CN111952567B - Organic lithium-philic composite negative electrode with three-dimensional conductive carbon material as substrate and preparation method thereof - Google Patents

Organic lithium-philic composite negative electrode with three-dimensional conductive carbon material as substrate and preparation method thereof Download PDF

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CN111952567B
CN111952567B CN202010833545.6A CN202010833545A CN111952567B CN 111952567 B CN111952567 B CN 111952567B CN 202010833545 A CN202010833545 A CN 202010833545A CN 111952567 B CN111952567 B CN 111952567B
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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 anode taking a three-dimensional conductive carbon material as a substrate, which is prepared by firstly carrying out surface oxidation modification treatment on the three-dimensional conductive carbon material; then carrying out amidation reaction on the modified three-dimensional carbon material and tetraminophthalocyanine, and modifying the tetraminophthalocyanine 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 anode. The invention prepares abundant lithium-philic active sites on a deposition substrate material of lithium by carrying out multi-scale design on a lithium metal battery cathode material, and utilizes lithium-philic groups to disperse interfacial lithium ion flow to guide Li + The uniform deposition/dissolution of the lithium metal anode can effectively inhibit the growth of lithium dendrites, reduce the structural stress change caused by volume effect in the circulation process, and effectively improve the safety and the circulation performance of the lithium metal anode.

Description

Organic lithium-philic composite negative electrode with 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 negative electrode with a three-dimensional conductive carbon material as a substrate and a preparation method thereof.
Background
Along with the rapid development of electric automobiles and energy storage equipment, the requirements of people on the endurance mileage and the safety of lithium batteries are higher and higher, and the lithium battery has more practical significance for the research of lithium batteries with high energy density and excellent electrochemical performance. Among the numerous lithium battery anode materials, metallic lithium is known to have a low density (0.534 g cm -3 ) High theoretical specific capacity (3860 mAh g) -1 ) And low potential (-3.04V versus standard hydrogen electrode) are considered to be the most desirable negative materials for lithium batteries. Lithium metal is an alkaline metal whose ionic radius is the smallest of all metals, which gives it excellent charge transport kinetics; in addition, lithium metal has the lowest potential and very high reactivity. Accordingly, lithium metal batteries are receiving increasing attention in academia and industry. However, lithium metal batteries face a great challenge in practical application, when lithium contacts with electrolyte, a layer of solid electrolyte interface film (SEI) is formed on the surface of the lithium metal batteries, and the SEI film is repeatedly broken due to huge volume change in the deposition/dissolution process of the lithium, so that the SEI film is unstable, and the cycle efficiency of the batteries is affected; second, metallic lithium tends to deposit in the electrolyte in a dendrite-like form, and when lithium dendrites grow to some extent, they may pierce the separator to cause internal short circuits of the battery, and may even cause explosion. In addition, breakage of lithium dendrites can also lead to the formation of "dead lithium" that loses electrical contact, resulting in a series of problems such as loss of lithium source, reduced coulomb efficiency, capacity fade, and reduced stability.
To solve the above problems, a stable artificial SEI film is constructed, electrolyte is optimized, diaphragm modification design is performed, and uniform Li is obtained + Methods such as flow negative electrode structure design are widely studied. The construction of an artificial SEI film requires not only that the prepared SEI film has a sufficiently strong toughness to be able to accommodate stress generated during lithium deposition, but also that the prepared film layer be uniform and dense throughout to prevent Li + The preparation process of the prior method is complex and the operation is complex; the electrolyte strategy is optimized by introducing necessary additives to enhance uniformity and stability of SEI film, but excessive additives cause metalThe lithium negative electrode is burdened to lower its specific capacity, and solvation effect increases side reaction, which is disadvantageous for Li + Is deposited uniformly. The separator as an indispensable component of the battery can improve Li by improving its hydrophilicity and wettability with a polar electrolyte + The problems of ion conductivity, mechanical strength and the like caused by the concentration distribution but membrane modification are to be studied and solved more intensively. Uniform Li + The structural design of the flow negative electrode is to reduce the current density by increasing the contact area of the lithium negative electrode and the electrolyte, thereby leading the Li to be + A common method of more uniform distribution, but it is difficult to put it into practical use because of the low lithium storage capacity of the lithium deposition substrate material used. Although the above strategy is solving the lithium dendrite problem and guiding Li + The uniform deposition aspect plays a role, but the methods have a great gap from the requirements of commercial lithium batteries. Therefore, by designing the surface lithium-philicity of the lithium deposition base material, li is effectively guided + Is important to alleviate the volume change of the lithium cathode and inhibit dendrite growth, and realizes long-life lithium metal batteries.
