CN113422055B - Lithium-philic graphene quantum dot/lithium composite material and preparation method and application thereof - Google Patents
Lithium-philic graphene quantum dot/lithium composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of lithium battery electrode materials, and particularly relates to a lithium-philic graphene quantum dot/lithium composite material and a preparation method and application thereof. The lithium-philic graphene quantum dot/lithium composite material provided by the invention has a main body of graphene quantum dots, wherein the graphene quantum dots are composed of a carbon core of a graphite phase and a polymer short-chain shell rich in elements such as oxygen, nitrogen and sulfur, and show strong lithium ion affinity. The coating is coated on the surface of metal lithium, so that the problem of lithium ion depletion on the surface of a lithium metal negative electrode under large current can be solved, the deposition behavior of the metal lithium is changed, and the deposition stripping of the metal lithium is stabilized. The lithium-philic graphene quantum dot/lithium cathode is applied to a lithium-air full battery, and the lithium-air battery with greatly improved rate capability and cycle life can be obtained. The preparation process is simple, can realize the lithium metal cathode with long cycle life under large current and large capacity, and has good application prospect in the field of quick charge of high-energy density batteries.
Description
Technical Field
The invention belongs to the technical field of lithium battery electrode materials, and particularly relates to a lithium-philic graphene quantum dot/lithium composite material as well as a preparation method and application thereof.
Background
With the development of society, the demand of human resources is more and more urgent. After 30 years of development, the energy density of the lithium ion battery is close to the theoretical value (350 watt-hour/kilogram), and the development requirement is difficult to meet. The lithium metal cathode has ultrahigh theoretical specific capacity and low electrode potential, is matched with a high-surface-capacity anode (such as oxygen, sulfur, metal fluoride and the like), and can break through the energy density limit of the conventional lithium ion battery. To achieve high energy output and rapid charging of such high energy density batteries, extremely high cell densities, such as over 30 milliamps per square centimeter or 3C charge rates, are often required to achieve the goal of fully charging within 20 minutes. However, under high current density, lithium ions at the interface of the metal lithium negative electrode are quickly exhausted, so that concentration polarization in the huge battery is caused, lithium ion current is unevenly distributed, and concentrated deposition is carried out at the defect position to form dendritic crystals. The formation of dendrites can cause the rapid degradation of battery performance, even cause the internal short circuit of the battery, and further cause safety accidents such as ignition and explosion.
In order to solve the problem of dendritic growth caused by uneven lithium ion current distribution on the surface of the lithium metal negative electrode, some research reports are reported at present. On one hand, the electrode structure is designed, the specific surface area of the electrode is increased, and the lithium ion flow can be uniformly dispersed. On the other hand, the electrolyte solution is optimized, for example, the electrolyte solution with high concentration is adopted, so that concentration polarization in the battery can be reduced, and lithium is promoted to be uniformly deposited. However, these methods mainly aim at the macroscopic distribution of lithium ion concentration in the whole electrolyte, and do not focus on the distribution of lithium ion concentration at the nanoscale of the interface between the lithium metal negative electrode and the electrolyte. The problems of uneven distribution and depletion of lithium ions mainly occur at the electrolyte-electrode interface, and under high current, the depletion of lithium ions at the interface is more serious. Therefore, at present, the lithium metal negative electrode can only be cycled at a lower current density, and the demand of the next generation of high energy density batteries is difficult to meet.
Disclosure of Invention
The invention aims to provide a lithium-philic graphene quantum dot/lithium composite material capable of effectively stabilizing deposition and stripping of metal lithium, and a preparation method and application thereof.
The lithium-philic graphene quantum dot/lithium composite material provided by the invention has a core-shell structure, wherein the core part is sp2The shell is a polymer short chain rich in high electronegativity elements such as oxygen, nitrogen, sulfur and the like: the lithium-philic graphene quantum dot can adsorb lithium ions with positive charges, so that the depletion of the concentration of the lithium ions on the surface of a lithium cathode is relieved, the rapid and uniform deposition of lithium metal under a large current is promoted, the adsorption of the lithium ions can be still kept under a large capacity, and the stable deposition stripping of the lithium metal under a high capacity is realized; in addition, the ultrathin graphene quantum dot coating has high modulus, can effectively inhibit the growth of lithium dendrites, and realizes the deposition and stripping of lithium metal without dendrites.
