CN115331964A - Method for detecting specific capacity of aluminum electrode foil - Google Patents
Method for detecting specific capacity of aluminum electrode foil Download PDFInfo
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- CN115331964A CN115331964A CN202210937815.7A CN202210937815A CN115331964A CN 115331964 A CN115331964 A CN 115331964A CN 202210937815 A CN202210937815 A CN 202210937815A CN 115331964 A CN115331964 A CN 115331964A
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 171
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 132
- 239000011888 foil Substances 0.000 title claims abstract description 131
- 238000000034 method Methods 0.000 title claims abstract description 38
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 157
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 90
- 238000005406 washing Methods 0.000 claims abstract description 50
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 40
- 230000000087 stabilizing effect Effects 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 20
- 238000009835 boiling Methods 0.000 claims abstract description 16
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims abstract description 13
- 235000019837 monoammonium phosphate Nutrition 0.000 claims abstract description 13
- 150000007524 organic acids Chemical class 0.000 claims abstract description 13
- 230000036571 hydration Effects 0.000 claims abstract description 8
- 238000006703 hydration reaction Methods 0.000 claims abstract description 8
- 238000010306 acid treatment Methods 0.000 claims abstract description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 21
- 239000004327 boric acid Substances 0.000 claims description 21
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims 1
- 239000003990 capacitor Substances 0.000 abstract description 9
- 239000000243 solution Substances 0.000 description 63
- 239000003792 electrolyte Substances 0.000 description 14
- 238000001514 detection method Methods 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 239000000758 substrate Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000005245 sintering Methods 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 6
- OTRAYOBSWCVTIN-UHFFFAOYSA-N OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N Chemical compound OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N OTRAYOBSWCVTIN-UHFFFAOYSA-N 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 230000006641 stabilisation Effects 0.000 description 5
- 238000011105 stabilization Methods 0.000 description 5
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000010405 anode material Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
- H01G9/052—Sintered electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
- H01G9/045—Electrodes or formation of dielectric layers thereon characterised by the material based on aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
- H01G9/052—Sintered electrodes
- H01G9/0525—Powder therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
- H01G9/055—Etched foil electrodes
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Abstract
The invention relates to the technical field of electrolytic capacitors, in particular to a method for detecting specific capacity of an aluminum electrode foil. The method for detecting the specific capacity of the aluminum electrode foil comprises the following steps: the aluminum electrode foil is put into organic acid solution for water boiling, the first formation is carried out, the formation voltage is 450V-520V, and the current is 0.5A/cm 3 ～2.5A/cm 3 The voltage stabilizing time is 3000 s-7500 s; washing with water, carrying out heat treatment at 350-550 ℃, and carrying out secondary formation; washing with water, and performing phosphoric acid treatment; washing with water, forming for the third time, performing heat treatment at 350-550 ℃, and forming for the fourth time; washing with water, and placing in ammonium dihydrogen phosphate solution for hydration resistance treatment. The method can detect the specific capacity of the high-thickness aluminum electrode foil and can improve the withstand voltage value of the aluminum electrode foil.
Description
Technical Field
The invention relates to the technical field of electrolytic capacitors, in particular to a method for detecting specific capacity of an aluminum electrode foil.
Background
Aluminum electrolytic capacitors are widely used in electronic components of electronic products. The electrode foil is a key material required for manufacturing the aluminum electrolytic capacitor, is specially used for manufacturing the anode and cathode materials of the aluminum electrolytic capacitor and is mainly used for storing electric charges. With the trend of miniaturization and weight reduction of electronic products, higher requirements are also placed on the performance of aluminum electrolytic capacitors, and in order to cope with such changes, aluminum electrolytic capacitors must be developed toward high specific volumes. The most effective method for realizing the miniaturization and high specific volume of the aluminum electrolytic capacitor is to improve the specific capacity of the anode foil.
The electrode foil is generally prepared by coating aluminum powder slurry on the surface of aluminum foil of a substrate. At present, in order to improve the specific capacity of the aluminum electrolytic capacitor, the thickness of the aluminum powder slurry layer is usually increased, that is, the aluminum powder slurry layer on the surface of the aluminum foil substrate is thicker (generally about 100 μm to 400 μm) compared with the conventional electrode foil (the thickness of the aluminum powder slurry layer is generally about 50 μm). However, the thickness of the aluminum powder slurry layer is increased to cause the thickness of the aluminum powder sintered layer formed by subsequent high-temperature sintering to be larger, so that when the specific capacity of the electrode foil is measured, the electrolyte cannot enter one side (i.e. the inner side of the aluminum powder sintered layer) close to the aluminum foil of the base layer, and further the thickness direction of the aluminum powder sintered layer is formed unevenly, so that the expected withstand voltage value cannot be achieved.
