CN110224177B - Protection method of lithium metal/sodium metal negative electrode and product - Google Patents
Protection method of lithium metal/sodium metal negative electrode and product Download PDFInfo
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- CN110224177B CN110224177B CN201910380977.3A CN201910380977A CN110224177B CN 110224177 B CN110224177 B CN 110224177B CN 201910380977 A CN201910380977 A CN 201910380977A CN 110224177 B CN110224177 B CN 110224177B
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- 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
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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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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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
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a lithium metal/sodium metal negative electrode protection method and a product, belonging to the field of lithium metal/sodium metal battery negative electrode materials and electrochemistry, wherein a type of interface modification material is constructed on a battery diaphragm in advance under any atmosphere to obtain a prefabricated diaphragm, the interaction between the interface modification material and a lithium negative electrode is stronger than that between the interface modification material and the diaphragm, and a battery assembly process is executed, wherein one surface of the prefabricated diaphragm with the interface modification material is tightly attached to an alloy lithium negative electrode, electrolyte is injected, and the interface modification material is spontaneously transferred from the diaphragm to the surface of the metal lithium negative electrode by utilizing the physical and chemical actions between the interface modification material and the metal lithium under the immersion of the electrolyte, so that the protection of the metal lithium negative electrode is automatically realized. The same principle applies to sodium metal batteries. The method does not need to directly operate the lithium cathode or the sodium cathode, is safe and reliable, has simple process and wide application conditions, and has stronger manufacturability and better practical effect.
Description
Technical Field
The invention belongs to the field of lithium metal/sodium metal battery cathode materials and electrochemistry, and particularly relates to a surface modification technology and a product of a lithium metal battery cathode or a sodium metal battery cathode.
Background
With the continuous development of industry, a large amount of harmful gas and smoke are generated in the combustion of the traditional fossil fuel, so that the natural environment and the social environment are seriously influenced, and the living environment of human beings is also greatly threatened. Therefore, it is urgent to develop renewable clean energy. Lithium ion batteries are widely used in portable electronic products due to their advantages of wide specific operating voltage, high discharge capacity, stable discharge, environmental friendliness, etc.
In recent years, with the rising of electric automobiles and the field of large-scale energy storage, corresponding electrode materials with higher specific capacity, higher energy power density and longer cycle life are required. However, the conventional lithium secondary battery is far from meeting the requirements of advanced energy storage devices due to the limited specific capacity.
The lithium metal cathode is regarded as a holy cup in the cathode material of the lithium secondary battery due to the ultrahigh theoretical specific capacity (3860mAh/g) and the lowest oxidation-reduction potential (-3.04V), can be applied to high-energy-density batteries such as lithium air, lithium sulfur and the like, and can be matched with a lithium ion anode material, so that the requirement of an advanced energy storage technology is met.
However, the lithium metal negative electrode is liable to form irregular lithium dendrite during deposition, and irreversible reaction of the lithium negative electrode with the organic electrolyte also causes irreversible capacity loss, so that cycle performance is rapidly degraded. On the one hand, the generated lithium dendrites are easy to fall off to form dead lithium, which not only reduces the coulomb efficiency of the battery but also aggravates the occurrence of side reactions. On the other hand, the formed lithium dendrites are easy to pierce through the membrane to cause internal short circuit, and even fire or explosion safety accidents occur.
In order to solve the problems, reasonable modification of the surface of the lithium negative electrode is important, and the construction of an interface modification layer is considered to be the most effective solution. The ideal interface modification layer needs to have excellent electronic insulation ion conduction characteristics to ensure the rapid migration of lithium ions and proper lithium deposition sites, and good chemical and electrochemical stability to ensure that the surface of metal lithium can be effectively protected in a long-cycle process and side reactions between the metal lithium and electrolyte can be reduced. In addition, the interface modification layer also has excellent mechanical properties to buffer the volume expansion during the lithium metal deposition and dissolution process and inhibit the continuous growth of dendrites.
