Microtexture porous multilayer structure composite current collector
By designing a microtextured porous multilayer composite current collector on the negative electrode current collector for solid-state lithium-ion batteries, the problems of corrosion and excessive lithium dendrite growth were solved, and the charging rate and corrosion resistance were improved.
Patent Information
- Application Number
- CN202423099685.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Utility models(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-16
- Publication Date
- 2025-12-16
- Estimated Expiration
- 2034-12-16
AI Technical Summary
Existing lithium-ion solid-state batteries face problems such as corrosion, excessive lithium dendrite growth, and slow charging rates in their negative electrode current collectors.
A composite current collector with a microtextured porous multilayer structure is designed, including a porous polymer membrane, a chemically plated metal layer, a microtextured copper layer, and a corrosion-resistant lithiophilic layer. These layers are uniformly deposited on the inner and outer surfaces of the porous polymer membrane to form a composite current collector.
It improves the surface area and corrosion resistance of the current collector, suppresses the abnormal growth of lithium dendrites, achieves a larger interfacial contact area and better corrosion resistance, and meets the corrosion resistance requirements of lithium-ion batteries.
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Figure CN223680131U_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The utility model belongs to lithium ion battery field especially relates to a micro -textured porous multilayer structure composite current collector. BACKGROUND
[0002] Lithium ion batteries are becoming an important part of future energy fields as an efficient and environmentally friendly energy storage device. In the future, the main development direction of lithium ion battery technology is high safety, high energy density and low cost. In order to achieve this goal, researchers are continuously exploring new battery materials and structural designs to further develop lithium ion battery technology. In various new battery technology fields, lithium-free anode batteries, especially solid-state lithium-free anode batteries, have become an important frontier position to break through battery endurance anxiety and safety hazards. Compared with traditional lithium ion batteries, lithium-free anode batteries directly plate limited lithium from the cathode to the current collector during charging and discharging, which puts new requirements on the current collector material, mainly including: (1) high electronic conductivity and low resistance; (2) excellent chemical and electrochemical stability to resist corrosion and side reactions of electrolyte, especially sulfide system electrolyte; (3) excellent mechanical strength; (4) lower lithium compound binding energy, which is conducive to the nucleation of lithium ions and the transition growth of lithium dendrites; (5) lower metal resource consumption.
[0003] To meet the requirements of lithium-free anode batteries for current collector materials, researchers have tested lithium deposition on a series of metal substrates and found that the substrate with the largest crystal mismatch with lithium metal exhibits the highest nucleation overpotential. Lithium metal has a body-centered cubic (BCC) crystal structure, so it is beneficial to deposit on substrates with a BCC structure. In addition, lithium is also beneficial to deposit on lithiumophilic materials that partially solubilize or alloy with lithium metal. Related research supports the development of existing electrolytic copper foil-based current collector materials. Secondly, to achieve higher energy density and faster charging rate, several possible methods for current collector design have emerged, mainly including: (1) completely replacing copper as a current collector; (2) coating a modification layer on copper; (3) porous structure.
[0004] At the same time, the existing negative electrode current collector for silicon-carbon anode batteries, solid-state batteries and other battery technologies also faces the problems of corrosion, excessive growth of lithium dendrites and slow charging rate, and there is an urgent need to develop new current collector technology for high-performance batteries. Utility model content
[0005] The utility model aims to provide a micro -textured porous multilayer structure composite current collector to solve the problems of corrosion, excessive growth of lithium dendrites and slow charging rate of the negative electrode current collector for solid-state batteries.
[0006] The utility model discloses the following technical scheme: A kind of micro-texture porous multilayer structure composite current collector, comprising: porous polymer membrane located in the middle, and the chemical plating metal layer located on both sides of porous polymer membrane, micro-texture metal copper layer located on the outer side of two chemical plating metal layers, corrosion-resistant lithium-philic layer located on the outer side of two micro-texture metal copper layers;
[0007] Two chemical plating metal layers, micro-texture metal copper layer, corrosion-resistant lithium-philic layer are sequentially and uniformly deposited on the inner surface and outer surface of the pores of porous polymer membrane;
[0008] The thickness of the porous polymer membrane is 4-13 μm;Pore size is 1.5-30 μm;Porosity is 30-60%;
[0009] The thickness of the composite current collector is 5.2-15 μm, pore size is 1.7-28 μm;Porosity is 25-45%;
[0010] The inner surface and outer surface of the pores of the composite current collector are attached with raised texture;The particle size of the raised texture is 0.05-0.1 μm.
