CN110323447B - Lithium-sulfur battery positive electrode framework material and preparation method thereof, lithium-sulfur battery positive electrode material and lithium-sulfur battery - Google Patents
Lithium-sulfur battery positive electrode framework material and preparation method thereof, lithium-sulfur battery positive electrode material and lithium-sulfur battery Download PDFInfo
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Abstract
The invention provides a lithium-sulfur battery positive electrode framework material and a preparation method thereof, a lithium-sulfur battery positive electrode material and a lithium-sulfur battery, and belongs to the field of lithium-sulfur batteries. The positive electrode framework material of the lithium-sulfur battery is a hollow porous carbon material doped with Co and N, the hollow porous carbon material is in a flower-shaped structure, the interior of the flower-shaped structure is in a hollow structure, petals of the flower-shaped structure are carbon nanosheets, Co and N active sites are attached to the petals, and the petals are in a porous structure. The positive electrode framework material of the lithium-sulfur battery provided by the invention can effectively relieve the volume expansion of an active substance in the charging and discharging processes; through double active sites of Co-N, polysulfide is effectively adsorbed, and the transformation of polysulfide into solid Li is accelerated2S2/Li2S, the shuttle effect of polysulfide is restrained from the source, so that the specific capacity, the rate capability and the stability of the anode material are improved.
Description
Technical Field
The invention relates to the field of lithium-sulfur batteries, in particular to a lithium-sulfur battery positive electrode framework material and a preparation method thereof, a lithium-sulfur battery positive electrode material and a lithium-sulfur battery.
Background
The theoretical specific capacity and the theoretical energy density of the lithium-sulfur battery can reach 1675mAh/g and 2600Wh/kg, and the lithium-sulfur battery has the advantages of environmental friendliness, low cost and the like, and is considered to be one of the most promising high-energy-density energy storage devices of the next generation. However, commercial application of lithium sulfur batteries still faces many serious challenges, such as volume effect during sulfur cycling, shuttle effect due to polysulfide dissolution, and slow polysulfide reaction kinetics. Slow polysulfide kinetics during high sulfur loading and long cycle discharge in lithium sulfur batteries can result in insoluble Li2S2And Li2S is obviously deposited on the surface of the electrode, so that the continuous loss of active substance sulfur is caused, and the capacity of the battery is seriously attenuated, thereby slowly losing the battery.
Disclosure of Invention
In order to solve the technical problems, the invention provides a lithium-sulfur battery positive electrode framework material which has a hollow porous structure, has a larger internal space, and effectively solves the problem of volume effect in a sulfur circulation process.
The invention provides a lithium-sulfur battery positive electrode framework material, which is a hollow porous carbon material doped with Co and N, wherein the hollow porous carbon material is in a flower-shaped structure, the interior of the flower-shaped structure is in a hollow structure, petals of the flower-shaped structure are carbon nanosheets, Co and N active sites are attached to the petals, and the petals are in a porous structure.
Preferably, the mass fraction of nitrogen element in the lithium-sulfur battery positive electrode framework material is 0.1-8%, and the mass fraction of cobalt element is 0.1-5%.
Preferably, the specific surface area of the lithium-sulfur battery positive electrode framework material is 100-800 m2Per g, pore volume of 0.1-0.8 cm3/g。
The invention also provides a preparation method of the lithium-sulfur battery positive electrode framework material, which comprises the following steps:
(1) mixing aluminum nitrate, cobalt nitrate, m-aminobenzene sulfonic acid, alkali and water to obtain a mixed solution;
(2) carrying out hydrothermal reaction on the mixed solution obtained in the step (1) to obtain layered double hydroxides;
(3) calcining the layered double hydroxide obtained in the step (2) in a protective atmosphere to obtain a carbonized material;
(4) and (4) soaking the carbonized material obtained in the step (3) in an acid solution to obtain the lithium-sulfur battery positive electrode framework material.
Preferably, in the step (1), the molar ratio of the aluminum nitrate to the cobalt nitrate to the m-aminobenzenesulfonic acid is 1: 2-5: 5-10, and the pH value of the mixed solution is 9-11.
Preferably, the temperature of the hydrothermal reaction in the step (2) is 50-150 ℃ and the time is 2-18 h.
Preferably, the temperature of the calcination treatment in the step (3) is 400-1000 ℃, the heating rate of the temperature to the calcination treatment temperature is 2-10 ℃/min, and the heat preservation time after the temperature is raised to the calcination treatment temperature is 0.5-5 h.
Preferably, the acidic solution in the step (4) is a hydrochloric acid solution, the mass concentration of the hydrochloric acid solution is 18%, and the soaking time is 0.5-48 h.
The invention also provides a lithium-sulfur battery positive electrode material, which comprises the lithium-sulfur battery positive electrode framework material in the technical scheme or the lithium-sulfur battery positive electrode framework material prepared by the method in the technical scheme.