However, the current interface modification layer construction technology has disadvantages and challenges, mainly because the key steps of the above process involve direct operation of lithium, and metallic lithium has ultrahigh chemical reactivity and is very easy to react with most atmospheres or reagents, and releases a large amount of heat or explosive gases such as hydrogen, which brings great insecurity and complexity to the operation and storage of metallic lithium. The high selectivity of atmosphere and reagent, and the high-purity and high-dry reagent and instrument equipment which are expensive, greatly limit the application popularity and large-scale commercialization of the process. In addition, many material systems are modification materials that can be used for the lithium negative electrode interface according to their own composition structure, but cannot be applied to the existing surface modification technology because of the incompatibility of the atmosphere and reagents with lithium.
Therefore, it is very important and significant to study an artificial interface layer construction technique using a lithium negative electrode metal which is low in cost, simple, free from environmental equipment limitations, and easy to handle.
Disclosure of Invention
The invention provides a lithium metal/sodium metal battery cathode protection method and a product aiming at the defects or improvement requirements of the prior art, wherein an interface modification material and a transfer process are researched and designed, the interface modification material is constructed on a diaphragm in advance, electrolyte is inevitably injected in the battery assembly process to infiltrate the interface modification material with the electrolyte, spontaneous transfer is carried out by utilizing the lithium-philic property or the sodium-philic property of the interface modification material infiltrated by the electrolyte, and the interface modification material is transferred to a lithium cathode or a sodium cathode from the diaphragm, so that the lithium cathode or the sodium cathode is protected.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for protecting a lithium negative electrode in a lithium metal battery, in which a kind of interface modification material is pre-formed on a battery separator under an arbitrary atmosphere to obtain a pre-formed separator, the interface modification material has a stronger interaction with the lithium negative electrode than with the separator, and a battery assembly process is performed, wherein one surface of the pre-formed separator having the interface modification material is closely attached to the lithium negative electrode, an electrolyte is injected, and the interface modification material is spontaneously transferred from the separator to the surface of the lithium negative electrode by a physicochemical interaction between the interface modification material and the lithium metal under the immersion of the electrolyte, thereby automatically protecting the lithium negative electrode.
Further, the interface modification material comprises one or more of the following materials: graphene oxide and derivatives thereof, carbon nanotubes and derivatives thereof, graphene, carbon nitride, black phosphorus, boron nitride, metal oxides, metal sulfides, metal carbides, metal nitrides, lithium fluoride, lithium nitride, lithium sulfide, lithium oxide, lithium carbonate, lithium lanthanum zirconium oxide solid electrolyte (LLZO) and its derivatives, lithium germanium phosphorus sulfur solid electrolyte (LGPS) and its derivatives, polyethylene oxide (PEO) and its derivatives, Polyacrylonitrile (PAN) and its derivatives, polyvinylidene fluoride (PVDF) and its derivatives, polymethyl methacrylate (PMMA) and its derivatives, polypropylene oxide (PPO) and its derivatives, polyvinylidene chloride (PVDC) and its derivatives, polyacrylic acid (PAA) and its derivatives, Polyurethane (PU) and its derivatives, Polydimethylsiloxane (PDMS) and its derivatives, carboxymethyl cellulose (CMC) and its derivatives.
Further, the interface modifier is constructed on the battery separator in advance in the following manner: and uniformly and compactly constructing the dispersion, solution or suspension of the interface modification material on the diaphragm for the battery in advance in one or more modes of suction filtration, spray coating, drop coating, spin coating and blade coating.
The interface modification material is one layer or multiple layers, when the interface modification material is multiple layers, the part close to the lithium layer is required to be selected from materials with strong interaction with lithium, and the part close to the diaphragm is preferably the interface material with weak interaction with the diaphragm, so that the constructed interface modification layer can spontaneously realize the transfer from the diaphragm to the lithium cathode.
In addition, the multilayer interface modification material can be constructed according to different components, morphologies, physicochemical properties and functions to realize optimization of comprehensive performance of the artificial interface layer, such as good electronic insulation ionic conductivity, stable electrochemical/chemical properties and excellent mechanical properties.
Further, the solvent in the dispersion, solution or suspension of the interface modifying material includes: one or more of water, isopropanol, ethanol, acetone, glycerol, ethylene glycol, Tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), chloroform, and cyclohexane.
