CN113346141B - Amino acid slow-release composite carbon skeleton for lithium metal and preparation method thereof - Google Patents

Amino acid slow-release composite carbon skeleton for lithium metal and preparation method thereof Download PDF

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CN113346141B
CN113346141B CN202110608710.2A CN202110608710A CN113346141B CN 113346141 B CN113346141 B CN 113346141B CN 202110608710 A CN202110608710 A CN 202110608710A CN 113346141 B CN113346141 B CN 113346141B
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amino acid
lithium
carbon skeleton
electrolyte
lithium metal
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CN113346141A (en
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张强
金成滨
刘兴江
杨明
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Tsinghua University
CETC 18 Research Institute
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CETC 18 Research Institute
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Abstract

The invention discloses an amino acid slow-release composite carbon skeleton for lithium metal and a preparation method thereof, belonging to the technical field of secondary batteries. The composite carbon skeleton takes the carbon skeleton as a slow release skeleton, takes amino acid as an additive, and the amino acid is fixed in structural pores of the carbon skeleton; along with the circulation reaction of the battery, the amino acid in the structural pores is gradually released into the electrolyte to make up for the consumption of the amino acid in the electrolyte. Amino acid loaded in the structural pores can be used as a lithium-philic group to induce the uniform deposition of lithium metal. Meanwhile, the slow-release amino acid is used as an additive, is gradually released and supplemented to be dissolved in the electrolyte, compensates the amino acid which is continuously consumed in the electrolyte along with the formation of SEI, and can be known through the obvious reduction peak presented in CV, the amino acid in the electrolyte takes amino and carboxyl as reaction units, in-situ promotes and participates in the formation of SEI, and the SEI on the surface of the deposited metal lithium is regulated, controlled and optimized, so that the electrochemical performance of the lithium metal cathode is improved.

Description

Amino acid slow-release composite carbon skeleton for lithium metal and preparation method thereof
Technical Field
The invention belongs to the technical field of secondary batteries, and particularly relates to an amino acid slow-release composite carbon skeleton for lithium metal and a preparation method thereof.
Background
With the increasing dependence and demand of the human society on energy devices, research and development of novel battery systems are imperative. Among them, lithium metal batteries are receiving much attention and are the hot spot and the center of gravity for the current high energy density battery system research. Because metallic lithium has a theoretical specific capacity as high as 3860mAh/g and a potential as low as-3.04V, it is an ideal negative electrode material for high specific energy batteries. However, lithium metal batteries have not been commercially used so far due to problems of lithium dendrite growth, unstable solid electrolyte interface film (SEI) formation, and severe volume effect during battery cycling due to active electrochemical properties of lithium metal. In recent years, researchers have developed a number of strategies to solve the above problems of lithium metal negative electrodes, and have advanced their commercial application processes, including preparation of artificial SEI, use of solid electrolytes, introduction of three-dimensional frameworks, regulation of electrolyte systems, and the like.
Based on the above, in the prior art, people introduce a layer of insoluble and gelatinous protein macromolecules on the lithium metal reaction surface, because peptide bonds in the protein molecular chains have better affinity with lithium, the protein macromolecules can be adsorbed on the lithium metal surface, at the moment, the protein structure is converted from alpha helix to beta folding and is tightly attached to the lithium surface, so that the protein and the lithium metal have better interaction to form a layer of membrane structure of the protein, and further the membrane structure serves as artificial SEI to play a role. In addition, since the protein is not conductive, the local electric field strength in the vicinity of the current collector can be reduced, and lithium deposition is promoted. But no specific influence on SEI formation by the protein molecule itself is known.
