CN108172755B - Aluminum foil for lithium ion battery, microporous aluminum foil and preparation method of microporous aluminum foil - Google Patents

Aluminum foil for lithium ion battery, microporous aluminum foil and preparation method of microporous aluminum foil Download PDF

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CN108172755B
CN108172755B CN201810020129.7A CN201810020129A CN108172755B CN 108172755 B CN108172755 B CN 108172755B CN 201810020129 A CN201810020129 A CN 201810020129A CN 108172755 B CN108172755 B CN 108172755B
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CN108172755A (en
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刘忆恩
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Shanxi Wote Haimer New Materials Technology Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/80—Porous plates, e.g. sintered carriers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
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    • H01M4/661—Metal or alloys, e.g. alloy coatings
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses an aluminum foil for a lithium ion battery, a microporous aluminum foil and a preparation method of the microporous aluminum foil, wherein the aluminum foil comprises 0.08-0.1wt% of Mg, less than or equal to 0.08 wt% of Si, less than or equal to 0.2 wt% of Fe, less than or equal to 0.03 wt% of Ga, less than or equal to 0.04 wt% of Cu, less than or equal to 0.04 wt% of Zn, less than or equal to 0.05 wt% of V, less than or equal to 0.03 wt% of Ti and 99.7 wt% of; preparing a microporous aluminum foil by adopting a chemical corrosion method; 300-6000 through holes and/or blind holes with the diameter of 6-12 mu m are distributed on each square centimeter of the microporous aluminum foil; compared with the existing series of aluminum alloy, the defined composition has higher yield strength, the pore diameter of the formed micropores is smaller and more uniform in the subsequent chemical corrosion process, the through holes and the blind holes are in arc transition with the material body, the stress concentration is reduced, the mechanical property is enhanced, the electrical property is not weakened, and the invention can be used in lithium batteries.

Description

Aluminum foil for lithium ion battery, microporous aluminum foil and preparation method of microporous aluminum foil
Technical Field
The invention belongs to the technical field of lithium battery material manufacturing, and particularly relates to an aluminum foil for a lithium ion battery, a microporous aluminum foil and a preparation method of the microporous aluminum foil.
Background
The new material and the clean energy are key development directions of the national level, the lithium ion battery is an energy storage battery cell which is most widely applied in the current energy storage technology, the improvement of the energy storage density of the battery cell is a target pursued all over the world, and the improvement of the energy density of the battery cell mainly depends on the development progress of the anode material and the cathode material of the battery cell, but is also related to the progress of materials such as the anode current collector, the anode binder, the cathode binder, the electrolyte, the diaphragm and the like of the lithium ion battery.
The current collector adopted by the anode of the lithium ion battery is generally composed of an aluminum foil and anode powder (lithium iron phosphate, lithium cobaltate or ternary material) coated on the aluminum foil. The positive electrolyte subset fluid for lithium batteries is aluminum foil. Such an aluminum foil is required to have high dimensional accuracy. The alloy typically used to make aluminum foil is 1235, which has typical properties that make lithium batteries typical. Meanwhile, the conventional current collector material generally adopts an aluminum foil with a smooth surface, and the aluminum foil with the purity of 99.7% is directly coated with active substances, but the aluminum foil with the smooth surface and the active materials are relatively loose in combination, so that the requirements on the quality of raw materials and auxiliary materials and the process are high, the active substances are easy to fall off or fall off in the processing and charging and discharging processes, the cyclic charging and discharging efficiency is reduced, the service life of the battery is prolonged, the contact resistance between components is improved, the conductivity of the positive plate is reduced, and the comprehensive performance of the battery is influenced. The comprehensive performance of the lithium ion is seriously influenced.
In order to improve the bonding state between the positive aluminum foil current collector and the positive slurry, nine through holes are prepared on each square centimeter of the existing microporous copper foil and microporous aluminum foil, and the diameter of each through hole is about 1 mm. However, the aluminum foil and the copper foil must be used in a specially-made automatic battery production line because the back side of the copper foil or the aluminum foil with the through hole diameter of 1mm is subjected to slurry permeation when the copper foil or the aluminum foil is used in the original automatic battery production line, and the coating on the other side is influenced.
