CN113871585B - Preparation method of composite three-dimensional metal lithium negative electrode for inhibiting growth of lithium dendrite - Google Patents
Preparation method of composite three-dimensional metal lithium negative electrode for inhibiting growth of lithium dendrite Download PDFInfo
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention relates to a preparation method of a composite three-dimensional metal lithium anode for inhibiting growth of lithium dendrites, which comprises the following steps: 1) Preparing a nano porous metal foil; 2) Preparing a three-dimensional porous copper foil; 3) Preparing a three-dimensional porous copper/copper sulfide composite foil: heating the three-dimensional porous copper prepared in the previous step to 100-300 ℃ in air, and preserving heat for 1-2h; cooling to room temperature, and then placing the three-dimensional porous copper into 1-3mol/L sodium sulfide aqueous solution for soaking for 1-2h; putting the impregnated three-dimensional porous copper into a hydrothermal reaction kettle containing sodium sulfide aqueous solution, and carrying out hydrothermal reaction at 90-120 ℃ for 12-24 hours; then taking out, cooling, cleaning and drying to obtain a three-dimensional porous copper/copper sulfide foil; 4) Preparing the three-dimensional porous copper/lithium sulfide/lithium metal composite lithium metal cathode.
Description
Technical Field
The invention belongs to the field of electrode materials of lithium metal secondary batteries, and particularly relates to a preparation method of a composite three-dimensional metal lithium negative electrode capable of effectively inhibiting growth of lithium dendrites.
Background
With the massive use of new energy, higher requirements are put on the performance of energy storage devices, however, the traditional lithium ion batteries cannot meet the increasing energy storage requirements. In recent years, li-S and Li-air batteries have received great attention for their higher energy density than existing lithium ion battery systems. Wherein the metallic lithium as the negative electrode has a high theoretical specific capacity (3860 mAh/g), a low standard potential (-3.04V), a low density (0.53 g/cm) 3 ) Advantages, etc., make it the most suitable material for secondary battery negative electrodeOne of them. However, uneven deposition of metallic lithium as a negative electrode material during charge and discharge may cause generation of lithium dendrites, which may fall off from an electrode pad and cannot be used in a subsequent charge and discharge process, resulting in a decrease in battery capacity; if lithium dendrites continue to grow, they may puncture the battery separator, causing a short circuit in the battery, which may cause explosion or fire; the growth of lithium dendrites also makes it difficult to form a stable Solid Electrolyte Interface (SEI) film on the surface of a battery, thereby accelerating consumption of lithium metal, resulting in low coulombic efficiency and rapid capacity fade. In the charge-discharge cycle process, the infinite volume change in the lithium metal deposition desorption process can cause the change of internal stress of the battery, and potential safety hazards are provided.
In view of the above problems, three-dimensional composite lithium metal anodes have received extensive attention. On one hand, the three-dimensional structure can effectively increase the specific surface area of the electrode, so that the effective current density of the electrode is reduced to inhibit the generation of lithium dendrite; on the other hand, the porous structure can limit the growth of lithium dendrites while storing metallic lithium; the three-dimensional framework of the three-dimensional composite metal lithium cathode can limit the volume change in the charge-discharge cycle process of the metal lithium, and reduce the change of internal stress of the battery.
Disclosure of Invention
The invention aims to provide the three-dimensional porous copper/lithium sulfide/lithium metal composite lithium metal negative electrode capable of inhibiting the generation of lithium dendrites, and the preparation method of the lithium metal composite negative electrode is simple in technical process and low in cost, and can effectively inhibit the growth of lithium dendrites in the charge and discharge processes. The technical proposal is as follows:
a preparation method of a composite three-dimensional metal lithium anode for inhibiting growth of lithium dendrites comprises the following steps:
1) Preparation of nanoporous metal foils
Preparing a Cu-Mn alloy foil, wherein the atomic percentage of Cu is 25% -40% and the atomic percentage of Mn is 60% -75%; and (3) placing the Cu-Mn alloy foil in a hydrochloric acid solution, performing dealloying through the reaction of hydrochloric acid and manganese, and cleaning and drying to obtain the nano porous metal foil.
