CN114373882B - Aluminum battery cathode and ALD preparation method and application thereof - Google Patents

Aluminum battery cathode and ALD preparation method and application thereof Download PDF

Info

Publication number
CN114373882B
CN114373882B CN202210074723.0A CN202210074723A CN114373882B CN 114373882 B CN114373882 B CN 114373882B CN 202210074723 A CN202210074723 A CN 202210074723A CN 114373882 B CN114373882 B CN 114373882B
Authority
CN
China
Prior art keywords
aluminum
aluminum foil
battery
ald
porous
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210074723.0A
Other languages
Chinese (zh)
Other versions
CN114373882A (en
Inventor
杜显锋
王世新
熊礼龙
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xian Jiaotong University
Original Assignee
Xian Jiaotong University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xian Jiaotong University filed Critical Xian Jiaotong University
Priority to CN202210074723.0A priority Critical patent/CN114373882B/en
Publication of CN114373882A publication Critical patent/CN114373882A/en
Application granted granted Critical
Publication of CN114373882B publication Critical patent/CN114373882B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0421—Methods of deposition of the material involving vapour deposition
    • H01M4/0428—Chemical vapour deposition
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/401—Oxides containing silicon
    • C23C16/402—Silicon dioxide
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/403—Oxides of aluminium, magnesium or beryllium
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/405—Oxides of refractory metals or yttrium
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
    • C23C16/45529—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations specially adapted for making a layer stack of alternating different compositions or gradient compositions
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/56—After-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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • 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
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Electrochemistry (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Cell Electrode Carriers And Collectors (AREA)

Abstract

The invention discloses an aluminum battery cathode and an ALD preparation method and application thereof, wherein the method comprises the following steps: taking the cleaned aluminum foil, and depositing an insulating medium layer by adopting an ALD method; carrying out laser etching on the aluminum foil deposited with the insulating medium layer to form a uniform pore channel structure, thereby obtaining a porous aluminum foil; and (3) taking an Al foil which is deposited with an insulating dielectric layer and subjected to laser etching as a negative electrode, taking expanded graphite as a positive electrode, taking a glass fiber filter membrane as a diaphragm, and taking AlCl 3/Et3 NHCl as an electrolyte to assemble the soft-packed battery. The invention adopts ALD atomic deposition and laser etching technology, the dielectric layer deposited on the surface of the negative pole piece can protect the pole piece from being corroded, and on the other hand, the invention can play a role of a framework, thereby avoiding pole piece disintegration caused by pulverization; the active sites on the surface of the pole piece are uniformly distributed by laser etching, so that dendrite problems caused by nonuniform electric field distribution on the surface of the battery in the charging and discharging process are avoided, the diaphragm is pierced, the battery is shorted, and the cycling stability and safety of the battery are greatly improved.

