KR-20260065478-A - Negative current collector for zinc ion battery, manufacturing method thereof and zinc ion battery comprising the same

Abstract

The present invention relates to a negative electrode current collector for a zinc-ion battery, a method for manufacturing the same, and a zinc-ion battery including the same. More specifically, the negative electrode current collector for a zinc-ion battery according to the present invention can prevent side reactions such as hydrogen evolution, corrosion, and dendritic growth of zinc by forming a carbon nanotube derivative-based protective film layer on the negative electrode current collector, and can significantly improve the electrochemical stability and interfacial stability of the electrode-electrolyte interface. Furthermore, a thin and uniform protective film layer can be formed through a simple manufacturing process and can be made large in area. Moreover, by applying this to a zinc-ion battery as a negative electrode current collector, it has the advantages of excellent charge-discharge efficiency, long lifespan, and rapid charging.

Inventors

• 이상영
• 김대우
• 김원영
• 손아현
• 권오찬

Assignees

• 연세대학교 산학협력단

Dates

Publication Date

20260508

Application Date

20250523

Priority Date

20241029

Claims (20)

1. cathode current collector; and A negative electrode current collector for a zinc-ion battery comprising: a protective film layer located on the negative electrode current collector and comprising a three-dimensional porous scaffold structure containing a carbon nanotube derivative.
2. A negative current collector for a zinc-ion battery according to claim 1, wherein the negative current collector is one or more selected from the group consisting of copper foil, graphite foil, carbon fiber, zinc foil, titanium, and stainless steel.
3. A negative current collector for a zinc-ion battery, wherein, in claim 1, the carbon nanotube derivative is a graphene nanoribbon or a graphene oxide nanoribbon.
4. A negative current collector for a zinc-ion battery according to claim 1, wherein the protective film layer has a thickness of 10 to 300 nm.
5. In paragraph 1, the negative current collector is copper foil, and The above carbon nanotube derivative is a graphene oxide nanoribbon, and The above protective film layer is a negative current collector for a zinc-ion battery having a thickness of 40 to 120 nm.
6. A zinc-ion battery comprising: a negative current collector of claim 1; a negative electrode located on the protective film layer of the negative current collector; an anode; and a separator located between the negative electrode and the anode.
7. A zinc-ion battery further comprising: a negative current collector of claim 1; a positive electrode; and a separator located between the protective film layer of the negative current collector and the positive electrode.
8. A zinc-ion battery according to claim 6 or 7, wherein the anode is a material selected from manganese or vanadium-based oxide, Prussian blue-based material, spinel-structured oxide, organic material and Chevral-phase complex, halogen material, and sulfur-based material.
9. In claim 6 or 7, the zinc-ion battery further comprises an electrolyte for a zinc-ion battery injected into the separator, and The above electrolyte for a zinc-ion battery comprises a solvent and a salt, and The above solvent is water or an organic solvent, or a mixture thereof, and The above salt includes zinc salt, and The above zinc salt is a zinc-ion battery comprising one or more anions selected from the group consisting of CF₃SO₃⁻ , Cl⁻ , Br⁻ , I⁻ , CH₃COO⁻ , NO₃⁻ , BF₄⁻ , ClO₄⁻ , SO₄²⁻ , FSI⁻ , PF₆⁻ , and TFSI⁻ .
10. In claim 9, the electrolyte for the zinc-ion battery additionally comprises one or more selected from lithium salt, magnesium salt, sodium salt, aluminum salt, and calcium salt, and The above-described aqueous-organic composite electrolyte for a zinc-ion battery is a zinc-ion battery that further comprises one or more additives selected from film-forming additives, surface adsorption additives, and organic solvent additives.
11. A zinc-ion battery according to claim 7, wherein the anode further comprises a negative electrode active material.
12. A zinc-ion battery according to claim 11, wherein the negative electrode active material is one or more selected from the group consisting of zinc powder, zinc oxide, and zinc calcium.
13. A device comprising a zinc-ion battery according to claim 6 or 7, wherein the device is selected from any one of a communication device, a transportation device, and an energy storage device.
14. Step of manufacturing a carbon nanotube derivative; A step of preparing a coating solution comprising the above carbon nanotube derivative and solvent; A step of applying the coating solution onto a cathode current collector; and A step of drying the applied coating solution to form a protective film layer comprising a three-dimensional porous scaffold structure containing a carbon nanotube derivative; A method for manufacturing a negative current collector for a zinc-ion battery comprising
15. In claim 14, the step of manufacturing the carbon nanotube derivative is A step of preparing a dispersion by dispersing carbon nanotubes in an acidic solvent; and A method for manufacturing a negative current collector for a zinc-ion battery, further comprising the step of reacting the above dispersion and an oxidizing agent to produce a carbon nanotube derivative.
16. A method for manufacturing a negative electrode current collector for a zinc-ion battery, wherein, in claim 15, the carbon nanotube is one or more selected from the group consisting of single-walled carbon nanotubes, double-walled carbon nanotubes, and multi-walled carbon nanotubes.
17. A method for manufacturing a negative current collector for a zinc-ion battery according to claim 15, wherein the acid solvent is one or more selected from the group consisting of sulfuric acid, exothermic sulfuric acid, potassium permanganate, chlorosulfonic acid, fluorosulfonic acid, and trifluoromethanesulfonic acid.
18. A method for manufacturing a negative current collector for a zinc-ion battery, wherein, in claim 15, the oxidizing agent is one or more selected from the group consisting of permanganate, ironate, osmate, ruthenate, chlorate, hypochlorite, nitrate, osmium tetroxide, ruthenium tetroxide, and lead dioxide.
19. A method for manufacturing a negative current collector for a zinc-ion battery, wherein, in claim 15, the mixing ratio of the dispersion and the oxidizing agent is 1:0.1 to 1:100 by weight.
20. A method for manufacturing a negative current collector for a zinc-ion battery according to claim 14, wherein the solvent is one or more selected from the group consisting of water, isopropyl alcohol (IPA), ethanol (EtOH), acetone, N-methyl-2-pyrrolidone (NMP), and dimethylformamide (DMF).

