CN109148895B - Electrochemical roughening treatment method for positive current collector of lithium ion battery - Google Patents
Electrochemical roughening treatment method for positive current collector of lithium ion battery Download PDFInfo
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- CN109148895B CN109148895B CN201811015634.9A CN201811015634A CN109148895B CN 109148895 B CN109148895 B CN 109148895B CN 201811015634 A CN201811015634 A CN 201811015634A CN 109148895 B CN109148895 B CN 109148895B
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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
- H01M4/72—Grids
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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
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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
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention relates to the technical field of etching, in particular to a method for electrochemically roughening a positive current collector of a lithium ion battery, which comprises the following steps: firstly, carrying out electrochemical polishing treatment on the rough surface of an aluminum foil of a positive current collector of a lithium ion battery in a bipolar chamber cationic membrane electrolytic cell; secondly, in a bipolar chamber cationic membrane electrolytic cell, taking a sodium silicate solution with abundant sources and low cost as a roughening solution, and roughening the surface of the aluminum foil by adopting a constant-pressure electrolysis mode; finally, cleaning and drying the roughened aluminum foil to obtain a roughened aluminum current collector with a compact aluminum oxide film on the surface; compared with the prior art, the aluminum foil with good coarsening effect can be prepared by only one-step electrolysis, the method is efficient, simple and pollution-free, can be directly applied to industrial production, and can solve the high requirements of dry etching on equipment, the serious drilling and etching of wet etching, poor pattern control and fidelity and high selectivity.
Description
[ technical field ]
The invention relates to the technical field of etching, in particular to a method for electrochemically roughening a positive current collector of a lithium ion battery.
[ background art ]
In the current semiconductor manufacturing field, aluminum metal is widely used in integrated circuits as a commonly used material for electrical interconnects, for forming metal interconnects, contact pads, and the like. With the development of the technology and the improvement of the requirements of people, in the semiconductor chip manufacturing industry, the line width of a chip is smaller and smaller, the integration level is higher and higher, and the requirements on a machine table are higher and higher. The aluminum etching is one of the main etching processes in the field of semiconductor manufacturing, the metal layer of the aluminum etching mostly uses pure aluminum, aluminum copper, aluminum silicon copper and other alloys, and the main function of the aluminum etching is to transfer the designed metal wiring pattern onto a product, thereby realizing the function of wiring or grid.
The traditional method mainly comprises dry etching and wet etching, but the defects are obvious, and the dry etching equipment has high requirements, so the cost is high, for example, patent 201610718552.5; wet etching, however, is very difficult to drill and control patterns, and cannot be used for small feature sizes, and generates a large amount of chemical waste, such as 201310263046.8. The electrochemical etching can overcome the defects of the common etching method, such as slow etching speed, serious lateral etching phenomenon in deep etching, and the like, for example, patent 200610172613.9.
The positive metal current collector for the lithium ion battery plays a role in conducting and bonding, but the positive metal current collector can be corroded by organic electrolyte with strong oxidizing property, so that the electrical property is reduced; the adhesion between the smooth aluminum foil and the active substance layer is poor, so that it is an added option to achieve both oxidation resistance and increase the adhesion of the current collector. Whereas patent 201611117185.X adopts jet chemistry to carry out the coarsening method, the coarsening speed is slow, and the coarsening liquid contains heavy metal ions, patent 201310627045.7 adopts acid-base liquid cleaning and high-oxidation ion-containing conversion liquid soaking to carry out the coarsening, which not only causes serious pollution, but also has complicated process.
Therefore, in order to pursue a highly environmentally friendly and highly efficient roughening method, it is of great importance to adopt a bipolar chamber cationic membrane electrolytic cell to roughen by one step based on the principle of electrochemical etching of aluminum foil, to make the raw material source rich and cheap, and to avoid heavy metal ion pollution.
[ summary of the invention ]
The invention aims to solve the defects and provide a method for electrochemically roughening the positive current collector of a lithium ion battery, which can meet the high requirements of dry etching on equipment, the serious drilling and etching of wet etching, poor pattern controllability and fidelity, high selectivity, no heavy metal ion pollution, rich raw material sources and low price.
In order to achieve the purpose, the method for electrochemically roughening the positive current collector of the lithium ion battery comprises the following steps: 1) firstly, placing the aluminum foil rough surface of a positive current collector of a lithium ion battery in a bipolar chamber cationic membrane electrolytic cell to perform electrochemical polishing treatment; 2) then, in a bipolar chamber cation exchange membrane electrolytic cell, taking a sodium silicate solution as a roughening solution, and roughening the surface of the aluminum foil in a constant-pressure electrolysis mode; 3) and finally, cleaning and drying the roughened aluminum foil to obtain the roughened aluminum current collector with the surface containing the compact aluminum oxide film.