Korean patent nos. CN 103618090a and CN 103617894a disclose an acid-base etching treatment of aluminum foil using an acidic or basic chemical. The obtained aluminum oxide foil has low contact resistance and reduced mechanical strength in the process of removing corrosion. The method for forming holes on the aluminum foil in other countries adopts rolling or laser ablation, the hole forming of the aluminum foil adopts a salt compound corrosion method, the technical routes are completely different, and the obtained microporous aluminum foil also has special structure and performance.
Disclosure of Invention
The invention overcomes the defects of the prior art and aims to provide an aluminum foil for a lithium ion battery, a microporous aluminum foil and a preparation method of the microporous aluminum foil.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows.
An aluminum foil for a lithium ion battery, comprising: 0.08-0.1wt% of Mg, less than or equal to 0.08 wt% of Si, less than or equal to 0.2 wt% of Fe, less than or equal to 0.03 wt% of Ga, less than or equal to 0.04 wt% of Cu, less than or equal to 0.04 wt% of Zn, less than or equal to 0.05 wt% of V, less than or equal to 0.03 wt% of Ti, 99.7 wt% of aluminum and the balance of impurities.
The resistivity of the aluminum foil for the lithium ion battery is less than or equal to 3 mu omega m.
A microporous aluminum foil for a lithium ion battery, comprising: 0.08-0.1wt% of Mg, less than or equal to 0.08 wt% of Si, less than or equal to 0.2 wt% of Fe, less than or equal to 0.03 wt% of Ga, less than or equal to 0.04 wt% of Cu, less than or equal to 0.04 wt% of Zn, less than or equal to 0.05 wt% of V, less than or equal to 0.03 wt% of Ti, 99.7 wt% of aluminum and the balance of impurities; 300-6000 through holes and blind holes with the diameter of 6-12 mu m are distributed on each square centimeter of the microporous aluminum foil, wherein the proportion of the number of the through holes to the total number of the through holes and the blind holes is more than 50 percent.
Preferably, 300-2000 through holes and blind holes with the diameter of 6-12 mu m are distributed on each square centimeter of the microporous aluminum foil.
Preferably, the upper and lower surfaces of the microporous aluminum foil are distributed with a plurality of scores, wherein the scores are 1-3 μm deep and 1-5 μm wide.
Preferably, the increase rate of the resistivity of the microporous aluminum foil is less than or equal to 2 percent compared with the resistivity of the aluminum foil before pore forming.
The yield strength of the microporous aluminum foil is 200-260 MPa; the breaking strength is 200-350 MPa; the elongation is 2% -3%.
The microporous aluminum foil is used for capacitor electrodes.
The thickness of the aluminum foil or the microporous aluminum foil for the lithium ion battery is 8-18 mu m.
A preparation method of microporous aluminum foil for lithium ion battery adopts chemical corrosion method; the corrosive liquid adopted in the chemical corrosion method is a salt solution containing Cl with the molar concentration of 0.1-3mol/L-Containing Fe in a molar concentration of 0.1 to 3mol/L3+And Cu2+A cation of (2).
In the chemical corrosion method, the corrosion time is 20-120s, and the corrosion temperature is 20-60 ℃.
Preferably, the corrosion time in the chemical corrosion method is 20-120s, and the corrosion temperature is 20-38 ℃.
Compared with the prior art, the invention has the following beneficial effects.
