CN114373882A - Aluminum battery cathode and ALD (atomic layer deposition) preparation method and application thereof - Google Patents

Aluminum battery cathode and ALD (atomic layer deposition) preparation method and application thereof Download PDF

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CN114373882A
CN114373882A CN202210074723.0A CN202210074723A CN114373882A CN 114373882 A CN114373882 A CN 114373882A CN 202210074723 A CN202210074723 A CN 202210074723A CN 114373882 A CN114373882 A CN 114373882A
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aluminum
ald
aluminum foil
battery
preparation
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杜显锋
王世新
熊礼龙
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Xian Jiaotong University
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    • H—ELECTRICITY
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    • 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
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    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
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    • 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
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    • 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
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    • 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
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
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    • 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
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    • 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
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    • 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
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    • 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
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses an aluminum battery cathode and an ALD (atomic layer deposition) preparation method and application thereof, wherein the method comprises the following steps: depositing a layer of insulating medium layer on the cleaned aluminum foil by an ALD method; performing laser etching on the aluminum foil deposited with the insulating medium layer to form a uniform pore channel structure to obtain a porous aluminum foil; using Al foil as cathode and expansive stoneInk as positive electrode, glass fibre filter membrane as diaphragm, AlCl3/Et3NHCl is electrolyte to assemble the soft package battery. According to the invention, ALD atomic deposition and laser etching technologies are adopted, 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 dielectric layer can also play a skeleton role, so that pole piece disintegration caused by pulverization is avoided; the active sites on the surface of the pole piece are uniformly distributed by laser etching, so that the problem of dendritic crystals caused by the uneven electric field distribution on the surface of the battery in the charging and discharging process is avoided, the diaphragm is pierced, the battery is short-circuited, and the cycling stability and the safety of the battery are improved to a great extent.

Description

Aluminum battery cathode and ALD (atomic layer deposition) preparation method and application thereof
Technical Field
The invention belongs to the field of aluminum batteries, relates to an aluminum battery cathode, and an ALD (atomic layer deposition) preparation method and application thereof, and particularly relates to Al2O3、TiO2、HfO2、ZrO2And SiO2And the application of the insulating medium layer and laser etching in limiting the growth of the aluminum dendrite.
Background
The emergence of lithium ion batteries brings great convenience to production and life of human beings, but the safety problem and the price problem of the lithium ion batteries greatly limit the wide application of the lithium ion batteries in large-scale energy storage systems. Compared with lithium ion batteries, aluminum batteries are well known for low cost and high safety, and the theoretical volume capacity and mass capacity of aluminum metal can reach 8048 mAh-cm-32981mAh g-1. Therefore, the aluminum battery has great application prospect in the field of next-generation large-scale power grid energy storage.
In recent years, positive electrode materials and electrolyte of aluminum batteries are research hotspots which are disputed and reported by researchers in various countries, on the contrary, attention to aluminum negative electrodes is less, but metal dendrites are inevitable problems for limiting battery development when metal batteries are involved. The aluminum dendrite is the uneven deposition of aluminum caused by the uneven current density on the surface of an electrode in the deposition and stripping processes of the aluminum, the accumulation of charges can exist at the site where the aluminum is preferentially deposited, and the aluminum is more easily deposited on the surface after induction to form the dendritic or moss-shaped aluminum dendrite. Generally, aluminum dendrites are higher than the electrode surface and can easily pierce the separator, causing short circuit failure of the battery. In addition, the aluminum dendrite has the problems of capacity attenuation of the battery, low coulombic efficiency and the like, which seriously affect the development and commercialization of the aluminum battery.
