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CN109004276A - A kind of cathode of lithium protective film, preparation method and lithium metal secondary cell - Google Patents

A kind of cathode of lithium protective film, preparation method and lithium metal secondary cell Download PDF

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Publication number
CN109004276A
CN109004276A CN201810795821.7A CN201810795821A CN109004276A CN 109004276 A CN109004276 A CN 109004276A CN 201810795821 A CN201810795821 A CN 201810795821A CN 109004276 A CN109004276 A CN 109004276A
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lithium
protective film
salt
negative electrode
nafion polymer
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CN109004276B (en
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陈人杰
赵利媛
屈雯洁
吴锋
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Beijing Institute of Technology BIT
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

本发明涉及一种锂负极保护膜、制备方法及锂金属二次电池，属于锂金属二次电池领域。所述锂负极保护膜由锂盐、离子液体、无机物纳米颗粒和锂化处理的Nafion聚合物组成；含锂盐的离子液体吸附在无机物纳米颗粒表面并均匀分散在锂化处理的Nafion聚合物中。通过配置锂盐与离子液体的混合溶液；将混合溶液及无机物纳米颗粒密封球磨混合得到准固态电解质；将准固态电解质与锂化处理的Nafion聚合物溶液混合后涂覆于锂或铜箔表面，溶剂挥发完全后制得所述保护膜。所述锂负极保护膜可抑制锂枝晶产生，具有良好机械性能和化学稳定性、高锂离子电导率以及良好成膜性能；具备所述锂负极保护膜的锂金属二次电池具有优异的电化学性能。

The invention relates to a lithium negative electrode protective film, a preparation method and a lithium metal secondary battery, belonging to the field of lithium metal secondary batteries. The lithium negative electrode protective film is composed of lithium salt, ionic liquid, inorganic nanoparticles and lithiated Nafion polymer; the lithium salt-containing ionic liquid is adsorbed on the surface of inorganic nanoparticles and uniformly dispersed on the lithiated Nafion polymer in things. By configuring the mixed solution of lithium salt and ionic liquid; mixing the mixed solution and inorganic nano-particles by sealed ball milling to obtain a quasi-solid electrolyte; mixing the quasi-solid electrolyte with the lithiated Nafion polymer solution and coating it on the surface of lithium or copper foil , the protective film is prepared after the solvent evaporates completely. The lithium negative electrode protective film can inhibit the generation of lithium dendrites, and has good mechanical properties and chemical stability, high lithium ion conductivity and good film-forming performance; the lithium metal secondary battery with the lithium negative electrode protective film has excellent battery life. chemical properties.

Description

A kind of cathode of lithium protective film, preparation method and lithium metal secondary cell
Technical field
The present invention relates to a kind of cathode of lithium protective film, preparation method and lithium metal secondary cells, belong to the secondary electricity of lithium metal Pool technology field.
Background technique
Along with social progress, the energy of human use is also growing day by day.Efficient energy storage and conversion are societies Progressive power, and the appearance of battery and use allow people more efficiently and easily to utilize the energy.Currently, plumbic acid is electric Pond, ickel-cadmium cell, nickel-metal hydride battery and lithium ion battery have been carried out business application.Especially lithium ion battery changes people Exchange and mode of transportation.As the actual energy density of lithium ion battery (especially graphite cathode) is moved closer in its theory Limiting value meets the requirement of emerging high-end energy storage device development there is an urgent need to more efficient electrode material.Lithium metal is negative Pole becomes ideal next-generation lithium with its high capacity density (3680mAh/g) and low standard electrode EMF (- 3.04V) Secondary battery cathode material.It include lithium-sulfur cell, lithium sky battery and oxidate for lithium electricity by the lithium metal battery of cathode of lithium metal Pond all shows high theoretical energy density.
