677 results about "Lithium dendrite" patented technology

The invention discloses a composite diaphragm for a battery and a preparation method thereof, belonging to the field of electrochemical cells. The composite diaphragm is a multilayer composite diaphragm structure composed of a conducting layer/a polymer layer or a conducting layer/a polymer layer/a conducting layer, wherein the conducting layer mainly comprises a carbon material or a conductive polymeric material and forms a film on a single surface or double surfaces of a polymer diaphragm. The composite diaphragm has the following characteristics: the conducting layer has strong electrolyte adsorption and storage capability, the process of ion transport is shortened, and large-current charge and discharge performance of the battery is improved; when the composite diaphragm is used in a metallic lithium battery, the conducting layer in the composite diaphragm contacting with metallic lithium can alleviate nonuniform corrosion on the surface of lithium and inhibit formation of lithium dendrite crystals. The preparation method for the composite diaphragm is simple and easily controllable, can realize large-quantity and low-cost industrial preparation of the composite diaphragm and has a high application value.

The invention relates to solid-state electrolytes, in particular to a polycarbonate all-solid-state polymer electrolyte, an all-solid-state secondary lithium battery made of the same and preparation and application thereof. The all-solid-state polymer electrolyte is prepared from polycarbonate macromolecules, lithium salt and a porous supporting material; the thickness is 20-800 micrometers, the mechanical strength is 10-80 MPa, the room temperature ion conductivity is 2*10<-5>S/cm-1*10<-3>S/cm, and the electrochemical window is higher than 4V. The all-solid-state polymer electrolyte is easy to prepare and form, good in mechanical property, high in ion conductivity and wide in electrochemical window; meanwhile, the solid-state electrolyte effectively inhibits growth of negative electrode lithium dendrites and improves interface stability and long circulation performance.

The invention discloses a preparation method of a composite lithium metal anode and belongs to the technical field of lithium metal batteries. The preparation method of the composite lithium metal anode comprises steps as follows: firstly, the surface of a framework material is modified, the framework material with the lithiophilic surface is prepared, the framework material is contacted with liquid metal lithium, so that the liquid metal lithium is injected into the framework material with the lithiophilic surface, and the composite lithium metal anode is prepared after cooling. The lithiophilic surface can be obtained through modification of various framework materials (including a conductive framework material and an insulated framework material), the framework materials are efficientlycomposited with the liquid metal lithium, and the composite lithium metal anode material is obtained. When the obtained composite lithium metal anode material is assembled in a total battery, growthof lithium dendrites can be effectively inhibited, the volume expansion effect of the anode is relieved, the pulverization phenomenon of the lithium metal anode is reduced, and the cycling stability and the safety of the lithium metal battery are substantially improved, and the cycle life of the lithium metal battery is substantially prolonged.

The present invention provides a composite quasi-solid-state electrolyte, a composite quasi-solid-state electrolyte membrane, preparation methods of composite quasi-solid-state electrolyte and the composite quasi-solid-state electrolyte membrane, and a lithium battery or a lithium ion battery containing the composite quasi-solid-state electrolyte membrane. The composite quasi-solid-state electrolyte comprises a solid electrolyte, a lithium salt-containing liquid electrolyte, inorganic nanoparticles and a binder, wherein the static electricity or functional groups on the surface of the inorganic nanoparticles can adsorb the electrolyte so as to make the composite quasi-solid-state electrolyte have strong adsorption capacity and strong liquid retention ability, and the inorganic nanoparticles can adsorb the lithium salt so as to change the lithium ion conduction mechanism, reduce the interfacial resistance between the liquid electrolyte and the solid-state electrolyte, change the deposition morphology of lithium, hinder the formation of lithium dendrite, and reduce the pulverization of lithium. In addition, by adding the solid electrolyte, the composite quasi-solid-state electrolyteof the present invention can maintain the high conductivity and can effectively reduce the content of the liquid electrolyte so as to improve the safety of the battery.

The invention discloses a rechargeable metal lithium secondary battery capable of preventing from generating lithium dendrites. The battery system consists of a lithium salt, a non-aqueous solvent and/or an electrolyte additive, wherein a ratio of mole of the lithium salt to volume of the non-aqueous solvent ranges from 2 mol/1L to 10 mol/1L. A proper system is selected, and the proportion of the salt and solvent in the system is regulated, so that the physical and chemical performances such as electrolyte lithium ion solvation degree and viscosity and physical and chemical performances of solid intermediate phase films generated on the surface of metal lithium in the electrochemical process are changed, growth of dendritic dendrites on the surface of metal lithium on the cathode due to non-uniform electrochemical deposition is effectively inhibited, and finally, the aim of improving the safety performance of the rechargeable metal lithium secondary battery is achieved.