Disclosure of Invention
In order to overcome the defects of the traditional aluminum negative electrode, the invention aims to provide a preparation method and application of a negative electrode material for limiting dendritic crystal growth of an aluminum battery. The preparation method of the aluminum battery cathode material disclosed by the invention is simple to operate and easy to realize, and can realize industrial production. In addition, the cathode of the aluminum battery prepared by the invention has extremely high electrochemical active area, improves the active sites of aluminum deposition, increases the contact area of electrolyte and electrodes, and enhances the energy density and 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 cathode for limiting aluminum dendrite growth by using ALD (atomic layer deposition), comprising the following steps of: depositing a layer of insulating medium layer on the cleaned aluminum foil by an ALD method; performing laser etching on the aluminum foil deposited with the insulating medium layer to form a uniform pore channel structure to obtain a porous aluminum foil;
and ultrasonically cleaning the porous aluminum foil to obtain the porous aluminum foil cathode of the dielectric layer.
Cleaning and pretreating the aluminum foil before depositing the insulating medium layer, sequentially carrying out ultrasonic treatment and cleaning on the aluminum foil in acetone, alcohol and deionized water, and then drying.
The ALD method deposits the insulating dielectric layer under a vacuum degree of 3-20mTorr and a temperature of 100-400 ℃.
When the ALD method deposits the insulating medium layer, the insulating medium layer is insulating metal oxide, the source temperature of a metal source in the insulating metal oxide is 25-200 ℃, the introduction time is 1-3s, the diffusion time is 1-60s, and the nitrogen purging time is 1-60 s.
Precursors of the insulating medium layer in the ALD deposition process are an aluminum source, a titanium source, a zirconium source, a hafnium source or a silicon source; the oxygen source of the reactant is O2，O3，H2O or H2O2The introduction time is 1-10s, and the diffusion time is 1-60 s.
The diameter of the pore canal formed by laser etching is 10-100 μm, and the pore space is 10-100 μm.
The laser moving speed is 0.001mms-1-2000mms-1The pulse repetition frequency is 10-100 kHZ, and the light source power is 10-50W.
The wavelength of the laser etching is set to 355nm, 532nm or 1064 nm.
Based on the application of the porous aluminum foil cathode with the dielectric layer obtained by the preparation method disclosed by the invention, the porous aluminum foil cathode with the dielectric layer is applied to 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) the traditional aluminum cathode has uneven aluminum deposition in the charging and discharging process, once large-scale protrusions or corrosion pits appear on the surface of the whole electrode, the surface of an Al foil electrode has poor electro-deposition form caused by uneven current density, and then dendritic crystals are formed. According to the invention, the current distribution on the surface of the aluminum cathode is homogenized by ALD and laser etching technologies, so that uniform electrodeposition is carried out on the surface of aluminum, the damage caused by penetrating a diaphragm by formed dendrites is avoided, and the safety and the cycle stability of the battery are improved.
(2) The traditional aluminum cathode provides fewer active sites in an aluminum battery, and the improvement of the energy density and rate capability of the traditional aluminum cathode is limited. According to the invention, by adopting a laser etching technology, the effective electrochemical area of the aluminum cathode is increased, so that the electrolyte can be fully contacted with the surface of the electrode, the charge transfer on the electrode/electrolyte interface is promoted, the long-cycle stability of the aluminum battery is improved, and the current density and the rate capability 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 the 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 surface of an aluminum negative electrode after cycling of an aluminum battery assembled with the aluminum foil as the negative electrode in example 1;
FIG. 2 shows Al in example 22O3SEM images of the anode surface after cycling for aluminum cells assembled with porous aluminum foil as the anode;
FIG. 3 shows the Al foil and TiO of example 32-constant current charge and discharge curve of aluminum cell assembled with porous aluminum foil as negative electrode material.
FIG. 4 shows the Al foil and TiO of example 42Rate curves for aluminum cells assembled with porous aluminum foil as negative electrode material.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or 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 invention aims to modify an aluminum cathode by an atomic layer deposition technology (ALD) and a laser etching technology (LBC). The medium protective layer is deposited on the surface of the aluminum foil through the ALD technology, the laser etching technology is utilized to punch holes on the surface of the aluminum foil, so that the electric field distribution of the negative electrode surface of the aluminum battery in the charging and discharging process is more uniform, the deposition process of the aluminum takes place in the pore channel, the phenomenon higher than the surface of the electrode can not occur, and the circulation stability and the safety of the aluminum battery are improved to a great extent.
