CN111799443A - Three-dimensional porous metal lithium cathode for secondary battery and preparation and application thereof - Google Patents
Three-dimensional porous metal lithium cathode for secondary battery and preparation and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of lithium metal batteries, and particularly discloses a three-dimensional porous metal lithium cathode for a secondary battery, and preparation and application thereof. The three-dimensional porous metal lithium negative electrode consists of a porous conductive current collector, an artificial SEI film compounded on the surface of the porous conductive current collector and metal lithium loaded on the skeleton of the porous conductive current collector. The porous conductive current collector can obviously reduce the apparent current density in the circulation process of the metal lithium cathode; the artificial SEI film can obviously reduce the contact between the lithium metal and the electrolyte, inhibit interface side reaction and realize stable circulation of long service life and high coulombic efficiency under high current density.
Description
Technical Field
The invention belongs to the field of lithium metal batteries, and particularly relates to a three-dimensional porous metal lithium cathode for a secondary battery, and preparation and application thereof.
Background
The lithium metal has extremely high theoretical capacity and extremely low electrode potential, so that the lithium metal becomes an extremely ideal negative electrode material, the negative electrode of the lithium metal battery is usually a simple substance of the lithium metal, and the deposition and dissolution of the lithium metal occur. The action mechanism of the battery is charging, wherein Li + + e is Li; discharging Li-e ═ Li +; lithium sulfur batteries and lithium air batteries in which lithium metal is the anode have been developed in recent years. However, the large volume effect of lithium dendrites and lithium metal battery cycling limits their practical applications. To counter the risk of dendrites and to mitigate volume effects. Numerous strategies, such as optimizing lithium salts, solvents, functional additives in electrolytes, and even ionic liquids, have been widely developed and studied. Malachi et al [ Zhang K, Li J, Li Q, et al].Applied SurfaceScience,2013,285:900-906.]Depositing Al of about 10nm on the surface of lithium metal by atomic/molecular vapor deposition2O3The SEI layer, which inhibits dendritic growth, and protects the lithium electrode behind these studies, researchers have achieved favorable results, and a large number of lithium dendrites are successfully inhibited, but the huge volume effect in the lithium metal battery cycle process at high current density still remains to be solved.
In recent years, researchers have found that loading metallic lithium in a three-dimensional porous current collector can effectively alleviate the huge volume change in the deposition/dissolution process of the metallic lithium. Meanwhile, the rich specific surface area of the three-dimensional porous current collector can sufficiently reduce the current density on the surface of the electrode, so that the lithium metal can be deposited without dendrites under lower current density, such as Yu-Guo Guo et al [ S. -H.Wang, Y. -X.yin, T. -T.Zuo, W.Dong, J. -Y.Li, J. -L.Shi, C. -H.Zhang, N. -W.Li, C. -J.Li, Y. -G.Guo, Stable Li metal and video sizing lithium sizing/linear geometry, Advanced Materials 29(40) (2017) 1703736.]By preparing the porous copper, the current density of 1mA/cm is realized2The lower 200 stable cycles. However, the three-dimensional porous current collector is a double-edged sword, and the ultrahigh specific surface area of the three-dimensional porous current collector reduces the current density on the surface of an electrode and also greatly increases the contact area of the lithium metal and the electrolyte. Thereby increasing the occurrence of interfacial side reactions. Therefore, the conventional three-dimensional porous metal current collector loaded with metallic lithium is difficult to be actually used in industry as an anode material of a lithium metal battery.
Disclosure of Invention
The invention aims to provide a three-dimensional porous metal lithium negative electrode for a secondary battery, aiming at the problems that the current density of a metal lithium anode can not be sufficiently reduced and lithium dendrite can not be effectively inhibited.
The second purpose of the invention is to provide a preparation method of the three-dimensional porous metal lithium negative electrode for the secondary battery.
The third purpose of the invention is to provide the application of the three-dimensional porous metallic lithium negative electrode for the secondary battery in the preparation of the lithium metal battery.
Through the structure regulation and the material preparation, the cathode which has no volume expansion and optimizes the electrochemical performance of the lithium metal battery is obtained.
