CN114335550A - Preparation method of three-dimensional organic framework composite material, lithium metal cathode and battery - Google Patents
Preparation method of three-dimensional organic framework composite material, lithium metal cathode and battery Download PDFInfo
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Abstract
The invention discloses a preparation method of a three-dimensional organic framework composite material, a lithium metal cathode and a battery. The preparation method comprises the following steps: constructing a three-dimensional network structure formed by high-molecular polymer nano fibers on the surface of a current collector; providing a plurality of slurries containing lithium fast ion conductors, a binder and optional lithium-philic additives, wherein the content of the lithium-philic additives in each slurry is different, and spraying or brushing the plurality of slurries on the three-dimensional network structure in sequence according to the descending order of the lithium-philic additives to form a composite material layer consisting of a plurality of composite sub-layers with the descending content of the lithium-philic additives along the direction far away from a current collector. The preparation method provided by the invention has simple process, does not need multi-step accumulation to form a film, and obviously reduces the preparation cost of the three-dimensional composite lithium metal cathode; in addition, the lithium metal battery formed by the organic frame composite material prepared by the method has the advantages of long service life, low internal resistance and high cycle performance.
Description
Technical Field
The invention relates to the technical field of lithium metal battery materials, in particular to a preparation method of a three-dimensional organic framework composite material, a lithium metal cathode and a battery.
Background
The metallic lithium has extremely high theoretical specific capacity (3860 mAh.g)−1) And the lowest redox potential (-3.04V vs. she (standard hydrogen electrode)), and is therefore a very desirable negative electrode material for rechargeable secondary batteries. However, the problems of the lithium metal negative electrode are also very prominent, which hinders the commercial application of the lithium metal secondary battery. The main problems of the lithium metal negative electrode include growth of lithium dendrites during charge and discharge, and continuous breakage and regeneration of a solid electrolyte membrane (SEI), resulting in reduction of coulombic efficiency and continuous loss of electrolyte. Uncontrolled dendrite growth eventually can cause a cell to short circuit, thereby initiating thermal runaway. The growing problem of dendrite of the negative pole of the metallic lithium caused by the non-uniform nucleation of lithium ions caused by the non-uniform surface of the metallic lithium and the high reactivity of the lithium easily causes the short circuit of the battery to generate safety risk. Reducing the cycle life of the metal lithium battery. Thus to metalModification of lithium negative electrodes is imperative.
CN110690420A discloses a composite material cathode, a battery and a preparation method thereof, wherein non-conductive porous dielectric layers and porous conductive layers which are alternately arranged are periodically assembled on the surface of a cathode substrate, and then active metal is embedded into a framework to form the composite material cathode; by utilizing the regulation and control of the periodic conductive framework on the electron transmission path and the ion concentration distribution, the composite material cathode can effectively improve the stability of the metal cathode in the circulation process, inhibit the growth of dendrites and improve the safety of the metal cathode.
However, the above prior art requires multi-step circulation and multi-layer deposition, and has complex process and high cost, and the dielectric layer and the conductive layer are alternately stacked, so that the separation between layers is easily generated during the electrochemical reaction process, thereby reducing the service life of the battery.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a preparation method of a three-dimensional organic framework composite material, a lithium metal negative electrode and a battery.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
in a first aspect, the present invention provides a method for preparing a three-dimensional organic framework composite material, comprising:
constructing a three-dimensional network structure formed by interweaving high-molecular polymer nano fibers on the surface of a current collector;
providing a plurality of slurries containing lithium fast ion conductors, a binder and optional lithium-philic additives, wherein the content of the lithium-philic additives in each slurry is different, spraying or brushing the plurality of slurries on the three-dimensional network structure in sequence according to the sequence that the content of the lithium-philic additives is decreased, filling at least part of the slurries into the three-dimensional network structure and drying to form a composite material layer consisting of a plurality of composite sub-layers with the content of the lithium-philic additives being decreased along the direction away from a current collector.
In a second aspect, the invention further provides a three-dimensional composite lithium metal negative electrode, which comprises the three-dimensional organic framework composite material prepared by the preparation method and lithium metal, wherein at least part of the lithium metal is filled into the three-dimensional organic framework composite material.
In a third aspect, the invention further provides a lithium metal battery, which comprises a positive electrode, a negative electrode and an electrolyte, wherein the negative electrode adopts the three-dimensional composite lithium metal negative electrode.