The invention is described in further detail below with reference to the accompanying drawings:
example 1:
the invention relates to a preparation method of an aluminum battery cathode material, which specifically comprises the following steps:
step 1: putting 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 and TMA as 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, and then introducing O2The reaction was carried out for 1s, then purged with nitrogen for 10s, and finally the deposition of 150cycles was repeated following the above procedure.
Step 2: a CAD software was used to prepare a distribution map of pore diameters and pore pitches, with pore diameters set to 10 μm and pore pitches set to 10 μm.
And step 3: the anodized aluminum foil was subjected to laser irradiation at a laser moving speed of 2000mm · s at a wavelength of 355nm in accordance with a drawing-1Carrying out laser etching under the conditions that the pulse repetition frequency is 20kHz and the light source power is 20W to obtain the required Al2O3-an aluminium foil of porous structure.
Assembling the prepared negative electrode material into a soft package aluminum battery in the following sequence: positive electrode material (three-dimensional graphite), diaphragm, electrolyte and negative electrode material (optical foil or Al)2O3-porous aluminium foil). And (4) carrying out constant current charging and discharging and cyclic stability testing on the assembled device by using a blue testing system. The test results were as follows:
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 cycled is shown in fig. 1, and it can be seen from the figure that the surface of the aluminum negative electrode subjected to charge and discharge cycling is seriously corroded due to the uneven aluminum deposition/stripping process, and dendrites exist in a corrosion pit, so that the cycling stability of the aluminum battery is seriously influenced.
Example 2:
step 1: and putting the cleaned aluminum foil into an ALD reaction chamber with the temperature of 200 ℃ and the vacuum degree of 5mTorr, keeping the temperature of the aluminum source at 25 ℃ by taking nitrogen as carrier gas and TMA as the aluminum source, introducing for 2s, and introducing nitrogen for purging for 10 s. Then introducing O3The reaction was carried out for 5s and then purged with nitrogen for 20 s. Then repeating the stepsAnd depositing 150 cycles.
Step 2: a CAD software was used to prepare a distribution map of pore diameters and pore pitches, with pore diameters set to 50 μm and pore pitches set to 50 μm.
And step 3: anodizing the aluminum foil according to a drawing at a wavelength of 532nm and a laser moving speed of 0.01mm · s-1Carrying out laser etching under the conditions that the pulse repetition frequency is 10kHZ and the light source power is 50W to obtain the required Al2O3-an aluminium foil of porous structure.
Assembling the prepared negative electrode material into a soft package aluminum battery in the following sequence: aluminum-plastic film, positive electrode material (three-dimensional graphite), diaphragm, electrolyte and negative electrode material (Al)2O3-porous aluminium foil) + aluminium plastic film. And (4) carrying out constant current charging and discharging and cyclic stability testing on the assembled device by using a blue testing system. The test results were as follows:
al in this example2O3The topographic map of the aluminum negative electrode surface after battery cycle with porous aluminum foil as negative electrode assembly is shown in FIG. 2, and Al can be clearly seen2O3The porous negative electrode material effectively limits dendrites to grow in the pore channels, and the surface appearance of the negative electrode is not basically changed due to Al on the surface2O3The insulating medium layer plays a role in protection, the problem of short circuit caused by growth of dendrites is avoided, and the safety of the battery is greatly improved.
Example 3:
step 1: and putting 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 and TTIP as a titanium source, keeping the temperature of the titanium source at 70 ℃, introducing the titanium source for 1s, and introducing nitrogen for purging for 30 s. Then introducing O3The reaction was carried out for 5s and then purged with nitrogen for 40 s. The deposition of 150cycles was then repeated as per the above steps.
Step 2: a CAD software was used to prepare a distribution map of pore diameters and pore pitches, with pore diameters set to 50 μm and pore pitches set to 50 μm.
