CN114242460B - All-solid-state aluminum electrolytic capacitor device and ALD preparation method thereof - Google Patents

All-solid-state aluminum electrolytic capacitor device and ALD preparation method thereof Download PDF

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CN114242460B
CN114242460B CN202111571126.0A CN202111571126A CN114242460B CN 114242460 B CN114242460 B CN 114242460B CN 202111571126 A CN202111571126 A CN 202111571126A CN 114242460 B CN114242460 B CN 114242460B
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electrolytic capacitor
aluminum electrolytic
ald
foil
conductive oxide
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CN114242460A (en
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杜显锋
郭媛
熊礼龙
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Xian Jiaotong University
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Abstract

The invention discloses a solid-state aluminum electrolytic capacitor device and an ALD (atomic layer deposition) preparation method thereof, belonging to the field of aluminum electrolytic capacitors; the method comprises the following steps: removing burrs, forming and supplementing the aluminum electrolytic capacitor anode aluminum foil; depositing a conductive oxide film on the surface of the anode foil dielectric layer by using an ALD (atomic layer deposition) method; and leading out a cathode electrode of the deposited conductive film layer. The method avoids the damage of reducing reactant gas molecules and plasma in the ALD deposited metal simple substance cathode film to the aluminum foil dielectric layer; the damage of acid substances, strong oxidants and the like to the aluminum foil dielectric layer in the process of preparing the cathode material by the liquid phase method is avoided, the cathode conductive oxide prepared by ALD has high conductivity, can more easily enter micro-nano pores of the anode aluminum foil, is uniform on the surface of the dielectric layer, has controllable and compact thickness, and ensures the miniaturization, high-capacity extraction rate, high breakdown field strength, low electric leakage, excellent frequency characteristic, low ESR, low loss, high temperature resistance and long service life of the solid-state aluminum electrolytic capacitor.

Description

All-solid-state aluminum electrolytic capacitor device and ALD (atomic layer deposition) preparation method thereof
Technical Field
The invention belongs to the field of aluminum electrolytic capacitors, and particularly relates to a method for preparing a cathode film by using an ALD (atomic layer deposition) conductive oxide.
Background
The rapid development of the mobile internet technology promotes the development of electronic products which are necessarily towards miniaturization, light weight and greenness. The conventional liquid aluminum electrolytic capacitor uses an ion conductive liquid electrolyte, and thus has problems of poor frequency characteristics, liquid leakage, poor temperature characteristics, short life, and the like. Therefore, a solid-state aluminum electrolytic capacitor having characteristics such as low cost, small volume, large capacity, low impedance, and excellent frequency characteristics is particularly important.
At present, the cathode curing material of the aluminum electrolytic capacitor is mainly manganese oxide and a conductive polymer prepared by a liquid phase method. Through research and study in literature, yasuoKudoh et al 1996 adopts a pyrolysis method to prepare manganese oxide on the surface of a dielectric layer of a solid aluminum electrolytic capacitor, and simultaneously adopts an electrochemical method to prepare a polypyrrole (PPY) conductive cathode material. Penjia et al 2006 and Gaokui et al 2007 adopt chemical oxidation and impregnation methods to synthesize conductive Polyaniline (PANI) as a solid cathode. In 2018, wakabayashi et al used a dipping method to prepare polyethylene dioxythiophene (PEDOT) as a solid cathode. However, in the above reports, the manganese oxide cathode material prepared by the liquid phase method has low conductivity, and thus the device has low capacity extraction rate, high ESR and poor frequency characteristics. The conductive polymer cathode material prepared by the liquid phase method has high conductivity, but is unstable at high temperature and is easy to age.
Furthermore, the method of liquid phase preparation of solid cathodes has the following disadvantages: (1) When a solvent or a dispersant is used, due to the existence of surface tension, large molecular size and other factors, a cathode material cannot enter micro-nano pores of an anode foil at a high coverage rate, so that the capacity extraction rate is low; (2) When a solvent or a dispersing agent is used, impurities are easy to remain in the cathode conducting layer, so that the conductivity of the cathode material is reduced, the equivalent series resistance and the loss are large, and the frequency characteristic is deviated; (3) The use of acidic substances, strong oxidants and the like can damage the dielectric layer of the aluminum electrolytic capacitor, thereby reducing the withstand voltage and increasing the leakage current; (4) The compactness of cathode films such as manganese oxide, conductive polymers and the like prepared on the surface of the anode foil dielectric layer by adopting a liquid phase method is poor, and the adhesive force is not strong, so that the capacity extraction rate of the device is low, and meanwhile, the anode foil dielectric layer is easily corroded by moisture and the like in the environment, so that the service life of the device is influenced; (5) In the process of preparing the cathode polymer material by the liquid phase method, the use of organic solvents and the like has great influence on the environment.