Disclosure of Invention
Therefore, it is necessary to provide a method for detecting the specific capacity of the aluminum electrode foil, which can detect the specific capacity of the high-thickness aluminum electrode foil and can improve the withstand voltage of the aluminum electrode foil.
The invention provides a method for detecting specific capacity of an aluminum electrode foil, which comprises the following steps:
a. putting the aluminum electrode foil in an organic acid solution for water boiling, and carrying out first formation, wherein the voltage of the first formation is 450V-520V, and the current is 0.5A/cm 3 ～2.5A/cm 3 The voltage stabilizing time is 3000 s-7500 s;
b. washing the aluminum electrode foil subjected to the first formation with water, performing heat treatment at 350-550 ℃, and performing second formation, wherein the voltage of the second formation is 450-520V, and the current is 0.5A/cm 3 ～2.5A/cm 3 The voltage stabilizing time is 500 s-1500 s;
c. washing the secondarily formed aluminum electrode foil with water, and then carrying out phosphoric acid treatment and water washing;
d. carrying out third formation on the aluminum electrode foil after water washing, wherein the voltage of the third formation is 450V-520V, and the current is 0.5A/cm 3 ～2.5A/cm 3 Is stable and stableThe pressing time is 500-1500 s;
e. washing the aluminum electrode foil after the third formation with water, performing heat treatment at 350-550 ℃, and performing the fourth formation, wherein the voltage of the fourth formation is 450-520V, and the current is 0.5A/cm 3 ～2.5A/cm 3 The voltage stabilizing time is 500-1500 s;
f. and (4) washing the fourth formed aluminum electrode foil with water, and placing the aluminum electrode foil in an ammonium dihydrogen phosphate solution for hydration resistance treatment.
In some embodiments, the organic acid solution has a pH of 3 to 6.
In some embodiments, the solute in the organic acid solution comprises one or more of acetic acid, formic acid, benzoic acid, and sulfonic acid.
In some embodiments, the chemical conversion solutions used in the first chemical conversion, the second chemical conversion, the third chemical conversion and the fourth chemical conversion are respectively and independently selected from boric acid solutions with a concentration of 50g/L to 100 g/L.
In some embodiments, the temperature of the first formation, the second formation, the third formation, and the fourth formation is 83 ℃ to 93 ℃ independently.
In some embodiments, the aluminum electrode foil has a thickness of 210 μm to 860 μm.
In some embodiments, the ammonium dihydrogen phosphate solution has a temperature of 55 ℃ to 70 ℃ and a concentration of 1g/L to 3g/L.
In some embodiments, the method for detecting the specific capacity of the aluminum electrode foil can measure that the withstand voltage value of the aluminum electrode foil is more than or equal to 500V.
In some embodiments, the temperature of the corrosion treatment in the phosphoric acid solution is 55-70 ℃ and the time is 5-10 min.
In some embodiments, the phosphoric acid solution has a conductivity of 25000 μ s/cm to 60000 μ s/cm.
Research shows that in the process of preparing the high-thickness aluminum electrode foil, because the aluminum powder sintered layer on the aluminum foil substrate is thick, the electrolyte cannot enter the inner side of the aluminum powder sintered layer (namely, the side close to the aluminum foil substrate) due to the generation of the oxide film in the aluminum powder sintered layer in the formation process, so that the oxide film cannot be formed on the inner side of the aluminum powder sintered layer, the formation of the aluminum powder sintered layer in the thickness direction is not uniform, and the expected pressure resistance value (more than or equal to 500V) cannot be achieved in the specific capacity detection process.
