CN107572486B - Nano sulfur particles, preparation and preparation of lithium-sulfur battery positive electrode - Google Patents
Nano sulfur particles, preparation and preparation of lithium-sulfur battery positive electrode Download PDFInfo
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Abstract
A nano sulfur particle, a preparation method thereof and a preparation method of a lithium sulfur battery anode belong to the field of inorganic nano materials and electrochemistry. The nano sulfur particles are prepared by decomposing sodium thiosulfate by using gelatin aqueous solution as a dispersing agent and a protective agent. The nano sulfur particles prepared by the method have uniform particle size distribution and good dispersibility. The prepared nano sulfur particles are used for preparing the positive electrode of the lithium sulfur battery. Electrochemical performance tests prove that the nano sulfur particles obtained by the method disclosed by the invention show excellent electrochemical performance. The method is simple and easy to operate, low in cost of used raw materials, environment-friendly and convenient to popularize.
Description
Technical Field
The invention relates to a preparation method of nano sulfur particles and a preparation method of a lithium sulfur battery positive pole piece by taking the nano sulfur particles as an active substance, belonging to the field of inorganic nano materials and electrochemistry.
Background
In recent years, with the gradual decrease of fossil energy and the increase of environmental protection pressure, the development and utilization of renewable clean energy are urgent. New secondary batteries have received much attention as a new generation of energy storage devices. The lithium ion battery is used as a secondary battery system with the best comprehensive performance at present, the energy density of the lithium ion battery can reach 250Wh/Kg, and the lithium ion battery has the advantages of long cycle life, small self-discharge, environmental friendliness and the like. However, with the rapid development of electric vehicles, lithium ion batteries have been far from meeting the requirements of people for long driving distance of electric vehicles. The lithium-sulfur battery not only has very high theoretical specific capacity (1675mAh/g) and theoretical energy density (2600Wh/Kg), but also has wide sources and is environment-friendly, so the lithium-sulfur battery is considered to be a new generation of high specific energy chemical power system with the most development potential.
Nevertheless, elemental sulfur and its discharge product have very low conductivity, and long-chain lithium polysulfide which is easily dissolved in the electrolyte is generated in the battery charging and discharging process, which further causes the shuttle effect and large volume change in the charging and discharging process, resulting in low elemental sulfur utilization rate, serious capacity attenuation, poor rate capability and short cycle life in the lithium sulfur battery cycle process, and restricting the commercial development thereof.
The positive electrode material is a hot spot in the research of lithium sulfur batteries and is also the key for improving the performance of the lithium sulfur batteries. Natural sublimed sulfurAs a typical non-metallic crystal, the conductivity is poor and the room temperature electron conductivity is about 5X 10-30S/cm, and the size is usually 10 μm or more, and thus it cannot be used as an electrode material as it is. Reducing the sulfur size can increase the contact area between sulfur and electrolyte, increase the electrochemical reaction rate and improve the utilization rate of sulfur. Ball milling and chemical reaction preparation are common methods for reducing the size of sulfur particles. Yi Cui et al (p.natl.acad.sci.usa,2013,110(18):7148-7153) of stanford university, usa, used polyvinylpyrrolidone (PVP) as a surfactant, produced PVP-encapsulated hollow sulfur nanospheres by decomposing sodium thiosulfate, and applied to the positive electrode of a lithium-sulfur battery. Under the discharge rate of 0.2C, after 300 times of circulation, the discharge specific capacity is about 790mAh/g, and the electrochemical performance is effectively improved. However, the preparation method is complex, is not beneficial to large-scale production, has low sulfur carrying capacity and large rate performance, and cannot meet the commercial requirements of the lithium-sulfur battery.
Disclosure of Invention
The invention aims to provide a novel method for simply preparing nano sulfur particles in order to improve the specific capacity of a lithium sulfur battery, particularly maintain the electrochemical performance of the material under high current density, and the novel method is used for preparing a positive electrode material of the lithium sulfur battery.