Description

Aluminum battery cathode and ALD preparation method and application thereof
Technical Field
The invention belongs to the field of aluminum batteries, relates to an aluminum battery negative electrode, an ALD preparation method and application thereof, and particularly relates to an insulating medium layer such as Al 2O3、TiO2、HfO2、ZrO2 and SiO 2 and application of laser etching in limiting growth of aluminum dendrites.
Background
The advent of lithium ion batteries has brought great convenience to human production and life, but the safety and price problems of lithium ion batteries have greatly limited their wide application in large-scale energy storage systems. Compared with lithium ion batteries, aluminum batteries are known with low cost and high safety, and the theoretical volume capacity and the mass capacity of aluminum metal are as high as 8048 mAh.cm -3 and 2981 mAh.g -1. Therefore, the aluminum battery has great application prospect in the field of energy storage of next-generation large-scale power grids.
In recent years, the positive electrode material and the electrolyte of the aluminum battery are research hot spots reported by scientific researchers in various countries, but attention on the aluminum negative electrode is less, and metal dendrites are unavoidable problems for limiting the development of the battery in all cases of metal batteries. Aluminum dendrites refer to non-uniform deposition of aluminum caused by non-uniform current density on the surface of an electrode during deposition and stripping of aluminum, and charge accumulation exists at sites where aluminum is preferentially deposited, so that aluminum is easier to deposit on the surface after induction, and dendritic or mossy aluminum dendrites are formed. Generally, aluminum dendrites are higher than the electrode surface, which can easily puncture the separator and cause cell shorting failure. In addition, aluminum dendrites have problems of battery capacity degradation, low coulombic efficiency, etc., which seriously affect the development and commercialization of aluminum batteries.
Disclosure of Invention
In order to overcome the defects of the traditional aluminum cathode, the invention aims to provide a preparation method and application of a cathode material for limiting dendrite growth of an aluminum battery. The preparation method of the aluminum battery anode material disclosed by the invention is simple to operate, easy to realize and capable of realizing industrial production, and the aluminum battery anode material prepared by the method can obviously limit the growth of aluminum dendrites, so that the cycle life and the safety performance of an aluminum battery are improved to a great extent. In addition, the anode of the aluminum battery prepared by the invention has extremely high electrochemical active area, improves the active site of aluminum deposition, increases the contact area of electrolyte and an electrode, and enhances the energy density and the rate capability of the aluminum battery to a certain extent.
The technical scheme of the invention is as follows: a preparation method of an aluminum battery anode for limiting aluminum dendrite growth by utilizing ALD comprises the following steps: taking the cleaned aluminum foil, and depositing an insulating medium layer by adopting an ALD method; carrying out laser etching on the aluminum foil deposited with the insulating medium layer to form a uniform pore channel structure, thereby obtaining a porous aluminum foil;
And ultrasonically cleaning the porous aluminum foil to obtain the porous aluminum foil cathode with the medium layer.
The aluminum foil is subjected to cleaning pretreatment before the insulating medium layer is deposited, and then the aluminum foil is sequentially subjected to ultrasonic cleaning in acetone, alcohol and deionized water, and is dried.
The vacuum degree is 3-20mTorr when the ALD method is used for depositing the insulating medium layer, and the temperature is 100-400 ℃.
When the ALD method is used for depositing the insulating dielectric layer, the insulating dielectric layer is insulating metal oxide, the source temperature of metal in the insulating metal oxide is 25-200 ℃, the introducing time is 1-3s, the diffusion time is 1-60s, and the nitrogen purging time is 1-60s.
The insulating dielectric layer precursor in the ALD deposition process is an aluminum source, a titanium source, a zirconium source, a hafnium source or a silicon source; the oxygen source of the reactant is O 2,O3,H2 O or H 2O2, the introducing time is 1-10s, and the diffusion time is 1-60s.
The diameter of the pore canal formed by laser etching is 10-100 mu m, and the distance between the pores is 10-100 mu m.
The laser moving speed is 0.001mms -1-2000mms-1, the pulse repetition frequency is 10-100 kHZ, and the light source power is 10-50W.
The wavelength of the laser etching was set to 355nm, 532nm or 1064nm.
Based on the application of the porous aluminum foil cathode with the dielectric layer obtained by the preparation method, the porous aluminum foil cathode is used for aluminum batteries and aluminum-air batteries.
The invention also provides an aluminum battery cathode which is obtained based on the preparation method.
Compared with the traditional aluminum cathode technology, the invention has the following remarkable effects:
(1) In the traditional aluminum cathode, uneven aluminum deposition exists in the charging and discharging process, and once large protrusions or corrosion pits appear on the whole electrode surface, electrodeposition morphology difference caused by uneven current density exists on the surface of the Al foil electrode, so that dendrites are formed. According to the invention, the current distribution on the surface of the aluminum cathode is homogenized through ALD and laser etching technologies, so that uniform electrodeposition is generated on the surface of the aluminum, the damage caused by the penetration of formed dendrites through a diaphragm is avoided, and the safety and the cycling stability of the battery are improved.
(2) Conventional aluminum cathodes provide fewer active sites in the aluminum cell, limiting the improvement in energy density and rate capability. According to the invention, the effective electrochemical area of the aluminum cathode is increased by a laser etching technology, so that the electrolyte can be fully contacted with the surface of the electrode, charge transfer on an electrode/electrolyte interface is promoted, the long-cycle stability of the aluminum battery is improved, and the current density and the multiplying power performance of the battery are increased to a certain extent. On the other hand, the porous structure provides a good channel and a stable frame for electrolyte to enter the cathode structure, so that the volume change in the aluminum deposition/stripping process can be effectively relieved, the aluminum cathode structure is kept complete, and the long-cycle stability of the aluminum battery is enhanced.
Drawings
Fig. 1 is an SEM image of the aluminum anode surface after cycling of the aluminum battery assembled with the aluminum optical foil of example 1 as the anode;
fig. 2 is an SEM image of the surface of the negative electrode after cycling of the Al 2O3 -porous aluminum foil of example 2 as the aluminum battery assembled as the negative electrode;
Fig. 3 is a constant current charge-discharge curve of an aluminum battery assembled by using an aluminum photo-foil and a TiO 2 -porous aluminum foil as a negative electrode material in example 3.
Fig. 4 is a graph showing the magnification of an aluminum battery assembled by using an aluminum optical foil and a TiO 2 -porous aluminum foil as a negative electrode material in example 4.
Detailed Description
