CN114023973A - Porous aluminum current collector and preparation method and application thereof - Google Patents

Porous aluminum current collector and preparation method and application thereof Download PDF

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CN114023973A
CN114023973A CN202111299405.6A CN202111299405A CN114023973A CN 114023973 A CN114023973 A CN 114023973A CN 202111299405 A CN202111299405 A CN 202111299405A CN 114023973 A CN114023973 A CN 114023973A
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current collector
aluminum foil
acid
porous aluminum
positive electrode
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CN114023973B (en
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冯金奎
张煜婵
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Shandong 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/30—Acidic compositions for etching other metallic material
    • 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
    • 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
    • H01M10/058—Construction or manufacture
    • 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
    • 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
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/80—Porous plates, e.g. sintered carriers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

The invention discloses a porous aluminum current collector and a preparation method and application thereof. The preparation method of the porous aluminum current collector is green and mild, and has a controllable structure; the etching solution is obtained by the combined action of any one of organic acid including formic acid, acetic acid, citric acid, oxalic acid, malic acid and salicylic acid and aluminum sulfate. The prepared porous aluminum current collector is used for three-dimensional all-solid-state lithium batteries, particularly lithium-sulfur batteries, and has the advantages of good cyclicity, high energy density, high safety and the like.

Description

Porous aluminum current collector and preparation method and application thereof
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a porous aluminum current collector and a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
For decades, Lithium Ion Batteries (LiBs) have been developed towards high energy density and high safety. However, there are still many drawbacks that hinder further development in order to realize a high energy density all solid-state lithium battery. For example, the positive electrode material needs to be coated on an aluminum foil current collector, but the realization of high energy density is influenced by the large mass of the positive electrode material; on the other hand, the positive electrode active material has poor conductivity, and a higher rate cannot be achieved with a general current collector. In addition, the safety problem is also large due to the high energy density to be achieved. It is considered to be an effective method to improve energy density by lightening the quality of the positive electrode by preparing a porous current collector, and to enhance rate performance by realizing a three-dimensional positive electrode. However, preparing porous aluminum foil current collectors by a green and mild process remains a significant challenge.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides a porous aluminum current collector for a three-dimensional all-solid-state lithium battery, and a preparation method and application thereof. The preparation method of the porous aluminum current collector is green and mild, the etching strength is easy to control, and the structure of the current collector is controllable; the prepared porous aluminum current collector has high energy density, and improves the safety and the electrochemical performance of the all-solid-state battery under the synergistic action of the porous aluminum current collector, the positive electrode material and the solid electrolyte.
In order to solve the technical problems, the invention provides the following technical scheme:
in a first aspect, the present invention provides a method for preparing a porous aluminum current collector, specifically comprising: adding a certain amount of organic acid into distilled water, and uniformly stirring to obtain an organic acid solution; mixing Al2(SO4)3Adding the powder into the organic acid solution, and uniformly stirring to obtain a mixed solution; and adding the cleaned aluminum foil into the prepared mixed solution, and heating and etching.
Preferably, the organic acid comprises one or more of citric acid, formic acid, acetic acid, oxalic acid, malic acid and salicylic acid;
preferably, the concentration of the organic acid in the organic acid solution is 1mol/L-3 mol/L;
preferably, the solution is mixedAl in liquid2(SO4)3The concentration of (A) is 0.1-0.3 mol/L;
preferably, the solution for cleaning the aluminum foil is alcohol, and the concentration of Na is low2CO3，NaHCO3One of (1);
preferably, the thickness of the aluminum foil is 10-20 μm;
preferably, the etching time is 2-24 h;
preferably, the etching temperature is 40-100 ℃.
The method is different from the problems of strong corrosivity of inorganic acid, rapid and uncontrollable reaction and environmental pollution, and has the advantages of milder reaction between the organic acid and aluminum sulfate, no toxicity, harmlessness, greenness, safety and the like, and can etch the current collector more effectively, simply and safely. The etched current collector effectively improves the electrochemical performance, realizes higher multiplying power, and improves the service life and the safety of the battery.
In a second aspect, the present invention provides a positive electrode material for an all-solid-state lithium battery, including a porous aluminum current collector, a positive electrode active material, a binder, and a conductive agent.
Preferably, the positive electrode active material is S, LiMn2O4、LiCoO2、LiNi0.8Co0.1Mn0.1O2、LiNi1/3Co1/3Mn1/ 3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.5Mn1.5O4、LiFePO4One kind of (1).
