CN111224088A - Nickel nitride @ nitrogen-doped porous carbon sphere material, preparation method thereof and application thereof in lithium-sulfur battery - Google Patents
Nickel nitride @ nitrogen-doped porous carbon sphere material, preparation method thereof and application thereof in lithium-sulfur battery Download PDFInfo
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Abstract
The invention belongs to the technical field of lithium-sulfur batteries, and particularly discloses a nickel nitride @ nitrogen-doped porous carbon sphere material which is a porous carbon sphere with a through hole structure and containing a plurality of template etching holes; the carbon skeleton of the porous carbon sphere is nitrogen-doped disordered carbon; active particles are dispersed and distributed in the framework in situ; the active particles are nickel nitride particles coated with surface in-situ graphitized carbon. The invention also provides a preparation method of the material and application of the material in a lithium-sulfur battery. The carbon material has uniform granularity, is rich in a through macroporous structure, can efficiently store active substance sulfur, provides rich reaction interface and lithium ion transmission channel, can provide high-efficiency electronic conductivity by local graphitization, and in addition, the nitrogen-doped porous carbon spheres can improve the polarity of a carbon substrate and have strong adsorption and conversion capacity on polysulfide in cooperation with high-dispersion nickel nitride particles.
Description
Technical Field
The invention relates to the field of battery electrode material preparation, in particular to a material for a lithium-sulfur battery anode.
Background
The gradual depletion of fossil energy, the rapid development of portable electronic devices, electric and hybrid vehicles, and large energy storage devices has forced the development of secondary batteries with higher energy densities. The sulfur is used as a light and multi-electron reaction positive electrode material, the theoretical specific capacity is up to 1675mAh/g, the sulfur storage capacity is rich, the price is low, the environment is friendly, and the lithium-sulfur battery formed by the sulfur and the metal lithium negative electrode is considered as the next generation of high specific energy battery with the most application potential. However, before the lithium-sulfur battery is brought to the market, many scientific problems remain to be solved, the most important of which is how to improve the cycle stability of the battery. As the most important part of the structural composition of lithium-sulfur batteries, the modification research of sulfur positive electrodes, especially the preparation of sulfur and porous material composite positive electrodes, is the hot spot of the current research. The compounding of the elemental sulfur and the porous material mainly realizes two functions, namely the improvement of the electronic conductivity of the sulfur-based composite anode and the provision of a pore structure for the loaded sulfur to inhibit the dissolution of polysulfide. However, with the advance of the industrialization of lithium sulfur batteries, the kinetics of chemical reactions of lithium sulfur batteries are poor under the conditions of high loading capacity and low liquid-sulfur ratio, so that the unreacted polysulfide shuttles between the positive electrode and the negative electrode of the batteries, thereby causing low coulombic efficiency and poor cycle stability. Therefore, catalyst materials are reasonably added, and the reduction of the energy barrier of the reaction is of great importance to the improvement of the electrochemical performance of the battery.
The prior art reports that the specific surface area of a catalyst used for a lithium-sulfur battery is too small, the catalyst is combined with a carbon substrate in an ex-situ manner, the catalytic activity is poor, the reaction interface is insufficient in the charging and discharging process, the sulfur loading capacity in a battery pole piece is too low, and the cost is high by adopting graphene and carbon nanotubes as the carbon substrate, so that the catalyst is not beneficial to the practical popularization of the lithium-sulfur battery.
Disclosure of Invention
In order to overcome the defects of the prior art, the first purpose of the invention is to provide a nickel nitride @ nitrogen doped porous carbon sphere material, and the invention aims to provide a material which is suitable for a lithium-sulfur battery and can improve the electrical performance of the lithium-sulfur battery.
The second purpose of the invention is to provide a preparation method of the nickel nitride @ nitrogen doped porous carbon sphere material.
The third purpose of the invention is to provide a lithium-sulfur battery positive electrode active material obtained by loading sulfur in the nickel nitride @ nitrogen-doped porous carbon sphere material.
The fourth purpose of the invention is to provide a preparation method of the positive electrode active material of the lithium-sulfur battery.
