CN114242956B - Polymer negative electrode protective layer and preparation method and application thereof - Google Patents

Polymer negative electrode protective layer and preparation method and application thereof Download PDF

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CN114242956B
CN114242956B CN202111390102.5A CN202111390102A CN114242956B CN 114242956 B CN114242956 B CN 114242956B CN 202111390102 A CN202111390102 A CN 202111390102A CN 114242956 B CN114242956 B CN 114242956B
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lithium
negative electrode
stirring
protective layer
polymer negative
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CN114242956A (en
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崔志明
罗飘
李威
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South China University of Technology SCUT
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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
    • H01M4/13—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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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

Abstract

The invention belongs to the technical field of electrochemical energy, and discloses a polymer negative electrode protective layer, a preparation method and application thereof; according to the invention, a lithium source and a polystyrene sulfonic acid solution are mixed and stirred to obtain a gel solution 1; adding N-methyl pyrrolidone into the gel solution 1, and stirring to obtain gel solution 2; adding poly (vinylidene fluoride-co-hexafluoropropylene) and solid thermoplastic polyurethane rubber into the gel solution 2, and uniformly stirring to obtain a gel solution 3; and (3) coating the gel liquid 3 on the pole piece, and drying the pole piece to obtain the polymer negative electrode protective layer. And carrying out lithium precipitation operation on the polymer negative electrode protective layer to obtain the metal lithium electrode. The preparation method of the polymer negative electrode protective layer has the advantages of simplicity, convenience in control, high yield, easiness in industrialization and the like. The prepared metallic lithium negative electrode plate with the high-toughness and fast ion conduction interface transmission layer has good electrochemical performance in the application aspect of lithium metal batteries.

Description

Polymer negative electrode protective layer and preparation method and application thereof
Technical Field
The invention belongs to the technical field of electrochemical energy, and particularly relates to a polymer negative electrode protective layer, and a preparation method and application thereof.
Background
With the continuous development of the energy industry, the demand of human beings for high energy density of energy storage devices is also increasing. Efficient energy storage and conversion are the motive power for technological development, and the appearance of batteries can help us to more efficiently and conveniently utilize energy. Since the last century, various battery forms have been commercially available, such as: lead-acid batteries, nickel-cadmium batteries, nickel-hydrogen batteries, lithium ion batteries, and the like. The appearance of lithium ion batteries changes the life style of people and promotes the rapid development of the fields of portable cameras, mobile phones, notebook computers, electric automobiles and the like.
However, despite lithiumIon batteries have evolved rapidly, but the energy density of these commercial batteries has grown slowly. In the past 150 years, the energy density of the battery was only 40 Wh.kg from the past lead-acid battery -1 Improving the current lithium ion battery to 200 Wh.kg -1 . Such growth rates are far from meeting the needs of people for energy. As the actual energy density of graphite negative electrodes in lithium ion batteries gradually approaches its theoretical limit, more efficient electrode materials are urgently needed to meet the emerging demands for high-end energy storage device development.
Lithium metal negative electrode has extremely high theoretical capacity (3860 mAh.g -1 ) And the lowest (negative) potential (-3.04 Vvs standard hydrogen electrode) are widely considered to be the most promising lithium ion negative electrode materials, and have received great attention from researchers. Currently, lithium metal batteries using lithium metal as a negative electrode mainly include: lithium-sulfur, lithium-air and lithium-oxide batteries, all of which exhibit very high theoretical energy densities (lithium-air battery: 3500 Wh-kg) -1 2600 Wh.kg lithium-sulfur cell -1 1000-1500 Wh.kg of lithium-oxide battery -1 . Therefore, a lithium metal battery using lithium metal as a negative electrode is likely to become a next-generation energy storage battery. However, these metallic lithium batteries have serious safety problems (lithium dendrite growth) and are difficult to stably recycle. Lithium dendrite growth can cause short circuiting of the battery, which in turn can cause thermal runaway, triggering the risk of ignition and even explosion. This problem directly leads to the failure of lithium metal secondary batteries to realize commercial applications. Since the commercial use of lithium ion batteries, most lithium metal battery products have been abandoned by the market. However, as a negative electrode material having an extremely high energy density, research into metallic lithium has never been stopped by researchers. In recent years, various emerging strategies have been developed to inhibit lithium dendrite growth of metallic lithium negative electrodes, thereby improving the safety and service life of batteries in hopes of their ultimate practical application.