1. A microporous aluminum foil composition for a lithium battery includes: 0.08-0.1wt% of Mg, less than or equal to 0.08 wt% of Si, less than or equal to 0.2 wt% of Fe, less than or equal to 0.03 wt% of Ga, less than or equal to 0.04 wt% of Cu, less than or equal to 0.04 wt% of Zn, less than or equal to 0.05 wt% of V, less than or equal to 0.03 wt% of Ti, 99.7 wt% of aluminum and the balance of impurities. Compared with 1 XX X series aluminum alloy, the limited composition has higher Mg content, higher yield strength, smaller and more uniform pore diameter of the formed micropores in the subsequent chemical corrosion process, the pore diameter is increased to 6-12 micrometers from the original pore diameter of 10-50 micrometers, and 300-6000 through holes and/or blind holes with the diameter of 6-12 micrometers are distributed on each square centimeter of the microporous aluminum foil; the two surfaces of the metal foil are not completely penetrated or isolated, ions and/or particles with the diameter of less than 6-12 mu m can effectively pass through the metal foil, such as lithium ions, so that the ions or particles with large diameter can be prevented from passing through the metal foil, the lithium ion activity is improved, the battery capacity is improved, the anode material coated on the metal foil is integrated with the aluminum foil, the adhesion force is obviously improved, and lithium dendrites cannot grow at the through holes and blind holes. While not affecting the properties of the material, for example: the average resistivity is increased by 1-3%, the average tensile strength is improved by 0-2%, and the average total elongation at break is improved by 0-21%.
2. Furthermore, nicks are distributed on the upper surface and the lower surface of the microporous aluminum foil, the depth of the nicks is 1-3 mu m, the width of the nicks is 1-5 mu m, the through holes and the blind holes are irregularly shaped and irregularly distributed, and the joints of the through holes and the blind holes and the surface of the microporous aluminum foil are irregularly arc-shaped in transition. The through holes and the blind holes are irregular in shape, the joints of the through holes and the blind holes and the surface of the aluminum foil are in irregular arc transition, the aperture size is changed within a certain range, and the diameter of each hole is also changed in different directions. When can promote micropore aluminium foil both sides and coat, promote the adhesive force of coating, through-hole and blind hole and material body circular arc transition reduce stress concentration, strengthen mechanical properties, can not weaken the electrical property.
3. The microporous aluminum foil is prepared by adopting a chemical liquid corrosion method. The corrosion method of the invention is different from the general acid-alkali solution corrosion solution, the chloride compound can be used as the corrosion solution in the corrosion method, the reaction degree is milder in the corrosion process, when the aluminum foil is put into the treatment solution, under the protection of chloride ions, copper ions or iron ions react with the surface of the aluminum, so that the surface of the aluminum forms a micropore structure, calcium ions, sodium ions and barium ions in the treatment solution enter the porous membrane to be fixed in the subsequent process, and the method plays a role in improving the surface performance of the aluminum.
The capacity of the lithium ion battery can be improved by 8-10% by the microporous aluminum foil. When the anode material is made of ternary material, the anode materials on two sides of the aluminum foil are connected into a whole by the microporous aluminum foil, so that the uniformity of the capacity, the charge-discharge characteristics and other performances of the battery is obviously improved, and the production yield of the battery is improved by 15-20%.
Drawings
Fig. 1 is a microscopic image of a microporous aluminum foil for a lithium battery according to the present invention.
Detailed Description
Example 1
The aluminum foil for the lithium ion battery is characterized in that 4000-6000 through holes and blind holes with the diameter of 6-12 mu m are distributed on each square centimeter of the microporous aluminum foil, wherein the proportion of the through holes is 55 percent; the upper surface and the lower surface of the microporous aluminum foil are distributed with a plurality of scores, the scores are 1-3 mu m deep, 1-5 mu m wide and 1000 mu m long, the through holes and the blind holes are irregular, and the joints with the surfaces of the microporous aluminum foil are in irregular arc transition. The resistivity of the microporous aluminum foil is increased by 2 percent compared with that before pore forming. The yield strength of the microporous aluminum foil is 200 MPa; the breaking strength is 350 MPa; the elongation was 2%.
The method comprises the following steps:
a method for preparing microporous aluminum foil for lithium battery, wherein the microporous aluminum foil is prepared by chemical liquid corrosion method, and other steps are the same as or similar to those in the prior art, and are not repeated herein.
1) Cleaning the surface of the rolled battery aluminum foil to remove a lubricant: the first cleaning solution comprises 5g/L NaOH and 70g/L Na2CO340g/L of Na3PO4The rolled aluminum foil was passed through the first cleaning solution, and the time for which the rolled aluminum foil was held in the first cleaning solution was 6 seconds.