The fifth purpose of the invention is to provide the application of the composite positive electrode active material in a lithium-sulfur battery.
A sixth object of the present invention is to provide a lithium-sulfur battery to which the composite positive electrode active material is added.
A nickel nitride @ nitrogen-doped porous carbon sphere material is a porous carbon sphere with a through hole structure and comprising a plurality of template etching holes;
the carbon skeleton of the porous carbon sphere is nitrogen-doped disordered carbon; active particles are dispersed and distributed in the framework in situ; the active particles are nickel nitride particles coated with surface in-situ graphitized carbon.
The material with special components and special in-situ morphology, which is loaded with sulfur, can show excellent conductivity and polysulfide catalytic activity in a lithium-sulfur battery, and can show excellent capacity, rate and cycle performance.
The nickel nitride @ nitrogen-doped porous carbon ball material is integrally spherical particles with a structure similar to a bowling ball, and a plurality of template etching holes formed by template etching are distributed in the carbon ball; the inner wall parts of the etching holes of the templates in the carbon spheres are communicated with each other to form a through hole structure. The carbon skeleton of the porous carbon sphere is nitrogen hybridized amorphous carbon, local graphitized coated active particles are embedded in situ in the carbon skeleton and/or embedded on the surface in situ, and the active particles are nickel nitride particles coated with the surface graphitized carbon in situ. The material with the special morphology has a through hole structure, is doped with nitrogen in a framework, is dispersed with nickel nitride particles in situ, and is graphitized in situ locally. The research finds that the material with the special composition and morphology can unexpectedly show excellent adsorption and catalytic conversion effects on polysulfide in a lithium-sulfur battery, and show excellent rate, specific capacity and cycle performance in the lithium-sulfur battery.
The spherical shape, the through hole formed by the mutual communication of the etching holes of the template in the structure, the nitrogen hybridized amorphous skeleton and the nickel nitride active particle coated by the in-situ local graphitization in the skeleton of the porous carbon material are the keys for realizing the good catalytic conversion of polysulfide compounds and the good electrochemical performance in a lithium-sulfur battery. The material with special components and morphology is applied to the lithium-sulfur battery, can integrate a plurality of functions such as physical confinement, chemical adsorption, catalytic conversion, rapid charge transfer and the like, plays a high-efficiency synergistic effect among the functions, is used in the lithium-sulfur battery after carrying sulfur, can effectively promote the lithium polysulfide conversion reaction, inhibits the shuttle effect, the polarization effect and the volume expansion effect, and improves the energy storage performance of the lithium-sulfur battery; the problems of low capacity, limited power density and short cycle life of the sulfur positive electrode of the lithium-sulfur battery are solved.
The research further finds that the further control of the pore structure, the N element hybridization amount, the local graphitization degree and the content of the nickel nitride of the porous carbon of the material is beneficial to further improving the adsorption and catalytic performance of the material on polysulfide compounds in a lithium-sulfur battery, and is beneficial to further improving the performances of the lithium-sulfur battery such as the multiplying power, the capacity and the like.
Preferably, the particle size of the porous carbon spheres is 1-50 microns; more preferably 5 to 25 μm.
Preferably, the porous carbon spheres are internally formed by etching hole structures through high-conductivity templates with thin-wall large hole volumes and communicated mutually, and the etching holes of the templates have the hole diameters of 50-500 nm; preferably uniform pores; more preferably, the deviation of the particle size of the template for forming the etching holes of the template is less than or equal to 3 percent. That is, the template used to prepare the template via holes has uniform particles having a particle size of 50 to 500nm (the deviation in particle size between particles is less than or equal to 3%). Researches find that the uniform holes are matched with the uniform hole intercommunicating structure, so that the performance of the material is further improved.
Preferably, the specific surface area of the porous carbon material is 1000-2500 m2(ii)/g; further preferably 1300 to 2000m2/g。
Preferably, the total pore volume is 1-5 cm3(ii)/g; the pore volume is 1.5-2.5 cm3/g。
Preferably, the ratio of Id/Ig is 0.2-2; preferably 0.8 to 1.
