CN109768323B - All-solid-state lithium metal-sulfur battery and preparation method thereof - Google Patents
All-solid-state lithium metal-sulfur battery and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an all-solid-state lithium metal-sulfur battery and a preparation method thereof. The prior all-solid-state lithium metal-sulfur battery has the defects of large contact resistance between the solid electrolyte and the anode and the cathode, over-thick solid electrolyte, difficult batch production of the solid electrolyte and the like. The electrolyte used by the all-solid-state lithium metal-sulfur battery is a film type composite solid electrolyte of bis (trifluoromethyl) sulfonyl imide lithium/polyoxyethylene/tetraethylene glycol dimethyl ether @ lithium ion battery diaphragm; the sulfur anode material comprises sulfur powder, nano magnesium oxide, carbon nano tubes, Ketjen black and polyethylene oxide; coating lithium bistrifluoromethylsulfonyl imide/polyethylene oxide/tetraethylene glycol dimethyl ether on the surface of the sulfur positive pole piece; the surface of the lithium metal negative electrode is coated with bis (trifluoromethyl) sulfonyl imide lithium/polyethylene oxide/tetraethylene glycol dimethyl ether. The film type composite solid electrolyte can avoid shuttle effect of the sulfur anode, and the prepared all-solid-state lithium metal-sulfur battery has higher cycling stability.
Description
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to an all-solid-state lithium metal-sulfur battery and a preparation method thereof.
Background
According to the technical route of energy-saving and new energy automobile in China, the specific energy of the power type lithium ion battery reaches 300Wh/Kg in 2020; by 2030, the specific energy reaches 500Wh/Kg, and after the conventional commercial lithium ion battery reaches 300Wh/Kg, the conventional commercial lithium ion battery basically reaches the theoretical ceiling limited by the current materials, and the specific energy of the lithium ion battery is further improved, so that the specific energy is difficult and unsafe. Only another vertical stove can thoroughly reform the old frame of the lithium ion battery and the corresponding battery materialIt is possible to greatly improve the specific energy of the lithium battery on the premise of ensuring safety. At present, lithium metal-sulfur batteries are widely concerned in the industry because lithium metal cathodes and elemental sulfur anodes have extremely high theoretical specific capacities, and the specific energy of the lithium metal-sulfur batteries is expected to exceed 500Wh/kg as generally considered in the industry. Lithium metal-sulfur batteries using liquid electrolytes face two difficult difficulties to overcome. Firstly, lithium is deposited on the surface of a lithium metal negative electrode in a dendritic mode during charging, and a diaphragm is easy to pierce to cause short circuit of a battery, so that a serious potential safety hazard exists. Secondly, during the discharging process, sulfur reacts with lithium ions to form polysulfide micromolecules which are easily dissolved in the electrolyte and then diffuse to one side of the negative electrode along with the electrolyte to generate side reaction with lithium metal, so that not only are active substances of the positive electrode and the negative electrode consumed, but also a layer of Li with extremely low lithium ion conductivity is formed on the surface of the lithium metal2S, thereby causing the failure of the negative electrode, which is the well-known "shuttle effect" of lithium metal-sulfur batteries. In order to completely solve the two problems, it is a very practical idea to use a solid electrolyte with high young's modulus and without soluble polysulfide micromolecules to replace the liquid electrolyte in the current lithium-sulfur battery.
However, the existing all-solid-state lithium metal-sulfur battery has the defects of large contact resistance between the solid electrolyte and the positive electrode and the negative electrode, over-thick solid electrolyte, difficult batch production of the solid electrolyte and the like. Therefore, the thin-film solid electrolyte is developed, has the advantages of good wettability to positive and negative electrodes, low cost and easy mass production, and has wide application prospect and great practical significance.
Disclosure of Invention
The invention aims to solve the problems of the existing all-solid-state lithium metal-sulfur battery and provides an all-solid-state lithium metal-sulfur battery using a novel film type composite solid electrolyte.