The invention discloses an organic-inorganic composite electrolyte membrane having a double layer structure including a first layer and a second layer, wherein each of the first layer and the second layer is prepared from slurry comprising the following same components: an inorganic solid electrolyte, lithium salt, a film forming agent, a conductive lithium ion polymer, a plasticizer, and a solvent; herein, the content of inorganic solid electrolyte in the first layer is higher than that in the second layer, and the content of conductive lithium ion polymer in the first layer is less than thatin the second layer. The invention also discloses a battery having the organic-inorganic composite electrolyte membrane. The membrane has good flexibility and high conductivity, can satisfy differentdemands of a cathode and an anode in a lithium ion battery at the same time, can inhibit growth of lithium dendrites, and improves comprehensive performance of the battery.

The invention discloses a high voltage-resistant multi-stage structure composite solid-state electrolyte and its preparation method and use in a solid-state lithium battery. The lithium battery utilizes a multi-stage structure solid-state electrolyte containing different components. A polymer electrolyte with excellent electrode interface compatibility is used as an electrolyte in the negative electrode side. A high voltage-resistant polymer electrolyte is used as an electrolyte in the positive electrode side. A polymer electrolyte or an inorganic electrolyte with high ionic conductivity is used as a middle layer. The multi-stage structure solid-state electrolyte has advantages such as high mechanical properties, high ionic conductivity, a wide electrochemical window, excellent electrode interfacial compatibility and lithium dendrite growth inhibition of different components. Compared with the traditional liquid lithium ion battery, the battery with the multi-stage composite solid-state electrolyte has higher safety and higher energy density.

The invention provides a composite solid electrolyte and a preparation method thereof, a flexible all-solid-state battery and a preparation method of the flexible all-solid-state battery and a wearable electronic device. The composite solid electrolyte comprises a ceramic-based solid electrolyte and a first polymer-based solid electrolyte, wherein the content of the ceramic-based solid electrolyte is 20-90wt% of total weight of the composite solid electrolyte. The composite solid electrolyte provided by the invention has good mechanical property, high ionic conductivity at a room temperature, good heat stability and electrochemical stability and high safety and can be effectively prevented from being perforated by lithium dendrites, and a good interface contact is formed by the composite solid electrolyte and a composite positive electrode, thereby obtaining the flexible all-solid-state battery which is high in area specific capacity and energy density, relatively small in battery internal resistance and high in flexibility and can be bent and cut and of which use is not affected.

The invention relates to a metal lithium negative electrode with organic and inorganic dual protection layers. The invention belongs to the technical field of electrochemistry, and relates to the metal lithium negative electrode with the organic and inorganic dual protection layers and application of the metal lithium negative electrode in a secondary lithium battery. The protection layers are characterized in that an organic protection layer is built on a surface of the metal lithium negative electrode from one or more of acrylate containing amino, cyan, nitro or nitroso, one or more of acrylic organic matters except several types of the acrylates and one or more of small molecule compounds containing nitrogen, meanwhile, a nitrogen-containing part in the organic layer reacts with metal lithium to form an inorganic protection layer at an interface in an in-situ way, so that the organic and inorganic dual protection layers are formed. When the metal lithium negative electrode with the protection layers is applied to a lithium battery, the coulombic efficiency of the battery can be effectively improved by a synergistic effect of the organic layer and the inorganic layer, the growth of lithium dendrites is prevented, the safety problem is improved, and the cycle lifetime is prolonged.

The invention discloses an anode material for a lithium metal battery. The anode material comprises a current collector and a carrier which is in tight fit with the current collector, wherein the carrier has a three-dimensional framework structure; a gap of the three-dimensional framework structure is filled with lithium metal; the carrier is selected from at least one of polymelamine, polyacrylonitrile, polyaniline, polyimide, polyvinylidene fluoride and polytetrafluoroethylene. The anode material disclosed by the invention has the advantages that a nonconductive polymer with the three-dimensional framework structure is used as the carrier, and stable deposition of lithium ions is realized by using interaction of functional groups contained in the carrier and the lithium ions; meanwhile,volumetric expansion is inhibited, internal stress of the battery is relieved, and thereby the aim of inhibiting growth of lithium dendrites is achieved. The coulombic efficiency, the safety of the lithium ion battery obtained by assembling the anode material prepared disclosed by the invention is remarkably improved and cycle life is obviously prolonged.