2) Preparation of three-dimensional porous copper foil
Placing the nano porous copper foil prepared in the previous step in inert gas and hydrogen atmosphere, heating to 800-1000 ℃, calcining for 0.5-5min at the temperature, and cooling with a furnace to obtain the three-dimensional porous copper with the pore size of 100nm-1 mu m;
3) Preparation of three-dimensional porous copper/copper sulfide composite foil
Heating the three-dimensional porous copper prepared in the previous step to 100-300 ℃ in air, and preserving heat for 1-2h; cooling to room temperature, and then placing the three-dimensional porous copper into 1-3mol/L sodium sulfide aqueous solution for soaking for 1-2h; putting the impregnated three-dimensional porous copper into a hydrothermal reaction kettle containing sodium sulfide aqueous solution, and carrying out hydrothermal reaction at 90-120 ℃ for 12-24 hours; then taking out, cooling, cleaning and drying to obtain a three-dimensional porous copper/copper sulfide foil;
4) Preparation of three-dimensional porous copper/lithium sulfide/lithium metal composite lithium metal cathode
Transferring the three-dimensional porous copper/copper sulfide foil prepared in the step 3) into a glove box; placing and heating the metal lithium to 200-300 ℃ to obtain molten metal lithium; and (3) placing a part of the three-dimensional porous copper/copper sulfide foil into molten metal lithium, obtaining lithium sulfide through in-situ reaction of the metal lithium and copper sulfide, and enabling the molten lithium to flow into the three-dimensional porous structure along a three-dimensional communicated copper/copper sulfide framework under the action of capillary force, so as to finally prepare the three-dimensional porous copper/lithium sulfide/metal lithium composite metal lithium cathode.
Preferably, in step 1), the corrosion is accelerated by heating in a water bath at 30-50 ℃ for 1-3 hours, and dealloying is performed by reacting hydrochloric acid with manganese.
Compared with the prior art, the invention has the following advantages:
(1) Lithium sulfide is generated by in situ growth of copper sulfide within a three-dimensional porous copper skeleton and in situ reaction of copper sulfide with molten metallic lithium. On the one hand, molten metallic lithium can be poured into the three-dimensional porous framework through in-situ reaction; on the other hand, the lithium sulfide has higher ionic conductivity, which is beneficial to improving the stability of SEI film of the metal lithium cathode.
(2) The three-dimensional porous copper/lithium sulfide/lithium metal composite lithium metal negative electrode obtained by the method has a continuous through three-dimensional pore structure, and improves the lithium ion transmission speed in the electrolyte, so that the three-dimensional porous copper/lithium sulfide/lithium metal composite lithium metal negative electrode has smaller voltage hysteresis in the circulation process; the three-dimensional porous structure can slow down the volume change of the metal lithium negative electrode in the charge and discharge process, and the metal lithium negative electrode with stable volume can be obtained; the three-dimensional porous structure increases the specific surface area of the electrode, and reduces the effective current density of the electrode, thereby inhibiting the generation of lithium dendrites.
Drawings
FIG. 1 is an SEM image of three-dimensional porous copper obtained in example 1 of the present invention;
FIG. 2 is an SEM image of three-dimensional porous copper/copper sulfide prepared in example 1 of the invention;
FIG. 3 is a photograph of three-dimensional porous copper/lithium sulfide/lithium metal prepared in example 1 of the present invention;
FIG. 4 is an SEM image of a three-dimensional porous copper/lithium sulfide/lithium metal prepared according to example 1 of the present invention;
fig. 5 is an XRD pattern after the three-dimensional porous copper/lithium sulfide/lithium metal electrode prepared in example 1 of the present invention was charged to 0.3V.
FIG. 6 is a constant current test result of a symmetrical battery in which three-dimensional porous copper/lithium sulfide/lithium metal electrode and lithium sheet electrode were assembled respectively, obtained in example 1, in which the circulating current density was 2mA/cm 2 The circulation capacity is 2mAh/cm 2 。
Fig. 7 shows the cycling performance of the full cell after matching the three-dimensional porous copper/lithium sulfide/lithium metal lithium electrode and lithium iron phosphate positive electrode material prepared in example 1.
The invention is applicable to the prior art where it is not described.
Detailed Description
The technical scheme of the invention is as follows:
the preparation method of the three-dimensional porous copper/lithium sulfide/lithium metal composite negative electrode adopts the following processes:
1) Preparation of nanoporous metal foils
And (3) putting Cu and Mn metals into a vacuum smelting furnace to prepare Cu-Mn alloy (the atomic percentage is 25-40% of Cu and 60-75% of Mn), and repeatedly rolling, annealing and rolling to obtain the Cu-Mn alloy foil with the thickness of 70-120 mu m. Then cutting Cu-Mn alloy foil with proper size, placing in 0.025-0.1mol/L hydrochloric acid solution, performing dealloying by hydrochloric acid and manganese reaction, heating in water bath at 30-50 ℃ to accelerate corrosion, and the corrosion time is 1-3h. The prepared nano porous metal foil is firstly washed by deionized water, then washed by absolute ethyl alcohol, and then dried in vacuum for 3-24 hours at room temperature for standby.