2) Pressing the cleaned aluminum foil into a chemical etching solution: the chemical corrosion liquid comprises the following components: 0.5mol/L NaCl, 0.1mol/L BaCl20.1mol/L of CaCl20.1mol/L NH4Cl, 0.1mol/L CuCl20.1mol/L FeCl3The dwell time of the aluminum foil in the corrosive agent is 20s, the corrosion temperature is 20 ℃, and in the stage, the upper surface and the lower surface of the aluminum foil are ensured to be simultaneously soaked in the corrosive liquid, and the corrosive liquid flows on the upper surface and the lower surface of the aluminum foil in a circulating flowing mode, so that the upper surface and the lower surface are corroded uniformly.
3) Cleaning the corroded aluminum foil: the second cleaning solution is 0.4-0.8 g/LNa2SO4、0.5—1g/LCaSO40.1-0.3 g/L of citric acid, and spraying a second cleaning solution on the upper surface and the lower surface of the aluminum foil by using a spray head for cleaning.
4) And (3) brightening treatment: the brightening solution is 2g/L CrO31g/L of Na2Cr2O7•2H2O and 0.1g/L NaF, and carrying out surface brightening treatment on the cleaned aluminum foil.
5) And (3) cleaning the brightened aluminum foil again: and cleaning the brightened aluminum foil again by using a second cleaning solution.
6) Drying treatment: and drying the aluminum foil cleaned again at the temperature of 200 ℃.
7) And (6) rolling a finished product.
The present embodiment was assembled into a lithium ion battery: 8.5g of lithium iron phosphate, 1.0g of acetylene black and 0.5g of PVDF are weighed, 20g of NMP is added, and the mixture is fully stirred to form uniformly mixed slurry. Then the obtained product is blade-coated on a microporous aluminum foil current collector processed in the embodiment 1 of the invention, dried to constant weight at 80 ℃ under the vacuum of 0.01MPa, rolled under the pressure of 10-15 MPa to form a lithium iron phosphate electrode, and cut into a positive electrode wafer. Similarly, 4.25g of graphite, 0.5g of acetylene black and 0.25g of styrene butadiene rubber binder are weighed, 10g of NMP is added, the mixture is fully stirred to form uniformly mixed slurry, and then the uniformly mixed slurry is blade-coated on a common copper foil cleaned by ethanol and pressed into a negative plate. Sequentially laminating a positive plate, a celgard2400 polypropylene porous membrane diaphragm and a negative plate to assemble a battery cell, sealing the battery cell by using a battery shell, and injecting 1mol/L LiBF into the battery shell4And filling the diethyl carbonate electrolyte, and sealing the liquid injection port to obtain the lithium ion battery.
The lithium ion battery assembled in the embodiment is subjected to 1C charge-discharge test by using a charge-discharge tester at the temperature of 60 ℃ and within the voltage range of 2.5-4.2V, the 3 rd discharge specific capacity is 179mAh/g, and after 300 charge-discharge cycles, the capacity retention rate is 95.6%.
To further illustrate the advantageous effects of the present invention, the following comparative examples were specifically set forth:
weighing 8.5g of lithium iron phosphate, 1.0g of acetylene black and 0.5g of PVDF, adding 20g of NMP,fully stirring to form evenly mixed slurry. Then the anode material is coated on a common aluminum foil cleaned by ethanol, dried to constant weight under the vacuum of 0.01MPa at the temperature of 80 ℃, rolled to form a lithium iron phosphate electrode under the pressure of 10-15 MPa, and cut into anode wafers. Similarly, 4.25g of graphite, 0.5g of acetylene black and 0.25g of styrene butadiene rubber binder are weighed, 10g of NMP is added, the mixture is fully stirred to form uniformly mixed slurry, and then the uniformly mixed slurry is blade-coated on a common copper foil cleaned by ethanol and pressed into a negative plate. Sequentially laminating a positive plate, a celgard2400 polypropylene porous membrane diaphragm and a negative plate to assemble a battery cell, sealing the battery cell by using a battery shell, and injecting 1mol/L LiBF into the battery shell4And filling the diethyl carbonate electrolyte, and sealing the liquid filling port to obtain the lithium ion battery.
