CN114351217B - Metal electroplating composite film and preparation method thereof - Google Patents
Metal electroplating composite film and preparation method thereof Download PDFInfo
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- CN114351217B CN114351217B CN202210029867.4A CN202210029867A CN114351217B CN 114351217 B CN114351217 B CN 114351217B CN 202210029867 A CN202210029867 A CN 202210029867A CN 114351217 B CN114351217 B CN 114351217B
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- 238000009713 electroplating Methods 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 239000002184 metal Substances 0.000 title claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 46
- 239000010949 copper Substances 0.000 claims abstract description 46
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229920001046 Nanocellulose Polymers 0.000 claims abstract description 41
- 230000037452 priming Effects 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000000265 homogenisation Methods 0.000 claims abstract description 10
- 238000004544 sputter deposition Methods 0.000 claims abstract description 9
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000003647 oxidation Effects 0.000 claims abstract description 3
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 3
- 229920002678 cellulose Polymers 0.000 claims description 17
- 239000001913 cellulose Substances 0.000 claims description 17
- 239000000835 fiber Substances 0.000 claims description 16
- 239000012528 membrane Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 10
- 239000002121 nanofiber Substances 0.000 claims description 9
- 238000007747 plating Methods 0.000 claims description 7
- 239000000020 Nitrocellulose Substances 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229920001220 nitrocellulos Polymers 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 229920003043 Cellulose fiber Polymers 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 5
- 239000007900 aqueous suspension Substances 0.000 claims description 5
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims description 5
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 8
- 239000011889 copper foil Substances 0.000 abstract description 8
- 229910052744 lithium Inorganic materials 0.000 abstract description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000003562 lightweight material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/20—Metallic material, boron or silicon on organic substrates
- C23C14/205—Metallic material, boron or silicon on organic substrates by cathodic sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Electrochemistry (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a metal electroplating composite film and a preparation method thereof. The nano cellulose layer is prepared by adopting a 2, 6-tetramethyl piperidine (Tempo) oxidation method and a high-pressure homogenization process, the nano copper priming layer is deposited on two sides of the nano cellulose layer by adopting a direct-current sputtering method, and the electroplated copper layer is electroplated on the outermost side of the copper priming layer. The composite film has excellent conductivity, the surface sheet resistance is 10-200mΩ, the Young's modulus is 2.5-6.5 GPa, the tensile strength is 30-85 MPa, the elongation at break is 2.5-7%, and the thickness is 5-30 μm; the heat stability reaches 300 ℃, the mass is effectively reduced by 60% -80% compared with the metal copper foil, the energy density of the battery used as the negative current collector of the lithium battery can be improved by 5% -10%, besides, the composite film has good mechanical flexibility, high conductivity and low thermal expansion coefficient, so that the composite film can serve as a radiator for electronic devices; the thermal stability reaches 324 ℃, and can be used in the high-temperature radio frequency field.
Description
Technical Field
The invention belongs to the technical field of electroplating, and particularly relates to a metal electroplating composite film and a preparation method thereof.
Background
With the rapid development of the lithium battery industry, higher demands are continuously put on the energy density of the lithium battery, and the energy density and higher cycle efficiency of the lithium battery are key to the development and promotion of the lithium battery. With the attention and importance of the international society on energy sources, the related mineral resources of lithium batteries are gradually scarce, wherein the price of copper is gradually raised along with the development of industry, how to use copper with the highest efficiency is also critical, and the thinnest 6 microns of copper foil in the prior art reaches the limit. In addition, the traditional copper foil has high density and heavy weight, the existing process capability is close to the limit, and the energy density of the battery cannot be further improved. The choice of lightweight materials for replacing a portion of the copper foil is a better choice. However, many high molecular polymers are often combined with metal layers in a weak manner, and the internal resistance of the current collector is increased, so that better battery cycle performance cannot be obtained effectively.
