CN114023973B - 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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Publication number
CN114023973B
CN114023973B CN202111299405.6A CN202111299405A CN114023973B CN 114023973 B CN114023973 B CN 114023973B CN 202111299405 A CN202111299405 A CN 202111299405A CN 114023973 B CN114023973 B CN 114023973B
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positive electrode
current collector
aluminum foil
acid
etching
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CN114023973A (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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  • General Chemical & Material Sciences (AREA)
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  • Manufacturing & Machinery (AREA)
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  • Battery Electrode And Active Subsutance (AREA)

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 has the advantages of green color temperature and controllable structure; the organic acid is obtained by etching through the coaction of any one of formic acid, acetic acid, citric acid, oxalic acid, malic acid and salicylic acid and aluminum sulfate. The prepared multi-hollow aluminum current collector is used for three-dimensional all-solid-state lithium batteries, particularly lithium sulfur batteries, and has the advantages of good circularity, 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 disclosure of this background section is only intended to increase the 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 already known to those of ordinary skill in the art.
Lithium Ion Batteries (LiBs) have been evolving towards high energy densities and high safety for decades. However, there are still many drawbacks to achieving high energy density all-solid-state lithium batteries that prevent further development. For example, the positive electrode material needs to be coated on an aluminum foil current collector, however, its larger mass affects the realization of high energy density; on the other hand, the positive electrode active material has poor conductivity, and a higher rate cannot be achieved by a general current collector. In addition, the safety problem is also relatively large, since a higher energy density is to be achieved. The preparation of porous current collectors to reduce the quality of the positive electrode to increase energy density and the realization of a three-dimensional positive electrode to enhance rate capability is considered as an effective method. However, preparing porous aluminum foil current collectors by green and gentle methods 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 the safety and electrochemical performance of the all-solid-state battery are improved by the synergistic effect of the porous aluminum current collector and 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; al is added with 2 (SO 4 ) 3 Adding the powder into the organic acid solution, and uniformly stirring to obtain a mixed solution; 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-3mol/L;
preferably, al is in the mixed solution 2 (SO 4 ) 3 The concentration of (2) is 0.1-0.3mol/L;
preferably, the solution for cleaning the aluminum foil is alcohol, and the concentration of Na is low 2 CO 3 ，NaHCO 3 One of the following;
preferably, the thickness of the aluminum foil is 10-20 μm;
preferably, the etching time is 2-24 hours;
preferably, the etching temperature is 40-100 ℃.
Unlike inorganic acid, which has strong corrosiveness, rapid and uncontrollable reaction and environmental pollution, the organic acid and aluminum sulfate react more gently, and the method has the advantages of no toxicity, no harm, green and safety, and the like, and can etch the current collector more effectively, simply and safely. The current collector obtained by etching effectively improves electrochemical performance, realizes higher multiplying power, and improves service life and safety of the battery.
In a second aspect, the present invention provides a positive electrode material for an all-solid lithium battery, comprising a porous aluminum current collector, a positive electrode active material, a binder, and a conductive agent.
Preferably, the positive electrode active material is S, liMn 2 O 4 、LiCoO 2 、LiNi 0.8 Co 0.1 Mn 0.1 O 2 、LiNi 1/3 Co 1/3 Mn 1/ 3 O 2 、LiNi 0.6 Co 0.2 Mn 0.2 O 2 、LiNi 0.5 Mn 1.5 O 4 、LiFePO 4 One of them.
Wherein the binder is PVDF dissolved in NMP solvent, and the mass percentage concentration is 3%.
Wherein the conductive agent is one of Super-p, acetylene black and ketjen black.
In a third aspect, the invention provides a method for preparing a three-dimensional all-solid-state lithium battery anode material by using the porous aluminum current collector, which comprises the following steps:
the aluminum foil is subjected to green and gentle etching by organic acid to obtain a porous aluminum current collector;
positive electrode active material, binder and conductive agent were passed through 8:1:1, uniformly mixing the materials in proportion to obtain anode slurry;
and uniformly coating the mixed positive electrode 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 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 polymer solid electrolyte, ceramic electrolyte or composite solid electrolyte.