[0011] Further, the porous polymer membrane is PET film, PE film, PP film or PSF film.
[0012] Further, the chemical plating metal layer is copper, nickel or copper-nickel layer.
[0013] Further, the corrosion-resistant lithium-philic layer is Ni-B, Ni-Sn, Ni-Zn, Ni-Ag or Ni-Graphite.
[0014] The utility model discloses the beneficial effects are:
[0015] The utility model discloses through setting up porous polymer membrane and micro-texture metal copper layer to improve the surface area of current collector, not only improves the charge-discharge current, also plays the role of inhibiting the abnormal growth of lithium dendrite;Through setting up chemical plating metal layer to realize the metallization of the outer surface of porous polymer membrane, realize low cost and high yield metallization;Through setting up corrosion-resistant lithium-philic layer to improve the corrosion resistance and lithium affinity of current collector, meet the corrosion resistance requirement of lithium ion battery represented by sulfide solid-state battery, and play the role of promoting the nucleation of lithium dendrite and inhibiting the abnormal growth of lithium dendrite;
[0016] The surface area of the composite current collector prepared by the utility model is large, and it is more corrosion-resistant;Compared with electrolytic copper foil or composite copper foil current collector, it has larger interface contact area and better corrosion resistance; BRIEF DESCRIPTION OF DRAWINGS
[0017] Figure 1 It is the schematic view of the composite current collector of the utility model embodiment 1;
[0018] Figure 2 This is a backlight image of the composite current collector in Embodiment 1 of this utility model;
[0019] Figure 3 This is a cross-sectional microstructure diagram of the composite current collector of Embodiment 1 of this utility model;
[0020] Figure 4 This is a surface morphology diagram of the composite current collector in Embodiment 1 of this utility model;
[0021] Figure 5 This is a pore morphology diagram of the composite current collector in Embodiment 1 of this utility model. Detailed Implementation
[0022] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments.
[0023] This utility model discloses a microtextured porous multilayer composite current collector, such as... Figure 1 As shown, it includes: a porous polymer membrane located in the middle, chemically plated metal layers located on both sides of the porous polymer membrane, a microtextured copper layer located outside the two chemically plated metal layers, and a corrosion-resistant lithium-loving layer located outside the two microtextured copper layers.
[0024] Two electroless metal plating layers, a microtextured copper layer, and a corrosion-resistant lithiophilic layer are sequentially and uniformly deposited on the inner and outer surfaces of the porous polymer membrane. The porous polymer membrane has a thickness of 4–13 μm, a pore size of 3–30 μm, and a porosity of 30–60%. The composite current collector has a thickness of 5.2–15 μm, a pore size of 1.7–28 μm, and a porosity of 25–45%. The inner and outer surfaces of the composite current collector are covered with raised textures. The particle size of the raised textures is 0.05–0.1 μm. The composite current collector has a tensile strength ≥200 MPa, an elongation ≥10%, and a resistivity ≤20 mΩ.
[0025] The porous polymer membrane is a PET membrane, PE membrane, PP membrane, or PSF membrane.
[0026] The electroless metal plating layer is copper, nickel, or a copper-nickel layer.
[0027] The corrosion-resistant lithiophilic layer is Ni-B, Ni-Sn, Ni-Zn, Ni-Ag, or Ni-Graphite.
[0028] The preparation method of this utility model is as follows: using a porous polymer membrane as a template for a composite current collector, chemically plated metal layers are deposited on both sides of the membrane. During deposition, a chemically plated metal layer is deposited on the outside of the porous polymer membrane using a colloidal palladium or colloidal copper catalyst. Then, a micro-textured copper layer and a corrosion-resistant lithiophilic layer are prepared by electroplating.