According to the preparation method of the lithium-philic graphene quantum dot/lithium composite material, a hydrothermal method is adopted, citric acid and thiourea are used as raw materials, and a polycondensation reaction is carried out in the hydrothermal process to generate the lithium-philic graphene quantum dot; spin-coating the lithium-philic graphene quantum dot solution on the surface of lithium metal; the method comprises the following specific steps:
(1) preparing lithium-philic graphene quantum dots:
dissolving 0.1-0.3 g of citric acid and 0.2-0.7 g of thiourea in 5-15 ml of deionized water to obtain a reaction solution; pouring the reaction liquid into a hydrothermal kettle, sealing and then placing the hydrothermal kettle into an oven, and carrying out hydrothermal reaction for 4-6 hours at the temperature of 140-; after the reaction is finished, cooling the reaction solution to room temperature, adjusting the pH value to 5-6 by using 0.5-1.0 mol/L sodium hydroxide solution, dialyzing for 4-8 hours by using a 3000-plus-4000 Dalton dialysis bag with molecular weight cut-off, and freeze-drying the lithium-philic graphene quantum dots for 24-48 hours to obtain a target product lithium-philic graphene quantum dot material, wherein the target product lithium-philic graphene quantum dot material is stored in an anhydrous oxygen-free environment;
(2) preparing a lithium-philic graphene quantum dot/lithium composite material:
dissolving a lithium-philic graphene quantum dot material in a mixed solution of an organic solvent dimethyl sulfoxide and acetonitrile, wherein the volume ratio of the dimethyl sulfoxide to the acetonitrile is 3: (4-6); spin-coating the lithium-philic graphene quantum dot solution on the surface of the lithium metal at the rotation speed of 1000-2000 rpm for 60-90 seconds, and repeating the spin-coating for 1-5 times to obtain the lithium-philic graphene quantum dot/lithium composite material; wherein, the lithium-philic graphene quantum dot coating is ultrathin, and the thickness is 20-100 nanometers.
The lithium-philic graphene quantum dot/lithium composite material prepared by the method has excellent electrochemical performance and can be used as a negative electrode in a lithium ion battery.
The lithium-philic graphene quantum dot/lithium composite material prepared by the invention is used as a negative electrode for a symmetrical battery, and comprises the following specific steps:
the battery electrolyte is formed by taking lithium bistrifluoromethanesulfonimide as electrolyte salt, 1, 3-dioxolane and 1, 2-glycol dimethyl ether as electrolyte solvents and lithium nitrate as electrolyte additives; and (3) assembling the symmetrical battery by using Celgard 2400 as a diaphragm and using the lithium-philic graphene quantum dot/lithium composite material as a negative electrode. Wherein the volume ratio of the 1, 3-dioxolane to the 1, 2-glycol dimethyl ether is 1: 1; the concentration of the lithium bis (trifluoromethanesulfonyl) imide is 0.5-1.5 mol/L, and the mass concentration of the lithium nitrate is 2-5%;
standing for 6-12 hours, and performing constant current charge-discharge cycle test at a current density of 1-60 milliampere/square centimeter and a surface capacity of 1-60 milliampere-hour/square centimeter. The lithium-philic graphene quantum dot/lithium composite cathode prepared by the invention shows stable deposition/stripping cycle performance under high current and high capacity, and no dendritic crystal growth.
