CN111952567A - Organic lithium-philic composite cathode taking three-dimensional conductive carbon material as substrate and preparation method thereof - Google Patents

Organic lithium-philic composite cathode taking three-dimensional conductive carbon material as substrate and preparation method thereof Download PDF

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CN111952567A
CN111952567A CN202010833545.6A CN202010833545A CN111952567A CN 111952567 A CN111952567 A CN 111952567A CN 202010833545 A CN202010833545 A CN 202010833545A CN 111952567 A CN111952567 A CN 111952567A
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lithium
dimensional
carbon material
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conductive carbon
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谌伟民
王洪峡
陈志高
喻发全
蔡宁
薛亚楠
王建芝
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Wuhan Institute of Technology
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Abstract

The invention discloses an organic lithium-philic layer composite cathode taking a three-dimensional conductive carbon material as a substrate, which is characterized in that firstly, the three-dimensional conductive carbon material is subjected to surface oxidation modification treatment; then carrying out amidation reaction on the modified three-dimensional carbon material and the tetra-amino phthalocyanine, and modifying the tetra-amino phthalocyanine on the surface of the carbon material; and finally, carrying out high-temperature molten lithium deposition in a protective atmosphere to obtain the organic lithium-philic layer composite cathode. The invention relates to a negative electrode material of a lithium metal batteryThe material is designed in multiple scales, rich lithium-philic active sites are manufactured on a deposition substrate material of lithium, and interface lithium ion current is dispersed by using the lithium-philic groups to guide Li+The uniform deposition/dissolution effectively inhibits the growth of lithium dendrites, reduces the structural stress change caused by the volume effect in the circulation process, and effectively improves the safety and the circulation performance of the lithium metal cathode.

Description

Organic lithium-philic composite cathode taking three-dimensional conductive carbon material as substrate and preparation method thereof
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to an organic lithium-philic composite cathode taking a three-dimensional conductive carbon material as a substrate and a preparation method thereof.
Background
With the rapid development of electric automobiles and energy storage equipment, the requirements of people on the endurance mileage and safety of lithium batteries are higher and higher, and the research on the lithium batteries with high energy density and excellent electrochemical performance is of practical significance. Among the numerous lithium battery negative electrode materials, metallic lithium is due to its low density (0.534g cm)-3) High theoretical specific capacity (3860mAh g)-1) And low potential (-3.04V, relative to standard hydrogen electrodes) are considered to be the most desirable negative electrode material for lithium batteries. Lithium metal is a basic metal with the smallest ionic radius of all metals, which makes it have excellent charge transport kinetics; in addition, lithium metal has the lowest potential and high reactivity. Therefore, lithium metal batteries are receiving increasing attention from both academia and industry. However, the lithium metal battery faces a great challenge in practical application, when lithium contacts an electrolyte, a solid electrolyte interface film (SEI) is formed on the surface of the lithium metal battery, and the SEI film is repeatedly broken due to a large volume change in the deposition/dissolution process of lithium, so that the stability of the SEI film is caused, and the cycle efficiency of the battery is affected; second, metalLithium tends to deposit in dendritic form in the electrolyte and may penetrate the separator when lithium dendrites grow to a certain extent to cause internal short circuits in the battery and even cause explosions. In addition, the breakage of lithium dendrites also leads to the generation of "dead lithium" which loses electrical contact, resulting in a series of problems of loss of lithium source, reduced coulombic efficiency, capacity fade, reduced stability, etc.
To solve the above problems, a stable artificial SEI film is constructed, an electrolyte is optimized, a diaphragm modification design is optimized, and Li is homogenized+Methods such as structural design of the cathode have been widely studied. The artificial SEI film is constructed, the prepared SEI film is required to have enough toughness to adapt to stress generated during lithium deposition, and the prepared film is required to be uniform and compact all over to prevent Li+The existing method has complex preparation process and complicated operation; the electrolyte solution strategy is optimized by introducing necessary additives to enhance the uniformity and stability of the SEI film, but excessive additives cause the burden of the metal lithium negative electrode, reduce the specific capacity of the metal lithium negative electrode, and the solvation effect causes the increase of side reactions, which are not beneficial to Li+Uniform deposition. Separator as an indispensable component of battery, and Li can be improved by improving its hydrophilicity and wettability to polar electrolyte+Concentration distribution, but the problems of ionic conductivity, mechanical strength and the like caused by membrane modification are to be studied and solved more deeply. Homogeneous Li+The structure design of the current negative electrode is that the contact area of the lithium negative electrode and the electrolyte is increased, and the current density is reduced, so that Li+A common method of more uniform distribution, but it is difficult to be put to practical use because of the low lithium storage capacity of the lithium deposition base material used. Although the above strategy is addressing the lithium dendrite problem and guiding Li+Uniform deposition has been a function, but these methods are far from the demand of commercial lithium batteries. Therefore, Li is effectively guided by designing the surface lithium affinity of the lithium deposition base material+The uniform deposition is crucial to the alleviation of volume change of the lithium negative electrode, the inhibition of dendritic crystal growth and the realization of a lithium metal battery with long service life.
