CN108232200A - A kind of preparation method of lithium ion battery aluminium foil, micropore aluminium foil and micropore aluminium foil - Google Patents
A kind of preparation method of lithium ion battery aluminium foil, micropore aluminium foil and micropore aluminium foil Download PDFInfo
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- CN108232200A CN108232200A CN201810019724.9A CN201810019724A CN108232200A CN 108232200 A CN108232200 A CN 108232200A CN 201810019724 A CN201810019724 A CN 201810019724A CN 108232200 A CN108232200 A CN 108232200A
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- aluminium foil
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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
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
- H01M4/662—Alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/06—Alloys based on aluminium with magnesium as the next major constituent
- C22C21/08—Alloys based on aluminium with magnesium as the next major constituent with silicon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/20—Acidic compositions for etching aluminium or alloys thereof
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention discloses the preparation method of a kind of lithium ion battery aluminium foil, micropore aluminium foil and micropore aluminium foil, and aluminium foil includes Mg, Si≤0.08wt%, Fe≤0.2wt%, Ga≤0.03wt%, Cu≤0.04wt%, Zn≤0.04wt%, V≤0.05wt%, Ti≤0.03wt% of 0.14 0.16wt%, aluminium is 99.7 wt%；Micropore aluminium foil is prepared into using chemical corrosion method；300-6000 a diameter of 6-12 μm of through-hole and/or blind hole are distributed on micropore aluminium foil is every square centimeter；Limit into being grouped as compared with existing series alloys, with higher yield strength, in subsequent chemical corrosion process, it is also more uniform for formed micropore size smaller, through-hole and blind hole and material body arc transition, reduce stress concentration, enhance mechanical property, electric property will not be weakened, the present invention can be used in lithium battery.
Description
Technical field
The invention belongs to lithium battery material manufacturing technology fields, and in particular to a kind of lithium ion battery aluminium foil, micropore aluminium
The preparation method of foil and micropore aluminium foil.
Background technology
New material and clean energy resource are all the prior development directions of State-level, and lithium ion battery is in current energy storage technology
Most widely used energy storage battery core, it is the target that the whole world is pursued to improve battery core energy storage density, and battery core energy density carries
Height depends on the progress of its positive and negative electrode material, but is also bonded with the positive and negative anodes collector of lithium ion battery, positive and negative anodes
The progress of the materials such as agent, electrolyte and diaphragm is related.
The positive mix that the collector that the anode of lithium ion battery uses is generally aluminium foil and is coated on（Ferric phosphate
Lithium, cobalt acid lithium or ternary material）It is formed.The positive electrode electronic collector of lithium battery is aluminium foil.This aluminium foil desired size precision
It is high.The alloy for being generally used for manufacture aluminium foil is 1235, and aluminium foil performance is general so that lithium battery performance is general.Meanwhile traditional collection
Fluent material generally selects the smooth aluminium foil in surface, is directly applied using the aluminium foil of 99.7% purity and is covered with active material, but surface light
Combination between sliding aluminium foil and active material more relaxes, high to raw material and auxiliary material quality and technological requirement, is processing and is filling
Active material easily occurs in discharge process to come off or lose powder phenomenon, reduces cycle charge discharge electrical efficiency and battery life, improves
Contact resistance between component causes positive plate electric conductivity to decline, so as to affecting the comprehensive performance of battery.Serious influence
The comprehensive performance of lithium ion.
In order to improve positive pole aluminium foil collector, the bond state between anode sizing agent, existing micropore copper foil and micropore
Nine through-holes are all prepared on aluminium foil is every square centimeter, the diameter of each through-hole is about 1mm.But such aluminium foil and copper foil must make
With special battery automatic assembly line, reason is on original battery automatic assembly line, is existed using such through-hole diameter
When the copper foil or aluminium foil of 1mm, it may appear that slurry phenomenon is oozed at the back side, influences the coating of another side.
Han Wei et al. utilizes acid, alkali electroless reagent in patent CN 103618090A and CN 103617894A, right
Aluminium foil carries out soda acid etching processing.Obtained alumina foil contact resistance reduces unobvious, and is reduced during corrosion removal
The mechanical strength of aluminium foil.The method of other countries' pore-forming on aluminium foil, employs rolling or laser ablation, and the aluminium of the present invention
Foil pore-forming is using salt compounds etch, and technology path is entirely different, and it is special that obtained micropore aluminium foil also has
Structure and performance.
Invention content
Overcome the deficiencies in the prior art of the present invention, it is therefore an objective to which a kind of lithium ion battery aluminium foil, micropore aluminium foil and micro- are provided
The preparation method of hole aluminium foil.