In a fifth aspect, the invention provides the porous aluminum current collector, a three-dimensional all-solid-state lithium battery anode material and application of the three-dimensional all-solid-state lithium battery in automobiles and electric vehicles.
Compared with the prior art, the above technical scheme of the invention has the following beneficial effects:
(1) The porous aluminum foil current collector prepared by the method is mild and green, does not pollute the environment, has no danger in the reaction process, and is easy to control the etching strength by adjusting the process conditions such as the etching temperature, the etching time and the like, so that the obtained current collector structure has controllability.
(2) The porous aluminum current collector prepared by the method is used for forming a three-dimensional structure battery from the positive electrode material, and enhances the high-rate performance of the aluminum foil while reducing the quality of the aluminum foil to improve the energy density of the whole positive electrode. Compared with the aluminum foil which is not etched, the battery prepared by the invention still has a specific discharge capacity of 503mAh/g after being cycled for 100 weeks under a high multiplying power, and the comparative battery only has a capacity of 282 mAh/g.
(3) The solid electrolyte prepared by the invention has good mechanical strength, and effectively improves the safety performance and the service life of the battery.
(4) The three-dimensional all-solid-state lithium battery prepared by the invention has the advantages of good circularity, high energy density, high safety and the like.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is a scanning electron microscope image 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 citric acid etching for 4 hours;
FIG. 3 is a scanning electron microscope picture of a porous aluminum foil sample obtained by citric acid etching for 6 hours;
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 picture of a porous aluminum foil sample obtained by oxalic acid etching for 3 hours;
FIG. 6 is a scanning electron microscope picture 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 for a three-dimensional all-solid-state lithium sulfur battery.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. 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 present invention. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
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; al is added with 2 (SO 4 ) 3 Adding the powder into the organic acid solution and uniformly stirring; 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 1mol/L to 3mol/L;
in some embodiments, al is in a mixed solution 2 (SO 4 ) 3 The concentration of (2) is 0.1-0.3mol/L;
in some embodiments, the solution for cleaning the aluminum foil is alcohol, low concentration Na 2 CO 3 ，NaHCO 3 One of the following;
in some embodiments, the aluminum foil has a thickness of 10-20 μm;
in a second aspect, the present invention provides a porous current collector for realizing a three-dimensional positive electrode material, comprising a positive electrode active material, a porous current collector, a binder and a conductive agent;
in some embodiments, the positive electrode active material includes S, liMn 2 O 4 、LiCoO 2 、LiNi 0.8 Co 0.1 Mn 0.1 O 2 、LiNi 1/3 Co 1/3 Mn 1/3 O 2 、LiNi 0.6 Co 0.2 Mn 0.2 O 2 、LiNi 0.5 Mn 1.5 O 4 、LiFePO 4 ；
In some embodiments, the PVDF in NMP solvent has a mass percent concentration of 3%;
in some embodiments, the conductive carbon black is one of Super-p, acetylene black, ketjen black;
in some embodiments, the content of the positive electrode active material to the binder and carbon black is 8:1:1.
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 at which the positive electrode is placed in a vacuum oven is heated from 70 to 90 ℃.
In a fourth aspect, the invention provides an all-solid-state lithium battery, wherein the positive electrode material of the all-solid-state lithium battery 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 polymer solid electrolyte, ceramic electrolyte or composite solid electrolyte.
Further, the metal lithium negative electrode is any one of a lithium foil, a lithium sheet, a lithium block, lithium powder, a lithium belt and a lithium alloy.
In a fifth aspect, the invention provides application of the porous aluminum current collector prepared by the green color temperature and method in three-dimensional all-solid-state lithium batteries in automobiles and electric vehicles.
The invention will be further described with reference to the drawings and detailed description.
In a specific embodiment of the present invention,the application of the positive pole piece is provided. Wherein the preparation method comprises the steps of adding conductive carbon black and simple substance S 8 Sulfur is melted at 155 ℃ according to the ratio of 3:7, and a positive electrode material is obtained; then it is passed through 8 with binder and conductive agent: 1:1, uniformly coating the mixed positive electrode slurry on a prepared porous aluminum current collector, and then placing the porous aluminum current collector into a vacuum oven to be dried at 80 ℃ for 24 hours.
