CN110350142B - Preparation method of integrated porous polypyrrole-loaded sodium electrode and sulfur electrode - Google Patents
Preparation method of integrated porous polypyrrole-loaded sodium electrode and sulfur electrode Download PDFInfo
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Abstract
The invention relates to the technical field of sodium batteries, and aims to provide a preparation method of an integrated porous polypyrrole loaded sodium electrode and sulfur electrode. The method comprises the following steps: taking deionized water, pyrrole and Na salt anion surfactant, and performing ultrasonic vibration dispersion to obtain pyrrole emulsion; then taking deionized water, a nano calcium carbonate template, an initiator sodium persulfate and a Na salt anion surfactant, uniformly mixing to obtain a suspension, and polymerizing pyrrole to obtain an integrated porous polypyrrole carrier material; and pressing the metal sodium foil with the same area in a glove box, and heating at 100 ℃ until the sodium foil is molten and enters a carrier material to obtain the sodium electrode for the low-temperature sodium-sulfur battery. The porous polypyrrole obtained by the invention has the characteristics of large specific surface area and large pore volume, and the pyrrole nitrogen on the polypyrrole becomes a metal sodium nucleation center, so that more metal sodium can be supported, and the porous polypyrrole is suitable for preparing a high-performance sulfur electrode material. The porous polypyrrole sodium-carrying and sulfur-carrying process is simple and easy to implement, is beneficial to large-scale production, reduces the cost and has market competitiveness.
Description
Technical Field
The invention relates to the technical field of sodium batteries, in particular to a preparation method of an integrated porous polypyrrole-loaded sodium electrode and sulfur electrode.
Background
Sodium sulfur batteries (NaS) have been developed since the time since as a new chemical source of power. The sodium-sulfur battery has small volume, large capacity, long service life and high efficiency, and is widely applied to the aspects of peak clipping and valley filling, emergency power supply, wind power generation and other energy storage in electric energy storage. Generally, a sodium-sulfur battery is composed of a positive electrode, a negative electrode, an electrolyte, a separator, and a case.
The traditional sodium-sulfur battery consists of a molten electrode and a solid electrolyte, wherein the active substance of a negative electrode is molten metal sodium, the active substance of a positive electrode is liquid sulfur and sodium polysulfide molten salt, the working temperature is 300-350 ℃, and the currently used electrolyte material is β -Al2O3β -Al only when the temperature is above 300 DEG C2O3When the cell is discharged, electrons are transported from the sodium anode (negative electrode) to the sulfur cathode (positive electrode) via an external circuit, and sodium ions pass through the solid electrolyte β -Al2O3And S2-The combination forms a sodium polysulfide product, the electrode reaction being opposite to the discharge during charging. The direct reaction of sodium with sulfur is severe, so twoThe reactants must be separated by a solid electrolyte, which must be a sodium ion conductor. Elemental sulfur is completely changed into S according to unit mass2-The theoretical specific discharge capacity of sulfur can be obtained by the provided electric quantity and is 1675mAh g-1. The chemical reaction formula of the sodium-sulfur battery is as follows: 2Na + xS ═ Na2Sx. In the initial stage of discharge, the sulfur content is 100% -78%, and the positive electrode is made of liquid sulfur and liquid Na2S3.2Forming a non-common solution phase, wherein the electromotive force of the battery is about 2.076V; when discharging to Na2S3When the electromotive force of the battery is reduced to 1.78V; when discharging to Na2S2.7When it appeared, the corresponding electromotive force was reduced to 1.74V until the liquid phase disappeared.
The sodium-sulfur battery mainly has the following characteristics: 1. theoretical energy density is as high as 760Wh kg-1. The actual specific energy is high, the volume and the weight of an energy storage system can be effectively reduced, and the energy storage system is suitable for application of high-capacity and high-power equipment; 2. the energy conversion efficiency is high, wherein the direct current end is more than 90%, and the alternating current end is more than 75%; 3. no electrochemical side reaction, no self-discharge and long service life which can be more than 15 years; 4. the operation temperature of the sodium-sulfur battery is kept constant at 300-350 ℃, so that the use condition of the sodium-sulfur battery is not limited by the temperature of the external environment, and the temperature stability of the system is good; 5. has high power characteristics, and can be discharged with large current and without damaging the battery; the system has nanosecond instantaneous speed, is within milliseconds of the system, and is suitable for various standby and emergency power stations; 6. the raw material resources are rich, the price is low, no pollution is caused, and the method is suitable for large-scale popularization and application. However, sodium-sulfur batteries have problems: (1) the working temperature is high; (2) the device is not suitable for intermittent work, and the leakage of the galvanic pile and the fatigue damage of materials are easily caused by the continuous switching of high and low temperatures; (3) the scale of the flow battery cannot be too large, and the like.