The present invention also provides a lithium sulfur battery comprising the lithium sulfur battery positive electrode material according to claim 9.
The invention provides a lithium-sulfur battery positive electrode framework material, which is a hollow porous carbon material doped with Co and N, wherein the hollow porous carbon material is in a flower-shaped structure, the interior of the flower-shaped structure is in a hollow structure, petals of the flower-shaped structure are carbon nanosheets, Co and N active sites are attached to the petals, and the petals are in a porous structure. The lithium-sulfur battery positive electrode framework material provided by the invention has a hollow flower-shaped structure, and volume expansion of an active substance in the charging and discharging processes is effectively relieved through the construction of the hollow structure; by doping Co-N double active sites, polysulfides are effectively adsorbed, the reaction kinetics between polysulfides are promoted, and the conversion of the polysulfides into solid Li is accelerated2S2/Li2S, inhibiting shuttle effect of polysulfide from the source, thereby improving specific capacity, rate capability and stability of the anode material; the lithium-sulfur battery positive electrode framework material provided by the invention is of a porous flower-shaped structure, and is beneficial to promoting the rapid conduction of electrons and ions, so that the conductivity is further improved. The embodiment result shows that the lithium-sulfur battery prepared from the lithium-sulfur battery positive electrode framework material provided by the invention has better electrochemical performance.
Drawings
FIG. 1 is an XRD spectrum of a layered aluminum cobalt hydroxide obtained in step (1) of example 1;
FIG. 2 is an XRD spectrum of a carbonized material prepared in the step (2) of example 1;
FIG. 3 is an XRD spectrum of a lithium-sulfur battery positive electrode framework material prepared in the step (3) of example 1;
FIG. 4 is a scanning electron micrograph of the layered aluminum cobalt hydroxide obtained in step (1) of example 1;
FIG. 5 is a scanning electron micrograph of a carbonized material prepared in step (2) of example 1;
FIG. 6 is a scanning electron microscope image of the lithium sulfur battery positive electrode framework material prepared in the step (3) of example 1;
FIG. 7 is a scanning electron microscope image of the positive electrode framework material of the lithium-sulfur battery prepared in step (3) of example 1;
fig. 8 is a nitrogen adsorption and desorption curve of the lithium sulfur battery positive electrode framework material prepared in the step (3) of example 1;
FIG. 9 is a pore size distribution diagram of a framework material of a positive electrode of a lithium sulfur battery prepared in step (3) of example 1;
fig. 10 is a charge-discharge curve of a lithium-sulfur battery assembled from the positive electrode framework material of the lithium-sulfur battery of example 1;
fig. 11 is a rate performance curve for a lithium sulfur battery assembled from the positive electrode framework material of the lithium sulfur battery of example 1;
FIG. 12 is a graph of the cycling performance of a lithium sulfur battery assembled from the positive electrode backbone material of the lithium sulfur battery of example 1;
FIG. 13 shows an assembled lithium sulfur-Li positive electrode framework material of a lithium sulfur battery of example 12S6Polarization curves of symmetric cells;
FIG. 14 shows an assembled lithium sulfur-Li positive electrode framework material of a lithium sulfur battery of example 12S8Fitting a graph of constant potential discharge time and current of the symmetrical battery;
FIG. 15 shows an assembled lithium sulfur-Li positive electrode framework material of a lithium sulfur battery of example 12S8Tafel curves for symmetric cells;
FIG. 16 is a charge-discharge curve of S @ carbon black assembled from a carbon black material of comparative example 1;
FIG. 17 is a graph of rate performance of S @ carbon black assembled from comparative example 1 carbon black material;
FIG. 18 is a carbon black-Li assembled from the carbon black material of comparative example 12S6Polarization curves of symmetric cells;
FIG. 19 is a carbon black-Li assembled from the carbon black material of comparative example 12S6Fitting a graph of constant potential discharge time and current of the symmetrical battery;
FIG. 20 is a carbon black-Li assembled from the carbon black material of comparative example 12S8Tafel curves for symmetric cells.
Detailed Description
The invention provides a lithium-sulfur battery positive electrode framework material which is a hollow porous carbon material doped with Co and N, wherein the hollow porous carbon material is in a flower-shaped structure, the interior of the flower-shaped structure is in a hollow structure, petals of the flower-shaped structure are carbon nanosheets, Co and N active sites are attached to the petals, and the petals are in a porous structure.
In the present invention, the diameter of the flower-like structure is preferably 0.5 to 5 μm, more preferably 1 to 4 μm, and still more preferably 2 to 3 μm.
In the invention, the lithium-sulfur battery positive electrode framework material comprises a carbon element, a nitrogen element, an oxygen element and a cobalt element, wherein the mass fraction of the carbon element is preferably 10-80%, more preferably 20-60%, and more preferably 30-50%, the mass fraction of the nitrogen element is preferably 0.1-10%, more preferably 1-7%, and more preferably 2-5%, the mass fraction of the cobalt element is preferably 0.1-5%, more preferably 1-4%, and more preferably 2-3%, and the mass fraction of the oxygen element is preferably 1-80%, more preferably 20-60%, and more preferably 30-50%.