In conclusion, the lithium battery taking the metal lithium as the negative electrode has wide application prospect in future energy development, and the lithium-philic negative electrode material capable of inducing lithium ions to be uniformly deposited, effectively inhibiting dendritic crystal growth and improving volume effect is further designed, so that the lithium battery has important significance in developing a lithium battery system with high specific energy, high safety and long service life.
Disclosure of Invention
The invention mainly aims to provide an organic lithium-philic composite cathode taking a three-dimensional conductive carbon material as a substrate and a preparation method thereof aiming at utilizing lithium-philic groups which are uniformly grown on the three-dimensional conductive carbon material to induce lithium ions to be uniformly deposited and taking the three-dimensional conductive carbon material as a substrate material for lithium deposition to provide enough lithium accommodating space, and a conductive frame can also promote the rapid conduction of electrons and reduce the current density; meanwhile, the growth of dendritic crystals is effectively inhibited by utilizing the synergistic effect of the lithium-philic group and the conductive frame, the volume effect in the circulation process is improved, and the circulation stability of the lithium-philic composite material as the negative electrode of the lithium battery is further improved.
In order to achieve the purpose, the invention adopts the technical scheme that:
an organic lithium-philic composite negative electrode with a three-dimensional conductive carbon material as a substrate is prepared by firstly carrying out oxidation modification treatment on the three-dimensional conductive carbon material, then introducing tetra-amino phthalocyanine for amidation modification, and finally carrying out high-temperature molten lithium deposition in a protective atmosphere.
In the above scheme, the amidation modification step is: placing the three-dimensional carbon material subjected to oxidation modification in a tetraaminophthalocyanine solution, adding 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride (EDCI) and N, N-hydroxysuccinimide (NHS) to obtain a mixed solution, and carrying out stirring reaction at normal temperature; the EDCI is used for activating carboxyl, the NHS is mainly used as a cross-linking agent, and the reaction of the carboxyl and the amino is facilitated, so that the amino on the tetra-amino phthalocyanine and the carboxyl on the modified carbon material are subjected to dehydration condensation to form an amido bond, and the amido bond is loaded on the three-dimensional carbon material in a covalent form.
In the scheme, the normal-temperature stirring reaction time is 2-4 d.
In the scheme, the concentration of the tetraaminophthalocyanine in the mixed solution is 0.6-1.4 mg/mL; the concentration of EDCI is 20-40 mg/mL; the concentration of NHS is 24-48 mg/mL.
In the above scheme, the three-dimensional carbon material is any one of carbon cloth, carbon paper, carbon felt, carbon nanotube, carbon nanosheet and three-dimensional graphene.
The organic lithium-philic composite cathode with the three-dimensional conductive carbon material as the substrate is prepared by a hydrothermal method and a high-temperature melting lithium deposition method, and specifically comprises the following steps:
1) carrying out surface impurity removal and oxidation modification treatment on the three-dimensional carbon material, and cleaning and drying the three-dimensional carbon material for later use;
2) dipping the three-dimensional carbon material obtained by the pretreatment in the step 1) in a tetraaminophthalocyanine solution, adding NHS and EDCI, carrying out stirring reaction at normal temperature, and then cleaning and drying for later use to obtain a modified three-dimensional carbon material;
3) and carrying out high-temperature melting lithium deposition on the obtained modified three-dimensional carbon material in a protective atmosphere to obtain the lithium-philic composite negative electrode.
In the scheme, the surface impurity removal step in the step 1) is to alternately clean the surface for 3-5 times by using ethanol or deionized water, and each time lasts for 8-15 min.
In the above scheme, the surface oxidation modification treatment in step 1) utilizes a mixed acid formed by nitric acid and sulfuric acid, wherein nitric acid (HNO)3) The concentration of (A) is 20-50 wt%; sulfuric acid (H)2SO4) Is 98 wt%; the soaking and ultrasonic treatment time is 25-35 min.
In the scheme, the surface oxidation modification method in the step 1) is preferably a hydrothermal method, the reaction temperature is 80-120 ℃, and the time is 8-12 h.