The traditional high-temperature sodium-sulfur battery has obvious advantages as an energy storage battery, has no superiority when used as a power supply of an electric automobile or other mobile appliances, and does not completely solve the problem of safety and reliability of the sodium-sulfur battery, so the high-temperature sodium-sulfur battery is not suitable for application in the aspect of vehicle energy. In order to solve the problems of the high-temperature sodium-sulfur battery, the key point is to reduce the working temperature of the sodium-sulfur battery. The low-temperature sodium-sulfur battery has the advantages of high specific power and specific energy, low raw material cost, no self-discharge, safety and the like, so that the low-temperature sodium-sulfur battery becomes the power battery with the most application prospect at present.
The low-temperature sodium-sulfur battery adopts liquid electrolyte, and the traditional diaphragm is easy to generate sodium dendrite to penetrate through the diaphragm in the charging and discharging process, so that short circuit is easy to cause during use, and the battery is unsafe to use. Secondly, a large amount of polysulfide ions dissolved in the electrolyte can be generated in the working process of the sodium-sulfur battery, and most polysulfide ions can move in the electrolyte along with the action of concentration gradient and electric field force because the molecules of the polysulfide ions are relatively small. When the long-chain polysulfide ions move to the negative electrode, the long-chain polysulfide ions react with sodium metal to generate short-chain polysulfide ions, and the short-chain polysulfide ions move to the positive electrode under the action of concentration gradient force and electric field force to react with sulfur simple substances to generate the long-chain polysulfide ions again, so that a so-called shuttle effect is formed. These polysulfide ions move continuously in the electrolyte and consume a large amount of energy in the reaction, so that the actual efficiency of the cell reaction is reduced. With the progress of charge and discharge reaction, the shuttle of polysulfide ions and sodium metal form sodium sulfide on the negative electrode to deposit, the content of effective active substance sulfur of the battery is continuously reduced, and the battery capacity is subjected to cycle decline.
In order to avoid the generation of negative sodium dendrite and the shuttling of positive sodium polysulfide, the invention provides an integrated porous polypyrrole material, which is respectively loaded with sodium and sulfur to obtain a sodium electrode and a sulfur electrode, so that the sodium dendrite generated by a negative electrode and the positive sodium polysulfide are prevented from migrating to the negative electrode, and a high-performance low-temperature sodium-sulfur battery is obtained.
In a lithium-sulfur battery similar to a low-temperature sodium-sulfur battery, carbon-coated sulfur is used as a positive electrode material, and the purpose is to prevent polysulfide ions from migrating to a negative electrode and to suppress shuttling of lithium polysulfide. However, compared with lithium ions, the radius of sodium ions is larger, the acting force between polysulfide ions and sodium ions is weaker, the polysulfide ions are easier to dissolve in the electrolyte, and the polysulfide ions are easier to shuttle. Because of the small radius of lithium ions, the carbon layer spacing is not as resistant to lithium conduction and can cause a large resistance to larger size sodium ion conduction. The conventional carbon coating realizes lithium ion conduction but hinders polysulfide ion transfer, but if the carbon coating is simply applied to a sodium-sulfur battery, although polysulfide ion transfer can be hindered, sodium ion conduction is also hindered, so that polarization of a sulfur electrode is aggravated, and performance is reduced. Because the radius of sodium ions is close to the radius of sulfur atoms, and polysulfide ions are linear molecular structures, the traditional carbon material is difficult to block the transmission of polysulfide ions but does not block the conduction of sodium ions. Generally, the larger the radius of the sodium ion conduction channel only promotes the shuttling of polysulfide ions, and the performance of the sodium-sulfur battery is difficult to improve. For this reason, it is necessary to design a selective conduction path of sodium ions and polysulfide ions, but the conventional carbon materials cannot achieve this goal.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects of the prior art and provides a preparation method of an integrated porous polypyrrole loaded sodium electrode and sulfur electrode.