In the invention, the specific surface area of the lithium-sulfur battery positive electrode framework material is preferably 100-800 m2(ii) g, more preferably 200 to 700m2(ii) g, more preferably 300 to 600m2A/g, most preferably 571.4m2The pore volume is preferably 0.1-0.8 cm/g3A more preferable range is 0.2 to 0.7 cm/g3A concentration of 0.3 to 0.6cm3In terms of/g, most preferably 0.535cm3/g。
The lithium-sulfur battery positive electrode framework material provided by the invention has a hollow flower-shaped structure, and volume expansion of an active substance in the charging and discharging processes is effectively relieved through the construction of the hollow structure; through double active sites of Co-N, polysulfide is effectively adsorbed, the reaction kinetics between polysulfides are promoted, and the conversion of polysulfide into solid Li is accelerated2S2/Li2S, inhibiting shuttle effect of polysulfide from the source, thereby improving specific capacity, rate capability and stability of the anode material; the lithium-sulfur battery positive electrode framework material provided by the invention is of a porous flower-shaped structure, and is beneficial to promoting the rapid conduction of electrons and ions, so that the conductivity is further improved.
The invention provides a preparation method of the lithium-sulfur battery positive electrode framework material, which comprises the following steps:
(1) mixing aluminum nitrate, cobalt nitrate, m-aminobenzene sulfonic acid, alkali and water to obtain a mixed solution;
(2) carrying out hydrothermal reaction on the mixed solution obtained in the step (1) to obtain layered double hydroxides;
(3) calcining the layered double hydroxide obtained in the step (2) in a protective atmosphere to obtain a carbonized material;
(4) and (4) soaking the carbonized material obtained in the step (3) in an acid solution to obtain the lithium-sulfur battery positive electrode framework material.
The method comprises the steps of mixing aluminum nitrate, cobalt nitrate, m-aminobenzene sulfonic acid, alkali and water to obtain a mixed solution.
In the present invention, the molar ratio of the aluminum nitrate to the cobalt nitrate to the m-aminobenzenesulfonic acid is preferably 1:3:10, and the pH of the mixed solution is preferably 8 to 11, and more preferably 10. In the present invention, the alkali preferably includes ammonium fluoride, hexamethylenetetramine and sodium hydroxide, the molar ratio of the ammonium fluoride to the hexamethylenetetramine to the sodium hydroxide is preferably 1-2: 1-5: 2-10, and more preferably 1-2: 2-4: 4-8, and the pH of the mixed solution is preferably controlled within the above range by the alkali. The invention preferably adopts the alkali to adjust the pH value, which is beneficial to controlling the hydrolysis speed of the alkali, thereby controlling the crystal synthesis of the layered double hydroxide.
In the present invention, the mixed solution is preferably disposed in a manner that: mixing aluminum nitrate, cobalt nitrate, ammonium fluoride, hexamethylenetetramine and water to obtain a solution A, and mixing m-aminobenzene sulfonic acid, sodium hydroxide and water to obtain a solution B; and then slowly adding the solution B into the solution A to obtain a mixed solution. The invention preferably adopts the mixing mode, and has the advantage of being beneficial to crystal nucleation of the layered double hydroxide and intercalation of the m-aminobenzene sulfonic acid.
In the present invention, the water in the mixed solution is preferably water obtained by degassing. According to the invention, the degassing treatment is preferably carried out by continuously introducing nitrogen, and the time for continuously introducing nitrogen is preferably 10-20 min. According to the invention, air and carbon dioxide in the water are preferably removed through degassing treatment, so that the influence of the air and carbon dioxide in the water on the subsequent preparation of the layered double hydroxide is avoided.
After the mixed solution is obtained, the mixed solution is subjected to hydrothermal reaction to obtain the layered double hydroxide. In the present invention, the temperature of the hydrothermal reaction is preferably 100 ℃ and the time is preferably 12 hours.
According to the invention, preferably, after the hydrothermal reaction is finished, the hydrothermal reaction product is cooled to room temperature, and then the hydrothermal reaction product is sequentially filtered, washed and dried to obtain the layered double hydroxide. In the present invention, the washing preferably includes water washing and ethanol washing in this order; the drying treatment temperature is preferably 100 ℃, and the drying time is preferably 12-24 h.
According to the invention, aluminum nitrate and cobalt nitrate are converted into a metal hydroxide layer under an alkaline condition through a hydrothermal reaction, metanilic acid is used as guest layer anions and is inserted between the metal hydroxide layer and the metal hydroxide layer, and the layered double hydroxide with a sandwich-like structure is formed. In the present invention, the layered double hydroxide has a flower-like structure.
After the layered double hydroxide is obtained, the layered double hydroxide is calcined in a protective atmosphere to obtain the carbonized material.