Disclosure of Invention
In order to overcome the problems, the invention aims to provide a metal electroplating composite film which is used for solving the problem of battery capacity density, reducing internal resistance and improving cycle performance. The composite film has excellent conductivity, the surface sheet resistance is 10-200mΩ, the elongation at break is 2.5% -7%, the thickness is 5-30 μm, and the mass is effectively reduced by 60% -80% compared with the metal copper foil, and the energy density of the negative current collector battery used as the lithium battery can be improved by 5% -10%. The nano-cellulose/nano-copper composite material is applied to a current collector of a lithium ion battery, the nano-cellulose disperses the nano-copper, and the internal resistance can be effectively reduced by 20-40%.
In order to achieve the above purpose, the invention provides a metal electroplating composite film, which comprises a nanocellulose film layer, a nanocopper priming layer and an electroplated copper layer.
Further, the nanocellulose film layer is made of nanocellulose in a semi-crystalline state, the nanocellulose film layer is made of 2, 6-tetramethylpiperidine (Tempo) through an oxidation method and a high-pressure homogenization process, the composite nano copper priming layer is deposited on two sides of the nanocellulose by a direct-current sputtering method, and the electroplated copper layer is deposited on the outer surface of the composite nano copper priming layer through electroplating.
Further, the length-diameter ratio of the nano cellulose film is more than or equal to 280nm, the diameter is selected to be 3.5-30 nm, and the length is selected to be 800 nm-3 mu m.
Further, the thickness of the nanocellulose film is 5-30 μm.
Further, the thickness of the nano copper priming layer is 30-200nm.
Further, the preparation method of the metal plating composite film is as follows:
1) Dispersing cellulose fiber in distilled water containing TEMPO and NaBr for 10-30min, and then adding into NaOH solution;
2) Dripping 15% NaClO until the pH value of the solution is unchanged, keeping the overall pH at about 10, washing the oxidized fiber with distilled water and filtering for 5-7 times;
3) Cooling the fiber to room temperature, and performing a high-pressure homogenization process to obtain a transparent gel-like sample;
dispersing the transparent gel sample in water to reach the mass concentration of 0.2-0.5%, and dispersing by using a high-speed stirrer;
4) Pouring the water suspension on an experimental paper with a nitrocellulose membrane at the bottom to obtain a wet cellulose nanofiber membrane;
5) Drying the wet cellulose nanofiber membrane under vacuum to ensure that the surface of the nanofiber membrane is smooth and regular;
6) Depositing a nano copper priming layer on the dried nano cellulose film by adopting direct current sputtering;
7) And electroplating a copper layer on the surface of the nanocellulose film deposited with the nanocopper priming layer.
Further, in step 3), the operating conditions of the high pressure homogenization process are set to a pressure of 600bar, pumping 1-2 wt.% of the fiber suspension at a temperature of 60-70 ℃. This procedure was repeated 7 times until a transparent gel-like sample was obtained.
Further, in step 5), the pore size of the nitrocellulose membrane is 0.22lm.
Further, the dispersion time in the step 1) is 15min.
Further, in step 6), the background pressure was 3X 10-7mbar and the argon pressure was 3.8X10-3 mbar.
Further, in step 8):
1) The electroplating solution comprises copper sulfate, sulfuric acid, hydrochloric acid and additives, and the PH value is controlled to be 1-3.
2) The electroplating unreeling tension is 80-150N, and the reeling tension is 100-140N.
3) The current is 130-300A and the voltage is 3-5V during electroplating.
Further, the electroplated layer is metallic copper, and the thickness is 200-2000nm.
Further, the electroplating temperature of the electroplating method is 20-25 ℃.
Further, the operation speed of the electroplating film of the electroplating method is 2-10m/min.
Further, the drying temperature of the composite film after being electroplated by the electroplating method is 60-80 ℃.
The beneficial effects of the invention are as follows:
1. the quality of the metal electroplating composite nano cellulose/nano copper film is greatly reduced by 60-80 percent compared with the metal copper foil.
