CN109585830B - Sulfur-selenium compound coated with conductive polymer and graphene oxide, and preparation and application thereof - Google Patents
Sulfur-selenium compound coated with conductive polymer and graphene oxide, and preparation and application thereof Download PDFInfo
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Abstract
The invention discloses a sulfur selenium compound coated with a conductive polymer and graphene oxide, and a preparation method and application thereof, and is characterized in that: based on a sulfur selenium compound generated by the reaction of sodium selenite and sodium sulfide, a layer of conductive polymer is coated on the outer layer to improve the conductivity, and finally a layer of graphene oxide is coated to obtain the selenium sulfide/conductive polymer/graphene oxide composite material. The conductive polymer is introduced into the selenium sulfide anode material, so that the conductivity of the selenium sulfide can be obviously improved, and the shuttle effect caused by diffusion loss of polysulfide and polyselenide can be relieved. In addition, the specific capacity of the selenium sulfide battery can be effectively improved by the graphene oxide of the outermost coating layer.
Description
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to a sulfur selenium compound coating a conductive polymer and graphene oxide, and preparation and application thereof.
Background
In today's society, human society is mainly facing two major crises: environmental problems and energy problems, so that the development of renewable energy sources as well as new green energy sources has become a common recognition of our human society. Nowadays, the development of high-performance batteries has become a burden on scientists, and electric vehicles and the like which use green energy and are free of pollution gradually move to the masses from the research and development stage. The lithium-sulfur battery is widely concerned at present due to higher theoretical specific capacity, but the sulfur has poor conductivity, and the selenium element with higher conductivity in the same main group with the sulfur has not high theoretical specific capacity, which is only 687 mAh/g. Selenium sulfide, which has both advantages, has gone into the field of view of scientists as an electrode material. Selenium sulfide is used as a positive electrode active material, the theoretical specific capacity of the selenium sulfide is lower than that of sulfur (the specific capacity is 1675mAh/g, and the energy density is 2600Wh/kg), but the conductivity of the selenium sulfide is higher than that of elemental sulfur. It can be seen that the theoretical energy density of selenium sulfide is also significant when it is combined with lithium metal to form a battery. In addition, the selenium sulfide also has the advantages of abundant resources, low price and the like. For this reason, batteries fabricated with selenium sulfide as the positive electrode are considered to be the next generation of very cost-effective high performance battery systems with great potential for development.
The battery prepared by taking metallic lithium as a negative electrode and selenium sulfide as a positive electrode is one of secondary battery systems which are most attractive to research nowadays, but the battery has own defects. For example, the shuttling effect caused by the dissolution of polysulfide, polyselenide, which is an intermediate product of the selenium sulfide positive electrode material, and the volume expansion effect, etc., lead to the shortening of the cycle life of the battery and the rapid attenuation of the specific capacity of the battery. Through extensive research, it has been found that the introduction of a conductive polymer is a relatively efficient way to handle the volume expansion effect, while it may increase the conductivity of the electrode. Scientists such as Zuiyi and the like synthesize a novel sulfur/polythiophene composite material by using an in-situ chemical oxidation polymerization method, and polythiophene plays a role in the composite material as a conductive agent and an absorbent. The polythiophene is coated on the surface of sulfur to form a core-shell structure, and the electrochemical performance of the battery can be effectively improved by the core-shell structure. (NanoLett.,2013,13,5534-5540) in 2012, Amine et al, who first proposed a view: mixing selenium disulfide (SeS)2) As the anode material of lithium ion battery. The working principle is as follows: as the stoichiometric number of elemental sulfur in the sulfur selenium compound increases, its specific capacity becomes higher, but with it the cycle stability becomes worse. (J.Am.chem.Soc.,2012,134,4505-4508)
After comparing the factors such as specific capacity, coulombic efficiency and cycle life, the selenium sulfide is considered to be a lithium ion electrode material with great research value. However, even though selenium sulfide has a very broad prospect, it is used as a positive electrode material because of problems such as shuttle effect generated by lithium polysulfide, lithium selenide which is an intermediate product of electrode reaction and is easily dissolved in electrolyte, volume change in the charging and discharging process, and the like, and thus electrochemical performance is poor. Therefore, the selenium sulfide with the coating structure can improve the conductivity of the selenium sulfide battery electrode, limit the shuttling effect and the volume expansion effect of the electrode.
