CN109841836B - Gel composite lithium metal electrode and preparation method and application thereof - Google Patents
Gel composite lithium metal electrode and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a gel composite lithium metal electrode and a preparation method and application thereof, belonging to the technical field of lithium ion batteries. The electrode consists of a current collector, a lithium metal layer and a gel layer on the lithium metal layer, wherein the lithium metal layer is attached to the current collector and is obtained by pressing a lithium sheet on the current collector through a roller; the gel layer is generated in situ on the surface of the lithium metal sheet by a polymerization precursor liquid coated on the lithium metal layer through an ultraviolet polymerization method, and the polymerization precursor liquid consists of polymer PVDF-HFP, a photopolymerization agent ETPTA, a photoinitiator HMPP, lithium salt, a metal oxide nano additive and an ether solvent. The invention also discloses a gel composite lithium metal electrode and application thereof in the preparation of a lithium metal battery. The method is simple and easy to implement, the prepared gel composite lithium metal electrode can be directly used, can be stably circulated under the conditions of high current density and high capacity, and does not generate lithium dendrite; meanwhile, the surface layer of the electrode is electrically insulated, and a diaphragm can be removed when the battery is assembled, so that the energy density of the battery can be effectively improved.
Description
Technical Field
The invention relates to a gel composite lithium metal electrode and a preparation method and application thereof.
Background
Through the development of the last two decades, lithium ion batteries have entered thousands of households by virtue of the characteristics of high efficiency, convenience and no pollution, however, with the rapid development of portable mobile devices represented by mobile phones and new energy vehicles represented by electric automobiles, people have raised higher and higher requirements on the lithium ion batteries, and particularly with the deepening of the worries about standby time and mileage, people pay more attention to the energy density of the lithium ion batteries. Under the background, the capacity potential of the traditional cathode material graphite is basically dug out, and the novel cathode materials such as silicon cathode and lithium titanate are difficult to meet the nearly infinite capacity requirement of consumers. Therefore, more and more researchers are focusing on lithium metal negative electrodes. Compared with other negative electrode materials, the lithium metal has the lowest reversible potential (-3.04V vs SHE) and the highest theoretical capacity (3860mAh/g), so the lithium metal is considered to be an ideal negative electrode material of next-generation lithium ion batteries, and particularly, for new-system batteries such as lithium-air batteries and lithium-sulfur batteries, the high specific energy advantage can be fully exerted only by using the lithium metal. In the last seventies, lithium metal batteries have been produced, however, in the using process, the direct use of lithium metal as the negative electrode of the battery is found to generate a large amount of lithium dendrites in the charging process, and the lithium dendrites easily penetrate through a diaphragm, so that the battery is short-circuited and even causes fire. For this reason, lithium metal inherently has many advantages over other materials, and also has many "wildness" that is difficult to be domesticated.
The lithium metal has extremely strong reactivity and can almost react with all liquid electrolyte contacted with the lithium metal, and in the charging process of the battery, the lithium metal reacts with the electrolyte to generate a Solid Electrolyte Interface (SEI) film, and the SEI film can prevent the lithium metal generated in the deposition process from being corroded by the electrolyte. However, as more and more lithium metal is deposited, the lithium metal is deposited unevenly, and uneven deposition morphology is generated, lithium dendrites are formed, the SEI film is broken, and even the battery is short-circuited by penetrating through the diaphragm. In addition, new lithium is continuously consumed, resulting in "dead lithium" which is not recyclable and continuously consuming electrolyte, resulting in pulverization failure of the negative electrode. In order to solve the above problems, in order to enable the lithium metal to be really applied to a battery, researchers have adopted various methods to protect a lithium negative electrode and suppress lithium dendrites.