In recent years, with the development of ALD deposition technology, research on the preparation of high conductivity elemental metals and the like as cathode materials of solid aluminum electrolytic capacitors has been gradually explored. However, in the ALD process of depositing a conductive thin film such as a simple metal substance, the reactant used is usually a gas or a plasma with strong reducibility, which will cause corrosive damage to the anode foil dielectric layer, thereby causing problems such as reduction of breakdown field strength and increase of leakage current.
Disclosure of Invention
In order to overcome the above-mentioned technical disadvantages, the present invention aims to provide a method for preparing a conductive oxide cathode thin film by ALD in a solid aluminum electrolytic capacitor, wherein the oxide cathode material with high conductivity is prepared by ALD, which not only solves the problems of low conductivity, no high temperature resistance and the like of the traditional solid cathode material, but also solves the problems of low capacity extraction rate, poor frequency characteristics, large ESR and the like of the solid aluminum electrolytic capacitor.
The invention is realized by the following technical scheme: an ALD preparation method of an all-solid-state aluminum electrolytic capacitor device comprises the following steps:
taking an anode foil of the aluminum electrolytic capacitor, and protecting the anode foil from leading out;
taking a conductive oxide source as a precursor, and depositing a conductive oxide cathode film on the surface of an anode foil dielectric layer of an aluminum electrolytic capacitor by using an ALD method, which specifically comprises the following steps: blowing a precursor of a conductive oxide into a deposition chamber in the form of vapor; introducing nitrogen or argon to blow out redundant precursors which are not adsorbed on the surface of the substrate, and then blowing in an oxygen source reactant, wherein the oxygen source reactant reacts with the precursors adsorbed on the surface of the substrate to generate a conductive oxide; introducing nitrogen or argon to blow out redundant reactants which do not react with the precursor;
and leading out a cathode electrode of the deposited conductive oxide cathode film to obtain the all-solid-state aluminum electrolytic capacitor device.
When two different conductive oxide sources are used as precursors and an ALD method is used for depositing a doped conductive oxide cathode film on the surface of an anode foil dielectric layer of an aluminum electrolytic capacitor: depositing a first oxide film for a plurality of periods, then depositing a second oxide film for a plurality of periods, and finally repeating the process to form periodic conductive oxide cathode films on two surfaces of the anode foil of the aluminum electrolytic capacitor.
The specific operation of depositing a layer of conductive oxide film on the surface of the anode foil dielectric layer is as follows:
under the conditions that the vacuum degree is 3-20 mTorr and the temperature is 114-275 ℃, nitrogen or argon is used as a carrier gas, a conductive oxide metal source is blown in a steam mode for 0.01-3 s, nitrogen or argon is blown in for blowing for 5-60 s, a reactant oxygen source is blown in for 0.01-60 s, nitrogen or argon is blown in for blowing for 5-180 s, and a period is completed; repeating the production cycle until a conductive oxide film with a set thickness is generated.
The corrosion aluminum foil or corrosion formed foil is provided with a porous dielectric layer, and the corrosion foil or the formation foil with a voltage section of 3-630V is adopted.
The method is characterized in that the aluminum electrolytic capacitor anode foil is subjected to deburring treatment, the specific process is carried out in one or more solutions of oxalic acid, acetic acid or hydrochloric acid, the temperature of the solution is controlled to be 25-90 ℃, and the current density is not more than 20mA/cm 2 The treatment time is controlled within 3-60 min.
The precursor source of the conductive oxide in the ALD deposition is a tin source, an indium source, a zinc source, an aluminum source, a platinum source, a ruthenium source, an iridium source, a manganese source or a cobalt source; the oxygen source of the reactant is O 2 、O 3 、H 2 O or H 2 O 2 。
Forming and compensating the corrosion foil;
during formation treatment: the temperature of the formed liquid is controlled between 25 and 90 ℃, and is controlled between 3 and 630V and between 5 and 300mA/cm 2 The conditions of (1) are changed into (1); the used formation liquid is one or more of boric acid, ammonium pentaborate, ammonium dihydrogen phosphate or ammonium adipate solution; the mass fraction of the formation liquid is 1-20%;
during the complementary formation treatment, the voltage value is maintained unchanged after the set voltage is reached, and the current density is reduced to 0.1-10 mA/cm 2 After cleaning the residual formation liquid on the surface of the aluminum foil, carrying out heat treatment on the aluminum foil in air at 350-550 ℃ for 2-60 min; after the heat treatment, the complementary formation is carried out under the same condition as the formation process; the formed foil is cut and then directly subjected to complementary formation.
