LU505370B1 - Porous Polymer-coated Copper Electrode, and Preparation Method and Application Thereof - Google Patents
Porous Polymer-coated Copper Electrode, and Preparation Method and Application Thereof Download PDFInfo
- Publication number
- LU505370B1 LU505370B1 LU505370A LU505370A LU505370B1 LU 505370 B1 LU505370 B1 LU 505370B1 LU 505370 A LU505370 A LU 505370A LU 505370 A LU505370 A LU 505370A LU 505370 B1 LU505370 B1 LU 505370B1
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- Luxembourg
- Prior art keywords
- polystyrene
- polyethylene glycol
- polymer
- block
- copper electrode
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- 229920000642 polymer Polymers 0.000 title claims abstract description 54
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 37
- 239000010949 copper Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 66
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 66
- 239000011248 coating agent Substances 0.000 claims abstract description 55
- 238000000576 coating method Methods 0.000 claims abstract description 55
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 15
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 16
- 239000004793 Polystyrene Substances 0.000 claims description 16
- 229920002223 polystyrene Polymers 0.000 claims description 16
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 3
- 229910001416 lithium ion Inorganic materials 0.000 claims description 3
- 239000012459 cleaning agent Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 abstract description 26
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 18
- 238000000034 method Methods 0.000 abstract description 14
- 230000008021 deposition Effects 0.000 abstract description 11
- 210000001787 dendrite Anatomy 0.000 abstract description 3
- 229920001400 block copolymer Polymers 0.000 abstract description 2
- 239000007772 electrode material Substances 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 238000001338 self-assembly Methods 0.000 abstract description 2
- 238000009827 uniform distribution Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 11
- 238000005406 washing Methods 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
Classifications
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a porous polymer-coated copper electrode and a preparation method and application thereof, and relates to the technical field of electrode materials. The porous polymer-coated copper electrode comprises a polymer coating and a copper substrate; the polymer used is polystyrene-b-polyethylene glycol, polystyrene-b-polymethyl methacrylate or polystyrene- b-poly-4-vinylpyridine. According to the invention, a porous polymer coating with controllable aperture and uniform distribution is prepared by a simple block copolymer self-assembly method, so that continuous and uniform deposition of lithium is successfully realized, the growth of lithium dendrites is inhibited, and the cycle life of lithium metal batteries is prolonged.
Description
DESCRIPTION LU505370
Porous Polymer-coated Copper Electrode, and Preparation Method and Application
Thereof
The invention relates to the technical field of electrode materials, in particular to a porous polymer-coated copper electrode and a preparation method and application thereof.
During the electroplating/stripping process of lithium metal battery, the infinite side reaction between active lithium and electrolyte, dendrite growth, infinitely increasing volume effect and other problems lead to the rapid decline of battery capacity and the decrease of battery cycle life.
Artificial design of solid electrolyte interface (SEI) film at the electrode/electrolyte interface is the most direct control method to solve the problem of lithium metal battery, so as to improve the battery performance. The "host-free" nature of lithium negative electrode makes its volume change greatly during the cycle, which is also a main reason for the poor performance of lithium metal battery.
Therefore, it is an effective method to design a "host" as a carrier for lithium deposition.
Previous methods reported that the method with micro-nano polymer SEI film/separator/solid electrolyte can effectively improve the stability of lithium metal battery. From this, it can be seen that nano-porous channels can be used as the preferred carrier for lithium deposition and guide lithium ions to transport in the pores. However, the previous methods have the defects of complicated process and difficult to effectively control the pore size, and at the same time, it is difficult to realize industrial production.
The invention aims to provide a porous polymer-coated copper electrode, a preparation method and an application thereof, so as to solve the problems existing in the prior art, ensure the performance of a lithium metal battery and improve the cycle life.
In order to achieve the above objectives, the present invention provides the following scheme: the invention provides a porous polymer-coated copper electrode, which comprises a polymer coating and a copper substrate; the polymer coating component is polystyrene-b-polyethylene glycol, polystyrene-b-polymethyl methacrylate or polystyrene-b-poly-4-vinylpyridine.