In addition, in the prior art, the introduction of the three-dimensional framework can effectively relieve the volume effect of the lithium metal cathode in the circulation process, and can regulate and control the deposition growth behavior of the lithium metal to a certain degree. More importantly, the framework material and the lithium-framework composite negative electrode are easy to grow and manufacture on a large scale, and have practical significance. However, the current framework materials are designed to introduce lithium-philic metal or metal oxide through a more complicated process to induce uniform deposition of lithium, but these materials increase the content of inactive components in the composite negative electrode, which is not favorable for the construction of high specific energy batteries. In addition, in the actual battery cycle process, the lithium cycle depth is greatly improved, and the lithium affinity design effect is difficult to meet the requirement.
Based on the above, it is urgently needed to provide a more practical functionalized framework design and a corresponding simple, efficient and low-cost preparation process, so as to effectively regulate and control the nucleation growth of lithium, and play a role in optimizing SEI, thereby effectively improving the cycle performance of the battery.
Disclosure of Invention
In order to solve the problems, the invention provides an amino acid slow-release composite carbon skeleton for lithium metal, which takes the carbon skeleton as a slow-release skeleton and takes amino acid as an additive, and the amino acid is fixed in structural pores of the carbon skeleton; along with the circulation reaction of the battery, the amino acid in the structural pores is gradually released into the electrolyte to make up for the consumption of the amino acid in the electrolyte.
The amino acid in the electrolyte takes amino and carboxyl as reaction units, promotes and participates in the formation of SEI in situ, regulates and optimizes the SEI on the surface of the deposited metal lithium, and further improves the electrochemical performance of the lithium metal cathode.
Meanwhile, amino acid loaded in the structural pores can be used as a lithium-philic group to induce the uniform deposition of lithium metal.
The thickness of the carbon skeleton is 50-200 μm; the surface loading of amino acid in carbon skeleton is 0.2-1mg/cm 2 。
The carbon skeleton is made of carbon cloth, graphite paper, carbon fiber paper or carbon nanotube paper; the amino acid is any one of nicotinic acid, proline, histidine, glycine or glutamic acid.
The preparation method of the amino acid slow-release composite carbon skeleton for lithium metal comprises the following steps:
1) Dissolving or dispersing amino acid in an organic solvent, and obtaining an organic dispersion liquid with uniformly dispersed amino acid for later use through magnetic stirring or ultrasonic treatment;
2) And (2) putting the carbon skeleton into the organic dispersion liquid obtained in the step 1), standing, and adsorbing amino acid into the carbon skeleton through the physical adsorption effect of the carbon skeleton to obtain the amino acid slow-release composite carbon skeleton.
The concentration of amino acid in the organic dispersion is 5.2-26g/mL.
The organic solvent in the step 1) is one of dimethyl carbonate, dimethyl sulfoxide, dimethylacetamide and dimethylformamide.
The application of the amino acid slow-release composite carbon skeleton for the lithium metal is that the composite carbon skeleton and a lithium belt or a lithium sheet with the thickness of 50 mu m are aligned and stacked, and the lithium belt or the lithium sheet is rolled by a rolling mill to obtain the lithium-amino acid slow-release composite carbon skeleton lithium metal cathode.
The invention has the beneficial effects that:
1. in the composite carbon skeleton of the present invention, amino acids play a dual role. The loaded amino acid can be used as a lithium-philic group to induce the uniform deposition of lithium metal; meanwhile, free amino acid released into the electrolyte along with the battery cycling reaction relieves the reduction of the concentration of the amino acid in the electrolyte, so that the amino acid can participate in the regulation and control and optimization of SEI on the surface of the deposited metal lithium for a long time, and the electrochemical performance of the lithium metal cathode is further optimized.
2. And rolling the composite carbon skeleton and a lithium metal sheet or a lithium belt into a whole by a mechanical roll-to-roll method, so that the metal lithium is also filled in the holes of the rest carbon skeleton structure, and preparing the lithium-amino acid slow-release composite carbon skeleton lithium metal cathode. According to the structure of the lithium metal negative electrode, metal lithium can be uniformly deposited on the surface of the carbon framework material, the generation of lithium dendrites is inhibited, the current density of a local surface is effectively reduced, and the cycle capacity performance of the battery is greatly improved; and the preparation operation process is simple, large-scale continuous production is realized, and the reproducibility among batches and the consistency of products are ensured.