In conclusion, the lithium battery taking the metal lithium as the negative electrode has wide application prospect in the future energy development, and the lithium-philic negative electrode material which can induce uniform deposition of lithium ions, effectively inhibit dendrite growth and improve the volume effect is further designed, so that the lithium-philic negative electrode material has important significance for developing a lithium battery system with high specific energy, high safety and long service life.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides an organic lithium-philic composite anode taking a three-dimensional conductive carbon material as a substrate and a preparation method thereof, and aims to induce lithium ions to be deposited uniformly by utilizing a lithium-philic group uniformly grown on the three-dimensional conductive carbon material, and provide enough lithium accommodating space by taking the three-dimensional conductive carbon material as a substrate material for lithium deposition, and a conductive framework can also promote rapid conduction of electrons and reduce current density; meanwhile, the synergistic effect of the lithium-philic group and the conductive framework is utilized to effectively inhibit dendrite growth, and the volume effect in the circulation process is improved, so that the circulation stability of the lithium-philic composite material serving as a lithium battery cathode is improved.
In order to achieve the above purpose, the invention adopts the following technical scheme:
an organic lithium-philic composite negative electrode with 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 to carry out amidation modification, and finally carrying out high-temperature molten lithium deposition under a protective atmosphere.
In the above scheme, the amidation modification step is as follows: placing the three-dimensional carbon material subjected to oxidation modification in a tetraminophthalocyanine solution, adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDCI) and N, N-hydroxysuccinimide (NHS) to obtain a mixed solution, and carrying out normal-temperature stirring reaction; 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 favorable for dehydrating and condensing the amino on tetraminophthalocyanine and the carboxyl on the modified carbon material to form an amide bond, so that the amide bond is supported on the three-dimensional carbon material in a covalent form.
In the scheme, the stirring reaction time at normal temperature is 2-4 d.
In the scheme, the concentration of the tetraminophthalocyanine 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 negative electrode with the three-dimensional conductive carbon material as a substrate is prepared by adopting a hydrothermal method and a high-temperature molten lithium deposition method, and specifically comprises the following steps of:
1) Carrying out surface impurity removal and oxidation modification treatment on the three-dimensional carbon material, and cleaning and drying for later use;
2) Immersing the three-dimensional carbon material pretreated in the step 1) in tetraminophthalocyanine solution, adding NHS and EDCI, stirring at normal temperature for reaction, and then cleaning and drying for standby to obtain a modified three-dimensional carbon material;
3) And (3) carrying out high-temperature molten 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 removing step in the step 1) is to alternately clean the surface impurity removing step by using ethanol or deionized water for 3-5 times, and 8-15 min each time.
In the above scheme, the surface oxidation modification treatment of step 1) uses a mixed acid formed from nitric acid and sulfuric acid, wherein nitric acid (HNO) 3 ) The concentration of (2) is 20-50wt%; sulfuric acid (H) 2 SO 4 ) The concentration of (2) is 98wt%; the soaking ultrasonic time is 25-35 min.
In the scheme, the surface oxidation modification method in the step 1) is preferably a hydrothermal method, wherein the reaction temperature is 80-120 ℃ and the reaction time is 8-12 h.
In the above scheme, the cleaning step in step 2) is to alternately clean deionized water and ethanol for 3-5 times, and wash away the residual acid on the surface of the three-dimensional carbon material, preferably, the cleaning time is 8-15 min each time.
Preferably, the drying step in the step 1) is vacuum drying for 8-12 h.
