached with the AAO/Cu foil is placed on a heating table at 120 ℃ and baked for 10min to ensure that the silver paste 4 is dried so that the Cu foil is more firmly adhered to the SiC sheet;
C. placing the bonded SiC piece adhered with the AAO/Cu foil on a laser heating table in a growth cavity of a pulse laser deposition system, and vacuumizing the background in the cavity to 5 × 10-7Torr below, the temperature of Cu foil is set at 400 deg.C, the heating rate is 20 deg.C/min, the laser energy is 300mJ, the frequency is 10Hz, and the flowing oxygen partial pressure is 1 × 10-5Torr, turn on the laser to bombard Fe3O4Target material of Fe3O4Deposited on an AAO/Cu foil;
D. the deposition time of step C is 60min, and the highly ordered material is preparedFe3O4And (4) nano arrays.
(4) After the deposition was complete, the samples were heated at 400 ℃ and 1 × 10-5Placing the sample under an oxygen pressure atmosphere of Torr for 10min, then slowly cooling to room temperature under the same oxygen partial pressure at a cooling rate of 10 ℃/min, taking out the sample, and then adhering the AAO template on the sample by using a polyimide high-temperature adhesive tape (see figure 5).
Specific application example 4
(1) As shown in fig. 2, a Cu foil with a size of 5 × 5mm is cut and subjected to a cleaning pretreatment, which specifically includes the following steps:
a. placing the Cu foil in a beaker filled with acetone, then placing the beaker in an ultrasonic cleaner filled with a certain amount of water, and carrying out ultrasonic cleaning for 10 min;
b. soaking the Cu foil in absolute ethyl alcohol, and ultrasonically cleaning for 10 min;
c. then soaking the Cu foil in deionized water, and ultrasonically cleaning for 10 min;
d. then, drying the Cu foil in a nitrogen atmosphere with the purity of 99.999 percent;
e. and finally, cleaning the surface of the Cu foil for 180s by using a plasma cleaning machine.
(2) The specific steps for preparing the AAO/Cu foil comprise the following steps:
(a) shearing a PMMA/AAO template into a shape and a size which are the same as those of the Cu foil, placing the PMMA/AAO template into a beaker filled with acetone, standing for 5min, and then slowly swaying the PMMA/AAO template in the acetone by using tweezers until the PMMA supporting layer is separated;
(b) aligning and tightly attaching the cleaned and pretreated Cu foil to an AAO template in acetone, and taking out the Cu foil after the clean and pretreated Cu foil is tightly attached to the AAO template, and referring to fig. 3;
(c) and finally, standing and drying the AAO/Cu foil in air.
(3) Preparation of Fe on AAO/Cu foil by pulsed laser deposition system3O4Nano array, KrF (lambda =248nm) excimer laser as the laser, and during deposition, the temperature of Cu foil is set at 400 deg.C, the heating rate is 20 deg.C/min, the laser energy is 300mJ, the frequency is 10Hz, and the flowing oxygen partial pressure is 3 × 10-6Torr, specifically includingThe method comprises the following steps:
A. mixing Fe3O4The target material is arranged in a pulse laser deposition rotating target position;
B. as shown in fig. 4, the back surface of the AAO/Cu foil obtained in step (2) is attached to a SiC sheet coated with uniform and undried high-temperature silver paste 4, and then the SiC sheet attached with the AAO/Cu foil is placed on a heating table at 120 ℃ and baked for 10min to ensure that the silver paste 4 is dried so that the Cu foil is more firmly adhered to the SiC sheet;
C. placing the bonded SiC piece adhered with the AAO/Cu foil on a laser heating table in a growth cavity of a pulse laser deposition system, and vacuumizing the background in the cavity to 5 × 10-7Torr below, the temperature of Cu foil is set at 400 deg.C, the heating rate is 20 deg.C/min, the laser energy is 300mJ, the frequency is 10Hz, and the flowing oxygen partial pressure is 3 × 10-6Torr, turn on the laser to bombard Fe3O4Target material of Fe3O4Deposited on an AAO/Cu foil;
D. the deposition time of the step C is 30min, and highly ordered Fe is prepared3O4And (4) nano arrays.
(4) After the deposition was completed, the sample was heated at 400 ℃ to 3 × 10-6And (3) placing for 10min under an oxygen pressure atmosphere of Torr, then slowly cooling to room temperature at a cooling speed of 10 ℃/min under the same oxygen partial pressure, taking out the sample, and then adhering the AAO template on the sample by using a polyimide high-temperature adhesive tape.