In the present invention, the protective atmosphere is preferably a nitrogen atmosphere or an argon atmosphere. In the invention, the temperature of the calcination treatment is preferably 650-750 ℃, more preferably 680-720 ℃, and more preferably 700 ℃; the heating rate for heating to the calcination treatment temperature is preferably 3 ℃/min; the holding time after the temperature is raised to the calcination treatment temperature is preferably 2 hours. The present invention preferably performs a cooling treatment after the calcination treatment to obtain the carbonized material, and the present invention does not particularly require a specific cooling manner, and may employ a manner known to those skilled in the art.
The invention makes aluminum react with oxygen to generate alumina through calcination treatment, and cobalt reacts with sulfur in m-aminobenzene sulfonic acid to generate Co9S8Some Co is also present in the calcined product; and the m-aminobenzene sulfonic acid of the guest layer is converted into carbon. In the present invention, the carbonized material still maintains a flower-like structure.
After the carbonized material is obtained, the carbonized material is soaked in an acid solution to obtain the lithium-sulfur battery positive electrode framework material. In the present invention, the acidic solution is preferably a hydrochloric acid solution; the mass concentration of the hydrochloric acid solution is preferably 18%. In the present invention, the soaking time is preferably 24 hours. According to the invention, preferably, after the soaking treatment is finished, washing and drying treatment are sequentially carried out, and the solvent for washing preferably comprises water and ethanol; the drying temperature is preferably 80 ℃, and the drying time is preferably 12-24 h. The method removes most of alumina, Co and Co in the carbonized material through soaking treatment9S8Thus, a hollow and porous structure is constructed. According to the invention, the cobalt-based and aluminum-based nanoparticles are removed, so that a porous structure is formed on the surface of the carbonized material, and the rapid conduction of electrons and ions is facilitated, thereby further improving the conductivity. In the invention, the lithium-sulfur battery positive electrode framework material is in a hollow and porous flower-shaped structure.
The invention also provides a lithium-sulfur battery positive electrode material, which comprises the lithium-sulfur battery positive electrode framework material in the technical scheme or the lithium-sulfur battery positive electrode framework material prepared by the method in the technical scheme. The sulfur carrying amount of the lithium-sulfur battery anode material provided by the invention can reach up to 82%.
In the present invention, the method for preparing the positive electrode material for a lithium sulfur battery preferably includes:
and mixing the lithium-sulfur battery positive electrode framework material with sublimed sulfur, and then carrying out melting treatment in a protective atmosphere to obtain the lithium-sulfur battery positive electrode material.
In the invention, the mass ratio of the lithium-sulfur battery positive electrode framework material to the sublimed sulfur is preferably 1: 4-5, the melting treatment temperature is preferably 150-160 ℃, more preferably 155 ℃, and the time is preferably 10-14 h, more preferably 12 h. In the present invention, the protective atmosphere is preferably a nitrogen atmosphere or an argon atmosphere.
The invention also provides a lithium-sulfur battery which comprises the positive electrode material of the lithium-sulfur battery in the technical scheme. The present invention does not require special components and assembly methods for the lithium sulfur battery, and the battery components and the battery assembly methods known to those skilled in the art can be used.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
Example 1
(1) 75g of aluminum nitrate nonahydrate, 58g of cobalt nitrate hexahydrate, 30g of ammonium fluoride and 140g of hexamethylenetetramine were dissolved in 2L of deionized water, and the solution was named as solution A; 344g of m-aminobenzenesulfonic acid was dissolved in 2L of a 1mol/L sodium hydroxide solution, designated as solution B; slowly adding the solution B into the solution A, transferring the mixed solution into a 5L reaction kettle, and keeping the reaction kettle at the temperature of 100 ℃ for 12 hours. And cooling to room temperature, fully washing the precipitate with water and ethanol, and drying at 100 ℃ for 20 hours to obtain flower-like layered aluminum cobalt hydroxide which is named as CoAl-LDH.
(2) And transferring the prepared CoAl-LDH into a tubular furnace, introducing nitrogen, heating at the speed of 5 ℃/min, carbonizing for 2 hours at the temperature of 700 ℃, and cooling to room temperature to obtain the flower-shaped carbonized material named as c-LDH.
(3) Soaking the prepared C-LDH in 1.5L of hydrochloric acid with the mass concentration of 18% for 24h, then fully washing precipitates with deionized water and ethanol, and drying at 80 ℃ for 20h to obtain the nitrogen-cobalt doped porous carbon material, namely the lithium-sulfur battery positive electrode framework material, which is abbreviated as Co-N/C.
Preparation of lithium-sulfur battery cathode material
Premixing the Co-N/C prepared in the step (3) with sublimed sulfur according to the mass ratio of 1:4.5, transferring into a tubular furnace, introducing nitrogen, and melting for 12 hours at 155 ℃ to obtain the S @ Co-N/C lithium sulfur battery positive electrode material.