[0029] Example 1
[0030] In this example, a PET porous polymer film with a thickness of 13 μm, a pore size of 30 μm and a porosity of 30% was used as the base film. First, the base film was metallized using colloidal copper, and a 0.1 μm chemical plating metal layer was deposited on the surface of the base film using a chemical plating method. Then, a micro-textured metal copper layer with a thickness of 0.8 μm was prepared using an electroplating method. Finally, a Ni-B layer with a thickness of 0.1 μm was prepared using an electroplating method, thereby obtaining a micro-textured porous multi-layer structure composite current collector with a thickness of 15 μm, a pore size of 28 μm, a porosity of 26.1%, and a protruding texture particle size of 0.1 μm. According to GB / T 29847-2013, the tensile strength of the composite current collector was 225 MPa, the elongation was 12.5%, and the resistivity was 15 mΩ.
[0031] The method for preparing the composite current collector of this example comprises:
[0032] The film was immersed in a 0.1 vol.% 3-aminopropyltrimethoxysilane acetone solution, and then high-temperature drying was performed at 125°C for 5 min to form a siliceous layer. Then, the surface-modified PET porous polymer film was irradiated with ultraviolet light with a wavelength of 254 nm for 1 min.
[0033] The surface-modified PET porous polymer film was subjected to colloidal copper activation. The solution was selected to be: CuCl2 (0.05 M / L), Na3C6H5O7 (0.1 M / L), DMAB (0.1 M / L), and H3BO3 (0.1 M / L), and the pH was adjusted to 5 with NaOH. Activation was performed at room temperature for 10 min.
[0034] The PET porous polymer film subjected to colloidal copper activation was subjected to chemical copper plating. The plating solution was selected to be: copper sulfate 10 g / L, potassium sodium tartrate 20 g / L, sodium hydroxide 10 g / L, and formaldehyde 10 mL / L. The sample was removed after 2 min, washed and dried to obtain a porous polymer film with a chemical plating metal layer.
[0035] The porous polymer film with a chemical plating metal layer was subjected to electroplating to obtain a micro-textured metal copper layer. The plating solution was selected to be: copper sulfate 250 g / L, sulfuric acid 50 g / L, chloride ion 50 ppm, sodium tungstate 30 ppm, SH110 50 ppm, temperature 40°C, cathode current density 2 A / dm 2 , and the sample was removed after 1.5 min to obtain a porous polymer film with a chemical plating metal layer and a micro-textured metal copper layer.
[0036] The porous polymer film with the chemical plated metal layer and the micro-textured metal copper layer is electroplated with a Ni-B corrosion-resistant lithium-philic layer, and the plating solution is selected as follows: nickel sulfate 250 g / L, nickel chloride 40 g / L, DMAB 5 g / L, boric acid 5 g / L, sodium dodecyl sulfate 0.1 g / L, temperature 50 ℃, cathode current density 30 g / L 5 A / dm 2 , and the composite current collector is obtained after being taken out after 0.5 min.
[0037] From Figure 1 it can be seen that the composite current collector is composed of a porous polymer film, a chemical plated metal copper layer, a micro-textured metal copper layer, and a corrosion-resistant lithium-philic layer. Figure 2 and Figure 3 it can be seen that the composite current collector has a large number of micro-porous structures. Figure 4 From Figure 5 it can be seen that the composite current collector has a protruding texture attached to the inner surface and the outer surface of the pores.
[0038] Example 2
[0039] In this example, a PE porous polymer film with a thickness of 4 μm, a pore size of 3.0 μm, and a porosity of 60% is used as the base film. First, the film is metallized using colloidal palladium, and then a 0.1 μm chemical plated metal layer is deposited on the surface of the film using chemical plating. Then, a 0.4 μm micro-textured metal copper layer is prepared using electroplating. Finally, a 0.1 μm Ni-Graphite layer is prepared using electroplating, obtaining a micro-textured porous multi-layer structure composite current collector with a thickness of 5.2 μm, a pore size of 1.8 μm, a porosity of 25%, and a protruding texture particle size of 0.05 μm. According to GB / T29847-2013, the tensile strength of the composite current collector is 310 MPa, the elongation is 14.5%, and the resistivity is 19 mΩ.
[0040] The preparation method of the composite current collector of this example includes:
[0041] The PE porous polymer film is cleaned with sulfuric acid with a concentration of 4 wt.%, obtaining a clean PE porous polymer film.