Therefore, the technical scheme adopted by the invention is as follows: an all-solid-state lithium metal-sulfur battery uses a thin film type composite solid electrolyte of bis (trifluoromethyl) sulfonyl imide lithium/polyoxyethylene/tetraethylene glycol dimethyl ether @ lithium ion battery diaphragm as an electrolyte; the sulfur anode material comprises sulfur powder, nano magnesium oxide, carbon nano tubes, Ketjen black and polyethylene oxide; coating lithium bistrifluoromethylsulfonyl imide/polyethylene oxide/tetraethylene glycol dimethyl ether on the surface of the sulfur positive pole piece; the surface of the lithium metal negative electrode is coated with bis (trifluoromethyl) sulfonyl imide lithium/polyethylene oxide/tetraethylene glycol dimethyl ether.
The film type composite solid electrolyte has high ionic conductivity and wide electrochemical window; the lithium metal anode has stable circulation to the lithium metal cathode, good wetting effect to the anode and the cathode, and small contact resistance to the anode and the cathode; the film type composite solid electrolyte can avoid shuttle effect of a sulfur anode, and the prepared all-solid-state lithium metal-sulfur battery has higher cycling stability; the all-solid-state lithium metal-sulfur battery has the advantages of low battery internal resistance, high specific capacity and the like.
As a supplement to the all-solid-state lithium metal-sulfur battery, in the film type composite solid electrolyte of the lithium bistrifluoromethylsulfonyl imide/polyethylene oxide/tetraethylene glycol dimethyl ether @ lithium ion battery diaphragm, the monomer molar ratio of the lithium bistrifluoromethylsulfonyl imide to the polyethylene oxide is 1:5, the mass ratio of the lithium bistrifluoromethylsulfonyl imide-polyethylene oxide to the tetraethylene glycol dimethyl ether is 1:1, the lithium ion battery diaphragm is used as a substrate, and the lithium conducting polymer electrolyte is coated on the surface of the lithium ion battery diaphragm.
As a supplement to the above all solid-state lithium metal-sulfur battery, the sulfur positive electrode is composed of sulfur powder, nano-magnesia, carbon nanotubes, ketjen black and polyethylene oxide, wherein the sulfur content is 50 wt% to 70wt%, as a positive electrode active material; 2-5 wt% of nano magnesium oxide as an adsorbent for polysulfide; 5wt-10wt% of carbon nano tube and 10wt-20wt% of Keqin black as conductive network and conductive agent; 10-20 wt% of polyethylene oxide as a binder.
As a supplement to the all-solid-state lithium metal-sulfur battery, the lithium bistrifluoromethylsulfonyl imide/polyethylene oxide/tetraethylene glycol dimethyl ether is coated on the surface of the sulfur positive pole piece and the surface of the lithium metal negative pole, the monomer molar ratio of the lithium bistrifluoromethylsulfonyl imide to the polyethylene oxide is 1:1, and the mass ratio of the lithium bistrifluoromethylsulfonyl imide-polyethylene oxide to the tetraethylene glycol dimethyl ether is 1: 1.
Another object of the present invention is to provide a method for preparing an all solid-state lithium metal-sulfur battery, which comprises the steps of: 1) under the protection of inert atmosphere, dissolving lithium bistrifluoromethylsulfonyl imide, polyethylene oxide and tetraethylene glycol dimethyl ether as raw materials in acetonitrile to prepare a dilute solution, then coating the surface of a lithium ion battery diaphragm on two sides, and then drying; 2) under the protection of inert atmosphere, uniformly coating the dilute solution on a sulfur anode piece, vacuumizing to enable the dilute solution to permeate into micropores of the sulfur anode, and then drying; 3) and coating the surface of the lithium metal negative electrode with the diluted solution under the protection of inert atmosphere, and then drying.
The preparation method of the all-solid-state lithium metal-sulfur battery has the advantages of simple preparation process, low cost, suitability for large-scale industrial production and the like.
As a supplement to the above preparation method, in steps 1) and 2), the inert atmosphere is an argon atmosphere or a nitrogen atmosphere, and the water content and the oxygen content in the inert atmosphere are less than 1ppm and less than 1ppm respectively; in the step 3), the inert atmosphere is argon atmosphere, the water content in the inert atmosphere is less than 1ppm, and the oxygen content in the inert atmosphere is less than 1 ppm.