Comparative example 1
Carbon black is used as a lithium-sulfur battery positive electrode framework material.
Performance testing
First, structural characterization
XRD test was carried out on the layered aluminum cobalt hydroxide prepared in step (1) of example 1, and the results are shown in FIG. 1; XRD test was carried out on the carbonized material prepared in the step (2) of example 1, and the result is shown in FIG. 2; XRD test was performed on the lithium sulfur battery positive electrode framework material prepared in step (3) of example 1, and the result is shown in fig. 3. As can be seen from FIG. 1, the layered double hydroxide intercalated with m-aminobenzene sulfonic acid is prepared in step (1) of the present invention; comparing the XRD peak in FIG. 2 with that of a standard card, it can be seen that the carbonized material obtained by the calcination treatment of the present invention mainly comprises carbon, alumina, Co (PDF card number 15-0806) and Co9S8(PDF card number 65-1765); as can be seen from FIG. 3, most of the alumina, Co and Co in the invention after acid washing9S8The particles are removed.
Scanning electron microscope test is carried out on the layered aluminum cobalt hydroxide prepared in the step (1) of the example 1, and the result is shown in fig. 4; scanning electron microscope tests are carried out on the carbonized material prepared in the step (2) of the example 1, and the results are shown in fig. 5; prepared by the step (4) of example 1The scanning electron microscope test of the lithium-sulfur battery positive electrode framework material is carried out, and the result is shown in fig. 6. As can be seen from FIG. 4, the layered double hydroxide obtained in step (2) of example 1 of the present invention has a flower-like structure, and the petal surface is smooth; as can be seen from FIG. 5, the carbonized layered double metal oxide has a flower-like structure, and nanoparticles having a size of about 1 to 20nm are clearly observed on the surface of the petals, which indicates that aluminum hydroxide and cobalt hydroxide in the carbonized material obtained after calcination are converted into aluminum oxide, Co and Co9S8A nanoparticle; as can be seen from fig. 6, most of the nanoparticles on the surface of the petals were removed during the pickling process, and a porous structure was formed on the surface of the carbonized material.
Fig. 7 is a scanning electron microscope analysis view of the lithium sulfur battery positive electrode framework material obtained in step (3) of example 1 of the present invention, and it can be seen from fig. 7 that the lithium sulfur battery positive electrode framework material provided by the present invention has a hollow structure. The lithium-sulfur battery positive electrode framework material with the hollow structure is beneficial to providing enough activity space for active sulfide.
The nitrogen adsorption and desorption performance of the lithium-sulfur battery positive electrode framework material prepared in the step (3) of example 1 was tested, and the test results are shown in fig. 8. As can be seen from FIG. 8, the specific surface area of the positive electrode framework material of the lithium-sulfur battery prepared in example 1 was 571.4m2/g。
The pore size distribution diagram of the lithium sulfur battery positive electrode framework material prepared in the step (3) of example 1 was tested, and the result is shown in fig. 9. As can be seen from FIG. 9, the pore size distribution of the positive electrode framework material of the lithium-sulfur battery is mainly centered at 1-20 nm.
Second, electrical property test
Premixing the lithium-sulfur battery positive electrode framework material prepared in example 1 and sublimed sulfur according to the mass ratio of 1:4.5, transferring the mixture into a tubular furnace, introducing nitrogen, melting for 12 hours at 155 ℃ to obtain S @ Co-N/C, mixing the S @ Co-N/C, Carbon Black (CB) and polyvinylidene fluoride (PVDF) according to the mass ratio of 9:1, adding NMP according to the mass-volume ratio of 100mg:3.5mL of PVDF and N-methylpyrrolidone (NMP) to prepare slurry, blade-coating the slurry on carbon paper to prepare a lithium-sulfur battery positive electrode sheet, wherein the mass of an active substance is controlled to be 2mg/cm2. The method is characterized in that CR2032 is taken as a battery shell, Celgard2500 is taken as a diaphragm, 35 mu L of electrolyte is added into each battery (the concentration of lithium bistrifluoromethanesulfonylimide (LiTFSI) in the electrolyte is 1mol/L, the solvent of the electrolyte comprises 1, 3-dioxolane and 1, 2-dimethoxyethane in a volume ratio of 1:1, and the mass fraction of lithium nitrate in the solvent of the electrolyte is 1%) to assemble the lithium-sulfur battery in a glove box.
And (3) carrying out charge and discharge tests on the prepared lithium-sulfur battery on a new Wille test system, wherein the voltage window is set to be 1.7-2.8V, and the current density is 0.1C and 1C. The test result is shown in fig. 10, and it can be seen from fig. 10 that the first circle specific capacity of the lithium-sulfur battery provided by the invention is up to 1374mAh/g under the condition of 0.1C; when the current density is increased to 1C, the specific capacity is still 738mAh/g, which shows that the specific capacity of the lithium-sulfur battery provided by the invention is higher.