The method for preparing the nano sulfur particles is characterized in that the nano sulfur particles are a sulfur nano composite material, and the method specifically comprises the following steps:
(1) respectively preparing a sodium thiosulfate aqueous solution and gelatin or a gelatin aqueous solution containing a conductive agent, and uniformly mixing to obtain a solution A; preferably, the mass concentration of the sodium thiosulfate in the solution A is 10-30%, the mass concentration of the gelatin is 1-5%, and the mass concentration of the conductive agent is 0-3%;
(2) preparing an acid solution B; the concentration of the acid solution B is preferably 2-4 mol/L;
(3) dropwise adding the solution B in the step (2) into the solution A in the step (1) under the condition of stirring, and reacting to obtain a solution C; preferably, the molar ratio of the sodium thiosulfate to the acid is 1:1-3, the reaction is carried out for 0.5h-2h, and the reaction temperature is 40-80 ℃;
(4) centrifuging and washing the solution C obtained in the step (3) for 0-2 times, adding deionized water, and performing ultrasonic treatment to obtain a suspension D;
(5) preparing a glutaraldehyde aqueous solution E; preferably 0.5 to 2 percent of mass fraction;
(6) and (3) under the condition of magnetic stirring, adding the solution E in the step (5) into the suspension D in the step (4), reacting for 0.5-2 h at room temperature, centrifuging to obtain powder, and drying to obtain the nano sulfur particles. Preferably, the volume ratio of suspension D to solution E is 2-5: 1.
The conductive agent in the step (1) is selected from one or more of acetylene black, Ketjen black, Super P, carbon nano tubes, graphene or porous carbon and other common conductive carbon materials.
The acid in the step (2) is hydrochloric acid, sulfuric acid or nitric acid.
The preparation method of the lithium-sulfur battery positive electrode comprises the following steps:
mixing the obtained nano sulfur particles, conductive agent and adhesive according to the mass ratio of 60-90:0-30:5-10, magnetically stirring for 10-72 h to obtain slurry, coating the slurry on an aluminum foil, drying, and cutting into a wafer with the diameter of 0.5-5.0 cm, wherein the wafer is used as a positive pole piece for later use; the conductive agent is selected from one or more of acetylene black, Ketjen black, Super P, carbon nano tubes, graphene and other common conductive carbon materials; the binder package is selected from common binders such as gelatin, polyglutamic acid, chitosan, LA132, PVDF, PEO, PVP and the like, and is added in the form of aqueous solution (such as gelatin, polyglutamic acid, chitosan, LA132, PEO, PVP) or non-aqueous solution (such as NMP used as solvent for PVDF), and the amount of the binder refers to the amount of dry binder.
When the nano sulfur particles contain a conductive agent, an additional conductive agent is added or not added during the preparation of the positive electrode of the lithium-sulfur battery; when the nano sulfur particles do not contain the conductive agent, an additional conductive agent is added when the positive electrode of the lithium-sulfur battery is prepared.
A lithium sheet is taken as a negative electrode, polypropylene is taken as a diaphragm, the positive electrode of the lithium-sulfur battery is taken as a positive electrode, lithium bis (trifluoromethylsulfonyl) imide is taken as an electrolyte, lithium nitrate is taken as an additive, and 1, 3-dioxolane and dimethyl ether in a volume ratio of 1:1 are taken as an electrolyte of a mixed solvent, the electrolyte is assembled into a button battery in a glove box (the humidity is less than 1 percent), and then an electrochemical test is carried out. Wherein the electrolyte concentration is 0.4-2mol/L, and the additive concentration is 0.1-1 mol/L.
Advantageous effects
1. The invention provides a novel method for preparing nano sulfur particles, which provides that gelatin aqueous solution is used as a dispersing agent and a protective agent, and the nano sulfur particles are prepared by decomposing sodium thiosulfate. The addition of the gelatin water solution can effectively prevent the agglomeration phenomenon caused by the traditional method, and the prepared nano sulfur particles have uniform particle size distribution and better dispersibility.
2. The nano sulfur particles prepared by the method have small size, and when the nano sulfur particles are used in the positive electrode of the lithium-sulfur battery, the contact area between sulfur and electrolyte is increased, the electrochemical reaction rate is increased, the utilization rate of sulfur is improved, and the discharge specific capacity and the electrochemical performance of the battery under high current density are improved.
3. The invention has low cost of raw materials and simple and easy operation method.
Detailed Description
The invention is described in more detail below with reference to examples, but the scope of protection of the invention is not limited to the examples listed.
Example 1:
the first step is as follows: preparing the nano sulfur particles.