Furthermore, the thickness of the interface modification layer material in the prefabricated diaphragm is 0.5-50 μm, and if the thickness is too thin, the transferred diaphragm is incomplete, and if the thickness is too thick, the internal resistance of the battery is increased, and the battery performance is adversely affected.
Further, the diaphragm is a polyethylene microporous membrane, a polypropylene microporous membrane, a polyethylene/polypropylene double-layer co-extrusion membrane, a polypropylene/polyethylene/polypropylene three-layer co-extrusion membrane, an aromatic polyamide diaphragm (PMIA), a polyethylene terephthalate diaphragm (PET), a poly (p-phenylene benzobisoxazole) diaphragm (PBO), a polyimide diaphragm or a cellulose diaphragm, and the diaphragm is used for a pre-load substrate of the interface modification material and a physical insulation layer between the anode and the cathode.
According to a second aspect of the present invention, there is also provided a lithium metal battery obtained by the method as described above.
According to the third aspect of the present invention, there is also provided a method for protecting a sodium metal battery negative electrode, which applies the above-mentioned method to sodium metal battery sodium negative electrode protection, but in which an interface modifier having a stronger interaction with sodium than with a separator is previously formed on the separator for a battery, and a lithium negative electrode is replaced with a sodium negative electrode. In fact, the method of protecting the lithium metal negative electrode is equally applicable to the sodium negative electrode of a sodium metal battery. However, the cathode of the sodium metal battery is sodium metal, and the interface modification material shows a property more hydrophilic to metal sodium than the affinity membrane under the soaking of the electrolyte, so that spontaneous transfer can occur under the soaking of the electrolyte.
According to a fourth aspect of the present invention, there is also provided a sodium metal battery obtained by the method as described above.
In general, compared with the prior art, the above technical solution contemplated by the present invention can achieve the following beneficial effects:
1) the whole construction process of the prefabricated diaphragm does not involve the direct operation of the ultrahigh-activity metal lithium and the metal sodium, so that no special requirements on atmosphere and chemical reagents are required, and the selection range of the reagents and interface modification materials can be greatly widened;
2) the prefabricated diaphragm is constructed by adopting processes of spin coating, spray coating, suction filtration and the like which are low in price and simple to operate and can be carried out in the air, instrument equipment which is high in price and provided with an inert atmosphere protection cabin body is not needed, the construction cost can be further reduced, and the prefabricated diaphragm is suitable for large-scale commercialization;
3) the transfer process is spontaneously carried out in the existing mature battery assembly process, no redundant operation is needed, and the intrinsic morphology, the physicochemical property and the mechanical property of the interface modification material can be effectively maintained.
4) The interface modification layer constructed by the invention is uniform and compact, can reduce the contact area between the lithium/sodium metal cathode and the electrolyte, reduce the occurrence of side reactions, reduce the consumption of the lithium metal and the electrolyte, and inhibit the repeated formation and cracking of a solid electrolyte interface film in the lithium deposition/stripping process. The existence of the interface modification layer can realize the optimization of the battery performance, and the specific expression is that the coulombic efficiency of the battery is improved, the cycle life is prolonged to hundreds to thousands of circles, and the deposition appearance is more smooth. In addition, different interface layer materials such as high-elasticity modulus materials such as black phosphorus, graphene, boron nitride and the like can be selected to effectively and mechanically inhibit the continuous growth of dendrites; for example, atoms with larger electronegativity such as O, F, N and the like exist in the interface material, and Li-O, Li-N, Li-F bonds and the like can be formed after the interface material is contacted with lithium, so that the concentration of lithium ions on the surface of the lithium negative electrode is effectively stabilized, and the deposition behavior of the lithium ions is regulated; for example, molybdenum disulfide, vanadium pentoxide and the like can generate oxidation-reduction reaction with a metal cathode to form a high-ion conducting layer, the transmission of lithium ions at an interface can be improved, dendritic crystals can be effectively inhibited from puncturing a diaphragm, the safety of a battery system is remarkably improved, and the battery performance can be remarkably improved when the battery is applied to a metal battery.