Concrete application example 5
(1) As shown in fig. 2, a Cu foil with a size of 5 × 5mm is cut and subjected to a cleaning pretreatment, which specifically includes the following steps:
a. placing the Cu foil in a beaker filled with acetone, then placing the beaker in an ultrasonic cleaner filled with a certain amount of water, and carrying out ultrasonic cleaning for 10 min;
b. soaking the Cu foil in absolute ethyl alcohol, and ultrasonically cleaning for 10 min;
c. then soaking the Cu foil in deionized water, and ultrasonically cleaning for 10 min;
d. then, drying the Cu foil in a nitrogen atmosphere with the purity of 99.999 percent;
e. and finally, cleaning the surface of the Cu foil for 180s by using a plasma cleaning machine.
(2) The specific steps for preparing the AAO/Cu foil comprise the following steps:
(a) shearing a PMMA/AAO template into a shape and a size which are the same as those of the Cu foil, placing the PMMA/AAO template into a beaker filled with acetone, standing for 5min, and then slowly swaying the PMMA/AAO template in the acetone by using tweezers until the PMMA supporting layer is separated;
(b) aligning and tightly attaching the cleaned and pretreated Cu foil to an AAO template in acetone, and taking out the Cu foil after the clean and pretreated Cu foil is tightly attached to the AAO template, and referring to fig. 3;
(c) and finally, standing and drying the AAO/Cu foil in air.
(3) Preparation of Fe on AAO/Cu foil by pulsed laser deposition system3O4Nano array, KrF (lambda =248nm) excimer laser as the laser, and during deposition, the temperature of Cu foil is set at 400 deg.C, the heating rate is 20 deg.C/min, the laser energy is 300mJ, the frequency is 10Hz, and the flowing oxygen partial pressure is 3 × 10-6Torr specifically comprises the following steps:
A. mixing Fe3O4The target material is arranged in a pulse laser deposition rotating target position;
B. as shown in fig. 4, the back surface of the AAO/Cu foil obtained in step (2) is attached to a SiC sheet coated with uniform and undried high-temperature silver paste 4, and then the SiC sheet attached with the AAO/Cu foil is placed on a heating table at 120 ℃ and baked for 10min to ensure that the silver paste 4 is dried so that the Cu foil is more firmly adhered to the SiC sheet;
C. placing the bonded SiC piece adhered with the AAO/Cu foil on a laser heating table in a growth cavity of a pulse laser deposition system, and vacuumizing the background in the cavity to 5 × 10-7Torr below, the temperature of Cu foil is set at 400 deg.C, the heating rate is 20 deg.C/min, the laser energy is 300mJ, the frequency is 10Hz, and the flowing oxygen partial pressure is 3 × 10-6Torr, turn on the laser to bombard Fe3O4Target material of Fe3O4Deposited on an AAO/Cu foil;
D. the deposition time of the step C is 90min, and highly ordered Fe is prepared3O4And (4) nano arrays.
(4) After the deposition was completed, the sample was heated at 400 ℃ to 3 × 10-6Placing the sample under an oxygen pressure atmosphere of Torr for 10min, then slowly cooling to room temperature under the same oxygen partial pressure at a cooling rate of 10 ℃/min, taking out the sample, and then adhering the AAO template on the sample by using a polyimide high-temperature adhesive tape (see figure 5).
Concrete application example 6
(1) Cutting the copper foil into Cu foils with the size of 5 multiplied by 5mm, and performing cleaning pretreatment on the Cu foils, wherein the method specifically comprises the following steps:
a. placing the Cu foil in a beaker filled with acetone, then placing the beaker in an ultrasonic cleaner filled with a certain amount of water, and carrying out ultrasonic cleaning for 10 min;
b. soaking the Cu foil in absolute ethyl alcohol, and ultrasonically cleaning for 10 min;
c. then soaking the Cu foil in deionized water, and ultrasonically cleaning for 10 min;
d. then, drying the Cu foil in a nitrogen atmosphere with the purity of 99.999 percent;
e. and finally, cleaning the surface of the Cu foil for 180s by using a plasma cleaning machine.
