CN111600036A - Three-dimensional porous copper oxide modified copper foil for lithium metal battery current collector and preparation method and application thereof - Google Patents
Three-dimensional porous copper oxide modified copper foil for lithium metal battery current collector and preparation method and application thereof Download PDFInfo
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- H01M4/00—Electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H—ELECTRICITY
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- 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
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/72—Grids
- H01M4/74—Meshes or woven material; Expanded metal
- H01M4/742—Meshes or woven material; Expanded metal perforated material
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Abstract
A three-dimensional porous copper oxide modified copper foil for a lithium metal battery current collector and a preparation method and application thereof belong to the technical field of batteries. The preparation method of the three-dimensional porous copper oxide modified copper foil comprises the following steps: and (2) mixing sodium hydroxide and ammonium thiosulfate solution in proportion to obtain etching solution, then immersing the clean copper foil into the etching solution for reaction to obtain the copper foil modified by the copper oxide nanowires, respectively cleaning the copper foil by using deionized water and absolute ethyl alcohol, and then drying the copper foil in vacuum to obtain the final modified copper foil (shown in figure 4). The copper foil obtained by the invention can be used as a negative current collector of a lithium metal battery, the surface copper oxide nanowire has good electrolyte wettability and good coating performance, and can store lithium electrochemically, guide lithium metal to be deposited uniformly and inhibit the growth of lithium dendrite; a compact Solid Electrolyte Interphase (SEI) film containing lithium oxide is formed in charge-discharge cycles, the mechanical strength is good, and the side reaction of metal lithium and an electrolyte can be inhibited, so that the coulombic efficiency, the safety and the cycle life of the battery are improved.
Description
Technical Field
The invention belongs to the field of lithium metal batteries, and particularly relates to a three-dimensional porous copper oxide modified copper foil for a lithium metal battery current collector, and a preparation method and application thereof.
Background
With the coming of the 3C era, people have higher and higher requirements on the specific energy of batteries, the theoretical capacity of the currently used commercial graphite cathode is lower, and the commercial graphite cathode is difficult to greatly improve, so that the development of the next generation lithium battery system is imperative. Lithium metal is considered to be an ideal high energy density negative electrode material due to its extremely high theoretical specific capacity (3860mAh/g) and extremely low electrode potential (-3.04V vs Standard Hydrogen Electrode (SHE)). In addition, it is also Li-O2And an important component of Li-S batteries.
Compared with a graphite cathode, the lithium metal cathode can form an unstable Solid Electrolyte Interphase (SEI) with poor mechanical property in the stripping/lithium plating process, so that lithium deposition is uneven, and the side reaction of the electrolyte is increased continuously. While lithium dendrites and dead lithium are formed during battery cycling, leading to potential safety hazards and low coulombic efficiency. These factors greatly limit the practical application of lithium metal batteries.
By regulating and controlling the lithium metal cathode interface, the uniform deposition of metal lithium can be realized, the growth of lithium dendrites is inhibited, and the generation of dead lithium is reduced, so that the safety of the lithium metal battery is improved.
In recent years, a great deal of research has been conducted on the problems of lithium dendrite growth, volume expansion, and low coulombic efficiency of lithium metal batteries. An excellent modified current collector can inhibit the side reaction of metallic lithium and electrolyte and improve the coulomb efficiency. Chinese patent (CN108950570B)The preparation method of the porous copper foil for the lithium ion battery negative electrode current collector is characterized in that a mixed corrosive agent is prepared by using ferric chloride, hydrochloric acid and hexadecyl trimethyl ammonium bromide, the copper foil is soaked in the mixed corrosive agent for corrosion, and the porous copper foil is obtained, wherein the surface of the copper foil is dense and uniform in pore structure, the pore diameter of the pores is below 5 microns, and the safety of the lithium ion battery is improved. Non-patent literature (adv. mater.2016,28,6932-6939) reports: commercial copper-zinc alloy (Cu)0.64Zn0.36) Immersion in HCl and NH4And carrying out chemical dealloying in the Cl mixed solution to obtain a three-dimensional copper current collector, wherein the three-dimensional copper current collector is used in a lithium metal negative electrode battery, so that the volume expansion can be effectively relieved, and the lithium metal is guided to be uniformly deposited. The method has a certain three-dimensional structure, prolongs the cycle life of the lithium metal battery to a certain extent, but has complex preparation method, and more importantly, the copper-based material has poor affinity with the lithium metal, so that the deposition is uneven, the growth of dendrite is caused to cause potential safety hazard, and the development of the lithium metal battery is limited.