Through detection, after the lithium ion battery obtained in the comparative example is subjected to 300 charge-discharge cycles, the capacity retention rate is 82.5%. Therefore, the microporous aluminum foil current collector prepared by the embodiment has the advantages that the irregular holes are more beneficial to improving the adhesive force between the aluminum foil and the anode slurry, the falling of the anode material can be avoided, and the cycle stability and the service life of the lithium ion battery are improved.
The micropore aluminum foil for the lithium battery has more uniform pore size due to specific pores and nicks with the size of 6-12 mu m, can pass lithium ions, and can not pass other non-functional particles or ions, so that the capacity of the lithium battery is increased, the surface smoothness of the micropore aluminum foil is higher, no flash or burr exists, the joint of the pore and the surface of the aluminum foil is in irregular arc transition, no 90-degree right angle exists, the occurrence of lithium dendrite in the charging and discharging process can be effectively prevented, and the service life of the battery is prolonged; in addition, the shapes of the micropores are different, the holes on the microporous aluminum foil obtained by the chemical etching method are irregular, the diameter of each hole is changed in different directions, and the irregular holes are more favorable for improving the binding force between the aluminum foil and the anode slurry. The method does not need to change the existing production process, is easy to popularize, and is suitable for single-side coating and double-side coating.
The present embodiment can increase the capacity of lithium ion battery by 8-10%. When the anode material is made of ternary material, the anode materials on two sides of the aluminum foil are connected into a whole by the microporous aluminum foil, so that the uniformity of the capacity, the charge-discharge characteristics and other performances of the battery is obviously improved, and the production yield of the battery is improved by 15-20%.
Example 2
The aluminum foil for the lithium ion battery is characterized in that 300-2000 through holes and blind holes with the diameter of 6-12 mu m are distributed on each square centimeter of the microporous aluminum foil, wherein the proportion of the through holes is 60 percent; the upper surface and the lower surface of the microporous aluminum foil are distributed with a plurality of scores, the scores are 1-3 mu m deep, 1-5 mu m wide and 1000 mu m long, the through holes and the blind holes are irregular, and the joints with the surfaces of the microporous aluminum foil are in irregular arc transition. The resistivity of the microporous aluminum foil is increased by 1% compared with that before pore forming. The yield strength of the microporous aluminum foil is 260 MPa; the breaking strength is 200 MPa; the elongation was 3%. The microporous aluminum foil is prepared by adopting a chemical liquid corrosion method and is carried out according to the following steps:
1) cleaning the surface of the rolled battery aluminum foil to remove a lubricant: the first cleaning solution comprises 30g/L NaOH and 70g/L Na2CO340g/L of Na3PO4The rolled aluminum foil was passed through the first cleaning solution and held in the first cleaning solution for 10 seconds.
2) Pressing the cleaned aluminum foil into a chemical etching solution: the chemical corrosion liquid comprises the following components: 1.5mol/L NaCl, 0.3mol/L BaCl20.5mol/L of CaCl20.5mol/L NH4Cl, 0.8mol/L CuCl21mol/L FeCl3The residence time of the aluminum foil in the corrosive agent is 120s, the corrosion temperature is 60 ℃, and in the stage, the upper surface and the lower surface of the aluminum foil are ensured to be simultaneously soaked in the corrosive liquid, and the corrosive liquid flows on the upper surface and the lower surface of the aluminum foil in a circulating flowing mode, so that the upper surface and the lower surface are corroded uniformly.
3) Cleaning the corroded aluminum foil: the second cleaning solution is 0.4-0.8 g/LNa2SO4、0.5—1g/LCaSO40.1-0.3 g/L of citric acid, and spraying a second cleaning solution on the upper surface and the lower surface of the aluminum foil by using a spray head for cleaning.
4) And (3) brightening treatment: the brightening solution is 5g/L CrO3、7g/L Na2Cr2O7•2H2O and 1.5g/L NaF, and carrying out surface brightening treatment on the cleaned aluminum foil.
5) And (3) cleaning the brightened aluminum foil again: and cleaning the brightened aluminum foil again by using a second cleaning solution.
