CN114628685A - Super-lithium-philic high-stability metal lithium composite negative plate and battery - Google Patents
Super-lithium-philic high-stability metal lithium composite negative plate and battery Download PDFInfo
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Abstract
The invention relates to the technical field of battery negative electrode materials, and discloses a super-lithium-philic high-stability metal lithium composite negative electrode plate which comprises an upper layerThe upper layer comprises a three-dimensional porous current collector modified by nickel nanoparticles and metal lithium deposited in the upper layer and on the surface of the upper layer; the lower layer comprises a sulfide solid electrolyte; the sulfide solid electrolyte includes Li6PS5Br、Li6PS5Cl or Li6PS5I. The three-dimensional porous current collector modified by the nickel nanoparticles reduces the local current density by providing a larger electroactive surface area, effectively regulates the deposition of lithium and the growth of lithium dendrites, and improves the affinity and distribution uniformity with metallic lithium; the sulfide solid electrolyte inhibits side reaction between the lithium metal composite negative electrode and the solid electrolyte, prolongs the cycle life of the lithium metal composite negative electrode, and improves the electrochemical performance of the battery.
Description
Technical Field
The invention relates to the technical field of battery negative electrode materials, in particular to a super-lithium-philic high-stability metal lithium composite negative electrode plate and a battery.
Background
The lithium metal battery formed by combining the lithium metal as the negative electrode and the high-energy positive electrode (such as selenium, sulfur and oxygen) has high theoretical specific energy, is considered as the most promising substitute battery in future fixed grid storage and transportation applications, and meanwhile, the increasingly wide application of energy storage of consumer electronic equipment, electric automobiles and smart grids promotes the development of the high-energy density lithium battery. However, metallic lithium still faces a series of technical difficulties including lithium dendrite formation, unstable Solid Electrolyte Interface (SEI), and large volume change of metallic lithium, resulting in poor safety, coulombic efficiency, and low cycle life of the battery.
The chinese patent publication No. CN108511708A discloses a solid-state composite metal lithium negative electrode, which is composed of a composite layer of metal lithium and a lithium-philic framework material and a solid electrolyte protective layer. The solid electrolyte protective layer includes an inorganic solid electrolyte and an organic solid electrolyte. The solid electrolyte protective layer is coated on the surface of the composite layer by methods of dipping, blade coating, spin coating, spray coating or sputtering and the like. The defects of the method are that the used lithium-philic framework material has low conductivity, the affinity with metal lithium cannot be effectively improved, and in addition, the instability of a solid electrolyte interface cannot be solved by simply coating the solid electrolyte protective layer, the solid electrolyte protective layer is easy to fall off or damage, and the method is not beneficial to improving the cycle performance of the battery.
Disclosure of Invention
The invention aims to provide a metallic lithium composite negative plate and a battery with super-lithium-philic high stability, which improve the affinity of a negative current collector and metallic lithium, effectively regulate the lithium deposition and the growth of lithium dendrites, and simultaneously improve the stability of a solid electrolyte interface and the cycle life of the battery.
The purpose of the invention is realized by the following technical scheme.
In a first aspect, the invention provides a super-lithium-philic high-stability metallic lithium composite negative plate, which comprises an upper layer and a lower layer, wherein the upper layer comprises a nickel nanoparticle modified three-dimensional porous current collector and metallic lithium deposited in the upper layer and on the surface of the current collector; the lower layer comprises a sulfide solid electrolyte; the sulfide solid electrolyte includes Li6PS5Br、Li6PS5Cl or Li6PS5I。
Compared with one-dimensional and two-dimensional materials, the three-dimensional porous current collector reduces local current density by providing larger electroactive surface area, can accommodate volume expansion, has high heat dissipation efficiency, and can effectively regulate lithium deposition and lithium dendrite growth. However, the inevitable volume change of metallic lithium caused by the lithium ion deintercalation process may cause the metallic lithium to be detached from the copper mesh substrate, resulting in the decay of cycle life. Although the wettability of the molten lithium metal to the substrate can be improved by increasing the reaction of the organic coating or the functional element additive with the molten lithium, the organic coating is decomposed during heating, and the formed product is deposited on the surface of the lithium metal to form an electronic insulating layer, thereby reducing the cycle life of the battery.