According to the method for detecting the specific capacity of the aluminum electrode foil, the hydration speed of the aluminum powder sintered layer can be reduced by boiling the aluminum electrode foil in water with the organic acid solution, so that the hydration layer can be formed in the aluminum powder sintered layer, and the efficiency of forming the oxide layer in the aluminum powder sintered layer is improved. The electrolyte can enter the inside of the aluminum powder sintering layer by regulating and controlling the current, the voltage stabilization time and the like of the first formation, so that an oxide film is formed in the inside, the oxide film which is not densified can be cracked by heat treatment, the electrolyte can enter the inside of the aluminum powder sintering layer more easily, and the crystal form of the oxide film can be converted to be densified. The subsequent second formation, third formation and fourth formation can further repair the defective oxide film, and simultaneously enable the aluminum powder sintered layer closer to the inner side to form the oxide film. In addition, the unstable hydrated film can be dissolved by phosphoric acid treatment, so that a stable oxide film can be formed by subsequent electrochemistry, and the stability of the aluminum electrode foil is improved. And phosphate radicals provided by ammonium dihydrogen phosphate can occupy active sites combined with water molecules and the oxide film, so that the oxide film is prevented from being damaged by water, and the integrity of the oxide film is ensured.
In conclusion, the oxide film can be formed on the inner side of the aluminum powder sintered layer by the detection method, so that the aluminum powder sintered layer is formed uniformly in the thickness direction, and the specific capacity and the pressure resistance value are high in the specific capacity detection process.
Detailed Description
Reference will now be made in detail to embodiments of the invention, one or more examples of which are described below. Each example is provided by way of explanation, not limitation, of the invention. In fact, it will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention. For instance, features illustrated or described as part of one embodiment, can be used on another embodiment to yield a still further embodiment.
It is therefore intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents. Other objects, features and aspects of the present invention are disclosed in or are apparent from the following detailed description. It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only, and is not intended as limiting the broader aspects of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Research shows that in the process of preparing the high-thickness aluminum electrode foil, because the aluminum powder sintered layer on the aluminum foil substrate is thick, the electrolyte cannot enter the inner side of the aluminum powder sintered layer (namely, the side close to the aluminum foil substrate) due to the generation of the oxide film in the aluminum powder sintered layer in the formation process, so that the oxide film cannot be formed on the inner side of the aluminum powder sintered layer, the formation of the aluminum powder sintered layer in the thickness direction is not uniform, and the expected pressure resistance value (more than or equal to 500V) cannot be achieved in the specific capacity detection process. Therefore, the invention provides a method for detecting the specific capacity of an aluminum electrode foil, which comprises the following steps of S100-S600:
step S100: boiling the aluminum electrode foil in organic acid solution, and performing first formation, wherein the voltage of the first formation is 450V-520V, and the current is 0.5A/cm 3 ～2.5A/cm 3 The voltage stabilizing time is 3000 s-7500 s. The hydration speed of the aluminum powder sintered layer can be reduced by boiling with the organic acid solution, so that the hydration layer can be formed in the aluminum powder sintered layer, and the efficiency of forming an oxide layer in the aluminum powder sintered layer is improved. The electrolyte can enter the inside of the aluminum powder sintering layer by regulating and controlling the current, the voltage stabilization time and the like of the first formation, and an oxide film is favorably formed inside.
In some embodiments, the voltage of the first formation may be 460V, 470V, 480V, 490V, 500V, 510V, and the current may be 0.6A/cm 3 、0.7A/cm 3 、0.8A/cm 3 、0.9A/cm 3 、1.0A/cm 3 、1.2A/cm 3 、1.5A/cm 3 、1.8A/cm 3 、2.0A/cm 3 、2.2A/cm 3 The voltage stabilization time can also be 3200s, 3500s, 3800s, 4000s, 4100s, 4400s, 4600s, 4700s, 5000s, 5500s, 5800s, 6000s, 6200s, 6500s and 7000s.
In some embodiments, the organic acid solution has a pH of 3 to 6. Preferably, the organic acid solution has a pH of 5.
In some embodiments, the solute in the organic acid solution comprises one or more of acetic acid, formic acid, benzoic acid, and sulfonic acid.
In some embodiments, the temperature of the water boiling is 80 ℃ to 100 ℃ and the time is 15min to 30min.
Step S200: washing the first formed aluminum electrode foil with water, performing heat treatment at 350-550 ℃, and performing second formation, wherein the voltage of the second formation is 450-520V, and the current is 0.5A/cm 3 ～2.5A/cm 3 The voltage stabilizing time is 500 s-1500 s.
In some embodiments, the time of the heat treatment in step S200 may be 1min to 5min.