The present invention discloses an inorganic-organic nano composite solid electrolyte membrane and a preparation method and application thereof. The composite solid electrolyte is a novel inorganic-organic nanocomposite combining the respective advantages of inorganic ceramic solid electrolyte and organic polymer electrolyte and is composed of a negative electrode protective layer, a support layerand a positive electrode interface layer. The support layer plays a supporting role, and the main component of the negative electrode protective layer is the inorganic solid electrolyte with good mechanical properties, which can effectively inhibit the growth of lithium dendrite; and the positive electrode interface layer is mainly composed of organic polymer electrolyte with good flexibility, ensures good contact with active materials and provides a continuous ion transport channel. In the present invention, the composite solid electrolyte with good interface compatibility is prepared by coating on both sides of the support layer, and the process is simple and efficient. The composite solid electrolyte can effectively inhibit dendritic crystal and reduces interface resistance so that a solid lithium metal battery has higher energy density and longer cycle life.

The invention provides a membrane and a preparation method thereof as well as a lithium ion battery. The membrane comprises a substrate and size layers arranged on two sides of the substrate, wherein the size layers comprise ceramic particles, a silane coupling agent and an adhesion agent, and the substrate is an insulating carbon fiber non-woven fabric. The membrane disclosed by the invention has the advantages of good heat-resistant property, chemical corrosion resistant property, high strength and capability of effectively avoiding short circuit in the battery caused by puncture of lithium dendrites. The lithium ion battery prepared from the membrane disclosed by the invention has the advantages of excellent safety performance and high temperature resistance and long service life.

The present invention relates to a negative electrode including a multi-protective layer and a lithium secondary battery including the same, and the multi-protective layer prevents lithium dendrite growth on a surface of the electrode, and does not cause overpotential during charge and discharge since the protective layer itself does not function as a resistive layer, and therefore, is capable of preventing battery performance decline and securing stability when operating a battery.

The invention discloses a high-power lithium ion power battery, comprising a plurality of single electrical cores connected in parallel. Each single electrical core consists of an anode plate, a cathode plate, a separator film, and two to eight anode tabs and cathode tabs. The anode tabs and the anode plate are integrated as a whole which is punched on the aluminum foil of the current collector of the anode; the cathode tabs and the cathode plate are integrated as a whole which is punched on the copper foil of the current collector of the cathode. All the tabs of the anodes of the single electrical cores are welded on a positive pole, while all the tabs of the cathodes are welded on a negative pole. By the structure of a variety of single electrical cores connected in parallel and a plurality of tabs integrated as a whole, the high-power lithium ion power battery leads the total essential resistances of the batteries to be further reduced and the currents of the anode and cathode plates to be distributed more uniformly, as a result, the high-power lithium ion power battery has the advantages of small essential resistances in total, high discharge rate, lower possibility of forming lithium dendrites, long cycle life and high specific power etc., and is widely used in electric vehicles, electric tools and other equipment in need of high-power batteries.

The invention discloses a battery diaphragm with high-temperature-resistant metal-organic frame material coating, and a preparation method and application thereof. The battery diaphragm takes a commercial diaphragm as the substrate, and the single surface or double surface is coated with the metal-organic frame material. Compared with the prior art, the battery diaphragm disclosed by the inventionhas the following advantages: the metal-organic frame material coating is high in porosity and large in specific area, and the electrolyte wetting property of the diaphragm can be improved; the metalorganic frame material coating can effectively improve the heat-insulating property of the diaphragm, and improve the safety performance of the battery in the high-temperature environment; the metal-organic frame material coating can effectively control the shuttle of the electrolyte ion, improve the ion transport number, restrain the bad and side effect, improve the battery capacity, and prolongthe circulating life; the uniform duct structure enables the lithium ions to be uniformly deposited/peeled, thereby fundamentally restraining the growth of the lithium dendrites; the battery diaphragm disclosed by the invention has good flexibility and mechanical performance, and can be used for assembling a practical soft-package battery.

