CN114141992A - Self-propagating alloyed lithium negative electrode and preparation method thereof - Google Patents
Self-propagating alloyed lithium negative electrode and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a self-propagating alloyed lithium negative electrode and a preparation method thereof, wherein the preparation method comprises the following steps: (1) taking a three-dimensional framework material as a host material, and soaking and grafting the three-dimensional framework material in an acid-base solution to obtain an oxygen-containing functional group; (2) drying the soaked three-dimensional framework to obtain a three-dimensional framework material containing lithium-philic sites; (3) and (3) extending one end of the three-dimensional framework material obtained in the step (2) into molten metal lithium liquid to carry out self-propagating technical alloying, so as to obtain the lithium cathode material. The cathode material can effectively solve the problems of cycling stability and safety of the lithium cathode. Meanwhile, the three-dimensional material has good mechanical properties as a framework material, and the structural stability of the cathode is improved in the process of battery equipment or charging and discharging.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a self-propagating alloyed lithium negative electrode and a preparation method thereof.
Background
In recent years, the demand of power batteries in terms of energy density and safety has been increasedThe lithium ion battery is gradually expanded, becomes a research hotspot of researchers and enterprise and public institutions, and particularly, a great deal of research is carried out on the lithium ion battery with high energy density. Most of the currently commercialized lithium secondary battery negative electrodes are selected from graphite electrodes, but the improvement of energy density thereof is almost close to the theoretical threshold, and significant progress is difficult to achieve. The metallic lithium negative electrode has extremely high theoretical specific capacity (3860mAh g)-1) And a negative potential (-3.040V vs standard hydrogen electrode), which is an electrode material with great potential in the negative electrode material. However, there still exist a number of problems in the whole battery system, including (i) non-uniformity of lithium ions during electrochemical deposition, resulting in growth of lithium dendrites, and volume expansion, which affects safety of the whole battery system; (II) the high reactivity of the metallic lithium reacts with the electrolyte to generate an unstable solid electrolyte interface film (SEI layer), which leads to the generation of "dead lithium" and the degradation of the electrolyte that affects the battery capacity and cycle stability; and (III) the storage environment of the lithium metal and the water-oxygen content of the battery equipment environment have high requirements, so that the water-oxygen content of the whole process needs to be strictly controlled to ensure that the lithium metal is not oxidized, and the cost of the battery is increased invisibly under the condition of battery assembly environment and material storage and transportation.
In order to solve the series of problems, researchers have conducted extensive research to modify lithium metal anode materials from various aspects to achieve certain improvements, including: the method comprises the steps of lithium alloying treatment, electrolyte additive regulation and control, solid electrolyte membrane adoption, current collector modification, protective film coating on the surface of metal lithium and the like. To date, no way has been found to overcome the above problems. Patent CN201910329991.0 provides a three-dimensional composite metal lithium negative electrode and a preparation method thereof, a lithium metal battery, and a lithium sulfur battery. The electric conductor with the three-dimensional porous structure can be any one of foamy copper, three-dimensional porous copper-zinc alloy and three-dimensional porous copper-silver alloy, and is immersed in metal lithium liquid with the temperature of 310-900 ℃, the infiltration time and temperature are controlled, then the electric conductor is taken out and cooled to obtain the three-dimensional composite metal lithium cathode, the generation of lithium dendrite and the change of volume caused in the battery circulation process are inhibited, and the commercial application of the metal lithium cathode is facilitated. Patent CN109167029A proposes a silicon nitride modified metal lithium negative electrode material of a lithium-sulfur battery and a preparation method thereof, in which, after ethyl orthosilicate is hydrolyzed, high-temperature nitridation is performed to obtain silicon nitride nanowires, and metal lithium is loaded inside the silicon nitride nanowires through carbothermic reduction, and the prepared metal lithium negative electrode material is formed by stacking the silicon nitride nanowires on the surface of a lithium metal phase to form a three-dimensional net-shaped coating layer, so that irreversible loss of lithium metal and damage to a diaphragm are reduced.
Disclosure of Invention
In order to solve the technical problems, the invention provides a self-propagating alloyed lithium negative electrode and a preparation method thereof. The host material is alloyed in situ by adopting a self-propagating alloying technology, so that the lithium composite cathode with uniformly distributed phases is formed. The three-dimensional framework material is used as a host material, and the lithium-philic element and the lithium-philic site are introduced through soaking or heating treatment. The material is beneficial to relieving the volume expansion effect caused in the electrochemical process; but also can reduce the local current density and homogenize the lithium ion transmission, thereby inhibiting the growth of lithium dendrite. The alloying negative electrode material can effectively solve the problems of the cycling stability and the safety of the lithium negative electrode. Meanwhile, the three-dimensional material has good mechanical properties as a framework material, and the structural stability of the cathode is improved in the process of battery equipment or charging and discharging.