2) Preparation of three-dimensional porous copper foil
And (3) putting the nano porous copper prepared in the previous step into a quartz boat, putting the quartz boat into a reaction tube furnace close to a tube orifice area, and introducing argon and hydrogen, wherein the ratio of the argon to the hydrogen is configured according to the flow of 500:200. The furnace temperature was then raised to 800-1000 ℃. After the furnace temperature is raised to the specified temperature, the quartz boat is quickly moved to a constant temperature area in the middle of the reaction tube, and calcined for 0.5-5min at the temperature. And then the quartz boat is quickly moved from a constant temperature area in the middle of the reaction tube to a tube orifice area, a furnace cover is opened, a sample is cooled to room temperature under the atmosphere of argon, and then the sample is taken out of the tube furnace, so that the three-dimensional porous copper foil with the aperture of 100nm-1 mu m can be obtained.
3) Preparation of three-dimensional porous copper/copper sulfide composite foil
Heating the porous copper foil prepared in the previous step to 100-300 ℃ in air, and preserving heat for 1-2h. After cooling to room temperature, the porous copper is placed into 1-3mol/L sodium sulfide aqueous solution for soaking for 1-2h. Then 50-75mL of sodium sulfide aqueous solution is poured into a hydrothermal reaction kettle with the capacity of 100mL, the impregnated porous copper is put into the reaction kettle, the reaction kettle is placed into a blast oven, and the hydrothermal reaction is carried out at the temperature of 90-120 ℃ for 12-24h. And then taking out the hydrothermal kettle, cooling to room temperature to obtain a three-dimensional porous copper/copper sulfide foil, taking out the prepared three-dimensional porous copper/copper sulfide foil, cleaning with deionized water, and cleaning with absolute ethyl alcohol. And drying the cleaned three-dimensional porous copper/copper sulfide foil in a vacuum oven at 60 ℃ for standby.
4) Preparation of three-dimensional porous copper/lithium sulfide/lithium metal composite lithium metal cathode
Transferring the three-dimensional porous copper/copper sulfide prepared in the step 3 into a glove box. The metallic lithium is placed in a stainless steel crucible in a glove box, and heated to 200-300 ℃ to obtain the metallic lithium in a molten state. And placing one edge of the three-dimensional porous copper/copper sulfide foil into molten metal lithium, obtaining lithium sulfide through in-situ reaction of the metal lithium and copper sulfide, and enabling the molten lithium to flow into the three-dimensional porous structure along the three-dimensional communicated copper/copper sulfide framework under the action of capillary force, so as to finally prepare the three-dimensional porous copper/lithium sulfide/metal lithium composite metal lithium cathode.
Specific examples of the preparation method of the present invention are given below. These examples are provided only for the detailed description of the preparation method of the present invention and do not limit the scope of the claims of the present application.
Example 1
(1) Preparing nano porous copper. Cu with thickness of 100 μm is selected 30 Mn 70 Alloy foil and cut it to a size of 1 x 1 cm. Then immersing the alloy foil into 0.05mol/L hydrochloric acid solution, performing dealloying for 2 hours in a water bath at 30 ℃, cleaning the foil by deionized water and alcohol in sequence after finishing, and then placing the foil into a vacuum drying oven for drying for 4 hours to obtain the nano-porous copper.
(2) Preparing three-dimensional porous copper. Putting nano porous copper into a quartz ark, putting the ark into a reaction tube furnace close to a tube orifice, and introducing argon and hydrogen, wherein the gas ratio is Ar to H 2 =500:200 sccm. The temperature of the tube furnace is raised to 900 ℃, and when the furnace temperature reaches 900 ℃, the quartz ark is quickly moved from the tube orifice area to the constant temperature area in the middle of the reaction tube, and the reaction is carried out for 5 minutes at the temperature. Then the quartz boat is quickly moved from the constant temperature area in the middle of the reaction tube to the tube orifice area, hydrogen is closed, the sample is cooled to room temperature under the atmosphere of argon, and then the sample is taken out. The three-dimensional porous copper has a three-dimensional through hole structure, and the pore diameter of the three-dimensional through hole structure is about 1 mu m.