Researchers have constructed the frame from less dense, chemically/electrochemically stable materials to deposit lithium into the frame, thereby reducing the local current density and providing a deposition space for lithium metal to inhibit lithium dendrites. (Nature Nanotechnology 2016,11: 626-2016,7(7): 1267; advanced Materials 2017,1700389.) however, the use of this method, while increasing the specific surface area of the material and reducing the local current density, does not guarantee uniform deposition of lithium metal and no generation of lithium dendrites. In addition, this method has problems of low material pore utilization rate and low charge-discharge current density, and thus cannot fully exert the advantages of the lithium metal negative electrode. Another idea is to artificially construct a stable SEI film on the surface of the lithium negative electrode, for example, coating LiPO on the surface of lithium by using an interface engineering method3、Al2O3Or BN, etc. (Advanced Materials,2016,28: 1853-. It has also been found that the use of polymer solid electrolytes such as beta-PVDF, PVDF-HFP, Al2O3The lithium deposition performance of the lithium can be effectively improved by a film-coated lithium negative electrode such as PVDF-HFP. (Advanced Energy Materials,2017,1701482; Advanced Functional Materials, 2018, 1705838; Advanced Materials,2016,28, 857-863.) however, the direct use of the polymer solid electrolyte to coat the lithium negative electrode also has the problems of low ionic conductivity and high contact resistance between the lithium negative electrode and the polymer film, and the polymer solid electrolyte film is generally used together with the diaphragm in the article, so that the polymer solid electrolyte film can not be intuitively determined to completely prevent the lithium dendrite. In recent studies on new batteries such as lithium-air batteries, there have been studies on the protection of a lithium negative electrode and improvement of battery performance to some extent by dissolving PVDF-HFP in NMP using a photopolymerization gel system and then mixing the solution with a light curing agent and irradiating the mixture with light. (Advanced Materials,2016, DOI: 10.1002/adma.201602800; Angewandte Chemie International Edition,2017,56, 7505-7509.) however, in this method NMP will always be present in the gel, whereas thermodynamically NMP reacts with lithium, causing uncontrolled side reactions and destruction of the gel layer and the lithium negative electrode.
Disclosure of Invention
The invention designs a gel composite lithium metal electrode and a preparation method thereof, and a lithium metal battery with stable circulation, safety and reliability is prepared by using the electrode.
The invention provides a new method, which is to directly dissolve polymer PVDF-HFP, a light curing agent ETPTA, a light initiator HMPP, lithium salt and an additive into an ether solvent, uniformly coat the surface of lithium, and then use an ultraviolet light curing method to polymerize a gel layer in situ to coat a lithium cathode. The method is simple and easy to implement, the obtained gel layer has stable chemical properties on the lithium metal electrode, the gel has certain flexibility, the lithium deposition section can be greatly improved, and the lithium deposition process is optimized. The gel composite lithium metal electrode prepared by the method can be directly used, can be stably circulated under high current density and high capacity, and does not generate lithium dendrite; meanwhile, the surface layer of the electrode is electrically insulated, and a diaphragm can be removed when the battery is assembled, so that the energy density of the battery can be effectively improved.
A gel composite lithium metal electrode is composed of a current collector, a lithium metal layer and a gel layer on the lithium metal layer, wherein the lithium metal layer is attached to the current collector and is obtained by pressing a lithium sheet onto the current collector through a roller; the gel layer is generated in situ on the surface of the lithium metal by ultraviolet light polymerization of a photopolymerization precursor liquid coated on the lithium metal layer, wherein the photopolymerization precursor liquid consists of polymer PVDF-HFP (polyvinylidene fluoride-hexafluoropropylene copolymer), a photopolymerization agent ETPTA (ethoxylated trimethylolpropane triacrylate), a photoinitiator HMPP (2-hydroxy-2-methyl-1-phenyl-1-acetone), lithium salt, a metal oxide nano additive and an ether solvent.
Preferably, in the photopolymerization precursor solution, the lithium salt is LiTFSI (lithium bistrifluoromethanesulfonimide) or LiNO3LiFSI (lithium bis (fluorosulfonyl) imide), LiCF3SO3、LiClO4And LiPF6One or more of the above; the metal oxide nano additive is nano Al2O3、SiO2One or more of LAGP (lithium aluminum germanium phosphate) and LATP (lithium aluminum titanium phosphate); the ether solvent is one or more of dimethyl ether, ethylene glycol dimethyl ether, triethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether, and 1, 3-dioxolane and/or 4-methyl-1, 3-dioxolane can be additionally added into the ether solvent.
Preferably, in the photopolymerization precursor liquid, the mass ratio of ETPTA to PVDF-HFP is 2: 1 to 5: 1, HMPP accounts for 0.05 to 5 percent of the mass of ETPTA; the mass ratio of the total mass of the three components to the ether solvent is 1: 4 to 1: 1. In the photopolymerization precursor liquid, the concentration of the lithium salt is between 0.1mol/L and 5 mol/L; the mass fraction of the nano additive is between 1% and 25%.
Preferably, the photopolymerization precursor liquid is coated to a thickness of 5 μm to 500 μm.
A preparation method of a gel composite lithium metal electrode comprises the following steps:
(1) preparing a photopolymerization precursor liquid: dissolving polymer PVDF-HFP, a photo-polymerization agent ETPTA, a photo-initiator HMPP, lithium salt and an oxide nano additive into an ether solvent, and uniformly mixing;
(2) coating: firstly, rolling and attaching a lithium metal sheet on a current collector, and then coating a polymer precursor liquid layer on the surface of the lithium metal layer;
(3) ultraviolet light curing: and carrying out ultraviolet light curing on the photopolymerization precursor liquid layer to obtain the gel composite lithium metal electrode.