6) Drying treatment: and drying the aluminum foil cleaned again at the temperature of 300 ℃.
7) And (6) rolling a finished product.
Example 3
The aluminum foil for the lithium ion battery is characterized in that 500-3000 through holes and blind holes with the diameter of 6-12 mu m are distributed on each square centimeter of the microporous aluminum foil, wherein the proportion of the through holes is 70 percent; the upper surface and the lower surface of the microporous aluminum foil are distributed with a plurality of scores, the scores are 1-3 mu m deep, 1-5 mu m wide and 1000 mu m long, the through holes and the blind holes are irregular, and the joints with the surfaces of the microporous aluminum foil are in irregular arc transition. The resistivity of the microporous aluminum foil is increased by 1% compared with that before pore forming. The yield strength of the microporous aluminum foil is 230 MPa; the breaking strength is 300 MPa; the elongation was 2.5%.
The battery microporous aluminum foil is prepared by adopting a chemical liquid hot corrosion method and is carried out according to the following steps:
1) cleaning the surface of the rolled battery aluminum foil to remove a lubricant: the first cleaning solution comprises 17g/L NaOH and 40g/L Na2CO325g/L of Na3PO4The temperature of the first cleaning liquid is kept at 45 +/-2 ℃. The rolled aluminum foil was passed through the first cleaning solution and held in the first cleaning solution for 15 seconds.
2) Pressing the cleaned aluminum foil into a chemical etching solution: the chemical corrosion liquid comprises the following components: 1mol/L NaCl, 0.2mol/L BaCl2、0.3mol/L CaCl2、0.3mol/L NH4Cl、0.45mol/LCuCl2、0.55mol/LFeCl3The temperature of the corrosive liquid is kept at 45 +/-2 ℃, the retention time of the aluminum foil in the corrosive liquid is 70s, and in the stage, the upper surface and the lower surface of the aluminum foil are ensured to be simultaneously soaked in the corrosive liquid and corrodedThe etching liquid flows on the upper surface and the lower surface of the aluminum foil in a circulating flow mode so as to achieve uniform corrosion of the upper surface and the lower surface.
3) Cleaning the corroded aluminum foil: the second cleaning solution is 0.4-0.8 g/LNa2SO4、0.5—1g/LCaSO40.1-0.3 g/L of citric acid, and the temperature of the second cleaning solution is kept at 45 +/-2 ℃. And spraying a second cleaning solution on the upper surface and the lower surface of the aluminum foil by using a spray head to clean.
4) And (3) brightening treatment: the brightening solution is 3.5g/L CrO3、4g/L Na2Cr2O7•2H2O and 0.8g/L NaF, and performing surface brightening treatment on the cleaned aluminum foil, wherein the temperature of the brightening solution is kept at 45 +/-2 ℃.
5) And (3) cleaning the brightened aluminum foil again: and cleaning the brightened aluminum foil again by using a second cleaning solution, wherein the temperature of the second cleaning solution is kept at 45 +/-2 ℃.
6) Drying treatment: and drying the aluminum foil cleaned again at the temperature of 60 ℃.
7) And (6) rolling a finished product.
Example 4
300-2000 through holes and blind holes with the diameter of 6-12 mu m are distributed on each square centimeter of the microporous aluminum foil, wherein the proportion of the through holes is 53 percent; the upper surface and the lower surface of the microporous aluminum foil are distributed with a plurality of scores, the scores are 1-3 mu m deep, 1-5 mu m wide and 1000 mu m long, the through holes and the blind holes are irregular, and the joints with the surfaces of the microporous aluminum foil are in irregular arc transition. The resistivity of the microporous aluminum foil is increased by 1% compared with that before pore forming. The yield strength of the microporous aluminum foil is 220 MPa; the breaking strength is 250 MPa; the elongation was 2.8%.
The battery microporous aluminum foil is prepared by adopting a chemical liquid hot corrosion method according to the following steps.