In order to solve the technical problem, the solution of the invention is as follows:
the preparation method of the integrated porous polypyrrole loaded sodium electrode comprises the following steps:
(1) taking 100mL of deionized water, adding 0.15-0.9 g of pyrrole and 1g of Na salt anionic surfactant, and performing ultrasonic vibration dispersion for 5 minutes to obtain pyrrole emulsion; then taking 50mL of deionized water, adding 0.5-3 g of nano calcium carbonate template, 0.1-0.5 g of initiator sodium persulfate and 1g of Na salt anion surfactant, and uniformly mixing to obtain a suspension; under the conditions of ice bath and stirring, dropwise adding the suspension into the pyrrole emulsion, and continuously reacting for one hour after dropwise adding; then, carrying out vacuum filtration by using filter paper made of polyacrylate, drying the filter cake and the filter paper, and dissolving the filter paper by using acetone to obtain a filter cake; washing the filter cake with dilute hydrochloric acid to remove the nano calcium carbonate template, rinsing with deionized water, and drying to obtain a sheet-shaped integrated porous polypyrrole carrier material;
(2) taking 150mg of the integrated porous polypyrrole carrier material obtained in the step (1), pressing a metal sodium foil with the same area with the integrated porous polypyrrole carrier material in a glove box, and controlling the thickness of the metal sodium foil to enable the mass ratio of metal sodium to the carrier material to be 1-10: 1; and then heating at 100 ℃ until the sodium foil melts into the carrier material, to obtain the sodium electrode for the low-temperature sodium-sulfur battery.
The invention provides a preparation method of an integrated porous polypyrrole-loaded sulfur electrode, which comprises the following steps:
(1) taking 100mL of deionized water, adding 0.15-0.9 g of pyrrole and 1g of Na salt anionic surfactant, and performing ultrasonic vibration dispersion for 5 minutes to obtain pyrrole emulsion; then taking 50mL of deionized water, adding 0.5-3 g of nano calcium carbonate template, 0.1-0.5 g of initiator sodium persulfate and 1g of Na salt anion surfactant, and uniformly mixing to obtain a suspension; under the conditions of ice bath and stirring, dropwise adding the suspension into the pyrrole emulsion, and continuously reacting for one hour after dropwise adding; then, carrying out vacuum filtration by using filter paper made of polyacrylate, drying the filter cake and the filter paper, and dissolving the filter paper by using acetone to obtain a filter cake; washing the filter cake with dilute hydrochloric acid to remove the nano calcium carbonate template, rinsing with deionized water, and drying to obtain a sheet-shaped integrated porous polypyrrole carrier material;
(2) dispersing elemental sulfur in DMSO in a mass ratio of 1:1, in ZrO2Performing ball milling in a ball milling tank for 30 minutes to obtain suspension; taking 150mg of the integrated porous polypyrrole carrier material obtained in the step (1), coating the suspension on a polypyrrole carrier, and controlling the mass ratio of sulfur to the carrier material to be 1-10: 1; heating at 90 deg.C for 1 hr, and vacuum drying to remove DMSO; and then moving the mixture to a nitrogen atmosphere, heating the mixture to 155 ℃ and keeping the temperature for 2 hours to ensure that the elemental sulfur is completely melted and enters the carrier material, thus obtaining the sulfur electrode for the low-temperature sodium-sulfur battery.
In the invention, the hydrophobic group of the Na salt anionic surfactant in the step (1) is long-chain alkyl, secondary alkyl or alkylaryl, and the hydrophilic group is carboxyl (RCOO) and sulfonic acid (R-SO)3) Or sulfate ester groups (R-OSO)3) (ii) a Correspondingly, the general formulas of the anionic surfactants are respectively expressed as RCOONa and R-SO3Na or R-OSO3Na, wherein R is long-chain alkyl, secondary alkyl or alkylaryl. In the present invention, in the step (1), the ultrasonic frequency is controlled to 40kHz when ultrasonic vibration dispersion is performed.
In the present invention, in the step (1), the dropping acceleration is controlled to be 10 mL/hr when the suspension is dropped into the pyrrole emulsion.
The invention further provides a low-temperature sodium-sulfur battery, which comprises a diaphragm, a positive electrode, a negative electrode and electrolyte; the sodium-sulfur battery takes a prepared sodium electrode as a negative electrode and a prepared sulfur electrode as a positive electrode, the sodium electrode and the sulfur electrode are respectively arranged on two sides of a diaphragm to form a sandwich structure, the electrode material sides on the positive electrode and the negative electrode face the diaphragm, and electrolyte is internally arranged in the sandwich structure;
the electrolyte is Na [ (CF)3SO2)2N]As a solute, a mixture of dioxolane and ethylene glycol monomethyl ether is used as a solvent; the volume ratio of dioxolane to ethylene glycol monomethyl ether is 1:1, one mole of solute is contained in each liter of electrolyte.
