CN113937252B - Laser-assisted positive electrode interface layer construction method - Google Patents

Laser-assisted positive electrode interface layer construction method Download PDF

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CN113937252B
CN113937252B CN202111181827.3A CN202111181827A CN113937252B CN 113937252 B CN113937252 B CN 113937252B CN 202111181827 A CN202111181827 A CN 202111181827A CN 113937252 B CN113937252 B CN 113937252B
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positive electrode
laser
precursor solution
electrode
interface layer
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CN113937252A (en
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马越
汤晓宇
白苗
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Northwestern Polytechnical University
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/352—Working by laser beam, e.g. welding, cutting or boring for surface treatment
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/028—Positive 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 a laser-assisted positive electrode interface layer construction method, which is characterized in that a specific precursor solution is decomposed on the surface of an electrode through pulse laser irradiation and deposited on the surface of the electrode, so that electrolyte decomposition and interface side reaction are inhibited, and the circulation stability is improved. The method is characterized in that the construction of the positive electrode protection layer is realized by inducing the additive in the precursor solution to decompose on the surface of the positive electrode through pulse laser. The pulse laser power is 20-200mJ cm ‑2 The precursor solution is used in an amount corresponding to the electrode area of 20 mu L-1mL cm ‑2 The laser wavelength is 1064cm ‑1 . The locality of laser heating can lead the additive with better thermal stability to be decomposed on the surface of the pole piece without damaging the electrode structure, thereby realizing the protection of the electrode. The construction method for the positive electrode protection layer can be used for mass production, and is simple to operate and low in cost.