In the above scheme, the tetra-amino phthalocyanine solution in step 2) adopts a polar solvent, and one or more of N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), acetone, acetonitrile, tetrahydrofuran and the like can be selected.
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 residual DMF, NHS and EDCI on the surface of the three-dimensional carbon material at least 3 times until the washed water is clear and transparent; and after the cleaning is finished, placing the mixture into a vacuum drying oven for drying for 8-12 hours for standby.
In the above scheme, the temperature adopted in the high-temperature molten lithium deposition in the step 3) is 250-300 ℃, the time is 5-20 min, and the melting temperature is preferably 250 ℃.
In the above scheme, in step 3), a layer of lithium with silvery white metallic luster is attached to the surface of the three-dimensional carbon material after the deposition is finished, and after the three-dimensional carbon material is not completely cooled, the three-dimensional carbon material with the lithium uniformly attached to the surface is flattened by a rolling device, so that the required lithium-philic composite anode is prepared.
The invention is an organic lithium-philic layer design scheme taking a three-dimensional conductive carbon material as a substrate, can provide a large number of lithium-philic groups, can manufacture abundant active sites, induces uniform deposition of lithium ions, effectively inhibits dendrite growth, improves the volume effect in the circulation process, and further improves 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) According to the invention, the three-dimensional conductive carbon material is used as a base material for lithium deposition, surface oxidation modification treatment is carried out on the three-dimensional conductive carbon material to generate a large number of carboxyl (-COOH) groups, amidation reaction is carried out on the three-dimensional conductive carbon material and tetramino phthalocyanine, the tetramino phthalocyanine is fixed on the three-dimensional conductive carbon material in a covalent bond form, and the uniformity of combination with lithium can be further promoted by utilizing a highly symmetrical structure (highly symmetrical lithium-philic sites) of the three-dimensional conductive carbon material while providing enough lithium accommodation space and exerting the effect of inducing and dispersing lithium ion current; meanwhile, the tetra-amino phthalocyanine is an N4 macrocyclic conjugated system with an 18 pi electron 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 the dendrite of lithium, and the unique structural advantage of the design strategy is that the original lithium-philic active site is reserved, so that lithium deposition is more uniform, the design strategy has better structural stability, and dendrite growth is effectively controlled through the synergistic effect of the two.
2) The introduced three-dimensional conductive framework can relieve Li + Structural stress fluctuation caused by volume effect in the deposition/dissolution process can prevent collapse of electrode structure and improve lithium metal pulverization problem, thereby prolonging cycle life and improving safety performance of lithium battery.
3) The composite design strategy can effectively improve dendrite growth and volume effect problems 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 a three-dimensional carbon anode material modified by an organic lithium-philic layer 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 infrared spectrum (FTIR) diagram 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.
Fig. 4 is a graph showing the lithium storage cycle performance of the organic lithium-philic layer modified three-dimensional carbon anode material prepared in example 1 of the present invention and the lithium metal battery assembled with the anode of comparative example 1, respectively.
Fig. 5 is a graph showing the lithium storage cycle rate performance of a lithium metal battery assembled by using the three-dimensional carbon negative electrode material modified by the organic lithium-philic layer prepared in example 1 of the present invention.
Detailed Description
In order to fully understand the technical scheme and the beneficial effects of the present invention, a detailed description of the present invention will be given below with reference to specific embodiments.