However, lithium metal is directly as negative electrode material, there are still many problems: metal lithium chemistry is active, can be with sky Gas and water, which reacts, causes battery assembly difficult；When charging, the lithium of deposition can react with electrolyte, lead to coulombic efficiency It is low；Metallic lithium surface form it is uneven, cause surface charge distribution uneven, be easy to produce dendrite pierce through diaphragm cause battery Short circuit causes security risk.These problems hinder the business application of lithium metal secondary cell.Nearly ten years, scientific research personnel has been The method for inhibiting lithium anode dendrite to generate through developing various new, to improve battery security and service life, mainly Include: 1) alloying, reduces the reactivity of lithium metal；2) cathode solid electrolyte interface (SEI) membrane modifying；3) solid state electrolysis Matter has high mechanical modulus, hinders lithium dendrite growth；4) reasonable battery structure design.Due to metallic lithium surface electrochemistry Matter mainly has the decision of SEI film, therefore constructs long-acting stable SEI film for improving lithium anode chemical property with important Meaning.Being added in the electrolytic solution and contributing to form the additive of stable SEI film is a kind of common method, such as current LiNO3? It is used widely in lithium-sulfur cell.But as the cycle progresses, additive is constantly consumed, and battery impedance is gradually increased, property It can decline.Scientific research personnel forms one layer of artificial SEI film on cathode of lithium surface by pretreated mode, can avoid this problem, The generation for effectively inhibiting Li dendrite, improves battery life.Cui etc. deposits two-dimensional material h-BN and graphene atom on copper foil Layer effectively inhibits the generation of lithium metal dendrite in deposition due to h-BN and the high mechanical strength of graphene；Guo etc. passes through Pretreatment introduces Li on cathode of lithium surface3PO4, the lithium ion diffusion rate of lithium metal and electrolyte interface is improved, to inhibit branch Crystalline substance generates；In patent CN106935800A, poplar etc. forms a protective layer on cathode of lithium surface by impregnating or being electroplated.
Although the above method inhibits the generation of metal Li dendrite to a certain extent, in application process by many Limitation, such as the method for Cui etc. are at high cost, and Guo etc. prepares Li3PO4Harshness is required to environmental condition, what the methods of poplar was formed changes Property SEI film bad mechanical property, is unfavorable for the raising of battery cycle life.Therefore, how to be introduced and had by simple and effective way There is the SEI film of high mechanical strength and high ionic conductivity, for inhibiting metal Li dendrite to generate, improving battery security has Significance.
Summary of the invention
In view of this, an object of the present invention is to be to provide a kind of cathode of lithium protective film；The cathode of lithium protective film Can inhibit Li dendrite generation, have good mechanical performance and chemical stability, high lithium ion conductivity and it is good at Film properties.
The second object of the present invention is to be to provide a kind of preparation method of cathode of lithium protective film.
The third object of the present invention is to provide a kind of lithium metal secondary cell, and the lithium metal secondary cell has this hair A kind of bright cathode of lithium protective film, has excellent chemical property.
The purpose of the present invention is what is be achieved through the following technical solutions.
A kind of cathode of lithium protective film, the protective film are handled by lithium salts, ionic liquid, inorganic matter nano particle and lithiumation Nafion polymer composition；Wherein, ionic liquid containing lithium salt is adsorbed on inorganic matter nano grain surface and is dispersed in lithium In the Nafion polymer for changing processing.
The lithium salts is lithium salts, preferably di-oxalate lithium borate (LiB (C used in this field routine lithium battery2O4)2, LiBOB), difluorine oxalic acid boracic acid lithium (LiBF2(C2O4), LiODFB), trifluoromethanesulfonic acid lithium (LiCF3SO3), double fluoroform sulphonyl Imine lithium (Li (CF3SO2)2N, LiTFSI), double fluorine sulfimide lithium (Li (FSO2)2N, LiFSI), perfluoroethyl sulfonyl imine lithium (Li(C2F5SO2)2) and per-fluoroalkyl sulfonyl lithium methide (LiC (CF N3SO2)3One or more of).
The ionic liquid is ionic liquid, preferably 1- ethyl-3-methylimidazole used in this field routine lithium battery Bis-trifluoromethylsulfoandimide salt, 1- propyl -3- methylimidazole bis-trifluoromethylsulfoandimide salt, 1- butyl -3- methylimidazole double three The double fluorine sulfonamides of fluorine sulfonamide, 1- ethyl-3-methylimidazole, the double fluorine methylsulfonyls of 1- propyl -3- methylimidazole The double fluorine sulfonamides of inferior amine salt, 1- butyl -3- methylimidazole, N- methyl, propyl pyrrole bis-trifluoromethylsulfoandimide salt, N- Methyl, butyl pyrroles's bis-trifluoromethylsulfoandimide salt, N- methyl, the double fluorine sulfonamides of propyl pyrrole and N- methyl, butyl One or more of double fluorine sulfonamides of pyrroles.
The inorganic matter nano particle is inorganic oxide nanoparticles, preferably nano SiO 2 particle, titanium dioxide Zirconium nano particle, titania nanoparticles or aluminum oxide nanoparticles.
It is preferred that the protective film is with a thickness of 0.1 μm~100 μm.