Description

Laser-assisted positive electrode interface layer construction method
Technical Field
The invention belongs to the technical field of lithium ion battery preparation, and relates to a laser-assisted positive electrode interface layer construction method.
Background
With the rapid development of electric vehicles, insufficient endurance mileage becomes an important factor for restricting the popularization of pure electric vehicles to the public. The energy density of the power battery is a key point for directly affecting the endurance mileage of the electric automobile. In the current positive electrode material system of the power battery, the use of a high-voltage positive electrode to improve the energy density gradually becomes a development trend of the industry. For example, the upper charge voltage of ternary materials in half cells is typically 4.3V, and some materials charge up to a voltage of even up to 4.5V, which has exceeded the range of applications for conventional formulated electrolytes. Thus, the use of high voltage anodes places higher demands on the oxidation resistance of the electrolyte system.
In order to reduce side reactions between the high-voltage positive electrode and the electrolyte and improve the cycling stability, it is an effective strategy to construct an interface layer between the positive electrode and the electrolyte. For example, lim et al propose that the cycling stability and reversible capacity of the material can be improved and irreversible side reactions reduced by uniformly coating the surface of the high nickel ternary positive electrode particles with an amorphous Li-Zr-O protective layer by liquid phase chemical reaction. (Lim, y.j.et al, electrodischimica Acta 282,311-316 (2018)) but conventional solid or liquid phase coating methods require high temperature heating processes, which are long and energy-intensive.
It has also been considered by researchers that side reactions between the positive electrode and the electrolyte occur not only on the surface of the active material but also on the entire surface of the positive electrode sheet. However, due to the thermal stability of the pole piece, the traditional positive electrode coating method can only be used for active substances and is difficult to apply to the pole piece. The gas phase reaction method, such as atomic layer deposition, can realize uniform coating of the whole electrode surface (Liang, J.et al, nano Energy 78,105107 (2020)) but has high cost, and is not beneficial to large-scale commercial application.
In this regard, we propose a simple laser-induced film formation strategy. The high-energy pulse laser is used for directionally inducing the decomposition of specific precursor components on the surface of the electrode, so that a protective layer can be formed within a few minutes, thereby reducing the oxidation reaction of an electrolyte system under high voltage and improving the energy density and the cycling stability of an energy storage system. The method is simple, convenient and easy to use, wide in application range, adjustable in components and has commercial prospect.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a laser-assisted positive electrode interface layer construction method, which is characterized in that a precursor solution containing an additive is irradiated by pulse laser to decompose the precursor solution on the surface of an electrode to form a protective layer.
The invention aims to provide a method for constructing an anode interface layer, which can effectively improve the cycle performance of a high-voltage battery and inhibit self-discharge phenomenon;
the second purpose of the invention is to provide a construction method of the positive electrode plate interface layer, which is simple to operate, low in cost and easy to realize industrialization.
Technical proposal
A construction method of a laser-assisted positive electrode interface layer is characterized by comprising the following steps:
step 1: preparing a precursor solution, wherein the volume ratio of the additive to the solvent DEC is 2% -30%;
step 2: dropwise adding a precursor solution into the positive electrode plate;
step (a)3: the pulsed laser is adopted to irradiate the pole piece, and the laser power is 20-200mJ cm -2 The frequency is 20-100HZ;
step 4: cleaning the precursor solution remained on the pole piece by using diethyl carbonate DEC;
step 5: and (3) carrying out vacuum drying on the pole piece obtained in the step (4) at 60-120 ℃ to finish construction of an anode interface layer assisted by laser, so that a protective layer is formed on the surface of the electrode.
The additive species include, but are not limited to, tris (trimethylsilyl) phosphate or tris (trimethylsilyl) borate.
The step 2 is to drop the precursor solution into the positive electrode plate with the corresponding electrode area of 20 mu L-1mL cm -2 。
And 3, the irradiation time of the pulse laser irradiation pole piece is 2-10 minutes.
The laser wavelength of the step 3 is 1064cm -1 。
Advantageous effects
According to the laser-assisted positive electrode interface layer construction method, the specific precursor solution is decomposed on the surface of the electrode and deposited on the surface of the electrode through pulse laser irradiation, so that electrolyte decomposition and interface side reaction are inhibited, and the circulation stability is improved. The method is characterized in that the construction of the positive electrode protection layer is realized by inducing the additive in the precursor solution to decompose on the surface of the positive electrode through pulse laser. The pulse laser power is 20-200mJ cm -2 The precursor solution is used in an amount corresponding to the electrode area of 20 mu L-1mL cm -2 The laser wavelength is 1064cm -1 . The locality of laser heating can lead the additive with better thermal stability to be decomposed on the surface of the pole piece without damaging the electrode structure, thereby realizing the protection of the electrode. The construction method for the positive electrode protection layer can be used for mass production, and is simple to operate and low in cost.
The invention has the beneficial effects that:
1. the interface layer construction method provided by the invention has high processing speed. The precursor can be decomposed by the high-energy pulse laser in a few minutes, so that a complex high-temperature heating process is avoided, and the time cost and the energy consumption in the battery production process are reduced;
2. the method can realize coating on the whole electrode surface, and can simultaneously avoid interface side reaction caused by active substances and conductive additives;
3. according to the interfacial layer construction method provided by the invention, the accurate regulation and control of the interfacial protection layer component can be realized by adjusting the precursor component;
4. through contrast optimization, the phosphorus-rich protective layer converted from the tri (trimethylsilane) phosphate can effectively improve the structural stability of the high-voltage positive electrode in the circulating process, inhibit the oxidation of electrolyte and effectively avoid the self-discharge phenomenon of the battery at high temperature. The open circuit voltage of the modified positive electrode was 4.14V after charging to 4.3V and resting at 55 ℃ for 5 days, while the open circuit voltage of the unmodified positive electrode decayed to 4.03V. The capacity retention rate of the half cell 200 circles is improved from 12.8% to 69.5%.
Drawings
FIG. 1 is a flow chart of a method for constructing an interface layer of a positive electrode, which is provided by the embodiment of the invention, a certain amount of precursor solution is dripped on the surface of a prepared electrode slice, and then the electrode slice with a surface covered coating layer can be obtained after short-time high-energy pulse laser irradiation, washing and drying;
FIG. 2 is a graph showing the surface morphology and element distribution test results of the modified positive electrode provided in example 1 of the present invention, illustrating the uniform distribution of the coating layer over the entire electrode surface;
fig. 3 is a transmission electron microscope image of a modified positive electrode and a corresponding element distribution result provided in example 1 of the present invention, which shows that the present invention realizes a nanoscale positive electrode protection layer.
FIG. 4 shows the self-discharge test result of the modified positive electrode provided in example 1 of the present invention, wherein the modified electrode has a better voltage holding capability at high temperature, and the protective layer constructed by the present invention inhibits the oxidation reaction of the electrolyte at high voltage and high temperature;
fig. 5 is a graph of cycle performance of a lithium battery prepared by using the modified positive electrode provided in example 1 of the present invention, where the coulomb efficiency of the modified positive electrode is close to 100% in the positive electrode cycle process, and the specific capacities of charge and discharge are both about 200mAh/g, and the modified positive electrode is attenuated to about 69.5% after 200 charge and discharge cycles.
Detailed Description
The invention will now be further described with reference to examples, figures:
the construction method of the positive electrode interface layer adopted by the invention can effectively improve the cycle performance of the high-voltage battery and inhibit the self-discharge phenomenon; a flow chart is shown in fig. 1.
Example 1
Step 1, preparing a precursor solution, wherein the volume ratio of the tri (trimethylsilane) phosphate to the solvent DEC is 10%;
step 2, dropwise adding 40 mu L cm of precursor solution to the positive electrode plate -2 ；
Step 3, irradiating the pole piece by pulse laser with the laser power of 40mJ cm -2 The frequency is 50HZ, and the irradiation time is 4 minutes;
step 4, cleaning a precursor solution remained on the pole piece by using diethyl carbonate (DEC);
step 5, vacuum drying the pole piece obtained in the step 4 at 60 ℃;
and (3) testing charge and discharge performance:
the positive plate obtained in the embodiment 1 of the invention is assembled into the 2016 button battery in a glove box filled with high-purity argon gas, wherein the concentration of water and oxygen is less than 0.1ppm, and the metal lithium plate is taken as a negative electrode according to the assembly sequence of a negative electrode shell, a lithium plate, an electrolyte, the positive plate, a steel sheet, a spring plate and the positive electrode shell. After 12 hours of standing, in constant current mode, the battery had a charge limiting voltage of 4.3V and a discharge termination voltage of 3V. The charge current was 0.2C for the charge-discharge performance test. The test results are shown in fig. 4, and it can be seen that: the coulomb efficiency of the modified anode is close to 100% in the positive electrode circulation process, the specific capacities of charge and discharge are about 200mAh/g, and the specific capacities are attenuated to about 69.5% after 200 charge and discharge cycles.
High temperature self-discharge performance test:
the button cell assembled according to the steps is placed in an incubator at 55 ℃, charged and discharged three times with a constant current of 0.1C, then charged to 4.3V with 0.1C, the cell channel is set to be in a resting state, and the change of the open-circuit voltage is detected. It can be seen that the modified positive electrode has no obvious drop in voltage after 5 days, and exhibits good self-discharge inhibition capability.
Therefore, the lithium battery with the modified positive electrode prepared by the technical scheme of the invention has the advantages of high capacity, good cycle stability, small self-discharge and the like in the electrical property.
Example 2
Step 1, preparing a precursor solution, wherein the volume ratio of the tri (trimethylsilane) phosphate to the solvent DEC is 20%;
step 2, dropwise adding 1mL cm of precursor solution to the positive electrode plate -2 ；
Step 3, irradiating the pole piece by pulse laser with the laser power of 50mJ cm -2 The frequency is 60HZ, and the irradiation time is 10 minutes;
step 4, cleaning a precursor solution remained on the pole piece by using diethyl carbonate (DEC);
step 5, vacuum drying the pole piece obtained in the step 4 at 70 ℃;
example 3
Step 1, preparing a precursor solution, wherein the volume ratio of the tri (trimethylsilane) borate to the solvent DEC is 2%;
step 2, dropwise adding 20 mu L cm of precursor solution to the positive electrode plate -2 ；
Step 3, irradiating the pole piece by pulse laser with the laser power of 200mJ cm -2 The frequency is 20HZ, and the irradiation time is 2 minutes;
step 4, cleaning a precursor solution remained on the pole piece by using diethyl carbonate (DEC);
step 5, vacuum drying the pole piece obtained in the step 4 at 120 ℃;
example 4
Step 1, preparing a precursor solution, wherein the volume ratio of the tri (trimethylsilane) phosphate to the solvent DEC is 30%;
step 2, dropwise adding 20 mu L-1mL cm of precursor solution to the positive electrode plate -2 ；
Step 3, irradiating the pole piece by pulse laser with the laser power of 20mJ cm -2 The frequency is 100HZ, and the irradiation time is 10 minutes;
step 4, cleaning a precursor solution remained on the pole piece by using diethyl carbonate (DEC);
step 5, vacuum drying the pole piece obtained in the step 4 at 70 ℃;
example 5
Step 1, preparing a precursor solution, wherein the volume ratio of the tri (trimethylsilane) borate to the solvent DEC is 10%;
step 2, dropwise adding 200 mu L cm of precursor solution to the positive electrode plate -2 ；
Step 3, irradiating the pole piece by pulse laser with the laser power of 60mJ cm -2 The frequency is 50HZ, and the irradiation time is 7 minutes;
step 4, cleaning a precursor solution remained on the pole piece by using diethyl carbonate (DEC);
step 5, vacuum drying the pole piece obtained in the step 4 at 120 ℃;
the interface layer structure method provided by the invention is characterized in that the whole electrode surface is coated with the interface layer with adjustable component structure, so that the structural stability of the high-voltage positive electrode in the circulating process is effectively improved, the oxidation of electrolyte is inhibited, and the self-discharge phenomenon of the battery at high temperature is effectively avoided.