According to the invention, nickel nanoparticles are selected as functional element additives to modify the copper mesh substrate, the three-dimensional porous current collector modified by the nickel nanoparticles can reduce the surface energy of lithium deposition and generate Laplace stress, and the stress can be used as a planar driving force (parallel to the copper substrate) 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 ionic conductivity and electrochemical stability, the microstructure defect caused by the deposition of metal lithium is improved, and the formation of lithium dendrite 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 Li6PS5Br。
Preferably, the preparation method comprises the following steps:
(a) soaking the three-dimensional reticular copper foil in an acid solution, and then sequentially washing, drying and carrying out aerobic 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 metal lithium in an inert gas atmosphere for standing, taking out the NiNP-Cu matrix and cooling the NiNP-Cu matrix in the inert gas atmosphere to obtain a Li-NiNP-Cu matrix;
(d) in the environment with the water oxygen content lower than 10ppm, Li with the molar ratio of 3-5:0.5-1:0.5-1.52S、P2S5And LiBr are added into hydroxyl-containing alkyl ether for ultrasonic treatment; and (c) adding an organic solvent into the obtained suspension to form a precursor solution, then contacting one side of the Li-NiNP-Cu matrix in the step (c) 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, and has high conductivity, so that the total output potential can be improved. However, the three-dimensional reticulated copper foil has a low affinity for metallic lithium and direct use can lead to large nucleation overpotentials, poor contact and formation of "dead lithium" during cycling. Therefore, the sintering process in step (a) can generate a thin copper oxide layer on the surface, and improve the lithium affinity of the copper foil.
In the step (b), after nickel nanoparticles are deposited and oxidized, a Cu-CuO-Ni hybrid structure can be generated, the heterogeneous nucleation overpotential is lower, the surface lithium affinity is more excellent, and the distribution uniformity of the subsequent molten metal lithium in the three-dimensional reticular copper foil is improved.
In the step (c), the lithium metal is deposited by a melting method, microscopic structural defects are easily generated in the Li-NiNP-Cu matrix, and the local current density of the defects is too high, so that lithium dendrites are easily generated. In order to further optimize the method, in the step (d), one side of the Li-NiNP-Cu matrix is loaded with one sulfide solid electrolyte layer. Li6PS5The Br solid electrolyte has excellent ion conductivity and electrochemical stability, the conductivity of the Br solid electrolyte can exceed that of a conventional liquid electrolyte, and the Br solid electrolyte is an ideal electrolyte of a solid battery, but Li6PS5The critical current density of the Br solid electrolyte is low, and the charge and discharge current of the solid battery is limited. In the invention, Li6PS5Br is coated on the surface of the lithium metal deposited by the three-dimensional reticular copper foil and sintered, and the three-dimensional reticular copper foil has two main functions: on one hand, the generation of lithium dendrite is avoided by improving the conductivity of the micro defects in the Li-NiNP-Cu matrix; on the other hand by increasing Li6PS5The critical current density of Br optimizes the interface performance of the lithium metal composite cathode. In addition, the three-dimensional reticulated copper foil matrix of the present invention provides a higher specific surface area, promoting Li, than a planar matrix6PS5And the distribution of the charges on the surface of the Br solid electrolyte is uniform.
In addition, the Li-NiNP-Cu matrix surface contains metallic lithium, which is sensitive to the water oxygen content, and the environment with the water oxygen content lower than 10ppm can avoid the metallic lithium from generating side reaction and improve the electrochemical performance of the metallic lithium composite cathode.