Further, in step 1), in the electrochemical polishing process, the polishing solution is prepared by adding 120ml of phosphoric acid, 32ml of sulfuric acid, and 8ml of ethylene glycol to 400ml of water.
Further, in the step 1), in the process step of the electrochemical polishing treatment, the polishing process is carried out at a current density of 100-2Heated to 90 ℃ and polished under magnetic stirring.
Further, in the step 2), the constant-voltage electrolytic roughening treatment process comprises the following steps: in a bipolar chamber cation exchange membrane electrolytic cell, a sodium silicate solution is used as an anolyte, a sodium hydroxide solution is used as a catholyte, a lithium ion battery anode current collector aluminum foil is used as an anode, an inert electrode is used as a cathode, and electrolysis is carried out for 10-30min at 20-60 ℃ in a constant-pressure electrolysis mode.
Further, in the step 2), a cation membrane adopted by the bipolar chamber cation exchange membrane is a perfluorosulfonic acid ion exchange membrane, the concentration of the sodium silicate solution is 0.0001-0.1mol/L, the concentration of the sodium hydroxide solution is 0.0001-0.1mol/L, the inert electrode is a stainless steel electrode or a titanium electrode, and the voltage of constant-voltage electrolysis is 10-400V.
Further, in the step 3), the cleaning and drying process after coarsening comprises the following steps: and washing the coarsened aluminum foil with absolute ethyl alcohol until the pH value is close to neutral, and then putting the aluminum foil into a forced air drying oven to dry at 60-100 ℃.
Compared with the prior art, the invention has the following advantages:
(1) the cation membrane adopted in the preparation process has certain selective permeability, and particularly, the Nafion series perfluorinated sulfonic acid cation exchange membrane can enable Na + ions in the anode chamber to permeate the ion membrane to enter the cathode chamber, so that the influence of Na + ion impurities on the coarsening effect is eliminated;
(2) the method has short reaction time, and as can be seen from the specific embodiment, the electrolytic preparation time is less than 0.5h, so that the aluminum foil positive current collector with good roughening effect can be obtained, the roughening treatment is simple, and the preparation cost is reduced;
(3) the aluminum foil with good coarsening effect can be prepared by only one-step electrolysis, and the method is efficient, simple and pollution-free and can be directly applied to industrial production;
(4) the corrosion resistance of the positive current collector obtained by the method to the electrolyte is greatly improved, and the current collector contains irregular pits, so that the bonding performance of the current collector and an active substance layer is improved.
[ description of the drawings ]
FIG. 1 is an SEM photograph of an untreated aluminum foil in example 1 of the present invention;
FIG. 2 is an SEM photograph of the aluminum foil after electrochemical polishing in example 1 of the present invention;
FIG. 3 is an SEM image of 50V roughened aluminum obtained in example 1 of the present invention;
FIG. 4 is an SEM image of 100V roughened aluminum obtained in example 1 of the present invention;
FIG. 5 is an SEM image of 150V roughened aluminum obtained in example 1 of the present invention;
FIG. 6 is an SEM image of 200V roughened aluminum obtained in example 1 of the present invention;
FIG. 7 is an SEM image of 250V roughened aluminum obtained in example 1 of the present invention;
FIG. 8 is a SEM image of 300V coarsened obtained in example 1 of the present invention;
FIG. 9 is an SEM photograph of room temperature-roughened aluminum obtained in example 2 of the present invention;
FIG. 10 is an SEM image of 35 ℃ roughened aluminum obtained in example 2 of the present invention;
FIG. 11 is an SEM image of 55 ℃ roughened aluminum obtained in example 2 of the present invention.
[ detailed description of the invention ]
The invention provides a method for electrochemically roughening a positive current collector of a lithium ion battery, which specifically comprises the following steps: firstly, carrying out electrochemical polishing treatment on the rough surface of an aluminum foil of a positive current collector of a lithium ion battery in a bipolar chamber cationic membrane electrolytic cell, then roughening the surface of the aluminum foil in the bipolar chamber cationic membrane electrolytic cell by using a sodium silicate solution with abundant sources and low price as a roughening solution in a constant-pressure electrolysis manner, and finally cleaning and drying the roughened aluminum foil to obtain a roughened aluminum current collector with a compact aluminum oxide film on the surface.