3. In the composite carbon skeleton, the abundant pore structure of the skeleton material can play the effect of relieving and inhibiting volume expansion, and the cycling stability of the battery is effectively improved. In addition, the large specific surface area of the electrolyte can effectively load amino acid, improve the content of the amino acid, break through the limitation of the solubility of the amino acid in the electrolyte, spontaneously relieve the loss of the amino acid in the electrolyte, and enable the amino acid to play a role in optimizing the performance of the battery for a long time.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of a carbon fiber paper of example 1;
FIG. 2 is a voltage-time curve for a lithium symmetric cell of example 3;
FIG. 3 is a lithium-ternary full cell cycle capacity plot of example 3;
FIG. 4 is the cyclic voltammetry curve of-0.4-1V for the coin cell composed of the composite negative electrode prepared from the lithium-proline slow-release carbon fiber paper and the pure carbon paper and the stainless steel sheet in example 3;
FIG. 5 is a cyclic voltammetry graph of 0-3V for a button cell composed of a composite negative electrode prepared from the lithium-proline slow-release carbon fiber paper and the pure carbon paper and a stainless steel sheet in example 3;
FIG. 6 is a schematic illustration of the amino acid sustained release process of the present invention;
wherein, 1-carbon skeleton, 2-metallic lithium, 3-amino acid absorbed and fixed in the pores of the carbon skeleton structure, 4-amino acid released in the electrolyte, 5-electrolyte, and 6-amino acid participate in the formed SEI.
Detailed Description
The invention is described in further detail below with reference to the following figures and specific examples:
the research of the invention finds that the amino acid can optimize the generation of SEI, and further optimize the performance of the battery. However, the solubility of amino acid in the electrolyte is low, and the amino acid is continuously consumed along with the formation of SEI, so that it is difficult for the initially dissolved amino acid molecules in the electrolyte to satisfy the continuous progress of the whole battery cycle reaction.
In order to overcome the difficulty, the solubility of amino acid in organic electrolyte is not ideal, so that the carbon skeleton is taken as a carrier, the characteristic of excellent large specific surface area of the carbon skeleton is fully exerted, the amino acid is taken as an additive, the amino acid is adsorbed and loaded in structural pores of the carbon skeleton, the limitation of the solubility of the amino acid is overcome, and the fixed amino acid is gradually released into the electrolyte along with the cyclic reaction of the battery, so that the carbon skeleton can be used as a long-acting slow-release amino acid composite carbon skeleton to optimize the performance of the lithium metal cathode.
Meanwhile, the amino acid in a fixed state is adsorbed, and the lithium metal is induced to be uniformly deposited due to the lithium-philic group.
The preparation method of the amino acid sustained-release composite carbon skeleton for the lithium metal can obtain the product only by one-time adsorption treatment, has simple operation process, and simultaneously ensures the consistency of the product and the reproducibility among batches on the premise of realizing continuous large-scale production.
As shown in fig. 6, the composite carbon skeleton provided by the present invention is composed of a carbon skeleton and amino acids 3 adsorbed and fixed in pores of the carbon skeleton structure. Along with the battery circulation reaction, the amino acid in the structural pores is gradually released into the electrolyte, and the amino acid 4 released in the electrolyte plays a role in compensating for the consumption of the amino acid in the electrolyte. Meanwhile, amino acid loaded in the structural pores can be used as a lithium-philic group to induce uniform deposition of lithium metal.
Meanwhile, the slow-release amino acid is used as an additive, is gradually released and supplemented to be dissolved in the electrolyte 5, compensates the amino acid which is continuously consumed in the electrolyte along with the formation of the SEI, and is assembled into a battery to test a CV curve of the battery, wherein an obvious reduction peak is shown, so that the amino acid in the electrolyte is proved to be capable of promoting and participating in the formation of the SEI in situ and regulating and optimizing the SEI on the surface of the deposited metal lithium by taking amino and carboxyl as reaction units, and the SEI 6 formed by the participation of the amino acid further improves the electrochemical performance of the lithium metal cathode.