The porous carbon spheres are thin-walled carbon materials, and the thickness of the hole wall of the template etching hole is preferably 2.5-3.5 nm.
Preferably, in the nickel nitride @ nitrogen-doped porous carbon sphere material, the content of N element is 1-10 wt%, and further preferably 4-9 wt%; more preferably 4 to 6 wt%. The content of nickel element is 1-10 wt%; preferably 1.4 to 1.6 wt%.
The invention also provides a spray pyrolysis preparation method of the nickel nitride @ nitrogen-doped porous carbon sphere material, which comprises the following steps of:
step (1): nickel source, carbon source and SiO2Dispersing a template and a surfactant in a solvent to obtain precursor slurry; the SiO2The particle size of the template is 50-500 nm;
step (2): and (2) carrying out spray pyrolysis on the precursor slurry obtained in the step (1) in an ammonia atmosphere at 800-1200 ℃, and then etching to remove the silicon dioxide template to obtain the silicon dioxide template.
The invention innovatively discovers that the carbon material with similar bowling ball shape, etched and left mutual through hole structure and catalytic local graphitization distributed in situ in a dispersed mode in a nitrogen-doped framework can be obtained in situ by the preparation method in one step, and researches show that the material with brand-new components and shape, which is constructed by the preparation method, can show excellent polysulfide adsorption and catalytic degradation effects and excellent electrical properties when applied to the field of lithium-sulfur batteries.
According to the preparation method, nickel nitride active particles coated with nickel in-situ catalytic local graphitized carbon can be obtained through ammoniation, pyrolysis and carbonization of the components, and are good in shape uniformity and distributed in the nitrogen-doped disordered carbon in a dispersed manner in situ. And then, matching with an etching process, the etched hole can be obtained, and the hole structure intercommunication is realized to a certain degree. Researches show that the innovative preparation process is further matched with the combined control of parameters such as the particle size of the silicon dioxide template, the dosage of the surfactant, the nickel source, the pyrolysis carbonization condition and the like, and is helpful for further improving the performance of the obtained material.
The research of the invention also finds that the particle size of the template in the step (1) is further controlled, which is helpful for further improving the performance of the template in the lithium-sulfur battery.
Preferably, in the step (1), SiO is used2SiO in template dispersion2The diameter of (a) is 50-500 nm; preferably 50 to 150 nm. It has been found that control at this preferred particle size, in conjunction with the particular process described in the present invention, contributes to an unexpected further improvement in the properties of the resulting material.
In the present invention, the SiO2The template is uniform hole (for example, the deviation of the particle size is less than or equal to 3%). Researches find that the template with the uniform pore structure is adopted to help the material with the special morphology to be constructed in one step by matching with the special preparation process, and the performance of the material is further improved.
In the step (1), the nickel source is one or more of nickel nitrate, nickel acetate, nickel sulfate and nickel chloride.
Preferably, the surfactant in step (1) is one or more of PVP, CTAB and SDS. The research of the invention finds that the surfactant is adopted to help the construction of the bowling-like structure and the uniform dispersion distribution of the active particles and help to improve the performance of the obtained material by matching with the preparation process of the invention.
Preferably, the carbon source is at least one of tapioca starch, sucrose, tapioca flour, pitch and phenolic resin.
Preferably, in the step (1), the weight ratio of the nickel source, the surfactant, the carbon source and the silica template is 0.1-5: 0.1-1: 45-50: 45-50.
Preferably, the nickel source accounts for 0.8-8 wt% of the weight of the carbon source.
Preferably, the surfactant is 1-2 wt% of the carbon source.
The weight ratio of the carbon source to the silicon dioxide template is 1-1.2: 1.
The solvent is at least one of water, alcohol, isopropanol and glycol.
In the spray pyrolysis precursor slurry, the content of the solvent is 10-90%.