Further, the ratio of hydrophilic block to hydrophobic block of the polymer coating component is 1-10: 1-10; specifically, in the polystyrene-b-polyethylene glycol, the ratio bE/505370 polystyrene block to polyethylene glycol block is 1: 10-10: 1; in the polystyrene-b-polymethyl methacrylate, the ratio of the polystyrene block to the polymethyl methacrylate block is 1: 10-10: 1; in the polystyrene-b-poly-4-vinylpyridine, the ratio of the polystyrene block to the poly-4- vinylpyridine block is 1:10-10:1.
Further, the thickness of the polymer coating is 80-300 nm.
The invention also provides a preparation method of the porous polymer-coated copper electrode, which comprises the following steps: dissolving the polymer in an organic solvent, and coating the obtained polymer solution on the surface of metal copper to obtain the porous polymer-coated copper electrode.
Further, the organic solvent includes toluene, chloroform, acetone, cyclohexane or acetic acid.
Further, after the polymer solution is coated, the steps of cleaning and removing hydrophilic blocks are also included.
Further, the cleaning agent used for cleaning is water or acetic acid.
The invention also provides the application of the porous polymer-coated copper electrode in lithium ion batteries.
The invention discloses the following technical effects: according to the invention, through a simple block copolymer self-assembly method, two blocks are separated in the solvent evaporation process, and then an enriched phase is washed by a selective solvent to form a porous structure, so that a porous polymer coating with controllable aperture and uniform distribution is prepared, continuous and uniform deposition of lithium is successfully realized, the growth of lithium dendrites is inhibited, and the cycle life of lithium metal batteries is prolonged.
In order to explain the embodiments of the present invention or the technical scheme in the prior art more clearly, the drawings needed in the embodiments will be briefly introduced below.
Obviously, the drawings described below are only some embodiments of the present invention, and other drawings can be obtained according to these drawings without creative work for ordinary people in the field.
Fig. 1 shows the morphology of polystyrene-b-polyethylene glycol-coated current collector prepared in Example 1 of the present invention;
Fig. 2 is a coulombic efficiency diagram of polymer-coated current collectors prepared k¥/505370
Example 1, Example 4 and Comparative Example 1 of the present invention;
Fig. 3 is a diagram of lithium deposition morphology of different electrodes; wherein A is the lithium deposition morphology of pure copper electrode in Comparative Example 1, and B is the lithium deposition morphology of porous polymer-coated electrode in Example 1.
A number of exemplary embodiments of the present invention will now be described in detail, and this detailed description should not be considered as a limitation of the present invention, but should be understood as a more detailed description of certain aspects, characteristics and embodiments of the present invention.
It should be understood that the terminology described in the present invention is only for describing specific embodiments and is not used to limit the present invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper limit and the lower limit of the range is also specifically disclosed. The intermediate value within any stated value or stated range and every smaller range between any other stated value or intermediate value within the stated range are also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded from the range.
Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention relates.
Although the present invention only describes the preferred methods and materials, any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe methods and/or materials related to the documents. In case of conflict with any incorporated document, the contents of this specification shall prevail.
It is obvious to those skilled in the art that many improvements and changes can be made to the specific embodiments of the present invention without departing from the scope or spirit of the present invention. Other embodiments will be apparent to the skilled person from the description of the invention. The description and example of that present invention are exemplary only.
The terms "including", "comprising", "having" and "containing" used in this article are all open terms, which means including but not limited to.
In the invention, the structure of polystyrene-b-polyethylene glycol is as follows: LU505370 j eA NL y im
The structure of polystyrene-b-polymethyl methacrylate is as follows:
CHI
Tr b | in i 00
GENS
7 | CH3
The structure of polystyrene-b-poly-4-vinylpyridine is as follows: ï 3 LA Ste
ES tb + r x i im
L AA
A SS
So N
Example 1
Step 1: dissolve polystyrene-b-polyethylene glycol with polystyrene block: polyethylene glycol block = 10: 1 in cyclohexane to prepare 8 mg/mL polystyrene-b-polyethylene glycol solution.
Step 2: using spin coater to spin-coat polystyrene-b-polyethylene glycol solution on the copper electrode to prepare a polystyrene-b-polyethylene glycol coating with the polymer coating thickness of 80 nm, and then washing in deionized water for 30 minutes to remove the polyethylene glycol block to obtain a current collector with the polystyrene-b-polyethylene glycol coating (the coating thickness is 80 nm).