In the scheme, in the step 2), the cleaning step is to alternately clean the three-dimensional carbon material with deionized water and ethanol for 3-5 times respectively, and wash off the residual acid on the surface of the three-dimensional carbon material, and preferably, the cleaning time is 8-15 min each time.
Preferably, the drying step in the step 1) is vacuum drying for 8-12 hours.
In the scheme, the tetraaminophthalocyanine solution in the step 2) adopts a polar solvent, and can be one or more of N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), acetone, acetonitrile, tetrahydrofuran and the like.
In the scheme, the stirring temperature in the step 2) is normal temperature, and the stirring time is 2-4 d; the cleaning and drying steps are as follows: taking out the three-dimensional carbon material from DMF, alternately washing with a large amount of deionized water and ethanol, and removing DMF, NHS and EDCI remained on the surface of the three-dimensional carbon material for at least 3 times until the washed water is clear and transparent; and after the cleaning, putting the mixture into a vacuum drying oven for drying for 8-12h for later use.
In the scheme, the high-temperature melting lithium deposition in the step 3) adopts the temperature of 250-300 ℃ and the time of 5-20 min, and the melting temperature is preferably 250 ℃.
In the scheme, a layer of lithium with silvery white metallic luster is attached to the surface of the three-dimensional carbon material after the deposition in the step 3), and the three-dimensional carbon material is flattened into the three-dimensional carbon material with uniformly attached lithium on the surface by a rolling device after the three-dimensional carbon material is not completely cooled, so that the required lithium-philic composite cathode is prepared.
The invention is a design scheme of an organic lithium-philic layer taking a three-dimensional conductive carbon material as a substrate, can provide a large number of lithium-philic groups, manufacture abundant active sites, induce lithium ions to be uniformly deposited, effectively inhibit dendritic crystal growth, improve the volume effect in the circulation process, and further improve the circulation stability of the lithium-philic composite material as a lithium battery cathode.
Compared with the prior art, the invention has the beneficial effects that:
1) the invention takes a three-dimensional conductive carbon material as a substrate material for lithium deposition, carries out surface oxidation modification treatment on the material to generate a large number of carboxyl (-COOH) groups, carries out amidation reaction with tetraaminophthalocyanine, fixes the tetraaminophthalocyanine on the three-dimensional conductive carbon material in a covalent bond form, provides enough lithium holding space and plays a role of inducing and dispersing lithium ion flow, and simultaneously utilizes a highly symmetrical structure (highly symmetrical lithium-philic sites) to further promote the uniformity of combination with lithium; meanwhile, the tetramino phthalocyanine is an N4 macrocyclic conjugated system with an 18 pi electronic structure, so that the stability of the obtained composite material can be further improved; the design strategy of the lithium-philic organic coating is different from the traditional method for inhibiting lithium dendrite, has unique structural advantages of keeping the original lithium-philic active sites, simultaneously ensuring that the lithium deposition is more uniform and the structural stability is better, and effectively controlling the growth of the dendrite through the synergistic effect of the two.
2) The introduced three-dimensional conductive framework can relieve Li+Structural stress fluctuation caused by volume effect during deposition/dissolution prevents collapse of electrode structure and improves lithium metal pulverization problem, thereby improving cycle life and safety performance of lithium battery.
3) The composite design strategy can effectively solve the problems of dendritic crystal growth and volume effect of the lithium metal battery and promote the lithium metal battery to be widely applied to the commercial field.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) image of the organic lithium-philic layer modified three-dimensional carbon negative electrode material prepared in example 1 of the present invention.
Fig. 2 is a Scanning Electron Microscope (SEM) image of the pure three-dimensional conductive carbon fiber cloth obtained in comparative example 1.
Fig. 3 is a fourier transform infrared spectroscopy (FTIR) graph of the organolithium philic lithium layer modified three-dimensional carbon anode material prepared in example 1 of the present invention and comparative example 1.
Fig. 4 is a graph comparing the lithium storage cycle performance of the three-dimensional carbon anode material modified by the organolithium-philic layer prepared in example 1 of the present invention and the lithium metal battery assembled by the anode in comparative example 1.
Fig. 5 is a lithium storage cycle rate performance diagram of a lithium metal battery assembled by the three-dimensional carbon negative electrode material modified by the organolithium-philic layer prepared in example 1 of the present invention.
Detailed Description
In order to make those skilled in the art fully understand the technical solutions and advantages of the present invention, the following detailed description of the present invention is provided with reference to specific embodiments.