Wherein, in the process steps of the electrochemical polishing treatment, the preparation of the polishing solution comprises the following steps: 120ml phosphoric acid, 32ml sulfuric acid and 8ml ethylene glycol, adding water to 400 ml; and (3) polishing process: the current density is 100 to 300mA/cm2Heated to 90 ℃ and polished under magnetic stirring. The constant-voltage electrolytic coarsening treatment process comprises the following steps of electrolyzing for 10-30min at 20-60 ℃ in a constant-voltage electrolysis mode in a double-chamber cationic membrane electrolytic cell by taking a sodium silicate solution as an anolyte, a sodium hydroxide solution as a catholyte, an aluminum foil serving as a current collector of a positive electrode of a lithium ion battery as an anode and an inert electrode as a cathode; wherein, the cation membrane adopted by the double-chamber cation exchange membrane is a perfluorinated sulfonic acid ion exchange membrane; the concentration of the sodium silicate solution is 0.0001-0.1 mol/L; the concentration of the sodium hydroxide solution is 0.0001-0.1 mol/L; the inert electrode is a stainless steel electrode or a titanium electrode; the voltage of constant voltage electrolysis is 10-400V. The cleaning and drying process after coarsening comprises the following steps: and washing the coarsened aluminum foil with absolute ethyl alcohol until the pH value is close to neutral, and then putting the aluminum foil into a forced air drying oven to dry at 60-100 ℃.
The invention is further illustrated below with reference to specific examples:
the perfluorosulfonic acid cation exchange membrane used in each example of the present invention was a Nafion perfluorosulfonic acid 212 type cation exchange membrane manufactured by dupont, usa.
Example 1
A method for electrochemical roughening treatment of a lithium ion battery positive current collector specifically comprises the following steps:
(1) the process steps of the electrochemical polishing treatment are as follows. Preparing a polishing solution: 120ml phosphoric acid, 32ml sulfuric acid and 8ml ethylene glycol, adding water to 400 ml; and (3) polishing process: current density of 100-2Heated to 90 ℃ and polished for 15min under magnetic stirring.
(2) Electrolyzing for 10-30min at normal temperature by using a constant-pressure electrolysis mode by using a sodium silicate solution as an anolyte, a sodium hydroxide solution as a catholyte, an aluminum sheet as an anode and an inert electrode as a cathode; wherein, the inert electrode is a DSA titanium mesh; the concentration of the sodium silicate solution is 0.00075 mol/L; the concentration of the sodium hydroxide solution is 0.001 mol/L; the cation membrane is a perfluorinated sulfonic acid cation exchange membrane; the electrolysis temperature is 25 ℃ at room temperature; the electrolysis time is 15 min; the voltage of the constant voltage electrolysis is respectively 50, 100, 150, 200, 250 and 300V;
(3) after the electrolysis, washing the aluminum sheet by absolute ethyl alcohol until the pH value is close to neutral; then the mixture is dried in a forced air drying oven at 70 ℃ for 1 h.
As shown in fig. 1 and 2, in order to better show the experimental effect thereof, the original aluminum foil and the electrochemically polished aluminum foil were also tested for SEM.
As shown in FIG. 3, it is an SEM image of the coarsened aluminum after electrolysis at 25 ℃ for 15min by 50V constant voltage electrolysis.
As shown in FIG. 4, it is an SEM image of the coarsened aluminum after electrolysis at 25 ℃ for 15min in 100V constant voltage electrolysis.
As shown in FIG. 5, it is an SEM image of the coarsened aluminum after electrolysis at 25 ℃ for 15min in 150V constant voltage electrolysis.
As shown in FIG. 6, it is an SEM image of the coarsened aluminum after electrolysis at 25 ℃ for 15min in 200V constant voltage electrolysis.
As shown in FIG. 7, it is an SEM image of the coarsened aluminum after electrolysis at 25 ℃ for 15min for constant voltage electrolysis at 250V.
As shown in FIG. 8, it is an SEM image of the coarsened aluminum after electrolysis at 25 ℃ for 15min in 300V constant voltage electrolysis.
Example 2
The electrochemical polishing and post-treatment steps were the same as in example 1.
The electrochemical coarsening process comprises the following steps: electrolyzing at room temperature for 10-30min by using phosphoric acid solution as anolyte, sodium hydroxide solution as catholyte, aluminum sheet as anode and inert electrode as cathode in a constant-pressure electrolysis manner; wherein, the inert electrode is a DSA titanium mesh; the pH value of the phosphoric acid solution is approximately equal to 6; the concentration of the sodium hydroxide solution is 0.001 mol/L; the cation membrane is a perfluorinated sulfonic acid cation exchange membrane; the electrolysis temperature is 25 ℃, 35 ℃ and 55 ℃ at room temperature; the electrolysis time is 15 min; the voltage of constant voltage electrolysis was 300V.
As shown in FIG. 9, SEM image of aluminum directional etching is performed for 300V constant voltage electrolysis at 25 ℃ for 15 min.
As shown in FIG. 10, SEM image of aluminum directional etching is performed for 300V constant voltage electrolysis at 35 ℃ for 15 min.
As shown in FIG. 11, SEM image of aluminum directional etching is performed for 300V constant voltage electrolysis at 55 ℃ for 15 min.
