CN114759191A - Current collector metal foil, preparation method thereof and lithium battery current collector - Google Patents
Current collector metal foil, preparation method thereof and lithium battery current collector Download PDFInfo
- Publication number
- CN114759191A CN114759191A CN202210323629.4A CN202210323629A CN114759191A CN 114759191 A CN114759191 A CN 114759191A CN 202210323629 A CN202210323629 A CN 202210323629A CN 114759191 A CN114759191 A CN 114759191A
- Authority
- CN
- China
- Prior art keywords
- current collector
- tank
- alkaline
- metal foil
- base material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 135
- 239000002184 metal Substances 0.000 title claims abstract description 135
- 239000011888 foil Substances 0.000 title claims abstract description 132
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 131
- 239000000463 material Substances 0.000 claims abstract description 87
- 238000004140 cleaning Methods 0.000 claims abstract description 58
- 239000000758 substrate Substances 0.000 claims abstract description 47
- 238000009736 wetting Methods 0.000 claims abstract description 27
- 239000002253 acid Substances 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 22
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 88
- 238000005554 pickling Methods 0.000 claims description 73
- 239000000243 solution Substances 0.000 claims description 44
- 239000007788 liquid Substances 0.000 claims description 28
- 239000008367 deionised water Substances 0.000 claims description 23
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000012670 alkaline solution Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 14
- 238000007599 discharging Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 abstract description 71
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 71
- 239000012535 impurity Substances 0.000 abstract description 5
- 239000002585 base Substances 0.000 description 78
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 24
- 239000011889 copper foil Substances 0.000 description 24
- 239000003513 alkali Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000013543 active substance Substances 0.000 description 6
- 235000021110 pickles Nutrition 0.000 description 6
- 230000003749 cleanliness Effects 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000011149 active material Substances 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910010199 LiAl Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Classifications
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
Abstract
The invention discloses a current collector metal foil, a preparation method thereof and a lithium battery current collector, wherein the preparation method comprises the steps of providing a metal substrate; and cleaning the metal base material, wherein the metal base material sequentially passes through an acid washing tank, an alkaline washing tank and a cleaning tank, and drying the cleaned metal base material to obtain the current collector metal foil. The preparation method is simple, and can effectively remove impurities on the surface of the metal base material and improve the surface wetting tension of the aluminum foil.
Description
Technical Field
The application relates to the technical field of lithium batteries, in particular to a current collector metal foil, a preparation method thereof and a lithium battery current collector.
Background
The current collector is one of indispensable components in the lithium battery, can bear active substances, and can collect and output current generated by the electrode active substances, so that the internal resistance of the lithium battery is reduced, and the coulomb efficiency, the cycle stability and the rate capability of the battery are improved. The current collector is a key material of the lithium battery, and on one hand, the current collector carries powdery active substances and on the other hand, the current collector plays a role in collecting current.
Copper foil and aluminum foil are generally used as a current collector of a lithium battery. The copper foil is easily oxidized at a high potential, and is mainly used for a negative electrode with a low potential. The aluminum foil has a serious corrosion problem at a low potential, and is mainly used for a positive current collector.
The aluminum foil for the lithium battery current collector meets the following requirements that 1, the cleanliness is high, and no debris, dust and other impurities are mixed on the surface of the aluminum foil; 2. the mechanical property of the aluminum foil is high; 3. the surface wetting tension of the aluminum foil is large.
Among them, the surface wetting tension is one of the most important technical indexes of the current collector metal foil, which affects the adhesion quality of the coating, especially affects the coating firmness of the carbon-coated foil, and when the dyne value is lower, the aluminum foil and the adhesive material are not firmly adhered, and the coating is missed.
Disclosure of Invention
The technical problem to be solved by the application is to provide a preparation method of a current collector metal foil, remove impurities on the current collector metal foil and improve the surface wetting tension of the current collector metal foil.
The technical problem to be solved in the present application is to provide a current collector metal foil, which has a large surface wetting tension and a good binding force with a conductive material or a battery active material.
The technical problem that this application will be solved lies in, provides a lithium cell mass flow body, and electrode active material can adhere to on the mass flow body better.
In order to solve the technical problem, the application provides a preparation method of a current collector metal foil, which comprises the following steps:
providing a metal substrate;
cleaning the metal base material, wherein the metal base material sequentially enters a pickling tank, an alkaline washing tank and a cleaning tank, and pickling solution in the pickling tank comprises HF and H2SO4The alkaline solution in the alkaline groove comprises Ca (OH)2And/or LiOH, wherein the cleaning tank contains deionized water, wherein the HF and the H are2SO4The total mass of the acid washing solution is 2-4 percent of the total mass of the acid washing solution, and the Ca (OH)2And/or the total mass of LiOH is 2% -4% of the total mass of the alkaline washing liquid;
and drying the cleaned metal base material.