Wherein the binder is PVDF dissolved in NMP solvent, and the mass percentage concentration of the PVDF is 3 percent.
Wherein the conductive agent is one of Super-p, acetylene black and Ketjen black.
In a third aspect, the invention provides a preparation method of the porous aluminum current collector for a three-dimensional all-solid-state lithium battery positive electrode material, which comprises the following steps:
the aluminum foil is subjected to green mild etching by organic acid to obtain a porous aluminum current collector;
passing a positive electrode active material, a binder and a conductive agent through a reaction vessel (8): 1:1 to obtain anode slurry;
and uniformly coating the mixed anode slurry on the porous aluminum current collector, and then putting the porous aluminum current collector into a vacuum oven for drying.
In a fourth aspect, the present invention provides a three-dimensional all-solid-state lithium battery, wherein the positive electrode material is a porous aluminum current collector coated with a positive electrode active material, and the solid electrolyte is any one of a polymer solid electrolyte, a ceramic electrolyte or a composite solid electrolyte.
In a fifth aspect, the invention provides the porous aluminum current collector, the three-dimensional all-solid-state lithium battery anode material and the application of the three-dimensional all-solid-state lithium battery in automobiles and electric vehicles.
Compared with the prior art, one or more technical schemes of the invention have the following beneficial effects:
(1) the porous aluminum foil current collector prepared by the invention does not cause pollution to the environment through a mild and green method, has no danger in the reaction process, and is easy to control the etching strength by adjusting the process conditions such as etching temperature, etching time and the like, so that the obtained current collector structure has controllability.
(2) The porous aluminum current collector prepared by the invention is used for forming a three-dimensional battery by using the anode material, and the high-rate performance of the aluminum foil is enhanced while the mass of the aluminum foil is reduced to improve the energy density of the whole anode. Compared with the aluminum foil which is not etched, under a large multiplying power, after the battery prepared by the invention is cycled for 100 weeks, the specific discharge capacity of 503mAh/g is still obtained, and the capacity of 282mAh/g is remained in the comparative example battery.
(3) The solid electrolyte prepared by the method has good mechanical strength, effectively improves the safety performance of the battery and prolongs the service life of the battery.
(4) The three-dimensional all-solid-state lithium battery prepared by the invention has the advantages of good cyclicity, high energy density, high safety and the like.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a scanning electron microscope photograph of a blank sample in a comparative example of the present invention;
FIG. 2 is a scanning electron microscope picture of a porous aluminum foil sample obtained by etching with citric acid for 4 hours;
FIG. 3 is a scanning electron microscope picture of a porous aluminum foil sample obtained by etching for 6 hours with citric acid;
FIG. 4 is a scanning electron microscope picture of a porous aluminum foil sample obtained by citric acid etching for 8 hours;
FIG. 5 is a scanning electron microscope image of a porous aluminum foil sample obtained by oxalic acid etching for 3 hours;
FIG. 6 is a scanning electron microscope image of a porous aluminum foil sample obtained by oxalic acid etching for 4 hours;
fig. 7 is a cycle test chart of the porous aluminum foil prepared in example 4 of the present invention used in a three-dimensional all-solid-state lithium sulfur battery.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In a first aspect, the invention provides a preparation method of a green and mild three-dimensional porous aluminum foil current collector, which comprises the following steps: adding a certain amount of organic acid into distilled water and uniformly stirring; mixing Al2(SO4)3Adding the powder into the organic acid solution and uniformly stirring; and adding the cleaned aluminum foil into the prepared solution, and heating and etching.
In some embodiments, the organic acid comprises one or more of citric acid, formic acid, acetic acid, oxalic acid, malic acid, salicylic acid;
in some embodiments, the concentration of the organic acid in the organic acid solution is from 1mol/L to 3 mol/L;
in some embodiments, Al in the mixed solution2(SO4)3The concentration of (A) is 0.1-0.3 mol/L;
in some embodiments, the solution for cleaning the aluminum foil is alcohol, low concentration Na2CO3，NaHCO3One of (1);
in some embodiments, the aluminum foil is 10-20 μm thick;
in a second aspect, the present invention provides a porous current collector implementing a three-dimensional positive electrode material, including a positive electrode active material, a porous current collector, a binder and a conductive agent;
in some embodiments, the positive active material includes S, LiMn2O4、LiCoO2、LiNi0.8Co0.1Mn0.1O2、LiNi1/3Co1/3Mn1/3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.5Mn1.5O4、LiFePO4；
In some embodiments, the PVDF dissolved in the NMP solvent is at a concentration of 3% by weight;
in some embodiments, the conductive carbon black is one of Super-p, acetylene black, ketjen black;
in some embodiments, the positive active material is present in an amount of 8:1:1 with the binder and carbon black.