In conclusion, the invention adopts the cation exchange membrane electrolysis method, so that the aluminum foil can be roughened with good effect by constant pressure electrolysis at 10-300V, the electrolysis temperature is 20-60 ℃, the electrolysis time is 10-30min, and the electrolytic preparation time is not more than 0.5h, so that the final aluminum foil has good roughening effect. Meanwhile, the wider the corrosion surface is along with the increase of the voltage, the better the coarsening effect is; and the temperature is reduced, so that the experimental effect is favorable.
The present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents and are included in the scope of the present invention.
Claims (5)
1. The method for electrochemically roughening the positive current collector of the lithium ion battery is characterized by comprising the following steps of:
1) firstly, placing the aluminum foil rough surface of a positive current collector of a lithium ion battery in a bipolar chamber cationic membrane electrolytic cell to perform electrochemical polishing treatment;
2) then, in a bipolar chamber cation exchange membrane electrolytic cell, taking a sodium silicate solution as a roughening solution, and roughening the surface of the aluminum foil in a constant-pressure electrolysis mode;
3) finally, cleaning and drying the roughened aluminum foil to obtain a roughened aluminum current collector with a surface containing a compact aluminum oxide film;
in the step 2), the constant-voltage electrolytic roughening treatment process comprises the following steps: in a bipolar chamber cation exchange membrane electrolytic cell, a sodium silicate solution is used as an anolyte, a sodium hydroxide solution is used as a catholyte, a lithium ion battery anode current collector aluminum foil is used as an anode, an inert electrode is used as a cathode, and electrolysis is carried out for 10-30min at 20-60 ℃ in a constant-pressure electrolysis mode.
2. The method of claim 1, wherein: in the step 1), in the electrochemical polishing process, the polishing solution is prepared by adding water to 400ml of 120ml of phosphoric acid, 32ml of sulfuric acid and 8ml of ethylene glycol.
3. The method of claim 2, wherein: in the step 1), in the process step of electrochemical polishing treatment, the polishing process is that the current density is 100-2Heated to 90 ℃ and polished under magnetic stirring.
4. The method of claim 1, wherein: in the step 2), a cation membrane adopted by the bipolar chamber cation exchange membrane is a perfluorinated sulfonic acid ion exchange membrane, the concentration of the sodium silicate solution is 0.0001-0.1mol/L, the concentration of the sodium hydroxide solution is 0.0001-0.1mol/L, the inert electrode is a stainless steel electrode or a titanium electrode, and the voltage of constant-voltage electrolysis is 10-400V.
5. The method of claim 1, wherein: in the step 3), the cleaning and drying process after coarsening comprises the following steps: and washing the coarsened aluminum foil with absolute ethyl alcohol until the pH value is close to neutral, and then putting the aluminum foil into a forced air drying oven to dry at 60-100 ℃.
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| CN101285208A (en) * | 2007-04-12 | 2008-10-15 | 深圳市比克电池有限公司 | Coursing and hole-distributing method at aluminum foil surface for lithium ion secondary battery |
| CN102534577A (en) * | 2010-12-10 | 2012-07-04 | 比亚迪股份有限公司 | Roughening liquid and preparation method thereof, and acrylonitrile-butadiene-styrene terpolymer surface electroplating method |
| CN106350842A (en) * | 2016-10-25 | 2017-01-25 | 南京工业大学 | Current collector coating resistant to high temperature liquid sulfur corrosion and preparation method thereof |
| JP2017066513A (en) * | 2015-09-29 | 2017-04-06 | 日立金属株式会社 | Manufacturing method of aluminum foil and aluminum foil |
| CN108122691A (en) * | 2017-12-25 | 2018-06-05 | 深圳市中金高能电池材料有限公司 | Lithium-ion capacitor collector foil and its manufacturing method |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101285208A (en) * | 2007-04-12 | 2008-10-15 | 深圳市比克电池有限公司 | Coursing and hole-distributing method at aluminum foil surface for lithium ion secondary battery |
| CN102534577A (en) * | 2010-12-10 | 2012-07-04 | 比亚迪股份有限公司 | Roughening liquid and preparation method thereof, and acrylonitrile-butadiene-styrene terpolymer surface electroplating method |
| JP2017066513A (en) * | 2015-09-29 | 2017-04-06 | 日立金属株式会社 | Manufacturing method of aluminum foil and aluminum foil |
| CN106350842A (en) * | 2016-10-25 | 2017-01-25 | 南京工业大学 | Current collector coating resistant to high temperature liquid sulfur corrosion and preparation method thereof |
| CN108122691A (en) * | 2017-12-25 | 2018-06-05 | 深圳市中金高能电池材料有限公司 | Lithium-ion capacitor collector foil and its manufacturing method |
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