In some embodiments, the voltage of the second formation may be 460V, 470V, 480V, 490V, 500V, 510V, and the current may be 0.6A/cm 3 、0.7A/cm 3 、0.8A/cm 3 、0.9A/cm 3 、1.0A/cm 3 、1.2A/cm 3 、1.5A/cm 3 、1.8A/cm 3 、2.0A/cm 3 、2.2A/cm 3 The voltage stabilizing time can also be 600s, 800s, 1000s, 1200s, 1300s and 1400s.
Step S300: and (4) washing the secondarily formed aluminum electrode foil with water, and then performing phosphoric acid treatment and water washing. The phosphoric acid treatment can dissolve part of the oxide film, improve the integral crystallinity of the oxide film and improve the specific capacity.
In some embodiments, the temperature for the corrosion treatment in the phosphoric acid solution may be 55 to 70 ℃ and the time may be 5 to 10min.
In some embodiments, the phosphoric acid solution can have a conductivity of 25000 μ s/cm to 60000 μ s/cm.
Step S400: carrying out third formation on the aluminum electrode foil after water washing, wherein the voltage of the third formation is 450V-520V, and the current is 0.5A/cm 3 ～2.5A/cm 3 The voltage stabilizing time is 500 s-1500 s.
In some embodiments, the voltage of the third formation may be 460V, 470V, 480V, 490V, 500V, 510V, and the current may be 0.6A/cm 3 、0.7A/cm 3 、0.8A/cm 3 、0.9A/cm 3 、1.0A/cm 3 、1.2A/cm 3 、1.5A/cm 3 、1.8A/cm 3 、2.0A/cm 3 、2.2A/cm 3 The voltage stabilizing time can also be 600s, 800s, 1000s, 1200s, 1300s and 1400s.
Step S500: washing the aluminum electrode foil after the third formation with water, performing heat treatment at 350-550 ℃, and performing the fourth formation at a voltage of 450-520V and a current of 0.5A/cm 3 ～2.5A/cm 3 The voltage stabilizing time is 500 s-1500 s.
The heat treatment in step S200 and step S500 can crack the undensified oxide film, so that the electrolyte can enter the sintered layer of aluminum powder more easily, and the crystal form of the oxide film can be transformed to densify the oxide film. The defective oxide film can be further repaired by the second formation, the third formation and the fourth formation, and the oxide film is formed on the sintered layer of the aluminum powder closer to the inner side.
In some embodiments, the time of the heat treatment in step S500 may be 1min to 5min.
In some embodiments, the voltage of the fourth formation may be 460V, 470V, 480V, 490V, 500V, 510V, and the current may be 0.6A/cm 3 、0.7A/cm 3 、0.8A/cm 3 、0.9A/cm 3 、1.0A/cm 3 、1.2A/cm 3 、1.5A/cm 3 、1.8A/cm 3 、2.0A/cm 3 、2.2A/cm 3 The voltage stabilizing time can also be 600s, 800s, 1000s, 1200s, 1300s and 1400s.
In some embodiments, the chemical conversion solutions used in the first chemical conversion, the second chemical conversion, the third chemical conversion and the fourth chemical conversion are respectively and independently selected from boric acid solutions with the concentration of 50g/L to 100 g/L.
In some embodiments, the temperature of the first formation, the second formation, the third formation, and the fourth formation are each independently 83 ℃ to 93 ℃.
Step S600: and (4) washing the fourth formed aluminum electrode foil with water, and placing the aluminum electrode foil in an ammonium dihydrogen phosphate solution for hydration resistance treatment. Phosphate radical provided by ammonium dihydrogen phosphate can occupy active sites combined with water molecules and the oxide film, so that the oxide film is prevented from being damaged by water, and the integrity of the oxide film is ensured.
In some embodiments, the ammonium dihydrogen phosphate solution may have a temperature of 55 ℃ to 70 ℃ and a concentration of 1g/L to 3g/L.
In some embodiments, the aluminum electrode foil has a thickness of 210 μm to 860 μm. The method for detecting the specific capacity of the aluminum electrode foil is more suitable for the electrode foil with high thickness.
In some embodiments, the method for detecting the specific capacity of the aluminum electrode foil detects that the withstand voltage value of the aluminum electrode foil is more than or equal to 500V. The detection method can form an oxide film on the inner side of the aluminum powder sintered layer, so that the aluminum powder sintered layer is formed more uniformly in the thickness direction, and the specific capacity and the pressure resistance value are higher in the specific capacity detection process.