[0042] The PE porous polymer film after surface pickling is subjected to surface colloidal palladium activation, and the solution is selected as follows: SnCl21.5 g / L, HCl solution 6%, colloidal palladium 0.5%, treatment temperature 30 ℃, treatment time 1.0 min, and then the colloidal palladium is dissolved using a 10% concentration hydrochloric acid solution, the treatment temperature is 40 ℃, and the treatment time is 1.0 min, so that the palladium is exposed to become a catalytically active center.
[0043] The PE porous polymer film activated by colloidal palladium is subjected to electroless nickel plating, and a plating solution is selected: 30 g / L of nickel chloride, 0.5 g / L of sodium borohydride, 60 g / L of ethylenediamine, 40 g / L of sodium hydroxide, and 3 g / L of sodium fluoride; the sample is taken out after 2 min, cleaned and dried, and a porous polymer film with an electroless plated metal layer is obtained.
[0044] The porous polymer film with the electroless plated metal layer is subjected to electroplating of a micro-textured copper layer, and a plating solution is selected: 150 g / L of copper sulfate, 100 g / L of sulfuric acid, 50 ppm of chloride ions, 30 ppm of sodium molybdate, a temperature of 40°C, and a cathode current density of 1 A / dm 2 ; the sample is taken out after 1.5 min to obtain a porous polymer film with the electroless plated metal layer and the micro-textured copper layer.
[0045] A Ni-B corrosion-resistant lithium-philic layer is electroplated on the porous polymer film with the electroless plated metal layer and the micro-textured copper layer, and a plating solution is selected: 250 g / L of nickel sulfate, 40 g / L of nickel chloride, 5 g / L of DMAB, 30 g / L of boric acid, 0.1 g / L of sodium dodecyl sulfate, and 0.5 g / L of Graphite; a temperature is 50°C, and a cathode current density is 5 A / dm 2 ; the sample is taken out after 0.5 min to obtain a composite current collector.
[0046] Example 3
[0047] In this example, a PSF porous polymer film with a thickness of 10 μm, a pore size of 10 μm, and a porosity of 50% is used as a base film. First, the film is metallized by colloidal palladium, and then a 0.1 μm electroless plated metal layer is deposited on the surface of the film by electroless plating. Then, a 1.0 μm micro-textured copper layer is prepared by electroplating. Finally, a 0.1 μm Ni-Sn layer is prepared by electroplating to obtain a micro-textured porous multilayer structure composite current collector with a thickness of 12.4 μm, a pore size of 7.6 μm, a porosity of 30%, and a protruding texture particle size of 0.1 μm. According to GB / T 29847-2013, the tensile strength of the composite current collector is 276 MPa, the elongation is 13.5%, and the resistivity is 14 mΩ.
[0048] The preparation method of the composite current collector of this example includes:
[0049] The PSF porous polymer film is cleaned with 4 wt.% sulfuric acid to obtain a clean PSF porous polymer film.
[0050] The acid-washed PSF porous polymer film is subjected to surface colloidal palladium activation, and the selected solution is SnCl21.5 g / L, HCl solution 6%, colloidal palladium 0.5%, the treatment temperature is 35°C, and the treatment time is 1.5 min, and then a 10% concentration hydrochloric acid solution is used to remove the colloid, the treatment temperature is 35°C, and the treatment time is 1.5 min, so that the palladium is exposed to become a catalytically active center.
[0051] The PE porous polymer film subjected to colloidal palladium activation is subjected to electroless copper-nickel plating, and the selected plating solution is copper sulfate 15 g / L, potassium sodium tartrate 60 g / L, sodium hydroxide 10 g / L, nickel chloride 4 g / L, and formaldehyde 15 mL / L, and the sample is taken out after 2 min, washed and dried to obtain a porous polymer film with an electroless plated metal layer.
[0052] The porous polymer film with an electroless plated metal layer and a micro-textured metal copper layer is subjected to electroplated metal copper layer, and the selected plating solution is copper sulfate 150 g / L, sulfuric acid 100 g / L, chloride ion 50 ppm, sodium molybdate 30 ppm, and titanium sulfate 50 ppm, the temperature is 40°C, and the cathode current density is 3.5 A / dm 2 , and the sample is taken out after 3.0 min to obtain a porous polymer film with an electroless plated metal layer and a micro-textured metal copper layer.