In some embodiments, the coating thickness of the positive electrode material on the porous aluminum foil is 50-400 μm.
In some embodiments, the temperature of the heating of the anode placed in the vacuum oven is 70-90 ℃.
In a fourth aspect, the present invention provides an all solid-state lithium battery, wherein the positive electrode material is a three-dimensional positive electrode formed by a porous current collector.
In some embodiments, the battery further comprises a solid state electrolyte and a metallic lithium negative electrode.
Further, the solid electrolyte includes: any one of a polymer solid electrolyte, a ceramic electrolyte or a composite solid electrolyte.
Further, the lithium metal negative electrode is any one of lithium foil, lithium sheet, lithium block, lithium powder, lithium ribbon and lithium alloy.
In a fifth aspect, the invention provides application of the porous aluminum current collector prepared by the green mild method in three-dimensional all-solid-state lithium batteries in automobiles and electric vehicles.
The invention is further described with reference to the following figures and detailed description.
In a specific embodiment of the invention, application of the positive pole piece is provided. Wherein the preparation method comprises the steps of mixing conductive carbon black with simple substance S8Melting sulfur at 155 ℃ according to the ratio of 3:7 to obtain a positive electrode material; then the mixture is mixed with a binder and a conductive agent, and the mixture is passed through a reactor 8:1:1, uniformly coating the mixed anode slurry on the prepared porous aluminum current collector, and then putting the porous aluminum current collector into a vacuum oven to be dried for 24 hours at the temperature of 80 ℃.
In a specific embodiment of the present invention, a PEO solid electrolyte is provided, wherein the PEO solid electrolyte is prepared by a method comprising: dissolving PEO in anhydrous acetonitrile, and adding LiTFSI salt, wherein the mass fraction of lithium salt is 10-30%. And after uniformly stirring, soaking the cut PE lithium battery diaphragm with the diameter of 16mm in the prepared slurry, taking out and drying to obtain the PEO solid electrolyte.
Example 1
Soaking an aluminum foil in alcohol to remove oil stain on the surface. Adding a certain amount of citric acid into distilled water, mixing uniformly, adding a certain amount of Al2(SO4)3And stirring uniformly again. And (3) heating the mixed solution in a water bath kettle at 80 ℃, then putting the cleaned aluminum foil into the prepared solution for etching for 2 hours, taking out, cleaning with distilled water, and drying. And coating the positive electrode material on the porous aluminum current collector to prepare the positive electrode piece.
And stacking and assembling the synthesized positive pole piece, the metal lithium piece, the PEO solid electrolyte and the positive and negative electrode shell layers of the battery, and then sealing the opening to assemble the 2032 type button battery.
Example 2
Soaking an aluminum foil in alcohol to remove oil stain on the surface. Adding a certain amount of citric acid into distilled water, mixing uniformly, adding a certain amount of Al2(SO4)3And stirring uniformly again. And (3) heating the mixed solution in a water bath kettle at 80 ℃, then putting the cleaned aluminum foil into the prepared solution, etching for 4 hours, taking out, cleaning with distilled water, and drying. And coating the positive electrode material on the current collector to prepare the positive electrode piece.
And stacking and assembling the synthesized positive pole piece, the metal lithium piece, the PEO solid electrolyte and the positive and negative electrode shell layers of the battery, and then sealing the opening to assemble the 2032 type button battery.
Fig. 2 shows a scanning electron microscope picture of a porous aluminum foil obtained by etching for 4 hours with citric acid, wherein the picture has more abundant and uniform pores, which can be clearly contrasted with the blank aluminum foil in fig. 1.
Example 3
Soaking an aluminum foil in alcohol to remove oil stain on the surface. Adding a certain amount of citric acid into distilled water, mixing uniformly, adding a certain amount of Al2(SO4)3And stirring uniformly again. And (3) heating the mixed solution in a water bath kettle at 80 ℃, then putting the cleaned aluminum foil into the prepared solution, etching for 6 hours, taking out, cleaning with distilled water, and drying. And coating the positive electrode material on the current collector to prepare the positive electrode piece.
And stacking and assembling the synthesized positive pole piece, the metal lithium piece, the PEO solid electrolyte and the positive and negative electrode shell layers of the battery, and then sealing the opening to assemble the 2032 type button battery.