Disclosure of Invention
The invention aims to prepare a double-layer coated positive electrode material for a selenium sulfide battery, which can effectively improve the conductivity of an electrode of the selenium sulfide battery, and limit the shuttle effect and the volume expansion effect of the electrode.
The technical scheme of the invention provides a sulfur selenium compound coated with a conductive polymer and graphene oxide, wherein the conductive polymer is coated on the outer layer of the sulfur selenium compound, and the graphene oxide is coated on the outer layer of the conductive polymer.
The conductive polymer is one or more than two of polythiophene, polyaniline or polypyrrole; the selenium sulfide compound is selenium sulfide.
The polythiophene takes 3, 4-ethylenedioxythiophene as a monomer; the polyaniline takes aniline as a monomer; the polypyrrole takes pyrrole as a monomer.
In another aspect, the invention also relates to a selenium sulfide battery positive plate, which comprises a current collector and the sulfur selenium compound coating which coats the conductive polymer and the graphene oxide and is coated on the current collector.
The coating comprises a conductive agent and a binder, and the mass ratio of the sulfur selenium compound coating the conductive polymer and the graphene oxide to the conductive agent to the binder is 7-8: 1-2: 1.
The conductive agent is one or more than two of acetylene black, ketjen black, conductive carbon black or graphene.
The binder is one or more of beta-carbonyl cyclodextrin, polyvinylidene fluoride, sodium carboxymethyl cellulose, polyacrylic acid and epoxy resin.
In another aspect, the present invention also relates to a preparation method of the above sulfur selenium compound coating conductive polymer and graphene oxide, comprising the following steps:
step (1): mixing selenite and sulfide salt in water according to the molar ratio of 1: 1-3: 1, wherein the water contains a surfactant, the concentration of the surfactant is 2-4 g/mL, the pH value is adjusted to 2-3, the reaction is carried out for 12-24 h, and an insoluble substance, namely selenium sulfide, is obtained through centrifugation; the surfactant is one or more of polyvinylpyrrolidone, cetyl trimethyl ammonium bromide or calcium dodecyl benzene sulfonate;
step (2): preparing the selenium sulfide obtained in the step (1) into a suspension with the concentration of 0.6-2 mg/mL, and coating a conductive polymer on the outer layer of the selenium sulfide to obtain the selenium sulfide coated with the conductive polymer;
and (3): and (3) mixing the selenium sulfide coated with the conductive polymer in the step (2) and the graphene oxide in a solution according to the mass ratio of the selenium sulfide to the graphene oxide of 10: 1-20: 1, stirring for 2-12 h, and centrifugally drying to obtain a selenium sulfide compound coated with the conductive polymer and the graphene oxide.
The step (2) of preparing the conductive polymer on the selenium sulfide outer layer specifically comprises the following steps:
a. sequentially adding 3, 4-ethylenedioxythiophene with the final concentration of 11-23 mmol/L, camphorsulfonic acid with the final concentration of 5-10 mmol/L and ammonium persulfate with the final concentration of 26-50 mmol/L into the selenium sulfide suspension, and reacting for 12-24 h to obtain a polythiophene-coated sulfur selenium compound; or
b. Sequentially adding aniline with the final concentration of 13-26 mmol/L, concentrated hydrochloric acid with the final concentration of 70-150 mmol/L and ammonium persulfate with the final concentration of 8-13 mmol/L into the selenium sulfide suspension, and reacting for 12-24 h to obtain a polythiophene-coated sulfur selenium compound; or
c. And sequentially adding 14-28 mmol/L pyrrole, 9-18 mmol/L ferric trichloride and 0.7-1.4 mmol/L sodium dodecyl sulfate into the selenium sulfide suspension, and reacting for 12-24 h to obtain the polypyrrole-coated sulfur selenium compound.
The invention has the following beneficial effects:
1. the double-layer coated positive electrode material obtained by the invention has the advantages of high conductivity, safety, environmental protection, low price, excellent rate performance and the like. The conductive polymer coating can improve the conductivity of the selenium sulfide electrode, improve the electrochemical performance of the selenium sulfide electrode, and further improve the overall electrochemical performance of the electrode material by coating the graphene again.