In order that those skilled in the art will better understand the present invention, a technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in which it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and the claims of the present invention and the above figures are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged where appropriate such that the embodiments of the invention described herein may be implemented in sequences other than those illustrated or otherwise described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The present invention is directed to modification of aluminum cathodes by Atomic Layer Deposition (ALD) and laser etching (LBC) techniques. The dielectric protection layer is deposited on the surface of the aluminum foil by the ALD technology, and then the surface of the aluminum foil is perforated by the laser etching technology, so that the electric field distribution of the surface of the negative electrode of the aluminum battery in the charge and discharge process is more uniform, the deposition process of aluminum is all generated in the pore channel, the phenomenon higher than the surface of the electrode is avoided, and the circulation stability and the safety of the aluminum battery are greatly improved.
The invention is described in further detail below with reference to the attached drawing figures:
Example 1:
the invention relates to a preparation method of an aluminum battery anode material, which specifically comprises the following steps:
Step 1: placing the cleaned aluminum foil into an ALD reaction chamber with the temperature of 100 ℃ and the vacuum degree of 3mTorr, taking nitrogen as carrier gas, taking TMA as a titanium source, keeping the temperature of the titanium source at 25 ℃, introducing 1s in a steam mode, diffusing for 10s, introducing nitrogen to purge for 5s, introducing O 2 to react for 1s, introducing nitrogen to purge for 10s, and finally repeatedly depositing 150cycles according to the steps.
Step 2: the pore diameter and pore spacing distribution was prepared using CAD software, and the pore diameter was set to 10 μm and the pore spacing was set to 10 μm.
Step 3: and carrying out laser etching on the anodized aluminum foil according to a drawing under the conditions that the wavelength is 355nm, the laser moving speed is 2000mm & s -1, the pulse repetition frequency is 20kHZ and the light source power is 20W, so as to obtain the aluminum foil with the required Al 2O3 -porous structure.
And assembling the prepared negative electrode material into a soft-package aluminum battery, wherein the assembling sequence is as follows: positive electrode material (three-dimensional graphite) +separator+electrolyte+negative electrode material (photo foil or Al 2O3 -porous aluminum foil). And (3) carrying out constant-current charge and discharge and cycle stability test on the assembled device by using a blue-ray test system. The test results were as follows:
In this embodiment, the appearance of the surface of the aluminum negative electrode after the aluminum battery assembled by using the optical foil as the negative electrode is circulated is shown in fig. 1, and it can be seen from the figure that the aluminum negative electrode after charge-discharge circulation has serious corrosion on the surface due to the uneven aluminum deposition/stripping process, and dendrites exist in corrosion pits, which seriously affects the circulation stability of the aluminum battery.
Example 2:
Step 1: placing the cleaned aluminum foil into an ALD reaction chamber with the temperature of 200 ℃ and the vacuum degree of 5mTorr, taking nitrogen as carrier gas, taking TMA as an aluminum source, keeping the temperature of the aluminum source at 25 ℃, introducing 2s, and then introducing nitrogen to purge for 10s. Then O 3 is introduced to react for 5s, and nitrogen is purged for 20s. And then depositing 150cycles repeatedly according to the steps.
Step 2: the pore diameter and pore spacing distribution map was prepared using CAD software, and the pore diameter was set to 50 μm and the pore spacing was set to 50 μm.
Step 3: and carrying out laser etching on the anodized aluminum foil according to a drawing under the conditions that the wavelength is 532nm, the laser moving speed is 0.01mm & s -1, the pulse repetition frequency is 10kHZ and the light source power is 50W, so as to obtain the aluminum foil with the required Al 2O3 -porous structure.
And assembling the prepared negative electrode material into a soft-package aluminum battery, wherein the assembling sequence is as follows: aluminum plastic film + positive electrode material (three-dimensional graphite) +diaphragm + electrolyte + negative electrode material (Al 2O3 -porous aluminum foil) +aluminum plastic film. And (3) carrying out constant-current charge and discharge and cycle stability test on the assembled device by using a blue-ray test system. The test results were as follows:
In the embodiment, the morphology graph of the aluminum cathode surface after the battery assembled by taking the Al 2O3 -porous aluminum foil as the cathode is circulated is shown in fig. 2, so that the Al 2O3 -porous cathode material can obviously limit dendrites to grow in a pore canal, and the morphology of the cathode surface is basically unchanged, because the Al 2O3 insulating medium layer on the surface plays a role in protecting, the problem of short circuit caused by dendrite growth is avoided, and the safety of the battery is greatly improved.
Example 3:
Step 1: placing the cleaned aluminum foil into an ALD reaction chamber with the temperature of 200 ℃ and the vacuum degree of 5mTorr, taking nitrogen as carrier gas, taking TTIP as a titanium source, keeping the temperature of the titanium source at 70 ℃, introducing 1s, and then introducing nitrogen to purge for 30s. Then O 3 is introduced to react for 5s, and nitrogen is purged for 40s. And then depositing 150cycles repeatedly according to the steps.
Step 2: the pore diameter and pore spacing distribution map was prepared using CAD software, and the pore diameter was set to 50 μm and the pore spacing was set to 50 μm.
Step 3: and carrying out laser etching on the anodized aluminum foil according to the drawing under the conditions that the wavelength is 1064nm, the laser moving speed is 1000mm & s -1, the pulse repetition frequency is 50kHZ and the light source power is 25W, so as to obtain the aluminum foil with the required TiO 2 -porous structure.
And assembling the prepared negative electrode material into a soft-package aluminum battery, wherein the assembling sequence is as follows: aluminum plastic film + positive electrode material (three-dimensional graphite) +diaphragm + electrolyte + negative electrode material (TiO 2 -porous aluminum foil) +aluminum plastic film. And (3) carrying out constant-current charge and discharge and cycle stability test on the assembled device by using a blue-ray test system. The test results were as follows:
In this example, the rate characteristic curve of the soft-pack battery assembled by using the TiO 2 -porous aluminum foil as the negative electrode is shown in fig. 3, and it is clear from the figure that when the TiO 2 -porous aluminum foil is used as the negative electrode, the soft-pack battery has a higher capacity at the current densities of 1a·g -1,2A·g-1,5A·g-1 and 10a·g -1 and is larger than the capacity when the aluminum foil is used as the negative electrode.
Example 4:
Step 1: placing the cleaned aluminum foil into an ALD reaction chamber with the temperature of 300 ℃ and the vacuum degree of 10mTorr, taking nitrogen as carrier gas, taking TTIP as a titanium source, keeping the temperature of the titanium source at 100 ℃, introducing 3s, and then introducing nitrogen to purge for 30s. H 2O2 was then introduced to react for 10s and purged with nitrogen for 40s. And then depositing 150cycles repeatedly according to the steps.