Disclosure of Invention
The invention aims to provide a three-dimensional porous copper oxide modified copper foil for a lithium metal battery current collector, and a preparation method and application thereof, aiming at the problems of complex preparation method, difficult raw material acquisition, high cost, safety and the like of the lithium metal negative current collector. The commercial copper foil current collector is modified through liquid phase etching which is strong in controllability and easy to amplify, and a three-dimensional CuO modified surface layer with a protection effect is constructed in situ, so that the performance of metal lithium can be improved. The CuO modified copper foil current collector has the advantages of lithium affinity, electrolyte wettability, guidance of uniform nucleation and deposition growth of lithium, formation of an SEI layer with excellent mechanical properties, stability of long cycle of a battery and the like, and has important significance for development of lithium metal batteries.
The technical scheme of the invention is as follows:
the three-dimensional porous copper oxide modified copper foil for the current collector of the lithium metal battery is characterized in that the surface of the modified copper foil is provided with a loose porous CuO nanowire surface layer with the thickness of 5-10 microns, and the pore diameter of pores is 0.5-1 micron.
The preparation method of the three-dimensional porous copper oxide modified copper foil for the current collector of the lithium metal battery comprises the following steps:
s1, preparing a clean copper foil substrate: wiping commercial copper foil with absolute ethyl alcohol/acetone to remove oil, then carrying out acid washing for a certain time for pretreatment, washing away residual acid liquor with deionized water and absolute ethyl alcohol, and drying at room temperature for later use;
s2, preparing an etching solution: dissolving soluble alkali in deionized water to prepare a clear alkali solution with a certain concentration, then adding an oxidant in a certain proportion into the alkali solution, stirring and cooling to obtain an etching solution for later use;
s3, etching treatment: and (4) placing the copper foil obtained in the step (S1) in the etching solution prepared in the step (S2) for chemical etching treatment, taking out after a certain time, respectively cleaning the surface etching solution with deionized water and absolute ethyl alcohol, and drying to obtain the three-dimensional porous copper oxide modified copper foil.
The copper foil in the step S1 is a commercially available double-sided photo-lithium battery copper foil, the preferred thickness is 6-12 microns, and the commercially available copper foil is low in price and is a commercialized product.
Preferably, in step S1, the acid cleaning is performed with 1-4 mol/L hydrochloric acid for 100-200S.
Preferably, in step S1, in the cleaning process, deionized water and absolute ethyl alcohol are used to clean the surface of the copper foil; and drying for 10-30 min.
Preferably, in step S2, the soluble alkali is sodium hydroxide, and the concentration of the clarified alkali solution is 2 to 4 mol/L; the oxidant is ammonium thiosulfate with the concentration of 0.1-1 mol/L; the amount ratio of the soluble alkali to the oxidant is 25-35: 1.
Preferably, in step S3, the etching process is single-sided etching, and the other side does not contact the etching solution; the etching temperature is 15-25 ℃, and the etching time is 8-12 h; the drying process is vacuum drying, the temperature is 40-60 ℃, and the time is 5-10 hours.
The invention further provides an application of the three-dimensional porous copper oxide modified copper foil, which is used for preparing a negative electrode of a composite lithium metal battery and comprises the following steps: taking a copper oxide modified copper foil as a substrate, and carrying out electrodeposition at the concentration of 1-10 mA/cm2Current densityAnd depositing lithium metal into the three-dimensional porous copper oxide framework on the surface of the copper foil to obtain the composite lithium metal battery cathode.
The invention has the advantages and beneficial effects that:
1. the invention adopts a chemical etching method, has low cost, simple manufacturing process, controllable etching degree and easy industrialization, and is beneficial to solving the problems of poor coating effect, poor performance and the like of the current plain copper foil.
2. The etching material and the copper foil used in the invention are common commercial raw materials, and the raw materials have wide sources, low cost and environmental friendliness.