In order to achieve the technical effects, the invention adopts the following technical scheme:
a method for preparing a self-propagating alloyed lithium negative electrode, comprising the following steps: (1) taking a three-dimensional framework material as a host material, and soaking and grafting the three-dimensional framework material in an acid-base solution to obtain an oxygen-containing functional group; then soaking in a metal salt solution; (2) drying the soaked three-dimensional framework to obtain a three-dimensional framework material containing lithium-philic sites; (3) and (3) extending one end of the three-dimensional framework material obtained in the step (2) into molten metal lithium liquid to carry out self-propagating technical alloying to obtain the lithium cathode material, wherein the self-propagating time is 5-120 s.
The acid-base solution can clean and corrode the three-dimensional framework material to form holes, aims to perform hole forming and oxygen-containing functional group grafting on the three-dimensional framework material, has lithium-philic sites, is immersed into salts of Ag, Al, Zn and the like to adsorb a certain content of Ag, Al and Zn, and the metal lithium has strong lithium-philic property and is beneficial to inducing lithium deposition.
The longer the self-propagating time is, the higher the lithiation degree of the metal is, but according to the matching of the positive and negative electrode capacities, the positive and negative electrode capacity ratio (N: P is 1:1) is only required to be achieved, and if the metal is soaked in the metal lithium liquid for a long time and self-propagates, the structural stability of the material is influenced.
The method is characterized in that the three-dimensional framework material is one or more selected from binary alloy framework materials, metal lithium organic framework compound materials and modified conductive carbon fiber materials, when the three-dimensional framework is the modified conductive carbon fiber materials, the step (1) further comprises soaking in metal salt solution, wherein the salt solution is one or more selected from silver nitrate solution and metal halide solution, and the metal salt solution is one or more selected from silver nitrate solution and metal halide solution.
The further technical proposal is that the modified conductive carbon fiber material is soaked in a metal salt solution for 3 to 24 hours at the temperature of between 25 and 60 ℃.
The further technical scheme is that the binary alloy framework material is selected from one or more of Mg-Al, Al-Zn, Cu-Al, Cu-Zn and Mg-Zn, and the binary alloy framework material is subjected to dealloying through acid treatment to obtain the porous three-dimensional framework material.
Further, the specific preparation method of the binary alloy framework material comprises the steps of adding two metals of Mg, Al, Zn and Cu into an alloy smelting furnace in an argon or other inert atmosphere, and heating and stirring for 4 hours in the smelting furnace at the temperature of 600-1200 ℃, wherein the mass ratio is 5: 5; 6: 4; 7: 3; or 8: 2. Slowly cooling to the phase transition temperature, pouring into a customized square die, and quickly cooling to below 150 ℃ to form an alloy plate; and rolling the alloy plate to obtain the binary alloy framework material.
The further technical scheme is that the metal lithium organic framework compound material is selected from one or more of MOFs, COFs and Mxene.
The further technical scheme is that the modified conductive carbon fiber material is obtained by a biaxial electrostatic spinning method, wherein the spinning conditions are as follows: spinning temperature is 20-50 deg.C, spinning voltage is 10-40kV, advancing speed is 1-10 μ L/min, spinning distance is 1-20cm, and water content is controlled below 0.1-10 ppm.
Further, the preparation method of the modified conductive carbon fiber material specifically comprises the steps of using PS-polystyrene, PAN-polyacrylonitrile and Zn (Ac)2Dissolving in N, N-Dimethylformamide (DMF) solvent, and electrospinning to obtain fibrous material.
The further technical scheme is that the acid-base solution is selected from potassium hydroxide solution, sodium hydroxide solution, hydrochloric acid solution, potassium permanganate solution, dilute sulfuric acid and phosphoric acid solution.
The further technical proposal is that the metal halide is ZnCl2、ZnF2、AlCl3Or AlF3。
The further technical proposal is that the soaking time is 1-12h and the temperature is 25-60 ℃.
The further technical proposal is that the temperature of the drying treatment is 60-120 ℃ and the time is 2-6 h.