Step 2: the pore diameter and pore spacing distribution map was prepared using CAD software, and the pore diameter was set to 100 μm and the pore spacing was set to 100 μm.
Step 3: and carrying out laser etching on the anodized aluminum foil according to a drawing under the conditions that the wavelength is 355nm, the laser moving speed is 1000mm & s -1, the pulse repetition frequency is 10kHZ and the light source power is 50W, so as to obtain the aluminum foil with the required TiO 2 -porous structure.
And assembling the prepared negative electrode material into a soft-package aluminum battery, wherein the assembling sequence is as follows: aluminum plastic film + positive electrode material (three-dimensional graphite) +diaphragm + electrolyte + negative electrode material (TiO 2 -porous aluminum foil) +aluminum plastic film. And (3) carrying out constant-current charge and discharge and cycle stability test on the assembled device by using a blue-ray test system. The test results were as follows:
In this example, as shown in fig. 4, the constant current charge-discharge curve of the soft-pack battery assembled by using TiO 2 -porous aluminum foil as the negative electrode shows that when TiO 2 -porous aluminum foil is used as the negative electrode, the capacity of 80 mAh-g -1 is maintained at a current density of 10a·g -1, and the capacity retention rate is greater than 95%. In order to prove that the battery assembled by the negative electrode of the aluminum battery prepared by the invention has higher capacity and better capacity retention rate.
Example 5:
step 1: placing the cleaned aluminum foil into an ALD reaction chamber with the temperature of 200 ℃ and the vacuum degree of 20mTorr, taking nitrogen as carrier gas, taking HfCl 4 as a titanium source, keeping the temperature of the titanium source at 150 ℃, introducing 1s, and then introducing nitrogen to purge for 60s. Then O 3 is introduced to react for 5s, and nitrogen is purged for 60s. And then depositing 150cycles repeatedly according to the steps.
Step 2: the pore diameter and pore spacing distribution was prepared using CAD software, the pore diameter was set to 50 μm and the pore spacing was set to 100 μm.
Step 3: and carrying out laser etching on the anodized aluminum foil according to a drawing under the conditions that the wavelength is 355nm, the laser moving speed is 0.01mm & s -1, the pulse repetition frequency is 10kHZ and the light source power is 10W, so as to obtain the required aluminum foil with the HfO 2 -porous structure.
And assembling the prepared negative electrode material into a soft-package aluminum battery, wherein the assembling sequence is as follows: aluminum plastic film + positive electrode material (three-dimensional graphite) +diaphragm + electrolyte + negative electrode material (HfO 2 -porous aluminum foil) +aluminum plastic film. And (3) carrying out constant-current charge and discharge and cycle stability test on the assembled device by using a blue-ray test system. The test results were as follows:
The HfO 2 -porous aluminum foil with the pore channels with different diameters and intervals prepared by the embodiment shows different cycle life and rate performance for the soft package battery assembled by the negative electrode, and the performance is obviously improved compared with that of the aluminum optical foil, so that the performance of the electrode material can be further improved by regulating the diameters and intervals of the pore channels.
Example 6:
step 1: placing the cleaned aluminum foil into an ALD reaction chamber with the temperature of 300 ℃ and the vacuum degree of 3-20mTorr, taking nitrogen as carrier gas, taking HfCl 4 as a titanium source, keeping the temperature of the titanium source at 200 ℃, introducing 2s, and then introducing nitrogen to purge for 30s. Then H 2 O is introduced to react for 10s, and nitrogen is purged for 20s. And then depositing 150cycles repeatedly according to the steps.
Step 2: the pore diameter and pore spacing distribution map was prepared using CAD software, and the pore diameter was set to 100 μm and the pore spacing was set to 100 μm.
Step 3: and carrying out laser etching on the anodized aluminum foil according to a drawing under the conditions that the wavelength is 532nm, the laser moving speed is 1000mm & s -1, the pulse repetition frequency is 80kHZ and the light source power is 20W, so as to obtain the required aluminum foil with the HfO 2 -porous structure.
And assembling the prepared negative electrode material into a soft-package aluminum battery, wherein the assembling sequence is as follows: aluminum plastic film + positive electrode material (three-dimensional graphite) +diaphragm + electrolyte + negative electrode material (HfO 2 -porous aluminum foil) +aluminum plastic film. And (3) carrying out constant-current charge and discharge and cycle stability test on the assembled device by using a blue-ray test system. The test results were as follows:
the HfO 2 -porous aluminum foils with different dielectric layer thicknesses are prepared and used as the negative electrode to assemble the soft-package battery, and the result shows that when the thickness of the HfO 2 dielectric layer is 40nm, the battery can reach the capacity of 95mAh g -1 under the current density of 10A g -1, which is far greater than the capacity of the negative electrode with other dielectric layers, and the performance of the electrode material can be further improved by regulating the thickness of the dielectric layer.
Example 7:
Step 1: placing the cleaned aluminum foil into an ALD reaction chamber with the temperature of 300 ℃ and the vacuum degree of 5mTorr, taking nitrogen as carrier gas, taking ZrCl 4 as a titanium source, keeping the temperature of the titanium source at 100 ℃, introducing 3s, and then introducing nitrogen to purge for 30s. Then H 2 O is introduced to react for 30s, and nitrogen is purged for 10s. And then depositing 150cycles repeatedly according to the steps.
Step 2: the pore diameter and pore spacing distribution was prepared using CAD software, the pore diameter was set to 30 μm and the pore spacing was set to 10 μm.
Step 3: and carrying out laser etching on the anodized aluminum foil according to a drawing under the conditions that the wavelength is 355nm, the laser moving speed is 2000mm & s -1, the pulse repetition frequency is 10kHZ and the light source power is 50W, so as to obtain the aluminum foil with the required ZrO 2 -porous structure.
And assembling the prepared negative electrode material into a soft-package aluminum battery, wherein the assembling sequence is as follows: aluminum plastic film + positive electrode material (three-dimensional graphite) +separator + electrolyte + negative electrode material (ZrO 2 -porous aluminum foil) +aluminum plastic film. And (3) carrying out constant-current charge and discharge and cycle stability test on the assembled device by using a blue-ray test system. The test results were as follows:
The ZrO 2 -porous aluminum foils assembled in the embodiment with different pore depths show different capacities and dendrite growth conditions for the soft-packed batteries assembled with the negative electrode. At a cell depth of 65 μm, the cell can reach a capacity of 92 mAh.g -1 at a current density of 10A.g -1, while at a cell depth of less than 65 μm, the cell capacity can only reach 80 mAh.g -1 at maximum, and the grown dendrites are higher than the ZrO 2 interface layer. This is probably because the effective electrochemical area of exposed aluminum, which is determined by the channel depth, affects the contact area with the electrolyte when less aluminum is exposed, affects the charge transfer at the interface, and thus affects the performance of the cell. Therefore, it can be explained that adjusting the depth of the pore canal can further improve the performance of the electrode material.