(2) The specific steps for preparing the AAO/Cu foil comprise the following steps:
(a) shearing a PMMA/AAO template into a shape and a size which are the same as those of the Cu foil, placing the PMMA/AAO template into a beaker filled with acetone, standing for 5min, and then slowly swaying the PMMA/AAO template in the acetone by using tweezers until the PMMA supporting layer is separated;
(b) aligning and tightly attaching the cleaned and pretreated Cu foil to an AAO template in acetone, and taking out the Cu foil after the clean and pretreated Cu foil is tightly attached to the AAO template, and referring to fig. 3;
(c) and finally, standing and drying the AAO/Cu foil in air.
(3) Preparation of Fe on AAO/Cu foil by pulsed laser deposition system3O4Nano array, KrF (lambda =248nm) excimer laser as the laser, and in the deposition process, the temperature of Cu foil is set to 400 ℃, the heating rate is 20 ℃/min, the laser energy is 280mJ, the frequency is 10Hz, and the flowing oxygen partial pressure is 3 × 10-6Torr specifically comprises the following steps:
A. mixing Fe3O4The target material is arranged in a pulse laser deposition rotating target position;
B. as shown in fig. 4, the back surface of the AAO/Cu foil obtained in step (2) is attached to a SiC sheet coated with uniform and undried high-temperature silver paste 4, and then the SiC sheet attached with the AAO/Cu foil is placed on a heating table at 120 ℃ and baked for 10min to ensure that the silver paste 4 is dried so that the Cu foil is more firmly adhered to the SiC sheet;
C. placing the bonded SiC piece adhered with the AAO/Cu foil on a laser heating table in a growth cavity of a pulse laser deposition system, and vacuumizing the background in the cavity to 5 × 10-7Torr below, the temperature of Cu foil is set at 400 deg.C, the heating rate is 20 deg.C/min, the laser energy is 280mJ, the frequency is 10Hz, and the flowing oxygen partial pressure is 3 × 10-6Torr, turn on the laser to bombard Fe3O4Target material of Fe3O4Deposited on an AAO/Cu foil;
D. the deposition time of the step C is 60min, and highly ordered Fe is prepared3O4And (4) nano arrays.
(4) After the deposition was completed, the sample was heated at 400 ℃ to 3 × 10-6Placing the sample under an oxygen pressure atmosphere of Torr for 10min, then slowly cooling to room temperature under the same oxygen partial pressure at a cooling rate of 10 ℃/min, taking out the sample, and then adhering the AAO template on the sample by using a polyimide high-temperature adhesive tape (see figure 5).
Performance testing
Lithium ion battery cathode material Fe prepared in specific application example 13O4The nano-array column 3 is taken as SEM picture, and FIG. 6d is the cathode material Fe of the lithium ion battery3O4SEM image when the average particle size of the nano array column 3 is 90 nm; FIG. 6e shows the negative electrode material Fe of lithium ion battery3O4SEM image when the average particle diameter of the nano array column 3 is 260 nm; FIG. 6f shows the negative electrode material Fe of lithium ion battery3O4SEM image when the average particle size of the nano array column 3 is 350 nm; as is clear from FIGS. 6d-6f, Fe3O4The nano-array columns 3 are very orderly arranged and have uniform size.
Lithium ion battery cathode material Fe prepared in specific application example 13O4The nano-array column 3 is shown in a TEM image, as shown in FIG. 7, and FIGS. 7b-7d respectively show Fe element, O element and Cu element, it can be clearly seen that Fe3O4Fe element and O element in the nano array column 3, and Cu element at the bottom.
FIG. 8 shows the negative electrode material Fe of lithium ion battery prepared in application example 13O4XPS of the column 3, from which Fe can be clearly seen2+And Fe3+Fully proves Fe3O4Is present.
Fig. 9 is a cycle performance diagram of the lithium ion battery negative electrode material prepared in the specific application example 1 after being assembled into a battery, and the cycle performance diagram of a conventional battery (i.e., a battery using a thin film to form the lithium ion battery negative electrode material) is also shown in the diagram, so that it can be clearly seen that the specific capacity of the battery assembled by the lithium ion battery negative electrode material prepared in the specific application example 1 is obviously increased, and the coulombic efficiency is basically kept equal.