[0053] The porous polymer film with an electroless plated metal layer and a micro-textured metal copper layer is subjected to electroplated Ni-Sn corrosion-resistant lithium-friendly layer, and the selected plating solution is nickel sulfate 80 g / L, stannous chloride 10 g / L, DMAB, boric acid 30 g / L, and sodium dodecyl sulfate 0.1 g / L, the temperature is 45°C, and the cathode current density is 5 A / dm 2 , and the sample is taken out after 1.0 min to obtain a composite current collector.
[0054] Example 4
[0055] In this embodiment, a PE porous polymer film with a thickness of 8 μm, a pore size of 10 μm and a porosity of 60% is used as a base film. First, the film is metallized using colloidal copper, and then a 0.1 μm electroless plated metal layer is deposited on its surface using electroless plating method. Then, a 0.4 μm micro-textured metal copper layer is prepared by electroplating method. Finally, a 0.2 μm Ni-Zn layer is prepared by electroplating method. Thus, a micro-textured porous multi-layer structure composite current collector with a thickness of 9.4 μm, a pore size of 8.6 μm, a porosity of 45%, and a protruding texture particle size of 0.1 μm is obtained. According to GB / T 29847-2013, the tensile strength of the composite current collector is 210 MPa, the elongation is 10.5%, and the resistivity is 20 mΩ.
[0056] The preparation method of the composite current collector of this embodiment comprises:
[0057] The film was immersed in a 0.1 vol.% solution of 3-aminopropyltrimethoxysilane in acetone, and then high-temperature dried at 125°C for 5 min to form a siliceous layer. Further, the surface-modified PE porous polymer film after immersion and high-temperature drying was irradiated with ultraviolet light of a wavelength of 254 nm for 1 min.
[0058] The surface-modified PE porous polymer film was subjected to surface colloidal copper activation, and the solution was selected as follows: CuCl2(0.05 M / L), Na3C6H5O7(0.1 M / L), DMAB(0.1 M / L), and H3BO3(0.1 M / L), and the pH was adjusted to 5 with NaOH. The activation was performed at room temperature for 10 min.
[0059] The porous polymer film after surface colloidal copper activation was subjected to electroless copper plating, and the plating solution was selected as follows: copper sulfate 15 g / L, potassium sodium tartrate 30 g / L, sodium hydroxide 15 mL / L, and formaldehyde 15 mL / L. The sample was taken out after 1.5 min, washed and dried to obtain a porous polymer film with an electroless plated metal layer.
[0060] The porous polymer film with the electroless plated metal layer was subjected to electroplating of a micro-textured copper metal layer, and the plating solution was selected as follows: copper sulfate 250 g / L, sulfuric acid 50 g / L, chloride ion 50 ppm, collagen 20 ppm, SPS 50 ppm, temperature 40°C, cathode current density 5 A / dm 2 , and the sample was taken out after 1.0 min to obtain a porous polymer film with an electroless plated metal layer and a micro-textured copper metal layer.
[0061] A Ni-Zn corrosion-resistant lithium-philic layer was electroplated on the porous polymer film with the electroless plated metal layer and the micro-textured copper metal layer, and the plating solution was selected as follows: nickel sulfate 150 g / L, zinc sulfate 50 g / L, ammonium sulfate 20 g / L, sodium sulfate 50 g / L, boric acid 20 g / L, and sodium dodecyl sulfate 0.1 g / L, pH 3, temperature 50°C, cathode current density 5 A / dm 2 , and the sample was taken out after 0.5 min to obtain a composite current collector.
[0062] Comparative Example 1
[0063] In this comparative example, a PET polymer film with a thickness of 13 μm and without openings was used as the base film. First, the film was metallized using colloidal palladium, and then a 0.1 μm electroless plated copper layer was deposited on the surface of the film using an electroless plating method, and a 0.9 μm metal copper layer was prepared using an electroplating method to obtain a composite copper foil current collector.
[0064] The method for preparing the current collector of this example includes:
[0065] The PE porous polymer film is cleaned by using sulfuric acid with a concentration of 4wt.%, and a clean PE porous polymer film is obtained.