Example 8:
Step 1: placing the cleaned aluminum foil into an ALD reaction chamber with the temperature of 400 ℃ and the vacuum degree of 10mTorr, taking nitrogen as carrier gas, taking ZrCl 4 as a titanium source, keeping the temperature of the titanium source at 150 ℃, introducing 3s, and then introducing nitrogen to purge for 60s. H 2 O was then introduced to react for 10s, followed by a nitrogen purge for 60s. And then depositing 150cycles repeatedly according to the steps.
Step 2: the pore diameter and pore spacing distribution map was prepared using CAD software, and the pore diameter was set to 100 μm and the pore spacing was set to 20 μm.
Step 3: and carrying out laser etching on the anodized aluminum foil according to the drawing under the conditions that the wavelength is 1064nm, the laser moving speed is 500mm & s -1, the pulse repetition frequency is 30kHZ and the light source power is 50W, so as to obtain the aluminum foil with the required ZrO 2 -porous structure.
And assembling the prepared negative electrode material into a soft-package aluminum battery, wherein the assembling sequence is as follows: aluminum plastic film + positive electrode material (three-dimensional graphite) +separator + electrolyte + negative electrode material (ZrO 2 -porous aluminum foil) +aluminum plastic film. And (3) carrying out constant-current charge and discharge and cycle stability test on the assembled device by using a blue-ray test system. The test results were as follows:
The ZrO 2 -porous aluminum foils with different pore sizes assembled in the embodiment show different capacities and dendrite growth conditions for the soft package batteries assembled with the negative electrode. The cell pitch was set to 30. Mu.m, and at a cell diameter of 30. Mu.m, the cell was able to reach a capacity of 98mAh g -1 at a current density of 10A.g -1, and at a cell diameter of 100. Mu.m, the cell was only 70mAh g -1 at a current density of 10A.g -1. This is probably because the pore diameter determines the effective electrochemical area of exposed aluminum, which when less exposed affects the contact area with the electrolyte, affects the charge transfer at the interface, and thus affects the cell performance. Therefore, it can be explained that adjusting the pore size can further improve the performance of the electrode material.
Example 9:
Step 1: placing the cleaned aluminum foil into an ALD reaction chamber with the temperature of 300 ℃ and the vacuum degree of 5mTorr, taking nitrogen as carrier gas, taking SiCl 4 as a titanium source, keeping the temperature at 200 ℃, introducing 3s, and then introducing nitrogen to purge for 10s. H 2 O was then introduced to react for 10s, followed by a nitrogen purge for 10s. And then depositing 150cycles repeatedly according to the steps.
Step 2: the pore diameter and pore spacing distribution map was prepared using CAD software, and the pore diameter was set to 50 μm and the pore spacing was set to 50 μm.
Step 3: and carrying out laser etching on the anodized aluminum foil according to a drawing under the conditions that the wavelength is 532nm, the laser moving speed is 10mm & s -1, the pulse repetition frequency is 50kHZ and the light source power is 50W, so as to obtain the aluminum foil with the required SiO 2 -porous structure.
And assembling the prepared negative electrode material into a soft-package aluminum battery, wherein the assembling sequence is as follows: aluminum plastic film + positive electrode material (three-dimensional graphite) +diaphragm + electrolyte + negative electrode material (SiO 2 -porous aluminum foil) +aluminum plastic film. And (3) carrying out constant-current charge and discharge and cycle stability test on the assembled device by using a blue-ray test system. The test results were as follows:
The SiO 2 -porous aluminum foils assembled in the embodiment with different pore depths show different capacities and dendrite growth conditions for the soft-packed battery assembled with the negative electrode. The SiO 2 -porous aluminum foils assembled in the embodiment with different pore depths show different capacities and dendrite growth conditions for the soft-packed battery assembled with the negative electrode. At a channel depth of 65 μm, the cell can reach a capacity of 90 mAh.g -1 at a current density of 10A.g -1, while at a channel depth of less than 65 μm, the cell can only reach a maximum capacity of 75 mAh.g -1, and the grown dendrites are higher than the SiO 2 interface layer. This is probably because the effective electrochemical area of exposed aluminum, which is determined by the channel depth, affects the contact area with the electrolyte when less aluminum is exposed, affects the charge transfer at the interface, and thus affects the performance of the cell. Therefore, it can be explained that adjusting the depth of the pore canal can further improve the performance of the electrode material.
Example 10:
Step 1: placing the cleaned aluminum foil into an ALD reaction chamber with the temperature of 200 ℃ and the vacuum degree of 10mTorr, taking nitrogen as carrier gas, taking SiCl 4 as a titanium source, keeping the source temperature at 100 ℃, introducing for 1s, and then introducing nitrogen to purge for 30s. H 2 O was then introduced to react for 10s and purged with nitrogen for another 30s. And then depositing 150cycles repeatedly according to the steps.
Step 2: the pore diameter and pore spacing distribution map was prepared using CAD software, and the pore diameter was set to 80 μm and the pore spacing was set to 100 μm.
Step 3: and carrying out laser etching on the anodized aluminum foil according to a drawing under the conditions that the wavelength is 1064nm, the laser moving speed is 100mm & s -1, the pulse repetition frequency is 20kHZ and the light source power is 30W, so as to obtain the required aluminum foil with the SiO 2 -porous structure.
And assembling the prepared negative electrode material into a soft-package aluminum battery, wherein the assembling sequence is as follows: aluminum plastic film + positive electrode material (three-dimensional graphite) +diaphragm + electrolyte + negative electrode material (SiO 2 -porous aluminum foil) +aluminum plastic film. And (3) carrying out constant-current charge and discharge and cycle stability test on the assembled device by using a blue-ray test system. The test results were as follows:
The assembled soft package batteries with SiO 2 -porous aluminum foils with different pore sizes as the negative electrodes show different capacities and dendrite growth conditions. The cell pitch was set to 30. Mu.m, and at a cell diameter of 50. Mu.m, the cell was capable of reaching a capacity of 90mAh g -1 at a current density of 10A.g -1, and at a cell diameter of 80. Mu.m, the cell was only 61mAh g -1 at a current density of 10A.g -1. This is probably because the pore diameter determines the effective electrochemical area of exposed aluminum, which when less exposed affects the contact area with the electrolyte, affects the charge transfer at the interface, and thus affects the cell performance. Therefore, it can be explained that adjusting the pore size can further improve the performance of the electrode material.
The invention also provides an aluminum battery cathode which is obtained based on the preparation method in the embodiment.
The above is only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited by this, and any modification made on the basis of the technical scheme according to the technical idea of the present invention falls within the protection scope of the claims of the present invention.