As a supplement to the preparation method, the lithium ion battery separator is coated in a dilute solution on the surface of a lithium ion battery separator, the monomer molar ratio of the lithium bistrifluoromethylsulfonyl imide to the polyethylene oxide is 1:5, and the mass ratio of the lithium bistrifluoromethylsulfonyl imide-polyethylene oxide to the tetraethylene glycol dimethyl ether is 1: 1; the total mass fraction of the lithium bistrifluoromethylsulfonyl imide/polyethylene oxide/tetraethylene glycol dimethyl ether is within 5 wt%.
As a supplement to the preparation method, the lithium-iron-based composite material is coated in a dilute solution on the surface of a sulfur positive pole piece and the surface of a lithium metal negative pole, the monomer molar ratio of the lithium bistrifluoromethylsulfonyl imide to the polyethylene oxide is 1:1, and the mass ratio of the lithium bistrifluoromethylsulfonyl imide-polyethylene oxide to the tetraethylene glycol dimethyl ether is 1: 1; the total mass fraction of the lithium bistrifluoromethylsulfonyl imide/polyethylene oxide/tetraethylene glycol dimethyl ether is within 5 wt%.
Supplementing the preparation method, the sulfur positive electrode consists of sulfur powder, nano-magnesia, carbon nano-tubes, Ketjen black and polyethylene oxide, wherein the sulfur content is 50-70 wt% and is used as a positive electrode active substance; 2-5 wt% of nano magnesium oxide as an adsorbent for polysulfide; 5wt-10wt% of carbon nano tube and 10wt-20wt% of Keqin black as conductive network and conductive agent; 10-20 wt% of polyethylene oxide as a binder.
In addition to the above preparation method, the preparation method of the sulfur positive electrode is as follows: taking sulfur powder, nano magnesium oxide, carbon nano tubes, Keqin black and polyethylene oxide as raw materials, taking N-methyl pyrrolidone as a solvent to prepare slurry, then mechanically stirring to prepare uniform slurry, coating the uniform slurry on the surface of an aluminum foil, and carrying out vacuum drying to remove the N-methyl pyrrolidone; then, lithium bistrifluoromethylsulfonyl imide, polyethylene oxide and tetraethylene glycol dimethyl ether are used as raw materials, acetonitrile is used as an organic solvent, a dilute solution is prepared in an inert atmosphere, the dilute solution is coated on the surface of a sulfur positive pole piece in the inert atmosphere, then, vacuum pumping is carried out so as to facilitate the dilute solution to permeate into pores on the surface of the positive pole piece, and finally, drying is carried out.
The invention has the following beneficial effects: the film type composite solid electrolyte can avoid shuttle effect of a sulfur anode, and the prepared all-solid-state lithium metal-sulfur battery has higher cycling stability; the all-solid-state lithium metal-sulfur battery has the advantages of low battery internal resistance, high specific capacity and the like. The preparation method of the all-solid-state lithium metal-sulfur battery has the advantages of simple preparation process, low cost, suitability for large-scale industrial production and the like.
Drawings
FIGS. 1(a) and (b) are optical microscope photographs of thin film type composite solid electrolyte of a commercial type lithium ion battery separator and a bis (trifluoromethyl) sulfonimide lithium/polyethylene oxide/tetraethylene glycol dimethyl ether @ lithium ion battery separator in example 1 of the present invention; fig. 1(c) and (d) are scanning electron microscope pictures of the sulfur positive electrode and the sulfur positive electrode to which the thin film type composite solid electrolyte is attached in example 1 of the present invention.