If the current density value is reduced by more than 0.1mA/cm after the compensation is formed 2 Then, the operation of heat treatment and compensation is carried out for one or more times until the concentration is between 0.001 and 0.01mA/cm 2 The withstand voltage can be smoothly raised to the set voltage under the boosting current.
And leading out the deposited cathode conducting layer by using conductive carbon paste, silver paste, aluminum foil or silver wires.
The total thickness of the conductive cathode oxide film of the all-solid-state aluminum electrolytic capacitor device prepared by the preparation method is 1-500 nm, and the conductive cathode oxide film is a plurality of single conductive oxide films or a plurality of two alternate conductive oxide films.
Compared with the prior art, the invention has the following beneficial effects:
1) The invention discloses that the conductive oxide film prepared by Atomic Layer Deposition (ALD) is used as the cathode of the solid-state aluminum electrolytic capacitor for the first time, and compared with the manganese oxide material prepared by the traditional liquid phase method, the conductive oxide film prepared by ALD has good conductivity; compared with the traditional conductive polymer material, the conductive oxide film prepared by ALD has good wide temperature range; compared with the metal simple substance cathode material prepared by ALD, in the process of preparing the conductive oxide film by ALD, no gas or plasma with strong reducibility causes corrosive damage to the anode foil dielectric layer;
2) Compared with the traditional film coating method and liquid phase method for preparing cathode materials, the method has the advantages that the ALD self-limits the growth characteristic, the repeatability of the deposited conductive film can be realized without controlling the uniformity of the flow of the precursor and the reactant in the deposition process, and the thickness of the conductive film can be accurately controlled by controlling the reaction cycle times. ALD deposition is also suitable for growing in voids on deep aspect ratio or high aspect ratio structures as well as complex surface structures, easily into micro-nano-scale pores of etched foils, and can adhere more strongly to substrates. Precursors and reactants deposited by ALD react through saturated chemical adsorption, so that the coverage rate of step deposition of the substrate is high, and simultaneously, the large-area uniformity of deposition can be ensured, thereby effectively improving the capacity extraction rate and frequency characteristics of the solid-state aluminum electrolytic capacitor, and reducing loss and equivalent series resistance. In addition, compared with the process of preparing the cathode material by a liquid phase method, the ALD deposited conductive oxide cathode film can avoid the damage of acidic substances, strong oxidants and the like in the solution to the aluminum foil dielectric layer, and can effectively isolate the damage of moisture and the like in the air to the dielectric layer, thereby reducing the leakage current of the device, improving the breakdown field strength and prolonging the service life.
Furthermore, in the complementary formation process of anodic oxidation, the medium is subjected to one or more heat treatment operations at 350-550 ℃ for 2-60 minThe micro cracks of the layer are exposed completely for many times, and then the current density is reduced to 0.001-0.1 mA/cm by the constant voltage value after the applied voltage is increased to the set voltage 2 Then 0.001-0.01 mA/cm 2 The boost current of (2) is boosted. The step is carried out once or for many times, so that the microcracks of the dielectric layer are completely repaired after being exposed for many times, and the current density is 0.001-0.1 mA/cm 2 The withstand voltage can be raised to a set voltage.
Drawings
FIG. 1 is a schematic structural diagram of a solid-state aluminum electrolytic capacitor;
FIG. 2 is a cross-sectional SEM image of an anode aluminum foil with an ALD deposited conductive oxide cathode: wherein, (a) is a cross-sectional morphology; and (b) is a local enlarged view of the sectional morphology.
FIG. 3 is a magnified SEM image of a portion of the outer surface of an ALD deposited conductive oxide cathode of anodic aluminum foil.
Detailed Description
In order to make those skilled in the art better understand the technical solutions of the present invention, 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 provides a method for preparing a conductive oxide cathode film in an ALD (atomic layer deposition) mode in a solid aluminum electrolytic capacitor, wherein the ALD mode is used for preparing a high-conductivity oxide cathode material, so that the problems of low conductivity, no high temperature resistance and the like of the traditional solid cathode material are solved, and the problems of low capacity extraction rate, poor frequency characteristic, large ESR and the like of the solid aluminum electrolytic capacitor are solved. In addition, in the ALD conductive oxide deposition process, the reactants do not corrode and damage the dielectric layer of the anode foil, and the aluminum electrolytic capacitor is further promoted to develop towards miniaturization, high capacity, high breakdown field strength, high frequency, low impedance, high temperature resistance and long service life.
Referring to fig. 1-2, the principle of the present invention for preparing a cathode conductive oxide thin film on the surface of an anode foil dielectric layer of an aluminum electrolytic capacitor is illustrated, and the ALD deposited cathode oxide conductive layer is shown to be suitable for growth into high aspect ratio hole structures. The invention uses ALD method to deposit conductive oxide film on the surface of anode foil dielectric layer of aluminum electrolytic capacitor, and then leads out cathode electrode, thus preparing all-solid-state aluminum electrolytic capacitor device with high capacity lead-out rate and good frequency characteristic.