And step 3: anodizing the aluminum foil according to the drawing at a wavelength of 1064nm and a laser moving speed of 1000mm · s-1Pulse repetition frequencyCarrying out laser etching under the conditions that the rate is 50kHZ and the light source power is 25W to obtain the required TiO2-an aluminium foil of porous structure.
Assembling the prepared negative electrode material into a soft package aluminum battery in the following sequence: aluminum-plastic film, positive electrode material (three-dimensional graphite), diaphragm, electrolyte and negative electrode material (TiO)2-porous aluminium foil) + aluminium plastic film. And (4) carrying out constant current charging and discharging and cyclic stability testing on the assembled device by using a blue testing system. The test results were as follows:
this example uses TiO2The rate characteristic curve of the pouch cell assembled by the porous aluminum foil as the negative electrode is shown in fig. 3, from which TiO can be clearly seen2When a porous aluminum foil is used as a negative electrode, the concentration is 1 A.g-1，2A·g-1，5A·g-1And 10A. g-1The current density of (a) is higher than the capacity of aluminum foil as a negative electrode.
Example 4:
step 1: and putting the cleaned aluminum foil into an ALD reaction chamber with the temperature of 300 ℃ and the vacuum degree of 10mTorr, keeping the temperature of the titanium source at 100 ℃ by taking nitrogen as carrier gas and TTIP as a titanium source, introducing 3s, and introducing nitrogen for purging 30 s. Then introducing H2O2The reaction was carried out for 10s and then purged with nitrogen for 40 s. The deposition of 150cycles was then repeated as per the above steps.
Step 2: the pore diameter and pore pitch profiles were prepared using CAD software, with pore diameters set at 100 μm and pore pitches set at 100 μm.
And step 3: anodizing the aluminum foil, the wavelength of which was 355nm and the laser moving speed was 1000mm · s according to the drawing-1Carrying out laser etching under the conditions that the pulse repetition frequency is 10kHZ and the light source power is 50W to obtain the required TiO2-an aluminium foil of porous structure.
Assembling the prepared negative electrode material into a soft package aluminum battery in the following sequence: aluminum-plastic film, positive electrode material (three-dimensional graphite), diaphragm, electrolyte and negative electrode material (TiO)2-porous aluminium foil) + aluminium plastic film. And (4) carrying out constant current charging and discharging and cyclic stability testing on the assembled device by using a blue testing system. The test results were as follows:
this example uses TiO2FIG. 4 shows the constant current charge/discharge curve of a pouch cell assembled with a porous aluminum foil as the negative electrode, from which it is clear that TiO210A g for a porous aluminum foil as a negative electrode-1At a current density of 80mAh g-1And the capacity retention is greater than 95%. Therefore, the battery assembled by the aluminum battery cathode prepared by the invention has higher capacity and better capacity retention rate.
Example 5:
step 1: putting 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 and HfCl4The temperature of the titanium source is kept at 150 ℃, the titanium source is introduced for 1s, and then nitrogen is introduced for purging for 60 s. Then introducing O3The reaction was carried out for 5s and then purged with nitrogen for 60 s. The deposition of 150cycles was then repeated as per the above steps.
Step 2: the pore diameter and pore pitch profiles were prepared using CAD software, with pore diameters set at 50 μm and pore pitches set at 100 μm.
And step 3: anodizing the aluminum foil, the wavelength of which was 355nm and the laser moving speed was 0.01mm · s according to the drawing-1Carrying out laser etching under the conditions that the pulse repetition frequency is 10kHZ and the light source power is 10W to obtain the required HfO2-an aluminium foil of porous structure.
Assembling the prepared negative electrode material into a soft package aluminum battery in the following sequence: aluminum-plastic film, positive electrode material (three-dimensional graphite), diaphragm, electrolyte and negative electrode material (HfO)2-porous aluminium foil) + aluminium plastic film. And (4) carrying out constant current charging and discharging and cyclic stability testing on the assembled device by using a blue testing system. The test results were as follows:
HfO with different diameter and spacing pore channels prepared in this example2The soft package battery with the negative electrode assembled by the porous aluminum foil shows different cycle life and rate performance, and the performance is obviously improved compared with that of an aluminum foil, which shows that the performance of the electrode material can be further improved by regulating and controlling the diameter and the distance of the pore channel.