Fig. 2(a) is an impedance spectrum at room temperature of an all solid-state lithium metal-sulfur battery in example 1 of the present invention; fig. 2(b) is a charge-discharge diagram of an all-solid-state lithium metal-sulfur battery at room temperature, with a magnification of 0.1C; fig. 2(c) and (d) are a summary of the capacity and coulombic efficiency of all solid-state lithium metal-sulfur battery charging and discharging at room temperature;
fig. 3(a) is a charge-discharge diagram of an all solid-state lithium metal-sulfur battery in example 2 of the present invention at room temperature, with a magnification of 0.2C; fig. 3(b) and (c) are a summary of the capacity and coulombic efficiency of all solid-state lithium metal-sulfur battery charging and discharging at room temperature;
fig. 4(a) is a charge-discharge diagram of an all solid-state lithium metal-sulfur battery in example 3 of the present invention at 40 ℃, with a magnification of 0.1C; fig. 4(b) is a summary of the charge and discharge capacities of the all solid-state lithium metal-sulfur battery at room temperature;
fig. 5(a) is an impedance spectrum at room temperature of an all solid-state lithium metal-sulfur battery in comparative example 1 of the present invention; fig. 5(b) is a charge-discharge diagram of an all-solid-state lithium metal-sulfur battery at room temperature, with a magnification of 0.1C;
fig. 6 is a charge-discharge diagram at room temperature of a lithium metal-sulfur battery using a liquid electrolyte according to comparative example 2 of the present invention, with a magnification of 0.1C.
Detailed Description
The invention is further illustrated and described below with reference to the drawings and the detailed description of the invention.
Example 1
The method comprises the steps of taking bis (trifluoromethyl) sulfonyl imide lithium, polyethylene oxide and tetraethylene glycol dimethyl ether as raw materials, taking acetonitrile as an organic solvent, and preparing a dilute solution in an inert atmosphere, wherein the monomer molar ratio of the bis (trifluoromethyl) sulfonyl imide lithium to the polyethylene oxide is 1:5, and the mass ratio of the bis (trifluoromethyl) sulfonyl imide lithium to the polyethylene oxide to the tetraethylene glycol dimethyl ether is 1: 1. Coating on both sides of the surface of the diaphragm, vacuumizing and drying at 60 ℃ for 1 hour.
Sublimed sulfur powder, nano magnesium oxide powder, carbon nano tubes, Ketjen black and polyethylene oxide are used as raw materials, N-methyl pyrrolidone is used as a solvent to prepare slurry, then the slurry is mechanically stirred for 24 hours to prepare uniform slurry, then the uniform slurry is coated on the surface of an aluminum foil, and vacuum drying is carried out for 24 hours at the temperature of 60 ℃ to remove the N-methyl pyrrolidone. Then, lithium bistrifluoromethylsulfonyl imide, polyethylene oxide and tetraethylene glycol dimethyl ether are used as raw materials, acetonitrile is used as an organic solvent, a dilute solution is prepared in an inert atmosphere, the dilute solution is coated on the surface of the positive pole piece in the inert atmosphere, then, the vacuum pumping is carried out to facilitate the dilute solution to permeate into pores on the surface of the positive pole piece, and finally, the drying is carried out for 1 hour at the temperature of 60 ℃. And (3) coating a layer of the dilute solution on the surface of the lithium metal negative electrode, drying at 60 ℃ for 1 hour, and finally assembling into a lithium-sulfur button cell (CR2032) and testing the internal resistance and the cycle efficiency of the cell.
Fig. 1a is a photograph taken by an optical microscope of a commercial lithium ion battery separator, and fig. 1b is a photograph taken by an optical microscope of a thin film type solid electrolyte of the lithium bistrifluoromethylsulfonyl imide/polyethylene oxide/tetraethylene glycol dimethyl ether @ lithium ion battery separator prepared in the embodiment, and a layer of polymer is adhered to the lithium ion battery separator. Fig. 1c is a scanning electron microscope picture of the sulfur positive electrode prepared in this example, and fig. 1d is a scanning electron microscope picture of the sulfur positive electrode to which lithium bistrifluoromethylsulfonimide/polyethylene oxide/tetraethylene glycol dimethyl ether has been adhered in this example, and it is clear that the polymer electrolyte is on the surface of the positive electrode sheet.
