CN109830647B - 3D lithium metal battery cathode, lithium metal battery, preparation and application thereof - Google Patents
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Abstract
The invention belongs to the field of lithium metal battery materials, and particularly discloses a 3D lithium metal cathode; the lithium ion battery consists of a 3D metal framework and a metal lithium layer compounded in the framework; the porosity of the 3D metal framework is 20-80%; the thickness is 25 to 800 μm. The invention also provides a preparation method of the 3D lithium metal negative electrode and an application method of the 3D lithium metal negative electrode in a lithium metal battery. The 3D metal framework has the advantages of adjustable porosity, controllable structure, high mechanical strength and simple and convenient preparation process. The obtained 3D lithium metal negative electrode with high specific surface area can remarkably reduce the apparent current density. Meanwhile, the controllable specific surface area and the regular nucleation sites can effectively realize uniform lithium deposition and relieve the volume effect of the lithium metal battery, and finally the lithium metal battery with high coulombic efficiency and long cycle life is obtained.
Description
Technical Field
The invention belongs to the field of high-energy batteries, and particularly relates to preparation and application of a 3D lithium metal cathode.
Background
Metallic lithium is known as a holy-cup electrode material by virtue of its ultra-high theoretical specific capacity (3860mAh/g) and its lowest electrode potential (-3.04V). Thus, batteries in which metallic lithium is used as a negative electrode are widely manufactured and studied. However, the dendrite problem and the continuous interfacial reaction generated when the metal lithium is directly used as the negative electrode greatly limit the improvement of the cycle performance, so that the lithium metal battery is difficult to replace the secondary battery which uses graphite as the negative electrode and is widely used at present.
To address this problem, a number of researchers have addressed the lithium dendrite problem and the corresponding interface stability. For example, Chen spring academy subject group (Suo, L.; Hu, Y. -S.; Li, H.; Armand, M.; Chen, L.; A new class of Solvent-in-Salt electrolyte for high-energy rechargeable metallic lithium batteries Nature Communications 2013,4,1481-1489.) use a high concentration of lithium Salt to mitigate dendritic growth at the lithium interface. In the back of these studies, the performance of lithium metal anodes was greatly improved and dendrites were successfully mitigated. However, the huge volume effect in the cycle process of the lithium metal battery still needs to be solved.
In view of this, researchers have found that loading metallic lithium in a porous current collector can effectively mitigate the volume effect of lithium metal negative electrodes. Thus, a large number of current collectors have been developed and studied. Such as Zhang, R.; Chen, X. -R.; Chen, X.; Cheng, X. -B.; Zhang, X. -Q.; Yan, C.; Zhang, Q.; lithographical sites in a bonded graphene-free metal alloys, Angewandte Chemie International Edition 2017,56(27), 7764-. And the group of researchers in Guo and Yuan of the institute of chemical of Chinese academy of sciences (Wang, S. -H.; Yin, Y. -. X.; Zuo, T. -. T.; Dong, W.; Li, J. -. Y.; Shi, J. -. L.; Zhang, C. -. H.; Li, N. -. W.; Li, C. -J.; Guo, Y. -. G., Stable Li metal alloys video sizing/sizing in vertical aligned porous films 2017,29(40), 1703729. one 3717036.) use porous copper obtained by laser micromachining to achieve Stable deposition of metallic lithium. However, it is difficult to put the lithium metal negative electrode obtained from these expensive raw materials or a complicated production process into practical use. Therefore, it is still desired to obtain a lithium metal negative electrode which can be put to practical use.
Disclosure of Invention
Aiming at the problems commonly existing in the 3D lithium metal negative electrode, the invention aims to provide a low-cost 3D lithium metal battery negative electrode.
The second purpose of the invention is to provide a preparation method of the negative electrode of the 3D lithium metal battery.
The third purpose of the invention is to provide the application of the 3D lithium metal battery negative electrode in a lithium metal battery.
A fourth object of the present invention is to provide a lithium metal battery equipped with the negative electrode.
Lithium metal batteries differ from lithium ion batteries in the nature of their mechanism of action, for example, the mechanism of action of the negative electrode of a lithium metal battery in a battery is the deposition and dissolution of lithium metal, and the basic reaction formula is: charging of Li++ e ═ Li; discharge Li-e ═ Li+(ii) a While the negative electrode of the conventional lithium ion battery is subject to intercalation and deintercalation of lithium ions in the graphite negative electrode. The difference between the lithium metal battery and the lithium ion battery in the mechanism of action is essentially different in the requirements for the material.