The invention also provides the self-propagating alloyed lithium negative electrode prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects: the invention uses self-propagating alloying technology to carry out in-situ alloying on the host material, thereby forming the lithium composite cathode with uniformly distributed phases. The three-dimensional framework material is used as a host material, and the lithium-philic element and the lithium-philic site are introduced through soaking or heating treatment. The material is beneficial to relieving the volume expansion effect caused in the electrochemical process; but also can reduce the local current density and homogenize the lithium ion transmission, thereby inhibiting the growth of lithium dendrite. The alloying negative electrode material can effectively solve the problems of the cycling stability and the safety of the lithium negative electrode. Meanwhile, the three-dimensional material has good mechanical properties as a framework material, and the structural stability of the cathode is improved in the process of battery equipment or charging and discharging. In addition, the content of metal lithium in the negative electrode is reduced, the lithium accommodating capacity of the negative electrode is improved, and the energy density of the whole battery system can be effectively improved.
Drawings
FIG. 1 is a graph comparing electrochemical cycle performance of examples and comparative examples.
Detailed Description
Comparative example 1
Pure copper is adopted as a negative electrode material, and LiNi is adopted0.8Co0.1Mn0.1O2The positive plate is assembled into a 2032 button cell by adopting EC: DEC: DMC ═ 1:1:1 as electrolyte, and then electrochemical performance test is carried out. The test data are shown in figure 1.
Comparative example No. two
Graphite is used as a negative electrode material and LiNi is used0.8Co0.1Mn0.1O2The positive plate is assembled into a 2032 button cell by adopting EC: DEC: DMC ═ 1:1:1 as electrolyte, and then electrochemical performance test is carried out.
Example one
Selecting Mg-Al alloy material, soaking in dilute hydrochloric acid for 4h, heating at 80 deg.C, soaking in 60 deg.C 0.5M KOH solution for 5h, and drying at 80 deg.C. Alloying the obtained three-dimensional material with molten metal lithium liquid, and controlling the infiltration amount of the metal lithium through self-propagating time. Finally, rolling to obtain a cathode material with a smooth surface, punching to obtain a cathode wafer, and mixing with LiNi0.8Co0.1Mn0.1O2And (3) matching the positive plates, assembling a 2032 button cell by adopting EC: DEC: DMC ═ 1:1:1 as electrolyte, and then carrying out electrochemical performance test.
Example two
Selecting a Cu-Zn alloy material, soaking the Cu-Zn alloy material in dilute hydrochloric acid for 4 hours, then carrying out heating treatment at 80 ℃, soaking the Cu-Zn alloy material in a 0.5M KOH solution at 60 ℃ for 5 hours, and drying the Cu-Zn alloy material at 80 ℃. Alloying the obtained three-dimensional material with molten metal lithium liquid, and controlling the infiltration amount of the metal lithium through self-propagating time. Finally, rolling to obtain a cathode material with a smooth surface, punching to obtain a cathode wafer, and mixing with LiNi0.8Co0.1Mn0.1O2And (3) matching the positive plates, assembling a 2032 button cell by adopting EC: DEC: DMC ═ 1:1:1 as electrolyte, and then carrying out electrochemical performance test.
EXAMPLE III
ZIF-8 in MOFs materials is selected for research, the MOFs materials are placed into dilute sulfuric acid to be soaked for 2 hours, then heating treatment is carried out at 80 ℃, the obtained three-dimensional materials are alloyed with molten metal lithium liquid, and the infiltration amount of the metal lithium is controlled through self-propagating time. Finally, rolling to obtain a cathode material with a smooth surface, punching to obtain a cathode wafer, and mixing with LiNi0.8Co0.1Mn0.1O2And (3) matching the positive plates, assembling a 2032 button cell by adopting EC: DEC: DMC ═ 1:1:1 as electrolyte, and then carrying out electrochemical performance test.
Example four
Selecting three-dimensional conductive carbon fiber obtained by electrostatic spinning, firstly soaking the three-dimensional conductive carbon fiber in a mixed solution of nitric acid and sulfuric acid for 6 hours, then cleaning the three-dimensional conductive carbon fiber with deionized water to be neutral, and then AgNO3Soaking in the solution for 6h, and drying by heating at 60 deg.C. Alloying the obtained three-dimensional material with molten metal lithium liquid, and controlling the infiltration amount of the metal lithium through self-propagating time. Finally, rolling to obtain a cathode material with a smooth surface, punching to obtain a cathode wafer, and mixing with LiNi0.8Co0.1Mn0.1O2And (3) matching the positive plates, assembling a 2032 button cell by adopting EC: DEC: DMC ═ 1:1:1 as electrolyte, and then carrying out electrochemical performance test.
The performance test data of the comparative example and the example are shown in table 1, wherein the test data are tested in an environment at 25 ℃, the charge and discharge multiplying power is 0.5C, and the charge and discharge voltage interval is 3-4.3V.