In order to solve the above technical problems, the technical solution adopted in the present invention is.
A kind of lithium ion battery aluminium foil, including：Mg, Si of 0.14-0.16wt%≤0.08wt%, Fe≤0.2wt%,
Ga≤0.03wt%, Cu≤0.04wt%, Zn≤0.04wt%, V≤0.05wt%, Ti≤0.03wt%, aluminium 99.7
Wt%, remaining is impurity.
The μ Ω m of the resistivity of the lithium ion battery aluminium foil≤3.
A kind of lithium ion battery micropore aluminium foil, including：Mg, Si of 0.14-0.16wt%≤0.08wt%, Fe≤
0.2wt%, Ga≤0.03wt%, Cu≤0.04wt%, Zn≤0.04wt%, V≤0.05wt%, Ti≤0.03wt%, aluminium are
99.7 wt%, remaining is impurity；300-6000 a diameter of 6-12 μm are distributed on the micropore aluminium foil is every square centimeter
Through-hole and blind hole, wherein number of openings account for the ratio ＞ 50% of through-hole and blind hole sum.
Be distributed on the preferred micropore aluminium foil is every square centimeter 300-2000 a diameter of 6-12 μm through-hole and
Blind hole.
The upper and lower surface of the preferred micropore aluminium foil is dispersed with multiple indentations, and indentation is 1-3 μm deeply, 1-5 μm wide.
The resistivity of the preferred micropore aluminium foil is compared with resistivity growth rate≤2% of aluminium foil before pore-forming.
The yield strength of the preferred micropore aluminium foil is 180-230MPa；Fracture strength is 220-340MPa；Extension
Rate is 0.5% -2.8%.
The micropore aluminium foil is used for capacitance electricity grade.
The thickness of lithium ion battery aluminium foil or micropore aluminium foil is 8-18 μm.
A kind of lithium ion battery preparation method of micropore aluminium foil, is prepared using chemical corrosion method；The chemical attack
The corrosive liquid used in method contains the Cl that molar concentration is 0.1-3mol/L for salting liquid-Anion, contain molar concentration
Fe for 0.1-3mol/L3+And Cu2+Cation.
Etching time is 20-120s in the chemical corrosion method, and corrosion temperature is 20-60 DEG C.
Etching time is 20-120s in the preferred chemical corrosion method, and corrosion temperature is 20-38 DEG C.
Compared with prior art the invention has the advantages that.
1st, a kind of lithium battery micropore aluminium foil ingredient includes：Mg, Si of 0.14-0.16wt%≤0.08wt%, Fe≤
0.2wt%, Ga≤0.03wt%, Cu≤0.04wt%, Zn≤0.04wt%, V≤0.05wt%, Ti≤0.03wt%, aluminium are
99.7 wt%, remaining is impurity.Limit into being grouped as compared with 1 ××× series alloys, there is higher Mg contents,
It is also more uniform for formed micropore size smaller in subsequent chemical corrosion process with higher yield strength, by
Original diameter is that 10-50 μm of aperture is promoted to 6-12 μm, is distributed with 300-6000 on the micropore aluminium foil is every square centimeter
A a diameter of 6-12 μm of through-hole and/or blind hole；So that two surfaces of metal foil both not completely through and also not completely every
From, can effectively by the ion of smaller less than 6-12 μm of diameter and particle, if lithium ion passes through, and prevent major diameter
Ion or particle pass through, improve lithium ion activity, improve battery capacity, it is whole into one with aluminium foil coated in positive electrode above
Body, adhesive force significantly improve, and Li dendrite will not be grown at through-hole and blind hole.Do not influence the performance of material simultaneously, such as：It is flat
Equal resistivity increases by 1-3%, and average tensile strength promotes 0-2%, is averagely broken breaking elongation and promotes 0-21%.
2nd, it is further, indentation is dispersed in the upper and lower surface of the micropore aluminium foil, indentation is 1-3 μm deep, wide 1-5 μ
M, the through-hole and blind hole are irregular shape and irregular distribution, and are irregular circular arc with micropore aluminium foil surface junction
Transition.The through-hole and blind hole are irregular shape, and are irregular arc transition with aluminium foil surface junction, aperture size
Change in a certain range, the diameter of each hole is also varied from different directions.Can be promoted micropore aluminium foil two sides into
During row coating, the adhesive force of coating, through-hole and blind hole and material body arc transition are promoted, reduces stress concentration, enhances mechanics
Performance will not weaken electric property.