Description of the inventive principles:
according to the invention, the porous material is used for carrying sodium, so that the electrochemical reaction of the metal sodium is limited to be carried out in the pores, and the growth of sodium dendrite can be effectively inhibited. Meanwhile, the porous material for sodium ion selective conduction is used as a carrier for carrying sodium, so that the sodium ion conduction can be enhanced, and the polarization of a sodium cathode can be effectively reduced. The pure pyrrole monomer is colorless oily liquid at normal temperature and is a C, N five-membered heterocyclic molecule. Polypyrrole is a common conductive polymer, is a heterocyclic conjugated conductive polymer, is usually an amorphous black solid, is a conductive polymer which has good air stability and is easy to electrochemically polymerize into a film, is insoluble and infusible, and has properties such as conductivity, mechanical strength and the like closely related to polymerization conditions such as anions, solvents, pH values, temperatures and the like of an electrolyte. Pyrrole is used as a monomer and is prepared by oxidative polymerization, and the oxidant is ferric trichloride, ammonium persulfate and the like. The conductive polypyrrole has a conjugated chain oxidation structure and a corresponding anion doping structure, the conductivity of the conductive polypyrrole can reach 102-103S/cm, the tensile strength of the conductive polypyrrole can reach 50-100 MPa, and the conductive polypyrrole has good electrochemical oxidation-reduction reversibility. The conduction mechanism is as follows: the polypyrrole structure has a conjugated structure formed by alternately arranging carbon-carbon single bonds and carbon-carbon double bonds, wherein the double bonds are formed by sigma electrons and pi electrons, the sigma electrons are fixed and cannot move freely, and covalent bonds are formed between carbon atoms. The 2 pi electrons in the conjugated double bonds are not fixed to a carbon atom and they can be translocated from one carbon atom to another, i.e. have a tendency to extend throughout the molecular chain. I.e. the overlapping of the pi electron clouds within the molecule creates an energy band common to the whole molecule, the pi electrons being similar to the free electrons in a metal conductor. When an electric field is present, electrons constituting pi bonds can move along the molecular chain. In the polymer, pyrrole structural units are mainly connected with each other in alpha position, and the large hydrophobic anion doped polypyrrole can be stored in air for years without significant change. The pyrrole hydrogen on polypyrrole can exchange with Na ion and become a good conductor of Na ion. Particularly, when the polypyrrole is prepared by using a large anion surfactant, anion is embedded while the polypyrrole is synthesized, and then the adsorption center of polysulfide ions is formed through anion exchange, so that the effect of inhibiting the shuttling of the polysulfide ions is achieved.
The invention provides an integrated porous polypyrrole material, a negative electrode and a positive electrode preparation method thereof, wherein the negative electrode and the positive electrode are obtained by carrying sodium and carrying sulfur, and the preparation method aims at overcoming the defect that the traditional carbon coating hinders the sodium ion conduction. By adding Na salt anionic surfactant, such as sodium fatty acid surfactant (RCOONa), sodium sulfonate type surfactant (RSO) during pyrrole polymerization3Na), sulfate sodium salt surfactant (ROSO)3Na) during the polymerization of pyrrole, sodium ions exchange with pyrrole hydrogen to form a conducting network of sodium ions. The transmission of sodium ions on a polypyrrole chain is realized, the transmission of the sodium ions in a porous material is enhanced depending on the three-dimensional polypyrrole network structure of the porous polypyrrole, the deposition of sodium outside pores during charging is inhibited, and the problem of sodium dendrite of a sodium-sulfur battery is solved. Anions RCOO-, RSO3―、ROSO3Polypyrrole is embedded and then polysulfide ion exchange is carried out, so that a polysulfide ion adsorption center is formed, and the polysulfide ion adsorption center is used as a positive electrode sulfur-carrying material to play a role in inhibiting the shuttling of polysulfide ions, so that the low-temperature sodium-sulfur battery with high reliability, safety and long service life is obtained.