3. The three-dimensional porous copper oxide modified copper foil prepared by the invention can be used as a negative current collector of a lithium metal battery, can realize uniform deposition of lithium metal, inhibits side reaction and dendritic crystal growth, effectively improves the coulombic efficiency of the battery, and prolongs the cycle life.
Drawings
FIG. 1 is a flow chart of the preparation;
FIG. 2 is a scanning electron microscope image of a commercial bifocal copper foil;
FIG. 3 is a scanning electron micrograph of the surface of a surface-porous copper foil according to example 1;
FIG. 4 is a scanning electron micrograph of a cross section of a surface porous copper foil of example 1;
FIG. 5 is a scanning electron micrograph of the surface of a surface-porous copper foil of example 2;
FIG. 6 is a surface porous copper foil XRD of example 2;
fig. 7 shows cycle performance of the lithium metal battery according to the present invention.
Detailed Description
Example 1
A preparation method of a three-dimensional porous copper oxide modified copper foil for a lithium metal battery current collector is shown in a flow chart 1 and comprises the following steps:
s1, preparing a clean commercial copper foil substrate: the copper foil used was a commercially available double-sided polished copper foil, and the results of observation under SEM are shown in fig. 2. Carrying out acid washing and oil removal on a commercial battery-grade copper foil with a double-sided light thickness of 9 microns by using 2.5mol/L hydrochloric acid solution for 150s, washing away residual acid solution by using deionized water and absolute ethyl alcohol after acid washing, and drying at room temperature for 20min for later use;
s2, preparing an etching solution: dissolving sodium hydroxide powder in deionized water to obtain a clear alkali solution, and adding ammonium thiosulfate into the alkali solution according to a ratio, wherein the concentration of the sodium hydroxide solution is 3mol/L, the concentration of the ammonium thiosulfate solution is 0.5mol/L, and the ratio is 30:1 for later use;
s3, etching treatment: and (3) carrying out chemical etching treatment on the copper foil in the step S1 by using the etching solution prepared in the step S2, controlling the temperature at 20 ℃, the time at 10h, carrying out single-side etching in the etching process, not contacting the etching solution on the other side for etching, respectively cleaning the surface of the copper foil by using deionized water and absolute ethyl alcohol after the etching is finished, and then carrying out vacuum drying for 8h at the temperature of 50 ℃ to obtain the porous copper foil.
The porous copper foil obtained in this example was observed under SEM, and the results are shown in fig. 3; as can be seen in fig. 3: the surface of the copper foil prepared by the embodiment is distributed with dense and uniform pore structures, the surface of the copper foil is provided with copper oxide nanowires and a large number of space networks, and the pore diameter of pores is between 0.5 and 1 micron.
The FIB section test was performed on the porous copper foil obtained in this example, and the result is shown in fig. 4; as can be seen in fig. 4: the thickness of the copper oxide layer on the surface of the copper foil prepared by the embodiment is 5 micrometers, the diameter of the nano copper oxide wire is 500 nanometers, the size is uniform, and the space structure is excellent.
Elemental analysis was performed on the surface porous copper foil prepared in this example, and the results are shown in table 1;
TABLE 1
| Element(s) | Line type | Apparent concentration | k ratio | wt％ | wt％Sigma | Atomic percent |
| O | K line system | 10.63 | 0.03577 | 19.26 | 0.35 | 48.65 |
| Cu | L-shaped wire system | 16.53 | 0.16533 | 80.74 | 0.35 | 51.35 |
| Total amount: | 100.00 | 100.00 |
as can be seen from table 1: the elements on the surface of the copper foil prepared in the embodiment are mainly Cu and O, and the proportion of the Cu and O is 1:1, it was confirmed that the surface component thereof was copper oxide.