Example 1
An organic lithium-philic composite cathode is prepared by taking three-dimensional conductive carbon fiber cloth as a substrate and adopting a hydrothermal method and a high-temperature fused lithium deposition method, and comprises the following preparation steps:
1) cutting the three-dimensional conductive carbon fiber cloth into a wafer with the aperture of 8mm, and putting the wafer into an ultrasonic cleaning instrument to alternately and ultrasonically clean the wafer for 3 times by using ethanol and deionized water in sequence, wherein each time is 10min, so as to remove impurities on the surface of the wafer; preparing 30mL of 40 wt% nitric acid solution, adding 5mL of concentrated sulfuric acid (98 wt%), soaking the three-dimensional conductive carbon fiber cloth in the nitric acid solution for 30min by ultrasonic treatment, placing the cloth in a reaction kettle, placing the cloth in a forced air drying oven for hydrothermal treatment at 120 ℃ for 10h, and carrying out oxidation modification treatment on the surface of the cloth; finally, alternately cleaning the three-dimensional conductive carbon fiber cloth for 3 times by using deionized water and ethanol respectively, washing off acid remained on the surface of the three-dimensional conductive carbon fiber cloth, and drying the three-dimensional conductive carbon fiber cloth in a vacuum drying oven for 8-12 hours for later use after cleaning;
2) dissolving 25mg of tetraaminophthalocyanine in 25mL of DMF, putting the three-dimensional conductive carbon fiber cloth obtained by pretreatment in the step 1) into the mixed solution for amidation reaction, and adding 0.9g of NHS and 0.75g of EDCI to stir for 3d at normal temperature; after the reaction is finished, taking out the modified three-dimensional conductive carbon fiber cloth (the tetraaminophthalocyanine modified three-dimensional conductive carbon fiber cloth) from the solution, and alternately washing with deionized water and ethanol to remove residual DMF, NHS and EDCI on the surface of the carbon cloth; after the cleaning, putting the mixture into a vacuum drying oven for drying for 12 hours for later use;
3) weighing the fully dried tetraaminophthalocyanine modified three-dimensional conductive carbon fiber cloth in the step 2), and then putting the cloth into a glove box; and (2) setting the temperature of an electric furnace to be 250 ℃ in an argon glove box (wherein the water content is 0.1ppm, and the oxygen content is less than 0.5ppm), melting a proper amount of lithium sheets in a crucible, clamping the tetraaminophthalocyanine modified three-dimensional conductive carbon fiber cloth by using tweezers after the lithium sheets are completely melted, putting the tetraaminophthalocyanine modified three-dimensional conductive carbon fiber cloth into molten lithium for deposition for 15min, taking out the tetraaminophthalocyanine modified three-dimensional conductive carbon fiber cloth by using tweezers, and flattening the surface by using a rolling device after the tetraaminophthalocyanine modified three-dimensional conductive.
Comparative example 1
To highlight the performance characteristics of the lithium-philic composite anode prepared in example 1, this example is used for comparison: and (3) cutting the three-dimensional conductive carbon fiber cloth into a wafer with the aperture of 8mm, and preparing the comparative anode material to be used according to the process in the step 3) of the embodiment 1 without surface oxidation and modification treatment.
Fig. 1 and 2 are Scanning Electron Microscope (SEM) images of the organic lithium-philic layer modified three-dimensional carbon negative electrode material prepared in example 1 of the present invention and comparative example 1 (pure three-dimensional conductive carbon fiber cloth), respectively. As can be seen from fig. 1 and 2, after lithium deposition, a layer of silvery white metal lithium is uniformly attached to the surface of the surface-modified three-dimensional conductive carbon fiber cloth, which indicates that the lithium-philic layer design on the surface of the three-dimensional conductive carbon fiber cloth can effectively induce lithium to be uniformly deposited, and improve the problem of dendritic crystal growth.
Fig. 3 is a graph of fourier transform infrared spectroscopy (FTIR) of the organic lithium-philic layer modified three-dimensional carbon negative electrode material prepared in example 1 of the present invention and comparative example 1 (pure three-dimensional conductive carbon fiber cloth). As can be seen, at 802cm-1And 1098cm-1And the characteristic absorption peak of phthalocyanine ring appears, which proves that the tetraaminophthalocyanine is successfully modified on the conductive carbon fiber cloth.
Fig. 4 is a comparison graph of lithium storage cycle performance of a lithium metal battery assembled by the organic lithium-philic layer modified three-dimensional carbon negative electrode material prepared in example 1 of the present invention and the pure three-dimensional conductive carbon fiber cloth as a negative electrode in comparative example 1. The figure shows that at 0.2C (1C 170 mAg)-1) The first discharge specific capacity of the full cell assembled with the negative electrode obtained in example 1 was 150.8mAh g during low rate cycling-1After 95 times of circulation, the reversible specific capacity can still be kept at 151.8mAh g-1. The first discharge specific capacity of the pure three-dimensional conductive carbon fiber cloth negative electrode of the comparative example 1 is only 66.1mAh g-1After short-term circulation, the specific capacity is obviously attenuated, and the obtained three-dimensional carbon negative electrode material modified by the organic lithium-philic layer has good circulation stability while the lithium storage performance is improved.