Claims (7)

1. The ALD preparation method of the aluminum battery cathode is characterized by comprising the following steps of: taking the cleaned aluminum foil, and depositing an insulating medium layer by adopting an ALD method; carrying out laser etching on the aluminum foil deposited with the insulating medium layer to form a uniform pore channel structure, thereby obtaining a porous aluminum foil;
ultrasonically cleaning the porous aluminum foil to obtain a medium layer porous aluminum foil cathode;
When the ALD method is used for depositing the insulating dielectric layer, the insulating dielectric layer is insulating metal oxide, the source temperature of metal in the insulating metal oxide is 25-200 ℃, the introducing time is 1-3s, the diffusion time is 1-60s, and the nitrogen purging time is 1-60s; the insulating dielectric layer precursor in the ALD deposition process is an aluminum source, a titanium source, a zirconium source, a hafnium source or a silicon source; the oxygen source of the reactant is O 2,O3,H2 O or H 2O2, the introducing time is 1-10s, and the diffusion time is 1-60s;
The porous structure is formed by arranging the porous holes according to the set pore diameter and the pore spacing, the diameter of pore channels formed by laser etching is 30-100 mu m, and the pore spacing is 20-100 mu m.
2. The ALD process of claim 1, wherein the aluminum foil is pre-cleaned prior to depositing the dielectric layer, and the aluminum foil is sequentially sonicated, rinsed, and then baked in acetone, alcohol, and deionized water.
3. The ALD process of claim 1, wherein the ALD process deposits the dielectric layer at a vacuum level of 3-20mTorr and a temperature of 100-400 ℃.
4. The ALD process of claim 1, wherein the laser is moved at a speed of 0.001mms -1-2000mms-1, the pulse repetition rate is 10kHZ-100kHZ, and the source power is 10W-50W.
5. The ALD process of claim 1, wherein the laser etching wavelength is set at 355nm, 532nm or 1064nm.
6. Use of a porous aluminum foil anode based on a dielectric layer obtained by the method according to any one of claims 1-5, characterized in that it is used in an aluminum cell.
7. An aluminum battery anode, characterized in that it is obtained based on the preparation method according to any one of claims 1 to 5.
CN202210074723.0A 2022-01-21 2022-01-21 Aluminum battery cathode and ALD preparation method and application thereof Active CN114373882B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210074723.0A CN114373882B (en) 2022-01-21 2022-01-21 Aluminum battery cathode and ALD preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210074723.0A CN114373882B (en) 2022-01-21 2022-01-21 Aluminum battery cathode and ALD preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN114373882A CN114373882A (en) 2022-04-19
CN114373882B true CN114373882B (en) 2024-05-14