Based on the technical scheme, compared with the prior art, the invention has the beneficial effects that at least:
1. the preparation method provided by the invention has simple preparation process, does not need multi-step accumulation film formation, and obviously reduces the preparation cost of the three-dimensional organic framework composite material.
2. According to the three-dimensional organic framework composite material prepared by the preparation method provided by the invention, the conductive medium is positioned in the three-dimensional network structure and is tightly combined with the three-dimensional network structure to form an integral structure instead of a laminated structure, so that the interlayer separation phenomenon is avoided, and the service life is prolonged; meanwhile, the three-dimensional network structure enables the dispersion degree of the conductive medium to be higher, the specific surface area to be greatly improved, and the internal resistance of the lithium metal battery to be reduced.
3. In the three-dimensional organic frame composite material prepared by the preparation method provided by the invention, the concentration of the lithium-philic additive is reduced along the direction far away from the current collector, and lithium ions are guided to be gradually deposited in the three-dimensional network structure from the direction close to the current collector to the direction far away from the current collector, so that the uniformity and the stability of lithium ion deposition are improved, and the cycle performance of the lithium metal battery is further improved.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to enable those skilled in the art to more clearly understand the technical solutions of the present invention and to implement them according to the content of the description, the following description is made with reference to the preferred embodiments of the present invention and the detailed drawings.
Drawings
FIG. 1 is a process diagram of a method for preparing a three-dimensional organic framework composite according to an embodiment of the present invention;
fig. 2 is a schematic diagram of a method for attaching lithium metal to a three-dimensional network structure according to an embodiment of the present invention;
FIG. 3 is a schematic diagram of another method for attaching lithium metal to a three-dimensional network structure according to an embodiment of the present invention;
description of reference numerals:
1. a current collector; 2. a three-dimensional network structure; 3. a three-dimensional organic framework;
201. a lithium fast ion conductor; 202. a lithium philic additive.
Detailed Description
In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to provide technical solutions of the present invention. The technical solution, its implementation and principles, etc. will be further explained as follows.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced otherwise than as specifically described herein, and thus the scope of the present invention is not limited by the specific embodiments disclosed below.
Referring to fig. 1, an embodiment of the present invention provides a method for preparing a three-dimensional organic framework composite material, including the following steps S101 to S102:
step S101: and constructing a three-dimensional network structure 2 formed by interweaving high-molecular polymer nano fibers on the surface of the current collector 1.
Step S102: providing a plurality of slurries containing a lithium-containing fast ion conductor 201, a binder and optionally a lithium-philic additive 202, wherein the content of the lithium-philic additive 202 in each slurry is different, spraying or brushing the plurality of slurries onto the three-dimensional network structure 2 in sequence according to the decreasing content of the lithium-philic additive 202, and filling at least part of the slurries into the three-dimensional network structure 2 and drying to form a composite material layer consisting of a plurality of composite sublayers with decreasing content of the lithium-philic additive 202 in the direction away from the current collector 1.
In some embodiments, the above preparation method may specifically include: and providing a high molecular polymer solution as a spinning solution, and constructing the three-dimensional network structure 2 on the surface of the current collector 1 by adopting an electrostatic spinning mode. The three-dimensional network structure 2 can limit the volume expansion of a lithium electrode in a circulation process, stabilize an SEI (solid electrolyte interphase) film, has a high specific surface area and can promote the uniform deposition of lithium by reducing the local current of the electrode; the fast lithium ion conductor 201 can accelerate the transmission rate of lithium ions, so that the electrochemical kinetics of the lithium metal anode is obviously improved.
Wherein, in the above embodiment, the high molecular polymer may include one or a combination of two or more of polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), polyacrylic acid (PAA), Polyimide (PI), Polyacrylonitrile (PAN), polyethylene oxide (PEO); the molecular weight of the high molecular polymer may preferably be 10000-; the solvent of the high molecular polymer solution can comprise any one or the combination of more than two of Tetrahydrofuran (THF), N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP) and dimethyl sulfoxide (DMSO); the water content of the solvent is preferably less than 50 ppm; the solid content of the high molecular polymer solution may preferably be 10 to 50 wt%; the working voltage of the electrospinning may preferably be 10-30 kV.
In some embodiments, the lithium fast ion conductor 201 may include Li3N、LiAlSiO4、Li2ZnSiO4、LiTaSiO5、Li6KBiO6、Li7La3Zr2O12、Li1.3Al0.3Ti1.7(PO4)3、Li6PS5Any one or a combination of two or more of Cl and a heteroatom-doped lithium salt complex; the heteroatom-doped lithium salt complex may include Li10GeP2S12(ii) a The lithium fast ion conductor 201 may preferably have an ionic conductivity of 10-4-10-3 S·cm-1The content in the slurry may preferably be 1 to 10 wt%, and the particle diameter may preferably be 50 nm to 20 μm.