1) Cleaning the surface of the rolled battery aluminum foil to remove a lubricant: the first cleaning solution comprises 30g/L NaOH and 70g/L Na2CO340g/L of Na3PO4The temperature of the first cleaning liquid is kept at 45 +/-2 ℃. The rolled aluminumThe foil is passed through the first cleaning liquid for a time of 10 s.
2) Pressing the cleaned aluminum foil into a chemical etching solution: the chemical corrosion liquid comprises the following components: 1.5mol/L NaCl, 0.3mol/L BaCl20.5mol/L of CaCl20.5mol/L NH4Cl, 0.8mol/L CuCl21mol/L FeCl3The temperature of the etching solution was maintained at 38 ℃. The residence time of the aluminum foil in the corrosive agent is 120s, and in the stage, the upper surface and the lower surface of the aluminum foil are ensured to be simultaneously soaked in the corrosive liquid, and the corrosive liquid flows on the upper surface and the lower surface of the aluminum foil in a circulating flow mode, so that the upper surface and the lower surface are corroded uniformly.
3) Cleaning the corroded aluminum foil: the second cleaning solution is prepared by collecting 0.4-0.8 g/L Na2SO40.5-1 g/L of CaSO40.1-0.3 g/L of citric acid, and the temperature of the second cleaning solution is kept at 45 +/-2 ℃. And spraying a second cleaning solution on the upper surface and the lower surface of the aluminum foil by using a spray head to clean.
4) And (3) brightening treatment: the brightening solution is 5g/L CrO3、7g/L Na2Cr2O7•2H2O, 1.5g/L NaF, and the temperature of the brightening solution 1 is kept at 45 +/-2 ℃. And performing surface brightening treatment on the cleaned aluminum foil.
5) And (3) cleaning the brightened aluminum foil again: and cleaning the brightened aluminum foil again by using a second cleaning solution, wherein the temperature of the second cleaning solution is kept at 45 +/-2 ℃.
6) Drying treatment: and drying the aluminum foil cleaned again at the temperature of 300 ℃.
7) And (6) rolling a finished product.
Example 5
2000-6000 through holes and/or blind holes with the diameter of 6-12 mu m are distributed on each square centimeter of the microporous aluminum foil, wherein the proportion of the through holes is more than 50 percent; the upper surface and the lower surface of the microporous aluminum foil are distributed with a plurality of scores, the scores are 1-3 mu m deep, 1-5 mu m wide and 1000 mu m long, the through holes and the blind holes are irregular, and the joints with the surfaces of the microporous aluminum foil are in irregular arc transition. The resistivity of the microporous aluminum foil is increased by 0.5 percent compared with that before pore forming. The yield strength of the microporous aluminum foil is 250 MPa; the breaking strength is 330 MPa; the elongation was 2.9%.
The battery microporous aluminum foil is prepared by adopting a chemical liquid corrosion method and is carried out according to the following steps:
1) cleaning the surface of the rolled battery aluminum foil to remove a lubricant: the first cleaning solution comprises 17g/L NaOH and 40g/L Na2CO325g/L of Na3PO4The rolled aluminum foil was passed through the first cleaning solution and held in the first cleaning solution for 15 seconds.
2) Pressing the cleaned aluminum foil into a chemical etching solution: the chemical corrosion liquid comprises the following components: 1mol/L NaCl, 0.2mol/L BaCl20.3mol/L of CaCl20.3mol/L NH4Cl, 0.45mol/L CuCl20.55mol/L FeCl3The staying time of the aluminum foil in the corrosive agent is 70s, the corrosion temperature is 30 ℃, and in the stage, the upper surface and the lower surface of the aluminum foil are ensured to be simultaneously soaked in the corrosive liquid, and the corrosive liquid flows on the upper surface and the lower surface of the aluminum foil in a circulating flowing mode, so that the upper surface and the lower surface are corroded uniformly.
3) Cleaning the corroded aluminum foil: the second cleaning solution is prepared by collecting 0.4-0.8 g/L Na2SO40.5-1 g/L of CaSO40.1-0.3 g/L of citric acid, and spraying a second cleaning solution on the upper surface and the lower surface of the aluminum foil by using a spray head for cleaning.