The invention is described by combining figure 3, on the surface of the anode foil dielectric layer of the aluminum electrolytic capacitor, the cathode conductive oxide film prepared by ALD is uniform and is tightly attached to the dielectric layer, the damage of moisture in the air to the dielectric layer can be effectively isolated, and the service life of the all-solid-state aluminum electrolytic capacitor is prolonged.
Comparative example 1
Step 1: and cutting out the formed aluminum foil with the anode leading-out end by using an aluminum foil cutting die, and performing heat treatment and compensation on the formed aluminum foil.
And 2, step: and (2) sequentially immersing the formed anode foil obtained after the treatment in the step (1) into a 3, 4-ethylenedioxythiophene solution (EDOT) and a p-toluenesulfonic acid iron solution by an in-situ polymerization method to obtain a polymer cathode conducting layer, taking out and drying.
And step 3: and (3) dripping conductive carbon paste on the surface of the polymer cathode obtained in the step (2), solidifying at room temperature, dripping silver paste, placing silver wires as a cathode leading-out end, and solidifying.
The conductivity of the cathode conductive layer prepared in this example was 9.27S/cm.
Comparative example 2
Step 1: and cutting out the corrosion-formed aluminum foil with the anode leading-out end by using an aluminum foil cutting die, and carrying out heat treatment and compensation on the aluminum foil.
Step 2: and (3) immersing the corroded anode foil obtained after the treatment in the step (1) in a poly (3, 4-ethylenedioxythiophene)/polystyrene sulfonate solution (PEDOT/PSS) in vacuum, preparing a conductive polymer cathode conductive layer, and drying.
And step 3: and (3) dripping a layer of conductive carbon paste on the surface of the polymer cathode obtained in the step (2), solidifying at room temperature, dripping silver paste, placing silver wires as a cathode leading-out end, and solidifying.
The conductivity of the cathode conductive layer prepared in this example was 102.5S/cm.
The invention discloses a method for preparing a conductive oxide cathode film by ALD, which is used for respectively carrying out anodic oxidation or compensation after deburring on a corrosion aluminum foil or a corrosion formed foil. Then protecting the anode, then placing the anode in the conditions that the vacuum degree is 3-20 mTorr and the temperature is 114-275 ℃, blowing in a conductive oxide metal source in the form of steam by taking nitrogen or argon as carrier gas for 0.01-3 s when using, blowing in nitrogen or argon for 5-60 s when blowing in a reactant oxygen source for 0.01-60 s, and blowing in nitrogen or argon for 5-180 s when blowing in the reactant oxygen source for 0.01-60 s, and finishing a period; repeating the production cycle until a compact conductive oxide film with a set thickness is generated, and then carrying out cathode extraction on the conductive oxide film to obtain the all-solid-state aluminum electrolytic capacitor device.
The method is characterized in that the aluminum electrolytic capacitor anode foil is subjected to deburring treatment in one or more solutions of oxalic acid, acetic acid or hydrochloric acid, the temperature of the solution is controlled to be 25-90 ℃, and the current density is not more than 0-20 mA/cm 2 The treatment time is controlled within 3-60 min.
During formation treatment: transformingThe temperature of the finished liquid is controlled between 25 and 90 ℃, and is controlled between 3 and 630V and between 5 and 300mA/cm 2 The conditions of (1) are changed into (1); the used formation liquid is one or more of boric acid, ammonium pentaborate, ammonium dihydrogen phosphate or ammonium adipate solution; the mass fraction of the formation liquid is 1-20%;
during the complementary formation treatment, the voltage value is maintained unchanged after the set voltage is reached, and the current density is reduced to 0.1-10 mA/cm 2 After cleaning the residual formation liquid on the surface of the aluminum foil, carrying out heat treatment on the aluminum foil in air at 350-550 ℃ for 2-60 min; after the heat treatment, complementary formation is carried out under the same condition as the formation process; for the formed foil, the complementary formation is directly carried out after cutting, and for the corrosion foil, the forming treatment is carried out after cutting, and then the complementary formation is carried out.
If the current density value is reduced by more than 0.1mA/cm after the compensation is formed 2 Then, the operation of heat treatment and compensation is carried out for one or more times until the concentration is between 0.001 and 0.01mA/cm 2 The withstand voltage can be smoothly raised to the set voltage under the boosting current.
Example 1
Step 1: cutting the formed aluminum foil with the anode leading-out end by using an aluminum foil cutting die, and then putting the formed aluminum foil into an oxalic acid solution at 25 ℃ for deburring, wherein the current density is set to be 5mA/cm 2 The treatment time was 10min.
