Preparation method and device of negative current collector
阅读说明：本技术 一种负极集流体的制备方法及其装置 (Preparation method and device of negative current collector ) 是由 罗军 廖斌 陈琳 庞盼 吴先映 张旭 于 2020-07-10 设计创作，主要内容包括：本发明公开了一种负极集流体的制备方法及其装置,其结构包括基材PET、金属化层和表面铜膜。利用离子注入技术实现柔性有机材料PET表面金属化,制备膜基结合强度超过1.5N/mm,厚度3-8μm的新型PET基柔性覆铜材料锂电池负极集流体。本发明利用磁过滤技术制备的铜膜,铜膜厚度可控,能够制备传统技术难以实现的超薄型铜箔。通过离子注入优化界面晶格突变,有效地提高膜基结合力。此外,本发明技术是通过卷绕方式在柔性PET表面沉积铜膜,可以连续生产,在在重量、柔韧性以及耐用性优于传统压延法或电解法的铜箔。(The invention discloses a preparation method and a device of a negative current collector. The surface metallization of the flexible organic material PET is realized by utilizing an ion implantation technology, and the novel PET-based flexible copper-clad material lithium battery negative electrode current collector with the film-substrate bonding strength exceeding 1.5N/mm and the thickness of 3-8 mu m is prepared. The copper film prepared by the magnetic filtration technology has controllable thickness, and can be used for preparing ultra-thin copper foil which is difficult to realize by the traditional technology. And the interface lattice mutation is optimized through ion implantation, so that the film-substrate binding force is effectively improved. In addition, the technology of the invention is to deposit the copper film on the surface of the flexible PET in a winding mode, can be continuously produced, and is superior to the copper foil of the traditional rolling method or electrolytic method in weight, flexibility and durability.)
1. A preparation method of a negative electrode current collector is characterized by comprising the following steps:
a degassing and surface activation of the substrate PET: the degassing and activating comprises the steps of placing the base material PET in an environment with the temperature of 30-80 ℃ and the humidity of 20-60% for 10-24 hours;
b, carrying out Ni metallization on the base material PET through a cold roller under the action of traction force of 2-50N in a vacuum environment;
the C implantation ion source is a pure Ni ion source with the purity of 99.99 percent, and the implantation condition is that the vacuum degree is 1 × 10-3～6×10-3Pa, injection arc pressure of 50-70V, high voltage of 6-12 kV, arc flow of 3-6 mA, and injection dosage of 1 × 1014～1×1015Ni/cm2；
D, depositing a Cu film on the surface of the substrate PET subjected to Ni metallization by a magnetic filtration ion beam technology.
2. The preparation method of the negative electrode current collector of claim 1, wherein the deposition arc source for depositing the Cu film is a Cu arc source with a purity of 99.99%, and the vacuum degree is 1 × 10-3～6×10-3Pa, deposition arc flow: 80-130A, negative bias: -50V to-350V, and the duty ratio is 10-90%.
3. The method for preparing the negative electrode current collector according to claim 1, wherein the temperature of the cold roll is controlled to be-20-0 ℃.
4. The method for preparing the negative electrode current collector of claim 1, wherein the thickness regulation of the Cu film deposition is realized by adjusting the reciprocating times of a winding system, and the winding system is cycled for 50-200 times.
5. The method of claim 1, wherein the metallized layer is formed by vacuum arc ion implantation of metal vapor into the substrate PET, and the source of metal ions used comprises but is not limited to Ti, Ni, Zr, or Cr.
6. A negative electrode current collector of a lithium battery prepared by the preparation method of any one of claims 1 to 5, wherein the negative electrode current collector comprises a substrate PET, a metallized layer and a surface copper film, the bonding strength of the surface copper film and the substrate PET is greater than 1.5N/mm, the thickness of the copper film is 3-8 μm, and the bonding strength of the Cu film exceeds 1.5N/mm and the thickness is 3-8 μm.
7. The utility model provides a preparation facilities of negative pole mass flow body, includes the casing, the entrance point of casing is provided with unreels storehouse, its characterized in that: be provided with vacuum cavity, chill roll, ion implantation system and magnetic filtration ion beam deposition system in the casing, the exit end that unreels the storehouse is provided with it is a plurality of to unreel the roller the deflector roll with the entrance connection of chill roll, the chill roll is longitudinal symmetry structure, the side of chill roll has set gradually ion implantation system and magnetic filtration ion beam deposition system are used for realizing metal steam vacuum arc ion implantation and copper film deposition.
Technical Field
The invention belongs to the technical field of material surface modification, and particularly relates to a preparation method and a device of a negative current collector.
Technical Field
With the development of times and science and technology, the application market of the lithium ion battery is continuously expanded, and the lithium ion battery becomes the mainstream of the power battery. High energy density, high safety and long life of the battery are the development directions and market demands. The current collector is an important component of the lithium battery, is an important factor influencing the charge and discharge of the battery, and has the function of collecting and outputting current generated by the active substances of the battery. A positive electrode current collector and a negative electrode current collector are included, and an aluminum foil is generally used as a positive electrode and a copper foil is used as a negative electrode.