2. The energy density of the composite film used as the negative current collector of the lithium battery can be improved by 5-10%.
3. The nano-cellulose/nano-copper composite material is applied to a current collector of a lithium ion battery, and the nano-cellulose disperses the nano-copper, so that the resistance between an electrode and the current collector can be reduced, the charge transmission rate between the electrodes is promoted, and the internal resistance can be effectively reduced by 20-40%.
4. Young's modulus of the metal plating composite nano cellulose/nano copper film is 2.5-6.5 GPa, tensile strength is 30-85 MPa, elongation at break is 2.5-7%, and thickness is 5-30 mu m; the thermal stability reaches 300 ℃.
5. The nano-cellulose/nano-copper composite material is applied to a current collector of a lithium ion battery, and the nano-cellulose disperses the nano-copper, so that the resistance between an electrode and the current collector can be reduced, the charge transmission rate between the electrodes is promoted, and the internal resistance can be effectively reduced by 20-40%.
Drawings
FIG. 1 is a schematic view of a structure of a metal plating composite film;
wherein 1 is a nanocellulose film layer; 2 is a nano copper priming layer of direct current sputtering; 3 is an electroplated copper layer
Detailed Description
The technical solutions of the embodiments of the present invention will be specifically and clearly described below, but the present invention is not limited to the following embodiments, and all other embodiments obtained by those skilled in the art without making any creative effort based on the embodiments of the present invention are within the protection scope of the present invention.
Example 1
The nanocellulose/nanocopper priming film is obtained by the following steps:
1) Dispersing cellulose fiber in distilled water containing TEMPO and NaBr for 15min;
2) Dripping 15% NaClO until the pH value of the solution is unchanged, keeping the overall pH at about 10, washing oxidized fibers with distilled water and filtering for five times;
3) Before the high-pressure homogenization process, the fiber is cooled to room temperature, the operating conditions are set to a pressure of 600bar, 1wt% fiber suspension is pumped at a temperature of 60 ℃, and this process is repeated 7 times until a transparent gel-like sample is obtained;
4) Dispersing the gel in water to reach a mass concentration of 0.2%, and dispersing by using a high-speed stirrer;
5) Pouring the water suspension on an experimental paper with a nitrocellulose membrane (with the aperture of 0.22 lm) at the bottom to obtain a wet cellulose nanofiber membrane;
6) Drying the wet film under vacuum to ensure that the surface of the nano cellulose film is smooth and regular, and preparing the nano cellulose film with the thickness of 6 mu m;
7) And D, depositing a 50nm copper priming layer on the dried nano cellulose film by adopting direct current sputtering, wherein the background pressure is 3 multiplied by 10 < -7 > mbar, and the argon pressure is 3.8 multiplied by 10 < -3 > mbar.
8) Electroplating the nanocellulose film deposited with the nanocopper priming layer, wherein the electroplating solution comprises copper sulfate, sulfuric acid, hydrochloric acid and additives, and the PH value is controlled to be 2. The electroplating unreeling tension is 120N, and the reeling tension is 100N. The current during electroplating is 150A and the voltage is 3V. The operation speed of the electroplating film is 2m/min, the drying temperature is 60 ℃, and the copper layer with the thickness of 500nm of the electroplated layer is prepared. Finally obtaining the metal plating composite nano-cellulose/nano-copper film with the thickness of 7 mu m.