Preferably, the current collector is a copper foil, a copper mesh, an aluminum foil, an aluminum mesh, a stainless steel foil or a stainless steel mesh; and the lithium metal sheet is attached to the current collector by rolling. The electrode lug can be welded on the current collector, or the electrode lug can be directly led from the current collector or the lithium sheet to be used as the electrode lug.
Preferably, the lithium salt in the material for preparing the photopolymerization precursor solution is LiTFSI or LiNO3、LiFSI、LiCF3SO3、LiClO4、LiPF6One or more of the above; the additive is nano-grade Al2O3、SiO2One or more of LAGP and LATP; the ether solvent is dimethyl ether, ethylene glycol dimethyl ether, triethylene glycol dimethyl ether and/or tetraethylene glycol dimethyl ether, and 1, 3-dioxolane and/or 4-methyl-1, 3-dioxolane can be additionally added into the ether solvent.
Preferably, in the preparation method of the gel composite lithium metal electrode, the mass ratio of ETPTA to PVDF-HFP is 2: 1 to 5: 1, HMPP is between 0.05% and 5% of the mass of ETPTA. The ratio of the total mass of the three components to the organic solvent is 1: 4 to 1: 1. The concentration of the lithium salt in the organic solvent is between 0.1mol/L and 5 mol/L. The mass fraction of the nano additive in the gel precursor liquid is between 1% and 25%.
Preferably, the photopolymerizable precursor solution is coated on the surface of the lithium metal by a doctor blade method or a spin coating method. More preferably, the precursor liquid is applied to a thickness of between 5 μm and 500 μm.
Preferably, the UV wavelength range should be less than 395nm and the photocuring time is 10-60 s.
Preferably, the above operations (coating and UV curing) are carried out in a drying chamber or glove box.
The gel composite lithium metal electrode is applied to the preparation of the lithium metal battery, and can effectively improve the cycling stability of the lithium metal battery.
The invention has the beneficial effects that: the method is simple and easy to implement, the prepared gel composite lithium metal electrode can be directly used, can be stably circulated under the conditions of high current density and high capacity, and does not generate lithium dendrite; meanwhile, the surface layer of the electrode is electrically insulated, and a diaphragm can be removed when the battery is assembled, so that the energy density of the battery can be effectively improved.
Drawings
FIG. 1 is a schematic diagram of a gel composite lithium metal electrode fabrication process;
FIG. 2 is an electron micrograph of the working surface/cross-section of an unprotected lithium metal electrode;
FIG. 3 is an electron micrograph of the surface/cross-section of a gel composite lithium metal electrode after operation;
FIG. 4 is the cycle performance of the "experimental cell" in comparative experiment 1;
FIG. 5 is the cycle performance of the "control cell" of comparative experiment 1;
FIG. 6 is a graph of the ionic conductivity of the gel layer after doping with different proportions of the nano-additive in comparative experiment 2;
FIG. 7 is an assembly of Li-O using a gel composite lithium metal electrode in example 32Cycling profile of the cell.
Description of the main reference numerals:
1 lithium metal 2 current collector
3 negative electrode lug 4 in-situ photopolymerization gel layer
Detailed Description
The gel composite lithium metal electrode consists of a lithium metal layer and a gel layer. The gel layer is formed on the surface of the lithium metal in situ by a method of ultraviolet photopolymerization of polymer polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), a photopolymerization agent ethoxylated trimethylolpropane triacrylate (ETPTA), a photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-acetone (HMPP), lithium salt, a nano additive and ether electrolyte.
As shown in fig. 1, firstly, a lithium metal sheet 1 is attached to a current collector 2 by rolling, and then cut; the current collector 2 is a copper foil/copper mesh, an aluminum foil/aluminum mesh or a stainless steel foil/stainless steel mesh. And welding a negative electrode tab 3 on a current collector 2, coating a photopolymerization precursor solution on the surface of the lithium metal sheet 1, performing photocuring, and performing in-situ photopolymerization on the surface of the lithium metal to form a gel layer 4. In the method for preparing the photo-polymerization gel, firstly, polymer PVDF-HFP, a light curing agent ETPTA, a light initiator HMPP, lithium salt and an additive are directly dissolved in an ether solvent, uniformly mixed to prepare a photo-polymerization precursor solution, and then the photo-polymerization precursor solution is coated on the surface of lithium metal for curing.