A preparation method of an amino acid sustained-release composite carbon skeleton for lithium metal comprises the following steps:
1) Dissolving or dispersing amino acid in an organic solvent, and performing magnetic stirring or ultrasonic treatment to obtain an organic dispersion liquid with uniformly dispersed amino acid for later use, wherein the organic solvent is one of dimethyl carbonate, dimethyl sulfoxide, dimethylacetamide and dimethylformamide, and the amino acid is one of nicotinic acid, proline, histidine, glycine or glutamic acid. The concentration of amino acid in the organic dispersion liquid is 5.2-26g/mL;
2) Putting the carbon skeleton 1 with the thickness of 50-200 mu m into the carbon skeleton 1) obtained in the step 1), and uniformly dispersingThe amino acid organic solution is statically placed, the amino acid is absorbed into a carbon skeleton through the physical adsorption effect of the carbon skeleton to obtain the amino acid slow-release composite carbon skeleton, the carbon skeleton adopts one of carbon cloth, graphite paper, carbon fiber paper or carbon nanotube paper, and the surface loading amount of the amino acid in the carbon skeleton is controlled to be 0.2-1mg/cm 2 。
And (3) aligning and stacking the obtained composite carbon skeleton and the lithium metal 2, and rolling by using a rolling mill to obtain the lithium-amino acid slow-release composite carbon skeleton lithium metal negative electrode. The lithium metal is selected from a lithium belt or a lithium sheet with the thickness of 50 mu m. The lithium tapes used in the examples were purchased from Tianjin lithium industries, inc. The rolling equipment is a combined fertilizer crystal MSK-MR100DC electric rolling machine, the gap between two pairs of rollers is adjusted between 0.02 mm and 1mm, and the pressure is 0.1 MPa to 100MPa.
The following specific examples are presented to further understand the present invention; in the examples, unless otherwise specified, all the techniques used are conventional in the art.
Example 1
The proline sustained-release carbon fiber paper for the lithium metal is prepared by the following steps:
1) Dissolving proline in dimethyl carbonate to prepare an organic dispersion liquid, and carrying out magnetic stirring or ultrasonic treatment for 2 hours to completely dissolve proline, wherein the concentration of proline is controlled to be 12g/mL, so as to obtain a uniform organic dispersion liquid for later use.
2) Placing carbon fiber paper with thickness of 50 μm into organic proline dispersion liquid, soaking for 7 hr, and controlling the surface loading amount of proline in carbon fiber paper to be 0.5mg/cm 2 And obtaining the amino acid slow-release composite carbon skeleton, namely the proline slow-release carbon fiber paper.
And (3) aligning and stacking the proline slow-release carbon fiber paper and a lithium band with the thickness of 50 mu m, rolling by using a rolling mill, and adjusting the gap between two pairs of rollers to be 0.02-1mm to obtain the lithium metal cathode of the lithium-proline slow-release composite carbon fiber paper.
Comparative example 1
The lithium tape and the carbon fiber paper of example 1 were directly stacked and rolled by a rolling mill to obtain a lithium-pure carbon paper as a battery negative electrode.
Comparative example 2
The lithium tape and the carbon fiber paper of example 1 were directly stacked, rolled by a rolling mill, and used as a battery negative electrode, and proline was directly added to the electrolyte in the same amount as in example 1.