In some embodiments, the lithium philic additive 202 may include silver (Ag), gold (Au), magnesium (Mg), aluminum (Al), zinc (Zn), tin (Sn), gallium (Ga), aluminum oxide (Al)2O3) Zinc oxide (ZnO), oxygenAny one or a combination of two or more of the Silicon (SiO) compounds, the content of the lithium philic additive 202 in the slurry may preferably be 0 to 15 wt%, and the particle diameter may preferably be 20 nm to 20 μm. Herein, it is understood that, in the present invention, when the content of the lithium-philic additive 202 is 0, that means that the slurry does not contain the lithium-philic additive 202, the slurry should be finally sprayed or brushed on the three-dimensional network structure 2.
In some embodiments, each of the composite sub-layers may preferably have a thickness of 2 to 20 μm and an areal density of 0.5 to 2 mg-cm-2Preferably, the adjacent concentration difference of the plurality of slurries may be 3 to 10 wt%, and the viscosity of the slurries is preferably less than 100 cPs.
In some embodiments, the binder is selected from non-aqueous based binders including any one or a combination of two or more of polyvinylidene fluoride, polyacrylic acid, polyacrylate, styrene acrylate, polyacrylonitrile, polyacrylamide, polyimide; the relative molecular mass of the binder is 10000-1000000.
Specifically, in some specific application examples, the preparation method provided by the present invention can be implemented by adopting the following specific steps: firstly, dissolving a high molecular polymer in an organic solvent to prepare nano fibers on a current collector 1 through an electrostatic spinning method, then mixing and dispersing a lithium fast ion conductor 201, a metal or metal compound lithium-philic additive 202 and a binder in the organic solvent according to a certain proportion to prepare pulp in multiple steps, wherein the content of the lithium-philic additive 202 in the pulp in each step is decreased progressively, spraying the pulp in the polymer nano fibers on the current collector 1 in a drying chamber to prepare a three-dimensional organic frame 3 composite current collector 1 for efficient ionic electron transportation, and finally preparing a three-dimensional composite lithium metal negative electrode through lithiation. The lithium metal battery assembled by the three-dimensional composite lithium metal cathode has good cycling stability.
In some embodiments, the organic solvent of the spray coating slurry is the same as the organic solvent of the formulated slurry.
Specifically, a high molecular polymer can be dissolved in an organic solvent to prepare nanofibers on a current collector 1 through an electrostatic spinning method, then a lithium-philic additive 202 consisting of a fast lithium ion conductor, a metal or a metal compound and a binder are mixed and dispersed in the organic solvent according to a certain proportion to prepare pulp in multiple steps, the content of the lithium-philic additive 202 in the pulp in each step is decreased progressively, and the pulp is sprayed or brushed on the current collector 1 at the side containing the polymer nanofibers to prepare the ionic-electronic conductive three-dimensional organic frame 3 composite current collector 1. The multi-step pulping is at least two steps, the concentration of the lithium-philic additive 202 is the highest and is close to the current collector 1, and the outward concentration gradient of the current collector 1 is gradually reduced.
Referring to fig. 2 and fig. 3, an embodiment of the present invention further provides a method for preparing a three-dimensional composite lithium metal negative electrode, in which the three-dimensional organic framework 3 composite material provided in the above embodiment is used as a substrate, and the three-dimensional composite lithium metal negative electrode is formed through lithiation treatment, including the following steps:
step S201: the lithium metal is attached to the three-dimensional organic framework 3 by electrochemical deposition.
In some embodiments, the current density of the electrochemical deposition may be from 0.01C to 0.1C.
Specifically, a lithium sheet and the prepared composite current collector 1 can be assembled into a single battery, so that lithium is filled in the framework of the three-dimensional composite current collector 1, and the three-dimensional composite lithium metal cathode is obtained. The current density is 0.01-0.1C, and the deposition capacity is the corresponding deposition time set according to the requirement.
Alternatively, step S202: metallic lithium in a molten state is applied to the three-dimensional organic framework 3, and after cooling, the metallic lithium is attached to the three-dimensional network structure 2.
Specifically, the lithium foil may be heated to a temperature above the melting point to a molten state and poured into the three-dimensional frame.