Step 2: putting the anode foil obtained by the treatment in the step 1 into ammonium adipate (9%) solution at 85 ℃ for complementary formation treatment, and specifically operating as follows: maintaining the voltage value unchanged after reaching the set voltage, and when the current density is reduced to 0.01-0.02 mA/cm 2 When it is used, 0.01mA/cm is used 2 Is compensated by the boost current.
And step 3: and (3) soaking the anode foil obtained after the treatment in the step (2) by clean water for three times, cleaning, drying at 60 ℃ for 5min, then carrying out heat treatment at 500 ℃ for 2min, and then supplementing the anode foil by the method in the step (2). The heat treatment and complementary formation in this step were repeated twice until the temperature was 0.01mA/cm 2 The withstand voltage can be smoothly raised to the set voltage under the boosting current. As shown in fig. 3, a dense alumina medium layer (B) is formed on the surface of the anode aluminum foil (a).
And 4, step 4: atomic Layer Deposition (ALD) techniques to deposit tin oxide (SnO) 2 ) And a cathode film. The specific operation is as follows: firstly, protecting an anode leading-out end of the anode foil obtained after the treatment in the step 3, putting the anode foil into an ALD reaction chamber with the vacuum degree of 5mTorr at 200 ℃, controlling the source temperature of TDMASn at 40 ℃ by taking nitrogen (99.999%) as carrier gas, blowing 1.0s of TDMASn in a steam mode, diffusing for 10s, and blowing for 30s by introducing nitrogen at the nitrogen flow rate of 300sccm. Then 30s of O is introduced 3 ，O 3 The flow rate was 500sccm, and nitrogen gas was introduced for 40 seconds to purge. Thus depositing 150 cycles on both surfaces of the anode foil obtained in step 3. As shown in fig. 2 and 3, a dense conductive oxide cathode film (C) is finally deposited on the surface of the alumina dielectric layer (B).
And 5: the sample subjected to the step 4 was immersed in the conductive carbon paste to an immersion height of 98% of the working area, and dried at 100 ℃ for 60min. Then dipping the aluminum wire into silver paste, wherein the dipping height is 95% of the working area, placing an aluminum wire on the silver paste as a cathode leading-out terminal, and then sequentially carrying out gradient curing at 75 ℃, 80 ℃, 120 ℃, 130 ℃ and 150 ℃ for 60min respectively.
The conductivity of the cathode conductive layer prepared in this example was 1700S/cm.
Example 2
The parameter conditions in the preparation process differ from those in example 1 in that: deposition of indium oxide (In) by Atomic Layer Deposition (ALD) techniques 2 O 3 ) And a cathode film. And (4) carrying out anode leading-out end protection on the formed anode foil, and then putting the anode foil into an ALD reaction chamber with the vacuum degree of 5 mTorr. The deposition temperature was 150 ℃, nitrogen (99.999%) was used as a carrier gas, the temperature of the trimethylindium (TMIn) source was controlled at 50 ℃, 1.0s of TMIn was blown in as vapor and diffused for 9s, and purging was performed for 15s by introducing nitrogen. Then introducing O for 9s 3 Then, nitrogen gas was introduced for 30 seconds to purge. In was thus deposited on both surfaces of the anode foil, respectively 2 O 3 50 cycles each.
The conductivity of the cathode conductive layer prepared in this example was 333S/cm.
Example 3
The parameter conditions in the preparation process of example 2 were different: this example deposited In ALD 2 O 3 By doping with small amounts of SnO 2 The method for preparing the ITO cathode film can effectively improve the conductivity of the oxide film, and comprises the following specific operations:
and (4) carrying out anode leading-out end protection on the formed anode foil, and then putting the anode foil into an ALD reaction chamber with the vacuum degree of 5mTorr, wherein the deposition temperature is 275 ℃. First 1 cycle of SnO deposition 2 The method comprises the following specific steps: using nitrogen (99.999%) as carrier gas, TDMASn source temperature was controlled at 40 deg.C, 1.0s TDMASn was blown in as vapor and diffused for 5s, and then nitrogen was blown in for 30s. Then 1s of H is introduced 2 O 2 Then introducing nitrogen for 5s for purging; post-deposition of 19 cycles of In 2 O 3 The method comprises the following specific steps: inCp source temperature is controlled to be 40 ℃ by taking nitrogen (99.999%) as carrier gas, inCp is blown in 2.0s in the form of steam and diffused for 10s, then nitrogen is blown in for 5s, and then O is blown in for 2s 3 Then, nitrogen gas was introduced for 30 seconds to purge. Thus, on both surfaces of the anode foil, ITO was deposited for 10 periods (1 period of SnO), respectively 2 And 19 periods of In 2 O 3 Alternating as 1 period of ITO). Other condition parameters were the same as in example 1.