The interface transmission layer is used as a protective layer of the metal lithium cathode, so that the side reaction with the electrolyte in the metal lithium deposition process can be reduced, and the growth of lithium dendrites can be effectively inhibited. (D.Luo, L.Zheng, Z.Zhang, M.Li, Z.Chen, R.Cui, Y.Shen, G.Li, R.Feng, S.Zhang, G.Jiang, L.Chen, A.Yu, X.Wang, nat.Commun.2021,12,186.) however, ion transport rate and ion transport uniformity during metal lithium deposition are critical for uniform metal lithium deposition, and at the same time, due to the volume expansion during metal lithium deposition and the tendency to undergo irreversible side reactions with the electrolyte, the research on the metal lithium interfacial transport layer is not sufficient at present. Therefore, the material of the lithium metal anode interface transmission layer needs to be studied more intensively.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a preparation method of a high-toughness and fast-ion-conduction polymer negative electrode protection layer, which aims to regulate and control the ion transmission speed of the surface of a current collector, limit the growth range of metal lithium and inhibit the formation of metal lithium dendrites.
The invention prepares the metal lithium composite negative electrode by designing and constructing the fast ion transmission layer.
According to the property characteristics of the ion interface transmission layer, the polymer negative electrode protection layer with high toughness and fast ion conduction characteristics is prepared by utilizing the material containing polystyrene sulfonic acid, vinylidene fluoride-co-hexafluoropropylene and thermoplastic polyurethane for the first time, and the composite metal lithium negative electrode is prepared.
The object of the invention is achieved by at least one of the following technical solutions.
A preparation method of a high-toughness and fast-ion-conduction polymer negative electrode protection layer comprises the following steps:
(1) Mixing a lithium source with a polystyrene sulfonic acid solution, and stirring to obtain gel liquid 1;
(2) Adding N-methyl pyrrolidone (NMP) into the gel liquid 1 in the step (1), and stirring to obtain gel liquid 2;
(3) Adding poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) and solid thermoplastic polyurethane rubber (TPU) into the gel solution 2 in the step (2), and uniformly stirring to obtain gel solution 3;
(4) And (3) coating the gel liquid 3 in the step (3) on a pole piece, and drying the pole piece to obtain the polymer negative electrode protective layer.
Preferably, the polystyrene sulfonic acid solution in the step (1) has a mass percentage concentration of 5% -40%; the polystyrene sulfonic acid solution is a solution obtained by uniformly mixing polystyrene sulfonic acid and water.
Further preferably, the polystyrene sulfonic acid solution has a mass percentage concentration of 30%;
preferably, the molar ratio of the lithium source to polystyrene sulfonic acid of step (1) is (1:1) - (3:1);
further preferably, the molar ratio of the lithium source to polystyrene sulfonic acid is 1:1;
preferably, the lithium source in step (1) is LiCl, liOH, li 2 CO 3 、LiF、LiNO 3 More than one of LiTFSI and LiFSI;
further preferably, the lithium source is LiOH H 2 O。
Preferably, the stirring treatment in the step (1) is carried out for 30-90min at normal temperature.
Further preferably, the stirring treatment is performed for 60 minutes.
Preferably, the volume ratio of the N-methyl pyrrolidone in the step (2) to the gel solution 1 in the step (1) is (5:1) - (20:1);
further preferably, the volume ratio of the N-methyl pyrrolidone to the gel solution 1 in the step (1) is 10:1;
preferably, the stirring treatment in the step (2) is performed for 30-90min.