A kind of preparation method of cathode of lithium protective film of the present invention, the method comprises the following steps:
(1) mixed solution of lithium salts and ionic liquid is configured in oxygen-free environment of the moisture content less than or equal to 0.1ppm；
(2) mixed solution made from step (1) and inorganic matter nano particle are placed in ball grinder and are sealed, ball milling is mixed After closing uniformly, quasi-solid electrolyte is obtained；
(3) the Nafion polymer solution for taking quasi-solid electrolyte made from step (2) and lithiumation to handle is mixed, will Obtained material is mixed to proceed as follows in oxygen-free environment of the moisture content less than or equal to 0.1ppm:
1) it is coated on metallic lithium surface, is stood, after solvent volatilization completely, obtains the lithium metal for being covered with film, it is described thin Film is a kind of cathode of lithium protective film of the present invention；Or
2) coating on surfaces of the copper foil, is stood, and after solvent volatilization completely, the metal copper foil for being covered with film is obtained, by copper The film removing formed on foil surface, the film are a kind of cathode of lithium protective film of the present invention；The protective film uses Interlayer between Shi Zuowei lithium anode and diaphragm has the function of protecting lithium anode.
In step (1):
It is preferred that concentration of the lithium salts in ionic liquid is 0.5mol/L~2mol/L.
In step (2):
It is preferred that the mass ratio of mixed solution and inorganic matter nano particle is 0.5~1.5:1.
It is preferred that Ball-milling Time is 20min~200min, preferably ball milling speed is 300r/min~600r/min, preferably ball material Than for 25~30:1.
In step (3):
It is preferred that the mass ratio of quasi-solid electrolyte and the Nafion polymer of lithiumation processing is 0.2~5:1.
Wherein, the Nafion polymer powder that the Nafion polymer solution of lithiumation processing is handled by lithiumation has been dissolved in Solvent obtains, and preferable organic solvent is dimethyl sulfoxide or N-Methyl pyrrolidone；It is preferred that the Nafion of lithiumation processing is poly- The Nafion polymer powder mass fraction that lithiumation is handled in polymer solution is 5%~30%.
The Nafion polymer powder of lithiumation processing can be made by the method in existing literature, such as:
Lithium hydroxide solution is added in Nafion solution, carries out lithiumation processing, until pH value is 8, at 40 DEG C~120 DEG C Lower vacuum drying obtains the Nafion polymer powder of lithiumation processing.
In step (1) and (3):
The moisture content less than or equal to 0.1ppm oxygen-free environment can be used full of inert gas and moisture content it is small It is realized in the glove box equal to 0.1ppm.
A kind of lithium metal secondary cell, the lithium metal secondary cell have a kind of cathode of lithium protection of the present invention Film.
Beneficial effect
1. the growth of Li dendrite, the Nafion of lithiumation processing can be inhibited the present invention provides a kind of cathode of lithium protective film Polymer makes protective film have high elastic modulus, and inorganic matter nano particle improves the mechanical strength of protective film, to hinder The growth of Li dendrite improves lithium metal secondary cell cycle life；
2. lithium salts, which is dissolved in ionic liquid and is evenly coated at inorganic matter, to be received the present invention provides a kind of cathode of lithium protective film Rice grain surface is conducive to lithium ion uniform deposition and falls off, to press down so that the protective film has high ionic conductivity The generation of Li dendrite processed；In addition, the Nafion polymer of lithiumation processing has single permeability for lithium ion, can inhibit to be electrolysed Through protective film and lithium metal side reaction occurs for other ions in liquid, is conducive to keep the lower internal resistance of cell；
3. the protective film thermal stability is good the present invention provides a kind of cathode of lithium protective film, high temperature lithium can be applied to In metal secondary batteries；
4. the protection membrane preparation method is simple the present invention provides a kind of cathode of lithium protective film, environmentally protective, it is easy to big Batch production.
Detailed description of the invention
Fig. 1 is the scanning electron microscope diagram of the obtained lithium anode with protective film in embodiment 1.
Fig. 2 is Li obtained in embodiment 1 | Li is to cycle performance of battery curve.
Specific embodiment
The invention will be described in further detail with reference to the accompanying drawings and examples.But the present invention is not limited to following implementations Example.
In following embodiment, used analysis test method is as follows:
Scanning electron microscope (SEM) test: model HITACHI S-4800, Japan；
Electrochemical property test: Land, Wuhan.