The conductivity of the cathode conductive layer prepared in this example was 2564S/cm.
Example 4
The parameter conditions in the preparation process differ from those in example 1 in that:
in the step 1, the deburring treatment is carried out by using an acetic acid solution at 90 ℃, wherein the current density is set to be 20mA/cm 2 The treatment time is 3min; in the step 2, a 25 ℃ aqueous solution of boric acid (10%) and ammonium pentaborate (12%) is used for complementary formation treatment; the heat treatment process in step 3 is completed at 350 ℃ for 60min.
And 4, depositing a zinc oxide (ZnO) cathode film by using an Atomic Layer Deposition (ALD) technology. And (4) carrying out anode leading-out end protection on the formed anode foil, and then putting the anode foil into an ALD reaction chamber with the vacuum degree of 3 mTorr. The deposition temperature is 170 ℃, nitrogen (99.999 percent) is used as carrier gas,the source temperature of diethyl zinc (DEZ) was controlled at 50 ℃, 1.0s of DEZ was blown in as steam and diffused for 10s, and then purged for 5s with nitrogen. Then 30s of H is introduced 2 And O, and introducing nitrogen for 60 seconds for purging. Thus, 100 periods of each ZnO were deposited on both surfaces of the anode foil.
Other condition parameters are the same as example 1, and the conductivity of the cathode conductive layer prepared in this example is 170S/cm.
Example 5
The parameter conditions in the preparation process differ from those in example 4 in that: in the embodiment, a small amount of aluminum oxide is doped in the process of depositing ZnO in ALD to prepare the AZO cathode film, and the method can effectively improve the conductivity of the oxide film and specifically comprises the following steps:
and (4) carrying out anode leading-out end protection on the repaired anode foil, and then putting the anode foil into an ALD reaction chamber with the vacuum degree of 3 mTorr. First, 1 cycle of Al is deposited 2 O 3 The method comprises the following specific steps: the deposition temperature was 200 ℃, nitrogen (99.999%) was used as a carrier gas, the temperature of the Trimethylaluminum (TMA) source was controlled at 25 ℃, 0.01s of TMA was blown and diffused for 10s, and purging was performed for 5s with nitrogen. Then introducing 10s of oxygen source H 2 O, and then introducing nitrogen for 5s for purging; and depositing ZnO for 20 periods, wherein the method comprises the following specific steps: depositing at 150 deg.C, using nitrogen (99.999%) as carrier gas, controlling temperature of diethyl zinc (DEZ) source at 25 deg.C, blowing DEZ in form of vapor for 2.0s, diffusing for 10s, purging with nitrogen for 30s, and then introducing oxygen source H for 60s 2 And O, and introducing nitrogen for 40 seconds for purging. Thus, 60 cycles of AZO (1 cycle of Al) were deposited on both surfaces of the anode foil, respectively 2 O 3 Alternating with 20 cycles of ZnO deposited as 1 cycle of AZO). Other condition parameters were the same as in example 1.
The conductivity of the cathode conductive layer prepared in this example was 1754S/cm.
Example 6
The parameter conditions in the preparation process differ from those in example 1 in that:
in step 1, a hydrochloric acid solution at 30 ℃ was used for deburring, wherein the current density was set to 0.5mA/cm 2 Treatment time of 60min; in the step 2, 90 ℃ aqueous solution of ammonium adipate (1.5%) and ammonium dihydrogen phosphate (1%) is used for complementary formation treatment; the heat treatment process in step 3 is completed at 550 ℃ for 2 min.
Step 4, platinum oxide (PtO) is deposited by Atomic Layer Deposition (ALD) technology 2 ) And a cathode film. And (4) carrying out anode leading-out end protection on the formed anode foil, and then putting the anode foil into an ALD reaction chamber with the vacuum degree of 5 mTorr. Deposition temperature 140 deg.C, argon (99.999%) as carrier gas, pt (acac) 2 The source temperature was controlled at 110 deg.C, and 1.0s of Pt (acac) was blown in as vapor 2 And diffused for 10s, and then purged with argon for 30s. Then introducing O for 10s 3 Then, argon gas was introduced for 40 seconds to purge. Thus, ptO is deposited on both surfaces of the anode foil 2 50 cycles each.
The conductivity of the cathode conductive layer prepared in this example was 90909S/cm under the same other condition parameters as in example 1.