The invention also provides a lithium metal battery provided with the three-dimensional porous lithium metal negative electrode for the secondary battery. The invention relates to a three-dimensional porous metal lithium cathode for a secondary battery, which comprises a porous conductive current collector, a porous conductive current collector skeleton formed by an artificial SEI (solid electrolyte interphase) film compounded on the surface of the porous conductive current collector, and metal lithium loaded on the porous conductive current collector skeleton.
The three-dimensional porous metal lithium cathode for the secondary battery is characterized in that an artificial SEI film is innovatively compounded on a porous conductive current collector framework, and then metal lithium is loaded on the porous conductive current collector framework compounded with the artificial SEI film. The structure is matched with the material components, so that the apparent current density in the circulation process can be effectively reduced, the interface side reaction is inhibited, and the stable circulation of long service life and high coulombic efficiency under high current density is realized.
Preferably, the material of the porous conductive current collector is at least one of porous titanium, chromium, copper, nickel, iron, cobalt and manganese;
preferably, the porous conductive current collector is any one of porous titanium, porous chromium, porous manganese, porous iron, porous cobalt, porous nickel, porous copper and the like, and binary and ternary porous conductive current collectors thereof.
Preferably, the porous conductive binary current collector is any one of porous nickel-copper, porous nickel-titanium, porous nickel-chromium, porous nickel-iron, porous nickel-cobalt, porous nickel-manganese, porous iron-titanium, porous iron-chromium, porous iron-copper, porous iron-cobalt, porous iron-manganese, porous cobalt-titanium, porous cobalt-copper and porous cobalt-manganese alloy. The porous conductive binary alloy has any component proportion.
Preferably, the porous conductive ternary alloy current collector is any one of porous nickel-copper-titanium, porous nickel-copper-iron, porous nickel-copper-cobalt, porous nickel-copper-manganese, porous iron-cobalt-nickel, porous iron-chromium-nickel and porous nickel-copper-chromium alloy. The porous conductive ternary alloy has any component proportion.
Further preferably, the material of the porous metal current collector is porous nickel, porous copper, porous nickel-chromium, porous nickel-iron, porous nickel-copper, porous iron-copper, porous cobalt-copper, porous nickel-copper-titanium, porous nickel-copper-iron, porous nickel-copper-cobalt, porous nickel-copper-manganese. The preferred metallic current collector has superior performance. Most preferably, the material of the 3D porous metal current collector is porous nickel, porous titanium (also called nickel foam, titanium foam).
The thickness of the porous conductive current collector is 5-900 μm; further preferably 30 to 300 μm;
the porosity of the porous conductive current collector is 20-99%; further preferably 30 to 80%; the inventors have found that the use of a higher porosity current collector helps to improve the electrical properties of the resulting anode, particularly the cycling performance at high current densities.
The porosity of the porous conductive current collector is most preferably 40-70%.
The pore space of the porous conductive current collector is 0.5-400 μm; more preferably 5 to 300. mu.m. The larger pore size helps to further enhance the electrical performance of the resulting anode.
The artificial SEI film compounded on the surface of the porous conductive current collector consists of solid electrolyte nano particles and an adhesive.
Preferably, the thickness of the coating layer of the artificial SEI film is 10 to 300 μm; further preferably 10 to 100 μm;
preferably, the nanoparticles are 50-1200nm in size; further preferably 100-800 nm; more preferably 200-400 nm;
the solid electrolyte is of a perovskite structure, a garnet structure and a NASICON structure, such as: at least one of lithium aluminum germanium phosphate, lithium lanthanum zirconium oxygen and lithium aluminum titanium phosphate.
The adhesive is at least one of polyoxyethylene, polyacrylonitrile, polyvinylidene fluoride, polyolefins, polyvinyl alcohol, fluorinated rubber, polyurethane and sodium carboxymethylcellulose, and preferably polyvinylidene fluoride.
The invention provides a preparation method of the three-dimensional porous metal lithium cathode for the secondary battery, which comprises the following steps: mixing a solid electrolyte and a binder according to a certain proportion to obtain a coating, uniformly coating the coating on a porous conductive current collector in a spraying, blade coating or transfer coating mode, drying, taking the coating as a working electrode, taking a metal lithium sheet as a counter electrode, and loading metal lithium by an electrodeposition method, or mixing the dried porous conductive current collector with molten metal lithium to load metal lithium, thereby obtaining the three-dimensional porous metal lithium cathode for the secondary battery.