Embodiment 1
(1) in full of the glove box of Ar gas and moisture content less than or equal to 0.1ppm, by the bis- fluoroform sulphurs of 1.4354g Imide li is dissolved in the 1- ethyl-3-methylimidazole bis-trifluoromethylsulfoandimide salt of 10ml, and mixed dissolution obtains mixing molten Liquid, concentration of double trifluoromethanesulfonimide lithiums in 1- ethyl-3-methylimidazole bis-trifluoromethylsulfoandimide salt are 0.5mol/ L；
(2) mixed solution 0.5g made from step (1) and 1g the average grain diameter zirconium dioxide for being 50nm are placed in ball milling In tank, and 37.5g Ceramic Balls are put into, with planetary ball mill mixing and ball milling, ball milling speed 300r/min, Ball-milling Time is 30min is uniformly mixed, then takes out, obtain quasi-solid electrolyte；
(3) Nafion solution 20g is weighed, 0.1g lithium hydroxide is dissolved in 20g deionized water and obtains lithium hydroxide solution, Be added dropwise lithium hydroxide solution carries out lithiumation processing in Nafion solution, until pH be 8, be then dried in vacuo and obtain at 80 DEG C The Nafion polymer powder of lithiumation processing；The Nafion polymer powder for taking 100mg lithiumation to handle is dissolved in 2ml dimethyl sulfoxide It after middle stirring 2h, is uniformly mixed, obtains the Nafion polymer solution that the lithiumation that mass fraction is 5% is handled；
500mg quasi-solid electrolyte is added in the Nafion polymer solution of the lithiumation processing, in room temperature with 300r/ 30min is mixed in min；Then after being mixed in full of the glove box of Ar gas and moisture content less than or equal to 0.1ppm Material be coated on metallic lithium surface, stand 48h at room temperature, after dimethyl sulfoxide volatilization completely after, obtain being covered with film Lithium metal, the film are a kind of cathode of lithium protective film of the present invention.
The lithium metal of lithium metal and unprotect film made from the present embodiment with protective film is used to assemble respectively as cathode Li | for Li to battery, electrolyte is double trifluoromethanesulfonimide lithiums (LiTFSI) and LiNO3It is dissolved in 1,3- dioxolanes (DOL) it is obtained with the mixed solution of glycol dimethyl ether (DME), wherein the volume ratio of DOL and DME is 1:1, the concentration of LiTFSI For 0.6M, LiNO3Concentration be 0.4M.
A kind of lithium metal with protective film manufactured in the present embodiment is tested, as a result as follows:
(1) scanning electron microscope (SEM) is tested:
As shown in Figure 1, SEM test shows the protective film even compact, zirconium dioxide nanoparticles are dispersed in lithium In the Nafion polymer for changing processing, without agglomeration.
(2) Li | Li tests battery performance:
Fig. 2 is Li | Li is charging and discharging currents 1mA/cm to the electric data of the indigo plant of battery, test condition2, charge/discharge capacity 1mAh/cm2.As shown in Figure 2, after pure metal lithium comparative experiments has recycled 120h, lithium metal deposition is peeled off overpotential and is gradually increased, Internal resistance increases, this is because electrolyte constantly reacts with lithium anode in cyclic process, SEI film, which is continuously generated, gradually to be become Thickness, to increase the internal resistance of cell.Overpotential is more than 200mV after 140h, and the internal resistance of cell is excessive.And there is the lithium metal of protective film to follow Ring 260h overpotential is still stable in 50mV, and circulating battery is stablized.
Embodiment 2
(1) in full of the glove box of Ar gas and moisture content less than or equal to 0.1ppm, by 3.7414 pairs of fluorine sulfimides Lithium is dissolved in the N- methyl of 10ml, and in propyl pyrrole bis-trifluoromethylsulfoandimide salt, mixed dissolution obtains mixed solution, double trifluoros Concentration of the sulfonyl methane imine lithium in N- methyl, propyl pyrrole bis-trifluoromethylsulfoandimide salt is 2mol/L；
It (2) is that 100nm silica is placed in ball grinder by mixed solution 0.5g made from step (1) and 1g average grain diameter In, and 37.5g Ceramic Balls are put into, with planetary ball mill mixing and ball milling, ball milling speed 300r/min, Ball-milling Time is 30min is uniformly mixed, then takes out, obtain quasi-solid electrolyte；
(3) Nafion solution 20g is weighed, 0.1g lithium hydroxide is dissolved in 20g deionized water and obtains lithium hydroxide solution, Be added dropwise lithium hydroxide solution carries out lithiumation processing in Nafion solution, until pH be 8, be then dried in vacuo and obtain at 80 DEG C The Nafion polymer powder of lithiumation processing；The Nafion polymer powder for taking 600mg lithiumation to handle is dissolved in 2ml N- methyl pyrrole It after stirring 2h in pyrrolidone, is uniformly mixed, obtains the Nafion polymer solution that the lithiumation that mass fraction is 30% is handled；
120mg quasi-solid electrolyte is added in the Nafion polymer solution of the lithiumation processing, in room temperature with 300r/ 30min is mixed in min；Then after being mixed in full of the glove box of Ar gas and moisture content less than or equal to 0.1ppm Material be coated on metallic lithium surface, stand 48h at room temperature, after N-Methyl pyrrolidone volatilization completely after, obtain being covered with thin The lithium metal of film, the film are a kind of cathode of lithium protective film of the present invention.