Example 2
The nanocellulose/nanocopper priming film is obtained by the following steps:
1) Dispersing cellulose fiber in distilled water containing TEMPO and NaBr for 30min;
2) Dripping 15% NaClO until the pH value of the solution is unchanged, keeping the overall pH at about 10, washing oxidized fiber with distilled water, and filtering for 7 times;
3) Before the high-pressure homogenization process, the fiber is cooled to room temperature, the operating conditions are set to a pressure of 600bar, a 2wt% fiber suspension is pumped at a temperature of 60 ℃, and this process is repeated 7 times until a transparent gel-like sample is obtained;
4) Dispersing the gel in water to reach a mass concentration of 0.5%, and dispersing by using a high-speed stirrer;
5) Pouring the water suspension on an experimental paper with a nitrocellulose membrane (with the aperture of 0.22 lm) at the bottom to obtain a wet cellulose nanofiber membrane;
6) Drying the wet film under vacuum to ensure that the surface of the nano cellulose film is smooth and regular, and preparing the nano cellulose film with the thickness of 8 mu m;
7) And D, depositing a 50nm copper priming layer on the dried nano cellulose film by adopting direct current sputtering, wherein the background pressure is 3 multiplied by 10 < -7 > mbar, and the argon pressure is 3.8 multiplied by 10 < -3 > mbar.
8) Electroplating the nanocellulose film deposited with the nanocopper priming layer, wherein the electroplating solution comprises copper sulfate, sulfuric acid, hydrochloric acid and additives, and the PH value is controlled to be 2. The electroplating unreeling tension is 150N, and the reeling tension is 140N. The current during electroplating is 150A and the voltage is 3V. The operation speed of the electroplating film is 2m/min, the drying temperature is 60 ℃, and the copper layer with the thickness of 500nm of the electroplated layer is prepared. Finally, the metal plating composite nano-cellulose/nano-copper film with the thickness of 9 mu m is obtained.
Example 3
The nanocellulose/nanocopper priming film is obtained by the following steps:
1) Dispersing cellulose fiber in distilled water containing TEMPO and NaBr for 15min;
2) Dripping 15% NaClO until the pH value of the solution is unchanged, keeping the overall pH at about 10, washing oxidized fibers with distilled water and filtering for five times;
3) Before the high-pressure homogenization process, the fiber is cooled to room temperature, the operating conditions are set to a pressure of 600bar, 1wt% fiber suspension is pumped at a temperature of 60 ℃, and this process is repeated 7 times until a transparent gel-like sample is obtained;
4) Dispersing the gel in water to reach a mass concentration of 0.2%, and dispersing by using a high-speed stirrer;
5) Pouring the water suspension on an experimental paper with a nitrocellulose membrane (with the aperture of 0.22 lm) at the bottom to obtain a wet cellulose nanofiber membrane;
6) Drying the wet film under vacuum to ensure that the surface of the nano cellulose film is smooth and regular, and preparing the nano cellulose film with the thickness of 6 mu m;
7) And D, depositing a 50nm copper priming layer on the dried nano cellulose film by adopting direct current sputtering, wherein the background pressure is 3 multiplied by 10 < -7 > mbar, and the argon pressure is 3.8 multiplied by 10 < -3 > mbar.
8) Electroplating the nanocellulose film deposited with the nanocopper priming layer, wherein the electroplating solution comprises copper sulfate, sulfuric acid, hydrochloric acid and additives, and the PH value is controlled to be 2. The electroplating unreeling tension is 120N, and the reeling tension is 100N. The current during electroplating is 300A and the voltage is 5V. The operation speed of the electroplating film is 5m/min, the drying temperature is 80 ℃, and the copper layer with the thickness of 750nm of the electroplated layer is prepared. Finally obtaining the metal plating composite nano-cellulose/nano-copper film with the thickness of 7.5 mu m.
Based on the scheme, the metal electroplating composite nano-cellulose/nano-copper film has the following relevant performance parameters:
as can be seen from comparison of examples 1 and 2, the thicker the mass concentration of the fiber suspension is, the thicker the synthesized nanocellulose film is, the tensile property is improved, and the tension which can be born during electroplating is larger; as is clear from comparative examples 1 and 3, in the nanocellulose film of the same thickness, the thickening of the metal layer of the copper electroplated layer with larger thickness can reduce the elongation at break of the film, but can also reduce the surface sheet resistance and the internal resistance of the pole piece, and increase the conductivity.