The lithium metal battery theoretically has better specific discharge capacity, but the research progress is slower, which mainly means that the lithium metal battery cathode is difficult to synergistically solve the problems of reducing apparent current density, relieving volume effect, inhibiting interface reaction and the like.
In order to solve the problems, the invention provides a 3D lithium metal battery cathode which is composed of a 3D metal framework and a metal lithium layer compounded in the framework;
the 3D metal framework is obtained by heat treatment of any one metal particle of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zirconium, molybdenum and tungsten;
the porosity of the 3D metal framework is 20-80%; the thickness is 25 to 800 μm.
In order to solve the problems that the conventional lithium metal battery metal cathode is difficult to cooperate in reducing the apparent current density, relieving the volume effect and inhibiting the interface reaction and the electrical property of the cathode is not ideal, the invention provides a brand new solution idea, namely, a product with a proper pore structure, required porosity and thickness, which is obtained by required heat treatment of metal particles, is used as a metal framework, and is used as a metal lithium carrier to load lithium, so that the metal lithium battery cathode which is capable of reducing the apparent current density, relieving the volume effect and inhibiting the interface is obtained. The negative electrode provided by the invention omits various additive components such as a conductive carbon material and the like commonly added in the existing negative electrode material, and only consists of the 3D metal framework and an active material metal lithium; the material can effectively improve the discharge specific capacity of the lithium metal cathode after elements are omitted, and the cycle performance is obviously improved.
The present inventors have also found that by controlling the type of metal material, pore structure, and thickness of the 3D lithium metal battery negative electrode, a lithium metal battery negative electrode having excellent performance can be further obtained.
Preferably, the 3D metal framework is titanium and/or copper.
Preferably, in the 3D lithium metal battery negative electrode, the porosity of the 3D metal framework is 40-70%. The inventors have surprisingly found that at this preferred porosity the electrical properties, in particular the cycling properties, of the material are further significantly improved.
More preferably, in the 3D lithium metal battery negative electrode, the porosity of the 3D metal framework is 45-65%.
The 3D metal framework disclosed by the invention has high specific surface area and aperture ratio besides porosity more suitable for a lithium metal battery, and researches find that the electrical property of the cathode can be further improved in a synergistic manner by further matching with thickness control.
Preferably, the thickness of the 3D metal framework is 35-680 mu m; more preferably 39 to 240 μm; more preferably 60 to 100 μm. The study finds that the electrical property of the negative electrode of the metal lithium battery can be further improved unexpectedly under the condition of the optimal thickness by matching with the control of the metal material and the porosity.
According to the 3D lithium metal battery cathode, the optimal heat treatment temperature of the 3D metal framework is 400-1000 ℃ and 450-950 ℃; further preferably 550-800 ℃; more preferably 550 to 650 ℃. Through the heat treatment, the performance of the material is improved, and the pore structure of the material is regulated and controlled, so that the electrical performance of the material is improved.
In the invention, the 3D metal framework is preferably an ordered 3D metal framework.
In the invention, the lithium carrying amount of the 3D lithium metal battery negative electrode is 3-32 mAh/cm 2.
The invention also provides a preparation method of the 3D lithium metal battery cathode, which comprises the following steps:
step (1): preparation of the 3D metal framework:
carrying out heat treatment on metal particles with the particle size of 50 nm-10 mu m at 400-1000 ℃ in a protective atmosphere to prepare the 3D metal framework; the metal of the metal particles is any one of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zirconium, molybdenum and tungsten;
step (2): carrying lithium;
and loading lithium on the 3D metal framework to prepare the 3D lithium metal battery cathode.
The key of the preparation method of the invention is that: and carrying out heat treatment on the metal particles with the types and the particle sizes under the conditions, and then depositing lithium to obtain the 3D lithium metal battery negative electrode. The invention firstly proposes that the problems of reduction of apparent current density, alleviation of volume effect, inhibition of interface reaction, difficulty in cooperation and non-ideal electrical property of the cathode, which are puzzled in the field of cathodes of lithium metal batteries, are solved by controlling the particle size of metal and the cooperative control of temperature; researches show that the electrical property of the prepared lithium metal battery cathode can be synergistically improved by controlling the metal type, the metal particle size and the heat treatment temperature, and particularly, the cycle performance of the prepared material is remarkably improved.
The negative electrode disclosed by the invention has the advantages that the porosity is too small, the specific surface area is too small, the apparent current density cannot be sufficiently reduced in the electroplating process, and when the lithium carrying amount is increased, the metal lithium is enriched outside the 3D metal framework, so that lithium dendrite is inevitably generated. In addition, if the porosity is too large, the mechanical strength of the electrode is greatly reduced. Although the apparent current density of the electrode can be sufficiently reduced, a high specific surface area also causes severe interfacial side reactions, making it difficult to improve the coulombic efficiency of the battery.
The preparation method can innovatively achieve the aim of effectively adjusting the porosity and the pore structure of the 3D metal framework through the cooperative control of the metal types, the particle morphology, the particle size and the heat treatment temperature parameters; thereby improving the performance of the material.
In the preparation method of the invention, the metal particles are preferably titanium and/or copper particles.
Preferably, the metal particles have a particle size of 70nm to 7 μm; more preferably 100nm to 3 μm; most preferably 100nm to 2 μm. According to the technical scheme, the particle size of the metal particles is controlled within a required range, the current density and the lithium carrying amount of the negative electrode can be adjusted and controlled in an auxiliary mode, and therefore the electrical performance of the negative electrode of the lithium metal battery is improved.
In the invention, the heat treatment process is carried out under the protective atmosphere; the protective atmosphere is, for example, argon.
According to the invention, the pore structure of the material can be innovatively regulated and controlled by matching the particle size of the metal particles with the heat treatment temperature, so that the electrical property of the negative electrode of the lithium metal battery is improved.
Preferably, the heat treatment temperature is 450-950 ℃; further preferably 550-800 ℃; more preferably 550 to 650 ℃. Researches show that the framework structure can be further improved at the optimal heat treatment temperature by matching with the control of the particle sizes of the metal material and the metal particles, and the electrical property of the negative electrode can be further improved.
In the invention, under the condition of the heat treatment temperature and the proper heat treatment time, the electrical property of the prepared cathode can be further improved.
Preferably, the heat treatment time is 0.5-10 h; further preferably 1.5-8 h; further preferably 2-6 h; most preferably 3-5 h.
The method of the invention, the method for loading lithium can adopt the existing method.
Preferably, the material obtained in the step (1) can be loaded with lithium by adopting a direct current, constant potential or pulse plating method, and finally the 3D lithium metal battery negative electrode is obtained.
The invention also provides application of the 3D lithium metal battery cathode, and the 3D lithium metal battery cathode is used as a cathode of a lithium metal battery.
The invention also provides a lithium metal battery which comprises the 3D lithium metal battery negative electrode.
Preferably, the lithium metal battery is a lithium sulfur battery, a lithium oxygen battery, a lithium nitrogen battery or a lithium water battery.
Has the advantages that:
1. the invention provides a brand new cathode of a lithium metal battery; which is obtained by heat-treating the metal particles as claimed in the invention under the stated conditions;
the cathode of the lithium metal battery can obviously reduce the current density of the battery and relieve the volume effect in the circulation process, and realizes the stable circulation of the metal lithium battery under high current density and high area capacity. Meanwhile, the uniform spatial structure provides uniform lithium nucleation and deposition sites, effectively avoiding the formation and uncontrolled growth of dendrites. Most notably, low manufacturing costs are conducive to the application of 3D lithium metal negative electrode industrialization.
2. The invention also provides a 3D metal framework prepared by regulating and controlling parameters of the metal material, the particle size of the metal particles and the heat treatment temperature, so that the problem of non-ideal electrical properties of the lithium metal battery cathode is solved, and the effect of improving the material properties is achieved.
Description of the drawings:
fig. 1 is an SEM image of the 3D copper skeleton prepared in example 1.
Fig. 2 is an element distribution diagram of the 3D copper skeleton prepared in example 1.
Fig. 3 is an SEM image of commercial copper foam in comparative example 1.
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
Spherical copper particles (120nm) were placed in an argon atmosphere and heat-treated at 600 ℃ for 3 hours to obtain a 3D copper skeleton with a porosity of 42% and a thickness of 100 μm (FIG. 1, 3D copper skeleton with ordered structure, suitable pore structure). The 3D copper framework is used as a working electrode, a metal lithium sheet is used as a counter electrode, and the ratio of 1M LiTFSI/DOL: DME (1: 1 by volume) contains 2 wt.% LiNO3And (5) assembling the button cell for the electrolyte, and carrying out charge-discharge cycle test. Tests show that the 3D copper framework prepared by the scheme consists of pure copper (figure 2), uniform lithium deposition without dendrites is realized, and lithium dendrites are effectively avoided. At 3mA/cm2Can exceed 600 cycles of stable cycling at a current density of 4mAh/cm2 area capacity (Table 1).
Comparative example 1
Commercial copper foam (porosity 91%) (fig. 3) was used as the working electrode, a lithium metal sheet as the counter electrode, and a 1M LiTFSI/DOL: DME (1: 1 by volume) contains 2 wt.% LiNO3Assembling the button cell for the electrolyte at 3mA/cm2And 4mAh/cm2 area capacity, a charge-discharge cycle test was performed. The corresponding test results are shown in table 1.
Comparative example 2
Commercial copper foil (porosity 0%) was used as a working electrode, a lithium metal sheet was used as a counter electrode, and a 1M LiTFSI/DOL: DME (1: 1 by volume) contains 2 wt.% LiNO3Assembling the button cell for the electrolyte at 3mA/cm2And 4mAh/cm2 area capacity, a charge-discharge cycle test was performed. The corresponding test results are shown in table 1.
Comparative example 3
Mixing spherical copper particles (120nm) and carbon nanotubes at a mass ratio of (3:1), and placing the mixture on a heating furnaceAnd carrying out heat treatment for 3h at 600 ℃ in an argon atmosphere to obtain the porous copper-carbon nanotube composite material with the porosity of about 17% and the thickness of about 100 microns. The porous copper-carbon nanotube composite material is used as a working electrode, a metal lithium sheet is used as a counter electrode, and the mass ratio of the metal lithium sheet to the counter electrode is 1M LiTFSI/DOL: DME (1: 1 by volume) contains 2 wt.% LiNO3Assembling the button cell for the electrolyte at 3mA/cm2And 4mAh/cm2 area capacity, a charge-discharge cycle test was performed. The corresponding test results are shown in table 1.
TABLE 1
The result shows that the cycle performance of the 3D copper framework prepared by the technical scheme of the invention is more than 6 times of the cycle life of the foam copper electrode, more than 26 times of the cycle life of the copper foil electrode and more than 3 times of the cycle life of the porous copper-carbon nanotube composite material.
Example 2
The 3D copper skeleton obtained in example 1 is used as a working electrode, then under the current density of 0.1mA/cm2, 5mAh/cm2 of metal lithium is electroplated on the electrode to prepare a composite negative electrode material, and then the composite negative electrode material and a graphene positive electrode rich in S simple substance form a lithium-sulfur battery, wherein the ratio of the metal lithium to the graphene positive electrode is 1M LiTFSI/DOL: DME (1: 1 by volume) electrolyte containing 1 wt.% LiNO3 was subjected to charge-discharge cycling tests at 0.5C. The corresponding test results are shown in table 2.
Comparative example 4
Commercial foamy copper (porosity 91%) is used as a working electrode, then under the current density of 0.1mA/cm2, 5mAh/cm2 metal lithium is electroplated on the electrode to prepare a composite negative electrode material, and then the composite negative electrode material and a graphene positive electrode rich in S simple substance form a lithium-sulfur battery, wherein the ratio of the lithium-sulfur battery to the graphene positive electrode is 1M LiTFSI/DOL: DME (1: 1 by volume) electrolyte containing 1 wt.% LiNO3 was subjected to charge-discharge cycling tests at 0.5C. The corresponding test results are shown in table 2.
Comparative example 5
The commercial copper foil (porosity is 0%) is used as a working electrode, then under the current density of 0.1mA/cm2, 5mAh/cm2 metal lithium is electroplated on the electrode to prepare a composite negative electrode material, and then the composite negative electrode material and a graphene positive electrode rich in S simple substance form a lithium-sulfur battery, wherein the porosity is determined in the following steps of 1M LiTFSI/DOL: DME (1: 1 by volume) electrolyte containing 1 wt.% LiNO3 was subjected to charge-discharge cycling tests at 0.5C. The corresponding test results are shown in table 2.
Comparative example 6
And (2) taking the porous copper-carbon nanotube composite material obtained in the comparative example 3 as a working electrode, electroplating 5mAh/cm2 of lithium metal on the electrode under the current density of 0.1mA/cm2 to prepare a composite negative electrode material, and then forming a lithium-sulfur battery together with a graphene positive electrode rich in S simple substance, wherein the ratio of the lithium-sulfur battery to the graphene positive electrode is 1M LiTFSI/DOL: DME (1: 1 by volume) electrolyte containing 1 wt.% LiNO3 was subjected to charge-discharge cycling tests at 0.5C. The corresponding test results are shown in table 2.
TABLE 2
The results show that the lithium sulfur full cell composed of the negative electrode prepared in example 1 exhibited better cycle performance.
Example 3
Placing titanium, iron, nickel, copper and tungsten particles (the particle diameters of the particles are about 250nm) in an argon atmosphere at 660 ℃ for heat treatment for 4 hours to obtain a 3D titanium skeleton, a 3D iron skeleton, a 3D nickel skeleton, a 3D copper skeleton and a 3D tungsten skeleton, wherein the porosity of the 3D titanium skeleton, the 3D iron skeleton, the 3D nickel skeleton, the 3D copper skeleton and the 3D tungsten skeleton are about 47% and the thickness of the 3D titanium skeleton, the 3D. These electrodes were used as working electrodes, a lithium metal plate as a counter electrode, and a lithium ion battery using 1M LiTFSI/DOL: DME (1: 1 by volume) contains 2 wt.% LiNO3Button cell assembly was performed for the electrolyte and charge-discharge cycling tests were performed at a current density of 3mA/cm2 and an area capacity of 3mAh/cm 2. The corresponding test results are shown in table 3.
TABLE 3
The results show that copper and titanium as the 3D framework material can show better cycle performance.
Example 4
Placing copper particles (with the particle size of 500nm) in an argon atmosphere, and performing heat treatment at 300 ℃, 450 ℃, 640 ℃, 800 ℃, 950 ℃ and 1100 ℃ for 3.6 hours respectively to obtain porosities of 81%, 73%, 62%, 47%, 26% and 15% respectively; 3D copper skeleton with thickness of 263, 185, 132, 95, 68, 59 μm. These electrodes were used as working electrodes, a lithium metal sheet as a counter electrode, and a lithium ion battery using a 1M LiTFSI/DOL: DME (1: 1 by volume) contains 2 wt.% LiNO3Button cell assembly was performed for the electrolyte and charge-discharge cycling tests were performed at a current density of 4mA/cm2 and an area capacity of 4mAh/cm 2. The corresponding test results are shown in table 4.
TABLE 4
The results show that the best cycling performance of the 3D copper skeleton is obtained within the preferred heat treatment temperature range.
Example 5
Placing nickel particles (320nm) in an argon atmosphere and performing heat treatment at 640 ℃ for 0.3h, 1.5h, 3h, 5h, 8h and 12h respectively to obtain porosities of about 82%, 74%, 61%, 47%, 27% and 18% respectively; 3D nickel skeleton with thickness of about 178, 123, 82, 60, 44, 39 μm, respectively. These electrodes were used as working electrodes, a lithium metal sheet as a counter electrode, and a lithium ion battery using a 1M LiTFSI/DOL: DME (1: 1 by volume) contains 2 wt.% LiNO3Button cell assembly was performed for the electrolyte and charge-discharge cycling tests were performed at a current density of 5mA/cm2 and an area capacity of 4mAh/cm 2. The corresponding test results are shown in table 5.
TABLE 5
The results show that the best cycling performance of the 3D nickel framework is obtained within the preferred heat treatment time range.
Example 6
Copper particles (particle size 23nm, 77nm, 245nm, 1.9 μm, 6.9 μm, 13.6 μm, respectively) were placed in an argon atmosphere and heat treated at 550 ℃ for 4.6h, respectively, to give a 3D copper skeleton with a porosity of about 15%, 23%, 46%, 67%, 77%, 83%, and a thickness of 25, 27, 39, 63, 91, 124 μm, respectively. These electrodes were used as working electrodes, a lithium metal sheet as a counter electrode, and a lithium ion battery using a 1M LiTFSI/DOL: DME (1: 1 by volume) contains 2 wt.% LiNO3Button cell assembly was performed for the electrolyte and charge-discharge cycling tests were performed at a current density of 5mA/cm2 and an area capacity of 4mAh/cm 2. The corresponding test results are shown in table 6.
TABLE 6
The results show that the cycling performance of the 3D copper skeleton is best in the preferred thickness range.
Example 7
Copper particles (particle size 280nm, mass 1, 3.8, 7.5, 20, 57, 83g, respectively) were placed in an argon atmosphere and heat treated at 550 ℃ for 3.6h, respectively, to give a 3D copper skeleton with a porosity of about 48% and a thickness of 12, 46, 90, 240, 680, 1000 μm, respectively. These electrodes were used as working electrodes, a lithium metal sheet as a counter electrode, and a lithium ion battery using a 1M LiTFSI/DOL: DME (1: 1 by volume) contains 2 wt.% LiNO3Button cell assembly was performed for the electrolyte and charge-discharge cycling tests were performed at a current density of 5mA/cm2 and an area capacity of 5mAh/cm 2. The corresponding test results are shown in table 6.
TABLE 6
The results show that the cycling performance of the 3D copper skeleton is best in the preferred thickness range.
Claims (19)
1. A preparation method of a 3D lithium metal battery cathode is characterized by comprising the following steps:
step (1): preparation of the 3D metal framework:
carrying out heat treatment on metal particles with the particle size of 50 nm-10 microns in a protective atmosphere at 400-1000 ℃ to prepare the 3D metal framework; the metal of the metal particles is any one of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zirconium, molybdenum and tungsten;
step (2): carrying lithium;
and loading lithium on the 3D metal framework to prepare the 3D lithium metal battery cathode.
2. The method of preparing a negative electrode for a 3D lithium metal battery according to claim 1, wherein the metal particles have a particle size of 70nm to 7 μm.
3. The method of preparing a negative electrode for a 3D lithium metal battery according to claim 2, wherein the metal particles have a particle size of 100nm to 3 μm.
4. The method for preparing the negative electrode of the 3D lithium metal battery according to claim 1, wherein the heat treatment temperature is 450-950 ℃.
5. The method for preparing the negative electrode of the 3D lithium metal battery according to claim 1, wherein the heat treatment temperature is 550-800 ℃.
6. The method for preparing a negative electrode of a 3D lithium metal battery according to claim 1, wherein the heat treatment time is 0.5 to 10 hours.
7. The method for preparing a 3D lithium metal battery cathode according to claim 1, wherein the heat treatment time is 1.5 to 8 hours.
8. The method for preparing a 3D lithium metal battery cathode according to claim 1, wherein the heat treatment time is 2-6 hours.
9. The method for preparing a negative electrode of a 3D lithium metal battery according to claim 1, wherein the heat treatment time is 3-5 hours.
10. A3D lithium metal battery cathode prepared by the preparation method of any one of claims 1 to 9, which is characterized by comprising a 3D metal framework and a metal lithium layer compounded in the framework;
the 3D metal framework is obtained by heat treatment of any one metal particle of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zirconium, molybdenum and tungsten;
the porosity of the 3D metal framework is 20-80%; the thickness is 25 to 800 μm.
11. The 3D lithium metal battery negative electrode of claim 10, wherein the 3D metal skeleton is titanium or copper.
12. The negative electrode of the 3D lithium metal battery according to claim 10, wherein the porosity of the 3D metal skeleton in the negative electrode of the 3D lithium metal battery is 40 to 70%.
13. The negative electrode of the 3D lithium metal battery of claim 10, wherein the porosity of the 3D metal skeleton in the negative electrode of the 3D lithium metal battery is 45 to 65%.
14. The negative electrode of the 3D lithium metal battery according to claim 10, wherein the thickness of the 3D metal skeleton is 35 to 680 μm.
15. The negative electrode of the 3D lithium metal battery according to claim 10, wherein the thickness of the 3D metal skeleton is 39 to 240 μm.
16. The negative electrode of the 3D lithium metal battery according to claim 10, wherein the thickness of the 3D metal skeleton is 60 to 100 μm.
17. The negative electrode of the 3D lithium metal battery according to claim 10, wherein the negative electrode of the 3D lithium metal battery has a lithium loading of 3 to 32mAh/cm2。
18. A lithium metal battery comprising the 3D lithium metal battery negative electrode prepared by the preparation method of any one of claims 1 to 9.
19. The lithium metal battery of claim 18, wherein the lithium metal battery is a lithium sulfur battery, a lithium oxygen battery, a lithium nitrogen battery, or a lithium water battery.
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