And carrying out rate performance test on the prepared lithium-sulfur battery on a new Wille test system, setting a voltage window to be 1.7-2.8V, setting current densities to be 0.1C, 0.2C, 0.5C, 1C, 2C, 1C, 0.5C, 0.2C and 0.1C, and circulating each current density for 10 circles. As shown in fig. 11, it can be seen from fig. 11 that the first-turn specific capacities of the lithium-sulfur batteries at 0.1C, 0.2C, 0.5C, 1C and 2C are 1374, 957, 841, 738 and 611mAh/g, respectively, and the first-turn specific capacities at 1C, 0.5C, 0.2C and 0.1C are 768, 797, 813 and 829mAh/g, respectively, indicating that the lithium-sulfur batteries provided by the present invention have better rate capability.
And (3) carrying out cycle performance test on the prepared lithium-sulfur battery on a new Wille test system, wherein the voltage window is set to be 1.7-2.8V, the current density is set to be 0.5C, and the cycle is 500 circles. As shown in fig. 12, it can be seen from fig. 12 that the specific capacity attenuation rate per cycle is only 0.069% and the average coulombic efficiency is as high as 100% for 500 cycles of the lithium-sulfur battery, which indicates that the lithium-sulfur battery provided by the present invention has high cycle stability.
The lithium-sulfur battery positive electrode framework material prepared in example 1 is assembled into lithium-sulfur-Li2S6Symmetrical cells, testing polarization curves of lithium-sulfur symmetrical cells, lithium-sulfur-Li2S6The symmetrical battery assembly method is as follows:
mixing all the materialsThe positive electrode frame material of the lithium-sulfur battery prepared in example 1 and PVDF were mixed at a mass ratio of 9:1, NMP (100 mg/3.5 mL/NMP) was added to prepare a slurry, and the slurry was spread on carbon paper with the mass of the active material controlled to 1.5mg/cm2Using CR2032 as a battery shell and Celgard2500 as a diaphragm, 35 μ L of electrolyte (Li in the electrolyte) is added into each battery2S6The concentration of the electrolyte is 0.5mol/L, the electrolyte takes ethylene glycol dimethyl ether as a solvent), and the lithium sulfur-Li is assembled in a glove box2S6A symmetrical cell. Setting a voltage window of-0.7V and a scanning speed of 100mV/s on an electrochemical workstation, and testing a CV curve. As shown in FIG. 13, it can be seen from FIG. 13 that under the high sweep rate condition, Li-S-Li2S6The symmetrical battery still maintains good peak shape, and the highest peak value reaches 82mA/cm2The preparation method of the lithium-sulfur battery positive electrode framework material has excellent polysulfide catalytic capability and can effectively inhibit the shuttle effect of polysulfide.
The lithium-sulfur battery cathode framework material of example 1 is assembled into lithium-sulfur-Li2S8Batteries, testing of lithium sulfur-Li at 2.05V2S8The constant potential discharge time and current fitting graph of the battery is characterized in that the test method comprises the following steps: the lithium-sulfur battery positive electrode framework material prepared in example 1 and PVDF were uniformly ground in a mass ratio of 3:1, NMP (100 mg:3.5 mL) was added to the ground material to prepare a slurry, the slurry was spread on carbon paper, and the mass of the active material was controlled to 2.5mg/cm2(ii) a With CR2032 as a battery case and Celgard2500 as a diaphragm, 25 μ L of Li was added to the negative electrode side2S8Electrolyte (Li in electrolyte)2S8Is 1mol/L, the solvent of the electrolyte is DME), the same volume of the positive electrode side does not contain Li2S8DME electrolyte, assembled into lithium sulfur-Li in a glove box2S8A battery. On a new Wille test system, the discharge is carried out at a constant current of 2.06V under 0.1mA and then at a constant voltage of 2.05V until the current is less than 10-5A. The test results are shown in FIG. 14, and it can be seen from FIG. 14 that lithium sulfur-Li2S8Li of battery2The S nucleation response time is 5816S, the peak value is 0.32mA, and Li2The amount of S deposited was 497.1 mAh/g. From FIG. 14, it can be said thatThe lithium-sulfur battery positive electrode framework material prepared by the invention has strong catalytic Li2S nucleation capability, thereby being beneficial to improving the catalytic conversion capability of polysulfide and inhibiting the shuttle effect of polysulfide.
For lithium sulfur-Li2S8The method for testing the Tafel curve of the battery comprises the following steps: preparation of lithium Sulfur-Li according to the same procedure as in the previous paragraph2S8The cell was tested in electrochemical workstation Tafel (Tafel) mode at a sweep rate of 2mV/s and a voltage range of open circuit voltage to + -30 mV. Before testing, the cell was left at open circuit voltage for more than 12 h. The test results are shown in FIG. 15, and it can be seen from FIG. 15 that lithium sulfur-Li2S8The cell exhibited a smaller Tafel slope (0.053mV/dec) and a higher exchange current density of 0.225mA/cm2The positive framework material of the lithium-sulfur battery provided by the invention has stronger polysulfide catalytic capability, thereby inhibiting the shuttle effect of polysulfide.