Example 3
The negative electrode materials obtained in example 1, comparative example 1 and comparative example 2 were placed in lithium-lithium symmetric battery systems (lithium salt and concentration thereof in electrolyte: 1M LiPF), respectively 6 The organic solvent is: FEC and DMC in a volume ratio of 1; current density: 1.0mA/cm 2 (ii) a Circulation capacity: 3.0mA h/cm 2 ) And (6) testing. The lithium-proline slow-release composite carbon fiber paper lithium metal negative electrode obtained in the embodiment 1 can be stably circulated for more than 600 hours, and the charge-discharge polarization voltage of the battery is not obviously increased; while comparative example 1 lithium-pure carbon paper shows a significant increase in cell polarization after 300 hours of cycling; comparative example 2 a battery of lithium-pure carbon paper with the same amount of proline added to the electrolyte increased cycle life to only 400 hours. Thus, the lithium-proline slow-release composite carbon fiber paper lithium metal negative electrode obtained in example 1 shows a smaller polarization voltage and a longer cycle life than the lithium-pure carbon paper of comparative example 1 and the lithium-pure carbon paper of comparative example 2 in which the same amount of proline is added to the electrolyte (fig. 2). Through the comparison of the performances of the comparative example 1 and the comparative example 2, the effect of the amino acid additive on the optimization of the battery performance can be effectively proved; and the comparison of the performances of the embodiment 1 and the comparative example 2 proves the effectiveness of the proline sustained-release framework design, and the performance of the battery is further improved by ensuring that the proline is continuously dissolved in the battery.
In a lithium-ternary positive electrode battery system (lithium salt and its concentration in the electrolyte: 1M LiPF 6 The organic solvent is: FEC and DMC in a volume ratio of 1; the positive electrode surface capacity is 3.0mA h/cm 2 The current density: 1.2mA; charge cut-off voltage 4.3V, discharge cut-off voltage 3.0V), example 1, cycle capacity reached 2.5mA h cm -2 The circulation can be stabilized for 150 circles, and the capacity retention rate is over 80 percent; comparative example 1, capable of 70 cycles; in the comparative example 2,proline is directly added into the electrolyte, and the electrolyte can only circulate for 100 circles, and is the same as the electrolyte in comparative example 1 in the follow-up process, so that the electrolyte shows a rapid attenuation trend (figure 3); therefore, the lithium-proline slow-release composite carbon fiber paper lithium metal negative electrode also shows better cycle capacity and stability than the battery of the control group. The results prove that the proline introduction has a positive effect on improving the performance of the battery, and the design of the slow-release skeleton has a better effect compared with the method of directly taking proline as an electrolyte additive.
Further, a button cell is assembled by a composite lithium metal cathode prepared by pure carbon paper and the lithium metal cathode prepared by the lithium-proline slow-release composite carbon fiber paper of the invention and a stainless steel sheet respectively, a cyclic voltammetry test is carried out (a voltage interval is 3-0V, and a sweep rate is 0.5 mV/S), and the following curves can be found through comparison: in the battery with the proline loaded in the pore structure, an obvious reduction peak is shown in a range of 0-1V, and is corresponding to the fact that proline is reduced on the surface of lithium, which indicates that proline participates in the SEI formation process in the lithium battery circulation process and plays a role in optimizing the SEI of the lithium metal negative electrode (fig. 4). Cyclic voltammetry tests were carried out on the same cells at-0.4-1V, (sweep rate 0.5 mV/S), and by comparing the curves it was found that: in the battery with proline, which is obtained by the method, the polarization potential of a nucleation platform of lithium is-0.084V; while the polarization potential of the lithium nucleation platform of the proline-free cell was-0.125V. Clearly, in the cells with proline, the nucleation plateau overpotential was reduced by 41 mv, and the nucleation plateau polarization potential of lithium was lower, making nucleation of lithium more likely to occur (fig. 5).
Example 4
A nicotinic acid slow-release carbon cloth for lithium metal is prepared by the following steps:
1) Nicotinic acid is dissolved in dimethyl sulfoxide according to the concentration of 20g/mL, and hydrochloric acid is completely dissolved by magnetic stirring or ultrasonic treatment for 2.5 hours to obtain a uniform organic dispersion liquid for later use.
2) Putting a carbon cloth with the thickness of 200 mu m into organic dispersion liquid of nicotinic acid, soaking for 5 hours, and controlling the surface loading amount of the nicotinic acid in the carbon cloth to be 1mg/cm 2 And obtaining the nicotinic acid slow-release carbon cloth.