2. The conductivity of sulfur is not good, the conductivity of selenium in the same main group is good, but the theoretical specific capacity of selenium is not high, so the selenium sulfide with the advantages of the sulfur and the selenium sulfide is used as an electrode material, and has the advantages of high theoretical specific capacity, high energy density, environmental friendliness of the selenium sulfide, low price and the like.
Drawings
Fig. 1 is an SEM image of a selenium sulfide battery positive electrode material of example 1 of the present invention;
FIG. 2 is an SEM image of a positive electrode material of a selenium sulfide battery of comparative example 1 of the present invention;
FIG. 3 is a graph of the cycling performance of the selenium sulfide cells of examples 1-3 of the present invention and comparative example 1 at a current density of 200 mA/g.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention are further described below with reference to specific examples, which are only exemplary and should not be construed as limiting the technical solutions.
Example 1
Preparing a selenium sulfide battery double-layer coated positive electrode material: 2g of polyvinylpyrrolidone (surfactant) and 0.346g of sodium selenite were dissolved in 50mL of water, and 0.96g of sodium sulfide was dissolved in 30mL of water by sonication and added to the above solution, followed by addition of 2mol/L HCl to a pH of 2. Reacting for 12h, centrifuging and washing.
And then dissolving the centrifuged sample in 100mL of water, sequentially adding 120uL of 3, 4-ethylenedioxythiophene, 0.12g of camphorsulfonic acid and 0.6g of ammonium persulfate, coating for 12 hours, changing to dark green, dissolving the centrifuged sample in 100mL of water, simultaneously adding 0.1mg/mL of graphene oxide aqueous solution, stirring and coating for 2 hours, centrifuging, drying at 80 ℃, and then obtaining the selenium sulfide/polythiophene/graphene oxide composite material. And then uniformly mixing the composite material, acetylene black and polyvinylidene fluoride according to the mass ratio of 7:2:1, performing ball milling to obtain a uniformly mixed positive electrode material, coating the uniformly mixed positive electrode material on an aluminum foil current collector, drying at 60 ℃, and clamping into a positive electrode plate with the diameter of 12 mm.
A lithium sheet is taken as a negative electrode, the adopted electrolyte is prepared by dissolving LITFSI in a mixed solvent of DME and DOL, the concentration of LITFSI in the electrolyte is 1M (the volume ratio of DME to DOL in the electrolyte is 1:1, LITFSI is bis (trifluoromethane) sulfimide lithium, DME is ethylene glycol dimethyl ether, DOL is 1, 3-dioxolane), a Celgard 2400 conventional diaphragm is used as the diaphragm, and the cathode material prepared in the embodiment is adopted to assemble the button cell. And then testing the performance of the battery on a blue test system, cycling for 200 circles under the current density of 200mA/g, testing the cycling performance of the battery, and measuring the specific capacity of 380mAh/g after 200 circles. The results are shown in FIG. 3.
Example 2
Preparing a selenium sulfide battery double-layer coated positive electrode material: 2g of polyvinylpyrrolidone and 0.346g of sodium selenite are dissolved in 50mL of water, and 0.96g of sodium sulfide is dissolved in 30mL of water by sonication and added to the solution, followed by addition of 2mol/L HCl to a pH of 2. The reaction was overnight, centrifuged and washed.
And then dissolving the centrifuged sample in 100mL of water, sequentially adding 120uL of aniline, 240uL of concentrated hydrochloric acid and 0.2g of ammonium persulfate, coating for 12 hours, changing to dark green, dissolving in 100mL of water after centrifugation, simultaneously adding 0.1mg/mL of graphene oxide aqueous solution, stirring, coating for 2 hours, centrifuging, drying at 80 ℃, and then mixing the sample to obtain the selenium sulfide/polyaniline/graphene oxide composite material. And then uniformly mixing the composite material, acetylene black and polyvinylidene fluoride according to the mass ratio of 7:2:1, performing ball milling to obtain a uniformly mixed positive electrode material, coating the uniformly mixed positive electrode material on an aluminum foil current collector, drying at 60 ℃, and clamping into a positive electrode plate with the diameter of 12 mm.