Preferably, in the step (a), the acid solution is diluted hydrochloric acid or diluted sulfuric acid, and the concentration is 0.03-0.1 mol/L; the soaking is carried out at 30-45 ℃ for 30-90 min; the washing is repeated for 3-5 times by respectively using deionized water and absolute ethyl alcohol; the drying is drying for 10-24 hours at 50-90 ℃; the sintering is carried out for 4 to 8 hours at the temperature of 200 ℃ and 250 ℃ in the air.
Preferably, in the step (b), the nickel source solution is a nickel nitrate solution, a nickel sulfate solution or a nickel acetate solution, and the concentration is 0.02-0.06 mol/L; the soaking is carried out at 60-90 ℃ for 2-5 h; the inert gas is argon; the calcination is carried out in a tubular furnace at the temperature of 1000 ℃ and 1500 ℃ for 30-80 min; the reducing gas is hydrogen or argon, and the mass ratio of the raw material to the reducing gas is 3-6: 94-97; the reduction is carried out in a tube furnace at 600-800 ℃ for 40-90 min.
Preferably, in step (c), the inert gas is argon; the standing is to stand for 10-30min at the temperature of 200 ℃ and 250 ℃.
The three-dimensional reticular copper foil is placed in molten lithium metal under argon atmosphere and is kept stand for 10-30min at the temperature of 200-250 ℃, so that the molten lithium metal can be effectively diffused into the copper foil under the action of the nickel nanoparticles.
Preferably, in 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 ethyl alcohol, propyl alcohol, acetone, methanol, glycol or diethyl ether.
Preferably, in step (d), the hydroxyalkyl ether is reacted with Li2S、P2S5And LiBr in a ratio of 0.5-1.5: 10-20 parts of; the ultrasonic treatment is carried out for 1-2h under the conditions of 300-350K and 20-30 kHz; the standing time is 30-60 min; the drying is drying for 6-12h at 60-90 ℃; the vacuum sintering is carried out for 4-8h at the temperature of 200-300 ℃.
The vacuum sintering process at 200-300 ℃ can lead Li to be6PS5Densification of Br solid electrolyte, Li6PS5The interface of Br and metallic lithium is filled by amorphous phase, so that the defect of the interface is reduced.
In a second aspect, the invention further provides a battery, and the battery comprises the metal lithium composite negative plate with super-lithium-philic high stability.
Compared with the prior art, the invention has the following beneficial effects:
(1) the nickel nanoparticle modified three-dimensional porous current collector reduces the local current density by providing a larger electroactive surface area, effectively regulates the lithium deposition and the growth of lithium dendrites, and improves the affinity and the distribution uniformity with metallic lithium;
(2) the sulfide solid electrolyte inhibits side reaction between the lithium metal composite negative electrode and the solid electrolyte, prolongs the cycle life of the lithium metal composite negative electrode, and improves the electrochemical performance of the battery.
Detailed Description
The technical solution of the present invention is illustrated by the following specific examples, but the scope of the present invention is not limited thereto:
general examples
A super-lithium-philic high-stability lithium metal composite negative plate comprises an upper layer and a lower layer, wherein the upper layer comprises a nickel nanoparticle modified three-dimensional net-shaped copper foil and lithium metal deposited in the upper layer and on the surface of the upper layer, and the lower layer comprises Li6PS5Br sulfide solid electrolyte.
The preparation method comprises the following steps:
(a) placing the three-dimensional net-shaped copper foil into 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 50-90 deg.C for 10-24 hr, and sintering at 200-250 deg.C in air for 4-8 hr to form copper oxide thin layer on the surface.
(b) Placing the three-dimensional reticular copper foil treated in the step (a) in 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 argon atmosphere; and then reducing the alloy in a hydrogen atmosphere in a tube furnace at the temperature of 600-800 ℃ for 40-90min, wherein the mass ratio of the raw material 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 metal lithium in an argon atmosphere, standing for 10-30min at the temperature of 200-250 ℃, taking out, and cooling in the argon atmosphere to obtain the Li-NiNP-Cu matrix.