The lithium-philic graphene quantum dot/lithium composite material prepared by the invention is used as a negative electrode and can be used in a lithium-air battery, and the specific steps are as follows:
the preparation method comprises the steps of assembling a lithium metal composite electrode modified by lithium-philic graphene quantum dots as a negative electrode, an oriented carbon nanotube film as a positive electrode, lithium trifluoromethanesulfonate as electrolyte salt, tetraethylene glycol dimethyl ether as an electrolyte solvent, lithium iodide as an electrolyte additive and a diaphragm by adopting Woltmann glass fiber filter paper to obtain a Shiviaoke (Swagelok) lithium-air full cell. Wherein the concentration of the lithium trifluoromethanesulfonate is 0.5-1.5 mol/L.
The assembled cells were placed directly in air for testing. Electrochemical test parameters were 1000 milliamps/gram current density, 500 milliamp-hours/gram specific capacity. Due to the stabilizing effect of the lithium-philic graphene quantum dot ultrathin coating on the deposition stripping process of the metal lithium, the growth of lithium dendrites is inhibited, and the rate capability and the cycle life of the lithium-air battery are greatly improved.
Drawings
Fig. 1 is a schematic diagram of a surface deposition process of a pure lithium negative electrode and a lithium-philic graphene quantum dot/lithium composite material. Wherein, a is the deposition/stripping process of lithium on a pure lithium electrode; and b, depositing/stripping lithium on the lithium-philic graphene quantum dot/lithium composite negative electrode.
Fig. 2 is a representation of lithium-philic graphene quantum dots. Wherein, a is a transmission electron microscope image of the prepared graphene quantum dot; b, scanning electron micrographs and optical photographs of the lithium-philic graphene quantum dot/lithium composite negative electrode; c, the size distribution of the lithium-philic graphene quantum dots; and d, an infrared spectrum of the graphene quantum dots.
Fig. 3 is an electron microscope image of the lithium-philic graphene quantum dot/lithium composite negative electrode after cycling. A, growing no dendrite on the surface of the lithium-philic graphene quantum dot/lithium composite negative electrode; and b, the dendritic growth on the surface of the pure lithium electrode is serious.
Fig. 4 shows the cycle performance of the lithium-philic graphene quantum dot/lithium composite electrode. Wherein a is the cycle performance of the lithium-philic graphene quantum dot/lithium composite electrode and the pure lithium negative electrode at the current density of 20 milliampere/square centimeter and the capacity of 40 milliampere-hour/square centimeter; and b, the cycle performance of the lithium-philic graphene quantum dot/lithium composite electrode and the pure lithium negative electrode is measured under the current density of 60 milliampere/square centimeter and the capacity of 60 milliampere-hour/square centimeter.
Fig. 5 is a lithium-air battery based on a lithium-philic graphene quantum dot/lithium composite negative electrode. Wherein, a is the cycle performance of the lithium-air battery based on the lithium-philic graphene quantum dot/lithium composite negative electrode. b, rate capability of lithium-air battery based on lithium-philic graphene quantum dot/lithium composite negative electrode.
Detailed Description
Example 1
(1) Preparation of lithium-philic graphene quantum dots
Preparing lithium-philic graphene quantum dots by a hydrothermal method: dissolving 0.21 g of citric acid and 0.46 g of thiourea in 10 ml of deionized water; then pouring the reaction liquid into a hydrothermal kettle, sealing and placing the hydrothermal kettle into a vacuum oven, and reacting for 4 hours at 160 ℃; after the reaction, the reaction solution was cooled to room temperature, and the pH was adjusted to 6 with 1 mol/L sodium hydroxide solution; dialyzing with a dialysis bag with molecular weight cut-off of 3500 Dalton for 6 hours; then freeze-drying the lithium-philic graphene quantum dots for 24 hours, and storing in an anhydrous and oxygen-free environment;
(2) preparation of lithium-philic graphene quantum dot/lithium composite cathode