The present invention will be described in further detail with reference to specific examples and comparative examples.
Example 1
1) Sintering the upper surface and the lower surface of an aluminum foil substrate with the thickness of 25 mu m respectively to form an aluminum powder sintered layer with the thickness of 200 mu m and an aluminum electrode foil with the thickness of 425 mu m;
2) Putting the aluminum electrode foil prepared in the step 1) into an acetic acid aqueous solution with the pH value of 5 and the temperature of 95 ℃ and boiling for 20min;
3) In step 2)And (4) carrying out formation treatment on the aluminum electrode foil after water boiling, and then washing with water. Wherein the formation solution is boric acid water solution with mass concentration of 80g/L, formation temperature of 88 deg.C, formation voltage of 450V, and formation current of 0.75A/cm 3 The voltage stabilizing time is 5500s;
4) Carrying out heat treatment on the aluminum electrode foil washed with water in the step 3) at 500 ℃ for 2min, and then carrying out formation and washing. Wherein the formation solution is boric acid water solution with mass concentration of 80g/L, formation temperature of 88 deg.C, formation voltage of 450V, and formation current of 0.75A/cm 3 The voltage stabilizing time is 1000s;
5) Placing the aluminum electrode foil washed by water in the step 4) in a phosphoric acid solution with the temperature of 60 ℃ and the conductivity of 50000 mu s/cm, treating for 7min by phosphoric acid, and washing with water;
6) And (4) carrying out chemical conversion treatment on the washed aluminum electrode foil in the step 5) and washing with water. Wherein the formation solution is boric acid water solution with mass concentration of 80g/L, formation temperature of 88 deg.C, formation voltage of 450V, and formation current of 0.75A/cm 3 The voltage stabilizing time is 1000s;
7) And (3) carrying out heat treatment on the aluminum electrode foil washed with water in the step 6) at 500 ℃ for 2min, and then carrying out formation and washing. Wherein the formation solution is boric acid water solution with mass concentration of 80g/L, formation temperature of 88 deg.C, formation voltage of 450V, and formation current of 0.75A/cm 3 The voltage stabilizing time is 1000s;
8) And (3) placing the aluminum electrode foil washed by water in the step 7) in an ammonium dihydrogen phosphate solution with the temperature of 60 ℃ and the concentration of 2g/L for treatment for 4min, and washing by water. Then, LCR digital bridge is adopted to test the specific capacity of the aluminum anode foil, ammonium pentaborate is taken as electrolyte under the frequency of 120Hz, the withstand voltage value is 501V, and the specific capacity is 37.6 muF/cm 2 The loss factor was 0.10.
Example 2
The present embodiment is basically the same as the detection method of embodiment 1, except that: the thickness of the aluminum anode foil is different, and the formation current in the step 3) is 1.25A/cm 3 . The method comprises the following specific steps:
1) Sintering the upper surface and the lower surface of the aluminum foil substrate with the thickness of 23 mu m respectively to form an aluminum powder sintered layer with the thickness of 200 mu m and form an aluminum electrode foil with the thickness of 423 mu m;
2) Putting the aluminum electrode foil prepared in the step 1) into an acetic acid aqueous solution with the pH value of 5 and the temperature of 95 ℃ and boiling for 20min;
3) And (3) carrying out formation treatment on the aluminum electrode foil boiled in the step 2) and then washing the aluminum electrode foil with water. Wherein the formation solution is boric acid water solution with mass concentration of 80g/L, formation temperature of 88 deg.C, formation voltage of 450V, and formation current of 1.25A/cm 3 The voltage stabilization time is 5500s;
4) Carrying out heat treatment on the aluminum electrode foil subjected to water washing in the step 3) at 500 ℃ for 2min, and then carrying out formation and water washing. Wherein the formation solution is boric acid aqueous solution with a mass concentration of 80g/L, the formation temperature is 88 ℃, the formation voltage is 450V, and the formation current is 0.75A/cm 3 The voltage stabilizing time is 1000s;
5) Placing the aluminum electrode foil washed by water in the step 4) in a phosphoric acid solution with the temperature of 60 ℃ and the conductivity of 50000 mu s/cm, treating the aluminum electrode foil by phosphoric acid for 7min, and washing the aluminum electrode foil by water;
6) And (3) carrying out formation treatment on the aluminum electrode foil washed with water in the step 5), and washing with water. Wherein the formation solution is boric acid water solution with mass concentration of 80g/L, formation temperature of 88 deg.C, formation voltage of 450V, and formation current of 0.75A/cm 3 The voltage stabilizing time is 1000s;
7) And (3) carrying out heat treatment on the aluminum electrode foil washed with water in the step 6) at 500 ℃ for 2min, and then carrying out formation and washing. Wherein the formation solution is boric acid water solution with mass concentration of 80g/L, formation temperature of 88 deg.C, formation voltage of 450V, and formation current of 0.75A/cm 3 The voltage stabilizing time is 1000s;
8) And (3) placing the aluminum electrode foil washed by water in the step 7) in an ammonium dihydrogen phosphate solution with the temperature of 60 ℃ and the concentration of 2g/L for treatment for 4min, and washing by water. Then, LCR digital bridge is adopted to test the specific capacity of the aluminum anode foil, ammonium pentaborate is taken as electrolyte under the frequency of 120Hz, the withstand voltage value is 536V, and the specific capacity is 25.5 mu F/cm 2 The loss factor was 0.09.