As a modification of the above, the HF and H2SO4The mass ratio of (1) to (2.5-5).
As an improvement of the scheme, the alkaline washing liquid in the alkaline washing tank comprises Ca (OH)2And LiOH, wherein the Ca (OH)2The mass ratio of LiOH to LiOH is 1 (3.5-6.5).
As a modification of the above, the HF and H2SO4The mass ratio of (1), (3-4), the Ca (OH)2And the mass ratio of LiOH to LiOH is 1 (4-5).
As an improvement of the above aspect, a method for performing a cleaning treatment on the metal substrate includes:
and an unreeling machine is adopted to pay coiled metal base materials to a tension roller, the metal base materials are sequentially conveyed to the pickling tank, the alkaline washing tank and the cleaning tank through the tension roller, and the speed of the metal base materials passing through the pickling tank, the alkaline washing tank and the cleaning tank is 130-160 m/min.
As an improvement of the scheme, a first squeezing roller for squeezing the pickling solution is arranged between the pickling tank and the alkaline washing tank, and a second squeezing roller for squeezing the alkaline washing solution is arranged between the alkaline washing tank and the washing tank.
As an improvement of the scheme, the thickness of the metal base material is 10-20 microns, and the speed of the metal base material passing through the pickling tank, the alkaline washing tank and the cleaning tank is 140-150 m/min.
As an improvement of the scheme, the temperature of the deionized water is 50-70 ℃.
Correspondingly, the application also provides a current collector metal foil prepared by the preparation method, and the surface wetting tension of the current collector metal foil is more than 55 x 10-3N/m。
Correspondingly, the application also provides a lithium battery current collector, which comprises a current collector metal foil and a conductive coating coated on the current collector metal foil, wherein the current collector metal foil is prepared by the preparation method.
The application has the following beneficial effects:
the metal substrate is firstly subjected to alkaline washing after being subjected to acid washing, and the acid washing solution in the acid washing tank and the alkaline washing solution in the alkaline washing tank are composed of specific components, so that impurities and oil stains on the surface of the metal substrate are effectively removed, the surface wetting tension of the metal substrate is improved, and the tensile strength of the metal substrate is not influenced.
The metal base material is washed by alkali and then by deionized water at a certain temperature, so that residual alkali washing liquid on the metal base material and decomposed products generated in the alkali washing process are removed, and the cleanliness and the surface wetting tension of the metal base material are effectively improved.
This application adopts the machine of unreeling to emit lapping metal substrate to the tension roll, and wherein metal substrate carries to the descaling bath, alkali wash groove and washing tank in proper order through the tension roll, and this application can adjust the dwell time of metal substrate in the descaling bath, alkali wash groove and washing tank through the speed of adjustment conveying roller, easy operation, and the cleaning performance is good, adapts to large batch production.
Drawings
Fig. 1 is a schematic view of the structure of a first current collector of the present application;
fig. 2 is a schematic view of a second current collector of the present application.
Detailed Description
To make the objects, technical solutions and advantages of the present application more clear, the present application will be further described in detail with reference to the accompanying drawings.
The application provides a preparation method of a current collector metal foil, which comprises the following steps:
s1, providing a metal base material;
the thickness of the metal base material in the present application is preferably 10 to 20 μm. In other embodiments of the present application, the thickness of the metal substrate may also be less than 10 μm or greater than 20 μm.
The metal substrate of the present application is an aluminum foil or a copper foil, but is not limited thereto. The aluminum foil is mainly used for a positive current collector because the corrosion problem is serious at a low potential, wherein the impure components of the aluminum foil can cause the incompact surface oxide film to generate pitting corrosion and even generate LiAl alloy.
In order to effectively get rid of impurity, greasy dirt and oxide layer etc. on aluminium foil or the copper foil, improve the cleanliness and the surface wetting tension of mass flow body metal foil to on conducting material or battery active material attached to mass flow body metal foil, this application need wash the processing to metal substrate.
S2, cleaning the metal base material;
the method for cleaning the metal base material comprises the steps of discharging a coiled metal base material to a tension roller by using an unreeling machine, conveying the metal base material to an acid washing tank, an alkali washing tank and a cleaning tank in sequence through the tension roller, wherein the metal base material sequentially enters the acid washing tank, the alkali washing tank and the cleaning tank.
Different from a common cleaning method, the method is characterized in that the method firstly carries out alkaline cleaning after acid cleaning, wherein the acid cleaning mainly has the function of removing oil stains and forming a rough structure on the surface of the metal base material, so that the surface area of the metal base material is increased, and the effect of primary etching is achieved; the main function of the alkali washing is to remove polar substances on the metal substrate and improve the surface wetting tension of the metal substrate. According to a large number of experiments and studies by the inventors, it was found that when the order of acid washing and alkali washing is changed, the cleaning effect is greatly affected, and not only the surface wetting tension of the metal substrate but also the tensile strength of the metal substrate are affected, although the order is simply changed. The cleaning agent is firstly subjected to acid cleaning and then subjected to alkaline cleaning, so that the cleanliness and the surface wetting tension of the current collector metal foil can be effectively improved, and the tensile strength of the current collector metal foil is not influenced.