The embodiments of the present invention are preferred embodiments of the present invention, and the scope of the present invention is not limited by these embodiments, so: all technical solutions obtained by equivalent substitutions or equivalent transformations of the present invention should be included in the scope of the present invention.

Claims (10)

1. A manufacturing method of a lithium ion battery cathode structure is characterized by comprising the following steps:
providing a current collector plate (1);
attaching a porous nano template (2) on the current collector plate (1);
forming a plurality of nano array columns (3) in the holes (21) of the porous nano template (2) in a pulsed laser deposition mode;
removing the porous nano template (2), and after removal, convexly arraying and fixing the nano array columns (3) on the current collector plate (1), wherein the diameter of the nano array columns (3) is between 90 and 300nm, the height of the nano array columns (3) is between 50 and 400nm, and the distance between the nano array columns (3) is between 65 and 125 nm.
2. The method for manufacturing a negative electrode structure of a lithium ion battery according to claim 1, wherein a height error of the nano-array columns (3) is within 10%.
3. The method for manufacturing the negative electrode structure of the lithium ion battery according to claim 1, wherein the height of the nano-array columns (3) is smaller than the depth of the holes (21) in the porous nano-template (2).
4. The method of claim 1, wherein the background vacuum in the growth chamber is evacuated to 5 × 10 degrees before the pulsed laser deposition-7TorrAnd maintaining a flowing oxygen partial pressure of less than 5 × 10 during the deposition process-5Torr。
5. The method for manufacturing the negative electrode structure of the lithium ion battery according to claim 4, wherein the porous nano template (2) is attached to the current collector plate (1), and the current collector plate (1) is heated before the pulsed laser deposition, and the temperature rise rate is controlled to be 10-30 ℃/min.
6. The method for manufacturing the negative electrode structure of the lithium ion battery according to any one of claims 1 to 5, wherein the current collector plate (1) is a copper foil, and the nano-array columns (3) are Fe3O4A nano-array column (3); before the pulse laser deposition, the copper foil is heated to the temperature of 300-500 ℃, the laser energy is 250-350mJ, and the laser frequency is 5-10 Hz.
7. The method for manufacturing the negative electrode structure of the lithium ion battery as claimed in claim 6, wherein the copper foil is bonded to the heat conducting sheet (5) by silver paste (4) before the pulsed laser deposition, and then the deposition is performed.
8. The method for manufacturing the negative electrode structure of the lithium ion battery according to claim 6, wherein in the step of attaching the porous nano template (2) to the current collector plate (1), the porous nano template (2) is a PMMA/AAO template, the PMMA/AAO template is soaked in an organic solvent to separate a PMMA support layer, and then the AAO template is attached to the Cu foil.
9. A kind of lithium ion battery negative pole structure, characterized by, including:
a collector plate (1);
a plurality of nano-array columns (3);
wherein the nanometer array columns (3) are convexly arrayed and fixed on the current collector plate (1), the diameter of the nanometer array columns (3) is between 90 and 300nm, the projection height of the nanometer array columns (3) is between 50 and 400nm, and the distance between the nanometer array columns (3) is between 65 and 125 nm.
10. The negative electrode structure of the lithium ion battery according to claim 9, wherein the height error of the nano array columns (3) is within 10%.
CN201911000230.7A 2019-10-21 2019-10-21 Manufacturing method of lithium ion battery cathode structure and lithium ion battery cathode structure Pending CN111740078A (en)

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CN106531989A (en) * 2016-11-01 2017-03-22 武汉理工大学 Ferroferric oxide@titanium dioxide nanorod array electrode on titanium substrate and preparation method of ferroferric oxide@titanium dioxide nanorod array electrode
CN108546919A (en) * 2018-03-28 2018-09-18 湘潭大学 A method of preparing independent dispersion cobalt ferrite nano-pillar using pulsed laser deposition
CN108598365A (en) * 2018-05-25 2018-09-28 哈尔滨工业大学 A kind of negative electrode for lithium secondary battery and preparation method thereof and its lithium secondary battery
CN108987724A (en) * 2018-08-16 2018-12-11 浙江衡远新能源科技有限公司 A kind of hollow Si/C composite negative pole material of lithium ion battery and preparation method thereof
CN109244435A (en) * 2018-11-19 2019-01-18 肇庆市华师大光电产业研究院 A kind of lithium sulfur battery anode material, preparation method and application

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Application publication date: 20201002