Description of the preparation method of the present invention:
in the step (1), the hydrophilic nano calcium carbonate template is difficult to keep good direct contact with the lipophilic pyrrole. Adding Na salt anionic surfactant into pyrrole-water mixed liquid, and performing ultrasonic emulsification to obtain pyrroleEmulsion, anionic surfactant molecules are arranged on the surface of emulsion droplets, and hydrophilic groups of the emulsion droplets face outwards uniformly. Na salt anion surfactant is added into the nano calcium carbonate-water suspension liquid, the anion surfactant molecules are arranged on the surface of calcium carbonate nano particles, the hydrophilic groups of the anion surfactant molecules and the oxygen on the surface of the nano particles are chemically adsorbed, and the hydrophobic groups of the anion surfactant molecules face outwards in a consistent manner. When the initiator-containing nano calcium carbonate-water suspension is dripped into the pyrrole emulsion, the surfactant-adsorbed calcium carbonate nano particles meet and fuse with the pyrrole emulsion droplets, the pyrrole naturally coats the calcium carbonate nano particles, the pyrrole polymerization is carried out under the action of the initiator to form polypyrrole-coated calcium carbonate particles, and meanwhile, the polypyrrole among the particles are mutually linked to form an aggregate. During the suction filtration process, the aggregates are self-assembled to form an integrated polypyrrole coated calcium carbonate material, polypyrrole forms a continuous phase, and nano calcium carbonate particles are distributed in the polypyrrole coated calcium carbonate material as a disperse phase. During the pickling process, the calcium carbonate decomposes to form water-soluble calcium chloride and gaseous CO2And leaving holes in the polypyrrole matrix to form the integrated porous polypyrrole carrier material.
And heating the pressfitting object of the porous polypyrrole and the metal sodium at 100 ℃, and melting the sodium to enter an inner hole of the porous polypyrrole to obtain the sodium electrode. The pyrrole nitrogen dispersed and distributed in the porous polypyrrole plays a role in the nucleation center of the metal sodium, the metal sodium is induced to form in the pores, the high specific surface area and the large pore volume ensure the high sodium-carrying capacity and the reaction speed, and therefore sodium dendrite formation is avoided.
And heating the integrated porous polypyrrole coated with elemental sulfur at 155 ℃ in a nitrogen atmosphere, and completely melting the elemental sulfur into an inner hole of the porous polypyrrole to obtain the sulfur electrode. Interaction of pyrrole nitrogen and sulfur in the porous polypyrrole dispersed distribution strengthens adsorption capacity of the porous polypyrrole on polysulfide ions, so that shuttle phenomenon of polysulfide ions in the sodium-sulfur battery is effectively inhibited, and service life of the battery is prolonged.
Compared with the prior art, the invention has the beneficial effects that:
the porous polypyrrole has the characteristics of large specific surface area and large pore volume, pyrrole nitrogen on the polypyrrole becomes a metal sodium nucleation center and can carry more metal sodium, and the polypyrrole pore wall has the capacity of resisting the puncture of sodium dendrites, so that the growth of the sodium dendrites to a diaphragm is avoided, and the short circuit of a battery is prevented. Similarly, the pyrrole nitrogen on the polypyrrole has strong affinity to polysulfide ions, and the pyrrole nitrogen dispersed on the porous carbon wall is favorable for adsorbing the polysulfide ions and inhibiting the shuttle of the polysulfide ions, so that the polypyrrole nitrogen porous carbon electrode material is suitable for preparing high-performance sulfur electrode materials. The porous polypyrrole sodium-carrying and sulfur-carrying process is simple and easy to implement, is beneficial to large-scale production of sodium electrodes and sulfur electrodes, reduces the cost and has market competitiveness.
Drawings
FIG. 1 is an electron micrograph (micrograph) of a porous polypyrrole material prepared in example 3.
Detailed Description
The invention is described in further detail below with reference to the following detailed description and accompanying drawings:
the following examples are presented to enable those skilled in the art to more fully understand the present invention and are not intended to limit the invention in any way.
Example 1 porous polypyrrole with sodium fatty acid as surfactant
The soap is the most common fatty acid salt anionic surfactant, 0.15g of pyrrole and 1g of soap are added into 100mL of deionized water, pyrrole emulsion is obtained after ultrasonic vibration (ultrasonic frequency 40kHz) is carried out for 5 minutes, then 50mL of deionized water is added into 0.5g of nano calcium carbonate template, 0.1g of initiator sodium persulfate and 1g of soap to obtain suspension, the suspension is dropwise added into the pyrrole emulsion while stirring in an ice bath, and the dropping speed is 10 mL/h; and after the dropwise addition is finished and the reaction is carried out for one hour, vacuum filtration is carried out, the template nano calcium carbonate is cleaned by dilute hydrochloric acid, and the flake-shaped integrated porous polypyrrole carrier material is obtained after rinsing and drying by deionized water.