Fig. 2a is an impedance spectrum of the all-solid-state lithium metal-sulfur button cell prepared in this example at room temperature, wherein the intercept between the semicircle and the x-axis is 58.6 Ω, which represents the resistance of the thin film type solid electrolyte; the diameter of the semicircle represents the sum of the contact resistances of the solid electrolyte and the positive and negative electrodes, and the total resistance is about 260 Ω, and it can be seen from the figure that the resistance of the solid electrolyte is relatively small, which also indicates that the wettability of the solid electrolyte film with the positive and negative electrodes is good. Fig. 2b is a charging and discharging curve of the all-solid-state lithium metal-sulfur button cell prepared in this example at room temperature, the charging and discharging rate is 0.1C, fig. 2C shows a summary of the charging and discharging capacity per turn, and fig. 2d is a summary of the corresponding coulombic efficiency per turn. The first circle of the charging capacity is 550mAh/gSThe discharge capacity is 460mAh/gS(ii) a After 50 circles, the charging capacity is about 420mAh/gSThe discharge capacity is about 335mAh/gS。
Example 2
The method comprises the steps of taking bis (trifluoromethyl) sulfonyl imide lithium, polyethylene oxide and tetraethylene glycol dimethyl ether as raw materials, taking acetonitrile as an organic solvent, and preparing a dilute solution in an inert atmosphere, wherein the monomer molar ratio of the bis (trifluoromethyl) sulfonyl imide lithium to the polyethylene oxide is 1:5, and the mass ratio of the bis (trifluoromethyl) sulfonyl imide lithium to the polyethylene oxide to the tetraethylene glycol dimethyl ether is 1: 1. Coating on both sides of the surface of the diaphragm, vacuumizing and drying at 60 ℃ for 1 hour.
Sublimed sulfur powder, nano magnesium oxide powder, carbon nano tubes, Ketjen black and polyethylene oxide are used as raw materials, N-methyl pyrrolidone is used as a solvent to prepare slurry, then the slurry is mechanically stirred for 24 hours to prepare uniform slurry, then the uniform slurry is coated on the surface of an aluminum foil, and vacuum drying is carried out for 24 hours at the temperature of 60 ℃ to remove the N-methyl pyrrolidone. Then, lithium bistrifluoromethylsulfonyl imide, polyethylene oxide and tetraethylene glycol dimethyl ether are used as raw materials, acetonitrile is used as an organic solvent, a dilute solution is prepared in an inert atmosphere, the dilute solution is coated on the surface of the positive pole piece in the inert atmosphere, then, the vacuum pumping is carried out to facilitate the dilute solution to permeate into pores on the surface of the positive pole piece, and finally, the drying is carried out for 1 hour at the temperature of 60 ℃. And (3) coating a layer of the dilute solution on the surface of the lithium metal negative electrode, drying at 60 ℃ for 1 hour, and finally assembling into a lithium-sulfur button cell (CR2032) and testing the internal resistance and the cycle efficiency of the cell.
Fig. 3a is a charging and discharging curve of the all-solid-state lithium metal-sulfur button cell prepared in this example at room temperature, the charging and discharging rate is 0.2C, fig. 3b shows a summary of the charging and discharging capacity per turn, and fig. 3C is a summary of the corresponding coulombic efficiency per turn. The first circle of charging capacity is 419mAh/gSDischarge capacity of 361mAh/gS(ii) a After 100 circles, the charging capacity is about 343mAh/gSThe discharge capacity is about 293mAh/gS。
Example 3
The method comprises the steps of taking bis (trifluoromethyl) sulfonyl imide lithium, polyethylene oxide and tetraethylene glycol dimethyl ether as raw materials, taking acetonitrile as an organic solvent, and preparing a dilute solution in an inert atmosphere, wherein the monomer molar ratio of the bis (trifluoromethyl) sulfonyl imide lithium to the polyethylene oxide is 1:5, and the mass ratio of the bis (trifluoromethyl) sulfonyl imide lithium to the polyethylene oxide to the tetraethylene glycol dimethyl ether is 1: 1. Coating on both sides of the surface of the diaphragm, vacuumizing and drying at 60 ℃ for 1 hour.