Dissolving lithium-philic graphene quantum dots in a mixed solution (3: 4 volume ratio) of dimethyl sulfoxide and acetonitrile, wherein the concentration is 0.5 mg/ml, spin-coating the lithium-philic graphene quantum dot solution on the surface of lithium metal at the rotating speed of 1000 revolutions per second for 60 seconds, and spin-coating for 3 times;
(3) application of lithium-philic graphene quantum dot/lithium composite cathode in symmetrical battery
Assembling a lithium-philic graphene quantum dot modified lithium metal cathode symmetrical battery by taking 1 mol/L lithium bistrifluoromethanesulfonimide as electrolyte salt, 1, 3-dioxolane and 1, 2-ethylene glycol dimethyl ether (1: 1 volume ratio) as electrolyte solvent, lithium nitrate as electrolyte additive and Celgard 2400 as a diaphragm; standing for 6 hours, and then carrying out charge-discharge cycle test at current density of 20 and 60 milliampere/square centimeter and capacity of 40 and 60 milliampere/square centimeter; as shown in fig. 4, the lithium-philic graphene quantum dot/lithium composite electrode can stably cycle for 1200 hours at a current density of 20 milliampere/square centimeter and a capacity of 40 milliampere-hour/square centimeter, while the voltage of the pure lithium electrode increases sharply after the pure lithium electrode cycles for 28 hours; under the current density of 60 milliampere/square centimeter and the capacity of 60 milliampere-hour/square centimeter, the lithium-philic graphene quantum dot/lithium composite electrode can stably cycle for 1000 hours, and a pure lithium cathode cannot normally work; the lithium-philic graphene quantum dot/lithium composite cathode prepared by the invention shows stable deposition/stripping cycle performance under high current and high capacity, and deposition/stripping behavior without dendritic crystal growth.
Example 2
(1) Preparation of lithium-philic graphene quantum dots
Preparing lithium-philic graphene quantum dots by a hydrothermal method: dissolving 0.1 g of citric acid and 0.2 g of thiourea in 5 ml of deionized water; then pouring the reaction liquid into a hydrothermal kettle, sealing and placing the hydrothermal kettle into a vacuum oven, and reacting for 4 hours at 160 ℃; after the reaction, the reaction solution was cooled to room temperature, and the pH was adjusted to 6 with 1 mol/L sodium hydroxide solution; dialyzing with a dialysis bag with molecular weight cut-off of 3500 Dalton for 6 hours; then freeze-drying the lithium-philic graphene quantum dots for 24 hours, and storing in an anhydrous and oxygen-free environment;
(2) preparation of lithium-philic graphene quantum dot/lithium composite cathode
Dissolving lithium-philic graphene quantum dots in a mixed solution (3: 4 volume ratio) of dimethyl sulfoxide and acetonitrile, wherein the concentration is 1 mg/ml, spin-coating the lithium-philic graphene quantum dot solution on the surface of lithium metal at the rotating speed of 1000 revolutions per second for 60 seconds, and spin-coating for 3 times;
(3) application of lithium-philic graphene quantum dot/lithium composite negative electrode in lithium-air battery
The lithium metal composite electrode modified by the lithium-philic graphene quantum dots is used as a negative electrode, the oriented carbon nanotube film is used as a positive electrode, 1 mol/L of lithium trifluoromethanesulfonate is used as electrolyte salt, tetraethylene glycol dimethyl ether is used as an electrolyte solvent, 0.5 mmol/L of lithium iodide is used as an electrolyte additive, a Woltmann glass fiber filter paper is adopted as a diaphragm, a Shiviaoke (Swagelok) lithium-air full cell is assembled and directly placed in the air for testing; electrochemical test parameters are 1000 milliampere/gram of current density and 500 milliampere-hour/gram of specific capacity; the result is shown in fig. 5, the lithium-air battery modified by the lithium-philic graphene quantum dots can stably circulate for 400 circles under the current density of 1000 milliampere/gram and the specific capacity of 500 milliampere-hour/gram, and the circulation is improved by 6 times; due to the stabilizing effect of the lithium-philic graphene quantum dot ultrathin coating on the deposition stripping process of the metal lithium, the growth of lithium dendrites is inhibited, and the cycle life of the lithium-air battery is greatly prolonged.