3rd, it includes and this micropore aluminium foil is prepared using the method for chemical corrosion.The present invention uses
Liquid is different, chloride salt compound also can be used as corrosive liquid in caustic solution of the present invention, the extent of reaction during corrosion
Milder, when aluminium foil is put into treatment fluid, under the protection of chlorion, copper ion or iron ion react with aluminium surface, make
Aluminium surface forms the structure of micropore, and calcium ion, sodium ion and the barium ions in treatment fluid enter in perforated membrane can be in follow-up mistake
It is fixed in journey, plays a part of improvement to aluminium surface performance.
Micropore aluminium foil can make the capacity of lithium ion battery improve 8-10%.When positive electrode uses ternary material, due to
Micropore aluminium foil makes the positive electrode on aluminium foil two sides be connected as an entirety, can make the performances such as capacity and the charge-discharge characteristics of battery
Uniformity is significantly improved, and battery production yield rate improves 15-20%.
Description of the drawings
Fig. 1 is a kind of micro image of lithium battery micropore aluminium foil of the present invention.
Specific embodiment
Embodiment 1
A kind of lithium ion battery aluminium foil, including：Including：The Fe of Si, 0.2wt% of Mg, 0.08wt% of 0.14wt%,
Ti, the aluminium 99.7 of V, 0.03wt% of Zn, 0.05wt% of Cu, 0.04wt% of Ga, 0.04wt% of 0.03wt%
Wt%, remaining is impurity；Its resistivity is 3 μ Ω m.The aluminium foil is prepared by the method for preparing lithium battery micropore aluminium foil
Micropore aluminium foil.
A kind of lithium battery micropore aluminium foil, including：The Fe of Si, 0.2wt% of Mg, 0.08wt% of 0.14wt%,
Ti, the aluminium 99.7 of V, 0.03wt% of Zn, 0.05wt% of Cu, 0.04wt% of Ga, 0.04wt% of 0.03wt%
Wt%, remaining is impurity.
2000-6000 a diameter of 6-12 μm of through-hole and blind is distributed on the micropore aluminium foil is every square centimeter
Hole, wherein through-hole ratio 55%；The upper and lower surface of the micropore aluminium foil is dispersed with multiple indentations, and the indentation is deep 1-3 μ
M, 1-5 μm wide, 100-1000 μm long, through-hole and blind hole are irregular shape, and be irregular with micropore aluminium foil surface junction
Arc transition.The resistivity of the micropore aluminium foil before pore-forming compared with increasing 2%.The yield strength of the micropore aluminium foil is
230MPa；Fracture strength is 220MPa；Elongation percentage is 2%.
It follows the steps below：
The step of a kind of method for preparing lithium battery micropore aluminium foil, wherein micropore aluminium foil are made of chemical liquids caustic solution is such as
Under, other steps are same as the prior art or similar, here, not repeating.
1）Surface clean is carried out to the battery aluminium foil after rolling and dispels lubricant：The composition of first cleaning solution is 5g/L
The Na of NaOH, 70g/L2CO3, 40g/L Na3PO4, by the aluminium foil after rolling by the first cleaning solution, in the first cleaning solution
The time of holding is 6s.
2）The aluminium foil cleaned is pressed into chemical corrosion liquid：The composition of chemical corrosion liquid is：The NaCl of 0.5mol/L,
The BaCl of 0.1mol/L2, 0.1mol/L CaCl2, 0.1mol/L NH4The CuCl of Cl, 0.1mol/L2, 0.1mol/L
FeCl3, residence time of the aluminium foil in the corrosive agent, corrosion temperature was 20 DEG C, in this stage, it is ensured that following table on aluminium foil in 20s
Face is immersed in corrosive liquid simultaneously, and the type of flow for recycling corrosive liquid is flowed in aluminium foil upper and lower surface, is made with reaching
Upper and lower surface corrosion is uniform.
3）Aluminium foil after corrosion is cleaned：The composition of second cleaning solution is to take 0.4-0.8g/LNa2SO4、0.5—
1g/LCaSO4, 0.1-0.3g/L citric acids, aluminium foil upper and lower surface using nozzle spray the second cleaning solution cleaned.
4）Brightization processing：The composition of brightening liquid is the CrO of 2g/L3, 1g/L Na2Cr2O7•2H2O, the NaF of 0.1g/L,
Surface brightening processing is carried out to the aluminium foil after cleaning.
5）Aluminium foil after brightening is cleaned again：The aluminium foil after brightening is cleaned again using the second cleaning solution.
6）Drying and processing：The aluminium foil cleaned again is dried, temperature is 200 DEG C.
7）Finished product is wound.