And (3) aligning and stacking the niacin sustained-release carbon cloth and a lithium belt with the thickness of 200 mu m, and rolling by using a rolling mill to obtain the lithium-niacin sustained-release composite carbon cloth lithium metal cathode.
Example 5
The negative electrode materials obtained in example 4 and comparative examples 1 and 2 were subjected to comparative tests.
In a lithium-lithium symmetric battery system (lithium salt and concentration thereof in electrolyte: 1M LiPF) 6 The organic solvent is: FEC and DMC in a volume ratio of 1; current density: 1.0mA/cm 2 (ii) a Circulation capacity: 3.0mA h/cm 2 ) In the present example, the lithium-nicotinic acid slow-release carbon cloth composite lithium metal negative electrode shows a lower polarization voltage and a longer cycle life than the battery with the comparative example 1 lithium-pure carbon paper and the comparative example 2 lithium-pure carbon paper with the same content of nicotinic acid added in the electrolyte.
In a lithium-ternary positive battery system (lithium salt and its concentration in the electrolyte: 1M LiPF 6 The organic solvent is: FEC and DMC in a volume ratio of 1; the capacity of the anode surface is 3.0mA h/cm 2 The current density: 1.2mA; charge cut-off voltage 4.3V, discharge cut-off voltage 3.0V), the lithium-nicotinic acid slow release carbon cloth composite lithium metal negative electrode of the embodiment shows better cycle capacity and stability than comparative example 1 and comparative example 2.
Example 6
A histidine sustained-release graphite paper for lithium metal is prepared by the following steps:
1) Dissolving histidine in dimethylformamide according to the concentration of 7g/mL, and completely dissolving histidine by magnetic stirring or ultrasonic treatment for 1 hour to obtain a uniform organic dispersion for later use.
2) Placing graphite paper with a thickness of 100 μm into organic dispersion of histidine, soaking for 10 hr to control the surface loading of histidine in the graphite paper to be 0.2mg/cm 2 And obtaining the histidine sustained-release graphite paper.
And (3) aligning and stacking the histidine slow-release graphite paper and a lithium band with the thickness of 100 mu m, and rolling by using a rolling mill to obtain the lithium-histidine slow-release composite graphite paper lithium metal negative electrode.
Example 7
The negative electrode materials obtained in example 6 and comparative examples 1 and 2 were subjected to comparative tests.
In a lithium-lithium symmetric battery system (lithium salt and concentration thereof in electrolyte: 1M LiPF) 6 The organic solvent is: FEC and DMC in a volume ratio of 1; current density: 1.0mA/cm 2 (ii) a Circulation capacity: 3.0mA h/cm 2 ) The lithium-histidine slow-release graphite paper composite lithium metal negative electrode of the present example exhibited a lower polarization voltage and a longer cycle life than the lithium-pure carbon paper of comparative example 1 and comparative example 2 and the lithium-pure carbon paper with the same content of histidine added to the electrolyte.
In a lithium-ternary positive electrode battery system (lithium salt and its concentration in the electrolyte: 1M LiPF 6 The organic solvent is: FEC and DMC in a volume ratio of 1; the capacity of the anode surface is 3.0mA h/cm 2 The current density: 1.2mA; the charge cut-off voltage is 4.3V, the discharge cut-off voltage is 3.0V), and the lithium-histidine slow-release graphite paper composite lithium metal negative electrode shows better cycle capacity and stability than a control group.
Example 8
A glycine slow-release carbon nanotube paper for lithium metal is prepared by the following steps:
dissolving glycine in dimethylacetamide at a concentration of 18g/mL, and treating for 1.5 hours by magnetic stirring or sonication to completely dissolve glycine, thereby obtaining a uniform organic dispersion for use.
Placing carbon nanotube paper with thickness of 50 μm into organic dispersion of glycine, soaking for 3 hr, and controlling surface loading amount of glycine in carbon nanotube to be 0.7mg/cm 2 And obtaining the glycine slow-release carbon nanotube paper.