Drawings
Fig. 1 is a schematic view of the construction of a lithium negative electrode/sodium negative electrode surface interface modification layer according to the present invention.
FIG. 2 shows the possible existence of the interface modification layer as one layer or as a multi-layer structure according to the composition, morphology, physical and chemical properties and functions.
FIG. 3 shows the use of carbon nitride (g-C) in an embodiment of the present invention3N4) Comparison of cycle performance of assembled lithium-copper half cells and unmodified lithium-copper half cells when used as interface repair materials. As can be seen from the figure, the dot symbols indicate the symbol containing g-C3N4The lithium-copper half cell assembled during the interface modification layer, the rectangular patch mark represents the non-modified lithium-copper half cell, and the comparison shows that g-C3N4The interface modification layer can obviously improve the coulombic efficiency and the cycle stability of the deposition and dissolution of the metal lithium cathode.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
In the prior art, most of protection methods for lithium cathodes or sodium cathodes involve direct operation on metal lithium cathodes or metal sodium cathodes, and due to the ultra-strong chemical/electrochemical activity of alkali metal cathodes, the alkali metal cathodes are prone to have adverse side reactions with air and moisture, so that the metal cathodes are ineffective and safe.
The invention discloses a construction process of a lithium metal or sodium metal battery cathode-electrolyte interface layer and a product. The method is applied to lithium metal batteries and sodium metal batteries and is used for protecting lithium metal cathodes and sodium metal cathodes. The spontaneous transfer method of the invention does not involve direct operation of lithium, the pre-construction process at the whole interface layer can be carried out in air atmosphere and any cheap and common nontoxic solvent can be used, and no requirement is made on whether the metallic lithium negative electrode or the sodium negative electrode is stable or not.
In addition, the interface layer spontaneously transferred on the surface of the metal lithium cathode or the sodium cathode can reduce the contact between the metal lithium cathode or the metal sodium cathode and the electrolyte, so that adverse side reactions can be reduced, further the irreversible consumption of the alkali metal cathode and the electrolyte can be relieved, the generation of dendrites can be effectively inhibited by utilizing the excellent mechanical property of the interface layer material or the good physicochemical action of the interface layer material and metal ions, the metal lithium cathode can be stabilized, and the safety and the electrochemical property of the metal battery can be improved.
Fig. 1 is a schematic view of the construction of a lithium negative electrode/sodium negative electrode surface interface modification layer according to the present invention, in which 1-position commercial separator, 2 is an interface modification material layer, 3 is a lithium metal/sodium metal negative electrode, and 4 is a positive electrode. As can be seen from the figure, the method of the invention has the following core steps:
the interface modification material is constructed on the diaphragm for the battery in advance in any atmosphere, and the process of injecting the electrolyte is inevitably existed in the battery assembling process, so the electrolyte can spontaneously infiltrate the diaphragm, and under the infiltration of the electrolyte, the interface modification layer can be spontaneously transferred from the diaphragm to the surface of the metal lithium cathode by utilizing the interaction between the interface modification material and the metal lithium cathode or the sodium cathode.
The interface construction technology avoids the direct operation of the metal lithium, does not need the protection of inert atmosphere, and does not relate to the selection of reagents such as active materials or dispersing solvents, thereby greatly reducing the process cost, obviously reducing the process complexity, widening the material system of the interface modification layer, providing a new idea for the construction of novel interface modification materials, and the interface modification layer constructed by the technology can effectively stabilize the metal lithium cathode, inhibit the growth of lithium dendrites, and prolong the cycle performance of the lithium cathode.
Wherein, under the immersion of the electrolyte, the affinity of the interface modification material and the metallic sodium or the metallic lithium is larger than the performance of the affinity membrane, so that the spontaneous transfer process can occur. Specifically, the lithium-philic or sodium-philic property of the interface modification material may be caused by a physicochemical reaction and/or a redox reaction, wherein the physicochemical reaction is electrostatic adsorption, and the redox reaction is an oxidation reaction of an oxidizing material and a reducing substance of lithium and sodium.
The interface modification material included in the method of the invention is selected from one or more of the following materials: graphene oxide and derivatives thereof, carbon nanotubes and derivatives thereof, graphene, carbon nitride, black phosphorus, boron nitride, metal oxides, metal sulfides, metal carbides, metal nitrides, lithium fluoride, lithium nitride, lithium sulfide, lithium oxide, lithium carbonate, lithium lanthanum zirconium oxide solid electrolyte (LLZO) and its derivatives, lithium germanium phosphorus sulfur solid electrolyte (LGPS) and its derivatives, polyethylene oxide (PEO) and its derivatives, Polyacrylonitrile (PAN) and its derivatives, polyvinylidene fluoride (PVDF) and its derivatives, polymethyl methacrylate (PMMA) and its derivatives, polypropylene oxide (PPO) and its derivatives, polyvinylidene chloride (PVDC) and its derivatives, polyacrylic acid (PAA) and its derivatives, Polyurethane (PU) and its derivatives, Polydimethylsiloxane (PDMS) and its derivatives, carboxymethyl cellulose (CMC) and its derivatives. The diaphragm matched with the interface modification material can be selected from a polyethylene microporous membrane, a polypropylene microporous membrane, a polyethylene/polypropylene double-layer co-extrusion membrane, a polypropylene/polyethylene/polypropylene three-layer co-extrusion membrane, an aromatic polyamide diaphragm (PMIA), a polyethylene terephthalate diaphragm (PET), a poly (p-phenylene benzobisoxazole) diaphragm (PBO), a polyimide diaphragm or a cellulose diaphragm, and the diaphragm is used for a pre-loaded substrate of the interface modification material and a physical insulation layer between a positive electrode and a negative electrode.
The mode of constructing the interface modification material on the battery diaphragm in advance is concretely as follows: the dispersion, solution or suspension of the interface modification material is uniformly and compactly constructed on the diaphragm for the battery in advance in one or more modes of suction filtration, spray coating, drop coating, spin coating and blade coating, and the interface modification material can be constructed into one layer or multiple layers. When the interface modification material is constructed into a plurality of layers, the plurality of layers can be the same or different, and when the battery is assembled, the part close to the lithium layer is required to be ensured to be selected from the materials with stronger interaction with lithium, and the part close to the diaphragm is preferably the interface material with weaker interaction with the diaphragm, so that the constructed interface modification layer can spontaneously realize the transfer from the diaphragm to the lithium cathode.
In addition, the multilayer interface modification material can be constructed according to different components, morphologies, physicochemical properties and functions to realize optimization of comprehensive performance of the artificial interface layer, such as good electronic insulation ionic conductivity, stable electrochemical/chemical properties and excellent mechanical properties. In actual engineering, the design can be carried out as required, but specific material selection between different layers, construction mode and the like need to be developed separately.
FIG. 2 shows the possible existence of the interface modification layer as one layer or as a multi-layer structure according to the composition, morphology, physical and chemical properties and functions. The interface modification material layer may be a single layer of a single compound, a single layer of a mixture, or multiple layers, and when multiple layers are provided, each layer may be a single compound or a mixture.
The solvent in the dispersion, solution or suspension of the interface modifying material includes: one or more of water, isopropanol, ethanol, acetone, glycerol, ethylene glycol, tetrahydrofuran, dimethyl sulfoxide, N-methylpyrrolidone (NMP), N-dimethylformamide, chloroform and cyclohexane.
The thickness of the interface modification layer material in the prefabricated diaphragm is 0.5-50 μm, and if the thickness is too thin, the transferred diaphragm is incomplete, and if the thickness is too thick, the internal resistance of the battery is increased, and adverse effects are brought to the performance of the battery. The existence form of the interface modification layer on the surface of the lithium metal cathode or the sodium cathode can completely copy the pre-constructed appearance on the diaphragm, and the change of the micro and macro structure of the interface modification layer can not be caused.
In the method, the interface layer modification material is constructed on the diaphragm under any atmosphere to obtain the prefabricated diaphragm. In the battery assembling process, for example, a negative electrode battery case, a spring plate, a gasket and a metal negative electrode (which may be a metal lithium foil or a metal sodium foil) may be sequentially placed in a glove box from bottom to top, then a commercial diaphragm is placed, the side loaded with the interface layer material faces the metal negative electrode, then a positive electrode sheet and a positive electrode casing are placed, finally the battery is compacted, and the battery is tested after standing.
To illustrate the process of the invention in more detail, specific examples are given below in tabular form:
the performance of the lithium metal/sodium metal cathode containing the interface modification layer obtained after the interface modification layer is constructed can be optimized to different degrees, and the performance is particularly shown in that the interface modification layer can effectively isolate side reactions generated by direct contact of the metal cathode and electrolyte, the coulomb efficiency of the battery is improved to 90% or above, the cycle life can be prolonged to hundreds to thousands of circles, and the deposition appearance is smoother. In addition, different interface layer materials such as high-elasticity modulus materials such as black phosphorus, graphene, boron nitride and the like can be selected to effectively and mechanically inhibit the continuous growth of dendrites; for example, atoms with larger electronegativity such as O, F, N and the like exist in the interface material, and Li-O, Li-N, Li-F bonds and the like (such as carbon nitride and Li-N bonds) can be formed after the interface material is contacted with lithium, so that the deposition behavior of lithium ions can be effectively stabilized by regulating the concentration of the lithium ions on the surface of the lithium cathode; such as molybdenum disulfide, vanadium pentoxide, etc., can react with the metal cathode to form a high ion conductive layer (such as vanadium pentoxide, Li)xV2O5) The transmission of lithium ions at the interface is improved, the dendritic crystal can be effectively prevented from puncturing the diaphragm, the safety problem of a battery system is obviously improved, and the battery performance can be obviously improved when the lithium ion battery is applied to a metal battery.
In the invention, no other redundant steps are needed, and the interface layer material can be completely transferred from the diaphragm to the surface of the metal cathode only under the natural soaking of the electrolyte in the mature battery assembly process. The method mainly utilizes slight ionization generated on the surface of the metallic lithium negative electrode under the wetting of the electrolyte and the physical and chemical action between the interface layer material and the metallic lithium negative electrode, such as the excellent metal-lithium affinity characteristic of the interface layer material or the oxidation-reduction reaction between the interface layer material and the metallic lithium. The characteristics are discovered and utilized, so that the interface material can be constructed on the diaphragm firstly, and then is infiltrated by the electrolyte and then is transferred spontaneously, and a protection method similar to 'treatment without a break' is realized. The method of the invention is safe, simple, strong in manufacturability, not harsh in implementation conditions, and has extremely strong manufacturability and practical use value.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (8)
1. A protection method of a lithium cathode in a lithium metal battery is characterized in that a kind of interface modification material is constructed on a diaphragm for the battery in advance under any atmosphere to obtain a prefabricated diaphragm, and the interaction of the interface modification material and the lithium cathode is stronger than that of the diaphragm;
executing a battery assembly process, wherein one surface of the prefabricated diaphragm with the interface modification material is tightly attached to the metal lithium negative electrode, and injecting electrolyte;
under the immersion of the electrolyte, the interface modification layer is spontaneously transferred to the metallic lithium cathode from the diaphragm by utilizing the physical and chemical action between the interface modification layer and the metallic lithium, so that the metallic lithium cathode is automatically protected;
wherein the interface modification material is constructed on the battery diaphragm in advance in a mode that: uniformly and compactly constructing the dispersion liquid of the interface modification material on a diaphragm for the battery in advance in one or more modes of suction filtration, spraying, dripping coating, spin coating and blade coating;
the interface modification material is one or more layers, when the interface modification material is a plurality of layers, the part close to the lithium layer is required to be selected from the materials with stronger interaction with lithium, and the part close to the diaphragm is required to be selected from the interface materials with weaker interaction with the diaphragm, so that the constructed interface modification layer can spontaneously realize the transfer from the diaphragm to the lithium cathode;
the interface modification material is one or more of graphene oxide and derivatives thereof, carbon nanotubes and derivatives thereof, graphene, carbon nitride, black phosphorus and boron nitride; or is that
One or more of polyethylene oxide and derivatives thereof, polyacrylonitrile and derivatives thereof, polyvinylidene fluoride and derivatives thereof, polymethyl methacrylate and derivatives thereof, polypropylene oxide and derivatives thereof, polyvinylidene chloride and derivatives thereof, polyacrylic acid and derivatives thereof, polyurethane and derivatives thereof, polydimethylsiloxane and derivatives thereof, and carboxymethyl cellulose and derivatives thereof; or is that
One or more of metal oxide, metal sulfide, metal carbide, metal nitride, lithium fluoride, lithium lanthanum zirconium oxygen solid electrolyte and derivatives thereof, and lithium germanium phosphorus sulfur solid electrolyte and derivatives thereof; and the metal oxide, the metal sulfide, the metal carbide, the metal nitride, the lithium fluoride, the lithium lanthanum zirconium oxygen solid electrolyte and the derivatives thereof, and the lithium germanium phosphorus sulfur solid electrolyte and the derivatives thereof are in a nanometer shape.
2. The method of claim 1, wherein the metal oxide is lithium oxide, the metal sulfide is lithium sulfide, the metal carbide is lithium carbonate, and the metal nitride is lithium nitride.
3. The method of claim 1, wherein the solvent in the dispersion of the interface-modifying material is: one or more of water, isopropanol, ethanol, acetone, glycerol, ethylene glycol, tetrahydrofuran, dimethyl sulfoxide, N-methylpyrrolidone, N-dimethylformamide, chloroform and cyclohexane.
4. The method of claim 1, wherein the thickness of the interface modification layer material in the pre-formed separator is 0.5 μ ι η to 50 μ ι η.
5. The method according to any one of claims 1 to 4, wherein the separator is a polyethylene microporous membrane, a polypropylene microporous membrane, a polyethylene/polypropylene double-layer co-extrusion membrane, a polypropylene/polyethylene/polypropylene three-layer co-extrusion membrane, an aromatic polyamide separator, a polyethylene terephthalate separator, a poly (p-phenylene benzobisoxazole) separator, a polyimide separator or a cellulose separator, and is used for a pre-loaded substrate of the interface modification material and a physical insulation layer between the positive electrode and the negative electrode.
6. A lithium metal battery prepared by the method according to any one of claims 1 to 5.
7. A method for protecting a negative electrode of a sodium metal battery, which is characterized in that a lithium metal battery in the method of any one of claims 1 to 5 is replaced by the sodium metal battery, a lithium negative electrode is replaced by the sodium negative electrode, and an interface modification material which has stronger interaction with sodium than with a diaphragm is constructed on the diaphragm for the battery in advance.
8. A sodium metal battery prepared by the method of claim 7.
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| CN111354906A (en) * | 2020-03-18 | 2020-06-30 | 肇庆市华师大光电产业研究院 | Modified diaphragm for lithium-sulfur battery and preparation method thereof |
| CN111525188B (en) * | 2020-05-14 | 2021-08-20 | 湘潭大学 | PEO-PMMA solid electrolyte membrane |
| CN111900373B (en) * | 2020-08-04 | 2021-08-06 | 大连理工大学 | Preparation method of lithium dendrite-resistant lithium metal battery cathode side separator material |
| CN112038541B (en) * | 2020-09-11 | 2022-10-14 | 嘉兴学院 | Composite diaphragm material and preparation method and application thereof |
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| CN112259741A (en) * | 2020-09-28 | 2021-01-22 | 江汉大学 | Current collector and preparation method and application thereof |
| CN112151761A (en) * | 2020-10-22 | 2020-12-29 | 珠海冠宇电池股份有限公司 | Lithium cathode and preparation method and application thereof |
| CN112909435A (en) * | 2021-01-14 | 2021-06-04 | 南开大学 | Composite diaphragm for lithium metal battery and preparation method and application thereof |
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| CN108565397A (en) * | 2018-05-31 | 2018-09-21 | 四川华昆能源有限责任公司 | Metal lithium electrode surface oxidation composite protection layer structure and preparation method |
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