The lithium metal of lithium metal and unprotect film made from the present embodiment with protective film is used to assemble respectively as cathode Li | for Li to battery, electrolyte is double trifluoromethanesulfonimide lithiums (LiTFSI) and LiNO3It is dissolved in 1,3- dioxolanes (DOL) it is obtained with the mixed solution of glycol dimethyl ether (DME), wherein the volume ratio of DOL and DME is 1:1, the concentration of LiTFSI For 0.6M, LiNO3Concentration be 0.4M.
A kind of lithium metal with protective film manufactured in the present embodiment is tested, as a result as follows:
(1) scanning electron microscope (SEM) is tested:
Similar with Fig. 1, SEM test shows that the protective film densification is smooth, and nano SiO 2 particle is dispersed in lithium In the Nafion polymer for changing processing, without agglomeration.
(2) Li | Li tests battery performance:
It is similar with Fig. 2, Li | Li is charging and discharging currents 1mA/cm to the blue electrical testing condition of battery2, charge/discharge capacity 1mAh/cm2.It is interior by test result it is found that overpotential increases to 200mV suddenly after pure metal lithium comparative experiments has recycled 100h It hinders excessive, and there is the lithium metal of protective film to recycle 250h and still keep stable, indicate to avoid metal due to the presence of protective film Lithium is reacted with electrolyte, and SEI film is stablized, and the internal resistance of cell is constant.
Embodiment 3
(1) in full of the glove box of Ar gas and moisture content less than or equal to 0.1ppm, by the bis- fluoroform sulphurs of 2.8708g Imide li is dissolved in 10ml N- methyl, and in propyl pyrrole bis-trifluoromethylsulfoandimide salt, mixed dissolution obtains mixed solution, double Concentration of the trifluoromethanesulfonimide lithium in N- methyl, propyl pyrrole bis-trifluoromethylsulfoandimide salt is 1mol/L；
(2) mixed solution 0.5g made from step (1) and 1g the average grain diameter titanium dioxide for being 50nm are placed in ball milling In tank, and 37.5g Ceramic Balls are put into, with planetary ball mill mixing and ball milling, ball milling speed 300r/min, Ball-milling Time is 200min is uniformly mixed, then takes out, obtain quasi-solid electrolyte；
(3) Nafion solution 20g is weighed, 0.1g lithium hydroxide is dissolved in 20g deionized water and obtains lithium hydroxide solution, Be added dropwise lithium hydroxide solution carries out lithiumation processing in Nafion solution, until pH be 8, be then dried in vacuo and obtain at 80 DEG C The Nafion polymer powder of lithiumation processing；The Nafion polymer powder for taking 100mg lithiumation to handle is dissolved in 2ml N- methyl pyrrole It after stirring 2h in pyrrolidone, is uniformly mixed, obtains the Nafion polymer solution that the lithiumation that mass fraction is 5% is handled；
400mg quasi-solid electrolyte is added in the Nafion polymer solution of the lithiumation processing, in room temperature with 300r/ 30min is mixed in min；Then after being mixed in full of the glove box of Ar gas and moisture content less than or equal to 0.1ppm Material be coated on copper foil surface, stand 48h at room temperature, after N-Methyl pyrrolidone volatilization completely after, obtain being covered with film Copper foil, the film formed on copper foil is removed, the film is a kind of cathode of lithium protective film of the present invention, when use As the interlayer between lithium anode and diaphragm.
The lithium metal of lithium metal and unprotect film made from the present embodiment with protective film is used to assemble respectively as cathode Lithium-sulfur cell places protective film interlayer between lithium metal and diaphragm, just extremely active carbon/S composite electrode pole piece, diaphragm are Celgard 2325, electrolyte are double trifluoromethanesulfonimide lithiums (LiTFSI) and LiNO3It is dissolved in 1,3- dioxolanes (DOL) it is obtained with the mixed solution of glycol dimethyl ether (DME), wherein the volume ratio of DOL and DME is 1:1, the concentration of LiTFSI For 0.6M, LiNO3Concentration be 0.4M.
A kind of lithium metal with protective film manufactured in the present embodiment is tested, as a result as follows:
(1) scanning electron microscope (SEM) is tested:
Similar with Fig. 1, SEM test shows that the protective film densification is smooth, and titania nanoparticles are dispersed in lithium In the Nafion polymer for changing processing, without agglomeration.