Preferably, the conditions of the spray pyrolysis are as follows: the spraying amount is 5-50 mL/min; preferably 5-20 mL/min, and the atomization pressure is 5-35 MPa; preferably 5 to 20 MPa. The nickel nitride @ nitrogen-doped porous carbon sphere material with the special morphology is successfully constructed by the combined control of the spraying solution and the spraying parameters.
The etching is alkali etching.
The alkali liquor adopted by the alkali etching is solution of alkali metal hydroxide.
The concentration of the alkali liquor is 5-10M, the temperature in the etching process is 80-120 ℃, and the time is 5-10 hours.
A preferred method of preparation, comprising the steps of:
(1) mixing nickel source, tapioca starch and SiO2Uniformly mixing the template, the surfactant and a certain amount of water to obtain carbonized precursor slurry.
(2) And (2) pyrolyzing the carbonized precursor slurry obtained in the step (1) at high temperature in an ammonia atmosphere, and removing the silicon dioxide template by using hot sodium hydroxide solution to obtain the material.
The invention also provides the nickel nitride @ nitrogen-doped porous carbon sphere material prepared by the method.
The porous carbon spheres prepared by the preparation method disclosed by the invention are uniform in particle size distribution, the particle size (1-50 micrometers) of the carbon spheres is regulated and controlled by regulating and controlling spray pyrolysis parameters, the inner parts of the carbon spheres are formed by thin-wall large-pore-volume high-conductivity porous structures which are mutually communicated, and SiO is regulated and controlled2The pore diameter (50-500 nm) of the internal pore structure of the prepared porous carbon sphere is regulated and controlled by the particle size of the template, and the electric conductivity is 103～105S·m-1The specific surface area of the porous carbon material is 1000-2500 m2(ii) a total pore volume of 1 to 5cm3/g。
The invention also provides a lithium-sulfur battery composite positive electrode active material which comprises the nickel nitride @ nitrogen-doped porous carbon sphere material and further comprises a simple substance sulfur source filled in porous carbon (such as template etching holes).
Preferably, the elemental sulfur source is sublimed sulfur or polymeric sulfur.
Preferably, the sulfur carrying amount of the composite positive electrode active material is 60-80 wt%.
The composite cathode active material can adopt the existing method to fill a simple substance sulfur source into the nickel nitride @ nitrogen doped porous carbon sphere material; for example, sulfur may be carried by sublimation of sulfur, or the polymerized sulfur may be filled by in situ polymerization of elemental sulfur.
The conductive agent and the adhesive can adopt materials which have conductive or adhesive functions and are available in the industry. The content of the components can be adjusted according to the use requirement.
Preferably, in the positive electrode material, the content of the conductive agent is 5-10%; the content of the binder is 5-10%.
The preparation method of the cathode material can adopt the conventional method, for example, the composite active material, the conductive agent and the binder are slurried by a solvent, coated and dried to obtain the cathode material.
The invention also provides a lithium-sulfur battery positive electrode which comprises a current collector and the positive electrode material compounded on the surface of the current collector.
The invention also provides a lithium-sulfur battery, wherein the composite positive electrode active material is compounded in the positive electrode of the lithium-sulfur battery.
The invention also provides a lithium-sulfur battery, and the material of the positive electrode of the lithium-sulfur battery comprises the positive electrode.
Compared with the prior art, the invention has the beneficial effects that:
1. a specially structured material is provided, which finds application in lithium sulfur batteries, can exhibit excellent polysulfide adsorption and catalytic properties, can exhibit more excellent electrical properties;
2. the slurry of the components is innovatively subjected to spray pyrolysis in an ammonia atmosphere, so that the in-situ composite material with the brand new appearance can be obtained;
3. the preparation method of the material is simple, the raw materials are low in price, and the method is suitable for large-scale industrial production and provides a method for industrial application of the lithium-sulfur battery.
Drawings
FIG. 1 is an SEM image of Ni-N doped porous carbon spheres obtained in example 1;
FIG. 2 is a TG diagram of the nickel nitride and nitrogen-doped porous carbon sphere/sulfur composite cathode material prepared in example 1;
FIG. 3 is a crystal structure diagram of nickel nitride;
FIG. 4 is a cycle diagram of a lithium-sulfur battery assembled by the nickel nitride and nitrogen-doped porous carbon sphere/sulfur composite positive electrode material prepared in example 1;
fig. 5 is a Raman chart of the nickel nitride, nitrogen-doped porous carbon spheres prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to examples, but the present invention is not limited to the scope of the present invention.