Sublimed sulfur powder, nano magnesium oxide powder, carbon nano tubes, Ketjen black and polyethylene oxide are used as raw materials, N-methyl pyrrolidone is used as a solvent to prepare slurry, then the slurry is mechanically stirred for 24 hours to prepare uniform slurry, then the uniform slurry is coated on the surface of an aluminum foil, and vacuum drying is carried out for 24 hours at the temperature of 60 ℃ to remove the N-methyl pyrrolidone. Then, lithium bistrifluoromethylsulfonyl imide, polyethylene oxide and tetraethylene glycol dimethyl ether are used as raw materials, acetonitrile is used as an organic solvent, a dilute solution is prepared in an inert atmosphere, the dilute solution is coated on the surface of the positive pole piece in the inert atmosphere, then, the vacuum pumping is carried out to facilitate the dilute solution to permeate into pores on the surface of the positive pole piece, and finally, the drying is carried out for 1 hour at the temperature of 60 ℃. And (3) coating a layer of the dilute solution on the surface of the lithium metal negative electrode, drying at 60 ℃ for 1 hour, and finally assembling into a lithium-sulfur button cell (CR2032) and testing the internal resistance and the cycle efficiency of the cell.
Fig. 4a is a charging and discharging curve of the all solid-state lithium metal-sulfur button cell prepared in this example at 40 ℃ with a charging and discharging rate of 0.1C, and fig. 4b shows a summary of the charging and discharging capacity per round. The first circle of the charge capacity is 795mAh/gSDischarge capacity of 662mAh/gS(ii) a After 12 circles, the charging capacity is about 778mAh/gSThe discharge capacity is about 620mAh/gSAnd almost no attenuation.
Comparative example 1
The preparation method comprises the steps of taking bis (trifluoromethyl) sulfimide lithium and polyoxyethylene as raw materials, taking acetonitrile as an organic solvent, preparing a dilute solution in an inert atmosphere, and taking no tetraethylene glycol dimethyl ether as a plasticizer, wherein the monomer molar ratio of the bis (trifluoromethyl) sulfimide lithium to the polyoxyethylene is 1: 5. Coating on both sides of the surface of the diaphragm, vacuumizing and drying at 60 ℃ for 1 hour.
Sublimed sulfur powder, nano magnesium oxide powder, carbon nano tubes, Ketjen black and polyethylene oxide are used as raw materials, N-methyl pyrrolidone is used as a solvent to prepare slurry, then the slurry is mechanically stirred for 24 hours to prepare uniform slurry, then the uniform slurry is coated on the surface of an aluminum foil, and vacuum drying is carried out for 24 hours at the temperature of 60 ℃ to remove the N-methyl pyrrolidone. Then, lithium bistrifluoromethylsulfonyl imide and polyethylene oxide are used as raw materials, acetonitrile is used as an organic solvent, a dilute solution is prepared in an inert atmosphere, the dilute solution is coated on the surface of the positive pole piece in the inert atmosphere, then, vacuum pumping is carried out so as to facilitate the dilute solution to permeate into pores on the surface of the positive pole piece, and finally, drying is carried out for 1 hour at the temperature of 60 ℃. And (3) coating a layer of the dilute solution on the surface of the lithium metal negative electrode, drying at 60 ℃ for 1 hour, and finally assembling into a lithium-sulfur button cell (CR2032) and testing the internal resistance and the cycle efficiency of the cell.
Fig. 5a is an impedance spectrum of the all solid-state lithium metal-sulfur button cell prepared in this example at room temperature, wherein the intercept between the semicircle and the x-axis is 140 Ω, which represents the resistance of the thin film type solid electrolyte; the diameter of the semicircle represents the sum of the contact resistances of the solid electrolyte and the positive and negative electrodes, and the resistance is about 700 Ω, and it can be seen from the figure that the resistance of the solid electrolyte is relatively large, which also indicates that the wettability of the solid electrolyte film with the positive and negative electrodes is poor. Fig. 5b is a charging and discharging curve of the all-solid-state lithium metal-sulfur button cell prepared in this example at room temperature, and the charging and discharging rate is 0.1C. The first circle of charging capacity is 150mAh/gSDischarge capacity of 96mAh/gS(ii) a After 40 cycles, the charging capacity was about 79mAh/gSThe discharge capacity is about 73mAh/gSThe overall capacity performance is poor.