Example 6:
step 1: putting 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 and HfCl4The temperature of the titanium source is kept at 200 ℃, 2s are introduced, and then nitrogen is introduced for purging for 30 s. Then introducing H2O reacted for 10s and then purged with nitrogen for 20 s. The deposition of 150cycles was then repeated as per the above steps.
Step 2: the pore diameter and pore pitch profiles were prepared using CAD software, with pore diameters set at 100 μm and pore pitches set at 100 μm.
And step 3: anodizing the aluminum foil according to a drawing at a wavelength of 532nm and a laser moving speed of 1000mm · s-1Carrying out laser etching under the conditions that the pulse repetition frequency is 80kHZ and the light source power is 20W to obtain the required HfO2-an aluminium foil of porous structure.
Assembling the prepared negative electrode material into a soft package aluminum battery in the following sequence: aluminum-plastic film, positive electrode material (three-dimensional graphite), diaphragm, electrolyte and negative electrode material (HfO)2-porous aluminium foil) + aluminium plastic film. And (4) carrying out constant current charging and discharging and cyclic stability testing on the assembled device by using a blue testing system. The test results were as follows:
this example prepares HfO of different dielectric layer thicknesses2Porous aluminum foil and as negative electrode a pouch cell was assembled, the results showing that in HfO2When the thickness of the dielectric layer is 40nm, the battery is at 10 A.g-1Can reach 95 mAh.g at the current density of-1The capacity of the electrode is far larger than that of the negative electrode with other dielectric layer thicknesses, so that the performance of the electrode material can be further improved by regulating the thickness of the dielectric layer.
Example 7:
step 1: putting 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 and ZrCl4The temperature of the titanium source is kept at 100 ℃, 3s are introduced, and then nitrogen is introduced for purging for 30 s. Then introducing H2O reacts for 30s, and nitrogen is used for purging for 10 s. The deposition of 150cycles was then repeated as per the above steps.
Step 2: a CAD software was used to prepare a distribution map of pore diameters and pore pitches, with pore diameters set to 30 μm and pore pitches set to 10 μm.
And step 3: the anodized aluminum foil was subjected to laser irradiation at a laser moving speed of 2000mm · s at a wavelength of 355nm in accordance with a drawing-1Carrying out laser etching under the conditions that the pulse repetition frequency is 10kHZ and the light source power is 50W to obtain the required ZrO2-an aluminium foil of porous structure.
Assembling the prepared negative electrode material into a soft package aluminum battery in the following sequence: aluminum plastic film, positive electrode material (three-dimensional graphite), diaphragm, electrolyte and negative electrode material (ZrO)2-porous aluminium foil) + aluminium plastic film. And (4) carrying out constant current charging and discharging and cyclic stability testing on the assembled device by using a blue testing system. The test results were as follows:
ZrO of different channel depths assembled in this example2Pouch cells assembled with porous aluminum foil as negative electrode show different capacities and dendrite growth. The cell was at 10A g at a pore depth of 65 μm-1Can reach 92mAh g under the current density-1The maximum battery capacity can only reach 80mAh g when the pore channel depth is less than 65 mu m-1And the grown dendrite is higher than ZrO2An interfacial layer. This is probably because the effective electrochemical area of exposed aluminum, determined by the channel depth, affects the contact area with the electrolyte when less aluminum is exposed, affecting the charge transfer at the interface and thus the cell performance. Therefore, it can be shown that adjusting the depth of the channel can further improve the performance of the electrode material.
Example 8:
step 1: putting 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 and ZrCl4The temperature of the titanium source is kept at 150 ℃, 3s are introduced, and nitrogen is introduced for purging for 60 s. Then introducing H2O reaction for 10s, and nitrogen purging for 60 s. The deposition of 150cycles was then repeated as per the above steps.
Step 2: the pore diameter and pore pitch profiles were prepared using CAD software, with pore diameters set at 100 μm and pore pitches set at 20 μm.