Example 2
A preparation method of a three-dimensional porous copper oxide modified copper foil for a lithium metal battery current collector comprises the following steps:
s1, preparing a clean commercial copper foil substrate: carrying out acid washing and oil removal on a commercial battery-grade copper foil with a double-sided light thickness of 9 microns by using 3mol/L hydrochloric acid solution for 180s, washing away residual acid solution by using deionized water and absolute ethyl alcohol after acid washing, and drying at room temperature for 20min for later use;
s2, preparing an etching solution: dissolving sodium hydroxide powder in deionized water to obtain a clear alkali solution, and adding ammonium thiosulfate into the alkali solution according to a ratio, wherein the concentration of the sodium hydroxide solution is 4mol/L, the concentration of the ammonium thiosulfate solution is 0.8mol/L, and the ratio is 35:1 for later use;
s3, etching treatment: and (3) carrying out chemical etching treatment on the copper foil in the step S1 by using the etching solution prepared in the step S2, controlling the temperature at 20 ℃, the time at 12h, carrying out single-side etching in the etching process, not contacting the etching solution on the other side for etching, respectively cleaning the surface of the copper foil by using deionized water and absolute ethyl alcohol after the etching is finished, and then carrying out vacuum drying for 9h at the temperature of 60 ℃ to obtain the porous copper foil.
The porous copper foil obtained in this example was observed under SEM, and the results are shown in fig. 5; as can be seen from fig. 5: the copper foil prepared by the embodiment has dense and uniform pore structures distributed on the surface, and the copper foil has a large amount of space networks, dense and uniform pore structures, uniform size and excellent space structures on the surface due to the copper oxide nanosheets.
Example 3
A preparation method of a three-dimensional porous copper oxide modified copper foil for a lithium metal battery current collector comprises the following steps:
s1, preparing a clean commercial copper foil substrate: carrying out acid washing and oil removal on a commercial battery-grade copper foil with a double-sided light thickness of 9 microns by using 2mol/L hydrochloric acid solution for 120s, washing away residual acid solution by using deionized water and absolute ethyl alcohol after acid washing, and drying at room temperature for 20min for later use;
s2, preparing an etching solution: dissolving sodium hydroxide powder in deionized water to obtain a clear alkali solution, and adding ammonium thiosulfate into the alkali solution according to a ratio, wherein the concentration of the sodium hydroxide solution is 2mol/L, the concentration of the ammonium thiosulfate solution is 0.2mol/L, and the ratio is 25:1 for later use;
s3, etching treatment: and (3) carrying out chemical etching treatment on the copper foil in the step S1 by using the etching solution prepared in the step S2, controlling the temperature at 20 ℃, the time at 8h, carrying out single-side etching in the etching process, not contacting the etching solution on the other side for etching, respectively cleaning the surface of the copper foil by using deionized water and absolute ethyl alcohol after the etching is finished, and then carrying out vacuum drying for 6h at the temperature of 40 ℃ to obtain the porous copper foil.
The porous copper foil obtained in this example was subjected to XRD measurement, and the result is shown in fig. 6; as can be seen in fig. 6: the copper foil prepared in this example possessed distinct lattice peaks of copper, 43 °, 51 ° and 76 °, respectively, while peaks of copper oxide appeared at 35.6 ° and 37.2 ° positions, demonstrating that the material was a copper oxide-modified commercial copper foil.
Test example
Placing a porous copper foil framework on a lithium metal sheet with the thickness of 300 microns, and forming a composite metal lithium cathode and lithium iron phosphate (LiFePO) after discharge deposition4) Assembling the half-cell with an electrolyte of 1M lithium hexafluorophosphate (LiPF)6) Ethylene Carbonate (EC) and diethyl carbonate (DEC) (1: 1 volume ratio).
The specific discharge capacity (curve 1) and the coulombic efficiency (curve 3) of the half-cell assembled by the composite lithium metal negative electrode and the lithium iron phosphate electrode are shown in fig. 7, and it can be known from the graph that under the condition of 1C multiplying power, after 300 cycles, the measured specific capacity of the cell still remains stable, the cyclic coulombic efficiency reaches 99%, and the capacity retention rate is 96%.
And (4) conclusion: the method can realize regulation and control of the surface thickness and the pore diameter of the obtained porous copper foil by controlling the etching time, and the preparation method is simple and convenient to operate, wide in raw material source, low in cost, small in environmental pollution and suitable for industrial large-scale production.
In summary, the above embodiments are merely illustrative of the related principles and embodiments, and not restrictive, and any modifications, equivalents, improvements, etc. made without departing from the principles of the present invention are intended to be included within the scope of the present invention.
Claims (6)
1. A three-dimensional porous copper oxide modified copper foil for a lithium metal battery current collector is characterized in that: the surface of the modified copper foil is provided with a loose porous CuO nanowire surface layer with the thickness of 5-10 microns, and the pore diameter of pores is 0.5-1 micron.