(3) Preparation of three-dimensional copper/copper sulfide. Heating the three-dimensional porous copper prepared in the previous step to 150 ℃ in air, and preserving heat for 1h. 3mol/L sodium sulfide solution is prepared, and three-dimensional porous copper cooled to room temperature is immersed in the sodium sulfide solution for 1h. 60mL of sodium sulfide aqueous solution is poured into a hydrothermal reaction kettle with the capacity of 100mL, the impregnated porous copper is put into the reaction kettle, the reaction kettle is placed into a blast oven, and the hydrothermal reaction is carried out at the temperature of 90 ℃ for 12h. And then taking out the hydrothermal kettle, cooling to room temperature, taking out the three-dimensional porous copper/copper sulfide, cleaning the prepared three-dimensional porous copper/copper sulfide with deionized water, and then cleaning with absolute ethyl alcohol. The washed three-dimensional porous copper/copper sulfide was dried in a vacuum oven at 60 ℃.
(4) Preparing a three-dimensional porous copper/lithium sulfide/metal lithium composite material. The three-dimensional porous copper/copper sulfide prepared in step 3 was transferred into a glove box. The metallic lithium was placed in a stainless steel crucible in a glove box and heated to 300 c to obtain metallic lithium in a molten state. And placing one side of the three-dimensional porous copper-copper sulfide into molten metal lithium, and enabling the molten lithium to flow into the three-dimensional framework to finally prepare the three-dimensional porous copper/lithium sulfide/metal lithium composite metal lithium cathode.
(5) And (5) testing electrochemical performance. The three-dimensional porous copper/lithium sulfide/lithium metal composite anode material prepared in the step 4 is directly used for an anode and a cathode, assembled into a symmetrical battery, and is subjected to a process of 2mA/cm 2 At a current density of 2mAh/cm 2 Constant current charge and discharge tests were performed at the cyclic capacity of (c). Meanwhile, in order to compare and explain the advantages of the three-dimensional porous copper/lithium sulfide/metal lithium composite anode material, a lithium sheet is directly adopted as an electrode, and the test is carried out under the same test conditions.
(6) And (5) assembling and testing the lithium iron phosphate full battery. And (3) selecting lithium iron phosphate, PVDF and acetylene black according to the mass ratio of 8:1:1, sequentially adding the lithium iron phosphate, the PVDF and the acetylene black into NMP solution, stirring for 4 hours to obtain uniformly dispersed slurry, coating the slurry on an aluminum foil, and then placing the aluminum foil into a vacuum oven at 60 ℃ for drying for 12 hours to obtain a sample, and cutting the sample into a proper size according to the requirement to obtain the lithium iron phosphate positive electrode plate. And (3) taking the lithium iron phosphate pole piece as an anode, taking a three-dimensional porous copper/lithium sulfide/metal lithium composite material as a cathode, and assembling a lithium iron phosphate full battery for testing. Meanwhile, in order to compare and explain the advantages of the three-dimensional porous copper/lithium sulfide/metal lithium composite negative electrode material, a lithium sheet is directly adopted as a negative electrode, a lithium iron phosphate sheet is adopted as a positive electrode, and the test is carried out under the same test conditions.
Example 2
Unlike example 1, the following is: (2) preparing three-dimensional porous copper. Putting nano porous nickel into a quartz ark, putting the ark into a reaction tube furnace close to a tube orifice, and introducing argon and hydrogen, wherein the gas ratio is Ar to H 2 =500:200 sccm. The temperature of the tube furnace is raised to 900 ℃, and when the furnace temperature reaches 900 ℃, the quartz ark is quickly moved from the tube orifice area to the constant temperature area in the middle of the reaction tube, and the reaction is carried out for 0.5 minutes at the temperature. The remainder is the same as embodiment 1 and will not be described here again.
The resulting current collector had a three-dimensional, through-hole structure with a pore size in the range of 100 nm.
Example 3
Unlike example 1, the following is: (3) preparation of three-dimensional copper/copper sulfide. Heating the three-dimensional porous copper to 300 ℃ in air, and preserving heat for 1h. 3mol/L sodium sulfide solution is prepared, and three-dimensional porous copper cooled to room temperature is immersed in the sodium sulfide solution for 1h. 60mL of sodium sulfide aqueous solution is poured into a hydrothermal reaction kettle with the capacity of 100mL, the impregnated porous copper is put into the reaction kettle, the reaction kettle is placed into a blast oven, and the hydrothermal reaction is carried out at the temperature of 100 ℃ for 24h. And then taking out the hydrothermal kettle, cooling to room temperature, taking out the three-dimensional porous copper/copper sulfide, cleaning the prepared three-dimensional porous copper/copper sulfide with deionized water, and then cleaning with absolute ethyl alcohol. The washed three-dimensional porous copper/copper sulfide was dried in a vacuum oven at 60 ℃. The remainder is the same as embodiment 1 and will not be described here again.