And step 3: oxidizing the anodeThe aluminum foil of (2) was drawn at a wavelength of 1064nm and a laser moving speed of 500mm · s-1Carrying out laser etching under the conditions that the pulse repetition frequency is 30kHZ and the light source power is 50W to obtain the required ZrO2-an aluminium foil of porous structure.
Assembling the prepared negative electrode material into a soft package aluminum battery in the following sequence: aluminum plastic film, positive electrode material (three-dimensional graphite), diaphragm, electrolyte and negative electrode material (ZrO)2-porous aluminium foil) + aluminium plastic film. And (4) carrying out constant current charging and discharging and cyclic stability testing on the assembled device by using a blue testing system. The test results were as follows:
ZrO of different pore sizes assembled in this example2Pouch cells assembled with porous aluminum foil as negative electrode show different capacities and dendrite growth. The pitch of the channels was set to 30 μm, and the cell was at 10 A.g. at a channel diameter of 30 μm-1Can reach 98 mAh.g under the current density-1The capacity of (a) is 10A · g at a cell pore diameter of 100 μm-1At a current density of only 70mAh g-1. This is probably because the pore diameter size determines the effective electrochemical area of exposed aluminum, which, when less aluminum is exposed, affects the contact area with the electrolyte, affects the charge transfer at the interface and thus the cell performance. Therefore, it can be shown that the performance of the electrode material can be further improved by regulating the pore size.
Example 9:
step 1: putting 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 and SiCl4The temperature was maintained at 200 ℃ for a titanium source, 3s were passed, and a nitrogen purge was passed for 10 s. Then introducing H2O reaction for 10s, and nitrogen purging for 10 s. The deposition of 150cycles was then repeated as per the above steps.
Step 2: a CAD software was used to prepare a distribution map of pore diameters and pore pitches, with pore diameters set to 50 μm and pore pitches set to 50 μm.
And step 3: anodizing the aluminum foil according to a drawing at a wavelength of 532nm and a laser moving speed of 10mm · s-1A pulse repetition frequency of 50kHZ and lightCarrying out laser etching under the condition that the source power is 50W to obtain the required SiO2-an aluminium foil of porous structure.
Assembling the prepared negative electrode material into a soft package aluminum battery in the following sequence: aluminum-plastic film, positive electrode material (three-dimensional graphite), diaphragm, electrolyte and negative electrode material (SiO)2-porous aluminium foil) + aluminium plastic film. And (4) carrying out constant current charging and discharging and cyclic stability testing on the assembled device by using a blue testing system. The test results were as follows:
SiO with different pore channel depths assembled in the embodiment2Pouch cells assembled with porous aluminum foil as negative electrode show different capacities and dendrite growth. SiO with different pore channel depths assembled in the embodiment2Pouch cells assembled with porous aluminum foil as negative electrode show different capacities and dendrite growth. The cell was at 10A g at a pore depth of 65 μm-1Can reach 90mAh g under the current density-1The maximum battery capacity can only reach 75mAh g when the pore channel depth is less than 65 mu m-1And the grown dendrite is higher than SiO2An interfacial layer. This is probably because the effective electrochemical area of exposed aluminum, determined by the channel depth, affects the contact area with the electrolyte when less aluminum is exposed, affecting the charge transfer at the interface and thus the cell performance. Therefore, it can be shown that adjusting the depth of the channel can further improve the performance of the electrode material.
Example 10:
step 1: putting 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 and SiCl4The source temperature was maintained at 100 ℃ for a titanium source, and 1s was passed through the tube, followed by purging with nitrogen for 30 s. Then introducing H2O reacted for 10s and then nitrogen purged for 30 s. The deposition of 150cycles was then repeated as per the above steps.
Step 2: the pore diameter and pore pitch profiles were prepared using CAD software, with pore diameters set at 80 μm and pore pitches set at 100 μm.