(2) lithium-sulfur cell electrochemical property test:
The blue electrical testing condition of lithium-sulfur cell be charging/discharging voltage 1.7V~3V, charge-discharge magnification: 2C, charge and discharge electro-temperature: 30℃.By the cycle performance curve of lithium-sulfur cell it is found that there is the lithium-sulfur cell of protective film to recycle at room temperature under 2C multiplying power 300 weeks There are also 715mAh/g for capacity later, and capacity only has 619mAh/g after 50 circle of the lithium-sulfur cell of unprotect film circulation.
Embodiment 4
(1) in full of the glove box of Ar gas and moisture content less than or equal to 0.1ppm, by the bis- fluoroform sulphurs of 2.8708g Imide li is dissolved in 10ml N- methyl, and in propyl pyrrole bis-trifluoromethylsulfoandimide salt, mixed dissolution obtains mixed solution, double Concentration of the trifluoromethanesulfonimide lithium in N- methyl, propyl pyrrole bis-trifluoromethylsulfoandimide salt is 1mol/L；
(2) mixed solution 0.5g made from step (1) and 1g the average grain diameter aluminum oxide for being 100nm are placed in ball In grinding jar, and 37.5g Ceramic Balls are put into, with planetary ball mill mixing and ball milling, ball milling speed 300r/min, Ball-milling Time is 200min is uniformly mixed, then takes out, obtain quasi-solid electrolyte；
(3) Nafion solution 20g is weighed, 0.1g lithium hydroxide is dissolved in 20g deionized water and obtains lithium hydroxide solution, Be added dropwise lithium hydroxide solution carries out lithiumation processing in Nafion solution, until pH be 8, be then dried in vacuo and obtain at 80 DEG C The Nafion polymer powder of lithiumation processing；The Nafion polymer powder for taking 100mg lithiumation to handle is dissolved in 2ml N- methyl pyrrole It after stirring 2h in pyrrolidone, is uniformly mixed, obtains the Nafion polymer solution that the lithiumation that mass fraction is 5% is handled；
400mg quasi-solid electrolyte is added in the Nafion polymer solution of the lithiumation processing, in room temperature with 300r/ 30min is mixed in min；Then the material after mixing is coated on copper foil surface, 48h is stood at room temperature, to N- methyl After pyrrolidones volatilization completely, the copper foil for being covered with film is obtained, the film formed on copper foil is removed, the film is this Invention a kind of cathode of lithium protective film, as the interlayer between lithium anode and diaphragm when using.
The lithium metal of lithium metal and unprotect film made from the present embodiment with protective film is used to assemble respectively as cathode Lithium sky battery, between lithium metal and diaphragm place protective film interlayer, just extremely ruthenic oxide load absorbent charcoal material electrode plates, Diaphragm is Glass fiber, and electrolyte is that double trifluoromethanesulfonimide lithiums (LiTFSI) are dissolved in triethylene glycol dimethyl ether (TEGDME) it is obtained in, the concentration of LiTFSI is 1M.
A kind of lithium metal with protective film manufactured in the present embodiment is tested, as a result as follows:
(1) scanning electron microscope (SEM) is tested:
Similar with Fig. 1, SEM test shows that the protective film densification is smooth, and aluminum oxide nanoparticles are dispersed in In the Nafion polymer of lithiumation processing, without agglomeration.
(2) lithium sky battery performance is tested:
The blue electrical testing condition of lithium-sulfur cell is limited capacity charge and discharge: 1000mAh/g, charging/discharging voltage 2.2V~4.5V fill Discharge current: 0.5mA/cm2, charge and discharge electro-temperature: 30 DEG C.By the cycle performance curve of lithium sky battery it is found that there is the lithium of protective film Empty circulating battery 200 weeks or more and capacity keep stablizing, and the lithium sky circulating battery 90 of unprotect film enclose after charge/discharge capacity Lower than 1000mAh/g.Dismantling battery discovery unprotect film cathode of lithium dusting seriously causes battery capacity to reduce, this is because without guarantor The cathode of lithium of cuticula easily in electrolyte water and oxygen react and generate lithium hydroxide and lithia, and have the lithium of protective film negative Pole still keeps blocky to be occurred without powder phenomenon-tion.
Although above the present invention is described in detail with a general description of the specific embodiments, On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause This, these modifications or improvements, fall within the scope of the claimed invention without departing from theon the basis of the spirit of the present invention.