In a specific embodiment of the present invention, there is provided a PEO solid electrolyte, wherein the PEO solid electrolyte is prepared by: PEO is dissolved in anhydrous acetonitrile, liTFSI salt is added, wherein the mass fraction of the lithium salt is 10% -30%. After being stirred uniformly, the cut PE lithium battery diaphragm with the diameter of 16mm is soaked in the prepared slurry, and the PEO solid electrolyte is obtained after being taken out and dried.
Example 1
Soaking an aluminum foil in alcohol to remove oil stains on the surface. Adding a certain amount of citric acid into distilled water, mixing, adding a certain amount of Al 2 (SO 4 ) 3 Stirring again to be uniform. 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 2 hours, taking out, cleaning with distilled water, and drying. And coating the anode material on the porous aluminum current collector to prepare an anode plate.
And stacking and assembling the synthesized positive electrode plate, the metal lithium plate, the PEO solid electrolyte and the positive and negative electrode shells of the battery, and then sealing to assemble the 2032 button battery.
Example 2
Soaking an aluminum foil in alcohol to remove oil stains on the surface. Adding a certain amount of citric acid into distilled water, mixing, adding a certain amount of Al 2 (SO 4 ) 3 Stirring again to be uniform. 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 a positive electrode plate.
And stacking and assembling the synthesized positive electrode plate, the metal lithium plate, the PEO solid electrolyte and the positive and negative electrode shells of the battery, and then sealing to assemble the 2032 button battery.
Fig. 2 shows a scanning electron microscope picture of a porous aluminum foil obtained by citric acid etching for 4 hours, wherein the picture has relatively rich and uniform pores, which can be in sharp contrast with the blank aluminum foil in fig. 1.
Example 3
Soaking an aluminum foil in alcohol to remove oil stains on the surface. Adding a certain amount of citric acid into distilled water, mixing, adding a certain amount of Al 2 (SO 4 ) 3 Stirring again to be uniform. 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 a positive electrode plate.
And stacking and assembling the synthesized positive electrode plate, the metal lithium plate, the PEO solid electrolyte and the positive and negative electrode shells of the battery, and then sealing to assemble the 2032 button battery.
Fig. 3 shows a scanning electron microscope picture of a porous aluminum foil obtained by citric acid etching for 6 hours, which has very rich and uniform pores, in sharp contrast to the blank aluminum foil in fig. 1.
Example 4
Soaking an aluminum foil in alcohol to remove oil stains on the surface. Adding a certain amount of citric acid into distilled water, mixing, adding a certain amount of Al 2 (SO 4 ) 3 Stirring again to be uniform. 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 a positive electrode plate.
And stacking and assembling the synthesized positive electrode plate, the metal lithium plate, the PEO solid electrolyte and the positive and negative electrode shells of the battery, and then sealing to assemble the 2032 button battery.
Fig. 4 shows a scanning electron microscope picture of a porous aluminum foil obtained by citric acid etching for 8 hours, in which the picture has very rich and more uniform pores, which can be clearly contrasted with the blank aluminum foil in fig. 1.
Fig. 7 shows the cycle performance test of the prepared porous aluminum foil etched for 8 hours in an all-solid lithium sulfur battery, and the cycle performance of a 2032 type coin cell made of aluminum foil not etched in the comparative example was compared at a large magnification. It is clear from the figure that the initial specific discharge capacity of both batteries is approximately 860mAh/g, however, after 100 weeks of cycling, the residual specific discharge capacities of both batteries are greatly different, the battery etched for 8 hours still has a specific discharge capacity of 503mAh/g, and the battery in the comparative column only has a capacity of 282 mAh/g.
Example 5
Soaking an aluminum foil in alcohol to remove oil stains on the surface. Adding a certain amount of citric acid into distilled water, mixing, adding a certain amount of Al 2 (SO 4 ) 3 Stirring again to be uniform. 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 10 hours, taking out, cleaning with distilled water, and drying. And coating the positive electrode material on the current collector to prepare a positive electrode plate.
And stacking and assembling the synthesized positive electrode plate, the metal lithium plate, the PEO solid electrolyte and the positive and negative electrode shells of the battery, and then sealing to assemble the 2032 button battery.