[0066] The PE porous polymer film after surface pickling is activated by surface colloidal palladium, and the solution is selected as follows: SnCl21.5g / L, HCl solution 6%, colloidal palladium 0.5%, the treatment temperature is 30°C, and the treatment time is 1.0min, and then the colloidal solution is dissolved by using 10% concentration hydrochloric acid solution, the treatment temperature is 40°C, and the treatment time is 1.0min, so that the palladium is exposed to become a catalytically active center.
[0067] The PE porous polymer film after colloidal copper activation is electroless plated with copper, and the plating solution is selected as follows: 15g / L copper sulfate, 30g / L sodium potassium tartrate, 15g / L sodium hydroxide, 15mL / L formaldehyde, the sample is taken out after 1.5min, cleaned and dried, and a porous polymer film with a chemical plated copper layer is obtained.
[0068] The porous polymer film with a chemical plated copper layer is electroplated with a copper layer, and the plating solution is selected as follows: copper sulfate 150g / L, sulfuric acid 100g / L, chloride ion 50ppm, SPS 50ppm, collagen 30ppm, HEC 50ppm, temperature 40°C, cathode current density 4A / dm 2 , and a composite copper foil current collector is obtained after 1.5min.
[0069] Comparative Example 2
[0070] In this example, a titanium cathode is selected as the substrate, and an electrolytic copper foil with a thickness of 8μm is prepared by electroplating.
[0071] The electrolytic copper foil preparation method of this example comprises:
[0072] The titanium cathode is polished by using sandpaper with a mesh size of not less than 1500, and a smooth titanium surface is obtained. The titanium is electroplated with a copper layer, and the plating solution is selected as follows: copper sulfate 80g / L, sulfuric acid 180g / L, chloride ion 50ppm, SPS 30ppm, collagen 20ppm, HEC 80ppm, temperature 55°C, cathode current density 20A / dm 2 , and the electrolytic copper foil is obtained after 3.0min.
[0073] Table 1
[0074] Sample Mass per area Surface area Corrosion resistance Lithiophilic Example 1 ★★★★★ ★★★★★ ★★★★★ ★★★★★ Example 2 ★★★★★ ★★★★ ★★★★★ ★★★★★ Example 3 ★★★★★ ★★★★★ ★★★★★ ★★★★★ Example 4 ★★★★★ ★★★★ ★★★★★ ★★★★★ Comparative Example 1 ★★★★★ ★★ ★ ★ Comparative Example 2 ★ ★★ ★ ★
[0075] Note: the more, the better the performance. Among them, GB / T29847-2013 test unit area mass; according to YY / T1154-2009 test surface area; according to GB / T 24196-2009 test corrosion resistance; according to JY / T 0584-2020 test whether lithium.
[0076] The above merely describes preferred embodiments of the present application and is not intended to limit the present application, and any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims
1. A microtextured porous multilayer composite current collector, characterized in that, include: The porous polymer membrane located in the middle, the electroless metal plating layers located on both sides of the porous polymer membrane, the microtextured copper metal layer located outside the two electroless metal plating layers, and the corrosion-resistant lithium-loving layer located outside the two microtextured copper metal layers. The two electroless metal layers, the microtextured copper layer, and the corrosion-resistant lithiophilic layer are sequentially and uniformly deposited on the inner and outer surfaces of the porous polymer membrane. The porous polymer membrane has a thickness of 4–13 μm, a pore size of 3–30 μm, and a porosity of 30–60%. The composite current collector has a thickness of 5.2–15 μm, a pore size of 1.7–28 μm, and a porosity of 25–45%. The composite current collector has raised textures attached to the inner and outer surfaces of the pores; the particle size of the raised textures is 0.05-0.1 μm.
2. The microtextured porous multilayer composite current collector according to claim 1, characterized in that, The porous polymer membrane is a PET membrane, PE membrane, PP membrane, or PSF membrane.
3. The microtextured porous multilayer composite current collector according to claim 1, characterized in that, The electroless metal plating layer is copper, nickel, or a copper-nickel layer.
4. The microtextured porous multilayer composite current collector according to claim 1, characterized in that, The corrosion-resistant lithiophilic layer is Ni-B, Ni-Sn, Ni-Zn, Ni-Ag, or Ni-Graphite.