Step 3: assemble the button battery and test the cycle performance of the battery, as follows: in a glove box filled with argon and with water and oxygen values less than 0.1 ppm, lithium tablets with a diameter of 14 mm and a thickness of 1 mm, a separator with a diameter of 18 mm (Celgard 2325), 1 mol/L of lithium bis (trifluoromethyl) sulfonyl imide, and an electrolyte of 1,3 dioxolane/ethylene glycol dimethyl ether (v/v=1:1) containing 2wt% lithium nitrate were used to assemble the button battery with model of CR2025. The diameter of the current collector with polymer coating was 16 mm. The assembly sequence is negative shell, elastic sheet, gasket, lithium sheet, interlayer, separator, porous polymer-coated copper electrode and positive shell, and th&/505370 battery is sealed by an electric packaging machine. When assembling a half batter, the lithium sheet is the working electrode and the porous polymer-coated copper electrode is the counter electrode. 5 Under the condition of current density of 1 mA/cm? and capacity of 1 mAh/cm?, it is stably circulated for 175 cycles.
The morphology of the polystyrene-b-polyethylene glycol-coated current collector prepared in Example 1 of the present invention is shown in Fig. 1.
Example 2
Step 1: dissolve polystyrene-b-polyethylene glycol with polystyrene block: polyethylene glycol block = 1: 10 in cyclohexane to prepare 8 mg/mL polystyrene-b-polyethylene glycol solution.
Step 2: using spin coater to spin-coat polystyrene-b-polyethylene glycol solution on the copper electrode to prepare a polystyrene-b-polyethylene glycol coating with the polymer coating thickness of 80 nm, and then washing in deionized water for 30 minutes to remove the polyethylene glycol block to obtain a current collector with the polystyrene-b-polyethylene glycol coating (the coating thickness is 80 nm).
Step 3: assemble the button battery and test the cycle performance of the battery. The assembling steps of button battery are the same as those in Example 1.
Under the condition of current density of 1 mA/cm? and capacity of 1 mAh/cm?, it is stably circulated for 200 cycles.
Example 3
Step 1: dissolve polystyrene-b-polyethylene glycol with polystyrene block: polyethylene glycol block = 1: 1 in chloroform to prepare 8 mg/mL polystyrene-b-polyethylene glycol solution.
Step 2: using spin coater to spin-coat polystyrene-b-polyethylene glycol solution on the copper electrode to prepare a polystyrene-b-polyethylene glycol coating with the polymer coating thickness of 80 nm, and then washing in deionized water for 30 minutes to remove the polyethylene glycol block to obtain a current collector with the polystyrene-b-polyethylene glycol coating (the coating thickness is 80 nm).
Step 3: assemble the button battery and test the cycle performance of the battery. The assembling steps of button battery are the same as those in Example 1.
Under the condition of current density of 1 mA/cm? and capacity of 1 mAh/cm?, it is stabl§J505370 circulated for 135 cycles.
Example 4
Step 1: dissolve polystyrene-b-polyethylene glycol with polystyrene block: polyethylene glycol block = 10: 1 in chloroform to prepared 8 mg/mL polystyrene-b-polyethylene glycol solution.
Step 2: using spin coater to spin-coat polystyrene-b-polyethylene glycol solution on the copper electrode to prepare a polystyrene-b-polyethylene glycol coating with the polymer coating thickness of 80 nm, and then washing in deionized water for 30 minutes to remove the polyethylene glycol block to obtain a current collector with the polystyrene-b-polyethylene glycol coating (the coating thickness is 80 nm).
Step 3: assemble the button battery and test the cycle performance of the battery. The assembling steps of button battery are the same as those in Example 1.
Under the condition of current density of 1 mA/cm? and capacity of 1 mAh/cm?, it is stably circulated for 130 cycles.
Example 5
Step 1: dissolve polystyrene-b-polyethylene glycol with polystyrene block: polyethylene glycol block = 1: 1 in cyclohexane to prepare 8 mg/mL polystyrene-b-polyethylene glycol solution.
Step 2: using spin coater to spin-coat polystyrene-b-polyethylene glycol solution on the copper electrode to prepare a polystyrene-b-polyethylene glycol coating with the polymer coating thickness of 80 nm, and then washing in deionized water for 30 minutes to remove the polyethylene glycol block to obtain a current collector with the polystyrene-b-polyethylene glycol coating (the coating thickness is 80 nm).