Example 3
This example is basically the same as the detection method of example 1, except that: the aluminum anode foils have different thicknesses, and the formation voltage in the step 3) is 500V. The method comprises the following specific steps:
1) Respectively sintering the upper surface and the lower surface of an aluminum foil substrate with the thickness of 18 mu m to form an aluminum powder sintered layer with the thickness of 200 mu m and an aluminum electrode foil with the thickness of 418 mu m;
2) Putting the aluminum electrode foil prepared in the step 1) into an acetic acid aqueous solution with the pH value of 5 and the temperature of 95 ℃ and boiling for 20min;
3) And (3) carrying out formation treatment on the aluminum electrode foil boiled in the step 2) and then washing the aluminum electrode foil with water. Wherein the formation solution is boric acid water solution with mass concentration of 80g/L, formation temperature of 88 deg.C, formation voltage of 500V, and formation current of 0.75A/cm 3 The voltage stabilizing time is 5500s;
4) Carrying out heat treatment on the aluminum electrode foil washed with water in the step 3) at 500 ℃ for 2min, and then carrying out formation and washing. Wherein the formation solution is boric acid water solution with mass concentration of 80g/L, formation temperature of 88 deg.C, formation voltage of 450V, and formation current of 0.75A/cm 3 The voltage stabilizing time is 1000s;
5) Placing the aluminum electrode foil washed by water in the step 4) in a phosphoric acid solution with the temperature of 60 ℃ and the conductivity of 50000 mu s/cm, treating the aluminum electrode foil by phosphoric acid for 7min, and washing the aluminum electrode foil by water;
6) And (3) carrying out formation treatment on the aluminum electrode foil washed with water in the step 5), and washing with water. Wherein the formation solution is boric acid water solution with mass concentration of 80g/L, formation temperature of 88 deg.C, formation voltage of 450V, and formation current of 0.75A/cm 3 The voltage stabilizing time is 1000s;
7) And (3) carrying out heat treatment on the aluminum electrode foil washed with water in the step 6) at 500 ℃ for 2min, and then carrying out formation and washing. Wherein the formation solution is boric acid water solution with mass concentration of 80g/L, formation temperature of 88 deg.C, formation voltage of 450V, and formation current of 0.75A/cm 3 The voltage stabilizing time is 1000s;
8) And (3) placing the aluminum electrode foil washed by water in the step 7) in an ammonium dihydrogen phosphate solution with the temperature of 60 ℃ and the concentration of 2g/L for treatment for 4min, and washing by water. Then, LCR digital bridge is adopted to test the specific capacity of the aluminum anode foil, ammonium pentaborate is taken as electrolyte under the frequency of 120Hz, the withstand voltage value is 543V, and the specific capacity is 25.0 mu F/cm 2 The loss factor was 0.09.