Example 1
An organic lithium-philic layer taking three-dimensional conductive carbon fiber cloth as a substrate is prepared into a lithium-philic composite anode by adopting a hydrothermal method and a high-temperature molten lithium deposition method, and the preparation method comprises the following steps:
1) Cutting the three-dimensional conductive carbon fiber cloth into wafers with the aperture of 8mm, putting the wafers into an ultrasonic cleaning instrument, and sequentially and alternately ultrasonically cleaning the wafers with ethanol and deionized water for 3 times, wherein each time is 10 minutes, so as to remove impurities on the surfaces of the wafers; preparing 30mL of nitric acid solution with the concentration of 40wt%, adding 5mL of concentrated sulfuric acid (98 wt%) into the nitric acid solution, soaking the three-dimensional conductive carbon fiber cloth in the nitric acid solution for 30min by ultrasound, placing the three-dimensional conductive carbon fiber cloth in a reaction kettle, putting the reaction kettle into a blast drying box, carrying out hydrothermal treatment at 120 ℃ for 10h, and carrying out oxidation modification treatment on the surface of the three-dimensional conductive carbon fiber cloth; finally, respectively and alternately cleaning with deionized water and ethanol for 3 times, 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 after the cleaning is finished;
2) Taking 25mg of tetra-amino phthalocyanine, dissolving in 25mL of DMF, placing the three-dimensional conductive carbon fiber cloth pretreated in the step 1) into the mixed solution for amidation reaction, adding 0.9g of NHS and 0.75g of EDCI, and stirring for 3d at normal temperature; after the reaction is finished, taking out the modified three-dimensional conductive carbon fiber cloth (tetra-amino phthalocyanine modified three-dimensional conductive carbon fiber cloth) from the solution, and alternately washing with deionized water and ethanol to remove DMF, NHS and EDCI remained on the surface of the carbon cloth; after the cleaning is finished, placing the mixture into a vacuum drying oven for drying for 12 hours for standby;
3) Weighing the tetra-amino phthalocyanine modified three-dimensional conductive carbon fiber cloth fully dried in the step 2), and then placing the three-dimensional conductive carbon fiber cloth into a glove box; in an argon glove box (wherein the water content is 0.1ppm and the oxygen content is less than 0.5 ppm), setting the temperature of an electric furnace to be 250 ℃, melting a proper amount of lithium sheets in a crucible, clamping tetra-amino phthalocyanine modified three-dimensional conductive carbon fiber cloth by forceps, placing the four-amino phthalocyanine modified three-dimensional conductive carbon fiber cloth in molten lithium for deposition for 15min, taking out by forceps, and flattening the surface by a rolling device after incomplete cooling, thus obtaining the lithium-philic composite negative electrode.
Comparative example 1
In order to highlight the performance characteristics of the lithium-philic composite anode prepared in example 1, this example is taken as a comparison: cutting the three-dimensional conductive carbon fiber cloth into wafers with the aperture of 8mm, and preparing the standby comparative anode material by the process of the step 3) of the example 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 fig. 2, after the surface-modified three-dimensional conductive carbon fiber cloth is deposited with lithium, a layer of silvery white metal lithium is uniformly attached to the surface of the carbon fiber, which indicates that the design of the lithium-philic layer on the surface of the three-dimensional conductive carbon fiber cloth can effectively induce the uniform deposition of lithium and improve the dendrite growth problem.
Fig. 3 is a fourier infrared spectrum (FTIR) diagram 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 from the figure, at 802cm -1 And 1098cm -1 Characteristic absorption peaks of phthalocyanine rings appear at the positions, and the tetraminophthalocyanine is proved to be successfully modified on the conductive carbon fiber cloth.
FIG. 4 is a three-dimensional carbon negative electrode material modified by an organic lithium-philic layer according to example 1 of the present inventionAnd a lithium storage cycle performance comparison chart of the lithium metal battery respectively assembled by taking the pure three-dimensional conductive carbon fiber cloth as a negative electrode in the comparative example 1. The graph shows that at 0.2C (1c=170 mAg -1 ) The initial discharge specific capacity of the full cell assembled by the negative electrode prepared in example 1 is 150.8mAh g during low-rate cycle -1 The reversible specific capacity can still be kept at 151.8mAh g after 95 times of circulation -1 . The first discharge specific capacity of the pure three-dimensional conductive carbon fiber cloth cathode of comparative example 1 is only 66.1mAh g -1 The specific capacity decay is obvious after short circulation, and the three-dimensional carbon anode material modified by the organic lithium-philic layer has good circulation stability while improving the lithium storage performance.