The current mainstream copper foil in the market is mainly single-sided wool or double-sided wool, and the two-sided structure of the copper foil cannot be completely symmetrical, so that the contact resistance of active material coatings loaded on two sides is asymmetrical, the capacity of two sides of a negative electrode is not uniformly released, the impact-discharge cycle life is seriously unbalanced, and the capacity attenuation of a battery is accelerated.
In addition, the thinning of the copper foil is a trend of further energy density of the lithium battery, and the thin lithium electrolytic copper foil means smaller resistance and lighter weight, so that the processing difficulty of the copper foil is higher, and the brittle fracture property is more serious.
Disclosure of Invention
The invention discloses a method for depositing an ultrathin, high-purity and low-density copper film on the surface of a flexible substrate PET (polyethylene terephthalate) by a magnetic filtration ion beam and ion implantation composite technology. Different from the traditional method for preparing the copper foil by a rolling method or an electrolytic method, the invention realizes the preparation of the negative current collector by a Physical Vapor Deposition (PVD) technology, and effectively combines the light and high-flexibility characteristics of the flexible base material PET with the ultrathin, high-purity and low-density characteristics of the copper film prepared by the PVD technology. The negative current collector structure comprises a substrate PET, a metallization layer and a surface copper film.
The invention comprises the following steps:
a degassing and surface activation of the substrate PET: the degassing and activating comprises the steps of placing the base material PET in an environment with the temperature of 30-80 ℃ and the humidity of 20-60% for 10-24 hours;
b, carrying out Ni metallization on the base material PET through a cold roller under the action of traction force of 2-50N in a vacuum environment;
the C implantation ion source is a pure Ni ion source with the purity of 99.99 percent, and the implantation condition is that the vacuum degree is 1 × 10-3～6×10- 3Pa, injection arc pressure of 50-70V, high voltage of 6-12 kV, arc flow of 3-6 mA, and injection dosage of 1 × 1014～1×1015Ni/cm2；
D, depositing a Cu film on the surface of the substrate PET subjected to Ni metallization by a magnetic filtration ion beam technology.
Further, the deposition arc source for depositing the Cu film is a Cu arc source with the purity of 99.99 percent and the vacuum degree is 1 × 10-3～6×10-3Pa, deposition arc flow: 80-130A, negative bias: -50V to-350V, and the duty ratio is 10-90%.
Further, the temperature of the cold roller is controlled to be-20-0 ℃.
Further, the thickness regulation and control of the Cu film deposition are realized by adjusting the reciprocating times of a winding system, and the winding system is cycled for 50-200 times.
Further, the metallization layer is formed by metal vapor vacuum arc ion implantation into the substrate PET using a source of metal ions including, but not limited to, Ti, Ni, Zr, or Cr.
A negative electrode current collector of a lithium battery prepared by the preparation method of any one of claims 1 to 5, which structurally comprises a substrate PET, a metallized layer and a surface copper film, wherein the bonding strength of the surface copper film and the substrate PET is more than 1.5N/mm, the thickness of the copper film is 3 to 8 μm, the bonding strength of the Cu film is more than 1.5N/mm, and the thickness of the Cu film is 3 to 8 μm.
The utility model provides a preparation facilities of negative pole mass flow body, includes the casing, the entrance point of casing is provided with and unreels the storehouse, the exit end that unreels the storehouse is provided with it is through a plurality of to unreel the roller the deflector roll with the entrance connection of chill roll, be provided with vacuum cavity, chill roll, ion implantation system and magnetic filtration ion beam deposition system in the casing, the chill roll is longitudinal symmetry structure, the side of chill roll has set gradually ion implantation system and magnetic filtration ion beam deposition system are used for realizing metal steam vacuum arc ion implantation and copper film deposition.
The invention has the following beneficial effects:
the copper film prepared by the magnetic filtration technology can theoretically realize complete impurity filtration, the purity of deposited copper can reach 100%, the thickness of the copper film is controllable, and the ultrathin copper foil which is difficult to realize by the traditional technology can be prepared. The novel PET-based flexible copper-clad material prepared by the composite technology of magnetic filtration ion beams and ion implantation optimizes the lattice mutation of an interface by ion implantation, and effectively improves the film-substrate binding force. In addition, the technology of the invention is to deposit the copper film on the surface of the flexible PET in a winding mode, can be continuously produced, and is superior to the copper foil of the traditional rolling method or electrolytic method in weight, flexibility and durability.
Drawings
Fig. 1 is a schematic structural view of a manufacturing apparatus of a negative electrode current collector of the present invention.