Family

ID=81146178

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210074723.0A Active CN114373882B (en) 2022-01-21 2022-01-21 Aluminum battery cathode and ALD preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114373882B (en)

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104966813A (en) * 2015-05-08 2015-10-07 中国科学院青岛生物能源与过程研究所 Sodium ion battery negative electrode sheet and sodium ion battery
CN105355433A (en) * 2015-11-27 2016-02-24 西安交通大学 Method for preparing high-dielectric composite film in combination with ALD (Atomic Layer Deposition)
CN105449225A (en) * 2015-12-02 2016-03-30 哈尔滨工业大学 Preparation method of aluminum collector in three-dimensional porous structure
CN108346716A (en) * 2018-03-29 2018-07-31 江苏微导纳米装备科技有限公司 A kind of manufacturing process of crystal silicon solar batteries
CN108376795A (en) * 2018-04-04 2018-08-07 天津大学 A kind of no dendrite, powerful aluminium ion battery
CN108819092A (en) * 2018-06-25 2018-11-16 无锡市恒利弘实业有限公司 A kind of preparation method of the aluminum or aluminum alloy material of high density holes
CN110042449A (en) * 2019-05-20 2019-07-23 水利部交通运输部国家能源局南京水利科学研究院 A kind of hydrophobic fluid injection aluminum alloy surface and preparation method thereof with liquid storage tank
CN110277246A (en) * 2019-07-03 2019-09-24 西安交通大学 It is a kind of to prepare electrolytic capacitor porous aluminium foil and method according to erosion with laser
CN110819965A (en) * 2019-10-25 2020-02-21 西安交通大学 Energy-saving preparation method of anode aluminum foil for aluminum electrolytic capacitor
CN111364016A (en) * 2020-04-10 2020-07-03 西安交通大学 Method for preparing porous anode aluminum foil by aid of ALD (atomic layer deposition) assisted nitrogen-doped micro-nano aluminum powder