Fig. 5 is a graph showing the lithium storage cycle rate performance of a lithium metal battery assembled by using the three-dimensional carbon negative electrode material modified by the organic lithium-philic layer prepared in example 1 of the present invention. The graph shows that the specific capacity of the full cell assembled by the negative electrode prepared in example 1 can still be kept at 144.7mAh g when the cycle rate is returned to 0.2C -1 Indicating that it has excellent cycle rate performance.
Example 2
An organic lithium-philic layer taking three-dimensional conductive carbon fiber cloth as a substrate is prepared into a lithium-philic composite anode by adopting a hydrothermal method and a high-temperature molten lithium deposition method, and the preparation method comprises the following steps:
1) Cutting the three-dimensional conductive carbon fiber cloth into wafers with the aperture of 8mm, putting the wafers into an ultrasonic cleaning instrument, and sequentially and alternately ultrasonically cleaning the wafers with ethanol and deionized water for 3 times, wherein each time is 10 minutes, so as to remove impurities on the surfaces of the wafers; preparing 30mL of 30wt% nitric acid solution, adding 5mL of concentrated sulfuric acid (98 wt%) into the solution, soaking the three-dimensional conductive carbon fiber cloth in the solution for 30min by ultrasound, placing the three-dimensional conductive carbon fiber cloth in a reaction kettle, putting the reaction kettle into a blast drying box, performing hydrothermal treatment at 100 ℃ for 12h, and performing oxidation modification treatment on the surface of the three-dimensional conductive carbon fiber cloth. Finally, respectively and alternately cleaning with deionized water and ethanol for 3 times, 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 after the cleaning is finished;
2) Taking 25mg of tetra-amino phthalocyanine, dissolving in 25mL of DMF, placing the three-dimensional conductive carbon fiber cloth pretreated in the step 1) into the mixed solution for amidation reaction, adding 0.9g of NHS and 0.75g of EDCI, and stirring for 3d at normal temperature; after the reaction is finished, taking the modified three-dimensional carbon material (tetra-amino phthalocyanine modified three-dimensional conductive carbon fiber cloth) out of the solution, alternately washing with a large amount of deionized water and ethanol to remove DMF, NHS and EDCI remained on the surface of the three-dimensional conductive carbon fiber cloth, and drying the three-dimensional carbon fiber cloth in a vacuum drying oven for 12 hours after the cleaning is finished;
3) Weighing the fully dried tetra-amino phthalocyanine modified three-dimensional conductive carbon fiber cloth loaded in the step 2), and then placing the three-dimensional conductive carbon fiber cloth into a glove box; in an argon glove box (wherein the water content is 0.1ppm and the oxygen content is less than 0.5 ppm), setting the temperature of an electric furnace to be 250 ℃, melting a proper amount of lithium sheets in a crucible, clamping tetra-amino phthalocyanine modified three-dimensional conductive carbon fiber cloth by forceps, placing the four-amino phthalocyanine modified three-dimensional conductive carbon fiber cloth in molten lithium for deposition for 20min, taking out by forceps, and flattening the surface by a rolling device after incomplete cooling, thus obtaining the lithium-philic composite negative electrode.