Claims (10)

1.一种锂负极保护膜，其特征在于：所述保护膜由锂盐、离子液体、无机物纳米颗粒和锂化处理的Nafion聚合物组成；含锂盐的离子液体吸附在无机物纳米颗粒表面并均匀分散在锂化处理的Nafion聚合物中；所述无机物纳米颗粒为无机氧化物纳米颗粒。1. A lithium negative electrode protective film, characterized in that: said protective film is made up of lithium salts, ionic liquids, inorganic nanoparticles and lithiated Nafion polymers; the ionic liquid containing lithium salts is adsorbed on the inorganic nanoparticles The surface is uniformly dispersed in the lithiated Nafion polymer; the inorganic nanoparticle is an inorganic oxide nanoparticle. 2.根据权利要求1所述的一种锂负极保护膜，其特征在于：所述锂盐为双草酸硼酸锂、二氟草酸硼酸锂、三氟甲磺酸锂、双三氟甲烷磺酰亚胺锂、双氟磺酰亚胺锂、全氟乙基磺酰亚胺锂和全氟烷基磺酰甲基锂中的一种以上；2. A lithium negative electrode protective film according to claim 1, wherein the lithium salt is lithium bisoxalate borate, lithium difluorooxalate borate, lithium trifluoromethanesulfonate, bistrifluoromethanesulfonyl One or more of lithium amide, lithium bisfluorosulfonyl imide, lithium perfluoroethylsulfonyl imide, and lithium perfluoroalkylsulfonylmethyl; 所述离子液体为1-乙基-3-甲基咪唑双三氟甲磺酰亚胺盐、1-丙基-3-甲基咪唑双三氟甲磺酰亚胺盐、1-丁基-3-甲基咪唑双三氟甲磺酰亚胺盐、1-乙基-3-甲基咪唑双氟甲磺酰亚胺盐、1-丙基-3-甲基咪唑双氟甲磺酰亚胺盐、1-丁基-3-甲基咪唑双氟甲磺酰亚胺盐、N-甲基,丙基吡咯双三氟甲磺酰亚胺盐、N-甲基,丁基吡咯双三氟甲磺酰亚胺盐、N-甲基,丙基吡咯双氟甲磺酰亚胺盐和N-甲基,丁基吡咯双氟甲磺酰亚胺盐中的一种以上；The ionic liquid is 1-ethyl-3-methylimidazole bis-trifluoromethanesulfonimide salt, 1-propyl-3-methylimidazole bis-trifluoromethanesulfonimide salt, 1-butyl- 3-Methylimidazole bis-trifluoromethanesulfonimide salt, 1-ethyl-3-methylimidazole bisfluoromethanesulfonyl imide salt, 1-propyl-3-methylimidazole bisfluoromethanesulfonyl imide Amine salt, 1-butyl-3-methylimidazole bisfluoromethanesulfonimide salt, N-methyl, propylpyrrole bistrifluoromethanesulfonimide salt, N-methyl, butylpyrrole bistrifluoromethanesulfonimide salt More than one of fluoromethanesulfonimide salt, N-methyl, propylpyrrole bisfluoromethanesulfonimide salt and N-methyl, butylpyrrole bisfluoromethanesulfonimide salt; 所述无机物纳米颗粒为二氧化硅纳米颗粒、二氧化锆纳米颗粒、二氧化钛纳米颗粒或三氧化二铝纳米颗粒。The inorganic nanoparticles are silicon dioxide nanoparticles, zirconium dioxide nanoparticles, titanium dioxide nanoparticles or aluminum oxide nanoparticles. 3.根据权利要求1所述的一种锂负极保护膜，其特征在于：所述保护膜厚度为0.1μm～100μm。3 . The lithium negative electrode protection film according to claim 1 , wherein the thickness of the protection film is 0.1 μm˜100 μm. 4 . 4.一种如权利要求1～3中任一项所述的锂负极保护膜的制备方法，其特征在于：所述方法步骤如下：4. A method for preparing the lithium negative electrode protective film according to any one of claims 1 to 3, characterized in that: the steps of the method are as follows: (1)在水分含量小于等于0.1ppm的无氧环境中配置锂盐与离子液体的混合溶液；(1) Configure a mixed solution of lithium salt and ionic liquid in an oxygen-free environment with a moisture content less than or equal to 0.1ppm; (2)将混合溶液及无机物纳米颗粒放置于球磨罐中并密封，球磨混合均匀后，得到准固态电解质；(2) Place the mixed solution and inorganic nanoparticles in a ball mill jar and seal it, and after ball milling and mixing evenly, a quasi-solid electrolyte is obtained; (3)取准固态电解质与锂化处理的Nafion聚合物溶液混合搅拌，将混合搅拌得到的材料在水分含量小于等于0.1ppm的无氧环境中进行如下操作：(3) Take the quasi-solid electrolyte and mix and stir the Nafion polymer solution treated with lithiation, and perform the following operations in an oxygen-free environment with a moisture content of less than or equal to 0.1ppm for the material obtained by mixing and stirring: 1)涂覆于金属锂表面，静置，溶剂挥发完全后，得到覆盖有薄膜的金属锂，所述薄膜即为本发明所述的一种锂负极保护膜；或1) coating on the surface of lithium metal, standing, after the solvent volatilizes completely, obtain the lithium metal that is covered with thin film, and described thin film is exactly a kind of lithium negative electrode protective film of the present invention; Or 2)涂覆在铜箔表面上，静置，溶剂挥发完全后，得到覆盖有薄膜的金属铜箔，将铜箔表面上形成的薄膜剥离，所述薄膜为本发明所述的一种锂负极保护膜。