Further preferably, the stirring treatment is performed for 60 minutes.
Preferably, the mass ratio of poly (vinylidene fluoride-co-hexafluoropropylene) to solid thermoplastic polyurethane rubber in step (3) is (1:10) - (10:1);
further preferably, the mass ratio of the poly (vinylidene fluoride-co-hexafluoropropylene) to the solid thermoplastic polyurethane rubber is 2:1;
preferably, the mass ratio of the total mass of the poly (vinylidene fluoride-co-hexafluoropropylene) and the solid thermoplastic polyurethane rubber in the step (3) to the gel solution 1 in the step (1) is (1:1) - (10:1).
Further preferably, the mass ratio of the total mass of the poly (vinylidene fluoride-co-hexafluoropropylene) and the solid thermoplastic polyurethane rubber to the gel solution 1 in the step (1) is 9:1.
Preferably, the stirring in the step (3) is carried out at normal temperature, and the stirring time is 6-20h.
Further preferably, the stirring time is 12 hours.
Preferably, the coating treatment in the step (4) is coating by using a coater with a diameter of 5-30 μm;
further preferably, the coating treatment is coating with a 25 μm coater;
preferably, the temperature of the drying treatment in the step (4) is 30-90 ℃, and the drying time is 3-12h.
Further preferably, the temperature of the drying treatment is 50 ℃ and the drying time is 6 hours.
The polymer negative electrode protective layer prepared by the preparation method is prepared.
The application of the polymer negative electrode protective layer in preparing a metal lithium electrode.
Preferably, the polymer negative electrode protective layer is subjected to lithium precipitation operation to obtain the metal lithium electrode.
Further preferably, the lithium sinking operation is a lithium sinking operation performed by assembling a polymer negative electrode protection layer in a button cell.
The metal lithium anode with the high-toughness and fast-ion-conduction polymer anode protective layer can be directly used as a metal lithium anode.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the high-toughness and fast-ion-conduction polymer negative electrode protective layer and the metal lithium negative electrode prepared by the method can effectively inhibit the generation of metal dendrites and greatly reduce side reactions of the metal lithium and electrolyte. The method is easy to synthesize and good in repeatability, and the obtained electrode material can be directly used as a metal lithium battery without dendrite and with high coulombic efficiency.
Drawings
FIG. 1 is a polarization curve of a metallic lithium electrode prepared in example 1;
FIG. 2 is a graph showing the impedance test of the metallic lithium electrode prepared in example 1 before and after polarization;
fig. 3 is a cycle chart of a lithium symmetric battery of the metallic lithium electrode prepared in example 1;
FIG. 4 is an SEM test chart of the electrode surface of a metallic lithium electrode prepared in example 1;
FIG. 5 is a polarization curve of a metallic lithium electrode prepared in example 2;
FIG. 6 is a graph showing the impedance test of the metallic lithium electrode prepared in example 2 before and after polarization;
fig. 7 is a cycle chart of a lithium symmetric battery of the metallic lithium electrode prepared in example 2;
FIG. 8 is an SEM test chart of the electrode surface of a metallic lithium electrode prepared in example 2;
FIG. 9 is a polarization curve of the metallic lithium electrode prepared in example 3;
FIG. 10 is a graph showing the impedance test of the metallic lithium electrode prepared in example 3 before and after polarization;
FIG. 11 is a cycle chart of a lithium symmetric battery of the metallic lithium electrode prepared in example 3;
FIG. 12 is an SEM test chart of the electrode surface of a metallic lithium electrode prepared in example 3;
FIG. 13 is a polarization curve of the metallic lithium electrode prepared in example 4;
FIG. 14 is a graph showing the impedance test of the metallic lithium electrode prepared in example 4 before and after polarization;
fig. 15 is a cycle chart of a lithium symmetric battery of the metallic lithium electrode prepared in example 4;
fig. 16 is an SEM test chart of the electrode surface of the lithium metal electrode prepared in example 4.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but are not intended to limit the practice and protection of the invention. It should be noted that the following processes, if not specifically described in detail, can be realized or understood by those skilled in the art with reference to the prior art. The reagents or apparatus used were not manufacturer-specific and were considered conventional products commercially available.