Example 7
The parameter conditions in the preparation process differ from those in example 1 in that: atomic Layer Deposition (ALD) techniques for depositing ruthenium oxide (RuO) 2 ) And a cathode film. And (4) carrying out anode leading-out end protection on the formed anode foil, and then putting the anode foil into an ALD reaction chamber with the vacuum degree of 5 mTorr. Deposition temperature 270 deg.C, argon (99.999%) as carrier gas, ru (CpEt) 2 The source temperature was controlled at 80 ℃ and Ru (CpEt) was blown as a vapor for 1.0s 2 And diffused for 10 seconds, and then purged with argon for 30 seconds. Then introducing O for 10s 2 Then, argon gas was introduced for 40 seconds to purge. Thus depositing RuO on both surfaces of the anode foil 2 100 cycles each. Other condition parameters were the same as in example 1.
The conductivity of the cathode conductive layer prepared in this example was 70000S/cm.
Example 8
The parameter conditions in the preparation process differ from those in example 1 in that: an Atomic Layer Deposition (ALD) technique deposits an iridium oxide (IrO 2) cathode thin film. And (4) carrying out anode leading-out end protection on the formed anode foil, and then putting the anode foil into an ALD reaction chamber with the vacuum degree of 5 mTorr. Deposition temperature 185 deg.C, with nitrogen (99.99 deg.C)9%) as carrier gas, ir (acac) 3 The source temperature was controlled at 155 deg.C, and Ir (acac) was blown as vapor for 1.0s 3 And diffused for 10 seconds, and then purged with nitrogen for 30 seconds. Then introducing O for 9s 3 Then, nitrogen gas was introduced for 40 seconds to purge. Thus, irO2 was deposited on both surfaces of the anode foil for 50 cycles, respectively. Other condition parameters were the same as in example 1.
The conductivity of the cathode conductive layer prepared in this example was 5882S/cm.
Example 9
The parameter conditions in the preparation process differ from those in example 1 in that:
in the step 2, 85 ℃ ammonium adipate (20%) aqueous solution is used for complementary formation treatment; the heat treatment process in step 3 is completed by treating at 450 ℃ for 5 min.
Step 4 depositing manganese oxide (MnO) by Atomic Layer Deposition (ALD) 2 ) And a cathode film. And (4) carrying out anode leading-out end protection on the formed anode foil, and then putting the anode foil into an ALD reaction chamber with the vacuum degree of 5 mTorr. Deposition temperature 230 deg.C, nitrogen (99.999%) as carrier gas, and tetradimethylamino titanium (Mn (thd) 3 ) The source temperature was controlled at 133 deg.C, and Mn (thd) was blown as vapor for 3.0s 3 And diffused for 10 seconds, and then purged with nitrogen for 60 seconds. Then 0.01s of O is introduced 3 Then, nitrogen gas was introduced for 40 seconds to purge. So as to deposit MnO on both surfaces of the anode foil respectively 2 1000 cycles each.
Other condition parameters were the same as in example 1, and the conductivity of the cathode conductive layer prepared in this example was 22S/cm.
Example 10
The parameter conditions in the preparation process differ from those in example 1 in that: deposition of cobaltosic oxide (Co) by Atomic Layer Deposition (ALD) technique 3 O 4 ) And a cathode film. And (4) carrying out anode leading-out end protection on the formed anode foil, and then putting the anode foil into an ALD reaction chamber with the vacuum degree of 20 mTorr. Deposition temperature was 114 ℃, nitrogen (99.999%) as carrier gas, co (thd) 2 The source temperature was controlled at 109.5 ℃ and Co (thd) was blown as vapor for 1.0s 2 And diffused for 20s, and then purged with nitrogen for 30s. Then 20s of O is introduced 3 Then, nitrogen gas was introduced for 180 seconds to purge. Thus, co is respectively deposited on both surfaces of the anode foil 3 O 4 1000 cycles each. Other condition parameters were the same as in example 1.
The conductivity of the cathode conductive layer prepared in this example was 8.2S/cm.
In summary, the present invention provides a method for preparing a conductive oxide film on the surface of an anode foil dielectric layer of an aluminum electrolytic capacitor by using an ALD method. The conductivity of the cathode conductive polymer film of the solid aluminum electrolytic capacitor prepared in the comparative example was 10 1 ～10 2 S/cm, and the conductivity of the cathode conductive oxide film of the solid aluminum electrolytic capacitor prepared by the method is 10 1 ～10 5 S/cm。
The solid-state aluminum electrolytic capacitor using the conductive oxide thin film as the cathode prepared in the above example was subjected to electrical property tests, and the experimental results obtained are shown in table 1 below:
table 1 electrical performance parameters of solid state aluminum electrolytic capacitors prepared
Figure BDA0003423362590000141
Figure BDA0003423362590000151
The results in table 1 show that the performance of the solid-state aluminum electrolytic capacitor obtained by the method of the present invention is greatly improved compared with the solid-state aluminum electrolytic capacitor prepared by the liquid-phase method.