The unprotected lithium metal electrode and the gel composite lithium metal electrode of the invention are respectively observed on the surface/cross section after working, as shown in fig. 2, a large amount of lithium dendrites are generated after the unprotected lithium metal electrode works, the lithium deposition is not uniform, and a deposited layer has a large amount of cavities. As shown in FIG. 3, after the gel composite lithium metal electrode works, no dendrite extends out from the surface, and the observation of the cross section shows that the lithium deposition is uniform and compact.
Example 1
A preparation method of a gel composite lithium metal electrode comprises the following steps:
(1) PVDF-HFP was mixed with ETPTA (containing 0.5 wt% HMPP) in a ratio of 1: 2, and adding 1M LiClO in an amount of 3 times the mass of the polymer mixture4Adding 5 percent of nano SiO by mass2Powder mixtureAnd uniformly stirring to prepare the photopolymerization precursor liquid.
(2) Rolling a lithium sheet (80 μm) onto a copper foil (9 μm), rolling to 70 μm, cutting the lithium sheet and the copper foil to 5 × 5cm, welding a negative electrode tab on the copper foil, scraping gel precursor liquid on the surface of the lithium sheet, and scraping to a height of 120 μm.
(3) Setting the wavelength of ultraviolet light rays at 365nm, and irradiating the gel precursor liquid for photocuring for 30s to prepare the single-sided gel composite lithium metal electrode.
Example 2
A preparation method of a gel composite lithium metal electrode comprises the following steps:
(1) PVDF-HFP and ETPTA (containing 1% HMPP) were mixed in a ratio of 1:3, and adding 0.6M LiTFSI in an amount of 1.5 times the mass of the polymer mixture&0.4M LiNO3DOL/DME solution, and adding nano Al with the total mass of 10%2O3And mixing and stirring the powder uniformly to prepare the photopolymerization precursor liquid.
(2) A copper mesh (10 μm) is sandwiched between two lithium sheets (100 μm), and rolled to form a double-sided lithium sheet electrode. The photopolymerization precursor solution was spin-coated on the upper surface of the lithium plate to a thickness of 30 μm using a spin coating method.
(3) Setting the wavelength of ultraviolet light at 365nm, and irradiating the gel precursor liquid for photocuring for 20 s. The electrode was inverted, and the other side was coated with a 30 μm thick gel precursor solution and cured for 20 seconds.
(4) And leading out a negative electrode lug on the copper mesh to prepare the double-sided gel composite lithium metal electrode.
PVDF-HFP is first dissolved in NMP to prepare a 20% solution, denoted as solution 1, according to the method described in Advanced Materials,2016, DOI: 10.1002/adma.201602800; adding ETPTA and HMPP accounting for 0.1 percent of the mass of the ETPTA into the solution 1 according to the proportion of PVDF-HFP to ETPTA being 1:3, and mixing to obtain solution 2; then, 1M LiCF with the same volume as the solution 2 was added3SO3The TEGDME solution of (1) is mixed and recorded as solution 3; and (3) coating the solution 3 on the surface of a lithium sheet, performing light polymerization for 30s to obtain a composite lithium metal electrode, and taking two identical reference electrodes to assemble a symmetrical battery, wherein the symmetrical battery is taken as a reference battery.
The composite lithium metal electrode obtained in example 1 was taken and designated as "experimental electrode", and two identical experimental electrodes were assembled into a symmetrical battery by the same method and designated as "experimental battery".
The current density was set to 0.5mA/cm for both the "control cell" and the "experimental cell2Constant volume is 6mAh/cm2Constant volume circulation and comparative circulation performance. As shown in FIGS. 4 and 5, the "experimental battery" is stable for more than 1400h, the charging and discharging overpotential is stable within 20mV, while the "comparison battery" is very unstable in cycle curve, the charging overpotential can reach more than 450mV, and the comparison can fully show that the gel layer is not stable to lithium when the gel layer contains non-ether solvents such as NMP.
Following the experimental procedure described in example 2, PVDF-HFP and ETPTA (containing 1% HMPP) were mixed in the ratio of 1:3, and adding 0.6M LiTFSI in an amount of 1.5 times the mass of the polymer mixture&0.4M LiNO3Adding nano-alumina powder with different proportions into DOL/DME solution to enable the nano-alumina to respectively account for 0% (not doped), 5%, 10% and 20% of the total mixed solution, carrying out photopolymerization to form gel layers, and testing the ionic conductivities of different gel layers at room temperature. As shown in fig. 6, it was found that the ionic conductivity of the gel layer was improved by more than one order of magnitude after doping with nano alumina (5%, 10%, 20% group) compared to the ionic conductivity of the gel layer without doping with nano alumina (0% group).