4) And (3) brightening treatment: the brightening solution is 3.5g/L CrO3、4g/L Na2Cr2O7•2H2O and 0.8g/L NaF, and carrying out surface brightening treatment on the cleaned aluminum foil.
5) And (3) cleaning the brightened aluminum foil again: and cleaning the brightened aluminum foil again by using a second cleaning solution.
6) Drying treatment: and drying the aluminum foil cleaned again at the temperature of 250 ℃.
7) And (6) rolling a finished product.
Table 1 is a table of resistivity and mechanical properties of a part of the microporous aluminum foil in the implementation process.
Figure DEST_PATH_IMAGE001
Table 2 shows the comparison of the mechanical properties of part of the microporous aluminum foil and the original aluminum foil during the implementation process as follows:
Figure DEST_PATH_IMAGE002
as can be seen from tables 1 and 2: after the metal material is corroded, compared with before the metal material is corroded: the average resistivity is increased by less than or equal to 2 percent, the average tensile strength is improved by 0 to 2 percent, and the average total elongation at break is improved by 0 to 21 percent.
The aluminum foil current collector manufactured by the invention is assembled into a lithium ion battery, and the tensile strength of the microporous aluminum foil is similar to that of the original aluminum foil; the resistivity of the microporous aluminum foil is only increased by less than 2 percent, and the capacity of the lithium ion battery can be improved by 8 to 10 percent. When the anode material is made of ternary material, the anode materials on two sides of the aluminum foil are connected into a whole by the microporous aluminum foil, so that the uniformity of the capacity, the charge-discharge characteristics and other performances of the battery is obviously improved, and the production yield of the battery is improved by 15-20%.
While the invention has been described in further detail with reference to specific preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (5)

1. The microporous aluminum foil for the lithium ion battery is characterized by comprising the following raw materials: 0.08-0.1wt% of Mg, less than or equal to 0.08 wt% of Si, less than or equal to 0.2 wt% of Fe, less than or equal to 0.03 wt% of Ga, less than or equal to 0.04 wt% of Cu, less than or equal to 0.04 wt% of Zn, less than or equal to 0.05 wt% of V, less than or equal to 0.03 wt% of Ti, 99.7 wt% of aluminum and the balance of impurities;
preparing the aluminum foil of the raw materials into a microporous aluminum foil by adopting a chemical corrosion method; the corrosive liquid adopted in the chemical corrosion method is a salt solution,containing Cl in a molar concentration of 0.1 to 3mol/L-Containing Fe in a molar concentration of 0.1 to 3mol/L3+And Cu2+A cation of (a);
the salt solution comprises NH4Cl；
300-6000 through holes and blind holes with the diameter of 6-12 mu m are distributed on each square centimeter of the microporous aluminum foil, wherein the proportion of the number of the through holes to the total number of the through holes and the blind holes is more than 50 percent;
the upper surface and the lower surface of the microporous aluminum foil are distributed with a plurality of scores, the scores are 1-3 mu m deep, 1-5 mu m wide and 1000 mu m long;
the yield strength of the microporous aluminum foil is 200-260 MPa; the breaking strength is 200-350 MPa; the elongation is 2% -3%.
2. The microporous aluminum foil for lithium ion batteries according to claim 1, wherein: 300-2000 through holes and blind holes with the diameter of 6-12 mu m are distributed on each square centimeter of the microporous aluminum foil.
3. The microporous aluminum foil for lithium ion batteries according to claim 1 or 2, characterized in that: the resistivity is increased by less than or equal to 2 percent compared with the resistivity before pore forming.
4. A method for preparing the microporous aluminum foil for lithium ion batteries according to claim 1 or 2, wherein:
preparing by adopting a chemical corrosion method; the corrosive liquid adopted in the chemical corrosion method is a salt solution containing Cl with the molar concentration of 0.1-3mol/L-Containing Fe in a molar concentration of 0.1 to 3mol/L3+And Cu2+The salt solution contains NH4Cl。
5. The method for preparing the microporous aluminum foil for the lithium ion battery according to claim 4, wherein: in the chemical corrosion method, the corrosion time is 20-120s, and the corrosion temperature is 20-60 ℃.
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