The present embodiment is assembled into lithium ion battery：8.5g LiFePO4s, 1.0g acetylene blacks and 0.5g PVDF are weighed,
And 20g NMP are added in, it is sufficiently stirred the slurry for making uniformly mixed.Then it is scratched at through the embodiment of the present invention 1
In the micropore aluminum foil current collector managed, 80 DEG C of dryings are to constant weight under the vacuum of 0.01MPa, and under 10-15MPa pressure
Iron phosphate lithium electrode is made in roll-in, and is cut into anode disk.Equally, 4.25g graphite, 0.5g acetylene blacks and 0.25g fourths are weighed
Benzene rubber cement, and 10g NMP are added in, the slurry for making uniformly mixed is sufficiently stirred, is then scratched in through second
On the common copper foil that alcohol cleaned, it is pressed into negative plate.By positive plate, celgard2400 polypropylene porous films diaphragm, cathode
Lamination assembling is into battery core in sequence for piece, then with battery housing seal battery core, toward battery case in inject the LiBF of 1mol/L4/
Diethyl carbonate electrolyte seals liquid injection port after being full of, obtains lithium ion battery.
At a temperature of 60 DEG C, using charge-discharge test instrument to being assembled in the present embodiment in the voltage range of 2.5-4.2V
Lithium ion battery carry out 1C charge-discharge tests, the specific discharge capacity of the 3rd time is 179mAh/g, carries out 300 charge and discharge and follows
After ring, capacity retention ratio 95.6%.
For the advantageous effect further illustrated the present invention, spy sets following comparative example：
8.5g LiFePO4s, 1.0g acetylene blacks and 0.5g PVDF are weighed, and adds in 20g NMP, is sufficiently stirred and makes mixed
Close uniform slurry.Then it is scratched in the normal aluminium foil cleaned through ethyl alcohol, is done for 80 DEG C under the vacuum of 0.01MPa
It is dry to be pressed into iron phosphate lithium electrode, and be cut into anode disk to constant weight, and in 10-15MPa pressure lower rolls.Equally, it weighs
4.25g graphite, 0.5g acetylene blacks and 0.25g butadiene-styrene rubber binding agents, and 10g NMP are added in, it is sufficiently stirred and makes mixed
Uniform slurry is closed, is then scratched on the common copper foil cleaned through ethyl alcohol, is pressed into negative plate.By positive plate,
Lamination assembling is electric into battery core, then with battery housing seal in sequence for celgard2400 polypropylene porous films diaphragm, negative plate
Core, toward battery case in inject 1mol/L LiBF4/ diethyl carbonate electrolyte, liquid injection port is sealed after filling, obtain lithium from
Sub- battery.
After testing, after 300 charge and discharge cycles, capacity retention ratio is lithium ion battery obtained by the comparative example
82.5%.It can be seen that micropore aluminum foil current collector made from the present embodiment, since the hole of this irregular shape thereon more has
Conducive to the cohesive force improved between aluminium foil and anode sizing agent, coming off for positive electrode can be avoided, so as to improve lithium ion battery
Cyclical stability and the service life.
A kind of lithium battery of the present invention is with micropore aluminium foil due to the hole and indentation of specific 6-12 μm of sizes, hole size
More uniformly, can be by lithium ion, and other adiaphorous particles or ion cannot pass through, and increase lithium battery capacity, make micro-
Hole aluminium foil surface smoothness higher is irregular arc transition without overlap, burr, and hole and aluminium foil surface junction, no
There are 90 ° of right angles, can effectively prevent the appearance of Li dendrite in charge and discharge process, extend the service life of battery；In addition, micropore
Shape is also different, and the hole on micropore aluminium foil obtained by chemical corrosion method is in irregular shape, and the diameter of each hole exists
It is also varied from different directions, the hole of this irregular shape is more advantageous to improving the bonding between aluminium foil and anode sizing agent
Power.And existing production technology is varied without, easy to spread, it is not only suitable for single side coating and is also applied for dual coating.
The present embodiment can make the capacity of lithium ion battery improve 8-10%.When positive electrode uses ternary material, due to
Micropore aluminium foil makes the positive electrode on aluminium foil two sides be connected as an entirety, can make the performances such as capacity and the charge-discharge characteristics of battery
Uniformity is significantly improved, and battery production yield rate improves 15-20%.
Embodiment 2
A kind of lithium ion battery aluminium foil, including：Including：The Fe of Si, 0.1wt% of Mg, 0.05wt% of 0.16wt%,
Ti, the aluminium 99.7 of V, 0.01wt% of Zn, 0.04wt% of Cu, 0.03wt% of Ga, 0.03wt% of 0.02wt%
Wt%, remaining is impurity；Its resistivity is 2.5 μ Ω m.It is by the method for preparing lithium battery micropore aluminium foil that the made with aluminum foil is standby
Into micropore aluminium foil.