Comparative example 2
Lithium bis (trifluoromethyl) sulfonyl imide is used as a solute, is dissolved in an ethylene glycol dimethyl ether solvent, and is prepared into liquid electrolyte with the concentration of 1 mol per liter in an inert atmosphere. Sublimed sulfur powder, nano magnesium oxide powder, carbon nano tubes, Ketjen black and polyethylene oxide are used as raw materials, N-methyl pyrrolidone is used as a solvent to prepare slurry, then the slurry is mechanically stirred for 24 hours to prepare uniform slurry, then the uniform slurry is coated on the surface of an aluminum foil, and vacuum drying is carried out for 24 hours at the temperature of 60 ℃ to remove the N-methyl pyrrolidone. Then, lithium bistrifluoromethylsulfonyl imide and polyethylene oxide are used as raw materials, acetonitrile is used as an organic solvent, a dilute solution is prepared in an inert atmosphere, the dilute solution is coated on the surface of the positive pole piece in the inert atmosphere, then, vacuum pumping is carried out so as to facilitate the dilute solution to permeate into pores on the surface of the positive pole piece, and finally, drying is carried out for 1 hour at the temperature of 60 ℃. And (3) coating a layer of the dilute solution on the surface of the lithium metal negative electrode, drying at 60 ℃ for 1 hour, and finally assembling into a lithium-sulfur button cell (CR2032) and testing the internal resistance and the cycle efficiency of the cell.
Fig. 6 is a charging and discharging curve of the lithium metal-sulfur button cell using liquid electrolyte prepared in this example at room temperature, and the rate of charging and discharging is 0.1C. The first circle of charging capacity is 1107mAh/gSAnd the discharge capacity is 756mAh/gS(ii) a After 10 cycles, the charging capacity is about 464mAh/gSThe discharge capacity is about 217mAh/gSThe overall capacity fade is very fast due to the shuttle effect of using the liquid type electrolyte.
Claims (8)
1. A preparation method of an all-solid-state lithium metal-sulfur battery is characterized in that an electrolyte used by the all-solid-state lithium metal-sulfur battery is a thin film type composite solid electrolyte of bis (trifluoromethyl) sulfimide lithium/polyoxyethylene/tetraethylene glycol dimethyl ether @ lithium ion battery diaphragm; the sulfur anode material comprises sulfur powder, nano magnesium oxide, carbon nano tubes, Ketjen black and polyethylene oxide; coating lithium bistrifluoromethylsulfonyl imide/polyethylene oxide/tetraethylene glycol dimethyl ether on the surface of the sulfur positive pole piece; coating lithium bistrifluoromethylsulfonyl imide/polyethylene oxide/tetraethylene glycol dimethyl ether on the surface of the lithium metal negative electrode; it is characterized in that the preparation method is characterized in that,
the preparation method of the all-solid-state lithium metal-sulfur battery comprises the following steps: 1) under the protection of inert atmosphere, dissolving lithium bistrifluoromethylsulfonyl imide, polyethylene oxide and tetraethylene glycol dimethyl ether as raw materials in acetonitrile to prepare a dilute solution, then coating the surface of a lithium ion battery diaphragm on two sides, and then drying; 2) under the protection of inert atmosphere, uniformly coating the dilute solution on a sulfur anode piece, vacuumizing to enable the dilute solution to permeate into micropores of the sulfur anode, and then drying; 3) and coating the surface of the lithium metal negative electrode with the diluted solution under the protection of inert atmosphere, and then drying.
2. The method for preparing an all-solid-state lithium metal-sulfur battery according to claim 1, wherein in the thin film type composite solid electrolyte of the lithium bistrifluoromethylsulfonyl imide/polyethylene oxide/tetraethylene glycol dimethyl ether @ lithium ion battery diaphragm, the monomer molar ratio of the lithium bistrifluoromethylsulfonyl imide to the polyethylene oxide is 1:5, the mass ratio of the lithium bistrifluoromethylsulfonyl imide-polyethylene oxide to the tetraethylene glycol dimethyl ether is 1:1, the lithium ion battery diaphragm is used as a substrate, and the surface of the lithium ion battery diaphragm is coated with a lithium conducting polymer electrolyte.