A lithium sheet is taken as a negative electrode, the adopted electrolyte is prepared by dissolving LITFSI in a mixed solvent of DME and DOL, the concentration of LITFSI in the electrolyte is 1M (the volume ratio of DME to DOL in the electrolyte is 1:1, LITFSI is bis (trifluoromethane) sulfimide lithium, DME is ethylene glycol dimethyl ether, DOL is 1, 3-dioxolane), a Celgard 2400 conventional diaphragm is used as the diaphragm, and the cathode material prepared in the embodiment is adopted to assemble the button cell. And then testing the performance of the battery on a blue test system, cycling for 200 circles under the current density of 200mA/g, and testing the cycling performance of the battery, wherein the specific capacity after 200 circles is 290 mAh/g. The results are shown in FIG. 3.
Example 3
Preparing a selenium sulfide battery double-layer coated positive electrode material: 2g of polyvinylpyrrolidone and 0.346g of sodium selenite are dissolved in 50mL of water, and 0.96g of sodium sulfide is dissolved in 30mL of water by sonication and added to the solution, followed by addition of 2mol/L of HCl to a pH of 3. The reaction was overnight, centrifuged and washed.
The centrifuged sample was then dissolved in 100mL of water, and 100uL of pyrrole and 0.15g of FeCl were added sequentially3And 0.02g of sodium dodecyl sulfate, coating for 12 hours to turn to dark green, centrifuging, dissolving in 100mL of water, simultaneously adding 0.1mg/mL of graphene oxide aqueous solution, stirring and coating for two hours, centrifuging, drying at 80 ℃, and then obtaining the selenium sulfide/polypyrrole/graphene oxide composite material. And then uniformly mixing the composite material, acetylene black and polyvinylidene fluoride according to the mass ratio of 7:2:1, performing ball milling to obtain a uniformly mixed positive electrode material, coating the uniformly mixed positive electrode material on an aluminum foil current collector, drying at 60 ℃, and clamping into a positive electrode plate with the diameter of 12 mm.
A lithium sheet is taken as a negative electrode, the adopted electrolyte is prepared by dissolving LITFSI in a mixed solvent of DME and DOL, the concentration of LITFSI in the electrolyte is 1M (the volume ratio of DME to DOL in the electrolyte is 1:1, LITFSI is bis (trifluoromethane) sulfimide lithium, DME is ethylene glycol dimethyl ether, DOL is 1, 3-dioxolane), a Celgard 2400 conventional diaphragm is used as the diaphragm, and the cathode material prepared in the embodiment is adopted to assemble the button cell. And then testing the performance of the battery on a blue test system, cycling for 200 circles under the current density of 200mA/g, and testing the cycling performance of the battery, wherein the specific capacity after 200 circles is 350 mAh/g. The results are shown in FIG. 3.
Comparative example 1
Preparing a selenium sulfide battery positive electrode material: 2g of PVP and 0.346g of sodium selenite are dissolved in 50mL of water, and an additional 0.96g of sodium sulfide is dissolved in 30mL of water with sonication and added to the solution, followed by addition of 2mol/L HCl to bring the pH to 2. The reaction was overnight, centrifuged and washed. And drying at 80 ℃ to obtain the selenium sulfide material. And then uniformly mixing the composite material, acetylene black and polyvinylidene fluoride according to the mass ratio of 7:2:1, performing ball milling to obtain a uniformly mixed positive electrode material, coating the uniformly mixed positive electrode material on an aluminum foil current collector, drying at 60 ℃, and clamping into a positive electrode plate with the diameter of 12 mm.
A lithium sheet is taken as a negative electrode, the adopted electrolyte is prepared by dissolving LITFSI in a mixed solvent of DME and DOL, the concentration of LITFSI in the electrolyte is 1M (the volume ratio of DME to DOL in the electrolyte is 1:1, LITFSI is bis (trifluoromethane) sulfimide lithium, DME is ethylene glycol dimethyl ether, DOL is 1, 3-dioxolane), a Celgard 2400 conventional diaphragm is used as the diaphragm, and the cathode material prepared in the embodiment is adopted to assemble the button cell. The cell performance was then tested on a blue test system, cycling at a current density of 200mA/g for 200 cycles, with the results shown in fig. 3.
As can be seen from fig. 3: the electrochemical performance of the selenium sulfide battery assembled by the positive electrode material coated with the conductive polymer and the graphene oxide is improved compared with that of the selenium sulfide battery without any coating, and the conductive polymer is introduced into the selenium sulfide positive electrode material, so that the conductivity of the selenium sulfide can be obviously improved, and the shuttle effect caused by diffusion loss of polysulfide and polyselenide can be relieved. And the graphene oxide can improve the specific capacity of the selenium sulfide battery. In addition, comparison of different conductive polymers shows that the electrochemical performance of the polythiophene coated selenium sulfide battery is the best compared with that of the polythiophene coated selenium sulfide battery.