Example 4
This example is basically the same as the detection method of example 1, except that: the aluminum anode foils have different thicknesses, and the formation voltage stabilization time in the step 3) is 7200s. The method comprises the following specific steps:
1) Sintering the upper surface and the lower surface of an aluminum foil base material with the thickness of 29 mu m respectively to form an aluminum powder sintered layer with the thickness of 200 mu m and form an aluminum electrode foil with the thickness of 429 mu m;
2) Putting the aluminum electrode foil prepared in the step 1) into an acetic acid aqueous solution with the pH value of 5 and the temperature of 95 ℃ for boiling for 20min;
3) And 2) carrying out formation treatment on the aluminum electrode foil boiled in the step 2) and then washing. Wherein the formation solution is boric acid aqueous solution with a mass concentration of 80g/L, the formation temperature is 88 ℃, the formation voltage is 450V, and the formation current is 0.75A/cm 3 The voltage stabilizing time is 7200s;
4) Carrying out heat treatment on the aluminum electrode foil washed with water in the step 3) at 500 ℃ for 2min, and then carrying out formation and washing. Wherein the formation solution is boric acid water solution with mass concentration of 80g/L, formation temperature of 88 deg.C, formation voltage of 450V, and formation current of 0.75A/cm 3 The voltage stabilizing time is 1000s;
5) Placing the aluminum electrode foil washed by water in the step 4) in a phosphoric acid solution with the temperature of 60 ℃ and the conductivity of 50000 mu s/cm, treating for 7min by phosphoric acid, and washing with water;
6) And (3) carrying out formation treatment on the aluminum electrode foil washed with water in the step 5), and washing with water. Wherein the formation solution is boric acid water solution with mass concentration of 80g/L, formation temperature of 88 deg.C, formation voltage of 450V, and formation current of 0.75A/cm 3 The voltage stabilizing time is 1000s;
7) And (3) carrying out heat treatment on the aluminum electrode foil washed with water in the step 6) at 500 ℃ for 2min, and then carrying out formation and washing. Wherein the formation solution is boric acid water solution with mass concentration of 80g/L, formation temperature of 88 deg.C, formation voltage of 450V, and formation current of 0.75A/cm 3 The voltage stabilizing time is 1000s;
8) And (3) placing the aluminum electrode foil washed by water in the step 7) in an ammonium dihydrogen phosphate solution with the temperature of 60 ℃ and the concentration of 2g/L for treatment for 4min, and washing by water. Then, miningThe specific capacity of the aluminum anode foil is tested by an LCR digital bridge, and the withstand voltage value is 506V and the specific capacity is 29.9 mu F/cm under the frequency of 120Hz and by taking ammonium pentaborate as electrolyte 2 The loss factor was 0.09.
Comparative example 1
And detecting the specific capacity of the aluminum electrode foil by adopting a traditional detection method. The method comprises the following specific steps:
1) Sintering the upper surface and the lower surface of an aluminum foil substrate with the thickness of 25 mu m respectively to form an aluminum powder sintered layer with the thickness of 200 mu m and an aluminum electrode foil with the thickness of 425 mu m;
2) Putting the aluminum electrode foil prepared in the step 1) into pure water at 95 ℃ and boiling for 10min;
3) And 2) carrying out formation treatment on the aluminum electrode foil boiled in the step 2) and then washing. Wherein the formation solution is boric acid water solution with mass concentration of 80g/L, formation temperature of 88 deg.C, formation voltage of 520V, and formation current of 2.5A/cm 3 The voltage stabilizing time is 1200s;
4) And (3) carrying out heat treatment on the aluminum electrode foil subjected to water washing in the step 3) at 500 ℃ for 2min, then carrying out formation, water washing and drying at 100 ℃ to obtain the aluminum anode foil with the thickness of 425 micrometers. Wherein the formation solution is boric acid water solution with mass concentration of 80g/L, formation temperature of 90 deg.C, formation voltage of 520V, and formation current of 2.5A/cm 3 The voltage stabilizing time is 300s. Then, the specific capacity of the aluminum anode foil was measured by using an LCR digital bridge and ammonium pentaborate as an electrolyte, and the formulation of the electrolyte was shown in table 1.
And (3) detection of a withstand voltage value: the formulation of the electrolyte is shown in table 1. The pressure resistance value was measured to be 200V, which is much lower than the expected pressure resistance value (500V), i.e., the expected pressure resistance value could not be reached.
TABLE 1
Comparative example 2
This comparative example is essentially the same as the test method of example 1, except that: acetic acid is not added during water boiling, and pure water is adopted for water boiling. The withstand voltage was 435V, and the expected withstand voltage (500V or more) could not be achieved.