And thirdly, testing the electrochemical performance of the comparative carbon black, and then comparing the electrochemical performance with the electrochemical performance of the positive framework material of the lithium-sulfur battery.
The carbon black is assembled into a lithium sulfur battery (abbreviated as S @ carbon black), and the charge-discharge curve of the S @ carbon black is tested. The preparation method of the S @ carbon black battery comprises the following steps: premixing Carbon Black (CB) and sublimed sulfur according to the mass ratio of 1:4.5, transferring the mixture into a tubular furnace, introducing nitrogen, melting the mixture for 12 hours at 155 ℃ to obtain S @ carbon black, mixing the S @ carbon black and polyvinylidene fluoride (PVDF) according to the mass ratio of 9:1, adding NMP according to the mass volume ratio of 100mg:3.5mL of PVDF to N-methylpyrrolidone (NMP) to prepare slurry, blade-coating the slurry on carbon paper to prepare a lithium-sulfur battery positive plate, wherein the mass of an active substance is controlled to be 1.5-2mg/cm2. The method is characterized in that CR2032 is taken as a battery shell, Celgard2500 is taken as a diaphragm, 35 mu L of electrolyte is added into each battery (the concentration of lithium bistrifluoromethanesulfonylimide (LiTFSI) in the electrolyte is 1mol/L, the solvent of the electrolyte comprises 1, 3-dioxolane and 1, 2-dimethoxyethane in a volume ratio of 1:1, and the mass fraction of lithium nitrate in the solvent of the electrolyte is 1%) to assemble the S @ carbon black battery in a glove box.
And (3) carrying out charge and discharge tests on the prepared S @ carbon black battery on a new Wille test system, wherein the voltage window is set to be 1.7-2.8V, and the current density is 0.1C and 1C. The test results are shown in fig. 16, and it can be seen from fig. 16 that the specific capacity of the S @ carbon black battery of the comparative example is 907mAh/g under the condition of 0.1C, and when the current density is increased to 1C, the S @ carbon black battery is obviously polarized, and the specific capacity is suddenly reduced to 203 mAh/g. As can be seen from comparison with fig. 10 in the embodiment of the present application, the positive electrode framework material of the lithium-sulfur battery of the present application has a higher charge-discharge specific capacity.
The rate capability of the S @ carbon black battery is tested: the voltage window was set to 1.7-2.8V and the current density was set to 0.1C, 0.2C, 0.5C, 1C, 2C, 10 cycles per current density cycle. As shown in fig. 17, it can be seen from fig. 17 that the first specific capacities of S @ carbon black batteries at 0.1C, 0.2C, 0.5C, 1C and 2C were 907, 788, 690, 206 and 168mAh/g, respectively, and 615, 694, 730 and 750mAh/g, respectively, when the current densities were reversed back to 1C, 0.5C, 0.2C and 0.1C, respectively. Comparing with fig. 11 in the embodiment of the present application, the rate performance of the positive electrode framework material of the lithium-sulfur battery of the present application is better.
Comparative example carbon Black and Li2S6And assembling the symmetrical battery, and testing the polarization curve of the symmetrical battery. The assembling method comprises the following steps:
mixing carbon black and PVDF at a mass ratio of 9:1, adding NMP (100 mg/3.5 mL) to obtain a slurry, coating on carbon paper, and controlling the mass of active substance at 1.5mg/cm2Using CR2032 as a battery shell and Celgard2500 as a diaphragm, 35 μ L of electrolyte (Li in the electrolyte) is added into each battery2S6The concentration of the electrolyte is 0.5mol/L, the electrolyte takes ethylene glycol dimethyl ether as a solvent), and carbon black-Li is assembled in a glove box2S6A symmetrical cell. Setting a voltage window of-0.7V and a scanning speed of 100mV/s on an electrochemical workstation, and testing a CV curve. As shown in FIG. 18, it can be seen from FIG. 18 that carbon black-Li is used under the high sweep rate condition2S6The symmetric cell is completely polarized and has no peak, and the highest current is 9.9mA/cm2。
Assembly of carbon black into carbon black-Li2S8Battery, testing carbon Black-Li at 2.05V2S8The constant potential discharge time and current fitting graph of the battery is characterized in that the test method comprises the following steps: uniformly grinding carbon black and PVDF according to the mass ratio of 3:1, adding NMP (100 mg of NMP: 3.5mL) to prepare slurry, blade-coating the slurry on carbon paper, and controlling the mass of an active substance to be 2.5mg/cm2(ii) a With CR2032 as a battery case and Celgard2500 as a diaphragm, 25 μ L of Li was added to the negative electrode side2S8Electrolyte (Li in electrolyte)2S8Is 1mol/L, the solvent of the electrolyte is DME), the same volume of the positive electrode side does not contain Li2S8DME electrolyte, assembled into carbon black-Li in a glove box2S8A battery. On a new Wille test system, the discharge is carried out at a constant current of 2.06V under 0.1mA and then at a constant voltage of 2.05V until the current is less than 10-5A. The results of the tests are shown in FIG. 19, and it can be seen from FIG. 19 that carbon black-Li2S8Li of battery2The S nucleation response time is 15542S, the highest peak value is 0.20mA, and Li2The amount of S deposited was 380.1 mAh/g. Comparing with the example of fig. 14, it is demonstrated that the lithium-sulfur battery positive electrode framework material prepared by the present invention has stronger catalytic Li for polysulfide2S nucleation capability, thereby being beneficial to improving the catalytic conversion capability of polysulfide and inhibiting the shuttle effect of polysulfide.