Fig. 5 is a lithium storage cycle rate performance diagram of a lithium metal battery assembled by the three-dimensional carbon negative electrode material modified by the organolithium-philic layer prepared in example 1 of the present invention. The graph shows that the full cell specific capacity of the negative electrode assembly prepared in example 1 still maintained 144.7mAh g when the cycling rate returned to 0.2C-1The result shows that the material has excellent cycle rate performance.
Example 2
An organic lithium-philic composite cathode is prepared by taking three-dimensional conductive carbon fiber cloth as a substrate and adopting a hydrothermal method and a high-temperature fused lithium deposition method, and comprises the following preparation steps:
1) cutting the three-dimensional conductive carbon fiber cloth into a wafer with the aperture of 8mm, and putting the wafer into an ultrasonic cleaning instrument to alternately and ultrasonically clean the wafer for 3 times by using ethanol and deionized water in sequence, wherein each time is 10min, so as to remove impurities on the surface of the wafer; preparing 30mL of 30 wt% nitric acid solution, adding 5mL of concentrated sulfuric acid (98 wt%), soaking the three-dimensional conductive carbon fiber cloth in the nitric acid solution for 30min by ultrasonic treatment, placing the cloth in a reaction kettle, placing the cloth in a forced air drying oven for hydrothermal treatment at 100 ℃ for 12h, and carrying out oxidation modification treatment on the surface of the cloth. Finally, alternately cleaning the three-dimensional conductive carbon fiber cloth for 3 times by using deionized water and ethanol respectively, washing off acid remained on the surface of the three-dimensional conductive carbon fiber cloth, and drying the three-dimensional conductive carbon fiber cloth in a vacuum drying oven for 8-12 hours for later use after cleaning;
2) dissolving 25mg of tetraaminophthalocyanine in 25mL of DMF, putting the three-dimensional conductive carbon fiber cloth obtained by pretreatment in the step 1) into the mixed solution for amidation reaction, and adding 0.9g of NHS and 0.75g of EDCI to stir for 3d at normal temperature; after the reaction is finished, taking the modified three-dimensional carbon material (the tetraaminophthalocyanine modified three-dimensional conductive carbon fiber cloth) out of the solution, alternately washing with a large amount of deionized water and ethanol to remove residual DMF, NHS and EDCI on the surface of the three-dimensional conductive carbon fiber cloth, and drying the three-dimensional conductive carbon fiber cloth in a vacuum drying oven for 12 hours for later use after the washing is finished;
3) weighing the fully dried tetraaminophthalocyanine-loaded modified three-dimensional conductive carbon fiber cloth in the step 2), and then putting the cloth into a glove box; setting the temperature of an electric furnace to 250 ℃ in an argon glove box (wherein the water content is 0.1ppm, and the oxygen content is less than 0.5ppm), melting a proper amount of lithium sheets in a crucible, clamping the tetraaminophthalocyanine modified three-dimensional conductive carbon fiber cloth by using tweezers after the lithium sheets are completely melted, putting the tetraaminophthalocyanine modified three-dimensional conductive carbon fiber cloth into molten lithium for deposition for 20min, taking out the tetraaminophthalocyanine modified three-dimensional conductive carbon fiber cloth by using the tweezers, and flattening the surface by using a rolling device after the tetraaminophthalocyanine modified three-dimensional conductive carbon fiber cloth is not.