Example 3
An organic lithium-philic layer taking three-dimensional conductive carbon fiber cloth as a substrate is prepared into a lithium-philic composite anode by adopting a hydrothermal method and a high-temperature molten lithium deposition method, and the preparation method comprises the following steps:
1) Cutting the three-dimensional conductive carbon fiber cloth into wafers with the aperture of 10mm, putting the wafers into an ultrasonic cleaning instrument, and sequentially and alternately ultrasonically cleaning the wafers with ethanol and deionized water for 3 times, wherein each time is 10 minutes, so as to remove impurities on the surfaces of the wafers; preparing 30mL of 50wt% nitric acid solution, adding 5mL of concentrated sulfuric acid (98 wt%) into the nitric acid solution, soaking the three-dimensional conductive carbon fiber cloth in the nitric acid solution for 30min by ultrasound, placing the three-dimensional conductive carbon fiber cloth in a reaction kettle, putting the reaction kettle into a blast drying box, performing hydrothermal treatment at 100 ℃ for 8h, and performing oxidation modification treatment on the surface of the three-dimensional conductive carbon fiber cloth; finally, respectively and alternately cleaning with deionized water and ethanol for 3 times, 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 after the cleaning is finished;
2) Taking 30mg of tetra-amino phthalocyanine, dissolving in 25mL of DMF, placing the three-dimensional conductive carbon fiber cloth pretreated in the step 1) into the mixed solution for amidation reaction, adding 0.96g of NHS and 0.8g of EDCI, and stirring for 3d at normal temperature; after the reaction is finished, taking out the modified three-dimensional conductive carbon fiber cloth (tetra-amino phthalocyanine modified three-dimensional conductive carbon fiber cloth) from the solution, and alternately washing with a large amount of deionized water and ethanol to remove DMF, NHS and EDCI remained on the surface of the three-dimensional conductive carbon fiber cloth; after the cleaning is finished, placing the mixture into a vacuum drying oven for drying for 12 hours for standby;
3) Weighing the fully dried three-dimensional conductive carbon fiber cloth loaded with tetramino phthalocyanine in the step 2), and then placing the three-dimensional conductive carbon fiber cloth into a glove box; in an argon glove box (wherein the water content is 0.1ppm and the oxygen content is less than 0.5 ppm), the electric furnace temperature is set to 250 ℃, and a proper amount of lithium tablets are melted in a crucible. And (3) after the lithium sheet is completely melted, clamping the tetra-amino phthalocyanine modified three-dimensional conductive carbon fiber cloth by using tweezers, placing the three-dimensional conductive carbon fiber cloth into molten lithium, depositing for 15min, taking out the three-dimensional conductive carbon fiber cloth by using the tweezers, and flattening the surface by using a rolling device after the lithium sheet is not completely cooled, thus obtaining the lithium-philic composite negative electrode.
Example 4
An organic lithium-philic layer taking three-dimensional conductive carbon fiber cloth as a substrate is prepared into a lithium-philic composite anode by adopting a hydrothermal method and a high-temperature molten lithium deposition method, and the preparation method comprises the following steps:
1) Cutting three-dimensional conductive self-supporting graphene paper into wafers with the aperture of 10mm, and putting the wafers into an ultrasonic cleaning instrument, and sequentially and alternately carrying out ultrasonic cleaning for 3 times with ethanol and deionized water for 10 minutes each time to remove impurities on the surfaces of the wafers; preparing 30mL of nitric acid solution with the concentration of 40wt%, adding 5mL of concentrated sulfuric acid (98 wt%) into the nitric acid solution, soaking the three-dimensional conductive self-supporting graphene paper into the nitric acid solution for 30min by ultrasound, placing the three-dimensional conductive self-supporting graphene paper into a reaction kettle, placing the reaction kettle into a blast drying box, performing hydrothermal treatment at the temperature of 100 ℃ for 10h, and performing oxidative modification treatment on the surface of the three-dimensional conductive self-supporting graphene paper; finally, respectively and alternately cleaning with deionized water and ethanol for 3 times, 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 after the cleaning is finished;
2) Taking 30mg of tetra-amino phthalocyanine, dissolving the tetra-amino phthalocyanine in 25mL of DMF, putting the three-dimensional conductive self-supporting graphene paper pretreated in the step 1) into the mixed solution for amidation reaction, adding 0.96g of NHS and 0.8g of EDCI, and stirring for 3d at normal temperature; after the reaction is finished, taking out the modified three-dimensional conductive carbon fiber cloth (tetra-amino phthalocyanine modified three-dimensional conductive carbon fiber cloth) from the solution, and alternately washing with a large amount of deionized water and ethanol to remove DMF, NHS and EDCI remained on the surface; after the cleaning is finished, placing the mixture into a vacuum drying oven for drying for 12 hours for standby;
3) Weighing the fully dried three-dimensional conductive self-supporting graphene paper loaded with tetraminophthalocyanine in the step 2), and then placing the three-dimensional conductive self-supporting graphene paper into a glove box; in an argon glove box (wherein the water content is 0.1ppm and the oxygen content is less than 0.5 ppm), setting the temperature of an electric furnace to be 250 ℃, and melting a proper amount of lithium tablets in a crucible; and (3) when the lithium sheet is completely melted, clamping the tetra-amino phthalocyanine modified three-dimensional conductive self-supporting graphene paper by using tweezers, placing the paper into molten lithium, depositing for 15min, taking out the paper by using the tweezers, and flattening the surface by using a rolling device after the paper is not completely cooled, thus obtaining the lithium-philic composite negative electrode.