Example 6
Soaking an aluminum foil in alcohol to remove oil stains on the surface. Adding a certain amount of citric acid into distilled water, mixing, adding a certain amount of Al 2 (SO 4 ) 3 Stirring again to be uniform. 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 a positive electrode plate.
And stacking and assembling the synthesized positive electrode plate, the metal lithium plate, the PEO solid electrolyte and the positive and negative electrode shells of the battery, and then sealing to assemble the 2032 button battery.
Example 7
Dipping an aluminum foilSoaking in alcohol to remove oil stain on the surface. Adding a certain amount of citric acid into distilled water, mixing, adding a certain amount of Al 2 (SO 4 ) 3 Stirring again to be uniform. 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 a positive electrode plate.
And stacking and assembling the synthesized positive electrode plate, the metal lithium plate, the PEO solid electrolyte and the positive and negative electrode shells of the battery, and then sealing to assemble the 2032 button battery.
Example 8
Soaking an aluminum foil in alcohol to remove oil stains on the surface. Adding a certain amount of citric acid into distilled water, mixing, adding a certain amount of Al 2 (SO 4 ) 3 Stirring again to be uniform. 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 a positive electrode plate.
And stacking and assembling the synthesized positive electrode plate, the metal lithium plate, the PEO solid electrolyte and the positive and negative electrode shells of the battery, and then sealing to assemble the 2032 button battery.
Example 9
Soaking an aluminum foil in alcohol to remove oil stains on the surface. Adding a certain amount of acetic acid into distilled water, mixing, adding a certain amount of Al 2 (SO 4 ) 3 Stirring again to be uniform. 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 a positive electrode plate.
And stacking and assembling the synthesized positive electrode plate, the metal lithium plate, the PEO solid electrolyte and the positive and negative electrode shells of the battery, and then sealing to assemble the 2032 button battery.
Example 10
Taking an aluminum foilSoaking in alcohol to remove oil stain on the surface. Adding a certain amount of acetic acid into distilled water, mixing, adding a certain amount of Al 2 (SO 4 ) 3 Stirring again to be uniform. 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 2 hours, taking out, cleaning with distilled water, and drying. And coating the positive electrode material on the current collector to prepare a positive electrode plate.
And stacking and assembling the synthesized positive electrode plate, the metal lithium plate, the PEO solid electrolyte and the positive and negative electrode shells of the battery, and then sealing to assemble the 2032 button battery.
Example 11
Soaking an aluminum foil in alcohol to remove oil stains on the surface. Adding a certain amount of acetic acid into distilled water, mixing, adding a certain amount of Al 2 (SO 4 ) 3 Stirring again to be uniform. 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 a positive electrode plate.
And stacking and assembling the synthesized positive electrode plate, the metal lithium plate, the PEO solid electrolyte and the positive and negative electrode shells of the battery, and then sealing to assemble the 2032 button battery.
Example 12
Soaking an aluminum foil in alcohol to remove oil stains on the surface. Adding a certain amount of acetic acid into distilled water, mixing, adding a certain amount of Al 2 (SO 4 ) 3 Stirring again to be uniform. 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 a positive electrode plate.
And stacking and assembling the synthesized positive electrode plate, the metal lithium plate, the PEO solid electrolyte and the positive and negative electrode shells of the battery, and then sealing to assemble the 2032 button battery.
Example 13
Dipping an aluminum foilSoaking in alcohol to remove oil stain on the surface. Adding a certain amount of oxalic acid into distilled water, mixing uniformly, adding a certain amount of Al 2 (SO 4 ) 3 Stirring again to be uniform. 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 a positive electrode plate.
And stacking and assembling the synthesized positive electrode plate, the metal lithium plate, the PEO solid electrolyte and the positive and negative electrode shells of the battery, and then sealing to assemble the 2032 button battery.
Example 14
Soaking an aluminum foil in alcohol to remove oil stains on the surface. Adding a certain amount of oxalic acid into distilled water, mixing uniformly, adding a certain amount of Al 2 (SO 4 ) 3 Stirring again to be uniform. And (3) putting the mixed solution into a water bath kettle with the temperature of 100 ℃ for heating, 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 a positive electrode plate.
And stacking and assembling the synthesized positive electrode plate, the metal lithium plate, the PEO solid electrolyte and the positive and negative electrode shells of the battery, and then sealing to assemble the 2032 button battery.