Example 3
An organic lithium-philic composite cathode is prepared by taking three-dimensional conductive carbon fiber cloth as a substrate and adopting a hydrothermal method and a high-temperature fused lithium deposition method, and comprises the following preparation steps:
1) cutting the three-dimensional conductive carbon fiber cloth into a wafer with the aperture of 10mm, and putting the wafer into an ultrasonic cleaning instrument to alternately and ultrasonically clean the wafer for 3 times by using ethanol and deionized water in sequence, wherein each time is 10min, so as to remove impurities on the surface of the wafer; preparing 30mL of 50 wt% nitric acid solution, adding 5mL of concentrated sulfuric acid (98 wt%), soaking the three-dimensional conductive carbon fiber cloth in the nitric acid solution for 30min by ultrasonic treatment, placing the cloth in a reaction kettle, placing the cloth in a forced air drying oven for hydrothermal treatment at 100 ℃ for 8h, and carrying out oxidation modification treatment on the surface of the cloth; finally, alternately cleaning the three-dimensional conductive carbon fiber cloth for 3 times by using deionized water and ethanol respectively, washing off acid remained on the surface of the three-dimensional conductive carbon fiber cloth, and drying the three-dimensional conductive carbon fiber cloth in a vacuum drying oven for 8-12 hours for later use after cleaning;
2) dissolving 30mg of tetraaminophthalocyanine in 25mL of DMF, putting the three-dimensional conductive carbon fiber cloth obtained by pretreatment in the step 1) into the mixed solution for amidation reaction, and adding 0.96g of NHS and 0.8g of EDCI to stir for 3d at normal temperature; after the reaction is finished, taking out the modified three-dimensional conductive carbon fiber cloth (the tetraaminophthalocyanine modified three-dimensional conductive carbon fiber cloth) from the solution, and alternately washing the three-dimensional conductive carbon fiber cloth with a large amount of deionized water and ethanol to remove residual DMF, NHS and EDCI on the surface of the three-dimensional conductive carbon fiber cloth; after the cleaning, putting the mixture into a vacuum drying oven for drying for 12 hours for later use;
3) weighing the three-dimensional conductive carbon fiber cloth loaded with the tetraaminophthalocyanine fully dried in the step 2), and then putting the cloth into a glove box; in an argon glove box (wherein the water content is 0.1ppm, and the oxygen content is less than 0.5ppm), the temperature of the electric furnace is set to be 250 ℃, and a proper amount of lithium sheets are melted in a crucible. And (3) clamping the tetraaminophthalocyanine modified three-dimensional conductive carbon fiber cloth by using a pair of tweezers after the lithium sheet is completely melted, putting the tetraaminophthalocyanine modified three-dimensional conductive carbon fiber cloth into the melted lithium for deposition for 15min, taking out the tetraaminophthalocyanine modified three-dimensional conductive carbon fiber cloth by using the tweezers, and flattening the surface by using a rolling device after the tetraaminophthalocyanine modified three-dimensional conductive carbon fiber cloth is not completely cooled.
Example 4
An organic lithium-philic composite cathode is prepared by taking three-dimensional conductive carbon fiber cloth as a substrate and adopting a hydrothermal method and a high-temperature fused lithium deposition method, and comprises the following preparation steps:
1) cutting the three-dimensional conductive self-supporting graphene paper into wafers with the aperture of 10mm, putting the wafers into an ultrasonic cleaning instrument, and sequentially and alternately ultrasonically cleaning the wafers for 3 times by using ethanol and deionized water, wherein each time is 10min, so as to remove impurities on the surfaces of the wafers; preparing 30mL of 40 wt% nitric acid solution, adding 5mL of concentrated sulfuric acid (98 wt%), soaking the three-dimensional conductive self-supporting graphene paper in the nitric acid solution for 30min by ultrasonic treatment, placing the three-dimensional conductive self-supporting graphene paper in a reaction kettle, placing the reaction kettle in a forced air drying oven for hydrothermal treatment at 100 ℃ for 10h, and carrying out oxidation modification treatment on the surface of the graphene paper; finally, alternately cleaning the three-dimensional conductive self-supporting graphene paper for 3 times by using deionized water and ethanol respectively, washing off acid remained on the surface of the three-dimensional conductive self-supporting graphene paper, and drying the three-dimensional conductive self-supporting graphene paper in a vacuum drying oven for 8-12 hours for later use after cleaning;
2) dissolving 30mg of tetraaminophthalocyanine in 25mL of DMF, putting the three-dimensional conductive self-supporting graphene paper obtained by pretreatment in the step 1) into the mixed solution for amidation reaction, and adding 0.96g of NHS and 0.8g of EDCI to stir for 3d at normal temperature; after the reaction is finished, taking out the modified three-dimensional conductive carbon fiber cloth (the tetraaminophthalocyanine modified three-dimensional conductive carbon fiber cloth) from the solution, and alternately washing the three-dimensional conductive carbon fiber cloth with a large amount of deionized water and ethanol to remove DMF, NHS and EDCI remained on the surface; after the cleaning, putting the mixture into a vacuum drying oven for drying for 12 hours for later use;
3) weighing the fully dried three-dimensional conductive self-supporting graphene paper loaded with the tetraaminophthalocyanine in the step 2), and then putting the paper into a glove box; in an argon glove box (wherein the water content is 0.1ppm, and the oxygen content is less than 0.5ppm), setting the temperature of an electric furnace to be 250 ℃, and melting a proper amount of lithium sheets in a crucible; and (3) when the lithium sheet is completely melted, clamping the tetraaminophthalocyanine modified three-dimensional conductive self-supporting graphene paper by using a pair of tweezers, putting the tetraaminophthalocyanine modified three-dimensional conductive self-supporting graphene paper into the melted lithium for deposition for 15min, taking out the tetraaminophthalocyanine modified three-dimensional conductive self-supporting graphene paper by using the tweezers, and flattening the surface by using a rolling device when the tetraaminophthalocyanine modified three-dimensional conductive self-.