(1) Dissolving 2.5g of gelatin in 100mL of deionized water, fully swelling, heating to 60 ℃, and stopping heating after complete dissolution to prepare a gelatin aqueous solution; dissolving 37.2g of sodium thiosulfate pentahydrate in 50mL of deionized water to prepare a sodium thiosulfate solution; adding the sodium thiosulfate solution into the gelatin water solution, and uniformly stirring;
(2) taking 25mL of concentrated hydrochloric acid into 75mL of deionized water, and mixing to obtain a dilute hydrochloric acid solution;
(3) dropwise adding the dilute hydrochloric acid obtained in the step (2) into the solution obtained in the step (1) under the condition of magnetic stirring, and reacting for 30min after dropwise adding, wherein the reaction temperature is 60 ℃;
(4) centrifuging the solution obtained in the step (3), washing with deionized water twice, adding the lower-layer precipitate obtained by centrifuging into 200mL of deionized water, and performing ultrasonic treatment for 5min to obtain a suspension;
(5) 1mL of 50% glutaraldehyde solution is taken and put in 49mL of deionized water, and the mixture is stirred uniformly;
(6) under the condition of magnetic stirring, dropwise adding the solution obtained in the step (5) into the suspension obtained in the step (4), and reacting for 2 hours after dropwise adding, wherein the reaction temperature is room temperature; and centrifuging after the reaction is finished to obtain a lower layer precipitate, and drying to obtain the nano sulfur particles. The sulfur content in the composite was 98.3 wt% as determined by thermogravimetric analysis.
The second step is that: and preparing the cathode material.
Uniformly mixing the dried nano sulfur particles, acetylene black and gelatin solution (2 wt%), wherein the mass ratio of the nano sulfur to the acetylene black to the gelatin is 63:30:7, magnetically stirring for 24 hours to obtain slurry, uniformly coating the slurry on an aluminum foil, drying the aluminum foil in a vacuum drying oven for 10 hours, and cutting the dried anode material into a wafer with the diameter of 1.2cm for later use.
The third step: and assembling the button lithium-sulfur battery.
The prepared anode material is taken as a battery anode, a lithium sheet is taken as a cathode, polypropylene is taken as a diaphragm, 0.6M lithium bis (trifluoromethylsulfonyl) imide is taken as an electrolyte, 0.4M lithium nitrate is taken as an additive, and a solvent is a mixed solvent of 1, 3-dioxolane and dimethyl ether in a volume ratio of 1:1, and the mixed solvent is assembled into the CR2025 button battery in a glove box (the humidity is less than 1%) in an argon atmosphere. The charge and discharge cut-off voltages were 2.8V and 1.7V, respectively, and charge and discharge cycles were performed at discharge rates of 0.1C, 0.2C, activation of 0.5C, and activation of 1C (first two turns of 0.05C), respectively. Under 0.2C (1C: 1675mAh/g), the initial specific discharge capacity is 1006.5mAh/g, and under 1C of activation, after 100 cycles, the specific discharge capacity is still maintained at 730.8 mAh/g.
Example 2:
the first step is as follows: preparing the nano sulfur particles.
(1) Dissolving 2.5g of gelatin in 100mL of deionized water, fully swelling, heating to 60 ℃, and stopping heating after complete dissolution to prepare a gelatin aqueous solution; dissolving 37.2g of sodium thiosulfate pentahydrate in 50mL of deionized water to prepare a sodium thiosulfate solution; adding the sodium thiosulfate solution into the gelatin water solution, and uniformly stirring;
(2) taking 25mL of concentrated hydrochloric acid into 75mL of deionized water, and mixing to obtain a dilute hydrochloric acid solution;
(3) under the condition of magnetic stirring, dropwise adding the dilute hydrochloric acid obtained in the step (2) into the solution obtained in the step (1), and reacting for 2 hours after dropwise adding, wherein the reaction temperature is 60 ℃;
(4) centrifuging the solution obtained in the step (3), washing with deionized water twice, adding the lower-layer precipitate obtained by centrifuging into 200mL of deionized water, and performing ultrasonic treatment for 5min to obtain a suspension;
(5) 1mL of 50% glutaraldehyde solution is taken and put in 49mL of deionized water, and the mixture is stirred uniformly;
(6) under the condition of magnetic stirring, dropwise adding the solution obtained in the step (5) into the suspension obtained in the step (4), and reacting for 2 hours after dropwise adding, wherein the reaction temperature is room temperature; and centrifuging after the reaction is finished to obtain a lower layer precipitate, and drying to obtain the nano sulfur particles. The sulfur content in the composite was 99.5 wt% as determined by thermogravimetric analysis.
The second step is the same as in example 1.
The third step was the same as in example 1. Under the condition of 0.2C (1C: 1675mAh/g), the first discharge specific capacity is 955.6mAh/g, and after 50 cycles, the discharge specific capacity is still kept at 657.2 mAh/g.
Example 3:
the first step is as follows: preparing the nano sulfur particles.