Claims (3)

1. A construction method of a laser-assisted positive electrode interface layer is characterized by comprising the following steps:
step 1: preparing a precursor solution, wherein the volume ratio of the additive to the solvent DEC is 2% -30%; the additive is tri (trimethylsilyl) phosphate or tri (trimethylsilyl) borate;
step 2: dropwise adding a precursor solution into the positive electrode plate;
step 3: the pulsed laser is adopted to irradiate the pole piece, and the laser power is 20-200mJ cm -2 The frequency is 20-100HZ, and the irradiation time is 2-10 minutes, so that the precursor is decomposed;
step 4: cleaning the precursor solution remained on the pole piece by using diethyl carbonate DEC;
step 5: and (3) carrying out vacuum drying on the pole piece obtained in the step (4) at 60-120 ℃ to finish construction of an anode interface layer assisted by laser, so that a protective layer is formed on the surface of the electrode.
2. The method for constructing a laser-assisted positive electrode interface layer according to claim 1, wherein: the step 2 is to dropwise add the precursor solution to the positive electrode plate, wherein the area of the electrode corresponding to the dosage of the precursor solution is 20 mu L-1mL cm -2 。
3. The method for constructing a laser-assisted positive electrode interface layer according to claim 1, wherein: the laser wavelength of the step 3 is 1064nm.
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