Example 2 porous polypyrrole with sodium Petroleum sulfonate as surfactant
The petroleum sodium sulfonate is an anionic surfactant obtained by sulfonating and neutralizing a high-carbon hydrocarbon byproduct obtained by a natural petroleum fraction or a chemical reaction by using caustic soda, and is a mixture of various hydrocarbon sulfonation products. Adding 0.5g of pyrrole and 1g of petroleum sodium sulfonate into 100mL of deionized water, dispersing for 5 minutes by ultrasonic vibration (ultrasonic frequency is 40kHz) to obtain pyrrole emulsion, adding 1g of nano calcium carbonate template, 0.25g of initiator sodium persulfate and 1g of petroleum sodium sulfonate into 50mL of deionized water to obtain suspension, and dropwise adding the suspension into the pyrrole emulsion while stirring in an ice bath at the dropping speed of 10 mL/h; and after the dropwise addition is finished and the reaction is carried out for one hour, vacuum filtration is carried out, the template nano calcium carbonate is cleaned by dilute hydrochloric acid, and the flake-shaped integrated porous polypyrrole carrier material is obtained after rinsing and drying by deionized water.
Example 3 porous polypyrrole with sodium fatty alcohol sulfate as surfactant
The sulfate type anionic surfactant mainly includes fatty alcohol sulfate (also called primary alkyl sulfate) and secondary alkyl sulfate. The sodium fatty alcohol sulfate is the earliest anionic surfactant appearing after the soap, and is prepared by esterifying and neutralizing C12-C14 fatty alcohol generated by hydrogenolysis of coconut oil with sulfuric acid.
100mL of deionized water was added with 0.9g of pyrrole and sodium lauryl sulfate (C)12H25OSO3Na)1g, dispersing for 5 minutes by ultrasonic vibration (ultrasonic frequency is 40kHz) to obtain pyrrole emulsion, adding 50mL of deionized water into 3g of nano calcium carbonate template, 0.5g of initiator sodium persulfate and 1g of sodium lauryl sulfate to obtain suspension, and dropwise adding the suspension into the pyrrole emulsion while stirring in an ice bath at the dropping speed of 10 mL/h; and after the dropwise addition is finished and the reaction is carried out for one hour, vacuum filtration is carried out, the template nano calcium carbonate is cleaned by dilute hydrochloric acid, and the flake integrated porous polypyrrole carrier material is obtained after rinsing and drying by deionized water, wherein an electron microscope photo of the flake integrated porous polypyrrole carrier material is shown in figure 1.
EXAMPLE 4 porous sodium polypyrrolide Supported
Adding 0.5g of pyrrole and 1g of sodium dodecyl benzene sulfonate into 100mL of deionized water, dispersing for 5 minutes by ultrasonic vibration (ultrasonic frequency is 40kHz) to obtain pyrrole emulsion, adding 50mL of deionized water into 1g of nano calcium carbonate template, 0.25g of initiator sodium persulfate and 1g of sodium dodecyl benzene sulfonate to obtain suspension, and dropwise adding the suspension into the pyrrole emulsion while stirring in an ice bath at the dropping speed of 10 mL/hour; and after the dropwise addition is finished and the reaction is carried out for one hour, vacuum filtration is carried out, the filter paper is made of polyacrylate, and after the filter cake and the filter paper are dried, the filter paper is dissolved by acetone to obtain the filter cake. Washing the filter cake with dilute hydrochloric acid to remove the template nano calcium carbonate, rinsing with deionized water and drying to obtain the flaky integrated porous polypyrrole carrier material.
Taking the 150mg of integrated porous polypyrrole, pressing a metal sodium foil (150mg) with the same area with the integrated porous polypyrrole in a glove box, wherein the mass ratio of the metal sodium to the polypyrrole is 1:1, and heating at 100 ℃ until the sodium foil is molten and enters the integrated porous polypyrrole.
Example 5 sodium electrode preparation
Adding 0.5g of pyrrole and 1g of sodium dodecyl sulfate into 100mL of deionized water, dispersing for 5 minutes by ultrasonic vibration (ultrasonic frequency is 40kHz) to obtain pyrrole emulsion, adding 1g of nano calcium carbonate template, 0.25g of initiator sodium persulfate and 1g of sodium dodecyl sulfate into 50mL of deionized water to obtain suspension, and dropwise adding the suspension into the pyrrole emulsion while stirring in an ice bath at the speed of 10 mL/h; and after the dropwise addition is finished and the reaction is carried out for one hour, vacuum filtration is carried out, the filter paper is made of polyacrylate, and after the filter cake and the filter paper are dried, the filter paper is dissolved by acetone to obtain the filter cake. Washing the filter cake with dilute hydrochloric acid to remove the template nano calcium carbonate, rinsing with deionized water and drying to obtain the flaky integrated porous polypyrrole carrier material.