Example 5
An organic lithium-philic composite cathode is prepared by taking three-dimensional conductive carbon fiber cloth as a substrate and adopting a hydrothermal method and a high-temperature fused lithium deposition method, and comprises the following preparation steps:
1) cutting the three-dimensional conductive carbon nanotube film into a wafer with the aperture of 10mm, putting the wafer into an ultrasonic cleaning instrument, and alternately and ultrasonically cleaning the wafer for 3 times by using ethanol and deionized water in sequence, wherein each time is 10min, so as to remove impurities on the surface of the wafer; preparing 30mL of 45 wt% nitric acid solution, adding 5mL of concentrated sulfuric acid (98 wt%), soaking the three-dimensional conductive carbon nanotube film in the nitric acid solution for 30min by ultrasonic treatment, placing the film in a reaction kettle, placing the film in a forced air drying oven for hydrothermal treatment at 110 ℃ for 10h, and carrying out oxidation modification treatment on the surface of the film; finally, alternately cleaning the three-dimensional conductive carbon nanotube film for 3 times by using deionized water and ethanol respectively, washing off acid remained on the surface of the three-dimensional conductive carbon nanotube film, and drying the three-dimensional conductive carbon nanotube film in a vacuum drying oven for 8-12 hours for later use after cleaning;
2) dissolving 30mg of tetra-amino phthalocyanine in 25mL of DMF (dimethyl formamide), dissolving the three-dimensional conductive carbon nanotube film obtained by pretreatment in the step 1) in the mixed solution for amidation reaction, and adding 0.96g of NHS and 0.8g of EDCI (ethylenediaminetetraacetic acid) and stirring for 3d at normal temperature; after the reaction is finished, taking out the modified three-dimensional conductive carbon fiber cloth (the tetraaminophthalocyanine modified three-dimensional conductive carbon fiber cloth) from the solution, and alternately washing the three-dimensional conductive carbon fiber cloth with a large amount of deionized water and ethanol to remove DMF, NHS and EDCI remained on the surface; after the cleaning, putting the mixture into a vacuum drying oven for drying for 12 hours for later use;
3) weighing the fully dried tetraaminophthalocyanine modified three-dimensional conductive carbon fiber cloth in the step 2), and then putting the cloth into a glove box; and (2) setting the temperature of an electric furnace to be 250 ℃ in an argon glove box (wherein the water content is 0.1ppm, and the oxygen content is less than 0.5ppm), melting a proper amount of lithium sheets in a crucible, clamping a three-dimensional conductive carbon nanotube film by using a pair of tweezers after the lithium sheets are completely melted, putting the three-dimensional conductive carbon nanotube film into the molten lithium for deposition for 15min, taking out the three-dimensional conductive carbon nanotube film by using the tweezers, flattening the surface by using a rolling device after the three-dimensional conductive carbon nanotube film is not completely cooled.