Description

Negative current collector for zinc ion battery, manufacturing method thereof and zinc ion battery comprising the same The present invention relates to a negative electrode current collector for a zinc-ion battery, a method for manufacturing the same, and a zinc-ion battery including the same. With the advent of the carbon neutrality era, global environmental regulations are intensifying worldwide, and the eco-friendly secondary battery business is garnering significant attention. While lithium-ion batteries currently lead the market, they face challenges such as high material and production costs, as well as safety concerns regarding the ignition and explosion risks associated with flammable organic electrolytes. Consequently, eco-friendly, low-cost zinc batteries are attracting interest as they utilize abundant natural materials and offer high safety. However, zinc metal used as a cathode corrodes in water-based electrolytes and generates hydrogen gas. Furthermore, during charging and discharging, the zinc metal grows into sharp dendritic crystals and forms a passivation film that prevents ions from passing through, which leads to problems such as reduced battery lifespan and efficiency. As a solution to these problems, the fabrication of a protective film that limits direct contact between water and zinc metal is attracting attention. Recently, various material-based protective films, such as porous organic frameworks, polymers, and carbon-based materials, have been proposed, but their practical application is limited due to complex synthesis and fabrication processes under high temperature and high pressure conditions, high costs, and difficulties in producing thin and uniform protective films and scaling up to large areas. Figure 1 is a diagram comparing a conventional zinc battery negative electrode and a negative electrode using a negative electrode current collector for a zinc-ion battery according to the present invention. FIG. 2 is a schematic diagram showing a method for manufacturing a negative electrode current collector for a zinc-ion battery according to the present invention. Figure 3 is a photograph showing the results of the solvent dispersibility evaluation for MWNT and GONR, which are the starting materials of Example 1 according to the present invention, in NMP, DMF, H₂O , IPA, EtOH, and Acetone solvents. FIG. 4 shows the GONR-Cu prepared in Example 1 according to the present invention This shows the SEM and EDS analysis results of the cathode current collector. Figure 5 is a photograph of the GONR-Cu cathode current collector manufactured in Example 1 according to the present invention using a slot die coater. Figure 6 is a graph of the Coulomb efficiency according to the number of cycles of a Zn||GONR-Cu battery and a Zn||p-Cu battery manufactured using the GONR-Cu negative current collector of Example 1 and the p-Cu negative current collector of Comparative Example 1, respectively, according to the present invention. FIG. 7 is a graph of the specific capacity and Coulomb efficiency over 3,000 cycles for the Zn@GONR-Cu||CVO cell of Example 3 and the Zn@p-Cu||CVO cell of Comparative Example 3 according to the present invention. FIG. 8 is a graph of the specific capacity and Coulomb efficiency over 150 cycles for the GONR-Cu||Zn x CVO anode-free cell of Example 4 and the p-Cu||Zn x CVO anode-free cell of Comparative Example 4 according to the present invention. The present invention will be described in more detail below with reference to one embodiment. The present invention relates to a negative electrode current collector for a zinc-ion battery, a method for manufacturing the same, and a zinc-ion battery including the same. As explained above, various material-based protective films, such as porous organic frameworks, polymers, and carbon-based materials, have been proposed to limit direct contact between water and zinc metal. However, their practical application has been limited due to complex synthesis and fabrication processes under high temperature and high pressure conditions, high costs, and difficulties in producing thin and uniform protective films and scaling up to large areas. Accordingly, the present invention manufactures a negative electrode current collector for a zinc-ion battery by forming a carbon nanotube derivative-based protective film layer on the negative electrode current collector, thereby preventing side reactions such as hydrogen evolution, corrosion, and dendritic growth of zinc, and significantly improving the electrochemical stability and interfacial stability of the electrode-electrolyte interface. Furthermore, a thin and uniform protective film layer can be formed through a simple manufacturing process, and large-area fabrication is possible. In addition, by applying the negative electrode current collector for a zinc-ion battery according to the present invention to a zinc-ion battery, there are advantages such as excellent charge-discharge efficiency,