2. A preparation method of a three-dimensional porous copper oxide modified copper foil for a lithium metal battery current collector at least comprises the following steps:
step 1, preparing an etching solution: dissolving soluble alkali in deionized water to obtain a clarified alkali solution, adding an oxidant into the alkali solution in proportion, stirring and cooling to obtain an etching solution for later use;
step 2, etching treatment: and (3) carrying out chemical etching treatment on the copper foil with the clean surface by using the etching solution prepared in the step (1), cleaning the surface etching solution by using deionized water and absolute ethyl alcohol after the treatment, and drying to obtain the three-dimensional porous copper oxide modified copper foil.
3. The method for preparing the three-dimensional porous copper oxide modified copper foil for the current collector of the lithium metal battery according to claim 2, wherein the surface cleaning of the copper foil substrate is further included before the etching, and the specific method is as follows: the method comprises the steps of taking a commercially available double-sided smooth lithium battery copper foil with the thickness of 6-12 microns as a raw material, wiping the commercial copper foil with absolute ethyl alcohol/acetone to remove oil, then carrying out acid washing in hydrochloric acid with the concentration of 1-4 mol/L to remove oil and a surface oxide layer for 100-200 s, then washing away residual acid liquor with deionized water and absolute ethyl alcohol, and drying at room temperature for later use.
4. The method for preparing the three-dimensional porous copper oxide modified copper foil for the current collector of the lithium metal battery as claimed in claim 2, wherein the etching solution in the step 1 is prepared by dissolving soluble alkali sodium hydroxide in deionized water to obtain a clear alkali solution, and adding ammonium thiosulfate serving as an oxidant into the alkali solution; the concentration of the sodium hydroxide solution is 2-4 mol/L; the concentration of ammonium thiosulfate is 0.1-1 mol/L; the mass ratio of the alkali to the oxidant is 25-35: 1.
5. The preparation method of the three-dimensional porous copper oxide modified copper foil for the current collector of the lithium metal battery, according to claim 2, is characterized in that the etching process in the step 2 is single-sided etching, the other side of the copper foil is not contacted with etching liquid, the etching temperature is controlled to be 15-25 ℃, the etching time is 8-12 hours, after the etching is finished, the surface of the copper foil is cleaned by deionized water and absolute ethyl alcohol respectively, and then the three-dimensional porous copper oxide modified copper foil is obtained by vacuum drying at the temperature of 40-60 ℃ for 5-10 hours.
6. The use of the three-dimensional porous copper oxide modified copper foil for the current collector of a lithium metal battery as claimed in claim 1 for the preparation of a composite lithium metal battery negative electrode comprising: the three-dimensional porous copper oxide modified copper foil for the current collector of the lithium metal battery, which is disclosed by claim 1, is used as a substrate, and the electrodeposition method is adopted to perform the electrodeposition at the concentration of 1-10 mA/cm2And depositing lithium metal into the three-dimensional porous framework on the surface of the copper oxide modified copper foil under the current density to obtain the composite lithium metal battery cathode.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112349875A (en) * | 2020-10-23 | 2021-02-09 | 四川大学 | Lithium ion battery copper-copper oxide integrated cathode based on hollow tubular three-dimensional nano porous structure and preparation method |
| CN112421050A (en) * | 2020-10-26 | 2021-02-26 | 浙江大学 | High-roughness copper foil for negative current collector of lithium ion battery and preparation method thereof |
| CN112909223A (en) * | 2021-03-10 | 2021-06-04 | 湖北大学 | Lithium ion battery cathode and preparation method and application thereof |
| CN113690435A (en) * | 2021-07-02 | 2021-11-23 | 青岛中科赛锂达新能源技术合伙企业(有限合伙) | Lithium ion secondary battery pole piece and preparation method and application thereof |