A kind of lithium battery micropore aluminium foil, including：The Fe of Si, 0.1wt% of Mg, 0.05wt% of 0.16wt%,
Ti, the aluminium 99.7 of V, 0.01wt% of Zn, 0.04wt% of Cu, 0.03wt% of Ga, 0.03wt% of 0.02wt%
Wt%, remaining is impurity.
300-2000 a diameter of 6-12 μm of through-hole and blind hole are distributed on the micropore aluminium foil is every square centimeter,
Wherein through-hole ratio 60%；The upper and lower surface of the micropore aluminium foil is dispersed with multiple indentations, and the indentation is 1-3 μm deeply,
1-5 μm wide, 100-1000 μm long, through-hole and blind hole are irregular shape, and are irregular roundness with micropore aluminium foil surface junction
Arc transition.The resistivity of the micropore aluminium foil before pore-forming compared with increasing 1%.The yield strength of the micropore aluminium foil is 180MPa；
Fracture strength is 340MPa；Elongation percentage is 2.8%.Micropore aluminium foil is made of chemical liquids caustic solution, according to following steps into
Row：
1）Surface clean is carried out to the battery aluminium foil after rolling and dispels lubricant：The composition of first cleaning solution is 30g/L
The Na of NaOH, 70g/L2CO3, 40g/L Na3PO4, by the aluminium foil after rolling by the first cleaning solution, in the first cleaning solution
The time 10s of holding.
2）The aluminium foil cleaned is pressed into chemical corrosion liquid：The composition of chemical corrosion liquid is：The NaCl of 1.5mol/L,
The BaCl of 0.3mol/L2, 0.5mol/L CaCl2, 0.5mol/L NH4The CuCl of Cl, 0.8mol/L2, 1mol/L
FeCl3, residence time of the aluminium foil in the corrosive agent, corrosion temperature was 60 DEG C, in this stage, it is ensured that following table on aluminium foil in 120s
Face is immersed in corrosive liquid simultaneously, and the type of flow for recycling corrosive liquid is flowed in aluminium foil upper and lower surface, is made with reaching
Upper and lower surface corrosion is uniform.
3）Aluminium foil after corrosion is cleaned：The composition of second cleaning solution is to take 0.4-0.8g/LNa2SO4、0.5—
1g/LCaSO4, 0.1-0.3g/L citric acids, aluminium foil upper and lower surface using nozzle spray the second cleaning solution cleaned.
4）Brightization processing：The composition of brightening liquid is 5g/L CrO3、7g/L Na2Cr2O7•2H2O, 1.5g/L NaF, to clear
Aluminium foil after washing carries out surface brightening processing.
5）Aluminium foil after brightening is cleaned again：The aluminium foil after brightening is cleaned again using the second cleaning solution.
6）Drying and processing：The aluminium foil cleaned again is dried, temperature is 300 DEG C.
7）Finished product is wound.
Embodiment 3
A kind of lithium ion battery aluminium foil, including：Including：The Fe of Si, 0.05wt% of Mg, 0.07wt% of 0.15wt%,
Ti, the aluminium 99.7 of V, 0.02wt% of Zn, 0.02wt% of Cu, 0.02wt% of Ga, 0.03wt% of 0.01wt%
Wt%, remaining is impurity；Its resistivity is 2 μ Ω m.The aluminium foil is prepared by the method for preparing lithium battery micropore aluminium foil
Micropore aluminium foil.
A kind of lithium battery micropore aluminium foil, including：The Fe of Si, 0.05wt% of Mg, 0.07wt% of 0.15wt%,
Ti, the aluminium 99.7 of V, 0.02wt% of Zn, 0.02wt% of Cu, 0.02wt% of Ga, 0.03wt% of 0.01wt%
Wt%, remaining is impurity.
3000-5000 a diameter of 6-12 μm of through-hole and blind is distributed on the micropore aluminium foil is every square centimeter
Hole, wherein through-hole ratio 70%；The upper and lower surface of the micropore aluminium foil is dispersed with multiple indentations, and the indentation is deep 1-3 μ
M, 1-5 μm wide, 100-1000 μm long, through-hole and blind hole are irregular shape, and be irregular with micropore aluminium foil surface junction
Arc transition.The resistivity of the micropore aluminium foil before pore-forming compared with increasing 1%.The yield strength of the micropore aluminium foil is
200MPa；Fracture strength is 280MPa；Elongation percentage is 2.2%.