And (3) aligning and stacking the glycine slow-release carbon nanotube paper and a lithium belt with the thickness of 50 mu m, and rolling by using a rolling mill to obtain the lithium metal cathode of the lithium-glycine slow-release composite carbon nanotube paper.
Example 9
The negative electrode materials obtained in example 8 and comparative examples 1 and 2 were subjected to comparative tests.
In a lithium-lithium symmetrical battery system (lithium salt and concentration thereof in the electrolyte solution are：1M LiPF 6 The organic solvent is: FEC and DMC in a volume ratio of 1; current density: 1.0mA/cm 2 (ii) a Circulation capacity: 3.0mA h/cm 2 ) (ii) a The lithium-glycine slow-release carbon nanotube paper composite lithium metal negative electrode shows lower polarization voltage and longer cycle life than lithium-pure carbon paper and a battery with the lithium-pure carbon paper and the same content of histidine added into electrolyte.
In a lithium-ternary positive battery system (lithium salt and its concentration in the electrolyte: 1M LiPF 6 The organic solvent is: FEC and DMC in a volume ratio of 1; the capacity of the anode surface is 3.0mA h/cm 2 The current density: 1.2mA; a charge cut-off voltage of 4.3V and a discharge cut-off voltage of 3.0V); the lithium-glycine slow-release carbon nanotube paper composite lithium metal negative electrode shows better cycle capacity and stability than a control group.

Claims (4)

1. The lithium-amino acid slow-release composite carbon skeleton lithium metal cathode is characterized in that the composite carbon skeleton takes a carbon skeleton as a slow-release skeleton and takes amino acid as an additive, and the amino acid is fixed in structural pores of the carbon skeleton; along with the progress of the battery circulation reaction, the amino acid in the structural hole is gradually released into the electrolyte to make up the consumption of the amino acid in the electrolyte; the thickness of the carbon skeleton is 50-200 μm; the surface loading of amino acid in carbon skeleton is 0.2-1mg/cm 2 (ii) a The preparation method comprises the following steps:
1) Dissolving or dispersing amino acid in an organic solvent, and obtaining an organic dispersion liquid with uniformly dispersed amino acid for later use through magnetic stirring or ultrasonic treatment;
2) Putting a carbon skeleton into the organic dispersion liquid obtained in the step 1), standing, and adsorbing amino acid into the carbon skeleton through the physical adsorption effect of the carbon skeleton to obtain an amino acid slow-release composite carbon skeleton;
3) The composite carbon skeleton and a lithium belt or a lithium sheet with the thickness of 50 mu m are aligned and stacked, and are rolled by a rolling mill to form a whole, so that the metal lithium is also filled in the holes of the rest carbon skeleton structure, and the lithium-amino acid slow-release composite carbon skeleton lithium metal cathode is prepared;
in the composite carbon skeleton, amino acid plays a dual role: the loaded amino acid is used as a lithium-philic group to induce uniform deposition of lithium metal; meanwhile, free amino acid released into the electrolyte along with the battery cycling reaction relieves the reduction of the concentration of the amino acid in the electrolyte, so that the amino acid can participate in the regulation and control and optimization of SEI on the surface of the deposited metal lithium for a long time, and the electrochemical performance of the lithium metal cathode is further optimized.
2. The lithium metal negative electrode according to claim 1, wherein the carbon skeleton is made of carbon cloth, graphite paper, carbon fiber paper or carbon nanotube paper; the amino acid is any one of nicotinic acid, proline, histidine, glycine or glutamic acid.
3. The lithium metal anode of claim 1, wherein the concentration of amino acids in the organic dispersion is 5.2-26g/mL.
4. The lithium metal negative electrode according to claim 1, wherein the organic solvent of step 1) is one of dimethyl carbonate, dimethyl sulfoxide, dimethylacetamide and dimethylformamide.
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