(2) Dissolving 3.6g of gelatin in 100mL of deionized water, fully swelling, heating to 60 ℃, and stopping heating after complete dissolution to prepare a gelatin aqueous solution; dissolving 37.2g of sodium thiosulfate pentahydrate in 50mL of deionized water to prepare a sodium thiosulfate solution; adding the sodium thiosulfate solution into the gelatin water solution, and uniformly stirring;
(2) taking 25mL of concentrated hydrochloric acid into 75mL of deionized water, and mixing to obtain a dilute hydrochloric acid solution;
(3) under the condition of magnetic stirring, dropwise adding the dilute hydrochloric acid obtained in the step (2) into the solution obtained in the step (1), and reacting for 2 hours after dropwise adding, wherein the reaction temperature is 60 ℃;
(4) centrifuging the solution obtained in the step (3), adding the lower layer precipitate obtained by centrifuging into 200mL of deionized water, and performing ultrasonic treatment for 5min to obtain a suspension;
(5) 1mL of 50% glutaraldehyde solution is taken and put in 49mL of deionized water, and the mixture is stirred uniformly;
(6) under the condition of magnetic stirring, dropwise adding the solution obtained in the step (5) into the suspension obtained in the step (4), and reacting for 2.5 hours after dropwise adding, wherein the reaction temperature is room temperature; and centrifuging after the reaction is finished to obtain a lower layer precipitate, and drying to obtain the nano sulfur particles.
The second step is the same as in example 1.
The third step was the same as in example 1. Under activation 1C (1C 1675mAh/g), the specific discharge capacity remained 716.6mAh/g after 50 cycles.
Example 4:
the first step is as follows: preparing acetylene black composite nano sulfur particles.
(1) Dissolving 2.5g of gelatin in 100mL of deionized water, fully swelling, heating to 60 ℃, and stopping heating after complete dissolution to prepare a gelatin aqueous solution; adding 0.5g of acetylene black into the gelatin water solution, and uniformly stirring; dissolving 37.2g of sodium thiosulfate pentahydrate in 50mL of deionized water to prepare a sodium thiosulfate solution; adding a sodium thiosulfate solution into a gelatin aqueous solution containing acetylene black, and uniformly stirring;
(2) taking 25mL of concentrated hydrochloric acid into 75mL of deionized water, and mixing to obtain a dilute hydrochloric acid solution;
(3) dropwise adding the dilute hydrochloric acid obtained in the step (2) into the solution obtained in the step (1) under the condition of magnetic stirring, and reacting for 30min after dropwise adding, wherein the reaction temperature is 60 ℃;
(4) centrifuging the solution obtained in the step (3), washing with deionized water twice, adding the lower-layer precipitate obtained by centrifuging into 120mL of deionized water, and performing ultrasonic treatment for 5min to obtain a suspension;
(5) 1mL of 50% glutaraldehyde solution is taken and put in 49mL of deionized water, and the mixture is stirred uniformly;
(6) under the condition of magnetic stirring, dropwise adding the solution obtained in the step (5) into the suspension obtained in the step (4), and reacting for 2 hours after dropwise adding, wherein the reaction temperature is room temperature; and centrifuging after the reaction is finished to obtain a lower layer precipitate, and drying to obtain the acetylene black composite nano sulfur particles. The sulfur content in the composite was 85.5 wt% as determined by thermogravimetric analysis.
The second step is that: and preparing the cathode material.
Uniformly mixing the dried acetylene black composite nano sulfur particles, acetylene black and gelatin solution (2 wt%), wherein the mass ratio of the acetylene black composite nano sulfur to the acetylene black to the gelatin is 8:1:1, magnetically stirring for 48 hours to form slurry, uniformly coating the slurry on an aluminum foil, drying for 10 hours in a vacuum drying oven, and cutting the dried anode material into a wafer with the diameter of 1.2cm for later use.
The third step was the same as in example 1. Under the condition of 0.2C (1C: 1675mAh/g), the first discharge specific capacity is 937.6mAh/g, and after 50 cycles, the discharge specific capacity is still kept at 632.1 mAh/g.
Example 5:
the first step is as follows: preparing Keqin black composite nano sulfur particles.