3. The preparation method of the all-solid-state lithium metal-sulfur battery according to claim 1 or 2, wherein the lithium bistrifluoromethylsulfonyl imide/polyethylene oxide/tetraethylene glycol dimethyl ether is coated on the surface of the sulfur positive electrode sheet and the surface of the lithium metal negative electrode, the monomer molar ratio of the lithium bistrifluoromethylsulfonyl imide to the polyethylene oxide is 1:1, and the mass ratio of the lithium bistrifluoromethylsulfonyl imide-polyethylene oxide to the tetraethylene glycol dimethyl ether is 1: 1.
4. The method for manufacturing an all-solid-state lithium metal-sulfur battery according to claim 1, wherein in steps 1) and 2), the inert atmosphere is an argon atmosphere or a nitrogen atmosphere, and the water content and the oxygen content in the inert atmosphere are less than 1ppm and less than 1ppm respectively; in the step 3), the inert atmosphere is argon atmosphere, the water content in the inert atmosphere is less than 1ppm, and the oxygen content in the inert atmosphere is less than 1 ppm.
5. The preparation method of the all-solid-state lithium metal-sulfur battery according to claim 1, wherein the lithium bis (trifluoromethyl) sulfonyl imide lithium is coated in a dilute solution on the surface of the lithium ion battery separator, the monomer molar ratio of the lithium bis (trifluoromethyl) sulfonyl imide to the polyethylene oxide is 1:5, and the mass ratio of the lithium bis (trifluoromethyl) sulfonyl imide-polyethylene oxide to the tetraethylene glycol dimethyl ether is 1: 1; the total mass fraction of the bis (trifluoromethyl) sulfonyl imide lithium/polyoxyethylene/tetraethylene glycol dimethyl ether is less than or equal to 5 wt%.
6. The preparation method of the all-solid-state lithium metal-sulfur battery according to claim 1, wherein the lithium bis (trifluoromethyl) sulfonyl imide lithium and the polyoxyethylene are coated in a dilute solution on the surface of the sulfur positive electrode piece and the surface of the lithium metal negative electrode, the monomer molar ratio of the lithium bis (trifluoromethyl) sulfonyl imide lithium to the polyoxyethylene is 1:1, and the mass ratio of the lithium bis (trifluoromethyl) sulfonyl imide lithium-polyoxyethylene to the tetraethylene glycol dimethyl ether is 1: 1; the total mass fraction of the bis (trifluoromethyl) sulfonyl imide lithium/polyoxyethylene/tetraethylene glycol dimethyl ether is less than or equal to 5 wt%.
7. The method for manufacturing an all-solid-state lithium metal-sulfur battery according to claim 1, wherein the sulfur positive electrode is composed of sulfur powder, nano-magnesium oxide, carbon nanotubes, ketjen black, and polyethylene oxide, wherein the sulfur content is 50 to 70wt% as a positive electrode active material; 2-5 wt% of nano magnesium oxide as an adsorbent for polysulfide; 5wt-10wt% of carbon nano tube and 10wt-20wt% of Keqin black as conductive network and conductive agent; 10-20 wt% of polyethylene oxide as a binder.
8. The method of manufacturing an all-solid-state lithium metal-sulfur battery according to claim 7, wherein the method of manufacturing the sulfur positive electrode is as follows: taking sulfur powder, nano magnesium oxide, carbon nano tubes, Keqin black and polyethylene oxide as raw materials, taking N-methyl pyrrolidone as a solvent to prepare slurry, then mechanically stirring to prepare uniform slurry, coating the uniform slurry on the surface of an aluminum foil, and carrying out vacuum drying to remove the N-methyl pyrrolidone; then, lithium bistrifluoromethylsulfonyl imide, polyethylene oxide and tetraethylene glycol dimethyl ether are used as raw materials, acetonitrile is used as an organic solvent, a dilute solution is prepared in an inert atmosphere, the dilute solution is coated on the surface of a sulfur positive pole piece in the inert atmosphere, then, vacuum pumping is carried out so as to facilitate the dilute solution to permeate into pores on the surface of the positive pole piece, and finally, drying is carried out.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201811482611.9A CN109768323B (en) | 2018-12-05 | 2018-12-05 | All-solid-state lithium metal-sulfur battery and preparation method thereof |
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