(d) In the environment with the water oxygen content lower than 10ppm, Li with the mol ratio of 3-5:0.5-1:0.5-1.5 is added2S、P2S5And adding LiBr into ethylene glycol monopropyl ether for ultrasonic treatment for 1-2h, wherein the quantity ratio of the ethylene glycol monopropyl ether to the total substances of Li2S, P2S5 and LiBr is 0.5-1.5: 10-20, wherein the ultrasonic condition is 300-350K and 20-30kHz, and white suspension is formed after ultrasonic treatment; adding anhydrous ethanol to the obtained suspension to form greenAnd (c) contacting one side of the Li-NiNP-Cu matrix in the step (c) with the precursor solution, standing for 30-60min, drying at 60-90 ℃ for 6-12h, and performing vacuum sintering at 200-300 ℃ for 4-8h to obtain the metal lithium composite negative plate.
A battery comprising the super-lithium-philic metal lithium composite negative plate with high stability.
Example 1
The preparation method of the super-lithium-philic high-stability metal lithium composite negative plate comprises the following steps of:
(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, washing with deionized water and absolute ethyl alcohol, and repeating for 4 times; dried at 80 ℃ for 20 hours and then sintered in air at 230 ℃ for 6 hours.
(b) Placing the three-dimensional reticular copper foil treated in the step (a) in a 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 the alloy in a hydrogen atmosphere in a tubular furnace at 725 ℃ for 75min, wherein the mass ratio of the raw material 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 metal lithium in an argon atmosphere, standing for 25min at 230 ℃, taking out, and cooling in the argon atmosphere to obtain the Li-NiNP-Cu matrix.
(d) In the environment with the water oxygen content lower than 10ppm, Li with the molar ratio of 4:0.6:0.92S、P2S5And LiBr is added into ethylene glycol monopropyl ether for ultrasonic treatment for 1.3h, and the ethylene glycol monopropyl ether and Li are2S、P2S5And LiBr in a total mass ratio of 1.2: 15, performing ultrasonic treatment under the ultrasonic conditions of 330K and 25kHz to form white suspension liquid after ultrasonic treatment; and (3) adding absolute ethyl alcohol into the obtained suspension to form a green and transparent precursor solution, then contacting one side of the Li-NiNP-Cu matrix in the step (c) 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.
Taking PEO as a solid electrolyte membrane, taking two metal lithium composite negative plates, and respectively adding Li6PS5The lower layer of Br was pressed against both sides of the PEO solid electrolyte membrane at 60 standard atmospheres towards the solid electrolyte membrane to assemble a 2032 type button symmetric cell.
Example 2
The difference from example 1 is that:
in the step (a), the concentration of dilute hydrochloric acid is 0.03 mol/L; soaking at 45 deg.C for 30 min; washing is repeated for 5 times; drying at 50 deg.C for 24 hr; sintering at 250 deg.C in air for 4 hr.
In the step (b), the concentration of the nickel nitrate solution is 0.06 mol/L; soaking at 90 deg.C for 2 h; calcining at 1000 deg.C for 30 min; then reducing for 90min at 600 ℃, wherein the mass ratio of the raw material to the reducing gas is 6: 94.
In step (c), the mixture was allowed to stand at 200 ℃ for 30 min.
In step (d), Li2S、P2S5And LiBr in a molar ratio of 3:1:0.5, ethylene glycol monopropyl ether and Li2S、P2S5And LiBr in a ratio of 0.5: 20; processing for 1h under the ultrasonic conditions of 350K and 20 kHz; standing for 60min, drying at 60 deg.C for 12h, and vacuum sintering at 300 deg.C for 4 h.
Example 3
The difference from example 1 is that:
in the step (a), the concentration of the dilute hydrochloric acid is 0.1 mol/L; soaking at 30 deg.C for 90 min; washing is repeated for 3 times; drying at 90 deg.C for 10 hr; sintering at 200 deg.C in air for 8 hr.