(1) Dissolving 2.5g of gelatin in 100mL of deionized water, fully swelling, heating to 60 ℃, and stopping heating after complete dissolution to prepare a gelatin aqueous solution; adding 0.5g Keqin black into gelatin water solution, stirring, and performing ultrasonic treatment for 10 min; dissolving 37.2g of sodium thiosulfate pentahydrate in 50mL of deionized water to prepare a sodium thiosulfate solution; adding sodium thiosulfate solution into gelatin water solution containing ketjen black, and stirring uniformly;
(2) taking 25mL of concentrated hydrochloric acid into 75mL of deionized water, and mixing to obtain a dilute hydrochloric acid solution;
(3) dropwise adding the dilute hydrochloric acid obtained in the step (2) into the solution obtained in the step (1) under the condition of magnetic stirring, and reacting for 30min after dropwise adding, wherein the reaction temperature is 60 ℃;
(4) centrifuging the solution obtained in the step (3), washing with deionized water twice, adding the lower-layer precipitate obtained by centrifuging into 120mL of deionized water, and performing ultrasonic treatment for 5min to obtain a suspension;
(5) 1mL of 50% glutaraldehyde solution is taken and put in 49mL of deionized water, and the mixture is stirred uniformly;
(6) under the condition of magnetic stirring, dropwise adding the solution obtained in the step (5) into the suspension obtained in the step (4), and reacting for 2 hours after dropwise adding, wherein the reaction temperature is room temperature; and centrifuging after the reaction is finished to obtain a lower layer precipitate, and drying to obtain the Ketjen black composite nano sulfur particles. The sulfur content in the composite was 82.5 wt% as determined by thermogravimetric analysis.
The second step is that: and preparing the cathode material.
Uniformly mixing the dried Ketjen black composite nano sulfur particles, acetylene black and gelatin solution (2 wt%), wherein the mass ratio of the Ketjen black composite nano sulfur to the acetylene black to the gelatin is 8:1:1, magnetically stirring for 48 hours to obtain slurry, uniformly coating the slurry on an aluminum foil, drying for 10 hours in a vacuum drying oven, and cutting the dried anode material into a wafer with the diameter of 1.2cm for later use.
The third step was the same as in example 1. Under 0.2C (1C: 1675mAh/g), the specific discharge capacity is still maintained at 643.4mAh/g after 50 cycles.
Claims (6)
1. The method for preparing the nano sulfur particles is characterized in that the nano sulfur particles are a sulfur nano composite material, and specifically comprises the following steps:
(1) respectively preparing a sodium thiosulfate aqueous solution and gelatin or a gelatin aqueous solution containing a conductive agent, and uniformly mixing to obtain a solution A;
(2) preparing an acid solution B;
(3) dropwise adding the solution B in the step (2) into the solution A in the step (1) under the condition of stirring, and reacting to obtain a solution C;
(4) centrifuging and washing the solution C obtained in the step (3) for 0-2 times, adding deionized water, and performing ultrasonic treatment to obtain a suspension D;
(5) preparing a glutaraldehyde aqueous solution E; 0.5-2% of mass fraction;
(6) and (3) under the condition of magnetic stirring, adding the solution E in the step (5) into the suspension D in the step (4), reacting for 0.5-2 h at room temperature, centrifuging to obtain powder, and drying to obtain the nano sulfur particles.
2. The method for preparing nano sulfur particles according to claim 1, wherein the mass concentration of sodium thiosulfate in the solution A in the step (1) is 10 to 30%, the mass concentration of gelatin is 1 to 5%, and the mass concentration of the conductive agent is 0 to 3%.
3. The method for preparing nano sulfur particles according to claim 1, wherein the concentration of the acid solution B in the step (2) is 2mol/L to 4 mol/L.
4. The method for preparing nano sulfur particles according to claim 1, wherein the molar ratio of the sodium thiosulfate to the acid in the step (3) is 1:1-3, and the reaction is carried out for 0.5h-2h at a temperature of 40 ℃ to 80 ℃.
5. The method for preparing nano sulfur particles according to claim 1, wherein the mass fraction of the glutaraldehyde aqueous solution E in step (5) is 0.5% to 2%; the volume ratio of the suspension D to the solution E in the step (6) is 2-5: 1.
6. The method for preparing nano sulfur particles according to claim 1, wherein the conductive agent in the step (1) is one or more selected from acetylene black, ketjen black, Super P, carbon nano tube, graphene or porous carbon; the acid in the step (2) is hydrochloric acid, sulfuric acid or nitric acid.
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| JP2012204332A (en) * | 2011-03-28 | 2012-10-22 | Tokyo Univ Of Agriculture & Technology | Positive electrode material for lithium-sulfur battery, lithium-sulfur battery, and composite and method for manufacturing the same |
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| CN104900902A (en) * | 2015-06-29 | 2015-09-09 | 北京化工大学 | High-performance lithium sulfur battery |
| CN106252642A (en) * | 2016-09-22 | 2016-12-21 | 清华大学深圳研究生院 | The preparation method and applications of sulfur nanoparticulate dispersion |
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| CN101399329A (en) * | 2007-09-26 | 2009-04-01 | 北京化工大学 | Positive pole plate of lithium-sulfur cell and manufacturing method thereof |
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