Example 3
The gel composite lithium metal electrode prepared in example 1 was used as a negative electrode, and 1M LiClO was used4The TEGDME solution is used as electrolyte and the carbon loading is 1mg/cm2The Super-P electrode is used as an air electrode, and Li-O is assembled2A battery with a setting of 0.1mA/cm2Constant volume of 2mAh/cm2(i.e., 2000 mAh/g). As shown in fig. 7, the cell was stably cycled for 20 weeks.
The above embodiments are only used for illustrating but not limiting the technical solutions of the present invention, and although the above embodiments describe the present invention in detail, those skilled in the art should understand that: modifications and equivalents may be made thereto without departing from the spirit and scope of the invention and any modifications and equivalents may fall within the scope of the claims.
Claims (9)
1. A gel composite lithium metal electrode, characterized by: the lithium ion battery is composed of a current collector, a lithium metal layer and a gel layer on the lithium metal layer, wherein the lithium metal layer is attached to the current collector and is obtained by pressing a lithium sheet onto the current collector through a roller; the gel layer is generated in situ on the surface of the lithium metal sheet by a method of ultraviolet polymerization from a photo-polymerization precursor liquid coated on the lithium metal sheet, wherein the photo-polymerization precursor liquid consists of polymer PVDF-HFP, photo-polymerization agent ETPTA, photo-initiator HMPP, lithium salt, metal oxide nano additive and ether solvent; in the photopolymerization precursor solution, lithium salt is LiTFSI and LiNO3、LiFSI、LiCF3SO3、LiClO4And LiPF6One or more of the above; the metal oxide nano additive is nano Al2O3、SiO2One or more of LAGP and LATP; the ether solvent is one or more of dimethyl ether, ethylene glycol dimethyl ether, triethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether; 1, 3-dioxolane and/or 4-methyl-1, 3-dioxolane are also added into the ether solvent; in the polymerization precursor liquid, the mass ratio of ETPTA to PVDF-HFP is 2: 1 to 5: 1, HMPP accounts for 0.05 to 5 percent of the mass of ETPTA; the mass ratio of the total mass of the three components to the ether solvent is 1: 4 to 1: 1; the mass fraction of the metal oxide nano additive is between 1% and 25%.
2. The gel composite lithium metal electrode of claim 1, wherein: the concentration of the lithium salt is between 0.1mol/L and 5 mol/L.
3. The method for preparing a gel composite lithium metal electrode according to claim 1 or 2, comprising the steps of:
(1) preparing a polymerization precursor solution: dissolving polymer PVDF-HFP, a photo-polymerization agent ETPTA, a photo-initiator HMPP, lithium salt and a nano additive into an ether solvent, and uniformly mixing;
(2) coating: firstly, a lithium metal sheet is attached to a current collector, the lithium metal sheet and the current collector are attached through rolling, and then a polymer precursor liquid layer is coated on the surface of the lithium metal sheet;
(3) ultraviolet light curing: and carrying out ultraviolet light curing on the photopolymerization precursor liquid layer to obtain the gel composite lithium metal electrode.
4. The method for preparing a gel composite lithium metal electrode according to claim 3, wherein: the current collector is a copper foil, a copper mesh, an aluminum foil, an aluminum mesh, a stainless steel foil or a stainless steel mesh.
5. The method for preparing a gel composite lithium metal electrode according to claim 4, wherein: and welding a tab on the current collector, or directly leading from the current collector or the lithium sheet to be used as the tab.
6. The method for preparing a gel composite lithium metal electrode according to claim 3, wherein: the coating method is a blade coating method or a spin coating method; the coating thickness of the photopolymerization precursor liquid is between 5 and 500 mu m.
7. The method for preparing a gel composite lithium metal electrode according to claim 3, wherein: in the ultraviolet light curing, the wavelength of the ultraviolet light is less than 395nm, and the light curing time is 10-60 s.
8. The method for preparing a gel composite lithium metal electrode according to claim 3, wherein: the coating and UV curing process should be performed in a drying room or a glove box.
9. Use of the gel composite lithium metal electrode according to claim 1 or 2 in the preparation of a lithium metal battery.
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| CN112467258A (en) * | 2020-11-25 | 2021-03-09 | 北京航空航天大学 | Preparation method of lithium-air battery based on gel electrolyte-lithium cathode integrated structure |
| CN114744158A (en) * | 2022-05-18 | 2022-07-12 | 中南大学 | Method for applying organic/inorganic composite coating to surface modification of lithium metal electrode |
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