The followingCase, the SiO2The templates are all uniform-particle-size particles, and the deviation of the particle size is less than or equal to 3%.
Example 1
Mixing 5 kg of starch and 5 kg of 50nm SiO2Adding the template dispersion liquid, 80 g of nickel acetate and 50 g of sodium dodecyl sulfate into 10L of deionized water, stirring for 5 hours at the temperature of 80 ℃ to prepare uniform spray slurry, adding the slurry into a spray pyrolysis system through a peristaltic pump, setting the spray amount passing through the spray system to be 5mL/min and the atomization pressure to be 5MPa in an ammonia atmosphere, carrying out spray pyrolysis on the spray solution in a high-temperature pyrolysis furnace chamber at the temperature of 1000 ℃, and collecting spray pyrolysis products. And mixing the product with 5mol/L of sodium hydroxide solution for 5L, and washing the silicon dioxide template in a reaction kettle at the temperature of 80 ℃. The material is uniform spherical particles with the particle size of about 5 microns, and the pore volume is 2.18cm3Per g, specific surface area 1668m2The,/g, as can be seen from fig. 1, the inside of the spherical particle is composed of hollow carbon with a diameter of about 50nm, the wall thickness of the inner hole of the carbon sphere is 3.31nm, a through hole structure is arranged in the carbon sphere, the nickel element content of the whole material is 1.6 wt.%, the N element content is 5.1 wt.%, and I is calculated from the raman data of fig. 5D/IG0.85, conductivity 10 by four-probe method3S·m-1。
High-speed ball milling and mixing the nickel nitride and nitrogen-doped porous carbon ball material with sulfur powder for 2h according to the mass ratio of 2:8, heating to 155-190 ℃ under the protection of argon, preserving heat for 24h to obtain the nickel nitride and nitrogen-doped porous carbon ball/sulfur composite cathode material, and obtaining the actual sulfur content of 79.8 wt% through thermogravimetric test.
The composite positive electrode material obtained in example 1, conductive carbon black and polyvinylidene fluoride (PVDF) are uniformly mixed according to the mass ratio of 8:1:1, and are dispersed in NMP with a certain mass to prepare slurry (the solid content is 80 wt%), and then the slurry is coated on an aluminum foil current collector and is dried in vacuum at the temperature of 60 ℃ to obtain the lithium-sulfur battery positive electrode sheet. The battery assembly and testing was: punching the positive plate into an electrode plate with the diameter of 13mm, taking a metal lithium plate as a negative electrode, and taking 1M LiTFSI/DOL (dimethyl Ether) (1:1) +2 percent LiNO as electrolyte3And assembled into a CR2025 button cell in a glove box filled with argon. At room temperatureAnd (25 ℃) carrying out constant current charge and discharge test at the current density of 0.5C (837mAh/g), wherein the charge and discharge cut-off voltage is 1.7-2.8V. The first discharge specific capacity is 1328mAh/g, and the specific capacity is maintained 1138mAh/g after 100 times of circulation.