Fig. 3 shows a scanning electron microscope picture of a porous aluminum foil obtained by citric acid etching for 6 hours, wherein the picture has very abundant and uniform pores, which can be contrasted with the blank aluminum foil in fig. 1.
Example 4
Soaking an aluminum foil in alcohol to remove oil stain on the surface. Will be fixedAdding a certain amount of citric acid into distilled water, uniformly mixing, and adding a certain amount of Al2(SO4)3And stirring uniformly again. And (3) heating the mixed solution in a water bath kettle at 80 ℃, then putting the cleaned aluminum foil into the prepared solution, etching for 8 hours, taking out, cleaning with distilled water, and drying. And coating the positive electrode material on the current collector to prepare the positive electrode piece.
And stacking and assembling the synthesized positive pole piece, the metal lithium piece, the PEO solid electrolyte and the positive and negative electrode shell layers of the battery, and then sealing the opening to assemble the 2032 type button battery.
Fig. 4 shows a scanning electron microscope picture of a porous aluminum foil obtained by citric acid etching for 8 hours, wherein the picture has very abundant and more uniform pores, which can be contrasted with the blank aluminum foil in fig. 1.
Fig. 7 shows the cycling performance test of the prepared porous aluminum foil etched for 8 hours in the all-solid-state lithium-sulfur battery, and compared with the cycling performance of a 2032 type button cell composed of aluminum foil not etched in the comparative example at a large rate. It is clear from the figure that the initial specific discharge capacities of both batteries are about 860mAh/g, however, after 100 cycles, the residual specific discharge capacities of both batteries are greatly different, and the battery etched for 8 hours still has a specific discharge capacity of 503mAh/g, while the battery in the comparative column has a capacity of only 282 mAh/g.
Example 5
Soaking an aluminum foil in alcohol to remove oil stain on the surface. Adding a certain amount of citric acid into distilled water, mixing uniformly, adding a certain amount of Al2(SO4)3And stirring uniformly again. And (3) heating the mixed solution in a water bath kettle at 80 ℃, then putting the cleaned aluminum foil into the prepared solution for etching for 10 hours, taking out, cleaning with distilled water, and drying. And coating the positive electrode material on the current collector to prepare the positive electrode piece.
And stacking and assembling the synthesized positive pole piece, the metal lithium piece, the PEO solid electrolyte and the positive and negative electrode shell layers of the battery, and then sealing the opening to assemble the 2032 type button battery.
Example 6
Soaking an aluminum foil in alcohol to remove oil stain on the surface. Adding a certain amount of citric acid into distilled water, mixing uniformly, adding a certain amount of Al2(SO4)3And stirring uniformly again. And (3) heating the mixed solution in a water bath kettle at 80 ℃, then putting the cleaned aluminum foil into the prepared solution, etching for 12 hours, taking out, cleaning with distilled water, and drying. And coating the positive electrode material on the current collector to prepare the positive electrode piece.
And stacking and assembling the synthesized positive pole piece, the metal lithium piece, the PEO solid electrolyte and the positive and negative electrode shell layers of the battery, and then sealing the opening to assemble the 2032 type button battery.
Example 7
Soaking an aluminum foil in alcohol to remove oil stain on the surface. Adding a certain amount of citric acid into distilled water, mixing uniformly, adding a certain amount of Al2(SO4)3And stirring uniformly again. And (3) heating the mixed solution in a water bath kettle at 80 ℃, then putting the cleaned aluminum foil into the prepared solution, etching for 14 hours, taking out, cleaning with distilled water, and drying. And coating the positive electrode material on the current collector to prepare the positive electrode piece.
And stacking and assembling the synthesized positive pole piece, the metal lithium piece, the PEO solid electrolyte and the positive and negative electrode shell layers of the battery, and then sealing the opening to assemble the 2032 type button battery.
Example 8
Soaking an aluminum foil in alcohol to remove oil stain on the surface. Adding a certain amount of citric acid into distilled water, mixing uniformly, adding a certain amount of Al2(SO4)3And stirring uniformly again. And (3) heating the mixed solution in a water bath kettle at 80 ℃, then putting the cleaned aluminum foil into the prepared solution, etching for 16 hours, taking out, cleaning with distilled water, and drying. And coating the positive electrode material on the current collector to prepare the positive electrode piece.
And stacking and assembling the synthesized positive pole piece, the metal lithium piece, the PEO solid electrolyte and the positive and negative electrode shell layers of the battery, and then sealing the opening to assemble the 2032 type button battery.