Comparative example 3
This comparative example is essentially the same as the test method of example 1, except that: the current formed in the step 3) is 5A/cm 3 . The pressure resistance was found to be 369V, and the expected pressure resistance (500V or more) could not be attained.
Comparative example 4
This comparative example is essentially the same as the test method of example 1, except that: the stabilized voltage time formed in the step 3) is 9000s. The specific capacity is measured to be 12 mu F/cm 2 And the volume value is too low, and the practical value is not achieved.
The conditions of the water boiling and first formation processes for preparing the aluminum electrode foils in examples 1 to 5 and comparative examples 2 to 4 and the results of the performance tests are shown in table 2:
TABLE 2
From the detection results in the table, the detection method provided by the invention can achieve the expected withstand voltage value (more than 500V) when the specific capacity of the aluminum electrode foil is detected.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A method for detecting specific capacity of an aluminum electrode foil is characterized by comprising the following steps:
a. putting the aluminum electrode foil in an organic acid solution for water boiling, and carrying out first formation, wherein the voltage of the first formation is 450V-520V, and the current is 0.5A/cm 3 ～2.5A/cm 3 The voltage stabilizing time is 3000 s-7500 s;
b. washing the aluminum electrode foil subjected to the first formation with water, performing heat treatment at 350-550 ℃, and performing second formation, wherein the voltage of the second formation is 450-520V, and the current is 0.5A/cm 3 ～2.5A/cm 3 The voltage stabilizing time is 500-1500 s;
c. washing the secondarily formed aluminum electrode foil with water, and then carrying out phosphoric acid treatment and water washing;
d. carrying out third formation on the aluminum electrode foil after water washing, wherein the voltage of the third formation is 450V-520V, and the current is 0.5A/cm 3 ～2.5A/cm 3 The voltage stabilizing time is 500-1500 s;
e. washing the aluminum electrode foil after the third formation with water, performing heat treatment at 350-550 ℃, and performing the fourth formation, wherein the voltage of the fourth formation is 450-520V, and the current is 0.5A/cm 3 ～2.5A/cm 3 The voltage stabilizing time is 500 s-1500 s;
f. and (4) washing the fourth formed aluminum electrode foil with water, and placing the aluminum electrode foil in an ammonium dihydrogen phosphate solution for hydration resistance treatment.
2. The method for detecting the specific capacity of the aluminum electrode foil as claimed in claim 1, wherein the organic acid solution has a pH of 3 to 6.
3. The method for detecting the specific capacity of the aluminum electrode foil as claimed in claim 2, wherein the solute in the organic acid solution comprises one or more of acetic acid, formic acid, benzoic acid and sulfonic acid.
4. The method for detecting the specific capacity of the aluminum electrode foil as claimed in claim 1, wherein the formation liquids used in the first formation, the second formation, the third formation and the fourth formation are respectively and independently selected from boric acid solutions with a concentration of 50g/L to 100 g/L.
5. The method for detecting the specific capacity of the aluminum electrode foil as claimed in claim 4, wherein the temperatures of the first formation, the second formation, the third formation and the fourth formation are 83 ℃ to 93 ℃ respectively and independently.
6. The method for detecting the specific capacity of the aluminum electrode foil as claimed in any one of claims 1 to 5, wherein the thickness of the aluminum electrode foil is 210 μm to 860 μm.
7. The method for detecting the specific capacity of the aluminum electrode foil as claimed in any one of claims 1 to 5, wherein the temperature of the ammonium dihydrogen phosphate solution is 55 ℃ to 70 ℃ and the concentration is 1g/L to 3g/L.
8. The method for detecting the specific capacity of the aluminum electrode foil as claimed in any one of claims 1 to 5, wherein the withstand voltage value of the aluminum electrode foil measured by the method for detecting the specific capacity of the aluminum electrode foil is not less than 500V.
9. The method for detecting the specific capacity of the aluminum electrode foil according to any one of claims 1 to 5, wherein the temperature of the corrosion treatment in the phosphoric acid solution is 55 to 70 ℃ and the time is 5 to 10min.
10. The method for detecting the specific capacity of the aluminum electrode foil as claimed in claim 9, wherein the conductivity of the phosphoric acid solution is 25000 μ s/cm to 60000 μ s/cm.
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