In some more specific embodiments, the method for preparing a three-dimensional composite lithium metal negative electrode of the present invention may specifically be:
firstly, dissolving a high molecular polymer in an organic solvent, preparing the nano-fiber on a copper foil substrate by an electrostatic spinning method, and constructing a three-dimensional frame (the volume expansion of a lithium electrode in a circulation process can be limited, an SEI (solid electrolyte interphase) film is stabilized, the specific surface area of a three-dimensional structure is higher, and the uniform deposition of lithium can be promoted by reducing the local current of the electrode).
Further, a lithium fast ion conductor 201 (the lithium fast ion conductor 201 can accelerate the transmission rate of lithium ions, so that the electrochemical kinetics of a lithium metal anode is obviously improved), a metal or metal compound lithium affinity additive 202 (the lithium affinity additive 202 reduces the nucleation overpotential of lithium in the deposition process, can play a role of a nucleation site to promote the uniform deposition of lithium on a three-dimensional host and effectively inhibit the growth of lithium dendrites) and a binder are mixed and dispersed in an organic solvent according to a certain proportion to prepare pulp in multiple steps, the content of the lithium affinity additive 202 in each step of pulp is gradually reduced (the lithium affinity additive 202 with gradually reduced concentration gradient can guide the lithium ions to deposit from top to bottom in a three-dimensional frame), and spraying the slurry into the polymer nano fibers on the copper foil in a drying chamber to prepare the three-dimensional organic framework 3 composite copper foil with efficient ionic electron transport.
With continuing reference to fig. 1-3, embodiments of the present invention further provide a three-dimensional composite lithium metal negative electrode prepared by the above preparation method, including the three-dimensional organic framework 3 composite material prepared by the preparation method in the above embodiment and lithium metal, and at least a portion of the lithium metal is filled into the three-dimensional organic framework 3 composite material.
The embodiment of the invention also provides a lithium metal battery which comprises a negative electrode, a positive electrode and electrolyte, wherein the negative electrode is the three-dimensional composite lithium metal negative electrode.
The technical scheme of the invention is further explained in detail by a plurality of embodiments and the accompanying drawings. However, the examples are chosen only for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention.
Example 1
Electrostatic spinning: the polymer solution was prepared by dissolving 20 wt% of PAA (polyacrylic acid, molecular weight 500000, the same below) in DMSO (dimethyl sulfoxide, the same below), applying a high voltage of 25 kV, injecting onto a current collector 1 made of a metal copper foil to prepare a PAA three-dimensional network structure 2 having a thickness of 50 μm, and then vacuum-drying it at 60 ℃ overnight.
Preparing spraying slurry: ag particles having a lithium-philic particle size of 50 nm at concentrations of 12 wt%, 6 wt% and 0 wt%, respectively, were mixed with 5 wt% Li3N fast lithium ion conductor and 5 wt% PAA binder (molecular weight is 1000000) are mixed and dispersed in organic solvent NMP to prepare three kinds of slurry with Ag concentration gradient, and the slurry is sprayed on the copper foil in the order of concentration from high to low to form PAA three-dimensional network structure 2 through electrostatic spinning to prepare three-dimensional organic frame 3, and vacuum drying is carried out at 60 ℃ overnight.
Preparing a three-dimensional composite lithium metal negative electrode: a battery was assembled from a 100 μm lithium sheet and a three-dimensional organic frame 3 at 0.5 mA cm-2The current density deposition is carried out for 10 h, the metal lithium is deposited in the three-dimensional network structure 2, and the three-dimensional composite lithium metal cathode is obtained after disassembly.
And the obtained negative electrode material, an NCM811 positive electrode plate, a Celgard2400 diaphragm and a local high-concentration electrolyte (LHCE, the injection amount: E/C = 3) are matched and assembled into a 1 Ah (0.2C nominal capacity) aluminum-plastic soft package battery with 5 positive electrodes and 6 negative electrodes. The battery formation conditions are as follows: 3-4.3V and 0.1C charging and discharging for 3 circles, and then carrying out long cycle test on the battery under the following test conditions: charging and discharging at 3-4.3V and 0.2C/0.5C for 200 times (constant voltage charging to 0.05C cut-off).
Example 2
This example is substantially the same as example 1, except that: no slurry of 0 wt% Ag concentration was formulated and used for coating.
Example 3
This example is substantially the same as example 1, except that: mixing lithium fast ion conductor 201 Li3The adding amount of N is increased from 5 wt% to 10 wt%.