Example 9
Soaking an aluminum foil in alcohol to remove oil stain on the surface. Adding a certain amount of acetic acid into distilled water, uniformly mixing, adding a certain amount of Al2(SO4)3And stirring uniformly again. And (3) heating the mixed solution in a water bath kettle at 80 ℃, then putting the cleaned aluminum foil into the prepared solution, etching for 1h, taking out, cleaning with distilled water, and drying. And coating the positive electrode material on the current collector to prepare the positive electrode piece.
And stacking and assembling the synthesized positive pole piece, the metal lithium piece, the PEO solid electrolyte and the positive and negative electrode shell layers of the battery, and then sealing the opening to assemble the 2032 type button battery.
Example 10
Soaking an aluminum foil in alcohol to remove oil stain on the surface. Adding a certain amount of acetic acid into distilled water, uniformly mixing, adding a certain amount of Al2(SO4)3And stirring uniformly again. And (3) heating the mixed solution in a water bath kettle at 80 ℃, then putting the cleaned aluminum foil into the prepared solution for etching for 2 hours, taking out, cleaning with distilled water, and drying. And coating the positive electrode material on the current collector to prepare the positive electrode piece.
And stacking and assembling the synthesized positive pole piece, the metal lithium piece, the PEO solid electrolyte and the positive and negative electrode shell layers of the battery, and then sealing the opening to assemble the 2032 type button battery.
Example 11
Soaking an aluminum foil in alcohol to remove oil stain on the surface. Adding a certain amount of acetic acid into distilled water, uniformly mixing, adding a certain amount of Al2(SO4)3And stirring uniformly again. And (3) heating the mixed solution in a water bath kettle at 80 ℃, then putting the cleaned aluminum foil into the prepared solution, etching for 3 hours, taking out, cleaning with distilled water, and drying. And coating the positive electrode material on the current collector to prepare the positive electrode piece.
And stacking and assembling the synthesized positive pole piece, the metal lithium piece, the PEO solid electrolyte and the positive and negative electrode shell layers of the battery, and then sealing the opening to assemble the 2032 type button battery.
Example 12
Soaking an aluminum foil in alcohol to remove oil stain on the surface. Adding a certain amount of acetic acid into distilled water, uniformly mixing, adding a certain amount of Al2(SO4)3And stirring uniformly again. And (3) heating the mixed solution in a water bath kettle at 40 ℃, then putting the cleaned aluminum foil into the prepared solution, etching for 4 hours, taking out, cleaning with distilled water, and drying. And coating the positive electrode material on the current collector to prepare the positive electrode piece.
And stacking and assembling the synthesized positive pole piece, the metal lithium piece, the PEO solid electrolyte and the positive and negative electrode shell layers of the battery, and then sealing the opening to assemble the 2032 type button battery.
Example 13
Soaking an aluminum foil in alcohol to remove oil stain on the surface. Adding a certain amount of oxalic acid into distilled water, uniformly mixing, and adding a certain amount of Al2(SO4)3And stirring uniformly again. And (3) heating the mixed solution in a water bath kettle at 80 ℃, then putting the cleaned aluminum foil into the prepared solution, etching for 1h, taking out, cleaning with distilled water, and drying. And coating the positive electrode material on the current collector to prepare the positive electrode piece.
And stacking and assembling the synthesized positive pole piece, the metal lithium piece, the PEO solid electrolyte and the positive and negative electrode shell layers of the battery, and then sealing the opening to assemble the 2032 type button battery.
Example 14
Soaking an aluminum foil in alcohol to remove oil stain on the surface. Adding a certain amount of oxalic acid into distilled water, uniformly mixing, and adding a certain amount of Al2(SO4)3And stirring uniformly again. And (3) heating the mixed solution in a water bath kettle at 100 ℃, then putting the cleaned aluminum foil into the prepared solution for etching for 2 hours, taking out, cleaning with distilled water, and drying. And coating the positive electrode material on the current collector to prepare the positive electrode piece.
And stacking and assembling the synthesized positive pole piece, the metal lithium piece, the PEO solid electrolyte and the positive and negative electrode shell layers of the battery, and then sealing the opening to assemble the 2032 type button battery.