The technical solution of the present invention is not limited to the above-mentioned examples, and other embodiments obtained according to the technical solution of the present invention should fall into the claims of the present invention.
Claims (9)
1. A preparation method of a sulfur selenium compound coating a conductive polymer and graphene oxide comprises the following steps:
step (1): mixing selenite and sulfide salt in water according to the molar ratio of 1: 1-3: 1, wherein the water contains a surfactant, the concentration of the surfactant is 2-4 g/mL, the pH value is adjusted to 2-3, the reaction is carried out for 12-24 h, and an insoluble substance, namely selenium sulfide, is obtained through centrifugation; the surfactant is one or more of polyvinylpyrrolidone, cetyl trimethyl ammonium bromide or calcium dodecyl benzene sulfonate;
step (2): preparing the selenium sulfide obtained in the step (1) into a suspension with the concentration of 0.6-2 mg/mL, and coating a conductive polymer on the outer layer of the selenium sulfide to obtain the selenium sulfide coated with the conductive polymer;
and (3): and (3) mixing the selenium sulfide coated with the conductive polymer in the step (2) and the graphene oxide in a solution according to the mass ratio of the selenium sulfide to the graphene oxide of 10: 1-20: 1, stirring for 2-12 h, and centrifugally drying to obtain a selenium sulfide compound coated with the conductive polymer and the graphene oxide.
2. The method of claim 1, wherein: the step (2) of preparing the conductive polymer on the selenium sulfide outer layer specifically comprises the following steps:
a. sequentially adding 3, 4-ethylenedioxythiophene with the final concentration of 11-23 mmol/L, camphorsulfonic acid with the final concentration of 5-10 mmol/L and ammonium persulfate with the final concentration of 26-50 mmol/L into the selenium sulfide suspension, and reacting for 12-24 h to obtain a polythiophene-coated sulfur selenium compound; or
b. Sequentially adding aniline with the final concentration of 13-26 mmol/L, concentrated hydrochloric acid with the final concentration of 70-150 mmol/L and ammonium persulfate with the final concentration of 8-13 mmol/L into the selenium sulfide suspension, and reacting for 12-24 h to obtain a polythiophene-coated sulfur selenium compound; or
c. And sequentially adding 14-28 mmol/L pyrrole, 9-18 mmol/L ferric trichloride and 0.7-1.4 mmol/L sodium dodecyl sulfate into the selenium sulfide suspension, and reacting for 12-24 h to obtain the polypyrrole-coated sulfur selenium compound.
3. The conductive polymer and graphene oxide coated sulfur selenium compound prepared by the preparation method of claim 1 or 2, wherein the conductive polymer is coated on the outer layer of the sulfur selenium compound, and the graphene oxide is coated on the outer layer of the conductive polymer.
4. The selenothiogen compound of claim 3, wherein the conductive polymer is one or more of polythiophene, polyaniline and polypyrrole; the selenium sulfide compound is selenium sulfide.
5. The selenothiogen compound of claim 4, wherein the polythiophene comprises 3, 4-ethylenedioxythiophene as a monomer; the polyaniline takes aniline as a monomer; the polypyrrole takes pyrrole as a monomer.
6. A positive plate of a selenium sulfide battery, comprising a current collector and a coating layer of the selenium sulfide compound coating the conductive polymer and the graphene oxide of claim 3,4 or 5 coated on the current collector.
7. The positive electrode sheet according to claim 6, wherein: the coating further comprises a conductive agent and a binder, and the mass ratio of the sulfur selenium compound coating the conductive polymer and the graphene oxide to the conductive agent to the binder is 7-8: 1-2: 1.
8. The positive electrode sheet according to claim 7, wherein: the conductive agent is one or more than two of acetylene black, ketjen black, conductive carbon black or graphene.
9. The positive electrode sheet according to claim 7, wherein: the binder is one or more of beta-carbonyl cyclodextrin, polyvinylidene fluoride, sodium carboxymethyl cellulose, polyacrylic acid and epoxy resin.
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