Example 1
A preparation method of a high-toughness and fast-ion-conduction polymer negative electrode protection layer and a metal lithium electrode comprises the following steps:
1mol of a 30wt.% polystyrene sulfonic acid solution and 1mol of LiOH were weighed, stirred at room temperature for 1h until the reaction was complete, 3.5mL of NMP was added, stirring was continued at room temperature for 30min until the reaction was complete and a hydrogel solution was formed. Then 6mol of PVDF-HFP are added to the solution and stirring is continued for 12 hours, after stirring evenly, 3mol of TPU is added and stirring is continued for 6 hours. After the treatment is finished, the obtained slurry is coated on a copper foil, the thickness of a coater is set to be 30 mu m, and then the coated pole piece is placed in an oven for drying treatment, wherein the drying condition is 60 ℃ for 6 hours. And then assembling the obtained pole piece in an R2032 button cell for lithium precipitation operation, and finally obtaining the metal lithium electrode with high toughness and fast ion conduction artificial SEI (negative electrode protection layer). As shown in fig. 1, 2 and 3, the metallic lithium anode material obtained according to the electrochemical test has lower resistance and higher ion migration number, and shows excellent reversible use of metallic lithium in a metered lithium symmetric battery; SEM images showed that the ion conducting layer was very flat, uniform on the edge surface of the pole piece (as shown in fig. 4).
Example 2
A preparation method of a high-toughness and fast-ion-conduction polymer negative electrode protection layer and a metal lithium electrode comprises the following steps:
1mol of a 30wt.% polystyrene sulfonic acid solution and 1mol of LiOH were weighed, stirred at room temperature for 1h until the reaction was complete, 3.5mL of NMP was added, stirring was continued at room temperature for 30min until the reaction was complete and a hydrogel solution was formed. Then 4.5mol of PVDF-HFP are added to the solution and stirring is continued for 6 hours, after stirring, 4.5mol of TPU is added and stirring is continued for 6 hours. After the treatment is finished, the obtained slurry is coated, the thickness of the coater is set to be 30 mu m, and the coated pole piece is placed in an oven for drying treatment under the drying condition of 60 ℃ for 6 hours. And then assembling the obtained pole piece in an R2032 button cell for lithium precipitation operation, and finally obtaining the metal lithium electrode with the high-toughness and fast ion conduction interface transmission layer. As shown in fig. 5, 6 and 7, the metallic lithium anode material obtained according to the electrochemical test has lower resistance and higher ion migration number, and shows excellent reversible use of metallic lithium in the metered lithium symmetric battery; SEM images showed that the ion conducting layer was very flat, uniform on the edge surface of the pole piece (as shown in fig. 8).
Example 3
A preparation method of a high-toughness and fast-ion-conduction polymer negative electrode protection layer and a metal lithium electrode comprises the following steps:
1mol of a 30wt.% polystyrene sulfonic acid solution and 1mol of LiOH were weighed, stirred at room temperature for 1h until the reaction was complete, 3.5mL of NMP was added, stirring was continued at room temperature for 30min until the reaction was complete and a hydrogel solution was formed. Then 3mol of PVDF-HFP are added to the solution and stirring is continued for 6 hours, after stirring evenly, 6mol of TPU is added and stirring is continued for 6 hours. After the treatment is finished, the obtained slurry is coated, the thickness of the coater is set to be 30 mu m, and the coated pole piece is placed in an oven for drying treatment under the drying condition of 60 ℃ for 6 hours. And then assembling the obtained pole piece in an R2032 button cell for lithium precipitation operation, and finally obtaining the metal lithium electrode with the high-toughness and fast ion conduction interface transmission layer. As shown in fig. 9, 10 and 11, the metallic lithium anode material obtained according to the electrochemical test has a low resistance and a high ion migration number, and shows excellent reversible use of metallic lithium in a metered lithium symmetric battery; SEM images showed that the ion conducting layer was very flat, uniform on the edge surface of the pole piece (as shown in fig. 12).