Step 3: assemble the button battery and test the cycle performance of the battery. The assembling steps of button battery are the same as those in Example 1.
Under the condition of current density of 1 mA/cm? and capacity of 1 mAh/cm?, it is stably circulated 180 cycles.
Example 6
Step 1: dissolve polystyrene-b-polyethylene glycol with polystyrene block: polyethylene glycol block = 1: 10 in chloroform to prepare 8 mg/mL polystyrene-b-polyethylene glycol solution.
Step 2: using spin coater to spin-coat polystyrene-b-polyethylene glycol solution on the copper electrode to prepare a polystyrene-b-polyethylene glycol coating with the polymer coatih&505370 thickness of 80 nm, and then washing in deionized water for 30 minutes to remove the polyethylene glycol block to obtain a current collector with the polystyrene-b-polyethylene glycol coating (the coating thickness is 80 nm).
Step 3: assemble the button battery and test the cycle performance of the battery. The assembling steps of button battery are the same as those in Example 1.
Under the condition of current density of 1 mA/cm? and capacity of 1 mAh/cm?, it is stably circulated for 125 cycles.
Example 7
Step 1: dissolve polystyrene-b-polyethylene glycol with polystyrene block: polyethylene glycol block = 1: 10 in cyclohexane to prepare 16 mg/mL polystyrene-b-polyethylene glycol solution.
Step 2: using spin coater to spin-coat polystyrene-b-polyethylene glycol solution on a copper electrode to prepare a polystyrene-b-polyethylene glycol coating with polymer coating thickness of 120 nm, and then washing in deionized water for 30 minutes to remove the polyethylene glycol block to obtain a current collector with the polystyrene-b-polyethylene glycol coating (the coating thickness is 120 nm).
Step 3: assemble the button battery and test the cycle performance of the battery. The assembling steps of button battery are the same as those in Example 1.
Under the condition of current density of 1 mA/cm? and capacity of 1 mAh/cm?, it is stably circulated for 180 cycles.
Example 8
Step 1: dissolve polystyrene-b-polyethylene glycol with polystyrene block: polyethylene glycol block = 1: 10 in cyclohexane to prepare 25 mg/mL polystyrene-b-polyethylene glycol solution.
Step 2: using spin coater to spin-coat polystyrene-b-polyethylene glycol solution on a copper electrode to prepare a polystyrene-b-polyethylene glycol coating with polymer coating thickness of 300 nm, and then washing in deionized water for 30 minutes to remove the polyethylene glycol block to obtain a current collector with the polystyrene-b-polyethylene glycol coating (the coating thickness is 300 nm).
Step 3: assemble the button battery and test the cycle performance of the battery. The assembling steps of button battery are the same as those in Example 1. LU505370
Under the condition of current density of 1 mA/cm? and capacity of 1 mAh/cm? it is stably circulated for 150 cycles.
Example 9
Step 1: dissolve polystyrene-b-polymethyl methacrylate with polystyrene block: polymethyl methacrylate block = 1: 1 in cyclohexane to prepare 8 mg/mL polystyrene-b-polymethyl methacrylate solution.
Step 2: using spin coater to spin-coat polystyrene-b-polymethyl methacrylate solution on the copper electrode to prepare a polystyrene-b-polymethyl methacrylate coating with polymer coating thickness of 80 nm, and then washing in acetic acid for 30 minutes to remove the polymethyl methacrylate block to obtain a current collector with the polystyrene-b-polymethyl methacrylate coating (with a coating thickness of 80 nm).
Step 3: assemble the button battery and test the cycle performance of the battery. The assembling steps of button battery are the same as those in Example 1.
Under the condition of current density of 1 mA/cm? and capacity of 1 mAh/cm?, it is stably circulated for 165 cycles.
Example 10
Step 1: dissolve polystyrene-b-poly-4-vinylpyridine with polystyrene block: poly-4- vinylpyridine block = 1: 1 in chloroform to prepare 8 mg/mL polystyrene-b-poly-4-vinylpyridine solution.