Fig. 2 is a schematic view of the structure of the negative current collector of the present invention;
in the figure: 101-vacuum chamber, 102-unwinding bin, 103-unwinding roller, 104-guide roller, 105-cold roller, 106-ion implantation system, 107-magnetic filtration ion beam deposition system, 108-winding roller, 109-winding bin, 201-flexible substrate PET, 202-metallization layer, 203-Cu film
Detailed Description
The invention discloses a process flow for preparing a novel PET-based flexible copper-clad material lithium battery negative electrode current collector by using a magnetic filtration ion beam and ion implantation composite technology by taking a Ni implantation ion source and a Cu arc source as examples and combining the following implementation steps:
the device comprises a shell, wherein an unwinding bin 102 is arranged at the inlet end of the shell, an unwinding roller 103 is arranged at the outlet end of the unwinding bin 102 and is connected with the inlet end of a cold roller 105 through a plurality of guide rollers 104, a vacuum cavity, the cold roller 105, an ion implantation system 106 and a magnetic filtration ion beam deposition system 107 are arranged in the shell, the cold roller 105 is of a vertically symmetrical structure, and the ion implantation system 107 and the magnetic filtration ion beam deposition system 108 are sequentially arranged on the side edge of the cold roller 105 and used for realizing metal vapor vacuum arc ion implantation and copper film deposition.
PET degassing and surface activation:
constant temperature and humidity treatment: a roll of flexible base material PET 201 is placed at the temperature of 30-80 ℃ and the humidity of 20-60%, and degassing and activation are carried out for 10-24 hours for standby.
2. Flexible substrate PET warehousing (unwinding) 102
The PET winding drum is fixed on the unwinding roller 103, and is wound to the winding roller 108 under the action of a traction belt, so that PET warehousing is completed.
3. Metallization layer
The PET is driven to the ion implantation system 106 under the action of 2-50N traction force to start the implantation process, the implantation ion source is a pure Ni ion source with the purity of 99.99%, and the implantation condition is that the vacuum degree is 1 × 10-3～6×10-3Pa, injection arc pressure of 50-70V, high voltage of 6-12 kV, arc flow of 3-6 mA, and injection dosage of 1 × 1014～1×1015Ni/cm2。
The ion implantation system of the present invention enables simultaneous metallization of both sides of PET, as shown in figure 1. Since the Ni ions generated by the ion implantation system are accelerated at high pressure and are driven into PET, the higher energy of the Ni ions releases heat energy. In order to prevent the high-energy Ni ions from damaging the PET, the temperature of a cold roller in a winding system is between 20 ℃ below zero and 0 ℃, and a deep cooling system is arranged in a vacuum environment to further reduce the temperature.
Cu film deposition
The
The thickness regulation and control of the
The novel PET-based flexible copper-clad material lithium battery negative electrode current collector can be prepared through the steps, the current collector is bright and smooth, the flexibility is excellent, the Cu film bonding strength exceeds 1.5N/mm, and the thickness is 3-8 microns.
The novel PET-based flexible copper-clad material lithium battery negative electrode current collector film-substrate bonding strength prepared by the magnetic filtration ion beam and ion implantation composite technology exceeds 1.5N/mm, and the copper film thickness is controllable (3-8 μm).
The metallization layer is an injection buffer layer formed in a well depth region of dozens of nanometers on the surface layer of the base material by accelerating bombardment under the action of a high-voltage electric field through metal ions generated by a metal vapor ion source (MEVVA source). The MEVVA source is Ti, Ni, Zr, Cr and the like, the injection dosage is 1000-8000 mc, and the injection energy is 6-15 kV.
The metallization layer is formed by taking a metal ion source (Ti, Ni, Zr, Cr and the like) as a cathode target material by utilizing an ion injection technology, forming metal plasma by high-voltage triggering in a vacuum environment, filtering electrons in the plasma by a gate electrode to obtain metal ions, accelerating the metal ions by high voltage and injecting the metal ions into the surface of the PET, so that the insulated organic material PET is conductive, and the formed metallization layer has the function of changing lattice mismatch of the PET and a subsequently deposited copper film. A uniform metallization layer is formed by optimizing the energy of the ion implantation, the dose of the implantation, and the frequency of the implantation.
The copper film is formed by generating copper plasma by a magnetic filtration ion source and performing magnetic filtration deposition. The arc flow is 70-130A, the negative bias is 50-350V, and the processing time is 20-40 min. The surface copper film is formed by utilizing a magnetic filtration ion beam technology to form a vacuum arc through direct current triggering, a high-purity copper target is gasified and ionized to form copper ions, substances generated by the vacuum arc only contain the copper ions and also contain uncharged copper particles and liquid drops, the uncharged copper particles and the liquid drops are filtered through magnetic field deflection (30-180 degrees), and the high-purity copper ions are led out to form the copper film. Ultra-thin, high-purity and low-density copper films are formed on the surface of the flexible base material PET by optimizing parameters such as arc flow, the intensity of a deflection magnetic field, pulse negative bias, deposition time and the like.
The film-substrate bonding strength of the negative current collector of the novel PET-based flexible copper-clad material lithium battery exceeds 1.5N/mm, and the thickness is 3-8 mu m.
It should be noted that the above-mentioned embodiments are provided for further detailed description of the present invention, and the present invention is not limited to the above-mentioned embodiments, and those skilled in the art can make various modifications and variations on the above-mentioned embodiments based on the above-mentioned teachings of the present invention, and these modifications and variations fall into the protection scope of the present invention. It will be appreciated by persons skilled in the art that the foregoing detailed description is provided for the purpose of illustrating the invention and is not to be construed as limiting the invention. The scope of the invention is defined by the claims and their equivalents.
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