The invention belongs to the field of lithium batteries, and discloses preparation and application of a lithium metal anode with a composite film. The preparation method comprises the following stepsof: (1) performing matching and composite load of an organic component and an inorganic lithium compound component according to the mass ratio of 1:1-98:1 on a current collector; and (2) assembling the obtained current collector with the surface coated with a composite film with a lithium sheet into a battery for electrochemical deposition to deposit the metal lithium on the current collector withthe surface coated with the composite film so as to obtain a lithium metal anode material with a composite film. According to the invention, the lithium metal anode material with the composite film is obtained by improving the overall design of the flow process of the anode material preparation method, the phenomenon of lithium dendrite caused by uneven deposition in the circulation process of the conventional lithium metal anode and the phenomenon of reduced circulation performance caused by dead lithium generated by the reaction of the lithium metal anode and electrolyte can be solved, andthe lithium metal anode material can be used as the anode in a lithium metal battery, so that the circulation life of the lithium metal battery is prolonged.

The invention discloses an anode material for lithium metal batteries. The anode material is prepared from a lithium slice and an artificial solid electrolyte interface film, wherein the artificial solid electrolyte interface film is deposited on the surface of the lithium slice by a magnetron sputtering method; the artificial solid electrolyte interface film is at least one selected from LiF, LiBr, LiCl, LiI, Li2CO3, LiOH, Li3P, Li3PO4, LiNO3, Li2S, Li2SO4 and Li3N. The anode material for the lithium metal batteries is formed by enabling inorganic lithium salt to be physically deposited on the lithium slice; the anode material for the lithium metal batteries can effectively inhibit the growth of lithium dendrites and improve the safety and cycle performance of the lithium metal batteries.

The invention specifically relates to an electrolyte for inhibiting lithium dendrites and a preparation method thereof, and a lithium battery, belonging to the technical field of lithium batteries. The electrolyte comprises a lithium salt, a nanometer additive, a dispersant and an organic solvent, wherein the concentration of the lithium salt is 0.5 to 10 mol/L, and the mass percent of the nanometer additive is 0.01 to 10%. The nonaqueous electrolyte prepared with fluoride-containing nanoparticles as the nanometer additive enables the battery to have better stability and security and longer service life; the fluoride-containing electrolyte has continuous and stable effect in the battery; compared with traditional film-forming nanometer additives, the fluoride-containing nanoparticles achieves the effect of on-site rapid film formation on the surface of a negative electrode, so the growth of lithium dendrites and side reactions on the surface of a positive electrode are effectively inhibited; moreover, the fluoride-containing nanoparticles stably exist in the electrolyte and is free of problems like decline in effect.

The invention belongs to the field of lithium ion batteries and relates to a negative pole piece. The negative pole piece comprises a negative current collector and a negative material layer adhered onto the surface of the negative current collector; the negative material layer comprises a first negative material layer and a second negative material layer; the first negative material layer comprises a first material area and a second material area positioned on the edge of the first material area and is adhered onto the surface of the negative current collector; the thickness of the first material area is greater than that of the second material area; the second negative material layer is adhered onto the surface of the second material area and is positioned on the edge of the first negative material layer. The negative pole piece provided by the invention has the benefits that the risk of battery short-circuit caused by potential production of lithium dendrites due to relatively low edge coating weight of a conventional negative sheet is reduced, the occurrence probability of safety accidents of the lithium ion battery is reduced, and the safety performance of the lithium ion battery is improved.

The invention discloses an interface modifying method of a lithium metal battery anode. The surface-modified metal lithium is used for a lithium metal battery. The interface modifying method has the advantages that a solution containing dissimilar metal ions, such as copper, manganese, cobalt, nickel, iron, zinc, gold, silver and platinum, is used as a treatment solution, and a dissimilar metal film is produced at the surface of a lithium piece in situ by a liquid phase chemical replacement method; the dissimilar metal film can be stabilized at the metal lithium/electrolyte surface, the production of lithium dendrites is effectively inhibited, the polarizing of electrochemistry is reduced, the charging property of the lithium metal anode is improved, and the property of the lithium metal battery is improved; the technique is simple, the implementing is easy, the scaled production is easy, and the application prospect is broad.

The invention discloses a dopamine-modifying ceramic composite separator and an application thereof. The dopamine-modifying ceramic composite separator comprises an organic separator base material and a ceramic layer arranged on the surface of the separator base material in a coated mode, wherein the thickness of the ceramic layer ranges from 0.1 micrometer to 20 micrometers. The dopamine-modifying ceramic composite separator further comprises dopamine polymers grown on the surfaces and the interiors of the separator base material and the ceramic layer in an in-situ mode. The dopamine polymers are copolymers of polydopamine or 5-hydroxy- polydopamine or polydopamine acrylamide and polydopamine acrylamide. The particle size of inorganic powder in the ceramic layer ranges from 5 nanometers to 10 micrometers. The molecular weight of materials of the organic separator base material ranges from 1,000 to 100,000,000. According to the dopamine-modifying ceramic composite separator, due to the dopamine polymers, potential safety hazards caused by powder falling and liquid leaking of the ceramic layer can be effectively reduced, and the physical performance and the electrochemical performance of the separator are effectively improved; meanwhile, due to the dopamine polymers, the stability of an interface between separator electrolysis and an electrode can be improved, lithium dendrites can be effectively suppressed through the improvement of the stability of the interface, and therefore the capacity holding capacity of a battery can be easily improved.

The invention discloses a lithium metal negative electrode dual protection method and application. The method comprises the steps of: infiltrating a lithium metal negative electrode in a mixture of ametal halide and an additive, and forming a composite protective layer in situ on the surface of the lithium metal negative electrode, wherein the composite protective layer comprises combination of an alloy and an inorganic salt; and coating the surface of a membrane with an organic polymer solution to obtain a membrane having an inner surface coated with an elastic organic modifying layer. The lithium metal negative electrode dual protection method and application are simple to operate, high in controllability, low in raw material cost, easy to obtain the raw materials and low in cost, and can form a layer of stable composite protective layer at the surface of the lithium metal negative electrode. The protective layer can effectively inhibit the growth of the lithium dendrites and can reduce the side reaction generated by contact of the lithium metal negative electrode and the electrolyte, and the obtained modified lithium metal negative electrode is stable in cycle performance to effectively inhibit the generation of the dendrites of the lithium metal negative electrode and can be widely applied to the novel high specific energy electrochemical energy storage device, such as a lithium ion battery and a lithium-sulfur battery.

The invention discloses a lithium battery electrode preparation method including polymer material with a stable interface and the application of a lithium battery electrode in a solid lithium battery. The preparation method is characterized in that the polymer material with the stable interface is poly-vinylene carbonate (PVCA) or copolymers thereof. The free radical triggers the monomer to perform mass polymerization to obtain a polymer, the polymer material with the stable interface can form a cover film on the surface of the electrode, thus destruction on the electrode material and decomposition of the solid electrolyte on the surfaces of the positive and negative electrodes can be effectively restrained. Meanwhile, the polymer material can form a stable protection layer on the surface of lithium metal to inhibit the growth of the lithium dendrites, thus the cycle performance of the solid lithium battery is improved. The invention also provides a preparation method of the electrochemical stable polymer material, and the solid lithium battery assembled by using the polymer material.

The invention discloses a passivated lithium metal-skeleton carbon composite material and a preparation method and application thereof. The composite material is prepared from a lithium metal-skeleton carbon composite material and a passivated layer, wherein the lithium metal-skeleton carbon composite material is prepared from a porous carbon material carrier and lithium metal which is at least distributed in holes of the porous carbon material carrier, and the passivated layer is at least used for stopping the lithium metal in the lithium metal-skeleton carbon composite material from directly contacting the outside world. As the artificial passivated layer is formed on the particle surface of the lithium metal-carbon skeleton composite material, the phenomenon that lithium metal is corroded by electrolyte in a circulating process is effectively reduced, and lithium dendrites are prevented from forming; thus, the obtained passivated lithium metal-carbon skeleton composite material has the advantages of good circulating stability, high coulombic efficiency and the like in electrochemical circulation, can be widely applied to chemical energy storing devices of rechargeable lithium batteries, rechargeable lithium ion batteries and the like, can effectively improve coulombic efficiency, circulating stability and energy density of batteries.

The invention provides a negative plate, a preparation method thereof and a lithium battery. The negative plate comprises a current collector, wherein the current collector is copper with a hole structure, and a protective layer is arranged on the surface of the current collector. Copper with the hole structure is taken as the current collector of the negative plate, so that inside space of the current collector can serve as lithium storage space for storing lithium precipitated in a battery charging process, meanwhile, lithium metal precipitates between the copper current collector and the protective layer by means of the inorganic protective film on the surface of the current collector, and production of lithium dendrites is inhibited. Compared with a common lithium ion battery with a graphite cathode, a lithium secondary battery provided with the lithium-free negative plate has the advantage that the energy density of the lithium battery can be improved substantially under the precondition that higher safety performance and better cycle performance are guaranteed.

The invention relates to a preparation method of a high-safety metal composite negative electrode. The preparation method comprises the following steps: (a) heating metal lithium to a fused state under the protection of inert gas; (b) adding an inorganic non-metal compound into the metal lithium with the fused state; after stirring and reacting, cooling, wherein the inorganic non-metal compound isselected from one or a mixture of more of sulfide, phosphide, nitride and fluoride, and the mass ratio of the metal lithium to the inorganic non-metal compound is (10 to 3) to 1. According to the preparation method, a compound protection layer can be formed on a lithium negative electrode so that electrolyte and a lithium sheet are effectively isolated and the lithium sheet is prevented from corrosion and reaction; uniform distribution of lithium ions is realized and lithium dendrites are prevented from being generated; a framework supporting effect is provided.

The invention discloses a lithium cathode used for a lithium battery and provided with a sandwich structure and a preparation method thereof. The lithium cathode is provided with the sandwich structure formed by a conductive current collector, a metal lithium layer and a high polymer material layer. The method for preparing the lithium cathode comprises a first step of preparing an electrode precursor by compounding a high polymer material and the conductive current collector; and a second step of causing metal lithium to enter an intermediate layer of the electrode precursor to form the lithium cathode with the sandwich structure. By introduction of the high polymer material as a protective layer, growth of metal lithium dendrites can be inhibited, the safety of the lithium battery is improved, the volume expansion in the lithium battery cyclic process can be adapted, and an effect of stabilizing an interface is achieved. In addition, the conductive high polymer material can form a conductive network on the surface of the lithium cathode, lithium ions are induced to be deposited evenly, and a buffer effect on the lithium ions can also be achieved under the conditions of high-current charging and discharging. The method is simple to operate, low in cost, has easiness in large-scale production and has great potential application values in the lithium battery.

The invention relates to a metallic lithium rechargeable electrochemical accumulator, comprising at least one lithium metal electrode and at least one polymeric electrolyte gel. Said accumulator is capable of operating at temperatures from −20 to 60° C., essentially without formation of lithium dendrites on the whole surface of the metallic lithium electrode. The above is also wherein a particularly long life, even with intensive use at low temperature. Said inventive rechargeable accumulator can be produced by use of a production method with particular application of temperature control during the specific production stages. As a result of the extremely high electrochemical performance of said accumulator, in particular the remarkable stability thereof, said accumulator can be used in new application fields such as hybrid vehicles, electric vehicles and emergency supply systems such as those of the UPS type.

The invention discloses a composite negative electrode, a preparation method of the negative electrode and a lithium-sulfur secondary battery with the negative electrode. The composite negative electrode comprises copper foil and a solid lithium ion conductive diaphragm tape, wherein one end of the copper foil is provided with a tab for conducting current, at least one side of the copper foil is closely provided with metal lithium foil or alloy lithium foil which is used as a battery negative electrode, and the solid lithium ion conductive diaphragm tape covers the battery negative electrode, so that the accumulation of lithium ions on a negative electrode lithium alloy surface and the short circuit, caused by lithium dendrites, between a positive electrode and the negative electrode of the battery can be prevented. In the manner, on the premise of maintaining high energy density, the safety performance of the lithium-sulfur battery can be improved. In addition, multi-element compound electrolyte is used for substituting for organic electrolyte, so that the dissolving and diffusion of sulfur in the electrolyte can be effectively prevented, and the cycling life of the battery can be greatly prolonged.

The invention relates to a lithium negative electrode protection film, a preparation method and a lithium metal secondary battery, belonging to the field of lithium metal secondary batteries. The lithium anode protective film is composed of lithium salt, ionic liquid, inorganic nanoparticles and lithium-treated Nafion polymer. Ionic liquids containing lithium salts are adsorbed on the surface of inorganic nanoparticles and uniformly dispersed in lithium-treated Nafion polymers. By arranging a mixed solution of lithium salts and ionic liquids; Mixing the mixed solution and the inorganic nanoparticles by sealed ball milling to obtain a quasi-solid electrolyte; The quasi-solid electrolyte is mixed with a lithium-treated Nafion polymer solution, coated on the surface of lithium or copper foil,and the protective film is prepared after the solvent is completely volatilized. As that lithium negative electrode protective film can inhibit the generation of lithium dendrite, the lithium negative electrode protective film has good mechanical properties and chemical stability, high lithium ionic conductivity and good film for performance; A lithium metal secondary battery provide with that lithium anode protective film has excellent electrochemical performance.