Battery micropore aluminium foil is made of chemical liquids heat erosion method, is followed the steps below：
1）Surface clean is carried out to the battery aluminium foil after rolling and dispels lubricant：The composition of first cleaning solution is 17g/L
The Na of NaOH, 40g/L2CO3, 25g/L Na3PO4, the temperature of the first cleaning solution is maintained at 45 ± 2 DEG C.By the aluminium after rolling
Foil is by the first cleaning solution, the time 15s kept in the first cleaning solution.
2）The aluminium foil cleaned is pressed into chemical corrosion liquid：The composition of chemical corrosion liquid is：1mol/L NaCl、0.2mol/
L BaCl2、0.3mol/L CaCl2、0.3mol/L NH4Cl、0.45mol/LCuCl2、0.55mol/LFeCl3, the temperature of corrosive liquid
Degree is maintained at 45 ± 2 DEG C, residence time of the aluminium foil in the corrosive agent in 70s, in this stage, it is ensured that aluminium foil upper and lower surface is simultaneously
It is immersed in corrosive liquid, and the type of flow for recycling corrosive liquid is flowed in aluminium foil upper and lower surface, makes upper following table to reach
Face corrosion is uniform.
3）Aluminium foil after corrosion is cleaned：The composition of second cleaning solution is to take 0.4-0.8g/LNa2SO4、0.5—
1g/LCaSO4, 0.1-0.3g/L citric acids, the temperature of the second cleaning solution is maintained at 45 ± 2 DEG C.Make in aluminium foil upper and lower surface
The second cleaning solution is sprayed with nozzle to be cleaned.
4）Brightization processing：The composition of brightening liquid is 3.5g/L CrO3、4g/L Na2Cr2O7•2H2O, 0.8g/L NaF are right
Aluminium foil after cleaning carries out surface brightening processing, and the temperature of brightening liquid is maintained at 45 ± 2 DEG C.
5）Aluminium foil after brightening is cleaned again：The aluminium foil after brightening is cleaned again using the second cleaning solution, the
The temperature of two cleaning solutions is maintained at 45 ± 2 DEG C.
6）Drying and processing：The aluminium foil cleaned again is dried, temperature is 60 DEG C.
7）Finished product is wound.
Embodiment 4
A kind of lithium ion battery aluminium foil, including：Fe, 0.02wt% of Si, 0.15wt% of Mg, 0.04wt% of 0.16wt%
The Ti of V, 0.03wt%, the aluminium of Zn, 0.02wt% of Cu, 0.01wt% of Ga, 0.01wt% be 99.7 wt%, remaining is
Impurity；Its resistivity is 1.5 μ Ω m.The aluminium foil is prepared by micropore aluminium foil by the method for preparing lithium battery micropore aluminium foil.
A kind of lithium battery micropore aluminium foil, including：The Fe of Si, 0.15wt% of Mg, 0.04wt% of 0.16wt%,
Ti, the aluminium 99.7 of V, 0.03wt% of Zn, 0.02wt% of Cu, 0.01wt% of Ga, 0.01wt% of 0.02wt%
Wt%, remaining is impurity.
1000-3000 a diameter of 6-12 μm of through-hole and blind is distributed on the micropore aluminium foil is every square centimeter
Hole, wherein through-hole ratio 53%；The upper and lower surface of the micropore aluminium foil is dispersed with multiple indentations, and the indentation is deep 1-3 μ
M, 1-5 μm wide, 100-1000 μm long, through-hole and blind hole are irregular shape, and be irregular with micropore aluminium foil surface junction
Arc transition.The resistivity of the micropore aluminium foil before pore-forming compared with increasing 1%.The yield strength of the micropore aluminium foil is
180MPa；Fracture strength is 260MPa；Elongation percentage is 0.5%.
Battery micropore aluminium foil is made of chemical liquids heat erosion method, is followed the steps below.
1）Surface clean is carried out to the battery aluminium foil after rolling and dispels lubricant：The composition of first cleaning solution is 30g/L
The Na of NaOH, 70g/L2CO3, 40g/L Na3PO4, the temperature of the first cleaning solution is maintained at 45 ± 2 DEG C.By the aluminium after rolling
Foil is by the first cleaning solution, the time 10s kept in the first cleaning solution.
2）The aluminium foil cleaned is pressed into chemical corrosion liquid：The composition of chemical corrosion liquid is：The NaCl of 1.5mol/L,
The BaCl of 0.3mol/L2, 0.5mol/L CaCl2, 0.5mol/L NH4The CuCl of Cl, 0.8mol/L2, 1mol/L FeCl3,
The temperature of corrosive liquid is maintained at 38 DEG C.Residence time of the aluminium foil in the corrosive agent in 120s, in this stage, it is ensured that above and below aluminium foil
Surface is immersed in corrosive liquid simultaneously, and the type of flow for recycling corrosive liquid is flowed in aluminium foil upper and lower surface, to reach
Make upper and lower surface corrosion uniform.