Example 4
This example is substantially the same as example 1, except that: 5 wt% of lithium fast ion conductor 201 Li3Replacement of N by LiTaSiO5。
Example 5
This example is substantially the same as example 1, except that: the high molecular polymer PAA was replaced by PVDF (polyvinylidene fluoride).
Example 6
This example is substantially the same as example 1, except that: the lithium philic additive 202Ag was replaced by ZnO nanoparticles with a particle size of 50 nm.
Example 7
This example is substantially the same as example 1, except that: the solids content of the polymer solution was replaced by 10% by weight from 20% by weight.
Example 8
This example is substantially the same as example 1, except that: the solids content of the polymer solution was replaced by 20% by weight to 50% by weight.
Example 9
This example is substantially the same as example 1, except that: the working voltage of electrostatic spinning is replaced by 10 kV from 25 kV.
Example 10
This example is substantially the same as example 1, except that: the molecular weight of the binder used for spraying the slurry was changed from 500000 to 10000.
Example 11
This example is substantially the same as example 1, except that: the molecular weight of the binder used for spraying the slurry was changed from 500000 to 1000000.
Example 12
This example is substantially the same as example 1, except that: the preparation method of the three-dimensional lithium metal cathode is a melt impregnation method, and the lithium sheet is placed on the three-dimensional organic frame 3, heated to 180 ℃, kept for 2 hours and naturally cooled for 5 hours.
Example 13
This example is substantially the same as example 1, except that: the preparation method of the three-dimensional lithium metal cathode is a melt impregnation method, and the lithium sheet is placed on the three-dimensional organic frame 3, heated to 300 ℃, kept for 2 hours and naturally cooled for 5 hours.
Example 14
This example is substantially the same as example 1, except that: the preparation method of the three-dimensional lithium metal cathode is a melt impregnation method, and the lithium sheet is placed on the three-dimensional organic frame 3, heated to 180 ℃, kept for 5 hours and naturally cooled for 5 hours.
Example 15
This example is substantially the same as example 1, except that: the preparation method of the three-dimensional lithium metal cathode is a melt impregnation method, and the lithium sheet is placed on the three-dimensional organic frame 3, heated to 300 ℃, kept for 5 hours and naturally cooled for 5 hours.
Comparative example 1
The comparative example battery assembly material, process and formation conditions are basically the same as those of example 1, and the difference is that: pure lithium sheets with a thickness of 100 μm were directly used as the negative electrode material.
Comparative example 2
The comparative example battery assembly material, process and formation conditions are basically the same as those of example 1, and the difference is that: directly electrodepositing 5 mAh cm by using a lithium sheet with the thickness of 100 mu m2In the three-dimensional network structure 21 of PAA in example 1, as a negative electrode material.
Comparative example 3
The comparative example battery assembly material, process and formation conditions are basically the same as those of example 1, and the difference is that: molten lithium was poured into 5 mAh.cm2In the three-dimensional network structure 21 of PAA in example 1, as a negative electrode material.
Comparative example 4
This comparative example is essentially the same as example 1, except that: the lithium philic additive 202 is not added.
Comparative example 5
This comparative example is essentially the same as example 1, except that: the lithium philic additive 202 was at a single concentration of 2 wt%.
Comparative example 6
This comparative example is essentially the same as example 1, except that: the lithium philic additive 202 was at a single concentration of 6 wt%.
Comparative example 7
This comparative example is essentially the same as example 1, except that: the lithium philic additive 202 was at a single concentration of 12 wt%.
Comparative example 8
This comparative example is essentially the same as example 1, except that: no lithium fast ion conductor 201 is added.
Comparative example 9
This comparative example is essentially the same as example 1, except that: the preparation of the three-dimensional nanofiber network was omitted and the slurry of example 1 was sprayed directly onto the copper foil.
Comparative example 10
This comparative example is essentially the same as example 1, except that: the slurry of example 1 was sprayed directly onto the carbon hollow sphere coating on the copper foil, replacing the three-dimensional nanofiber network with carbon hollow spheres.
Detection method
Measuring the voltage and the internal resistance of the battery:
open Circuit Voltage (OCV) and Alternating Current Internal Resistance (ACIR) tests were performed using the CHT3561 battery internal resistance tester by changzhou and general electronics technologies ltd.