Taking 150mg of the integrated porous polypyrrole, pressing a metal sodium foil (750mg) with the same area with the integrated porous polypyrrole in a glove box, wherein the mass ratio of the metal sodium to the polypyrrole is 5:1, and heating at 100 ℃ until the sodium foil is molten and enters the integrated porous polypyrrole to obtain a sodium electrode.
EXAMPLE 6 porous polypyrrole Sulfur Supported
Dispersing elemental sulfur (150mg) in DMSO (1: 1 mass ratio of sulfur to DMSO) in ZrO2And (3) performing ball milling for 30 minutes in a ball milling tank to obtain a suspension, taking 150mg of the integrated porous polypyrrole obtained in the example 3, coating the suspension on a polypyrrole carrier, heating at 90 ℃ for 1 hour, then performing vacuum drying to remove DMSO, moving to a nitrogen atmosphere, heating to 155 ℃, and heating for 2 hours to completely melt elemental sulfur into the polypyrrole, wherein the mass ratio of sulfur to polypyrrole is 1: 1.
Example 7 Sulfur electrode preparation
Dispersing elemental sulfur (750mg) in DMSO at a sulfur to DMSO mass ratio of 1:1, ZrO, in2And (3) performing ball milling in a ball milling tank for 30 minutes to obtain a suspension, taking 150mg of the integrated porous polypyrrole obtained in the example 3, coating the suspension on a polypyrrole carrier, heating at 90 ℃ for 1 hour, then performing vacuum drying to remove DMSO, moving to a nitrogen atmosphere, heating to 155 ℃, heating for 2 hours to completely melt elemental sulfur into the polypyrrole, wherein the mass ratio of sulfur to polypyrrole is 5:1, and thus obtaining a sulfur electrode containing 83 wt% of sulfur.
Example 8 sodium-sulfur battery based on integrated porous polypyrrole electrode material
150mg of the integrated porous polypyrrole obtained in example 3 was taken, and a metal sodium foil (1.5g) having an equal area was pressed against the integrated porous polypyrrole in a glove box at a mass ratio of metal sodium to polypyrrole of 10:1, and heated at 100 ℃ until the sodium foil was melted and entered the integrated porous polypyrrole to obtain a sodium electrode.
Dispersing elemental sulfur (1.5mg) in DMSO at a sulfur to DMSO mass ratio of 1:1, at ZrO2And (3) performing ball milling for 30 minutes in a ball milling tank to obtain a suspension, taking 150mg of the integrated porous polypyrrole obtained in the example 3, coating the suspension on a polypyrrole carrier, heating at 90 ℃ for 1 hour, then performing vacuum drying to remove DMSO, moving to a nitrogen atmosphere, heating to 155 ℃, heating for 2 hours to completely melt elemental sulfur into the polypyrrole, wherein the mass ratio of sulfur to polypyrrole is 10:1, and thus obtaining a sulfur electrode containing 91 wt% of sulfur.
Taking the sodium electrode, the sulfur electrode and the diaphragm to form a sandwich structure, and internally arranging electrolyte; the electrolyte is Na [ (CF)3SO2)2N](NaTFSI) as solute, dioxolane (C)3H6O2) And ethylene glycol methyl ether (C)4H10O2) The mixture of (A) is a solvent, and the volume ratio of dioxolane to ethylene glycol monomethyl ether is 1: one liter of electrolyte contains one mole (279g) of NaTFSI. And obtaining the low-temperature sodium-sulfur battery. Fig. 1 is a charge-discharge curve of the obtained sodium-sulfur battery at room temperature.