3）Aluminium foil after corrosion is cleaned：The composition of second cleaning solution is the Na for taking 0.4-0.8g/L2SO4、0.5—
The CaSO of 1g/L4, 0.1-0.3g/L citric acid, the temperature of the second cleaning solution is maintained at 45 ± 2 DEG C.In aluminium foil upper and lower surface
The second cleaning solution is sprayed using nozzle to be cleaned.
4）Brightization processing：The composition of brightening liquid is 5g/L CrO3、7g/L Na2Cr2O7•2H2O, 1.5g/L NaF are bright
The temperature of liquid 1 is maintained at 45 ± 2 DEG C.Surface brightening processing is carried out to the aluminium foil after cleaning.
5）Aluminium foil after brightening is cleaned again：The aluminium foil after brightening is cleaned again using the second cleaning solution, the
The temperature of two cleaning solutions is maintained at 45 ± 2 DEG C.
6）Drying and processing：The aluminium foil cleaned again is dried, temperature is 300 DEG C.
7）Finished product is wound.
Embodiment 5
A kind of lithium ion battery aluminium foil, including：Fe, 0.03wt%'s of Si, 0.2wt% of Mg, 0.08wt% of 0.15wt%
Ti, the aluminium of V, 0.03wt% of Zn, 0.05wt% of Cu, 0.04wt% of Ga, 0.04wt% are 99.7 wt%, remaining is miscellaneous
Matter；Its resistivity is 1 μ Ω m.The aluminium foil is prepared by micropore aluminium foil by the method for preparing lithium battery micropore aluminium foil.
A kind of lithium battery micropore aluminium foil, including：The Fe of Si, 0.2wt% of Mg, 0.08wt% of 0.15wt%,
Ti, the aluminium 99.7 of V, 0.03wt% of Zn, 0.05wt% of Cu, 0.04wt% of Ga, 0.04wt% of 0.03wt%
Wt%, remaining is impurity.
Be distributed on the micropore aluminium foil is every square centimeter 3000-6000 a diameter of 6-12 μm through-hole and/or
Blind hole, wherein through-hole ratio ＞ 50%；The upper and lower surface of the micropore aluminium foil is dispersed with multiple indentations, and the indentation is deep
1-3 μm, 1-5 μm wide, 100-1000 μm long, through-hole and blind hole are irregular shape, and be with micropore aluminium foil surface junction
Irregular arc transition.The resistivity of the micropore aluminium foil before pore-forming compared with increasing 0.5%.The yield strength of the micropore aluminium foil
For 230MPa；Fracture strength is 340MPa；Elongation percentage is 0.8%.
Battery micropore aluminium foil is made of chemical liquids caustic solution, is followed the steps below：
1）Surface clean is carried out to the battery aluminium foil after rolling and dispels lubricant：The composition of first cleaning solution is 17g/L
The Na of NaOH, 40g/L2CO3, 25g/L Na3PO4, by the aluminium foil after rolling by the first cleaning solution, in the first cleaning solution
The time 15s of holding.
2）The aluminium foil cleaned is pressed into chemical corrosion liquid：The composition of chemical corrosion liquid is：The NaCl of 1mol/L,
The BaCl of 0.2mol/L2, 0.3mol/L CaCl2, 0.3mol/L NH4The CuCl of Cl, 0.45mol/L2, 0.55mol/L
FeCl3, residence time of the aluminium foil in the corrosive agent, corrosion temperature was 30 DEG C, in this stage, it is ensured that following table on aluminium foil in 70s
Face is immersed in corrosive liquid simultaneously, and the type of flow for recycling corrosive liquid is flowed in aluminium foil upper and lower surface, is made with reaching
Upper and lower surface corrosion is uniform.
3）Aluminium foil after corrosion is cleaned：The composition of second cleaning solution is the Na for taking 0.4-0.8g/L2SO4、0.5—
The CaSO of 1g/L4, 0.1-0.3g/L citric acid, aluminium foil upper and lower surface using nozzle spray the second cleaning solution carry out it is clear
It washes.
4）Brightization processing：The composition of brightening liquid is 3.5g/L CrO3、4g/L Na2Cr2O7•2H2O, 0.8g/L NaF are right
Aluminium foil after cleaning carries out surface brightening processing.
5）Aluminium foil after brightening is cleaned again：The aluminium foil after brightening is cleaned again using the second cleaning solution.
6）Drying and processing：The aluminium foil cleaned again is dried, temperature is 250 DEG C.
7）Finished product is wound.