Claims (5)
1. A preparation method of a lithium-philic graphene quantum dot/lithium composite material is characterized in that citric acid and thiourea are used as raw materials, and a polycondensation reaction is carried out in a hydrothermal process to generate the lithium-philic graphene quantum dot; spin-coating the lithium-philic graphene quantum dot solution on the surface of lithium metal; the method comprises the following specific steps:
(1) preparing lithium-philic graphene quantum dots:
dissolving 0.1-0.3 g of citric acid and 0.2-0.7 g of thiourea in 5-15 ml of deionized water to obtain a reaction solution; pouring the reaction liquid into a hydrothermal kettle, sealing and then placing the hydrothermal kettle into an oven, and carrying out hydrothermal reaction for 4-6 hours at the temperature of 140-; after the reaction is finished, cooling the reaction solution to room temperature, adjusting the pH value to 5-6 by using 0.5-1.0 mol/L sodium hydroxide solution, dialyzing for 4-8 hours by using a 3000-plus-4000 Dalton dialysis bag with molecular weight cut-off, and freeze-drying the lithium-philic graphene quantum dots for 24-48 hours to obtain a target product lithium-philic graphene quantum dot material;
(2) preparing a lithium-philic graphene quantum dot/lithium composite material:
dissolving a lithium-philic graphene quantum dot material in a mixed solution of an organic solvent dimethyl sulfoxide and acetonitrile, wherein the volume ratio of the dimethyl sulfoxide to the acetonitrile is 3 (4-6); spin-coating the lithium-philic graphene quantum dot solution on the surface of the lithium metal at the rotation speed of 1000-2000 rpm for 60-90 seconds, and repeating the spin-coating for 1-5 times to obtain the lithium-philic graphene quantum dot/lithium composite material; wherein the thickness of the lithium-philic graphene quantum dot coating is 20-100 nanometers.
2. The lithium-philic graphene quantum dot/lithium composite material prepared by the preparation method of claim 1, wherein the graphene quantum dot has a core-shell structure, and the core part is sp2A graphite crystal phase consisting of hybridized carbon, and a shell part is a polymer short chain rich in oxygen, nitrogen and sulfur high electronegativity elements: the graphene quantum dot has high lithium ion affinity and can adsorb lithium ions, so that lithium on the surface of a lithium metal negative electrode is improvedThe problem of ion concentration depletion is solved, and the uniform and rapid deposition of the metal lithium is promoted; in addition, the lithium-philic graphene quantum dot ultrathin coating has high mechanical modulus and can effectively inhibit the growth of lithium dendrites.
3. The lithium-philic graphene quantum dot/lithium composite material as claimed in claim 2, which is used as a negative electrode material of a lithium ion battery.
4. The use according to claim 3, in a symmetrical battery, comprising the following steps:
the battery electrolyte is formed by taking lithium bistrifluoromethanesulfonimide as electrolyte salt, 1, 3-dioxolane and 1, 2-glycol dimethyl ether as electrolyte solvents and lithium nitrate as electrolyte additives; the method comprises the following steps of (1) assembling a symmetrical battery by taking Celgard 2400 as a diaphragm and taking a lithium-philic graphene quantum dot/lithium composite material as a negative electrode; wherein the volume ratio of the 1, 3-dioxolane to the 1, 2-glycol dimethyl ether is 1 (1-2); the concentration of the lithium bis (trifluoromethanesulfonyl) imide is 0.5-1.5 mol/L, and the mass concentration of the lithium nitrate is 2-5%.
5. The use according to claim 3, in a lithium-air battery, comprising the following steps:
assembling a diaphragm by using Woltmann glass fiber filter paper to obtain a Shiviaoke lithium-air full battery by using a lithium-philic graphene quantum dot/lithium composite material as a negative electrode, an oriented carbon nanotube film as a positive electrode, lithium trifluoromethanesulfonate as an electrolyte, tetraethylene glycol dimethyl ether as an electrolyte solvent and lithium iodide as an electrolyte additive; wherein the concentration of the lithium trifluoromethanesulfonate is 0.5-1.5 mol/L.
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