Example 15
Soaking an aluminum foil in alcohol to remove oil stain on the surface. Adding a certain amount of oxalic acid into distilled water, uniformly mixing, and adding a certain amount of Al2(SO4)3And stirring uniformly again. And (3) heating the mixed solution in a water bath kettle at 80 ℃, then putting the cleaned aluminum foil into the prepared solution, etching for 3 hours, taking out, cleaning with distilled water, and drying. And coating the positive electrode material on the current collector to prepare the positive electrode piece.
And stacking and assembling the synthesized positive pole piece, the metal lithium piece, the PEO solid electrolyte and the positive and negative electrode shell layers of the battery, and then sealing the opening to assemble the 2032 type button battery.
Fig. 5 shows a scanning electron microscope image of a porous aluminum foil obtained by 3 hours of oxalic acid etching, wherein holes are clearly shown, which is in sharp contrast to the blank aluminum foil in fig. 1.
Example 16
Soaking an aluminum foil in alcohol to remove oil stain on the surface. Adding a certain amount of oxalic acid into distilled water, uniformly mixing, and adding a certain amount of Al2(SO4)3And stirring uniformly again. And (3) heating the mixed solution in a water bath kettle at 80 ℃, then putting the cleaned aluminum foil into the prepared solution, etching for 4 hours, taking out, cleaning with distilled water, and drying. And coating the positive electrode material on the current collector to prepare the positive electrode piece.
And stacking and assembling the synthesized positive pole piece, the metal lithium piece, the PEO solid electrolyte and the positive and negative electrode shell layers of the battery, and then sealing the opening to assemble the 2032 type button battery.
Fig. 6 shows a scanning electron microscope image of a porous aluminum foil obtained by etching for 4 hours with oxalic acid, wherein the image has abundant and uniform pores, which can be clearly contrasted with the blank aluminum foil in fig. 1.
Comparative example
The sulfur melted at 155 ℃ is evenly mixed with the adhesive and the conductive agent, coated on a blank aluminum foil and dried.
And stacking and assembling the synthesized sulfur anode, the metal lithium sheet, the PEO solid electrolyte and the anode and cathode shells of the battery, and then sealing to assemble the 2032 type button battery.
Figure 1 shows a scanning electron microscope picture of a blank aluminum foil showing that the aluminum foil surface is very smooth without any voids.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The preparation method of the porous aluminum current collector is characterized in that a certain amount of organic acid is added into distilled water and stirred uniformly to obtain an organic acid solution; mixing Al2(SO4)3Adding the powder into the organic acid solution, and uniformly stirring to obtain a mixed solution; and adding the cleaned aluminum foil into the prepared mixed solution, and heating and etching.
2. The preparation method according to claim 1, wherein the organic acid comprises one or more of citric acid, formic acid, acetic acid, oxalic acid, malic acid, and salicylic acid.
3. The method according to claim 1, wherein the concentration of the organic acid in the organic acid solution is 1mol/L to 3mol/L, and Al in the mixed solution2(SO4)3The concentration of (A) is 0.1-0.3 mol/L.
4. The method according to claim 1, wherein the solution for washing the aluminum foil is alcohol and has a low Na concentration2CO3，NaHCO3One kind of (1).
5. The method of claim 1, wherein the aluminum foil has a thickness of 10 to 20 μm.
6. The method according to claim 1, wherein the etching time is 2 to 24 hours and the etching temperature is 40 to 100 ℃.
7. The porous aluminum current collector prepared by the preparation method according to any one of claims 1 to 6.
8. A positive electrode material for a three-dimensional all-solid-state lithium battery, comprising the porous aluminum current collector of claim 7, a positive electrode active material, a binder and a conductive agent; the positive electrode active material was S, LiMn2O4、LiCoO2、LiNi0.8Co0.1Mn0.1O2、LiNi1/3Co1/3Mn1/3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.5Mn1.5O4、LiFePO4One of (1); the binder is PVDF dissolved in NMP solvent, and the mass percentage concentration of the PVDF is 3%; the conductive agent is Super-p, acetylene black or Keqin black; the preparation method comprises the following steps: uniformly mixing the positive active substance with a binder and a conductive agent to obtain positive slurry; and uniformly coating the mixed anode slurry on the porous aluminum current collector, and then putting the porous aluminum current collector into a vacuum oven for drying.
9. A three-dimensional all-solid-state lithium battery, characterized in that the anode material is the anode material of the three-dimensional all-solid-state lithium battery of claim 8, and the solid electrolyte is any one of polymer solid electrolyte, ceramic electrolyte or composite solid electrolyte.
10. Use of the three-dimensional all solid-state lithium battery according to claim 9 in automobiles, electric vehicles.
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