Table 1 is the resistivity of partial pore aluminium foil and mechanical performance data table in implementation process.
Table 2 is in implementation process, and partial pore aluminium foil and the comparison of primary aluminum foil dynamic performance are as follows：
By Tables 1 and 2 it can be seen that：Before relatively corroding after metallic material corrosion：Average resistivity increases≤2%, average tensile
Strength enhancing 0-2% is averagely broken breaking elongation and promotes 0-21%.
The present invention is made into aluminum foil current collector and is assembled into lithium ion battery, the tensile strength of micropore aluminium foil and resisting for primary aluminum foil
Tensile strength is close；The resistivity of micropore aluminium foil is increased only can make the capacity of lithium ion battery improve 8-10% less than 2%.When just
During the materials'use ternary material of pole, since micropore aluminium foil makes the positive electrode on aluminium foil two sides be connected as an entirety, battery can be made
Capacity and the uniformities of the performances such as charge-discharge characteristics significantly improved, battery production yield rate improves 15-20%.
The above content is combine specific preferred embodiment to the further description of the invention done, it is impossible to assert
The specific embodiment of the present invention is only limitted to this, for those of ordinary skill in the art to which the present invention belongs, is not taking off
Under the premise of from the present invention, several simple deduction or replace can also be made, should all be considered as belonging to the present invention by being submitted
Claims determine scope of patent protection.
Claims (10)
1. a kind of lithium ion battery aluminium foil, which is characterized in that including：Mg, Si of 0.14-0.16wt%≤0.08wt%, Fe≤
0.2wt%, Ga≤0.03wt%, Cu≤0.04wt%, Zn≤0.04wt%, V≤0.05wt%, Ti≤0.03wt%, aluminium are
99.7 wt%, remaining is impurity.
2. a kind of lithium ion battery aluminium foil according to claim 1, it is characterised in that：The μ Ω m of resistivity≤3.
3. a kind of lithium ion battery micropore aluminium foil, which is characterized in that including：Mg, Si of 0.14-0.16wt%≤0.08wt%,
Fe≤0.2wt%, Ga≤0.03wt%, Cu≤0.04wt%, Zn≤0.04wt%, V≤0.05wt%, Ti≤0.03wt%,
Aluminium is 99.7 wt%, remaining is impurity；
300-6000 a diameter of 6-12 μm of through-hole and blind hole are distributed on the micropore aluminium foil is every square centimeter, wherein
Number of openings accounts for the ratio ＞ 50% of through-hole and blind hole sum.
4. a kind of lithium ion battery micropore aluminium foil according to claim 3, it is characterised in that：The micropore aluminium foil is every
300-2000 a diameter of 6-12 μm of through-hole and blind hole are distributed on square centimeter.
5. a kind of lithium ion battery micropore aluminium foil according to claim 3 or 4, it is characterised in that：The micropore aluminium
The upper and lower surface of foil is dispersed with multiple indentations, and the indentation is 1-3 μm deeply, 1-5 μm wide.
6. a kind of lithium ion battery micropore aluminium foil according to claim 3 or 4, it is characterised in that：Resistivity is compared with pore-forming
It is preceding to increase≤2%.
7. a kind of lithium ion battery micropore aluminium foil according to claim 3 or 4, it is characterised in that：The micropore aluminium foil
Yield strength be 180-230MPa；Fracture strength is 220-340MPa；Elongation percentage is 0.5% -2.8%.
8. a kind of lithium ion battery micropore aluminium foil according to claim 3 or 4, it is characterised in that：The micropore aluminium
Foil is used for capacitance electricity grade.
9. a kind of preparation method for preparing a kind of lithium ion battery micropore aluminium foil as described in claim 3 or 4, feature exist
In：It is prepared using chemical corrosion method；The corrosive liquid used in the chemical corrosion method is for salting liquid, containing molar concentration
The Cl of 0.1-3mol/L-Anion, contain molar concentration be 0.1-3mol/L Fe3+And Cu2+Cation.
10. a kind of preparation method for preparing lithium ion battery micropore aluminium foil according to claim 9, it is characterised in that：
Etching time is 20-120s in the chemical corrosion method, and corrosion temperature is 20-60 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112349962A (en) * | 2019-08-08 | 2021-02-09 | 宁德时代新能源科技股份有限公司 | Lithium ion battery |
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| CN107502936A (en) * | 2017-08-04 | 2017-12-22 | 西北工业大学 | A kind of method for obtaining large aperture doubled via AAO films |
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| JP2008231512A (en) * | 2007-03-20 | 2008-10-02 | Sachiko Ono | Aluminum substrate for etching, and aluminum electrode material for electrolytic capacitor using the same |
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