Example 5
An organic lithium-philic layer taking three-dimensional conductive carbon fiber cloth as a substrate is prepared into a lithium-philic composite anode by adopting a hydrothermal method and a high-temperature molten lithium deposition method, and the preparation method comprises the following steps:
1) Cutting the three-dimensional conductive carbon nanotube film into wafers with the aperture of 10mm, putting the wafers into an ultrasonic cleaning instrument, and sequentially and alternately ultrasonically cleaning the wafers with ethanol and deionized water for 3 times, wherein each time is 10 minutes, so as to remove impurities on the surfaces of the wafers; preparing 30mL of 45wt% nitric acid solution, adding 5mL of concentrated sulfuric acid (98 wt%) into the solution, soaking the three-dimensional conductive carbon nanotube film in the solution for 30min by ultrasound, placing the solution in a reaction kettle, putting the reaction kettle into a blast drying box, performing hydrothermal treatment at 110 ℃ for 10h, and performing oxidation modification treatment on the surface of the solution; finally, respectively and alternately cleaning for 3 times by using deionized water and ethanol, 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 after the cleaning is finished;
2) Dissolving 30mg of tetra-amino phthalocyanine in 25mL of DMF, dissolving the three-dimensional conductive carbon nanotube film pretreated in the step 1) in 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 (tetra-amino phthalocyanine modified three-dimensional conductive carbon fiber cloth) from the solution, and alternately washing with a large amount of deionized water and ethanol to remove DMF, NHS and EDCI remained on the surface; after the cleaning is finished, placing the mixture into a vacuum drying oven for drying for 12 hours for standby;
3) Weighing the tetra-amino phthalocyanine modified three-dimensional conductive carbon fiber cloth fully dried in the step 2), and then placing the three-dimensional conductive carbon fiber cloth into a glove box; in an argon glove box (wherein the water content is 0.1ppm and the oxygen content is less than 0.5 ppm), setting the temperature of an electric furnace to be 250 ℃, melting a proper amount of lithium sheets in a crucible, clamping a three-dimensional conductive carbon nano tube film by forceps, placing the three-dimensional conductive carbon nano tube film into molten lithium for deposition for 15min, taking out the three-dimensional conductive carbon nano tube film by forceps, and flattening the surface by a rolling device after the three-dimensional conductive carbon nano tube film is not completely cooled, thus obtaining the lithium-philic composite anode.