Example 6
An organic lithium-philic composite cathode is prepared by taking three-dimensional conductive carbon fiber cloth as a substrate and adopting a hydrothermal method and a high-temperature fused lithium deposition method, and comprises the following preparation steps:
1) cutting the three-dimensional conductive biomass carbon film into wafers with the aperture of 10mm, putting the wafers into an ultrasonic cleaning instrument, and alternately and ultrasonically cleaning the wafers for 3 times by using ethanol and deionized water in sequence, wherein each time is 10min, so as to remove impurities on the surfaces of the wafers; preparing 30mL of 45 wt% nitric acid solution, adding 5mL of concentrated sulfuric acid (98 wt%), soaking the three-dimensional conductive biomass carbon film in the nitric acid solution for 30min by ultrasonic treatment, placing the carbon film in a reaction kettle, placing the reaction kettle in a forced air drying oven for hydrothermal treatment at 110 ℃ for 10h, and carrying out oxidation modification treatment on the surface of the carbon film; finally, alternately cleaning the three-dimensional conductive biomass carbon film for 3 times by using deionized water and ethanol respectively, washing off acid remained on the surface of the three-dimensional conductive biomass carbon film, and drying the three-dimensional conductive biomass carbon film in a vacuum drying oven for 8-12 hours for later use after cleaning;
2) dissolving 30mg of tetra-amino phthalocyanine in 25mL of DMF (dimethyl formamide), dissolving the three-dimensional conductive biomass carbon film obtained by pretreatment in the step 1) in the mixed solution for amidation reaction, and adding 0.96g of NHS and 0.8g of EDCI (ethylenediaminetetraacetic acid) and stirring for 3d at normal temperature; after the reaction is finished, taking out the modified three-dimensional conductive carbon fiber cloth (the tetraaminophthalocyanine modified three-dimensional conductive carbon fiber cloth) from the solution, and alternately washing the three-dimensional conductive carbon fiber cloth with a large amount of deionized water and ethanol to remove DMF, NHS and EDCI remained on the surface; after the cleaning, putting the mixture into a vacuum drying oven for drying for 12 hours for later use;
3) weighing the fully dried tetraaminophthalocyanine modified three-dimensional conductive carbon fiber cloth in the step 2), and then putting the cloth into a glove box; in an argon glove box (wherein the water content is 0.1ppm, and the oxygen content is less than 0.5ppm), setting the temperature of an electric furnace to be 250 ℃, and melting a proper amount of lithium sheets in a crucible; and (3) when the lithium sheet is completely melted, clamping the three-dimensional conductive biomass carbon film by using a pair of tweezers, putting the three-dimensional conductive biomass carbon film into the molten lithium for deposition for 15min, taking out the three-dimensional conductive biomass carbon film by using the tweezers, and flattening the surface by using a rolling device when the three-dimensional conductive biomass carbon film is not completely cooled to obtain the lithium-philic composite cathode.
The above embodiments are merely examples for clarity of illustration and do not limit other embodiments. Any modification, equivalent replacement, and improvement made on the basis of the present invention shall be included in the protection scope of the present invention for the ordinary skilled person in the art.

Claims (10)

1. The organic lithium-philic composite negative electrode with the three-dimensional conductive carbon material as the substrate is characterized in that the organic lithium-philic composite negative electrode is prepared by firstly carrying out surface oxidation modification treatment on the three-dimensional conductive carbon material, then introducing tetra-amino phthalocyanine for amidation modification, and finally carrying out high-temperature molten lithium deposition in a protective atmosphere.
2. The organic lithium-philic composite anode according to claim 1, wherein the amidation modification step is: dipping the three-dimensional carbon material after oxidation modification in a tetraaminophthalocyanine solution, adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and N, N-hydroxysuccinimide to obtain a mixed solution, and stirring at normal temperature for reaction.
3. The organic lithium-philic composite anode according to claim 2, wherein the concentration of the tetraaminophthalocyanine in the mixed solution is 0.6 to 1.4 mg/mL; the concentration of the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride is 20-40 mg/mL; the concentration of the N, N-hydroxysuccinimide is 24-48 mg/mL.
4. The organic lithium-philic composite anode according to claim 1, wherein the three-dimensional carbon material is one of carbon cloth, carbon paper, carbon felt, carbon nanotube, carbon nanosheet, and three-dimensional graphene.
5. The method for preparing the organic lithium-philic composite anode with the three-dimensional conductive carbon material as the substrate as claimed in any one of claims 1 to 4, comprising the steps of:
1) carrying out surface impurity removal and oxidation modification treatment on the three-dimensional carbon material, and cleaning and drying the three-dimensional carbon material for later use;
2) dipping the three-dimensional carbon material pretreated in the step 1) in a tetraaminophthalocyanine solution, adding 1-ethyl- (3-dimethylaminopropyl) carbonyl diimine hydrochloride and N, N-hydroxysuccinimide, carrying out stirring reaction at normal temperature, and then cleaning and drying for later use to obtain an amidation improved three-dimensional carbon material;
3) and carrying out high-temperature molten lithium deposition on the amidation-modified three-dimensional carbon material under a protective atmosphere to obtain the lithium-philic composite cathode.
6. The preparation method according to claim 5, wherein the oxidative modification treatment is carried out by a hydrothermal method at a temperature of 80-120 ℃ for 8-12 hours.
7. The method according to claim 5, wherein the oxidative modification treatment is carried out using a mixed acid of nitric acid and sulfuric acid, wherein the nitric acid concentration is 20 to 50 wt%.
8. The preparation method according to claim 5, wherein the solvent used for the tetraaminophthalocyanine solution is one or more of N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, acetone, acetonitrile and tetrahydrofuran.
9. The preparation method according to claim 5, wherein the normal-temperature stirring reaction time is 2-4 d.
10. The preparation method according to claim 5, wherein the high-temperature molten lithium deposition is carried out at a temperature of 250 to 300 ℃ for 5 to 20 min.
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