Comparative example 1
Comparative analysis was performed using 12 mu copper foil with a rolling limit. The relevant performance parameters are as follows:
as can be seen from examples 1, 2 and 3 and comparative example 1, the use of the metal-plated composite nanocellulose/nanocopper film as a current collector improves the quality of the commercial rolled copper foil by 72-78%, improves the elongation at break, improves both the surface sheet resistance and the internal resistance of the pole piece, and improves the energy density by 4-5% when finally applied to a battery.
It should be noted that, based on the disclosure and the description of the foregoing specification, those skilled in the art may also make changes and modifications to the above-described embodiments. Therefore, the invention is not limited to the specific embodiments disclosed and described above, but equivalent modifications and variations of the invention should be made within the scope of the claims of the present invention. In addition, although specific terms are used in the present specification, these terms are for convenience of description only and do not limit the present invention in any way.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (4)
1. A metal plating composite film, characterized in that: the composite film comprises a nano cellulose layer, a nano copper priming layer and an electroplated copper layer, wherein the nano copper priming layer is arranged on two sides of the nano cellulose layer, the electroplated copper layer is arranged on the outer side of the nano copper priming layer, the nano cellulose layer is made of nano cellulose in a semi-crystalline state, the nano cellulose layer is made by adopting a 2, 6-tetramethyl piperidine oxidation method and a high-pressure homogenization process, the nano copper priming layer is deposited on two sides of the nano cellulose layer by adopting a direct current sputtering method, and the electroplated copper layer is deposited on the outer surface of the composite nano copper priming layer by electroplating;
the composite film is prepared based on the following steps:
1) Dispersing cellulose fiber in distilled water containing TEMPO and NaBr for 10-30min, and then adding into NaOH solution;
2) Dripping 15% NaClO until the pH value of the solution is unchanged, washing the oxidized fiber with distilled water and filtering for 5-7 times;
3) Cooling the fiber to room temperature, and performing a high-pressure homogenization process to obtain a transparent gel-like sample; the operating conditions of the high-pressure homogenization process are set to a pressure of 600bar, pumping 1-2 wt.% of the fiber suspension at a temperature of 60-70 ℃;
4) Dispersing the transparent gel sample in water to reach the mass concentration of 0.2-0.5%, and dispersing by using a high-speed stirrer;
5) Pouring the water suspension obtained in the step 4) on an experimental paper with a nitrocellulose membrane at the bottom to obtain a wet cellulose nanofiber membrane;
6) Drying the wet cellulose nanofiber membrane under vacuum to ensure that the surface of the nanofiber membrane is smooth and regular;
7) Depositing a nano copper priming layer on the dried nano cellulose film by adopting direct current sputtering;
8) Electroplating a copper layer on the surface of the nanocellulose film deposited with the nanocopper priming layer;
wherein the thickness of the nano cellulose layer is 5-30 mu m;
the thickness of the nano copper priming layer is 30-200nm;
the thickness of the electroplated copper layer is 200-2000nm.
2. The composite film of claim 1, wherein: in the step 8):
1) The electroplating solution comprises copper sulfate, sulfuric acid, hydrochloric acid and additives, and the PH value is controlled to be 1-3;
2) Electroplating unreeling tension is 80-150N, and reeling tension is 100-140N;
3) The current is 130-300A and the voltage is 3-5V during electroplating.
3. The composite film of claim 2, wherein: the running speed of the electroplating film is 2-10m/min.
4. A composite film according to claim 3, wherein: the drying temperature of the electroplated composite film is 60-80 ℃.
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| CN202210029867.4A CN114351217B (en) | 2022-01-12 | 2022-01-12 | Metal electroplating composite film and preparation method thereof |
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| CN114351217B true CN114351217B (en) | 2024-03-22 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN114351217A (en) | 2022-04-15 |
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