Example 4
A preparation method of a polymer negative electrode protective layer and a metal lithium electrode comprises the following steps:
4.5mol of PVDF-HFP was added to 3.5mL of NMP and stirring continued at room temperature for 30 minutes until complete reaction and formation of the hydrogel solution. Then, after stirring uniformly, 4.5mol of TPU was added and stirring was continued for 6 hours. After the treatment is finished, the obtained slurry is coated, the thickness of the coater is set to be 30 mu m, and the coated pole piece is placed in an oven for drying treatment under the drying condition of 60 ℃ for 6 hours. And then assembling the obtained pole piece in an R2032 button cell for lithium precipitation operation, and finally obtaining the metal lithium electrode with the high-toughness and fast ion conduction interface transmission layer. As shown in fig. 13, 14 and 15, the metallic lithium anode material obtained according to the electrochemical test has higher resistance and lower ion migration number, and shows poor reversible use of metallic lithium in the metered lithium symmetric battery; SEM images showed non-uniformity of the ion conducting layer at the edge surface of the pole piece (as shown in fig. 16).
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.

Claims (9)

1. The preparation method of the polymer negative electrode protective layer is characterized by comprising the following steps of:
(1) Mixing a lithium source with a polystyrene sulfonic acid solution, and stirring to obtain a gel solution 1; the mass percentage concentration of the polystyrene sulfonic acid solution is 5% -40%;
(2) Adding N-methyl pyrrolidone into the gel liquid 1 in the step (1), and stirring to obtain gel liquid 2;
(3) Adding poly (vinylidene fluoride-co-hexafluoropropylene) and solid thermoplastic polyurethane rubber into the gel liquid 2 obtained in the step (2), and uniformly stirring to obtain gel liquid 3; the mass ratio of the poly (vinylidene fluoride-co-hexafluoropropylene) to the solid thermoplastic polyurethane rubber is (1:10) - (10:1); the mass ratio of the total mass of the poly (vinylidene fluoride-co-hexafluoropropylene) to the solid thermoplastic polyurethane rubber to the gel solution 1 in the step (1) is (1:1) - (10:1);
(4) And (3) coating the gel liquid 3 in the step (3) on a pole piece, and drying the pole piece to obtain the polymer negative electrode protective layer.
2. The method of claim 1, wherein the molar ratio of lithium source to polystyrene sulfonic acid in step (1) is (1:1) - (3:1);
the lithium source is LiCl, liOH, li 2 CO 3 、LiF、LiNO 3 More than one of LiTFSI and LiFSI;
the stirring treatment time in the step (1) is 30-90min, and the temperature is normal temperature.
3. The method according to claim 1, wherein the volume ratio of the N-methylpyrrolidone in step (2) to the gel liquid 1 in step (1) is (5:1) - (20:1);
the stirring treatment time in the step (2) is 30-90min.
4. The method according to claim 1, wherein the stirring in the step (3) is performed at room temperature for 6 to 20 hours.
5. The method according to claim 1, wherein the coating treatment in the step (4) is coating with a coater of 5 to 30 μm;
the temperature of the drying treatment in the step (4) is 30-90 ℃, and the drying time is 3-12h.
6. The polymer negative electrode protective layer prepared by the preparation method of any one of claims 1 to 5.
7. Use of the polymer negative electrode protection layer of claim 6 for the preparation of a metallic lithium electrode.
8. The use according to claim 7, wherein the polymer negative electrode protection layer is subjected to a lithium precipitation operation to obtain a metallic lithium electrode.
9. The use according to claim 8, wherein the lithium sinking operation is a lithium sinking operation performed by assembling a polymer negative electrode protection layer in a button cell.
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