For carbon black-Li2S8The method for testing the Tafel curve of the battery comprises the following steps: preparation of carbon Black-Li in the same manner as in the previous paragraph2S8The cell was tested in electrochemical workstation Tafel (Tafel) mode at a sweep rate of 2mV/s and a voltage range of open circuit voltage to + -30 mV. Before testing, the cell was left at open circuit voltage for more than 12 h. The results of the tests are shown in FIG. 20, and it can be seen from FIG. 20 that carbon black-Li2S8The cell exhibited a greater Tafel slope (0.934mV/dec) and a lower exchange current density of 0.019mA/cm2. Comparing with fig. 15 in the examples of the present application, it is demonstrated that the lithium-sulfur battery positive electrode framework material prepared by the present invention has stronger catalytic ability to polysulfide, thereby inhibiting the shuttling effect of polysulfide.
In conclusion, the lithium-sulfur battery positive electrode framework material provided by the invention has better electrochemical performance and is superior to the carbon black material commonly used in the prior art.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The lithium-sulfur battery positive electrode framework material is a hollow porous carbon material doped with Co and N, the hollow porous carbon material is in a flower-shaped structure, the inside of the flower-shaped structure is in a hollow structure, petals of the flower-shaped structure are carbon nanosheets, Co and N active sites are attached to the petals, and the petals are in a porous structure.
2. The lithium-sulfur battery positive electrode framework material according to claim 1, wherein the mass fraction of nitrogen element in the lithium-sulfur battery positive electrode framework material is 0.1-8%, and the mass fraction of cobalt element in the lithium-sulfur battery positive electrode framework material is 0.1-5%.
3. The lithium-sulfur battery positive electrode framework material as claimed in claim 1, wherein the specific surface area of the lithium-sulfur battery positive electrode framework material is 100-800 m2Per g, pore volume of 0.1-0.8 cm3/g。
4. The method for preparing the positive electrode framework material of the lithium-sulfur battery as defined in any one of claims 1 to 3, comprising the steps of:
(1) mixing aluminum nitrate, cobalt nitrate, m-aminobenzene sulfonic acid, alkali and water to obtain a mixed solution;
(2) carrying out hydrothermal reaction on the mixed solution obtained in the step (1) to obtain layered double hydroxides;
(3) calcining the layered double hydroxide obtained in the step (2) in a protective atmosphere to obtain a carbonized material;
(4) and (4) soaking the carbonized material obtained in the step (3) in an acid solution to obtain the lithium-sulfur battery positive electrode framework material.
5. The preparation method according to claim 4, wherein the molar ratio of the aluminum nitrate to the cobalt nitrate to the m-aminobenzenesulfonic acid in the step (1) is 1:2 to 5:5 to 10, and the pH value of the mixed solution is 9 to 11.
6. The preparation method according to claim 4, wherein the temperature of the hydrothermal reaction in the step (2) is 50-150 ℃ and the time is 2-18 h.
7. The preparation method according to claim 4, wherein the temperature of the calcination treatment in the step (3) is 400 to 1000 ℃, the temperature rise rate for raising the temperature to the calcination treatment temperature is 2 to 10 ℃/min, and the holding time after raising the temperature to the calcination treatment temperature is 0.5 to 5 hours.
8. The preparation method according to claim 4, wherein the acidic solution in the step (4) is a hydrochloric acid solution, the mass concentration of the hydrochloric acid solution is 18%, and the soaking time is 0.5-48 h.
9. A lithium-sulfur battery positive electrode material, which is characterized by comprising the lithium-sulfur battery positive electrode framework material as defined in any one of claims 1 to 3 or the lithium-sulfur battery positive electrode framework material prepared by the preparation method as defined in any one of claims 4 to 8.
10. A lithium sulfur battery comprising the lithium sulfur battery positive electrode material according to claim 9.
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| CN114583165A (en) * | 2020-12-01 | 2022-06-03 | 河南大学 | Metal/metal oxide lithium-sulfur battery positive electrode framework structure |
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