The pickling solution in the pickling tank and the alkaline washing solution in the alkaline washing tank consist of specific components. Specifically, the pickling solution of the present application comprises HF and H2SO4The alkaline washing liquid in the alkaline washing tank comprises Ca (OH)2And/or LiOH in a cleaning tank of the present application containing deionized water. Wherein, the alkaline washing liquid can only contain Ca (OH)2It may be only LiOH, or both LiOH and Ca (OH)2。
Due to Ca (OH)2And LiOH is inherently a caustic wash and therefore can be a component of a caustic wash. However, according to the studies of the applicant, it was found that the metal substrate after pickling had been subjected to treatment containing Ca (OH)2And/or after alkaline washing with LiOH, the electrolyte wets more uniformly on the metal foil, which can affect the growth direction and production speed of dendritesAnd the dendritic crystal is prevented from growing towards the same direction, so that the influence of the dendritic crystal on the performance of the lithium battery is reduced.
Preferably, the alkaline wash comprises Ca (OH)2And LiOH.
Because the cleaning object is a metal substrate, the thickness is very thin, the amplitude is very long, and the metal substrate needs to be unreeled and reeled at the same time, the cleaning difficulty is high, and different from the common pickling solution and alkaline washing solution, the concentrations of the pickling solution and the alkaline washing solution cannot be too high, if the concentrations of the pickling solution and the alkaline washing solution exceed 4%, the tensile strength of the metal foil is easily affected, and the surface wetting tension of the metal foil cannot be effectively improved; if the concentrations of the acid washing solution and the alkali washing solution are less than 2%, the cleaning effect is influenced, and the surface wetting tension of the metal foil is low.
Specifically, HF and H2SO4The total mass of the pickling solution is 2 to 4 percent of the total mass of the pickling solution, and Ca (OH)2And/or the total mass of LiOH is 2% -4% of the total mass of the alkaline washing liquid. Wherein the alkaline solution comprises Ca (OH)2Then Ca (OH)2The mass of the alkaline washing liquid is 2% -4% of the total mass of the alkaline washing liquid; if the alkaline washing liquid comprises LiOH, the mass of the LiOH is 2% -4% of the total mass of the alkaline washing liquid; if the alkaline washing liquid comprises Ca (OH)2And LiOH, then Ca (OH)2And the total mass of the LiOH and the alkaline washing liquid is 2-4% of the total mass of the alkaline washing liquid.
Preferably, HF and H2SO4The total mass of the acid washing solution is 2.5-3.5 percent of the total mass of the acid washing solution, and Ca (OH)2And the total mass of the LiOH and the alkaline washing liquid is 2.5-3.5% of the total mass of the alkaline washing liquid.
It should be noted that the concentrations of HF and H in the pickling solution have an influence on the cleaning effect, tensile strength and electrochemical stability of the metal substrate2SO4In alkaline washing solution, Ca (OH)2And LiOH also have an effect on the cleaning effect, mechanical strength and electrochemical stability of the metal substrate.
Preferably, HF and H2SO4The mass ratio of (1) to (2.5-5); ca (OH)2The mass ratio of LiOH to LiOH is 1 (3.5-6.5).
More preferably, HF and H2SO4The mass ratio of (1), (3-4), Ca (OH)2And the mass ratio of LiOH to LiOH is 1 (4-5).
In actual batch production, an unreeling machine is needed to unreel the coiled metal base material to a tension roller, wherein the metal base material is sequentially conveyed to a pickling tank, an alkaline washing tank and a cleaning tank through the tension roller, and the retention time of the metal base material in the pickling tank, the alkaline washing tank and the cleaning tank directly influences the cleaning effect and the production efficiency of the metal base material. If the time for the metal base material to pass through the pickling tank, the alkaline washing tank and the washing tank is short, the washing time is short, and the washing effect is not good; if the time for the metal base material to pass through the pickling tank, the alkaline washing tank and the washing tank is long, the washing time is long, the production efficiency is reduced, and the mechanical strength and the electrochemical performance of the metal base material are influenced.
Correspondingly, the speed of the metal base material passing through the pickling tank, the alkaline washing tank and the cleaning tank is 130-160 m/min.
Preferably, the speed of the metal base material with the thickness of 10-20 mu m passing through the pickling tank, the alkaline washing tank and the cleaning tank is 140-150 m/min;
it should be noted that a first squeezing roller for squeezing out the pickling solution is arranged between the pickling tank and the alkaline washing tank, and the first squeezing roller is used for squeezing the pickling solution on the metal substrate back into the pickling tank, so as to achieve the purpose of preventing the pickling solution from running off and prevent the pickling solution from entering the alkaline washing tank and influencing the alkaline washing effect of the alkaline washing tank.
In addition, be equipped with the crowded liquid roller of second that is used for crowding out the alkali wash between alkali wash tank and the washing tank, the crowded liquid roller of second extrudees the alkali wash on the metal substrate back to the alkali wash inslot to reach the purpose that prevents the loss of alkali wash, and prevent that the alkali wash from getting into the washing tank, influence the cleaning performance of washing tank.
The metal substrate of this application washs through descaling bath and alkali-wash tank, still need wash through the washing tank at last, contains deionized water in the washing tank, and the main effect is the resolvent that produces in getting rid of remaining alkali-wash liquid and the alkali-wash process on the metal substrate, effectively improves metal substrate's cleanliness and surface wetting tension. If the cleaning tank is lacked, the alkaline cleaning solution and alkaline cleaning decomposition products remained on the metal base material can influence the conductivity or electrochemical performance of a conductive coating or an electrode active substance coated on the aluminum foil subsequently, and further influence the service life, cycle frequency, electric quantity and the like of the lithium battery.
In addition, the effect of carrying out alkaline washing after the acid washing is also because the influence of the acid washing liquid on the conductivity or electrochemical performance of the conductive coating or the active substance is larger, and the influence of the alkaline washing liquid is relatively smaller, and the alkaline washing liquid can neutralize the acid washing liquid, thereby effectively avoiding the acid washing liquid from remaining on the aluminum foil.
Preferably, the temperature of the deionized water is 50-70 ℃. Preferably, the temperature of the deionized water is 55-60 ℃.
And S3, drying the cleaned metal base material.
It should be noted that the drying temperature of the metal substrate has an important influence on the production cost, the production efficiency and the quality of the current collecting metal foil, and if the drying temperature is too low, the drying time is long, and the production efficiency is low; if the drying temperature is high, the energy consumption is high, the production cost is increased, the stress of the current collector metal foil is also improved, and the binding force between the current collector metal foil and the conductive coating or the active substance is influenced.
Preferably, the drying temperature of the metal base material is 130-160 ℃. Preferably, the drying temperature of the metal base material is 140-150 ℃.
Correspondingly, the application also provides a current collector metal foil which is prepared by the preparation method.
Preferably, the current collector metal foil of the present application has a surface wetting tension > 55 x 10 -3N/m。
The surface wetting tension is one of the most important technical indexes of the current collector metal foil, which affects the bonding quality and the coating firmness of the coating, and when the dyne value is low, the metal foil and the coating have the defects of poor bonding, coating omission and the like.
Correspondingly, referring to fig. 1 and fig. 2, the present application further provides a current collector for a lithium battery, which includes a current collector metal foil 1 and a conductive coating 2, wherein the conductive coating 2 is coated on one or both sides of the current collector metal foil 1. The current collector metal foil 1 is prepared by the preparation method.
The present application will be further illustrated by the following specific examples
Example 1
A preparation method of a current collector metal foil comprises the following steps:
s1, providing an aluminum foil substrate with the thickness of 15 mu m;
s2, discharging the coiled aluminum foil base material to a tension roller by using an unreeling machine, and sequentially conveying the aluminum foil base material to a pickling tank, an alkaline washing tank and a washing tank which are 1m in length through the tension roller at the speed of 130 m/min; wherein the pickling solution in the pickling tank comprises 0.55wt% of HF and 1.45wt% of H2SO4The alkaline solution in the alkaline washing tank comprises 2wt% of Ca (OH)2The cleaning tank contains deionized water with the temperature of 50 ℃;
s3, drying the aluminum foil base material cleaned in the step S2 at 130 ℃.
Example 2
A preparation method of a current collector metal foil comprises the following steps:
s1, providing an aluminum foil base material with the thickness of 15 mu m;
s2, paying off the coiled aluminum foil base material to a tension roller by using an unreeling machine, and conveying the aluminum foil base material to a pickling tank, an alkaline washing tank and a washing tank which are all 1m in length in sequence at a speed of 140m/min through the tension roller; wherein the pickling solution in the pickling tank comprises 0.6wt% of HF and 1.9wt% of H2SO4The alkaline washing liquid in the alkaline washing tank comprises 2.5wt% of LiOH, and the cleaning tank contains deionized water with the temperature of 55 ℃;
and S3, drying the aluminum foil base material cleaned in the step S2 at 130 ℃ to obtain a current collector aluminum foil.
Example 3
A preparation method of a current collector metal foil comprises the following steps:
s1, providing an aluminum foil substrate with the thickness of 15 mu m;
s2, paying off the coiled aluminum foil base material to a tension roller by using an unreeling machine, and conveying the aluminum foil base material to a pickling tank, an alkaline washing tank and a washing tank which are all 1m in length in sequence at the speed of 150m/min through the tension roller; wherein the pickling solution in the pickling tank comprises 0.65wt% of HF and 2.35wt% of H2SO4The alkaline solution in the alkaline tank comprises 0.55wt% of Ca (OH)2And 2.45wt% LiOH, the cleaning tank contains deionized water at a temperature of 60 ℃;
And S3, drying the aluminum foil base material cleaned in the step S2 at 140 ℃ to obtain a current collector aluminum foil.
Example 4
A preparation method of a current collector metal foil comprises the following steps:
s1, providing an aluminum foil base material with the thickness of 15 mu m;
s2, paying off the coiled aluminum foil base material to a tension roller by using an unreeling machine, and conveying the aluminum foil base material to a pickling tank, an alkaline washing tank and a washing tank which are all 1m in length in sequence at the speed of 150m/min through the tension roller; wherein the pickling solution in the pickling tank comprises 0.7wt% of HF and 2.8wt% of H2SO4The alkaline solution in the alkaline washing tank comprises 0.58wt% of Ca (OH)2And 2.92wt% LiOH, the cleaning tank containing deionized water at a temperature of 65 ℃;
and S3, drying the aluminum foil base material cleaned in the step S2 at 150 ℃ to obtain a current collector aluminum foil.
Example 5
A preparation method of a current collector metal foil comprises the following steps:
s1, providing an aluminum foil substrate with the thickness of 15 mu m;
s2, paying off the coiled aluminum foil base material to a tension roller by using an unreeling machine, and conveying the aluminum foil base material to a pickling tank, an alkaline washing tank and a washing tank which are all 1m in length in sequence at a speed of 160m/min through the tension roller; wherein the pickling solution in the pickling tank comprises 0.67wt% of HF and 3.33wt% of H 2SO4The alkaline solution in the alkaline washing tank comprises 0.55wt% of Ca (OH)2And 3.45wt% LiOH, the cleaning tank containing deionized water at a temperature of 70 ℃;
and S3, drying the aluminum foil base material cleaned in the step S2 at 150 ℃ to obtain a current collector aluminum foil.
Example 6
Unlike example 3, the pickle liquor in the pickle tank of example 6 comprised 1.5wt% HF and 1.5wt% H2SO4The alkaline solution in the alkaline groove comprises1.5wt%Ca(OH)2And 1.5wt% LiOH.
Example 7
Unlike example 3, the pickle liquor in the pickle tank of example 7 comprised 0.3wt% HF and 2.7wt% H2SO4The alkaline solution in the alkaline bath comprises 0.3wt% of Ca (OH)2And 2.7wt% LiOH.
Example 8
Unlike example 3, the aluminum foil substrate of step S2 in example 8 was conveyed to the acid washing tank, the alkali washing tank, and the washing tank in this order via the tension roller at a speed of 180 m/min.
Example 9
Unlike example 3, the temperature of the deionized water in the cleaning tank in example 9 was 30 ℃.
Example 10
A preparation method of a current collector metal foil comprises the following steps:
s1, providing a copper foil base material with the thickness of 10 mu m;
s2, paying off the coiled copper foil base material to a tension roller by using an unreeling machine, and conveying the copper foil base material to a pickling tank, an alkaline washing tank and a washing tank which are all 1m in length in sequence at a speed of 150m/min through the tension roller; wherein the pickling solution in the pickling tank comprises 0.65wt% of HF and 2.35wt% of H 2SO4The alkaline solution in the alkaline washing tank comprises 0.55wt% of Ca (OH)2And 2.45wt% LiOH, the cleaning tank contains deionized water at a temperature of 60 ℃;
and S3, drying the copper foil base material cleaned and processed in the step S2 at 140 ℃ to obtain the copper foil of the current collector.
Example 11
A preparation method of a current collector metal foil comprises the following steps:
s1, providing a copper foil base material with the thickness of 10 mu m;
s2, paying off the coiled copper foil base material to a tension roller by using an unreeling machine, and conveying the copper foil base material to a pickling tank, an alkaline washing tank and a washing tank which are all 1m in length in sequence at a speed of 150m/min through the tension roller; wherein the pickling solution in the pickling tank comprises 0.7wt% of HF and 2.8wt% of H2SO4The alkaline solution in the alkaline washing tank comprises 0.58wt% of Ca (OH)2And 2.92wt% LiOH, the cleaning tank containing deionized water at a temperature of 65 ℃;
and S3, drying the copper foil base material cleaned in the step S2 at 150 ℃ to obtain the current collector copper foil.
Example 12
A preparation method of a current collector metal foil comprises the following steps:
s1, providing a copper foil base material with the thickness of 10 mu m;
s2, paying off the coiled copper foil base material to a tension roller by using an unreeling machine, and conveying the copper foil base material to a pickling tank, an alkaline washing tank and a washing tank which are all 1m in length in sequence at a speed of 160m/min through the tension roller; wherein the pickling solution in the pickling tank comprises 0.67wt% of HF and 3.33wt% of H 2SO4The alkaline solution in the alkaline washing tank comprises 0.55wt% of Ca (OH)2And 3.45wt% LiOH, containing deionized water at a temperature of 70 ℃ in the cleaning tank;
and S3, drying the copper foil base material cleaned and processed in the step S2 at 150 ℃ to obtain the copper foil of the current collector.
Comparative example 1
A preparation method of a current collector metal foil comprises the following steps:
s1, providing an aluminum foil base material with the thickness of 15 mu m;
s2, paying off the coiled aluminum foil base material to a tension roller by using an unreeling machine, and sequentially conveying the aluminum foil base material to a pickling tank and a cleaning tank with the length of 1m through the tension roller at the speed of 150 m/min; wherein the pickling solution in the pickling tank comprises 0.65wt% of HF and 2.35wt% of H2SO4The cleaning tank contains deionized water with the temperature of 60 ℃;
and S3, drying the aluminum foil base material cleaned in the step S2 at 140 ℃ to obtain a current collector aluminum foil.
Comparative example 2
A preparation method of a current collector metal foil comprises the following steps:
s1, providing an aluminum foil substrate with the thickness of 15 mu m;
s2, paying off the coiled aluminum foil base material to a tension roller by using an unreeling machine, and sequentially conveying the aluminum foil base material to the length of the aluminum foil base material through the tension roller at the speed of 150m/minAn alkaline washing tank and a cleaning tank which are both 1 m; wherein the alkaline solution in the alkaline groove comprises 0.55 weight percent of Ca (OH) 2And 2.45wt% LiOH, the cleaning tank contains deionized water at a temperature of 60 ℃;
and S3, drying the aluminum foil base material cleaned in the step S2 at 140 ℃ to obtain a current collector aluminum foil.
Comparative example 3
A preparation method of a current collector metal foil comprises the following steps:
s1, providing an aluminum foil base material with the thickness of 15 mu m;
s2, paying off the coiled aluminum foil base material to a tension roller by using an unreeling machine, and conveying the aluminum foil base material to a pickling tank, an alkaline washing tank and a washing tank which are all 1m in length in sequence at the speed of 150m/min through the tension roller; wherein the pickling solution in the pickling tank comprises 3wt% of H2C2O4The alkaline washing liquid in the alkaline washing tank comprises 3wt% of NaOH, and the washing tank contains deionized water with the temperature of 60 ℃;
and S3, drying the aluminum foil base material cleaned in the step S2 at 140 ℃ to obtain a current collector aluminum foil.
Comparative example 4
A preparation method of a current collector metal foil comprises the following steps:
s1, providing an aluminum foil substrate with the thickness of 15 mu m;
s2, discharging the coiled aluminum foil base material to a tension roller by using an unreeling machine, and sequentially conveying the aluminum foil base material to an alkaline washing tank, a pickling tank and a cleaning tank which are 1m in length through the tension roller at the speed of 150 m/min; wherein the alkaline solution in the alkaline groove comprises 0.55 weight percent of Ca (OH) 2And 2.45 weight percent LiOH, the pickle liquor in the pickle tank comprises 0.65 weight percent HF and 2.35 weight percent H2SO4The cleaning tank contains deionized water with the temperature of 60 ℃;
and S3, drying the aluminum foil base material cleaned in the step S2 at 140 ℃ to obtain a current collector aluminum foil.
The aluminum foil substrates of examples 1 to 9 and comparative examples 1 to 4 were obtained from the same supplier and belong to the same batch, and the copper foil substrates of examples 9 to 12 were obtained from the same supplier and belong to the same batch. The aluminum foil substrate (blank group 1), the copper foil substrate (blank group 2), the current collector aluminum foils (experiment group 1) prepared in examples 1 to 9 and comparative examples 1 to 4, and the current collector copper foils (experiment group 2) prepared in examples 10 to 12 were tested to form 18 test groups, 3 samples of each test group were tested, and the results were averaged, wherein the test items include tensile strength and surface wetting tension, and the tensile strength reduction (%) of the aluminum foil (%) = (tensile strength of blank group-tensile strength of aluminum foil of experiment group)/tensile strength of blank group = 100% was calculated, and the results are shown in table 1:
TABLE 1
| Item | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| Surface wetting tension (dyn) | 60 | 60 | 70 | 70 | 70 | 60 |
| Tensile Strength decrease (%) | 0 | 0 | 0 | 0 | 0.54 | 3.24 |
| Item | Example 7 | Example 8 | Example 9 | Example 10 | Example 11 | Example 12 |
| Surface wetting tension (dyn) | 60 | 60 | 60 | 70 | 70 | 70 |
| Tensile Strength decrease (%) | 2.70 | 1.08 | 0 | 0 | 0 | 0 |
| Item | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Blank group 1 | |
| Surface wetting tension (dyn) | 40 | 40 | 50 | 50 | 30 | 30 |
| Tensile Strength decrease (%) | 0 | 0 | 5.4 | 3.78 | - | - |
As can be seen from the results in table 1, the wetting tension of the aluminum foil surface of the current collector in examples 1 to 9 of the present application is significantly improved and the reduction rate of the tensile strength is low as compared to the aluminum foil substrate (blank group 1); similarly, the surface wetting tension of the current collector copper foils of examples 10 to 12 of the present application was significantly improved and the reduction in tensile strength was low as compared to the copper foil base material (blank 2). It can be seen from the data of example 3 and comparative example 4 that the steps of pickling and pickling are reversed, and both the tensile strength and the surface wetting tension of the aluminum foil are affected. From the data of examples 3 and 6 to 7, it is clear that HF and H are contained in the pickling solution2SO4The mass ratio of (A) to (B) and Ca (OH) in the alkaline solution2The mass ratio of LiOH to LiOH is in a certain proportion range, and the surface wetting tension of the aluminum foil can be further improved under the condition that the tensile strength of the aluminum foil is not influenced. From the data of example 3 and examples 8 to 9, it can be seen that the speed of the aluminum foil substrate passing through the pickling, alkaline washing and cleaning tanks was too high or the temperature of the deionized water in the cleaning tank was too high Too low a degree will affect the surface wetting tension of the aluminum foil.
The above disclosure is only one preferred embodiment of the present application, and certainly does not limit the scope of the present application, which is therefore intended to cover all modifications and equivalents of the claims.
Claims (10)
1. A preparation method of a current collector metal foil is characterized by comprising the following steps:
providing a metal substrate;
cleaning the metal base material, wherein the metal base material sequentially enters a pickling tank, an alkaline washing tank and a cleaning tank, and pickling solution in the pickling tank comprises HF and H2SO4The alkaline solution in the alkaline groove comprises Ca (OH)2And/or LiOH, wherein deionized water is contained in the cleaning tank, wherein the HF and the H are2SO4The total mass of the acid washing liquid is 2 to 4 percent of the total mass of the acid washing liquid, and the Ca (OH)2And/or the total mass of LiOH is 2% -4% of the total mass of the alkaline washing liquid;
and drying the cleaned metal base material.
2. The method of preparing a current collector metal foil of claim 1, wherein the HF and H are2SO4The mass ratio of (1) to (2.5-5).
3. The method for preparing a current collector metal foil as claimed in claim 1, wherein the alkaline solution in the alkaline bath comprises Ca (OH) 2And LiOH, wherein the Ca (OH)2And the mass ratio of LiOH to LiOH is 1 (3.5-6.5).
4. The method of preparing a current collector metal foil of claim 3, wherein the HF and H are2SO4The mass ratio of (1), (3-4), the Ca (OH)2And the mass ratio of LiOH to LiOH is 1 (4-5).
5. The method for preparing a current collector metal foil as claimed in claim 1, wherein the method for performing a cleaning process on the metal substrate comprises:
and discharging the coiled metal substrate to a tension roller by using an unreeling machine, sequentially conveying the metal substrate to the pickling tank, the alkaline washing tank and the washing tank through the tension roller, wherein the speed of the metal substrate passing through the pickling tank, the alkaline washing tank and the washing tank is 130-160 m/min.
6. The method for preparing the current collector metal foil as claimed in claim 5, wherein a first squeezing roller for squeezing the pickling solution is arranged between the pickling tank and the alkaline washing tank, and a second squeezing roller for squeezing the alkaline washing solution is arranged between the alkaline washing tank and the washing tank.
7. The method for preparing the current collector metal foil as claimed in claim 1, wherein the thickness of the metal substrate is 10-20 μm, and the speed of the metal substrate passing through the pickling tank, the alkaline washing tank and the cleaning tank is 140-150 m/min.
8. The method for preparing a current collector metal foil as claimed in claim 1, wherein the temperature of the deionized water is 50-70 ℃.