2) Coating on the surface of copper foil, standing still, after the solvent volatilizes completely, obtain metal copper foil covered with film, peel off the film formed on the surface of copper foil, and the film is a lithium negative electrode according to the present invention protective film. 5.根据权利要求4所述的锂负极保护膜的制备方法，其特征在于：锂盐在离子液体中的浓度为0.5mol/L～2mol/L；5. The preparation method of lithium negative electrode protective film according to claim 4, characterized in that: the concentration of lithium salt in the ionic liquid is 0.5mol/L～2mol/L; 混合溶液与无机物纳米颗粒的质量比为0.5～1.5:1；The mass ratio of the mixed solution to the inorganic nanoparticles is 0.5-1.5:1; 准固态电解质与锂化处理的Nafion聚合物的质量比为0.2～5:1；The mass ratio of the quasi-solid electrolyte to the lithiated Nafion polymer is 0.2-5:1; 锂化处理的Nafion聚合物溶液中锂化处理的Nafion聚合物粉末质量分数为5％～30％。The mass fraction of the lithiated Nafion polymer powder in the lithiated Nafion polymer solution is 5%-30%. 6.根据权利要求4所述的锂负极保护膜的制备方法，其特征在于：球磨时间为20min～200min，球磨速度为300r/min～600r/min，球料比为25～30:1。6 . The preparation method of lithium anode protective film according to claim 4 , characterized in that: the ball milling time is 20 min to 200 min, the ball milling speed is 300 r/min to 600 r/min, and the ball-to-material ratio is 25 to 30:1. 7.根据权利要求4所述的锂负极保护膜的制备方法，其特征在于：锂化处理的Nafion聚合物溶液通过锂化处理的Nafion聚合物粉末溶解于二甲基亚砜或者N-甲基吡咯烷酮中得到。7. the preparation method of lithium negative electrode protective film according to claim 4 is characterized in that: the Nafion polymer solution of lithiation process is dissolved in dimethyl sulfoxide or N-methyl sulfoxide by the Nafion polymer powder of lithiation process obtained from pyrrolidone. 8.根据权利要求4所述的锂负极保护膜的制备方法，其特征在于：锂化处理的Nafion聚合物粉末通过如下方法制得：8. The preparation method of lithium negative electrode protection film according to claim 4, is characterized in that: the Nafion polymer powder of lithiation process is obtained by following method: 在Nafion溶液中加入氢氧化锂溶液，进行锂化处理，直到pH值为8，在40℃～120℃下真空干燥，得到锂化处理的Nafion聚合物粉末。Lithium hydroxide solution is added to the Nafion solution, and the lithiation treatment is carried out until the pH value is 8, and vacuum-dried at 40° C. to 120° C. to obtain lithiation-treated Nafion polymer powder. 9.根据权利要求4所述的锂负极保护膜的制备方法，其特征在于：所述水分含量小于等于0.1ppm的无氧环境采用在充满惰性气体且水分含量小于等于0.1ppm的手套箱实现。9. The preparation method of lithium negative electrode protective film according to claim 4, characterized in that: the oxygen-free environment with moisture content less than or equal to 0.1ppm is realized in a glove box filled with inert gas and with moisture content less than or equal to 0.1ppm. 10.一种锂金属二次电池，其特征在于：所述锂金属二次电池具有如权利要求1～3中任一项所述的锂负极保护膜。10. A lithium metal secondary battery, characterized in that the lithium metal secondary battery has the lithium negative electrode protective film according to any one of claims 1-3.
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CN115036447B (en) * 2022-07-15 2023-08-29 中国科学技术大学 Lithium/sodium metal battery electrode plate protective coating and preparation method thereof
CN115440935A (en) * 2022-09-02 2022-12-06 华南理工大学 A lithium metal negative electrode and its preparation method and application
CN119920901A (en) * 2023-10-31 2025-05-02 浙江吉利控股集团有限公司 A negative electrode protective layer, preparation method and negative electrode sheet

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