And step 3: anodizing the aluminum foil according to the drawing at a wavelength of 1064nm and a laser moving speed of 100mm · s-1Pulse and vesselPerforming laser etching under the conditions that the punching repetition frequency is 20kHz and the light source power is 30W to obtain the required SiO2-an aluminium foil of porous structure.
Assembling the prepared negative electrode material into a soft package aluminum battery in the following sequence: aluminum-plastic film, positive electrode material (three-dimensional graphite), diaphragm, electrolyte and negative electrode material (SiO)2-porous aluminium foil) + aluminium plastic film. And (4) carrying out constant current charging and discharging and cyclic stability testing on the assembled device by using a blue testing system. The test results were as follows:
SiO with different pore sizes assembled in the embodiment2Pouch cells assembled with porous aluminum foil as negative electrode show different capacities and dendrite growth. The pitch of the channels was set to 30 μm, and the cell was at 10 A.g. at a channel diameter of 50 μm-1Can reach 90mAh g under the current density-1The capacity of (a) is 10A · g at a cell pore diameter of 80 μm-1At a current density of only 61mAh g-1. This is probably because the pore diameter size determines the effective electrochemical area of exposed aluminum, which, when less aluminum is exposed, affects the contact area with the electrolyte, affects the charge transfer at the interface and thus the cell performance. Therefore, it can be shown that the performance of the electrode material can be further improved by regulating the pore size.
The invention also provides an aluminum battery cathode which is obtained based on the preparation method of the embodiment.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.

Claims (10)

1. An ALD preparation method of an aluminum battery cathode is characterized by comprising the following steps: depositing a layer of insulating medium layer on the cleaned aluminum foil by an ALD method; performing laser etching on the aluminum foil deposited with the insulating medium layer to form a uniform pore channel structure to obtain a porous aluminum foil;
and ultrasonically cleaning the porous aluminum foil to obtain the porous aluminum foil cathode of the dielectric layer.
2. The ALD preparation method of an aluminum battery cathode according to claim 1, characterized in that the aluminum foil is subjected to cleaning pretreatment before deposition of the insulating dielectric layer, and the aluminum foil is sequentially subjected to ultrasonic cleaning and drying in acetone, alcohol and deionized water.
3. The ALD preparation method of an aluminum battery cathode as claimed in claim 1, wherein the ALD method deposits the insulating dielectric layer under a vacuum degree of 3-20mTorr and at a temperature of 100-.
4. The ALD preparation method of an aluminum battery cathode according to claim 1, wherein when the ALD method deposits the insulating medium layer, the insulating medium layer is insulating metal oxide, the source temperature of a metal source in the insulating metal oxide is 25-200 ℃, the introduction time is 1-3s, the diffusion time is 1-60s, and the nitrogen purging time is 1-60 s.
5. The ALD preparation method of an aluminum battery cathode according to claim 1, characterized in that the precursor of the insulation medium layer 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 O2，O3，H2O or H2O2The introduction time is 1-10s, and the diffusion time is 1-60 s.
6. The ALD preparation method of an aluminum battery cathode as claimed in claim 1, wherein the diameter of a pore channel formed by laser etching is 10-100 μm, and the pore distance is 10-100 μm.
7. The ALD preparation method of an aluminum battery negative electrode as claimed in claim 1, characterized in that the laser moving speed is 0.001mms-1-2000mms-1The pulse repetition frequency is 10-100 kHZ, and the light source power is 10-50W.
8. The ALD preparation method of an aluminum battery negative electrode as recited in claim 1, wherein the wavelength of the laser etching is set to 355nm, 532nm or 1064 nm.
9. The application of the porous aluminum foil cathode with the dielectric layer prepared by the preparation method of any one of claims 1 to 8 is characterized in that the porous aluminum foil cathode is used for aluminum batteries and aluminum-air batteries.
10. An aluminum battery negative electrode, characterized by being obtained by the production method according to any one of claims 1 to 8.
CN202210074723.0A 2022-01-21 2022-01-21 Aluminum battery cathode and ALD (atomic layer deposition) preparation method and application thereof Pending CN114373882A (en)

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