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6768590B2 (en) * 2000-05-19 2004-07-27 Shipley Company, L.L.C. Method of fabricating optical filters
US7164165B2 (en) * 2002-05-16 2007-01-16 Micron Technology, Inc. MIS capacitor

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104966813A (en) * 2015-05-08 2015-10-07 中国科学院青岛生物能源与过程研究所 Sodium ion battery negative electrode sheet and sodium ion battery
CN105355433A (en) * 2015-11-27 2016-02-24 西安交通大学 Method for preparing high-dielectric composite film in combination with ALD (Atomic Layer Deposition)
CN105449225A (en) * 2015-12-02 2016-03-30 哈尔滨工业大学 Preparation method of aluminum collector in three-dimensional porous structure
CN108346716A (en) * 2018-03-29 2018-07-31 江苏微导纳米装备科技有限公司 A kind of manufacturing process of crystal silicon solar batteries
CN108376795A (en) * 2018-04-04 2018-08-07 天津大学 A kind of no dendrite, powerful aluminium ion battery
CN108819092A (en) * 2018-06-25 2018-11-16 无锡市恒利弘实业有限公司 A kind of preparation method of the aluminum or aluminum alloy material of high density holes
CN110042449A (en) * 2019-05-20 2019-07-23 水利部交通运输部国家能源局南京水利科学研究院 A kind of hydrophobic fluid injection aluminum alloy surface and preparation method thereof with liquid storage tank
CN110277246A (en) * 2019-07-03 2019-09-24 西安交通大学 It is a kind of to prepare electrolytic capacitor porous aluminium foil and method according to erosion with laser
CN110819965A (en) * 2019-10-25 2020-02-21 西安交通大学 Energy-saving preparation method of anode aluminum foil for aluminum electrolytic capacitor
CN111364016A (en) * 2020-04-10 2020-07-03 西安交通大学 Method for preparing porous anode aluminum foil by aid of ALD (atomic layer deposition) assisted nitrogen-doped micro-nano aluminum powder

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
应用于等离子体显示器的铝电极及其介质层制备研究;刘启发;王艳;汪红;丁桂甫;;真空科学与技术学报(第04期);全文 *
铝集流体表面处理对锂离子电池性能的影响;李俊鹏;党海峰;杨伟;薛建军;董新法;林维明;;电镀与涂饰(第16期);全文 *

Also Published As

Publication number Publication date
CN114373882A (en) 2022-04-19

Similar Documents

Publication Publication Date Title
CN107706421B (en) Preparation method of aluminum ion battery positive electrode material
CN109216681B (en) Based on TiO2Lithium metal cathode material of nanotube array/titanium foam and preparation method thereof
CN101981729A (en) Electrode for lithium secondary battery and method of manufacturing same
US10566615B2 (en) Battery and method for producing a battery
CN112349893A (en) Method for inhibiting growth of zinc dendrite by polydopamine film
WO2022259870A1 (en) Metal substrate for carbon nanowall growth, metal substrate equipped with carbon nanowalls, and production methods therefor
CN112467083A (en) Method for 3D printing of three-dimensional cathode
CN110828749B (en) Modified diaphragm of metal negative electrode battery, preparation method and application
JP3754374B2 (en) Method for producing electrode for lithium secondary battery
KR101654047B1 (en) anode for lithium secondary battery, manufacturing method thereof and lithium secondary battery comprising the same
CN108832081B (en) Preparation method of composite lithium metal cathode for enabling lithium metal to grow transversely
JP4183395B2 (en) Method for producing electrode for lithium secondary battery
CN114373882B (en) Aluminum battery cathode and ALD preparation method and application thereof
JP2024508021A (en) Artificial solid electrolyte interface layer material and its use
KR102085499B1 (en) Method for a porous electrode current collector for lithium metal battery using hydrogen bubble as a template and electrode current collector manufactured thereby
CN114497435A (en) Aluminum battery cathode and anodic oxidation preparation method and application thereof
CN102912437B (en) Flower-shaped multilevel-structure zinc oxide support frame and its preparation method and application
CN112310367A (en) Ultrathin porous metal material for lithium battery electrode and preparation method and application thereof
CN111162283A (en) Preparation method and application of nano porous foamed nickel current collector
CN114551803B (en) Three-dimensional gradient electrode for lithium metal negative electrode and preparation method thereof
KR20130119835A (en) Lithium battery electrode, method of manufacturing the same, and lithium battery including the same
CN110581263A (en) preparation method of manganese dioxide modified lithium-sulfur battery metal lithium cathode and lithium-sulfur battery
CN113690402B (en) Lithium ion battery, lithium ion battery cathode and preparation method thereof
CN114784287B (en) Current collector with electrostatic shielding function, preparation method thereof and composite lithium electrode
CN116314851B (en) Method for preparing lithium battery cathode porous current collector copper foil by template-stripping method, copper foil prepared by method and application of copper foil

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant