CN114759191B - 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
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- CN114759191B CN114759191B CN202210323629.4A CN202210323629A CN114759191B CN 114759191 B CN114759191 B CN 114759191B CN 202210323629 A CN202210323629 A CN 202210323629A CN 114759191 B CN114759191 B CN 114759191B
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 133
- 239000002184 metal Substances 0.000 title claims abstract description 133
- 239000011888 foil Substances 0.000 title claims abstract description 132
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 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
- 238000004140 cleaning Methods 0.000 claims abstract description 119
- 239000000758 substrate Substances 0.000 claims abstract description 108
- 238000005554 pickling Methods 0.000 claims abstract description 86
- 239000000463 material Substances 0.000 claims abstract description 24
- 238000009736 wetting Methods 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims description 88
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 62
- 239000007788 liquid Substances 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 23
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 abstract description 72
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 72
- 239000012535 impurity Substances 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 55
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 24
- 239000011889 copper foil Substances 0.000 description 24
- 239000002585 base Substances 0.000 description 18
- 239000003513 alkali Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 12
- 239000013543 active substance Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000003749 cleanliness Effects 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 210000001787 dendrite Anatomy 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000126 substance 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
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 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
- 238000002474 experimental method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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 and a preparation method thereof, and a lithium battery current collector, wherein the preparation method comprises the steps of providing a metal base material; and cleaning the metal substrate, wherein the metal substrate sequentially passes through a pickling tank, an alkaline tank and a cleaning tank, and drying the cleaned metal substrate to obtain the current collector metal foil. The preparation method is simple, and can effectively remove impurities on the surface of the metal substrate 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 and a preparation method thereof, and a lithium battery current collector.
Background
The current collector is one of indispensable component parts in the lithium battery, can not only bear active substances, but also collect and output current generated by electrode active substances, is beneficial to reducing the internal resistance of the lithium battery and improving the coulomb efficiency, the cycle stability and the multiplying power performance of the battery. The current collector is a key material of the lithium battery, and is used for carrying powdery active substances on one hand and collecting current on the other hand.
The lithium battery current collector generally employs copper foil and aluminum foil. The copper foil is easy to oxidize at a higher potential and is mainly used for a negative electrode with a lower potential. The aluminum foil has serious corrosion problem at low potential and is mainly used for the positive current collector.
The aluminum foil for the lithium battery current collector meets the following requirements that 1, the cleanliness is high, and any impurities such as scraps, dust and the like cannot be 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.
The surface wetting tension is one of the most important technical indexes of the current collector metal foil, affects the bonding quality of the coating, particularly affects the coating firmness of the carbon-coated foil, and has the defects of infirm bonding between the aluminum foil and the bonding material, missing coating and the like when the dyne value is low.
Disclosure of Invention
The technical problem to be solved by the application is to provide a preparation method of a current collector metal foil, which is used for removing impurities on the current collector metal foil and improving the surface wetting tension of the current collector metal foil.
The technical problem to be solved by the application is to provide a current collector metal foil which has high surface wetting tension and good binding force with conductive materials or battery active substances.
The technical problem to be solved by the application is to provide a lithium battery current collector, and electrode active substances can be better attached to the current collector.
In order to solve the technical problems, the application provides a preparation method of a current collector metal foil, which comprises the following steps:
providing a metal substrate;
the metal substrate is subjected to cleaning treatment, wherein the metal substrate sequentially passes through a pickling tank, an alkaline washing tank and a cleaning tank, and pickling solution in the pickling tank comprises HF and H 2 SO 4 The alkaline cleaning liquid in the alkaline cleaning tank comprises Ca (OH) 2 And/or LiOH, the cleaning tank containing deionized water, wherein the HF and H 2 SO 4 The total mass of the acid washing liquid is 2-4% of the total mass of the acid washing liquid, and the Ca (OH) 2 And/or the total mass of the LiOH is 2% -4% of the total mass of the alkaline washing liquid;
and drying the metal base material after the cleaning treatment.
As an improvement of the above scheme, the HF and H 2 SO 4 The mass ratio of (2.5-5) is 1.
As an improvement of the scheme, the alkaline cleaning solution in the alkaline cleaning tank comprises Ca (OH) 2 And LiOH, wherein the Ca (OH) 2 And LiOH is 1 (3.5-6.5).
As an improvement of the above scheme, the HF and H 2 SO 4 The mass ratio of (3) to (4) is 1, the Ca (OH) 2 And LiOH is 1 (4-5).
As an improvement of the above-described aspect, the method of cleaning the metal substrate includes:
and paying out the coiled metal base material to a tension roller by adopting an unreeling machine, sequentially conveying the metal base material to the pickling tank, the alkaline washing tank and the cleaning tank by the tension roller, wherein 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.
As an improvement of the scheme, a first liquid squeezing roller for squeezing out the pickling solution is arranged between the pickling tank and the alkaline washing tank, and a second liquid squeezing roller for squeezing out the alkaline washing solution is arranged between the alkaline washing tank and the cleaning tank.
As an improvement of the scheme, the thickness of the metal base material is 10-20 mu m, 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 which is prepared by the preparation method, and the surface wetting tension of the current collector metal foil is more than 55 multiplied by 10 -3 N/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.
By implementing the application, the method has the following beneficial effects:
the metal substrate of this application carries out the pickling earlier and carries out the alkali wash, and the pickling solution in the pickling tank, the alkali wash in the alkali wash tank comprise specific component, not only effectively get rid of impurity and the greasy dirt on metal substrate surface, improve metal substrate's surface wetting tension, still do not influence metal substrate's tensile strength.
The metal substrate is cleaned by alkaline washing and deionized water at a certain temperature, so that residual alkaline washing liquid on the metal substrate and decomposition products generated in the alkaline washing process are removed, and the cleanliness and surface wetting tension of the metal substrate are effectively improved.
The utility model provides an unreeling machine is adopted to this application emits coiled metal substrate to the tension roller, and wherein metal substrate carries to pickling tank, alkaline wash tank and washing tank in proper order through the tension roller, and this application can adjust the dwell time of metal substrate in pickling tank, alkaline wash tank and washing tank through the speed of adjustment conveying roller, easy operation, the cleaning performance is good, adapts to mass production.
Drawings
Fig. 1 is a schematic structural view of a first current collector of the present application;
fig. 2 is a schematic structural view of a second current collector of the present application.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present application more apparent, the present application will be described in further 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 substrate;
the thickness of the metal substrate in this application is preferably 10 to 20. Mu.m. 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 aluminum foil or copper foil, but is not limited thereto. The aluminum foil is severely corroded at low potential, so that the aluminum foil is mainly used for the positive electrode current collector, wherein the aluminum foil is impure in components, so that the surface oxide film is not compact, spot corrosion occurs, and LiAl alloy can be generated.
In order to effectively remove impurities, greasy dirt, an oxide layer and the like on an aluminum foil or a copper foil, the cleanliness and the surface wetting tension of a current collector metal foil are improved, so that a conductive material or a battery active substance is attached to the current collector metal foil.
S2, cleaning the metal substrate;
the method for cleaning the metal substrate comprises the steps of paying out coiled metal substrate to a tension roller by adopting an unreeling machine, and sequentially conveying the metal substrate to a pickling tank, an alkaline washing tank and a cleaning tank by the tension roller, wherein the metal substrate sequentially passes through the pickling tank, the alkaline washing tank and the cleaning tank.
Different from a general cleaning method, the method is characterized in that acid cleaning is firstly performed and then alkali cleaning is performed, wherein the acid cleaning mainly removes greasy dirt, forms a rough structure on the surface of a metal substrate, increases the surface area of the metal substrate, and has the effect of preliminary etching; the main function of alkali washing is to remove polar substances on the metal substrate and improve the surface wetting tension of the metal substrate. According to a great number of experiments and researches of the inventor, if the order of acid washing and alkali washing is changed, the simple order is changed, but the influence on the cleaning effect is very great, and not only the surface wetting tension of the metal substrate, but also the tensile strength of the metal substrate and the like are influenced. The application firstly carries out acid washing and then alkali washing, so that the cleanliness and 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 solution in the alkaline washing tank consist of specific components. Specifically, the pickling solution comprises HF and H 2 SO 4 The alkaline cleaning liquid in the alkaline cleaning tank comprises Ca (OH) 2 And/or LiOH, the cleaning tank of the present application contains deionized water. Wherein the alkali washing liquid can be Ca (OH) only 2 LiOH alone or in combination with Ca (OH) 2 。
Due to Ca (OH) 2 And LiOH is herein an alkaline wash substance and thus can be a component of an alkaline wash. However, according to the studies of the applicant, it was found that the metal substrate after pickling was subjected to a treatment containing Ca (OH) 2 And/or after the alkaline washing liquid of LiOH, the electrolyte is more uniformly wetted on the metal foil, so that the growth direction and the production speed of dendrites can be influenced, dendrites are prevented from growing in the same direction, and the influence of dendrites on the performance of the lithium battery is reduced.
Preferably, the alkaline cleaning solution comprises Ca (OH) 2 And LiOH.
Because the cleaning object is a metal substrate, the thickness is very thin and the amplitude is very long, and the metal substrate needs to be simultaneously subjected to unreeling and reeling actions, the cleaning difficulty is high, and unlike common pickling solutions and alkaline washing solutions, the concentration of the pickling solutions and the alkaline washing solutions cannot be too high, if the concentration of the pickling solutions and the alkaline washing solutions exceeds 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 concentration of the pickling solution and the alkali solution is less than 2%, the cleaning effect is affected, and the surface wetting tension of the metal foil is low.
Specifically, HF and H 2 SO 4 The total mass of (2) to (4) percent of the total mass of the pickling solution, ca (OH) 2 And/or the total mass of the LiOH is 2% -4% of the total mass of the alkaline washing liquid. Wherein, if the alkaline cleaning solution comprises Ca (OH) 2 Ca (OH) 2 The mass of the water-based alkaline cleaning solution is 2-4% of the total mass of the alkaline cleaning solution; 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 cleaning solution comprises Ca (OH) 2 And LiOH, ca (OH) 2 And the total mass of LiOH is 2% -4% of the total mass of the alkaline washing liquid.
Preferably, HF and H 2 SO 4 The total mass of the acid washing liquid is 2.5% -3.5%, ca (OH) 2 And the total mass of LiOH is 2.5% -3.5% of the total mass of the alkaline washing liquid.
In addition to the effect of the concentration of the pickling solution and the alkali solution on the cleaning effect, tensile strength and electrochemical stability of the metal substrate, HF and H in the pickling solution 2 SO 4 Ca (OH) in alkaline washing solution 2 And LiOH also have an effect on the cleaning effect, mechanical strength and electrochemical stability of the metal substrate.
Preferably, HF and H 2 SO 4 The mass ratio of (2.5-5); ca (OH) 2 And LiOH is 1 (3.5-6.5).
More preferably, HF and H 2 SO 4 The mass ratio of (3) to (4) is 1, ca (OH) 2 And LiOH is 1 (4-5).
In actual batch production, an unreeling machine is required to be adopted to pay out coiled metal substrates to a tension roller, wherein the metal substrates are sequentially conveyed to a pickling tank, an alkaline washing tank and a cleaning tank through the tension roller, and the residence time of the metal substrates in the pickling tank, the alkaline washing tank and the cleaning tank directly influences the cleaning effect and the production efficiency of the metal substrates. If the time for the metal substrate to pass through the acid washing tank, the alkali washing tank and the washing tank is short, the washing time is short, and the washing effect is poor; if the time that the metal substrate passes 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 substrate are affected.
Correspondingly, the speed of the metal base material passing through the acid washing tank, the alkali washing tank and the washing 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, be equipped with the first crowded liquid roller that is used for crowded acid washing liquid between pickling tank and the alkaline wash tank, first crowded liquid roller is used for squeezing the pickling liquid back in the pickling tank on the metal substrate to reach the purpose that prevents the loss of pickling liquid, and prevent that pickling liquid from getting into the alkaline wash tank, influence the alkaline wash effect of alkaline wash tank.
In addition, be equipped with the second crowded liquid roller that is used for crowded removal alkaline cleaning liquid between alkaline cleaning tank and the washing tank, the second crowded liquid roller extrudees the alkaline cleaning liquid on the metal substrate back into the alkaline cleaning tank to reach the purpose that prevents the loss of alkaline cleaning liquid, and prevent that the alkaline cleaning liquid from getting into the washing tank, influence the cleaning performance of washing tank.
The metal substrate of this application washs through sour groove and alkaline washing groove, still needs to wash through the washing tank at last, contains deionized water in the washing tank, and the main effect is the decomposition product that residual alkaline washing liquid and alkaline washing in-process produced on the removal metal substrate, effectively improves metal substrate's cleanliness and surface wetting tension. If the cleaning tank is absent, alkali cleaning solution and decomposition products of alkali cleaning remained on the metal substrate affect the conductive performance or electrochemical performance of the conductive coating or electrode active material subsequently coated on the aluminum foil, thereby affecting the service life, cycle number, electric quantity and the like of the lithium battery.
In addition, the effect of alkali washing after acid washing is performed firstly because the influence of the acid washing liquid on the conductivity or electrochemical performance of the conductive coating or the active substance is larger, the influence of the alkali washing liquid is relatively smaller, and the acid washing liquid can be neutralized, so that the acid washing liquid is effectively prevented from remaining on the aluminum foil.
Preferably, the deionized water is at a temperature of 50 to 70 ℃. More preferably, the deionized water temperature 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 collector 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 increased, the binding force between the current collector metal foil and the conductive coating or the active substance is affected, and the like.
Preferably, the drying temperature of the metal substrate is 130-160 ℃. More preferably, the drying temperature of the metal substrate 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 of > 55 x 10 -3 N/m。
The surface wetting tension is one of the most important technical indexes of the metal foil of the current collector, influences the bonding quality of the coating and the firmness of the coating, and has the defects of infirm bonding, missing coating and the like when the dyne value is low.
Correspondingly, referring to fig. 1 and 2, the application also provides a lithium battery current collector, which comprises 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 a thickness of 15 mu m;
s2, paying out the coiled aluminum foil substrate to a tension roller by adopting an unreeling machine, and sequentially conveying the aluminum foil substrate to a pickling tank, an alkaline washing tank and a cleaning tank which are all 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% HF and 1.45wt% H 2 SO 4 The alkaline cleaning solution in the alkaline cleaning tank comprises 2wt% Ca (OH) 2 The cleaning tank contains deionized water with the temperature of 50 ℃;
and S3, drying the aluminum foil substrate subjected to the cleaning treatment 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 substrate with a thickness of 15 mu m;
s2, paying out the coiled aluminum foil substrate to a tension roller by adopting an unreeling machine, and sequentially conveying the aluminum foil substrate to a pickling tank, an alkaline washing tank and a cleaning tank which are all 1m in length through the tension roller at a speed of 140 m/min; wherein the pickling solution in the pickling tank comprises 0.6wt% HF and 1.9wt% H 2 SO 4 The alkaline cleaning solution in the alkaline cleaning 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 subjected to the cleaning treatment in the step S2 at 130 ℃ to obtain the 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 a thickness of 15 mu m;
s2, paying out the coiled aluminum foil substrate to a tension roller by adopting an unreeling machine, and sequentially conveying the aluminum foil substrate to a pickling tank, an alkaline washing tank and a cleaning tank which are all 1m in length through the tension roller at a speed of 150m/min; wherein the pickling solution in the pickling tank comprises 0.65wt% of HF and 2.35wt% of H 2 SO 4 The alkaline cleaning solution in the alkaline cleaning tank comprises 0.55wt% Ca (OH) 2 And 2.45wt% lioh, the rinse tank containing deionized water at a temperature of 60 ℃;
and S3, drying the aluminum foil base material subjected to the cleaning treatment in the step S2 at 140 ℃ to obtain the current collector aluminum foil.
Example 4
A preparation method of a current collector metal foil comprises the following steps:
s1, providing an aluminum foil substrate with a thickness of 15 mu m;
s2, paying out the coiled aluminum foil substrate to a tension roller by adopting an unreeling machine, and sequentially conveying the aluminum foil substrate to a pickling tank, an alkaline washing tank and a cleaning tank which are all 1m in length through the tension roller at a speed of 150m/min; wherein the pickling solution in the pickling tank comprises 0.7wt% HF and 2.8wt% H 2 SO 4 The alkaline cleaning solution in the alkaline cleaning tank comprises 0.58wt% Ca (OH) 2 And 2.92wt% lioh, the rinse tank containing deionized water at 65 ℃;
and S3, drying the aluminum foil base material subjected to the cleaning treatment in the step S2 at 150 ℃ to obtain the 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 a thickness of 15 mu m;
s2, paying out the coiled aluminum foil substrate to a tension roller by adopting an unreeling machine, and sequentially conveying the aluminum foil substrate to a pickling tank, an alkaline washing tank and a cleaning tank which are all 1m in length through the tension roller at a speed of 160 m/min; wherein the pickling solution in the pickling tank comprises 0.67wt% of HF and 3.33wt% of H 2 SO 4 The alkaline cleaning solution in the alkaline cleaning tank comprises 0.55wt% Ca (OH) 2 And 3.45wt% LiOH, the rinse tank containing deionized water at a temperature of 70 ℃;
and S3, drying the aluminum foil base material subjected to the cleaning treatment in the step S2 at 150 ℃ to obtain the current collector aluminum foil.
Example 6
Unlike example 3, the pickling solution in the pickling tank of example 6 includes 1.5wt% HF and 1.5wt% H 2 SO 4 The alkaline cleaning solution in the alkaline cleaning tank comprises 1.5wt% Ca (OH) 2 And 1.5wt% LiOH.
Example 7
Unlike example 3, the pickling solution in the pickling tank of example 7 includes 0.3wt% HF and 2.7wt% H 2 SO 4 The alkaline wash solution in the alkaline wash tank included 0.3wt% Ca (OH) 2 And 2.7wt% LiOH.
Example 8
Unlike example 3, the aluminum foil substrate of step S2 in example 8 was sequentially transferred to the pickling tank, the alkaline washing tank and the cleaning tank at a speed of 180m/min via a tension roller.
Example 9
Unlike example 3, the deionized water temperature 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 substrate with the thickness of 10 mu m;
s2, paying out the coiled copper foil substrate to a tension roller by adopting an unreeling machine, and sequentially conveying the copper foil substrate to a pickling tank, an alkaline washing tank and a cleaning tank which are all 1m in length through the tension roller at a speed of 150m/min; wherein the pickling solution in the pickling tank comprises 0.65wt% of HF and 2.35wt% of H 2 SO 4 The alkaline cleaning solution in the alkaline cleaning tank comprises 0.55wt% Ca (OH) 2 And 2.45wt% lioh, the rinse tank containing deionized water at a temperature of 60 ℃;
and S3, drying the copper foil substrate subjected to the cleaning treatment in the step S2 at 140 ℃ to obtain the current collector copper foil.
Example 11
A preparation method of a current collector metal foil comprises the following steps:
s1, providing a copper foil substrate with the thickness of 10 mu m;
s2, paying out the coiled copper foil substrate to a tension roller by adopting an unreeling machine, and sequentially conveying the copper foil substrate to a pickling tank, an alkaline washing tank and a cleaning tank which are all 1m in length through the tension roller at a speed of 150m/min; wherein the pickling solution in the pickling tank comprises 0.7wt% HF and 2.8wt% H 2 SO 4 The alkaline cleaning solution in the alkaline cleaning tank comprises 0.58wt% Ca (OH) 2 And 2.92wt% lioh, the rinse tank containing deionized water at 65 ℃;
and S3, drying the copper foil substrate subjected to the cleaning treatment 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 substrate with the thickness of 10 mu m;
s2, paying out the coiled copper foil substrate to a tension roller by adopting an unreeling machine, and sequentially conveying the copper foil substrate to a pickling tank, an alkaline washing tank and a cleaning tank which are all 1m in length through the tension roller at a speed of 160m/minA washing tank; wherein the pickling solution in the pickling tank comprises 0.67wt% of HF and 3.33wt% of H 2 SO 4 The alkaline cleaning solution in the alkaline cleaning tank comprises 0.55wt% Ca (OH) 2 And 3.45wt% LiOH, the rinse tank containing deionized water at a temperature of 70 ℃;
and S3, drying the copper foil substrate subjected to the cleaning treatment in the step S2 at 150 ℃ to obtain the current collector copper foil.
Comparative example 1
A preparation method of a current collector metal foil comprises the following steps:
s1, providing an aluminum foil substrate with a thickness of 15 mu m;
s2, paying out the coiled aluminum foil substrate to a tension roller by adopting an unreeling machine, and sequentially conveying the aluminum foil substrate to a pickling tank and a cleaning tank with the lengths of 1m through the tension roller at the speed of 150m/min; wherein the pickling solution in the pickling tank comprises 0.65wt% of HF and 2.35wt% of H 2 SO 4 The cleaning tank contains deionized water with the temperature of 60 ℃;
and S3, drying the aluminum foil base material subjected to the cleaning treatment in the step S2 at 140 ℃ to obtain the 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 a thickness of 15 mu m;
s2, paying out the coiled aluminum foil substrate to a tension roller by adopting an unreeling machine, and sequentially conveying the aluminum foil substrate to an alkaline washing tank and a washing tank with the lengths of 1m through the tension roller at the speed of 150m/min; wherein the alkaline cleaning solution in the alkaline cleaning tank comprises 0.55wt% Ca (OH) 2 And 2.45wt% lioh, the rinse tank containing deionized water at a temperature of 60 ℃;
and S3, drying the aluminum foil base material subjected to the cleaning treatment in the step S2 at 140 ℃ to obtain the 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 substrate with a thickness of 15 mu m;
s2, adoptThe unreeling machine unreels the coiled aluminum foil substrate to a tension roller, and the aluminum foil substrate is sequentially conveyed to a pickling tank, an alkaline washing tank and a cleaning tank with the lengths of 1m through the tension roller at the speed of 150m/min; wherein the pickling solution in the pickling tank comprises 3wt% of H 2 C 2 O 4 The alkaline cleaning solution in the alkaline cleaning tank comprises 3wt% of NaOH, and deionized water with the temperature of 60 ℃ is contained in the cleaning tank;
and S3, drying the aluminum foil base material subjected to the cleaning treatment in the step S2 at 140 ℃ to obtain the 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 a thickness of 15 mu m;
s2, paying out the coiled aluminum foil substrate to a tension roller by adopting an unreeling machine, and sequentially conveying the aluminum foil substrate to an alkaline washing tank, a pickling tank and a cleaning tank which are all 1m in length through the tension roller at a speed of 150m/min; wherein the alkaline cleaning solution in the alkaline cleaning tank comprises 0.55wt% Ca (OH) 2 And 2.45wt% LiOH, the pickling solution in the pickling tank comprising 0.65wt% HF and 2.35wt% H 2 SO 4 The cleaning tank contains deionized water with the temperature of 60 ℃;
and S3, drying the aluminum foil base material subjected to the cleaning treatment in the step S2 at 140 ℃ to obtain the current collector aluminum foil.
The aluminum foil substrates of examples 1 to 9 and comparative examples 1 to 4 were from the same supplier and were in the same batch, and the copper foil substrates of examples 9 to 12 were from the same supplier and were in the same batch. The aluminum foil substrate (blank 1), the copper foil substrate (blank 2), the current collector aluminum foils prepared in examples 1 to 9 and comparative examples 1 to 4 (test 1), the current collector copper foil prepared in examples 10 to 12 (test 2) were tested to form 18 test groups, each test group was tested by taking 3 samples, and the results were averaged, wherein the test items included tensile strength and surface wetting tension, and the tensile strength decrease rate (%) of the aluminum foil = (tensile strength of blank-tensile strength of aluminum foil of test group)/tensile strength of blank × 100% were calculated, and the results are shown in table 1:
TABLE 1
As can be seen from the results of table 1, the current collector aluminum foils of examples 1 to 9 of the present application have significantly improved surface wetting tension and low tensile strength decrease rate, compared to the aluminum foil substrate (blank 1); similarly, the current collector copper foil surface wetting tension of examples 10 to 12 of the present application was significantly improved, and the tensile strength decrease rate was low, compared to the copper foil base material (blank group 2). From the data of example 3 and comparative example 4, it is understood that the tensile strength and the surface wetting tension of the aluminum foil are affected by the exchange of the pickling and the pickling steps. As can be seen from the data of example 3 and examples 6-7, HF and H in the pickling solution 2 SO 4 Is characterized by comprising Ca (OH) in alkaline cleaning solution 2 And the mass ratio of LiOH is in a certain proportion range, so that 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 8-9, it is clear that the too fast speed of the aluminum foil substrate through the pickling bath, alkaline bath and cleaning bath or too low temperature of the deionized water in the cleaning bath affects the surface wetting tension of the aluminum foil.
The foregoing disclosure is merely illustrative of a preferred embodiment of the present application and is not intended to limit the scope of the claims herein, as equivalent changes may be made in the claims herein without departing from the scope of the claims herein.
Claims (10)
1. The preparation method of the current collector metal foil is characterized by comprising the following steps of:
providing a metal substrate;
cleaning the metal substrate, wherein the metal substrate sequentially passes through a pickling tank, an alkaline washing tank and a cleaning tank, and the pickling solution in the pickling tank is packagedIncluding HF and H 2 SO 4 The alkaline cleaning liquid in the alkaline cleaning tank comprises Ca (OH) 2 And/or LiOH, the cleaning tank containing deionized water, wherein the HF and H 2 SO 4 The total mass of the acid washing liquid is 2% -4%, and Ca (OH) is contained in the acid washing liquid 2 And/or the total mass of the LiOH is 2% -4% of the total mass of the alkaline washing liquid; the speed of the metal substrate passing through the pickling tank, the alkaline washing tank and the cleaning tank is 130-160 m/min;
drying the cleaned metal base material to obtain surface wetting tension of 55 x 10 -3 N/m current collector metal foil.
2. The method of preparing a current collector metal foil according to claim 1, wherein said HF and H are 2 SO 4 The mass ratio of (2.5-5) is 1.
3. The method of making a current collector metal foil as in claim 1, wherein the alkaline wash solution in the alkaline wash tank comprises Ca (OH) 2 And LiOH, wherein the Ca (OH) 2 And LiOH is 1 (3.5-6.5).
4. A method of preparing a current collector metal foil as claimed in claim 3, wherein said HF and H are 2 SO 4 The mass ratio of (3-4) is 1, the Ca (OH) 2 And LiOH is 1 (4-5).
5. The method of preparing a current collector metal foil according to claim 1, wherein the method of cleaning the metal substrate comprises:
and paying out the coiled metal base material to a tension roller by adopting an unreeling machine, and sequentially conveying the metal base material to the pickling tank, the alkaline washing tank and the cleaning tank through the tension roller.
6. The method for preparing a current collector metal foil according to claim 5, wherein a first liquid squeezing roller for squeezing out the pickling solution is arranged between the pickling tank and the alkaline washing tank, and a second liquid squeezing roller for squeezing out the alkaline washing solution is arranged between the alkaline washing tank and the cleaning tank.
7. The method for preparing a current collector metal foil according to 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 according to claim 1, wherein the deionized water is at a temperature of 50-70 ℃.
9. A current collector metal foil, characterized in that it is produced by the production method according to any one of claims 1 to 8.
10. A lithium battery current collector, 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.
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| 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 |
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| 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 |
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