The three-dimensional copper/copper sulfide still has a three-dimensional through hole structure, and the pores of the obtained porous structure become smaller due to the intense reaction.
Table 1 shows examples 1-4 and lithium flakes at 2mA/cm 2 At a current density of 2mAh/cm 2 The capacity of (3) is compared with the voltage stability of the charge-discharge cycle.
| Group of | Can react with molten lithium | 50h | 100h | 500h | 1000h |
| Example 1 | Reaction | Stabilization | Stabilization | Stabilization | Stabilization |
| Example 2 | Reaction | Stabilization | Stabilization | Unstable state | / |
| Example 3 | Reaction | Stabilization | Unstable state | / | / |
| Lithium sheet | / | Stabilization | Unstable state | / | / |
The stable state means that the variation amplitude of the voltage platform between the adjacent circle numbers is smaller than 10%, and the unstable state means that the variation amplitude of the voltage platform between the adjacent circle numbers is larger than 10%.
Claims (2)
1. A preparation method of a composite three-dimensional metal lithium anode for inhibiting growth of lithium dendrites comprises the following steps:
1) Preparation of nanoporous metal foils
Preparing a Cu-Mn alloy foil, wherein the atomic percentage of Cu is 25% -40% and the atomic percentage of Mn is 60% -75%; placing the Cu-Mn alloy foil in hydrochloric acid solution, performing dealloying through the reaction of hydrochloric acid and manganese, and cleaning and drying to obtain a nano porous metal foil;
2) Preparation of three-dimensional porous copper foil
Placing the nano porous copper foil prepared in the previous step in inert gas and hydrogen atmosphere, heating to 800-1000 ℃, calcining for 0.5-5min at the temperature, and cooling with a furnace to obtain the three-dimensional porous copper with the pore size of 100nm-1 mu m;
3) Preparation of three-dimensional porous copper/copper sulfide composite foil
Heating the three-dimensional porous copper prepared in the previous step to 100-300 ℃ in air, and preserving heat for 1-2h; cooling to room temperature, and then placing the three-dimensional porous copper into 1-3mol/L sodium sulfide aqueous solution for soaking for 1-2h; putting the impregnated three-dimensional porous copper into a hydrothermal reaction kettle containing sodium sulfide aqueous solution, and carrying out hydrothermal reaction at 90-120 ℃ for 12-24 hours; then taking out, cooling, cleaning and drying to obtain a three-dimensional porous copper/copper sulfide foil;
4) Preparation of three-dimensional porous copper/lithium sulfide/lithium metal composite lithium metal cathode
Transferring the three-dimensional porous copper/copper sulfide foil prepared in the step 3) into a glove box; placing and heating the metal lithium to 200-300 ℃ to obtain molten metal lithium; and (3) placing a part of the three-dimensional porous copper/copper sulfide foil into molten metal lithium, obtaining lithium sulfide through in-situ reaction of the metal lithium and copper sulfide, and enabling the molten lithium to flow into the three-dimensional porous structure along a three-dimensional communicated copper/copper sulfide framework under the action of capillary force, so as to finally prepare the three-dimensional porous copper/lithium sulfide/metal lithium composite metal lithium cathode.
2. The method according to claim 1, wherein in step 1), the corrosion is accelerated by heating in a water bath at 30-50 ℃ for 1-3 hours, and the dealloying is performed by reacting hydrochloric acid with manganese.
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| CN105932295A (en) * | 2016-04-22 | 2016-09-07 | 清华大学深圳研究生院 | Metal lithium secondary battery and negative electrode and porous copper current collector thereof |
| CN107123811A (en) * | 2017-04-11 | 2017-09-01 | 华南理工大学 | Double yardstick porous copper-aluminum-manganese shape memory alloy composites and preparation method and application |
| CN107785586A (en) * | 2017-09-19 | 2018-03-09 | 天津大学 | Three-dimensional porous copper/graphene composite current collector for secondary metals cathode of lithium battery |
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| CN105932295A (en) * | 2016-04-22 | 2016-09-07 | 清华大学深圳研究生院 | Metal lithium secondary battery and negative electrode and porous copper current collector thereof |
| CN107123811A (en) * | 2017-04-11 | 2017-09-01 | 华南理工大学 | Double yardstick porous copper-aluminum-manganese shape memory alloy composites and preparation method and application |
| CN107785586A (en) * | 2017-09-19 | 2018-03-09 | 天津大学 | Three-dimensional porous copper/graphene composite current collector for secondary metals cathode of lithium battery |
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