Example 6
An organic lithium-philic layer taking three-dimensional conductive carbon fiber cloth as a substrate is prepared into a lithium-philic composite anode by adopting a hydrothermal method and a high-temperature molten lithium deposition method, and the preparation method comprises the following 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 sequentially and alternately ultrasonically cleaning the wafers with ethanol and deionized water for 3 times, wherein each time is 10 minutes, so as to remove impurities on the surfaces of the wafers; preparing 30mL of 45wt% nitric acid solution, adding 5mL of concentrated sulfuric acid (98 wt%) into the solution, soaking the three-dimensional conductive biomass carbon film in the solution for 30min by ultrasound, placing the solution in a reaction kettle, putting the reaction kettle into a forced air drying oven for hydrothermal treatment at 110 ℃ for 10h, and carrying out oxidation modification treatment on the surface of the solution; finally, respectively and alternately cleaning for 3 times by using deionized water and ethanol, 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 after the cleaning is finished;
2) Taking 30mg of tetra-amino phthalocyanine, dissolving the tetra-amino phthalocyanine in 25mL of DMF, dissolving the three-dimensional conductive biomass carbon film pretreated in the step 1) in the mixed solution for amidation reaction, adding 0.96g of NHS and 0.8g of EDCI, and stirring for 3d at normal temperature; after the reaction is finished, taking out the modified three-dimensional conductive carbon fiber cloth (tetra-amino phthalocyanine modified three-dimensional conductive carbon fiber cloth) from the solution, and alternately washing with a large amount of deionized water and ethanol to remove DMF, NHS and EDCI remained on the surface; after the cleaning is finished, placing the mixture into a vacuum drying oven for drying for 12 hours for standby;
3) Weighing the tetra-amino phthalocyanine modified three-dimensional conductive carbon fiber cloth fully dried in the step 2), and then placing the three-dimensional conductive carbon fiber cloth into a glove box; in an argon glove box (wherein the water content is 0.1ppm and the oxygen content is less than 0.5 ppm), setting the temperature of an electric furnace to be 250 ℃, and melting a proper amount of lithium tablets in a crucible; and (3) after the lithium sheet is completely melted, clamping the three-dimensional conductive biomass carbon film by using tweezers, placing the three-dimensional conductive biomass carbon film into molten lithium, depositing for 15min, taking out the three-dimensional conductive biomass carbon film by using the tweezers, and flattening the surface by using a rolling device after the three-dimensional conductive biomass carbon film is not completely cooled, thus obtaining the lithium-philic composite negative electrode.
The above examples are presented for clarity of illustration only and are not limiting of other embodiments. Any modifications, equivalent substitutions and improvements made by those skilled in the art based on the present invention shall fall within the protection scope of the present invention.

Claims (7)

1. An organic lithium-philic composite anode with a three-dimensional conductive carbon material as a substrate is characterized in that the organic lithium-philic composite anode is prepared by firstly carrying out surface oxidation modification treatment on the three-dimensional conductive carbon material, then introducing tetraminophthalocyanine to carry out amidation modification, and finally carrying out high-temperature molten lithium deposition under a protective atmosphere;
the amidation modification steps are as follows: immersing the three-dimensional carbon material subjected to oxidation modification in a tetraminophthalocyanine solution, adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and N, N-hydroxysuccinimide to obtain a mixed solution, and carrying out normal-temperature stirring reaction;
the oxidation modification treatment utilizes mixed acid formed by nitric acid and sulfuric acid, wherein the concentration of the nitric acid is 20-50wt%;
the stirring reaction time at normal temperature is 2-4 d.
2. The organic lithium-philic composite anode according to claim 1, wherein the concentration of tetra-amino phthalocyanine in the mixed solution is 0.6-1.4 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.
3. The organic lithium-philic composite negative electrode of claim 1, wherein the three-dimensional carbon material is one of carbon cloth, carbon paper, carbon felt, carbon nanotubes, carbon nanoplatelets, and three-dimensional graphene.
4. A method for preparing the organic lithium-philic composite negative electrode based on a three-dimensional conductive carbon material as defined in any one of claims 1 to 3, characterized by comprising the steps of:
1) Carrying out surface impurity removal and oxidation modification treatment on the three-dimensional carbon material, and cleaning and drying for later use;
2) Immersing the three-dimensional carbon material pretreated in the step 1) in a tetraminophthalocyanine solution, adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and N, N-hydroxysuccinimide, stirring at normal temperature for reaction, and then cleaning and drying for later use to obtain an amidated modified three-dimensional carbon material;
3) And (3) carrying out high-temperature molten lithium deposition on the obtained amidated modified three-dimensional carbon material under a protective atmosphere to obtain the lithium-philic composite anode.
5. The preparation method according to claim 4, wherein the oxidative modification treatment is performed by a hydrothermal method at a temperature of 80 to 120 ℃ for 8 to 12 hours.
6. The preparation method according to claim 4, wherein the solvent used in the tetra-amino phthalocyanine solution is one or more of N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, acetone, acetonitrile and tetrahydrofuran.
7. The method according to claim 4, wherein the high-temperature molten lithium deposition is carried out at a temperature of 250 to 300 ℃ for a time of 5 to 20 minutes.
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