And (3) measuring the cycle performance of the battery:
performing cycle test by using the Shenzhen Xinwei battery test system, wherein the test conditions are as follows: charging and discharging at 3-4.3V and 0.2C/0.5C for 200 times (constant voltage charging to 0.05C cut-off).
Analysis of results
The results of measuring the voltage and internal resistance of the batteries of the examples and comparative examples of the present invention are shown in table 1, and the results of measuring the cycle performance of the batteries are shown in table 2.
TABLE 1 measurement results of cell voltage and internal resistance of examples and comparative examples
TABLE 2 measurement results of cycle characteristics of batteries of examples and comparative examples
Based on the detection results, it is clear that the three-dimensional composite lithium metal cathode provided by the embodiment of the invention has the advantages of low internal resistance and good cycle performance through the synergistic effect of the three-dimensional network structure 2, the lithium fast ion conductor 201, the lithium-philic additive 202, the concentration gradient thereof and other means.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, which are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and therefore, the protection scope of the present invention is not limited thereby. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (6)
1. A preparation method of a three-dimensional organic framework composite material is characterized by comprising the following steps:
constructing a three-dimensional network structure formed by interweaving high-molecular polymer nano fibers on the surface of a current collector;
providing a plurality of slurries containing lithium fast ion conductors, a binder and optional lithium-philic additives, wherein the content of the lithium-philic additives in each slurry is different, and the plurality of slurries are sequentially sprayed or brushed on the three-dimensional network structure according to the sequence that the content of the lithium-philic additives is decreased, and at least part of the slurries are filled into the three-dimensional network structure and dried to form a composite material layer consisting of a plurality of composite sub-layers of which the content of the lithium-philic additives is decreased along the direction away from a current collector;
the lithium affinity additive comprises any one or the combination of more than two of silver, gold, magnesium, aluminum, zinc, tin, gallium, aluminum oxide, zinc oxide and silicon monoxide, the content of the lithium affinity additive in the slurry is 0-15 wt%, and the particle size is 20 nm-20 mu m;
each composite sublayer has a thickness of 2-20 μm and an areal density of 0.5-2 mg cm-2And the adjacent concentration difference of the plurality of the slurries is 3-10 wt%, and the viscosity of the slurries is less than 100 cPs.
2. The preparation method according to claim 1, which specifically comprises: providing a high molecular polymer solution as a spinning solution, and constructing the three-dimensional network structure on the surface of a current collector in an electrostatic spinning mode;
the high molecular polymer comprises one or the combination of more than two of polyvinylidene fluoride, polytetrafluoroethylene, polyacrylic acid, polyimide, polyacrylonitrile and polyethylene oxide; the molecular weight of the high molecular polymer is 10000-1000000; the solvent of the high molecular polymer solution comprises one or the combination of more than two of tetrahydrofuran, N-dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide; the water content of the solvent is less than 50 ppm; the solid content of the high molecular polymer solution is 10-50 wt%; the working voltage of the electrostatic spinning is 10-30 kV.
3. The method of claim 1, wherein the lithium fast ion conductor comprises Li3N、LiAlSiO4、Li2ZnSiO4、LiTaSiO5、Li6KBiO6、Li7La3Zr2O12、Li1.3Al0.3Ti1.7(PO4)3、Li6PS5Any one or a combination of two or more of Cl and a heteroatom-doped lithium salt complex; the heteroatom-doped lithium salt complex comprises Li10GeP2S12(ii) a The ionic conductivity of the lithium fast ion conductor is 10-4-10-3 S·cm-1The content in the slurry is 1-10 wt%, and the particle size is 50 nm-20 μm.
4. The preparation method according to claim 1, wherein the binder is selected from non-aqueous binders including any one or a combination of two or more of polyvinylidene fluoride, polyacrylic acid, polyacrylate, styrene acrylate, polyacrylonitrile, polyacrylamide, and polyimide; the relative molecular mass of the binder is 10000-1000000.
5. A three-dimensional composite lithium metal negative electrode comprising the three-dimensional organic framework composite material prepared by the preparation method according to any one of claims 1 to 4 and lithium metal, wherein at least part of the lithium metal is filled in the three-dimensional organic framework composite material.
6. A lithium metal battery comprising a positive electrode, a negative electrode and an electrolyte, wherein the negative electrode employs the three-dimensional composite lithium metal negative electrode of claim 5.
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| CN117096273B (en) * | 2023-10-20 | 2024-01-26 | 深圳市贝特瑞新能源技术研究院有限公司 | Protective layer modified lithium metal composite negative electrode, preparation method thereof and battery |
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