Example 15
Soaking an aluminum foil in alcohol to remove oil stains on the surface. Adding a certain amount of oxalic acid into distilled water, mixing uniformly, adding a certain amount of Al 2 (SO 4 ) 3 Stirring again to be uniform. 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 a positive electrode plate.
And stacking and assembling the synthesized positive electrode plate, the metal lithium plate, the PEO solid electrolyte and the positive and negative electrode shells of the battery, and then sealing to assemble the 2032 button battery.
Fig. 5 shows a scanning electron microscope picture of a porous aluminum foil obtained by oxalic acid etching for 3 hours, in which the picture has obvious holes, which can be clearly contrasted with the blank aluminum foil in fig. 1.
Example 16
Soaking an aluminum foil in alcohol to remove oil stains on the surface. Adding a certain amount of oxalic acid into distilled water, mixing uniformly, adding a certain amount of Al 2 (SO 4 ) 3 Stirring again to be uniform. 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 a positive electrode plate.
And stacking and assembling the synthesized positive electrode plate, the metal lithium plate, the PEO solid electrolyte and the positive and negative electrode shells of the battery, and then sealing to assemble the 2032 button battery.
Fig. 6 shows a scanning electron microscope picture of a porous aluminum foil obtained by oxalic acid etching for 4 hours, wherein the picture has relatively rich and uniform pores, which can be clearly contrasted with the blank aluminum foil in fig. 1.
Comparative example
Sulfur melted at 155 c was uniformly mixed with a binder and a 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 shell layers of the battery, and then sealing to assemble the 2032 button battery.
Fig. 1 shows a scanning electron microscope picture of a blank aluminum foil, which shows that the aluminum foil surface is very smooth without any voids.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (7)

1. A process for preparing porous aluminium current collector features that a certain amount of organic acid is added to itAdding the mixture into distilled water and uniformly stirring to obtain an organic acid solution; al is added with 2 (SO 4 ) 3 Adding the powder into the organic acid solution, and uniformly stirring to obtain a mixed solution; adding the cleaned aluminum foil into the prepared mixed solution, and heating and etching; the organic acid comprises one or more of citric acid, formic acid, acetic acid, oxalic acid, malic acid and salicylic acid;
the concentration of the organic acid in the organic acid solution is 1mol/L-3mol/L, and Al in the mixed solution 2 (SO 4 ) 3 The concentration of (2) is 0.1-0.3mol/L;
the etching time is 2-24h, and the etching temperature is 40-100 ℃.
2. The preparation method according to claim 1, wherein the solution for cleaning the aluminum foil is alcohol, low concentration Na 2 CO 3 ，NaHCO 3 One of them.
3. The method according to claim 1, wherein the aluminum foil has a thickness of 10-20 μm.
4. A porous aluminum current collector prepared according to the preparation method of any one of claims 1 to 3.
5. A positive electrode material of a three-dimensional all-solid-state lithium battery, characterized by comprising the porous aluminum current collector of claim 4, a positive electrode active material, a binder and a conductive agent; the positive electrode active material was S, liMn 2 O 4 、LiCoO 2 、LiNi 0.8 Co 0.1 Mn 0.1 O 2 、LiNi 1/3 Co 1/3 Mn 1/3 O 2 、LiNi 0.6 Co 0.2 Mn 0.2 O 2 、LiNi 0.5 Mn 1.5 O 4 、LiFePO 4 One of the following; the binder is PVDF dissolved in NMP solvent, and the mass percentage concentration is 3%; the conductive agent is one of Super-p, acetylene black and ketjen black; the preparation method comprises the following steps: uniformly mixing an anode active material with a binder and a conductive agent to obtain anode slurry; will be mixedAnd uniformly coating the good positive electrode slurry on the porous aluminum current collector, and then putting the porous aluminum current collector into a vacuum oven for drying.
6. A three-dimensional all-solid-state lithium battery, wherein the positive electrode material is the three-dimensional all-solid-state lithium battery positive electrode material according to claim 5, and the solid electrolyte is any one of polymer solid electrolyte, ceramic electrolyte and composite solid electrolyte.
7. Use of the three-dimensional all-solid-state lithium battery according to claim 6 in automobiles and electric vehicles.
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