9. A current collector metal foil is characterized by being prepared by the preparation method of any one of claims 1-8, and the surface wetting tension of the current collector metal foil is more than 55 x 10-3N/m。
10. A lithium battery current collector is characterized by comprising a current collector metal foil and a conductive coating coated on the current collector metal foil, wherein the current collector metal foil is prepared by the preparation method of any one of claims 1-8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210323629.4A CN114759191B (en) | 2022-03-29 | 2022-03-29 | Current collector metal foil, preparation method thereof and lithium battery current collector |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210323629.4A CN114759191B (en) | 2022-03-29 | 2022-03-29 | Current collector metal foil, preparation method thereof and lithium battery current collector |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114759191A true CN114759191A (en) | 2022-07-15 |
| CN114759191B CN114759191B (en) | 2023-12-29 |
Family
ID=82326705
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210323629.4A Active CN114759191B (en) | 2022-03-29 | 2022-03-29 | Current collector metal foil, preparation method thereof and lithium battery current collector |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114759191B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023184879A1 (en) * | 2022-03-29 | 2023-10-05 | 佛山市中技烯米新材料有限公司 | Current collector etched foil and preparation method therefor, electrode, and lithium battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105895922A (en) * | 2016-05-13 | 2016-08-24 | 合肥国轩高科动力能源有限公司 | Fabrication method of conductive coating aluminum foil |
| CN113714287A (en) * | 2020-12-31 | 2021-11-30 | 杭州五星铝业有限公司 | Production process of aluminum foil for Dada double-sided photocell |
-
2022
- 2022-03-29 CN CN202210323629.4A patent/CN114759191B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105895922A (en) * | 2016-05-13 | 2016-08-24 | 合肥国轩高科动力能源有限公司 | Fabrication method of conductive coating aluminum foil |
| CN113714287A (en) * | 2020-12-31 | 2021-11-30 | 杭州五星铝业有限公司 | Production process of aluminum foil for Dada double-sided photocell |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023184879A1 (en) * | 2022-03-29 | 2023-10-05 | 佛山市中技烯米新材料有限公司 | Current collector etched foil and preparation method therefor, electrode, and lithium battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114759191B (en) | 2023-12-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103620839B (en) | Collector foil that is chemically treated, being made up of aluminum or aluminum alloy | |
| CN114759191A (en) | Current collector metal foil, preparation method thereof and lithium battery current collector | |
| CN102634805B (en) | Method for preparing magnesium alloy with super-hydrophobic layer on surface | |
| JP2017210680A (en) | Metal foil, production method of metal foil, and production method of electrode using them | |
| CN111430726B (en) | Preparation method of aluminum current collector for lithium ion battery and aluminum current collector | |
| WO2023184877A1 (en) | Lithium-supplementing current collector and lithium-supplementing electrode | |
| CN114744208B (en) | Current collector etching foil, preparation method thereof, electrode and lithium battery | |
| CN104733181B (en) | Mesohigh anode deposits the method and device of disperse tin, zinc nucleus with high-purity aluminum foil surface spray | |
| CN101701348A (en) | Coarsening solution for electroplating pretreatment on surface of semiconductor N\P type cooling wafer and related electroplating pretreatment process | |
| CN115911402A (en) | Negative current collector for lithium ion battery and preparation method thereof | |
| CN103774193A (en) | Method for electrolytic-depositing dispersed zinc crystal nucleuses on surface of medium-high voltage electronic aluminum foil | |
| WO2009081526A1 (en) | Battery can, method of manufacturing the same, and battery | |
| CN113286917B (en) | Copper foil, negative electrode current collector for lithium ion battery containing copper foil, and method for producing same | |
| CN104726875A (en) | Method for preparation of super-hydrophobic CuO film on steel surface | |
| KR101029821B1 (en) | A manufacturing method of anode tap for secondary battery | |
| CN114552133B (en) | Preparation method of negative electrode lug with surface inert metal coating and lithium battery | |
| WO2022158188A1 (en) | Layered body, negative electrode current collector for lithium ion secondary battery, and negative electrode for lithium ion secondary battery | |
| CN115117303A (en) | Lithium metal negative electrode, preparation method thereof and lithium secondary battery | |
| CN108239743A (en) | A kind of preparation method of quartz crystal | |
| CN209953901U (en) | Copper foil guillootine with online grinding device | |
| CN114975851B (en) | Nano porous silicon electrode material, preparation method thereof and application thereof in preparation of silicon air battery | |
| JP2008300084A (en) | Electrode can plating method of flat form alkaline cell, anode can plating method of flat form alkaline cell, anode can plating device of flat form alkaline cell, anode can etching device of flat form alkaline cell, anode can surface reforming device of flat form alkaline cell, anode can cleaning device of flat form alkaline cell, and anode can drying device of flat form alkaline cell | |
| JP3435255B2 (en) | Manufacturing equipment for electro-galvanized steel sheet with excellent lubricity | |
| CN114843525A (en) | Porous current collector and preparation method thereof | |
| US20240044014A1 (en) | Roughening treatment method for stainless steel surface, method for manufacturing roughened stainless steel, and aqueous composition used in said methods |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |