CN114628685B - Super-lithium-philic high-stability metal lithium composite negative plate and battery - Google Patents
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Abstract
The invention relates to the technical field of battery cathode materials, and discloses a super-lithium-philic high-stability metal lithium composite cathode plate, which comprises an upper layer and a lower layer, wherein the upper layer comprises a three-dimensional porous current collector modified by nickel nano particles and metal lithium deposited in the inner part and the surface of the three-dimensional porous current collector; the lower layer includes a sulfide solid electrolyte; the sulfide solid electrolyte includes Li 6 PS 5 Br、Li 6 PS 5 Cl or Li 6 PS 5 I. The three-dimensional porous current collector modified by the nickel nano particles reduces local current density by providing larger electroactive surface area, effectively adjusts lithium deposition and growth of lithium dendrites, and improves affinity with metal lithium and distribution uniformity; the sulfide solid electrolyte inhibits side reaction between the metal lithium composite negative electrode and the solid electrolyte, prolongs the cycle life of the metal lithium composite negative electrode, and improves the electrochemical performance of the battery.
Description
Technical Field
The invention relates to the technical field of battery cathode materials, in particular to a super-lithium-philic high-stability metal lithium composite cathode plate and a battery.
Background
The metal lithium battery formed by combining the metal lithium serving as a negative electrode and a high-energy positive electrode (such as selenium, sulfur and oxygen) has high theoretical specific energy, is considered to be the most promising alternative battery in future fixed power grid storage and transportation application, and meanwhile, the application of energy storage of consumer electronic equipment, electric automobiles and smart power grids is increasingly wide, so that the development of the lithium battery with high energy density is promoted. However, metallic lithium still faces a range of technical challenges including lithium dendrite formation, unstable Solid Electrolyte Interface (SEI), and large volume changes of metallic lithium, resulting in poor safety, low coulombic efficiency, and low cycle life of the battery.
The Chinese patent publication No. CN108511708A discloses a solid composite metal lithium anode which consists of a composite layer of metal lithium and a lithium-philic framework material and a solid electrolyte protective layer. The solid electrolyte protective layer contains an inorganic solid electrolyte and an organic solid electrolyte. The solid electrolyte protective layer is coated on the surface of the composite layer by dipping, knife coating, spin coating, spraying or sputtering and the like. The lithium-philic framework material has the defects that the conductivity of the used lithium-philic framework material is low, the affinity with metal lithium cannot be effectively improved, in addition, the instability of a solid electrolyte interface cannot be solved by simple coating of a solid electrolyte protective layer, the solid electrolyte protective layer is easy to fall off or damage, and the cycle performance of a battery cannot be improved.
Disclosure of Invention
The invention aims to provide a super-lithium-philic high-stability metal lithium composite negative plate and a battery, which are used for improving the affinity between a negative current collector and metal lithium, effectively regulating lithium deposition and growth of lithium dendrites, and improving the stability of a solid electrolyte interface and the cycle life of the battery.
The aim of the invention is achieved by the following technical scheme.
In a first aspect, the invention provides a super-lithium-philic high-stability metal lithium composite negative plate, which comprises an upper layer and a lower layer, wherein the upper layer comprises a three-dimensional porous current collector modified by nickel nano particles and depositionLithium metal in the interior and surface thereof; the lower layer includes a sulfide solid electrolyte; the sulfide solid electrolyte includes Li 6 PS 5 Br、Li 6 PS 5 Cl or Li 6 PS 5 I。
The three-dimensional porous current collector reduces local current density by providing a larger electroactive surface area than one-and two-dimensional materials, and can accommodate volumetric expansion and high heat dissipation efficiency, effectively regulating lithium deposition and lithium dendrite growth. However, the change in volume of metallic lithium caused by the unavoidable lithium ion deintercalation process may cause it to fall off from the copper mesh substrate, resulting in a cycle life decay. Although the wettability of molten metallic lithium to a substrate can be improved by adding an organic coating or a functional element additive to react with the molten lithium, the organic coating can decompose during heating, and the resulting product can deposit on the surface of metallic lithium to form an electronic insulating layer, reducing the cycle life of the battery.
According to the invention, nickel nano particles are selected as functional element additives to modify a copper mesh matrix, the three-dimensional porous current collector modified by the nickel nano particles can reduce the surface energy of lithium deposition and generate Laplacian stress, and the stress can be used as a plane driving force (parallel to the copper matrix) for diffusion and deposition of molten metal lithium, so that the wettability of the metal lithium on the three-dimensional porous current collector is improved.
In the metal lithium composite negative plate, the sulfide solid electrolyte at the lower layer has high ion conductivity and electrochemical stability, so that the microstructure defect generated by depositing metal lithium is improved, and the formation of lithium dendrites is reduced. Meanwhile, the interface stability between the metal lithium composite negative plate and the solid electrolyte can be improved, and the cycle life of the battery is prolonged.
Preferably, the three-dimensional porous current collector is a three-dimensional mesh copper foil.
Preferably, the sulfide solid electrolyte is Li 6 PS 5 Br。
Preferably, the preparation method comprises the following steps:
(a) Soaking the three-dimensional netlike copper foil in an acid solution, and then sequentially washing, drying and aerobically sintering;
(b) Soaking the three-dimensional reticular copper foil treated in the step (a) in a nickel source solution, taking out, calcining in an inert gas atmosphere, and reducing in a reducing gas atmosphere to obtain a nickel nanoparticle modified three-dimensional reticular copper foil, namely a NiNP-Cu matrix;
(c) Placing the NiNP-Cu matrix in the step (b) in molten lithium metal under inert gas atmosphere, standing, taking out, and cooling under inert gas atmosphere to obtain a Li-NiNP-Cu matrix;
(d) Li with the molar ratio of 3-5:0.5-1:0.5-1.5 is added in the environment with the water and oxygen content of less than 10ppm 2 S、P 2 S 5 And LiBr is added into hydroxyl-containing alkyl ether for ultrasonic treatment; and (3) adding an organic solvent into the obtained suspension to form a precursor solution, then enabling one side of the Li-NiNP-Cu matrix in the step (c) to be in contact with the precursor solution, standing, drying, and performing vacuum sintering to obtain the metal lithium composite negative plate.
The three-dimensional reticular copper foil is selected as a three-dimensional porous current collector, has high conductivity and can improve the total output potential. However, three-dimensional reticulated copper foil has low affinity for metallic lithium, and direct use can lead to large nucleation overpotential, poor contact, and formation of "dead lithium" during cycling. Therefore, the sintering process in the step (a) can generate a copper oxide thin layer on the surface, so that the lithium-philicity of the copper foil is improved.
In the step (b), after the nickel nano particles are deposited, the Cu-CuO-Ni hybrid structure is generated by oxidation treatment, has lower heterogeneous nucleation overpotential and more excellent surface lithium affinity, and is beneficial to improving the distribution uniformity of the subsequent molten metal lithium in the three-dimensional reticular copper foil.
In step (c), metallic lithium is deposited by a fusion process, microscopic structural defects are easily generated inside the Li-NiNP-Cu matrix, and local current densities of these defects are too high, so that lithium dendrites are easily generated. To further optimize this, in step (d), a sulfide solid electrolyte layer is supported on one side of the Li-NiNP-Cu matrix. Li (Li) 6 PS 5 The Br solid electrolyte has excellent ionic conductivity and electrochemical stability, and the conductivity thereof can be used forIs an ideal electrolyte for solid batteries over conventional liquid electrolytes, but Li 6 PS 5 The critical current density of the Br solid electrolyte is low, and the charge and discharge current of the solid battery is limited. Li is as defined in the invention 6 PS 5 Br is coated on the surface of the metal lithium deposited on the three-dimensional reticular copper foil and sintered, and has two main functions: on one hand, the generation of lithium dendrites is avoided by improving the conductivity of microscopic defects in the Li-NiNP-Cu matrix; on the other hand by increasing Li 6 PS 5 And the critical current density of Br optimizes the interface performance of the lithium metal composite anode. In addition, compared with a planar substrate, the three-dimensional netlike copper foil substrate in the invention provides higher specific surface area and promotes Li 6 PS 5 Br solid electrolyte surface charge distribution uniformity.
In addition, the surface of the Li-NiNP-Cu matrix contains metal lithium, so that the lithium-nickel composite anode is sensitive to the water-oxygen content, and the environment with the water-oxygen content lower than 10ppm can avoid side reactions of the metal lithium, so that the electrochemical performance of the metal lithium composite anode is improved.
Preferably, in the step (a), the acid solution is dilute hydrochloric acid or dilute sulfuric acid, and the concentration is 0.03-0.1mol/L; the soaking is soaking at 30-45deg.C for 30-90min; the washing is carried out by using deionized water and absolute ethyl alcohol respectively, and the washing is repeated for 3-5 times; the drying is carried out for 10-24 hours at 50-90 ℃; the sintering is carried out for 4-8 hours in the air at 200-250 ℃.
Preferably, in the step (b), the nickel source solution is nickel nitrate solution, nickel sulfate solution or nickel acetate solution, and the concentration is 0.02-0.06mol/L; the soaking is carried out for 2-5 hours at 60-90 ℃; the inert gas is argon; calcining for 30-80min at 1000-1500 ℃ in a tube furnace; the reducing gas is hydrogen or argon, and the mass ratio of the raw materials to the reducing gas is 3-6:94-97; the reduction is carried out in a tube furnace at 600-800 ℃ for 40-90min.
Preferably, in step (c), the inert gas is argon; the standing is carried out at 200-250deg.C for 10-30min.
The three-dimensional netlike copper foil is placed in molten metal lithium under argon atmosphere and is kept stand for 10-30min at 200-250 ℃ in order that the molten metal lithium can be effectively diffused into the copper foil under the action of nickel nano particles.
Preferably, in step (d), the hydroxyalkyl ether comprises ethylene glycol monopropyl ether, glycerol butyl ether or polyethylene glycol allyl methyl ether; the organic solvent is absolute ethanol, propanol, acetone, methanol, ethylene glycol or diethyl ether.
Preferably, in step (d), the hydroxyalkyl ether is reacted with Li 2 S、P 2 S 5 And LiBr is 0.5 to 1.5:10-20 parts of a base; the ultrasonic treatment is carried out for 1-2 hours under the conditions of 300-350K and 20-30 kHz; the standing time is 30-60min; the drying is carried out for 6-12h at 60-90 ℃; the vacuum sintering is carried out for 4-8 hours at 200-300 ℃.
Vacuum sintering at 200-300 deg.C to make Li 6 PS 5 Br solid electrolyte densification, li 6 PS 5 The interface between Br and metallic lithium is filled with amorphous phase, so that interface defect is reduced.
In a second aspect, the invention also provides a battery, which comprises the super-lithium-philic high-stability metal lithium composite negative plate.
Compared with the prior art, the invention has the following beneficial effects:
(1) The three-dimensional porous current collector modified by the nickel nano particles reduces local current density by providing larger electroactive surface area, effectively regulates lithium deposition and growth of lithium dendrites, and improves affinity and distribution uniformity with metallic lithium;
(2) The sulfide solid electrolyte inhibits side reaction between the metal lithium composite negative electrode and the solid electrolyte, prolongs the cycle life of the metal lithium composite negative electrode, and improves the electrochemical performance of the battery.
Detailed Description
The technical scheme of the present invention is described below by using specific examples, but the scope of the present invention is not limited thereto:
general examples
A super-lithium-philic high-stability metal lithium composite negative plate comprises an upper layer and a lower layer, wherein the upper layer comprises nickel nanoThree-dimensional netlike copper foil modified by rice particles and metal lithium deposited in and on the inner part and surface of the three-dimensional netlike copper foil, wherein the lower layer comprises Li 6 PS 5 Br sulfide solid electrolyte.
The preparation method comprises the following steps:
(a) Placing the three-dimensional net-shaped copper foil in dilute hydrochloric acid with the concentration of 0.03-0.1mol/L, soaking for 30-90min at the temperature of 30-45 ℃, taking out, washing with deionized water and absolute ethyl alcohol, and repeating for 3-5 times to thoroughly remove impurities on the surface of the copper foil; drying at 50-90deg.C for 10-24 hr, and sintering in air at 200-250deg.C for 4-8 hr to form copper oxide thin layer on the surface.
(b) Placing the three-dimensional netlike copper foil treated in the step (a) into a nickel nitrate solution with the concentration of 0.02-0.06mol/L, soaking for 2-5h at the temperature of 60-90 ℃, taking out, and calcining for 30-80min at the temperature of 1000-1500 ℃ in a tubular furnace under the atmosphere of argon; and then reducing the copper foil in a tubular furnace at 600-800 ℃ for 40-90min in a hydrogen atmosphere, wherein the mass ratio of the raw materials to the reducing gas is 3-6:94-97, and obtaining the nickel nanoparticle modified three-dimensional reticular copper foil, namely the NiNP-Cu matrix.
(c) And (c) placing the NiNP-Cu matrix in the step (b) in molten metallic lithium under the argon atmosphere, standing for 10-30min at 200-250 ℃, taking out, and cooling under the argon atmosphere to obtain the Li-NiNP-Cu matrix.
(d) Li with the molar ratio of 3-5:0.5-1:0.5-1.5 is added in the environment with the water and oxygen content of less than 10ppm 2 S、P 2 S 5 And LiBr is added into ethylene glycol monopropyl ether for ultrasonic treatment for 1-2h, and the mass ratio of the ethylene glycol monopropyl ether to the total substances of Li2S, P S5 and LiBr is 0.5-1.5:10-20, wherein the ultrasonic conditions are 300-350K and 20-30kHz, and white suspension is formed after ultrasonic treatment; and (3) adding absolute ethyl alcohol into the obtained suspension to form a green transparent precursor solution, then enabling one side of the Li-NiNP-Cu matrix in the step (c) to be in contact with the precursor solution, standing for 30-60min, drying at 60-90 ℃ for 6-12h, and carrying out vacuum sintering at 200-300 ℃ for 4-8h to obtain the metal lithium composite negative plate.
A battery comprising the above super-lithium-philic high-stability metal lithium composite negative plate.
Example 1
The preparation method of the super-lithium-philic high-stability metal lithium composite negative plate comprises the following steps:
(a) Placing the three-dimensional reticular copper foil in dilute hydrochloric acid with the concentration of 0.06mol/L, soaking for 70min at 38 ℃, taking out, flushing with deionized water and absolute ethyl alcohol, and repeating for 4 times; drying at 80 ℃ for 20 hours, and sintering in air at 230 ℃ for 6 hours.
(b) Placing the three-dimensional netlike copper foil treated in the step (a) into nickel nitrate solution with the concentration of 0.05mol/L, soaking for 4 hours at 80 ℃, taking out, and calcining for 60 minutes at 1200 ℃ in a tube furnace under the argon atmosphere; and then reducing for 75min in a tube furnace at 725 ℃ in a hydrogen atmosphere, wherein the mass ratio of the raw materials to the reducing gas is 5:95, and obtaining the nickel nanoparticle modified three-dimensional reticular copper foil, namely the NiNP-Cu matrix.
(c) And (c) placing the NiNP-Cu matrix in the step (b) in molten metallic lithium under an argon atmosphere, standing at 230 ℃ for 25min, taking out, and cooling under the argon atmosphere to obtain the Li-NiNP-Cu matrix.
(d) Li with the molar ratio of 4:0.6:0.9 is added in an environment with the water and oxygen content of less than 10ppm 2 S、P 2 S 5 And LiBr are added into ethylene glycol monopropyl ether for ultrasonic treatment for 1.3 hours, and the ethylene glycol monopropyl ether and Li are added into the catalyst 2 S、P 2 S 5 And LiBr at a total mass ratio of 1.2:15, ultrasonic conditions are 330K and 25kHz, and white suspension is formed after ultrasonic treatment; and (3) adding absolute ethyl alcohol into the obtained suspension to form a green transparent precursor solution, then enabling one side of the Li-NiNP-Cu matrix in the step (c) to be in contact with the precursor solution, standing for 55min, drying at 80 ℃ for 10h, and carrying out vacuum sintering at 280 ℃ for 7h to obtain the metal lithium composite negative plate.
PEO is taken as a solid electrolyte membrane, two metal lithium composite negative plates are taken, and Li is contained respectively 6 PS 5 The lower layer of Br faces the solid electrolyte membrane and is pressed on two sides of PEO solid electrolyte membrane under 60 standard atmospheric pressures to assemble 2032 type button symmetrical cell.
Example 2
The difference from example 1 is that:
in the step (a), the concentration of the dilute hydrochloric acid is 0.03mol/L; soaking at 45deg.C for 30min; the washing was repeated 5 times; drying at 50deg.C for 24 hr; sintering for 4 hours at 250 ℃ in air.
In the step (b), the concentration of the nickel nitrate solution is 0.06mol/L; soaking for 2h at 90 ℃; calcining at 1000deg.C for 30min; then reducing for 90min at 600 ℃, wherein the mass ratio of the raw materials to the reducing gas is 6:94.
In step (c), the mixture was allowed to stand at 200℃for 30 minutes.
In step (d), li 2 S、P 2 S 5 And LiBr in a molar ratio of 3:1:0.5, ethylene glycol monopropyl ether to Li 2 S、P 2 S 5 And LiBr at a total mass ratio of 0.5:20, a step of; treating for 1h under the ultrasonic conditions of 350K and 20 kHz; standing for 60min, drying at 60deg.C for 12 hr, and vacuum sintering at 300deg.C for 4 hr.
Example 3
The difference from example 1 is that:
in the step (a), the concentration of the dilute hydrochloric acid is 0.1mol/L; soaking at 30deg.C for 90min; the flushing was repeated 3 times; drying at 90deg.C for 10 hr; sintering for 8 hours at 200 ℃ in air.
In the step (b), nickel sulfate solution is used to replace nickel nitrate solution, and the concentration is 0.02mol/L; soaking for 2h at 90 ℃; calcining at 1500 ℃ for 80min; then reducing for 40min at 800 ℃, wherein the mass ratio of the raw materials to the reducing gas is 3:97.
In step (c), the mixture was allowed to stand at 250℃for 10 minutes.
In step (d), li 2 S、P 2 S 5 And LiBr in a molar ratio of 5:0.5:1.5, ethylene glycol monopropyl ether to Li 2 S、P 2 S 5 And LiBr at a total mass ratio of 1.5:20, a step of; treating for 2 hours under the ultrasonic conditions of 300K and 30 kHz; standing for 30min, drying at 90 ℃ for 6h, and vacuum sintering at 200 ℃ for 8h.
Example 4
The difference from example 1 is that:
in step (d), li 2 S、P 2 S 5 And LiBr in a molar ratio of 3:1.0:1.5, ethylene glycol monopropyl etherWith Li 2 S、P 2 S 5 And LiBr at a total mass ratio of 1.5:10; the treatment is carried out for 2 hours under the ultrasonic conditions of 350K and 20 kHz.
Example 5
The difference from example 1 is that:
in step (b), the nickel nitrate solution is replaced by nickel acetate
The solid electrolyte membrane in the battery adopts lanthanum lithium zirconate, two metal lithium composite negative plates are taken, and Li is contained respectively 6 PS 5 The lower layer of Br was pressed against the solid electrolyte membrane on both sides of the lanthanum lithium zirconate solid electrolyte at 100 standard atmospheres.
Comparative example 1
The difference from example 1 is that: in the step (a), the three-dimensional net-shaped copper foil is not subjected to an in-air sintering process.
Comparative example 2
The difference from example 1 is that: the adopted three-dimensional net-shaped copper foil is not modified with nickel nano particles.
Comparative example 3
The difference from example 1 is that: the three-dimensional net-shaped copper foil adopted is not subjected to the treatment process of the step (a) and the modification of the nickel nano particles of the step (b).
Comparative example 4
The difference from example 1 is that: conventional metallic lithium sheet cathodes were used.
Comparative example 5
The difference from example 1 is that: lithium metal composite anode contains no Li 6 PS 5 And a lower layer of Br sulfide solid electrolyte.
Comparative example 6
The difference from example 1 is that: in the step (d), after one side of the Li-NiNP-Cu matrix is contacted with the precursor solution, the vacuum sintering treatment is not carried out, and the metallic lithium composite negative plate is obtained.
Test conditions:
at 30 ℃ and 60 ℃, the charge-discharge cycle is carried out at the multiplying power of 0.2C within the range of 2.5-4.0V, and the voltage drop speed exceeds 5mV/min until the battery is short-circuited. EIS test of solid by AC impedance Spectroscopy at the same temperatureImpedance of the body cell, frequency range of 1-10 6 HZ, the applied voltage amplitude is 5-10mV.
Table 1 results of performance test of battery
The invention adopts the symmetrical battery, does not contain the positive plate, can effectively avoid the influence of the positive plate on the internal resistance of the battery, and truly reflects the change of the internal resistance of the negative plate. Specific results are shown in table 1, and in combination with examples 1 to 5, it can be seen that the prepared lithium metal composite negative electrode sheet has excellent internal resistance and cycle life within the technical requirements of the invention, wherein example 1 has the best effect. As can be seen from the combination of the example 1 and the comparative examples 1-6, the heterogeneous nucleation overpotential is reduced, the continuous growth of lithium dendrites is inhibited, and the distribution uniformity of the metallic lithium in the three-dimensional reticular copper foil is improved by constructing the Cu-CuO-Ni hybrid structure; adding Li with high ion conductivity 6 PS 5 After the Br protective film is sintered, the micro defects in the composite anode can be reduced, the local current density in the anode can be improved, and Li can be reduced 6 PS 5 The critical current density of Br inhibits precipitation of lithium dendrite, thereby improving the lithium ion transmission performance of the solid battery and prolonging the cycle life. The results show that the method provided by the invention can effectively improve the comprehensive performance of the metallic lithium negative electrode, reduce the internal resistance of the battery and prolong the cycle life, and provides a reference path for researching high-performance solid batteries.
The foregoing description is only of the preferred embodiments of the present invention, and is not intended to limit the scope of the invention, but rather is intended to cover any equivalents of the structures disclosed herein or modifications in the equivalent processes, or any application of the structures disclosed herein, directly or indirectly, in other related arts.
Claims (7)
1. The super-lithium-philic high-stability metal lithium composite negative plate is characterized by comprising an upper layer and a lower layer, wherein the upper layer comprises a three-dimensional netlike copper foil modified by nickel nano particles and a sinking layerMetal lithium accumulated in the interior and surface thereof; the lower layer includes a sulfide solid electrolyte; the sulfide solid electrolyte is Li 6 PS 5 Br；
The preparation method of the metal lithium composite negative plate comprises the following steps:
(a) Soaking the three-dimensional netlike copper foil in an acid solution, and then sequentially washing, drying and aerobically sintering;
(b) Soaking the three-dimensional reticular copper foil treated in the step (a) in a nickel source solution, taking out, calcining in an inert gas atmosphere, and reducing in a reducing gas atmosphere to obtain a nickel nanoparticle modified three-dimensional reticular copper foil, namely a NiNP-Cu matrix;
(c) Placing the NiNP-Cu matrix in the step (b) in molten lithium metal under inert gas atmosphere, standing, taking out, and cooling under inert gas atmosphere to obtain a Li-NiNP-Cu matrix;
(d) Li with the molar ratio of 3-5:0.5-1:0.5-1.5 is added in the environment with the water and oxygen content of less than 10ppm 2 S、P 2 S 5 And LiBr is added into hydroxyl-containing alkyl ether for ultrasonic treatment; and (3) adding an organic solvent into the obtained suspension to form a precursor solution, then enabling one side of the Li-NiNP-Cu matrix in the step (c) to be in contact with the precursor solution, standing, drying, and performing vacuum sintering to obtain the metal lithium composite negative plate.
2. The super-lithium high-stability metal lithium composite negative electrode sheet according to claim 1, wherein in the step (a),
the acid solution is dilute hydrochloric acid or dilute sulfuric acid, and the concentration is 0.03-0.1mol/L;
the soaking is soaking at 30-45deg.C for 30-90min;
the washing is carried out by using deionized water and absolute ethyl alcohol respectively, and the washing is repeated for 3-5 times;
the drying is carried out for 10-24 hours at 50-90 ℃;
the sintering is carried out for 4-8 hours in the air at 200-250 ℃.
3. The super-lithium high-stability metal lithium composite negative electrode sheet according to claim 1, wherein in the step (b),
the nickel source solution is nickel nitrate solution, nickel sulfate solution or nickel acetate solution, and the concentration is 0.02-0.06mol/L;
the soaking is carried out for 2-5 hours at 60-90 ℃;
the inert gas is argon;
calcining for 30-80min at 1000-1500 ℃ in a tube furnace;
the reducing gas is hydrogen, and the mass ratio of the raw materials to the reducing gas is 3-6:94-97;
the reduction is carried out in a tube furnace at 600-800 ℃ for 40-90min.
4. The super-lithium high-stability metal lithium composite negative electrode sheet according to claim 1, wherein in the step (c),
the inert gas is argon;
the standing is carried out at 200-250deg.C for 10-30min.
5. The super-lithium high-stability metal lithium composite negative electrode sheet according to claim 1, wherein in the step (d),
the hydroxyl-containing alkyl ether comprises ethylene glycol monopropyl ether, glycerol butyl ether or polyethylene glycol allyl methyl ether; the organic solvent is absolute ethanol, propanol, acetone, methanol, ethylene glycol or diethyl ether.
6. The super-lithium high-stability metal lithium composite negative electrode sheet according to claim 5, wherein in the step (d),
the hydroxyl-containing alkyl ether and Li 2 S、P 2 S 5 And LiBr is 0.5 to 1.5:10-20 parts of a base;
the ultrasonic treatment is carried out for 1-2 hours under the conditions of 300-350K and 20-30 kHz;
the standing time is 30-60min;
the drying is carried out for 6-12h at 60-90 ℃;
the vacuum sintering is carried out for 4-8 hours at 200-300 ℃.
7. A battery comprising the superphilic high-stability metallic lithium composite negative plate of any of claims 1-6.
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