Step 2: using spin coater to spin-coat a polystyrene-b-poly-4-vinylpyridine solution on a copper electrode to prepare a polystyrene-b-poly-4-vinylpyridine coating with the polymer coating thickness of 80nm, and then washing in deionized water for 30 minutes to remove the poly-4- vinylpyridine block to obtain a current collector with the polystyrene-b-poly-4-vinylpyridine coating (the coating thickness is 80 nm)
Step 3: assemble the button battery and test the cycle performance of the battery. The assembling steps of button battery are the same as those in Example 1.
Under the condition of current density of 1 mA/cm? and capacity of 1 mAh/cm?, it is stably circulated for 160 cycles.
Comparative example 1
The button battery was assembled with copper electrode (bare copper) as the current collector,
and the cycle performance of the battery was tested. The assembly steps of the button battery wek&}505370 the same as in Example 1.
Under the condition of current density of 1 mA/cm? and capacity of 1 mAh/cm?, it is stably circulated for 60 cycles.
Fig. 2 is a coulombic efficiency diagram of polymer-coated current collectors prepared in
Example 1, Example 4 and Comparative Example 1. It can be seen from Fig. 2 that the structure of block polymer has a very obvious influence on the cycle stability of the battery. The coating formed without porous structure only slightly improves the cycle stability of the battery, but the cycle stability of the battery is greatly improved after the porous structure is formed. Thus, the invention provides a method for preparing the electrode coating of the battery with high cycle stability.
Fig. 3 is a diagram of lithium deposition morphology of different electrodes, where A is the lithium deposition morphology of pure copper electrode in Comparative Example 1, and B is the lithium deposition morphology of porous polymer-coated electrode in Example 1. It can be seen that the invention successfully realizes the continuous and uniform deposition of lithium by using the porous polymer coating.
The above-mentioned embodiments only describe the preferred mode of the invention, and do not limit the scope of the invention. Under the premise of not departing from the design spirit of the invention, various modifications and improvements made by ordinary technicians in the field to the technical scheme of the invention shall fall within the protection scope determined by the claims of the invention.
Claims (8)
1. A porous polymer-coated copper electrode, comprising a polymer coating and a copper substrate; the polymer coating component is polystyrene-b-polyethylene glycol, polystyrene-b- polymethyl methacrylate or polystyrene-b-poly-4-vinylpyridine.
2. The porous polymer-coated copper electrode according to claim 1, wherein in the polystyrene-b-polyethylene glycol, the ratio of polystyrene block to polyethylene glycol block is 1: 10-10: 1; in the polystyrene-b-polymethyl methacrylate, the ratio of the polystyrene block to the polymethyl methacrylate block is 1: 10-10: 1; in the polystyrene-b-poly-4-vinylpyridine, the ratio of the polystyrene block to the poly-4-vinylpyridine block is 1:10-10:1.
3. The porous polymer-coated copper electrode according to claim 1, wherein the thickness of the polymer coating is 80-300 nm.
4. A preparation method of the porous polymer-coated copper electrode according to any one of claims 1-3, characterized by comprising the following steps: dissolving a polymer in an organic solvent to obtain a polymer solution, and coating the obtained polymer solution on the surface of metal copper to obtain a porous polymer-coated copper electrode.
5. The preparation method according to claim 4, wherein the organic solvent comprises toluene, chloroform, acetone, cyclohexane or acetic acid.
6. The preparation method according to claim 4, wherein after the polymer solution is coated, the step of cleaning is further comprised.