Finally, it should be noted that the above-mentioned list is only a specific embodiment of the present invention. It is obvious that the present invention is not limited to the above embodiments, but many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
Claims (6)
1. A preparation method of an integrated porous polypyrrole loaded sodium electrode is characterized by comprising the following steps:
(1) taking 100mL of deionized water, adding 0.15-0.9 g of pyrrole and 1g of Na salt anionic surfactant, and performing ultrasonic vibration dispersion for 5 minutes to obtain pyrrole emulsion; then taking 50mL of deionized water, adding 0.5-3 g of nano calcium carbonate template, 0.1-0.5 g of initiator sodium persulfate and 1g of Na salt anion surfactant, and uniformly mixing to obtain a suspension; under the conditions of ice bath and stirring, dropwise adding the suspension into the pyrrole emulsion, and continuously reacting for one hour after dropwise adding; then, carrying out vacuum filtration by using filter paper made of polyacrylate, drying the filter cake and the filter paper, and dissolving the filter paper by using acetone to obtain a filter cake; washing the filter cake with dilute hydrochloric acid to remove the nano calcium carbonate template, rinsing with deionized water, and drying to obtain a sheet-shaped integrated porous polypyrrole carrier material;
(2) taking 150mg of the integrated porous polypyrrole carrier material obtained in the step (1), pressing a metal sodium foil with the same area with the integrated porous polypyrrole carrier material in a glove box, and controlling the thickness of the metal sodium foil to enable the mass ratio of metal sodium to the carrier material to be 1-10: 1; and then heating at 100 ℃ until the sodium foil melts into the carrier material, to obtain the sodium electrode for the low-temperature sodium-sulfur battery.
2. The preparation method of the integrated porous polypyrrole-supported sulfur electrode is characterized by comprising the following steps of:
(1) taking 100mL of deionized water, adding 0.15-0.9 g of pyrrole and 1g of Na salt anionic surfactant, and performing ultrasonic vibration dispersion for 5 minutes to obtain pyrrole emulsion; then taking 50mL of deionized water, adding 0.5-3 g of nano calcium carbonate template, 0.1-0.5 g of initiator sodium persulfate and 1g of Na salt anion surfactant, and uniformly mixing to obtain a suspension; under the conditions of ice bath and stirring, dropwise adding the suspension into the pyrrole emulsion, and continuously reacting for one hour after dropwise adding; then, carrying out vacuum filtration by using filter paper made of polyacrylate, drying the filter cake and the filter paper, and dissolving the filter paper by using acetone to obtain a filter cake; washing the filter cake with dilute hydrochloric acid to remove the nano calcium carbonate template, rinsing with deionized water, and drying to obtain a sheet-shaped integrated porous polypyrrole carrier material;
(2) dispersing elemental sulfur in DMSO in a mass ratio of 1:1, in ZrO2Performing ball milling in a ball milling tank for 30 minutes to obtain suspension; taking 150mg of the integrated porous polypyrrole carrier material obtained in the step (1), coating the suspension on a polypyrrole carrier, and controlling the mass ratio of sulfur to the carrier material to be 1-10: 1; heating at 90 deg.C for 1 hr, and vacuum drying to remove DMSO; and then moving the mixture to a nitrogen atmosphere, heating the mixture to 155 ℃ and keeping the temperature for 2 hours to ensure that the elemental sulfur is completely melted and enters the carrier material, thus obtaining the sulfur electrode for the low-temperature sodium-sulfur battery.
3. The method as claimed in claim 1 or 2, wherein the hydrophobic group of the Na salt anionic surfactant in step (1) is a long chain alkyl, secondary alkyl or alkylaryl group, and the hydrophilic group is a carboxyl group (RCOO), a sulfonic acid group (R-SO)3) Or sulfate ester groups (R-OSO)3) (ii) a Correspondingly, the general formulas of the anionic surfactants are respectively expressed as RCOONa and R-SO3Na or R-OSO3Na, wherein R is long-chain alkyl, secondary alkyl or alkylaryl.
4. The method according to claim 1 or 2, wherein in the step (1), the ultrasonic vibration dispersion is performed while controlling the ultrasonic frequency to be 40 kHz.
5. The method according to claim 1 or 2, wherein in the step (1), the suspension is added dropwise to the azole emulsion while controlling the dropping acceleration to be 10 mL/hr.
6. A low-temperature sodium-sulfur battery comprises a diaphragm, a positive electrode, a negative electrode and electrolyte; the sodium-sulfur battery is characterized in that a sodium electrode prepared by the method of claim 1 is used as a negative electrode, a sulfur electrode prepared by the method of claim 2 is used as a positive electrode, the sodium electrode and the sulfur electrode are respectively arranged on two sides of a diaphragm to form a sandwich structure, electrode material sides on the positive electrode and the negative electrode face the diaphragm, and electrolyte is internally arranged in the sandwich structure;
in the electrolyte: with Na [ (CF)3SO2)2N]Is a solute, and each liter of electrolyte contains one mole of solute; taking a mixture of dioxolane and ethylene glycol monomethyl ether as a solvent, wherein the volume ratio of dioxolane to ethylene glycol methyl ether is 1: 1.
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