| CN114744211A (en) * | 2022-05-13 | 2022-07-12 | 南京邮电大学 | Hyperbranched oxidized porous metal negative current collector and preparation method thereof |
| CN115172761A (en) * | 2022-09-08 | 2022-10-11 | 深圳市汉嵙新材料技术有限公司 | Composite copper-based current collector and preparation method thereof, battery electrode and lithium ion battery |
| CN116190559A (en) * | 2023-05-04 | 2023-05-30 | 北京金羽新材科技有限公司 | Lithium-free negative electrode plate and preparation method and application thereof |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11167922A (en) * | 1997-12-05 | 1999-06-22 | Mitsubishi Materials Corp | Surface-treated copper foil and battery electrode using the same |
| CN101264923A (en) * | 2008-04-22 | 2008-09-17 | 华东师范大学 | CuO straw-shaped nano structure and preparation method thereof |
| CN101343079A (en) * | 2008-08-26 | 2009-01-14 | 徐斗辰 | Method for preparing cupric oxide nano-material |
| WO2017143978A1 (en) * | 2016-02-22 | 2017-08-31 | The University Of Hong Kong | Method of producing a porous crystalline material with a highly uniform structure |
| CN108110258A (en) * | 2017-12-28 | 2018-06-01 | 上海应用技术大学 | A kind of building method of copper foil surface three-dimensional structure |
| CN108428858A (en) * | 2018-04-12 | 2018-08-21 | 清华大学深圳研究生院 | A kind of lithium an- ode of stabilization |
-
2020
- 2020-06-01 CN CN202010484074.2A patent/CN111600036A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11167922A (en) * | 1997-12-05 | 1999-06-22 | Mitsubishi Materials Corp | Surface-treated copper foil and battery electrode using the same |
| CN101264923A (en) * | 2008-04-22 | 2008-09-17 | 华东师范大学 | CuO straw-shaped nano structure and preparation method thereof |
| CN101343079A (en) * | 2008-08-26 | 2009-01-14 | 徐斗辰 | Method for preparing cupric oxide nano-material |
| WO2017143978A1 (en) * | 2016-02-22 | 2017-08-31 | The University Of Hong Kong | Method of producing a porous crystalline material with a highly uniform structure |
| CN108110258A (en) * | 2017-12-28 | 2018-06-01 | 上海应用技术大学 | A kind of building method of copper foil surface three-dimensional structure |
| CN108428858A (en) * | 2018-04-12 | 2018-08-21 | 清华大学深圳研究生院 | A kind of lithium an- ode of stabilization |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112349875A (en) * | 2020-10-23 | 2021-02-09 | 四川大学 | Lithium ion battery copper-copper oxide integrated cathode based on hollow tubular three-dimensional nano porous structure and preparation method |
| CN112349875B (en) * | 2020-10-23 | 2021-08-10 | 四川大学 | Lithium ion battery copper-copper oxide integrated cathode based on hollow tubular three-dimensional nano porous structure and preparation method |
| CN112421050A (en) * | 2020-10-26 | 2021-02-26 | 浙江大学 | High-roughness copper foil for negative current collector of lithium ion battery and preparation method thereof |
| CN112909223A (en) * | 2021-03-10 | 2021-06-04 | 湖北大学 | Lithium ion battery cathode and preparation method and application thereof |
| CN113690435A (en) * | 2021-07-02 | 2021-11-23 | 青岛中科赛锂达新能源技术合伙企业(有限合伙) | Lithium ion secondary battery pole piece and preparation method and application thereof |
| CN114744211A (en) * | 2022-05-13 | 2022-07-12 | 南京邮电大学 | Hyperbranched oxidized porous metal negative current collector and preparation method thereof |
| CN114744211B (en) * | 2022-05-13 | 2024-03-29 | 南京邮电大学 | Hyperbranched oxidized porous metal negative electrode current collector and preparation method thereof |
| CN115172761A (en) * | 2022-09-08 | 2022-10-11 | 深圳市汉嵙新材料技术有限公司 | Composite copper-based current collector and preparation method thereof, battery electrode and lithium ion battery |
| CN115172761B (en) * | 2022-09-08 | 2022-11-22 | 深圳市汉嵙新材料技术有限公司 | Composite copper-based current collector, preparation method thereof, battery electrode and lithium ion battery |
| WO2024060417A1 (en) * | 2022-09-22 | 2024-03-28 | 深圳先进技术研究院 | Three-dimensional porous current collector for lithium battery, preparation method therefor and use thereof |
| CN116190559A (en) * | 2023-05-04 | 2023-05-30 | 北京金羽新材科技有限公司 | Lithium-free negative electrode plate and preparation method and application thereof |
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