7. The preparation method according to claim 6, wherein the cleaning agent used for cleaning is water or acetic acid.
8. An application of the porous polymer-coated copper electrode according to any one of claims 1-3 in lithium ion batteries.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210382931.7A CN114678515B (en) | 2022-04-12 | 2022-04-12 | Porous polymer coating copper electrode and preparation method and application thereof |
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| Publication Number | Publication Date |
|---|---|
| LU505370B1 true LU505370B1 (en) | 2024-01-09 |
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| LU505370A LU505370B1 (en) | 2022-04-12 | 2023-03-14 | Porous Polymer-coated Copper Electrode, and Preparation Method and Application Thereof |
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| Country | Link |
|---|---|
| CN (1) | CN114678515B (en) |
| LU (1) | LU505370B1 (en) |
| WO (1) | WO2023197806A1 (en) |
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| CN114678515B (en) * | 2022-04-12 | 2024-05-31 | 珠海中科先进技术研究院有限公司 | Porous polymer coating copper electrode and preparation method and application thereof |
| CN115838557B (en) * | 2022-09-23 | 2023-12-08 | 上海交通大学 | Preparation method of high-molecular functional coating for metal negative electrode |
| CN120388990B (en) * | 2025-04-29 | 2025-11-21 | 广东工业大学 | A hydrophobic-zinc-loving interface protective layer for high-rate zinc metal anodes, its preparation and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN102130323B (en) * | 2011-02-12 | 2013-02-13 | 中南大学 | Lithium ion battery film cathode containing porous polymer elastomer and preparation method thereof |
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| EP3278383A4 (en) * | 2015-03-30 | 2018-09-05 | Solidenergy Systems | Composite coating systems and methods for lithium metal anodes in battery applications |
| US10576431B2 (en) * | 2016-08-15 | 2020-03-03 | Pall Corporation | Fluoropolymers and membranes comprising fluoropolymers (II) |
| KR101984723B1 (en) * | 2016-09-07 | 2019-05-31 | 주식회사 엘지화학 | Porous current collector for lithium electrode and lithium electrode comprising the same |
| ES2873258T3 (en) * | 2016-10-12 | 2021-11-03 | Prologium Tech Co Ltd | Lithium metal electrode and its associated lithium metal battery |
| WO2019104365A1 (en) * | 2017-11-30 | 2019-06-06 | Nano-Nouvelle Pty Ltd | Current collector |
| CN108777307A (en) * | 2017-12-29 | 2018-11-09 | 上海其鸿新材料科技有限公司 | A kind of lithium battery collector conductive coating |
| CN110098409B (en) * | 2018-01-30 | 2021-11-02 | 宁德时代新能源科技股份有限公司 | A secondary battery current collector and a secondary battery using the same |
| CN111656584A (en) * | 2018-01-31 | 2020-09-11 | 日立化成株式会社 | Negative electrode active material for lithium ion secondary battery, negative electrode for lithium ion secondary battery, and lithium ion secondary battery |
| CN109161047B (en) * | 2018-09-03 | 2021-07-09 | 江苏科技大学 | Preparation method of polystyrene or polystyrene copolymer porous permeable membrane |
| CN112216818B (en) * | 2019-07-11 | 2022-02-08 | 比亚迪股份有限公司 | Lithium ion battery cathode, preparation method thereof, lithium ion battery and battery module |
| CN110364739A (en) * | 2019-07-29 | 2019-10-22 | 中国科学院宁波材料技术与工程研究所 | A kind of current collector and its preparation method and application |
| CN110474053B (en) * | 2019-08-21 | 2021-03-23 | 厦门大学 | Lithium metal negative electrode material, preparation method and application |
| CN111129504A (en) * | 2020-01-17 | 2020-05-08 | 清华大学深圳国际研究生院 | Preparation method of modified current collector, electrode plate and lithium battery |
| WO2021212428A1 (en) * | 2020-04-23 | 2021-10-28 | 宁德时代新能源科技股份有限公司 | Lithium metal battery and preparation method therefor, and apparatus comprising lithium metal battery and negative electrode plate |
| CN112968210A (en) * | 2021-02-24 | 2021-06-15 | 珠海中科先进技术研究院有限公司 | Zwitterionic liquid gel electrolyte and preparation method and application thereof |
| CN114220947B (en) * | 2021-12-09 | 2024-04-02 | 厦门大学 | Lithium metal battery negative electrode, current collector, preparation method of current collector and battery |
| CN114678515B (en) * | 2022-04-12 | 2024-05-31 | 珠海中科先进技术研究院有限公司 | Porous polymer coating copper electrode and preparation method and application thereof |
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2022
- 2022-04-12 CN CN202210382931.7A patent/CN114678515B/en active Active
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2023
- 2023-03-14 LU LU505370A patent/LU505370B1/en active
- 2023-03-14 WO PCT/CN2023/081320 patent/WO2023197806A1/en not_active Ceased
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| WO2023197806A1 (en) | 2023-10-19 |
| CN114678515A (en) | 2022-06-28 |
| CN114678515B (en) | 2024-05-31 |
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