Further, mixing the solid electrolyte and the binder according to a certain proportion, adding the mixture into a N-methyl pyrrolidone (NMP) solution, performing ball milling and stirring to obtain uniform slurry, and coating the uniform slurry on a foamed copper current collector.
Preferably, the solid electrolyte is lithium aluminum germanium phosphate.
Preferably, the adhesive is polyvinylidene fluoride.
Preferably, the content of the adhesive is 5 to 95%, preferably 10 to 80%.
Preferably, the method for supporting metallic lithium is electrodeposition or melting; electrodeposition is preferred.
Preferably, the electrodeposition step is: the porous conductive current collector loaded with the artificial SEI film is used as a working electrode, a lithium sheet is used as a counter electrode, and metal lithium is loaded by electrodeposition in an organic solvent containing lithium salt.
Metal lithium content 10-90 Wt.%; preferably 25-80 wt.%.
Preferably, the amount of electrodeposited lithium metal is 1-15mAh/cm2(ii) a Further preferably 2 to 8mAh/cm2. At a preferred amount of deposited lithium, the resulting anode material is excellent in electrical properties, particularly cycle performance.
The invention also provides application of the three-dimensional porous metal lithium negative electrode for the secondary battery, and the three-dimensional porous metal lithium negative electrode is used for preparing the lithium metal battery.
Preferably, the lithium metal battery is a lithium sulfur battery, a lithium iodine battery, a lithium selenium battery, a lithium tellurium battery, a lithium oxygen battery or a lithium carbon dioxide battery.
The invention also provides a metal lithium battery which is prepared from the three-dimensional porous metal lithium cathode for the secondary battery.
Advantageous effects
According to the three-dimensional porous metal lithium cathode for the secondary battery, the high specific surface area of the porous metal lithium cathode can obviously reduce the apparent current density of the metal lithium cathode in the circulating process, and stable circulation of the metal lithium under high current density is realized. Meanwhile, the artificial SEI film can effectively avoid direct contact between the electrolyte and the lithium metal, inhibit the occurrence of side reaction of a lithium anode interface and the loss of continuous lithium metal, and further realize stable circulation of long service life and high coulombic efficiency under high current density.
Detailed Description
The following is a detailed description of the preferred embodiments of the invention and is not intended to limit the invention in any way, i.e., the invention is not intended to be limited to the embodiments described above, and modifications and alternative compounds that are conventional in the art are intended to be included within the scope of the invention as defined in the claims.
Example 1
The thickness of the foamed nickel current collector (Ni foam) is 40 μm, the porosity is 50%, and the pore spacing is 90 μm;
mixing Lithium Aluminum Germanium Phosphate (LAGP) and polyvinylidene fluoride (PVDF) according to a mass ratio of 80: 20, mixing and adding the mixture into a Nitrogen Methyl Pyrrolidone (NMP) solution, performing ball milling and stirring to obtain a uniform slurry of a LAGP-PVDF composite layer, coating the slurry of the composite layer on a foamed nickel current collector, wherein the coating thickness is 20 mu M, drying the slurry for 8 hours in a drying oven at 60 ℃ to obtain the LAGP-PVDF @ Ni foam, and then taking a metal lithium sheet as a counter electrode, and performing the following steps of 1M LiTFSI/DOL: DME (1: 1 by volume) contains 1 wt.% LiNO3And (5) assembling the button cell for the electrolyte, and carrying out charge-discharge cycle test. Meanwhile, pure foam nickel is used as a comparison sample to carry out corresponding charge-discharge cycle test.
Tests have found that the concentration of the active carbon in the solution is 5mA/cm2The cycle life of the foam nickel modified by the LAGP-PVDF composite layer is more than 5 times of that of the pure foam nickel under the current density of the composite layer. The relevant specific data are shown in table 1.
TABLE 1
Example 2
The thickness of the copper foam current collector (Cu foam) is 50 μm, the porosity is 60%, and the pore spacing is 100 μm;
mixing Lithium Aluminum Germanium Phosphate (LAGP) and polyvinylidene fluoride (PVDF) according to a mass ratio of 90: 10, mixing and adding the mixture into a Nitrogen Methyl Pyrrolidone (NMP) solution, performing ball milling and stirring to obtain a uniform slurry of a LAGP-PVDF composite layer, coating the slurry of the LAGP-PVDF composite layer on a foamed copper current collector to a thickness of 20 mu M, drying for 8 hours in a drying oven at 60 ℃ to obtain LAGP-PVDF @ Cu foam, and then taking a metal lithium sheet as a counter electrode, and performing a reaction on the metal lithium sheet by using a 1M LiTFSI/DOL: DME (1: 1 by volume) contains 1 wt.% LiNO3And (5) assembling the button cell for the electrolyte, and carrying out charge-discharge cycle test. Meanwhile, pure foam nickel is used as a comparison sample to carry out corresponding charge-discharge cycle test.
Tests show that the concentration of the active carbon is 3mA/cm2Current density ofAnd the cycle life of the foam copper modified by the LAGP-PVDF composite layer is more than 4 times of that of the pure foam copper. The relevant specific data are shown in table 2.
TABLE 2
Example 3
The thickness of the copper foam current collector (Cu foam) is 40 μm, the porosity is 45%, and the pore spacing is 90 μm;
mixing Lithium Aluminum Germanium Phosphate (LAGP) and polyvinylidene fluoride (PVDF) according to a mass ratio of 80: 20, mixing and adding the mixture into a Nitrogen Methyl Pyrrolidone (NMP) solution, performing ball milling and stirring to obtain a uniform slurry of a LAGP-PVDF composite layer, coating the slurry of the LAGP-PVDF composite layer on a foamed copper current collector to a thickness of 20 mu M, drying the coated slurry for 8 hours at a temperature of 60 ℃ in a drying oven to obtain the LAGP-PVDF @ Cu foam, and then taking a metal lithium sheet as a counter electrode and adding the metal lithium sheet into a 1M LiTFSI/DOL: DME (1: 1 by volume) contains 1 wt.% LiNO3And (5) assembling the button cell for the electrolyte, and carrying out charge-discharge cycle test. Meanwhile, pure foam nickel is used as a comparison sample to carry out corresponding charge-discharge cycle test.
Tests found that the concentration of the active carbon in the solution is 4mA/cm2The cycle life of the foam copper modified by the LAGP-PVDF composite layer is more than 3 times of that of pure foam copper under the current density of the composite layer.
Example 4
The thickness of the titanium foam current collector (Ti foam) is 30 μm, the porosity is 80%, and the pore spacing is 90 μm;
mixing Lithium Aluminum Germanium Phosphate (LAGP) and polyvinylidene fluoride (PVDF) according to a mass ratio of 80: 20, mixing and adding the mixture into a Nitrogen Methyl Pyrrolidone (NMP) solution, performing ball milling and stirring to obtain a uniform slurry of a LAGP-PVDF composite layer, coating the slurry of the composite layer on a foamed titanium current collector, wherein the coating thickness is 20 mu M, drying the slurry for 8 hours in a drying oven at 60 ℃ to obtain the LAGP-PVDF @ Ti foam, and then taking a metal lithium sheet as a counter electrode, and performing the following steps of 1M LiTFSI/DOL:DME (1: 1 by volume) contains 1 wt.% LiNO3And (5) assembling the button cell for the electrolyte, and carrying out charge-discharge cycle test. Meanwhile, pure foam titanium is used as a comparison sample to carry out corresponding charge-discharge cycle test.
Tests show that the concentration of the active carbon is 3mA/cm2The cycle life of the foam titanium modified by the LAGP-PVDF composite layer is more than 4 times of that of the pure foam titanium under the current density of the composite layer. The relevant specific data are shown in table 3.
TABLE 3
Example 5
The thickness of the porous nickel-manganese current collector is 30 micrometers, the porosity is 50%, and the pore spacing is 80 micrometers;
aluminum lithium germanium phosphate (LAGP) and polyvinylidene fluoride (PVDF) are mixed according to the mass ratio of 85: 15, mixing and adding the mixture into a N-methyl pyrrolidone (NMP) solution, performing ball milling and stirring to obtain a uniform slurry of a LAGP-PVDF composite layer, coating the slurry of the composite layer on a porous nickel-manganese current collector, coating the porous nickel-manganese current collector to a thickness of 20 mu M, drying the porous nickel-manganese current collector for 8 hours at a temperature of 60 ℃ in a drying oven to obtain the LAGP-PVDF @ Ni/Mnfoam, then taking a metal lithium sheet as a counter electrode, and taking 1M LiTFSI/DOL: DME (1: 1 by volume) contains 1 wt.% LiNO3And (5) assembling the button cell for the electrolyte, and carrying out charge-discharge cycle test. Meanwhile, pure foam nickel is used as a comparison sample to carry out corresponding charge-discharge cycle test.
Tests found that the concentration of the active carbon in the solution is 4mA/cm2The cycle life of the foam titanium modified by the LAGP-PVDF composite layer is more than 4 times of that of pure foam nickel manganese under the current density of the composite layer. The relevant specific data are shown in table 4.
TABLE 4
Comparative example 1
Compared with example 1, the difference is only that lithium aluminum germanium phosphate (lag) and polyvinylidene fluoride (PVDF) are mixed in a mass ratio of 90: 10 specifically comprises the following steps:
the thickness of the foamed nickel current collector (Ni foam) is 40 μm, the porosity is 50%, and the pore spacing is 90 μm;
mixing Lithium Aluminum Germanium Phosphate (LAGP) and polyvinylidene fluoride (PVDF) according to a mass ratio of 90: 10, mixing and adding the mixture into a Nitrogen Methyl Pyrrolidone (NMP) solution, performing ball milling and stirring to obtain a uniform slurry of a LAGP-PVDF composite layer, coating the slurry of the composite layer on a foamed nickel current collector, wherein the coating thickness is 20 mu M, drying for 8h in a drying oven at 60 ℃ to obtain the LAGP-PVDF @ Ni foam, and then taking a metal lithium sheet as a counter electrode, and performing the steps of 1M LiTFSI/DOL: DME (1: 1 by volume) contains 1 wt.% LiNO3Assembling the button cell for the electrolyte at 3mA/cm2The charge-discharge cycle test was carried out at the current density of (1).
Comparative example 2
Compared with example 1, the difference is only that the mass ratio of Lithium Aluminum Germanium Phosphate (LAGP) to polyvinylidene fluoride (PVDF) is 50: 50 specifically comprises the following steps:
the thickness of the foamed nickel current collector (Ni foam) is 40 μm, the porosity is 50%, and the pore spacing is 90 μm;
mixing Lithium Aluminum Germanium Phosphate (LAGP) and polyvinylidene fluoride (PVDF) according to a mass ratio of 50: 50, mixing and adding the mixture into a N-methyl pyrrolidone (NMP) solution, performing ball milling and stirring to obtain uniform slurry of a LAGP-PVDF composite layer, coating the slurry of the composite layer on a foamed nickel current collector, coating the slurry to a thickness of 20 mu M, drying the slurry for 8 hours in a drying oven at 60 ℃ to obtain the LAGP-PVDF @ Ni foam, then taking a metal lithium sheet as a counter electrode, and performing the steps of 1M LiTFSI/DOL: DME (1: 1 by volume) contains 1 wt.% LiNO3Assembling the button cell for the electrolyte at 3mA/cm2The charge-discharge cycle test was carried out at the current density of (1).
Comparative example 3
Compared with example 1, the difference is only that the mass ratio of Lithium Aluminum Germanium Phosphate (LAGP) to polyvinylidene fluoride (PVDF) is 20: 80, specifically:
the thickness of the foamed nickel current collector (Ni foam) is 40 μm, the porosity is 50%, and the pore spacing is 90 μm;
mixing Lithium Aluminum Germanium Phosphate (LAGP) and polyvinylidene fluoride (PVDF) according to a mass ratio of 20: 80 are mixed and added to a solution of azotoluidinone (NMP),and (2) obtaining uniform slurry of the LAGP-PVDF composite layer by ball milling and stirring, coating the composite layer slurry on a foamed nickel current collector, wherein the coating thickness is 20 microns, drying for 8 hours in a drying oven at 60 ℃ to obtain LAGP-PVDF @ Ni foam, and then taking a metal lithium sheet as a counter electrode, and taking 1M LiTFSI/DOL: DME (1: 1 by volume) contains 1 wt.% LiNO3Assembling the button cell for the electrolyte at 3mA/cm2The charge-discharge cycle test was carried out at the current density of (1). The results of the tests on the batteries obtained are shown in the attached Table 5.
TABLE 5
The result shows that when the mass ratio of the Lithium Aluminum Germanium Phosphate (LAGP) to the polyvinylidene fluoride (PVDF) is 80: at 20, the electrochemical performance is optimal.
Example 6
The LAGP-PVDF @ Ni foam prepared in example 1 is used as a working electrode and then is combined with a mesoporous carbon positive electrode rich in S simple substance to form a lithium sulfur battery, and the lithium sulfur battery is prepared in a volume ratio of 1M LiTFSI/DOL: DME (1: 1 by volume) contains 1% wt LiNO3The charge-discharge cycle test was performed at 0.5C in the electrolyte of (1).
Comparative example 6-1
Pure Ni foam is used as a working electrode, and then the pure Ni foam and a mesoporous carbon anode rich in S simple substance form a lithium sulfur battery, wherein the mass ratio of the pure Ni foam to the mesoporous carbon anode is 1MLiTFSI/DOL: DME (1: 1 by volume) contains 1% wt LiNO3The charge-discharge cycle test was carried out in the electrolyte solution of (1). The results of the tests on the obtained batteries are shown in the attached Table 6.
TABLE 6
The comparison between the example 6 and the comparative example 6-1 shows that the coulomb efficiency and the cycle performance of the negative electrode of the three-dimensional conductive current collector are obviously improved.
Example 7
The thickness of the titanium foam current collector (Ti foam) is 50 μm, the porosity is 50%, and the pore spacing is 100 μm;
the mass ratio is 90: 10, mixing aluminum lithium germanium phosphate (LAGP) and polyvinylidene fluoride (PVDF) and adding the mixture into a Nitrogen Methyl Pyrrolidone (NMP) solution, carrying out ball milling and stirring to obtain uniform slurry of a LAGP-PVDF composite layer, coating the slurry of the composite layer on a foamed titanium current collector to a coating thickness of 20 mu M, drying the foamed titanium current collector for 8 hours at a temperature of 60 ℃ in a drying oven to obtain the LAGP-PVDF @ Ti foam, and then taking a metal lithium sheet as a counter electrode, and carrying out the following steps of 1M LiTFSI/DOL: DME (1: 1 by volume) contains 1 wt.% LiNO3And (5) assembling the button cell for the electrolyte, and carrying out charge-discharge cycle test. Meanwhile, pure foam titanium is used as a comparison sample to carry out corresponding charge-discharge cycle test.
Tests have found that the concentration of the active carbon in the solution is 2mA/cm2The cycle life of the foam titanium modified by the LAGP-PVDF composite layer is more than 5 times of that of pure foam titanium under the current density of the composite layer. The results of the tests on the obtained batteries are shown in the attached Table 7.
TABLE 7
Example 8
The LAGP-PVDF @ Cu foam prepared in example 2 was used as a working electrode, a lithium metal sheet was used as a counter electrode, and 1M LiTFSI/DOL: DME (volume ratio: 1) contained 1 wt.% LiNO3As an electrolyte, at 0.5mA/cm2Bottom deposition of 5mAh/cm2So as to obtain the three-dimensional porous metal lithium cathode for the secondary battery rich in metal lithium. And then the lithium sulfur battery is formed with a mesoporous carbon anode rich in S simple substance, and the lithium sulfur battery is formed in a state that 1M LiTFSI/DOL: DME (1: 1 by volume) contains 1 wt.% LiNO3In the electrolyte of (1), a charge-discharge cycle test was performed at 1C.
Example 9
And (3) contacting the LAGP-PVDF @ Cu foam prepared in the step (2) with molten metal lithium at the temperature of 300 ℃ in an oxygen-free dry environment to prepare the three-dimensional porous metal lithium cathode for the secondary battery. Then the lithium sulfur battery is formed with a mesoporous carbon anode rich in S simple substance, and the lithium sulfur battery contains 1 wt.% LiNO in the volume ratio of 1MLiTFSI/DOL to DME (1: 1)3In the electrolyte of (1), a charge-discharge cycle test was performed at 1C. The results of the experimental tests are shown in Table 8.
TABLE 8
The results show that a three-dimensional porous metallic lithium negative electrode for a secondary battery is obtained by electrodeposition, and the electrochemical performance of the three-dimensional porous metallic lithium negative electrode is optimal.
Claims (10)
1. The three-dimensional porous metal lithium negative electrode for the secondary battery is characterized by comprising a porous conductive current collector, a porous conductive current collector skeleton formed by an artificial SEI film compounded on the surface of the porous conductive current collector, and metal lithium loaded on the porous conductive current collector skeleton.
2. The three-dimensional porous metallic lithium negative electrode for a secondary battery according to claim 1, wherein the material of the porous conductive current collector is at least one of porous titanium, chromium, copper, nickel, iron, cobalt, and manganese; preferably porous nickel or porous copper;
preferably, the thickness of the porous conductive current collector is 5-900 μm; further preferably 30 to 300 μm;
preferably, the porosity of the porous conductive current collector is 20-99%; further preferably 30 to 80%;
preferably, the porous conductive current collector has a pore spacing of 0.5 to 400 μm; more preferably 5 to 300. mu.m.
3. The three-dimensional porous metallic lithium negative electrode for a secondary battery according to claim 1, wherein the artificial SEI film compounded on the surface of the porous conductive current collector consists of solid electrolyte nanoparticles and a binder;
preferably, the thickness of the coating layer of the artificial SEI film is 10 to 300 μm; further preferably 10 to 100 μm;
preferably, the solid electrolyte nanoparticles are 50-1200nm in size; further preferably 100-800 nm; more preferably 200-400 nm.
4. The three-dimensional porous metallic lithium negative electrode for a secondary battery according to claim 3, wherein the solid electrolyte has a perovskite structure, a garnet structure, a NASICON structure, and preferably: at least one of lithium aluminum germanium phosphate, lithium lanthanum zirconium oxygen and lithium aluminum titanium phosphate.
5. The three-dimensional porous metallic lithium negative electrode for a secondary battery according to claim 3, wherein the binder is at least one of polyoxyethylene, polyacrylonitrile, polyvinylidene fluoride, polyolefins, polyvinyl alcohol, fluorinated rubber, polyurethane, and sodium carboxymethyl cellulose.
6. The three-dimensional porous lithium metal anode for a secondary battery according to claim 5, wherein the content of the binder is 5 to 95%; preferably 10 to 80%.
7. The method for preparing the three-dimensional porous metallic lithium negative electrode for the secondary battery according to any one of claims 1 to 6, wherein a solid electrolyte is mixed with a binder in a certain ratio to obtain a coating, the coating is uniformly coated on the porous conductive current collector by means of spraying, blade coating or transfer coating and dried, and then the porous conductive current collector is used as a working electrode, a metallic lithium sheet is used as a counter electrode to load metallic lithium by means of electrodeposition, or the dried porous conductive current collector is mixed with molten metallic lithium to load metallic lithium, so that the three-dimensional porous metallic lithium negative electrode for the secondary battery is obtained.
8. The method of claim 7, wherein the lithium metal content in the three-dimensional porous lithium metal negative electrode for a secondary battery ranges from 10 to 90 wt.%; preferably 25-80 wt.%.
9. Use of the three-dimensional porous metallic lithium anode for secondary batteries according to any one of claims 1 to 6, or the three-dimensional porous metallic lithium anode for secondary batteries produced by the production method according to any one of claims 7 to 8, characterized in that: preparing a lithium metal battery from the lithium metal oxide powder;
preferably, the lithium metal battery is a lithium sulfur battery, a lithium iodine battery, a lithium selenium battery, a lithium tellurium battery, a lithium oxygen battery or a lithium carbon dioxide battery.
10. A lithium metal battery, characterized by being produced from the three-dimensional porous lithium metal negative electrode for a secondary battery according to any one of claims 1 to 6, or the three-dimensional porous lithium metal negative electrode for a secondary battery produced by the method according to any one of claims 7 to 8.
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