In the step (b), a nickel sulfate solution is used for replacing a nickel nitrate solution, and the concentration is 0.02 mol/L; soaking at 90 deg.C for 2 h; calcining at 1500 deg.C for 80 min; then reducing the mixture for 40min at 800 ℃, wherein the mass ratio of the raw material to the reducing gas is 3: 97.
In step (c), the mixture was allowed to stand at 250 ℃ for 10 min.
In step (d), Li2S、P2S5And LiBr in a molar ratio of 5:0.5:1.5, ethylene glycol monopropyl ether and Li2S、P2S5And LiBr in a total mass ratio of 1.5: 20; processing for 2 hours under the ultrasonic condition of 300K and 30 kHz; standing for 30min, drying at 90 deg.C for 6h, and vacuum sintering at 200 deg.C for 8 h.
Example 4
The difference from example 1 is that:
in step (d), Li2S、P2S5And LiBr in a molar ratio of 3:1.0:1.5, ethylene glycol monopropyl ether and Li2S、P2S5And LiBr in a total mass ratio of 1.5: 10; treating for 2h under the ultrasonic condition 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 respectively contained6PS5The lower layer of Br was pressed against the solid electrolyte membrane on both sides of the lanthanum lithium zirconate solid electrolyte at 100 atm.
Comparative example 1
The difference from example 1 is that: in the step (a), the three-dimensional reticular copper foil is not subjected to an air sintering process.
Comparative example 2
The difference from example 1 is that: the adopted three-dimensional reticular copper foil unmodified nickel nano-particles.
Comparative example 3
The difference from example 1 is that: the adopted three-dimensional reticular copper foil does not go through the treatment process in the step (a) and the modification of the nickel nano particles in the step (b).
Comparative example 4
The difference from example 1 is that: a conventional lithium metal sheet negative electrode was used.
Comparative example 5
The difference from example 1 is that: the metallic lithium composite negative electrode does not contain Li6PS5Br sulfide solid electrolyte lower layer.
Comparative example 6
The difference from example 1 is that: in the step (d), one side of the Li-NiNP-Cu matrix is contacted with the precursor solution, and then the metal lithium composite negative plate is obtained without vacuum sintering treatment.
And (3) testing conditions are as follows:
at 30 deg.C and 60 deg.C, in the range of 2.5-4.0V, 0.2C multiplying power makes charge-discharge cycle, and the voltage drop speed is over 5mV/min, until the short circuit of battery is produced. Testing the impedance of the solid battery by using an alternating current impedance spectroscopy EIS at the same temperature, wherein the frequency range is 1-106HZ, the applied voltage amplitude is 5-10 mV.
Table 1 performance test results of the batteries
The invention adopts the symmetrical battery without the positive plate, thereby effectively avoiding the influence of the positive plate on the internal resistance of the battery and truly reflecting the change of the internal resistance of the negative plate. Specific results as shown in table 1, in combination with examples 1 to 5, it can be seen that the lithium metal composite negative electrode sheet prepared within the technical requirements of the present invention has excellent internal resistance and cycle life, of which example 1 is the most effective. By combining the embodiment 1 and the comparative examples 1-6, the invention can be seen that the heterogeneous nucleation overpotential is reduced, the continuous growth of lithium dendrites is inhibited and the distribution uniformity of the metal lithium in the three-dimensional reticular copper foil is improved by constructing the Cu-CuO-Ni hybrid structure; addition of Li of high ionic conductivity6PS5After Br protective film is sintered, the microscopic defects in the composite cathode can be reduced, the local current density in the cathode can be improved, and Li can be reduced6PS5The critical current density of Br inhibits the 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 lithium metal cathode, reduce the internal resistance of the battery, prolong the cycle life and provide a reference path for researching high-performance solid batteries.