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 (7)

1. An ALD preparation method of an all-solid-state aluminum electrolytic capacitor device is characterized by comprising the following steps:
taking an anode foil of the aluminum electrolytic capacitor, and protecting the anode foil from leading out;
taking a conductive oxide source as a precursor, and depositing a conductive oxide cathode film on the surface of an anode foil dielectric layer of an aluminum electrolytic capacitor by using an ALD method, which specifically comprises the following steps: blowing a precursor of a conductive oxide into a deposition chamber in the form of vapor; introducing nitrogen or argon to blow out the redundant precursors which are not adsorbed on the surface of the substrate, and then blowing in an oxygen source reactant, wherein the oxygen source reactant reacts with the precursors adsorbed on the surface of the substrate to generate a conductive oxide; introducing nitrogen or argon to blow out redundant reactants which do not react with the precursor;
leading out a cathode electrode of the deposited conductive oxide cathode film to obtain an all-solid-state aluminum electrolytic capacitor device;
the corrosion aluminum foil or corrosion formed foil is provided with a porous dielectric layer, and the corrosion foil or the formed foil with the voltage section of 3-630V is adopted;
carrying out formation and compensation treatment on the corrosion foil;
during formation treatment: the temperature of the formed liquid is controlled at 25-90 ℃, and is controlled at 3-630V and 5-300 mA/cm 2 The conditions of (1) are changed into (1); the used formation liquid is one or more of boric acid, ammonium pentaborate, ammonium dihydrogen phosphate or ammonium adipate solution; the mass fraction of the formation liquid is 1-20%;
during the complementary formation treatment, the voltage value is maintained unchanged after the set voltage is reached, and the current density is reduced to 0.1-10 mA/cm 2 After cleaning the residual formation liquid on the surface of the aluminum foil, carrying out heat treatment on the aluminum foil in air at 350-550 ℃ for 2-60 min; after the heat treatment, the complementary formation is carried out under the same condition as the formation process; for the formed foil, directly performing complementary formation after cutting; if the current density value is reduced by more than 0.1mA/cm after the compensation is formed 2 Then, the operation of heat treatment and compensation formation is carried out for one or more times until the temperature is between 0.001 and 0.01mA/cm 2 The withstand voltage can be smoothly raised to the set voltage under the boosting current; the precursor sources for the conductive oxide in the ALD deposition are a tin source, an indium source, a zinc source, an aluminum source, a platinum source, a ruthenium source, an iridium source, a manganese source, or a cobalt source.
2. The ALD preparation method of the all-solid-state aluminum electrolytic capacitor device, according to claim 1, characterized in that, when two different conductive oxide sources are used as precursors and the ALD method is used to deposit the doped conductive oxide cathode thin film on the surface of the anode foil dielectric layer of the aluminum electrolytic capacitor: depositing a first oxide film for a plurality of periods, then depositing a second oxide film for a plurality of periods, and finally repeating the process to form periodic conductive oxide cathode films on two surfaces of the anode foil of the aluminum electrolytic capacitor.
3. The ALD preparation method of the all-solid-state aluminum electrolytic capacitor device according to claim 1 or 2, characterized in that the specific operation of depositing a layer of conductive oxide thin film on the surface of the anode foil dielectric layer is as follows:
under the conditions that the vacuum degree is 3-20 mTorr and the temperature is 114-275 ℃, nitrogen or argon is used as carrier gas, a conductive oxide metal source is blown in a steam mode for 0.01-3 s, nitrogen or argon is blown in for blowing for 5-60 s, a reactant oxygen source is blown in for 0.01-60 s, nitrogen or argon is blown in for blowing for 5-180 s, and a period is completed; the production cycle is repeated until a conductive oxide film with a set thickness is generated.
4. The ALD preparation method of the all-solid-state aluminum electrolytic capacitor device according to claim 1 or 2, characterized in that the aluminum electrolytic capacitor anode foil is deburred in one or more solutions of oxalic acid, acetic acid or hydrochloric acid, etc., the solution temperature is controlled to be 25-90 ℃, and the current density is not more than 20mA/cm 2 The treatment time is controlled within 3-60 min.
5. The ALD manufacturing method for all-solid-state aluminum electrolytic capacitor devices according to claim 1 or 2, wherein the reactant oxygen source is O 2 、O 3 、H 2 O or H 2 O 2 。
6. The ALD preparation method of the all-solid-state aluminum electrolytic capacitor device according to claim 1 or 2, characterized in that the deposited cathode conductive layer is led out by using conductive carbon paste, silver paste, aluminum foil or silver wire.
7. The all-solid-state aluminum electrolytic capacitor device prepared by the preparation method of any one of claims 1 to 6, wherein the total thickness of the conductive cathodic oxide film is 1 to 500nm, and the conductive cathodic oxide film is a plurality of single conductive oxide films or a plurality of alternating two conductive oxide films.
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