TABLE 1
| Sample (I) | Number of cycles (circle) | Multiplying factor of charge and discharge | Capacity retention (%) |
| Comparative example 1 | 100 | 0.5C | 31.06％ |
| Comparative example No. two | 100 | 0.5C | 70.80％ |
| Example one | 100 | 0.5C | 85.90％ |
| Example two | 100 | 0.5C | 82％ |
| EXAMPLE III | 100 | 0.5C | 78.60％ |
| Example four | 100 | 0.5C | 90.50％ |
From the electrochemical cycle performance diagram of fig. 1, it can be clearly seen that the modified sample shows a significant improvement in electrochemical cycle performance, and the capacity retention rate of the example four is as high as 90.5% after being cycled for 100 times at 0.1C charge-discharge rate, whereas the capacity retention rate of the battery system assembled by the comparative example-copper negative electrode is 31.06% after being cycled for only 100 times, which is mainly attributed to the following two points: (1) lithium ion active sites on the surface of the pure copper negative electrode cannot be uniformly distributed, and due to the fact that excessive local current density on the surface causes rapid growth of lithium dendrites and continuous generation of dead lithium, active lithium of the whole battery system is gradually reduced, and capacity is declined; (2) a lithium ion deposition space is provided in the three-dimensional alloying framework material, and meanwhile, uniformly distributed lithium-philic sites can induce the uniform deposition of lithium ions, but do not deposit on the surface of a negative electrode to react with electrolyte to form dead lithium, so that the stability of the lithium ion active material is maintained in the circulation process, and the loss of active lithium is reduced.
Although the present invention has been described herein with reference to the illustrated embodiments thereof, which are intended to be preferred embodiments of the present invention, it is to be understood that the invention is not limited thereto, and that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this disclosure.
Claims (10)
1. A preparation method of a self-propagating alloyed lithium negative electrode is characterized by comprising the following steps: (1) taking a three-dimensional framework material as a host material, and soaking and grafting the three-dimensional framework material in an acid-base solution to obtain an oxygen-containing functional group; (2) drying the soaked three-dimensional framework to obtain a three-dimensional framework material containing lithium-philic sites; (3) and (3) extending one end of the three-dimensional framework material obtained in the step (2) into molten metal lithium liquid to carry out self-propagating technical alloying to obtain the lithium cathode material, wherein the self-propagating time is 5-120 s.
2. The method for preparing the self-propagating alloyed lithium negative electrode according to claim 1, wherein the three-dimensional framework material is selected from one or more of a binary alloy framework material, a metallic lithium organic framework compound material and a modified conductive carbon fiber material, and when the three-dimensional framework is the modified conductive carbon fiber material, the step (1) further comprises soaking in a metal salt solution selected from one or more of a silver nitrate solution and a metal halide solution.
3. The method for preparing a self-propagating alloyed lithium negative electrode according to claim 2, wherein the binary alloy framework material is selected from one or more of Mg-Al, Al-Zn, Cu-Al, Cu-Zn and Mg-Zn, and the binary alloy framework material is subjected to dealloying by acid treatment to obtain a porous three-dimensional framework material.
4. The method for preparing a self-propagating alloyed lithium anode according to claim 2, characterized in that the metallic lithium organic framework compound material is selected from one or more of the group consisting of MOFs, COFs, Mxene.
5. The method for preparing a self-propagating alloyed lithium negative electrode according to claim 2, characterized in that the modified conductive carbon fiber material is obtained by a biaxial electrospinning method, wherein the spinning conditions are as follows: spinning temperature is 20-50 deg.C, spinning voltage is 10-40kV, advancing speed is 1-10 μ L/min, spinning distance is 1-20cm, and water content is controlled below 0.1-10 ppm.
6. The method for preparing the self-propagating alloyed lithium negative electrode according to claim 1, wherein the acid-base solution is selected from one or more of potassium hydroxide solution, sodium hydroxide solution, hydrochloric acid solution, potassium permanganate solution, dilute sulfuric acid and phosphoric acid solution.
7. Method for the preparation of a self-propagating alloyed lithium anode according to claim 2, characterized in that the metal halide is ZnCl2、ZnF2、AlCl3Or AlF3。
8. The method for preparing a self-propagating alloyed lithium negative electrode as claimed in claim 1, wherein the soaking time is 1-12h and the temperature is 25-60 ℃.
9. The method for preparing a self-propagating alloyed lithium negative electrode as claimed in claim 1, wherein the temperature of the drying treatment is 60 ℃ to 120 ℃ and the time is 2 to 6 hours.
10. A self-propagating alloyed lithium negative electrode, characterized in that it is produced by the production method according to any one of claims 1 to 9.
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