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
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 nickel nano particle modified three-dimensional porous current collector and metal lithium deposited in the upper layer and on the surface of the current collector; the lower layer comprises a sulfide solid electrolyte; the sulfide solid electrolyte includes Li6PS5Br、Li6PS5Cl or Li6PS5I。
2. The lithium-super-philic high-stability lithium metal composite negative electrode sheet as claimed in claim 1, wherein the three-dimensional porous current collector is a three-dimensional mesh copper foil.
3. The lithium-super-philic high-stability lithium metal composite negative electrode sheet as claimed in claim 2, wherein the sulfide solid electrolyte is Li6PS5Br。
4. The super-lithium-philic high-stability metallic lithium composite negative plate as claimed in claim 3, characterized in that the preparation method comprises the following steps:
(a) soaking the three-dimensional reticular copper foil in an acid solution, and then sequentially washing, drying and carrying out aerobic 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 metal lithium in an inert gas atmosphere for standing, taking out the NiNP-Cu matrix and cooling the NiNP-Cu matrix in the inert gas atmosphere to obtain a Li-NiNP-Cu matrix;
(d) in the environment with the water oxygen content lower than 10ppm, Li with the mol ratio of 3-5:0.5-1:0.5-1.5 is added2S、P2S5And LiBr is added toUltrasonic treatment in hydroxyalkyl ether; and (c) adding an organic solvent into the obtained suspension to form a precursor solution, then contacting one side of the Li-NiNP-Cu matrix in the step (c) with the precursor solution, standing, drying, and performing vacuum sintering to obtain the metal lithium composite negative plate.
5. The lithium metal composite negative electrode sheet with high super-lithium affinity and stability of claim 4, wherein in the step (a),
the acid solution is dilute hydrochloric acid or dilute sulfuric acid, and the concentration is 0.03-0.1 mol/L;
the soaking is carried out at 30-45 ℃ for 30-90 min;
the washing is repeated for 3-5 times by respectively using deionized water and absolute ethyl alcohol;
the drying is carried out for 10 to 24 hours at a temperature of between 50 and 90 ℃;
the sintering is carried out in air at 200 ℃ and 250 ℃ for 4-8 hours.
6. The lithium metal composite negative electrode sheet with high lithium-philic stability as claimed in claim 4, wherein in the step (b),
the nickel source solution is a nickel nitrate solution, a nickel sulfate solution or a nickel acetate solution, and the concentration is 0.02-0.06 mol/L;
the soaking is carried out at 60-90 ℃ for 2-5 h;
the inert gas is argon;
the calcination is carried out in a tubular furnace at the temperature of 1000 ℃ and 1500 ℃ for 30-80 min;
the reducing gas is hydrogen, and the mass ratio of the raw material to the reducing gas is (3-6): 94-97;
the reduction is carried out in a tube furnace at 600-800 ℃ for 40-90 min.
7. The lithium metal composite negative electrode sheet with high stability and super-lithium affinity according to claim 4, wherein in the step (c),
the inert gas is argon;
the standing is to stand for 10-30min at the temperature of 200 ℃ and 250 ℃.
8. The lithium metal composite negative electrode sheet with high stability and super-lithium affinity according to claim 4, 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 ethyl alcohol, propanol, acetone, methanol, glycol or diethyl ether.
9. The lithium metal composite negative electrode sheet with high stability and super-lithium affinity of claim 8, wherein in the step (d),
the hydroxyl-containing alkyl ether and Li2S、P2S5And LiBr in a ratio of 0.5-1.5: 10-20 parts of;
the ultrasonic treatment is carried out for 1-2h under the conditions of 300-350K and 20-30 kHz;
the standing time is 30-60 min;
the drying is drying for 6-12h at 60-90 ℃;
the vacuum sintering is vacuum sintering at 200-300 ℃ for 4-8 h.
10. A battery comprising the lithium-super-philic high-stability metallic lithium composite negative electrode sheet as defined in any one of claims 1 to 9.
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