Example 2
Mixing 5 kg of starch and 5 kg of 500nm SiO2Adding the template dispersion liquid, 80 g of nickel acetate and 50 g of sodium dodecyl sulfate into 10L of deionized water, stirring for 5 hours at the temperature of 80 ℃ to prepare uniform spray slurry, adding the slurry into a spray pyrolysis system through a peristaltic pump, setting the spray amount passing through the spray system to be 50mL/min and the atomization pressure to be 35MPa in an ammonia atmosphere, carrying out spray pyrolysis on the spray solution in a high-temperature pyrolysis furnace chamber at the temperature of 1000 ℃, and collecting spray pyrolysis products. And mixing the product with 5mol/L of sodium hydroxide solution for 5L, and washing the silicon dioxide template in a reaction kettle at the temperature of 80 ℃. The material is uniform spherical particles with the particle size of about 25 microns, and the pore volume is 2.21cm3Per g, specific surface area of 1748m2The interior of the spherical particles is formed by hollow carbon with the diameter of about 500 nanometers, the thickness of the inner hole wall of the carbon ball is 3.24nm, the content of nickel element in the whole material is 1.4 wt%, and the content of nitrogen element is 5.3 wt%. High-speed ball milling and mixing the nickel nitride and nitrogen-doped porous carbon ball material with sulfur powder for 2h according to the mass ratio of 2:8, heating to 155-190 ℃ under the protection of argon, preserving heat for 24h to obtain the nickel nitride and nitrogen-doped porous carbon ball/sulfur composite cathode material, and obtaining the actual sulfur content of 79.3 wt% through thermogravimetric test.
The composite positive electrode material obtained in example 2, conductive carbon black and polyvinylidene fluoride (PVDF) are uniformly mixed according to the mass ratio of 8:1:1, and are dispersed in NMP with a certain mass to prepare slurry (the solid content is 80 wt%), and then the slurry is coated on an aluminum foil current collector and is dried in vacuum at 60 ℃ to obtain the lithium-sulfur battery positive electrode sheet. The battery assembly and testing was: punching the positive plate into an electrode plate with the diameter of 13mm, taking a metal lithium plate as a negative electrode, and taking 1M LiTFSI/DOL (dimethyl Ether) (1:1) +2 percent LiNO as electrolyte3And assembled into a CR2025 button cell in a glove box filled with argon. And carrying out constant-current charge and discharge tests at room temperature (25 ℃) at a current density of 0.5C (837mAh/g), wherein the charge and discharge cut-off voltage is 1.7-2.8V. Specific capacity of initial discharge1290mAh/g, and the specific capacity is kept at 1010mAh/g after 100 cycles.
Example 3
Mixing 5 kg of starch and 5 kg of 150nm SiO2Adding the template dispersion liquid, 400 g of nickel acetate and 50 g of sodium dodecyl sulfate into 10L of deionized water, stirring for 5 hours at the temperature of 80 ℃ to prepare uniform spray slurry, adding the slurry into a spray pyrolysis system through a peristaltic pump, setting the spray amount passing through the spray system to be 20mL/min and the atomization pressure to be 20MPa in an ammonia atmosphere, carrying out spray pyrolysis on the spray solution in a high-temperature pyrolysis furnace chamber at the temperature of 1000 ℃, and collecting spray pyrolysis products. And mixing the product with 5mol/L of sodium hydroxide solution for 5L, and washing the silicon dioxide template in a reaction kettle at the temperature of 80 ℃. The material is uniform spherical particles with the particle size of about 10 microns, and the pore volume is 1.64cm3Per g, specific surface area 1356m2The inner part of the spherical particles is composed of hollow carbon with the diameter of about 150 nanometers, the thickness of the inner hole wall of the carbon ball is 2.98nm, the content of nickel element in the whole material is 7.8 wt.%, and the content of nitrogen element is 8.4 wt.%.
High-speed ball milling and mixing the nickel nitride and nitrogen-doped porous carbon ball material with sulfur powder for 2h according to the mass ratio of 2:8, heating to 155-190 ℃ under the protection of argon, and preserving heat for 24h to obtain the nickel nitride and nitrogen-doped porous carbon ball/sulfur composite cathode material, wherein the actual sulfur content is 78.5. wt.% through thermogravimetric testing.
The composite positive electrode material obtained in example 3, conductive carbon black and polyvinylidene fluoride (PVDF) are uniformly mixed according to the mass ratio of 8:1:1, and are dispersed in NMP with a certain mass to prepare slurry (the solid content is 80 wt%), and then the slurry is coated on an aluminum foil current collector and is dried in vacuum at 60 ℃ to obtain the lithium-sulfur battery positive electrode sheet. The battery assembly and testing was: punching the positive plate into an electrode plate with the diameter of 13mm, taking a metal lithium plate as a negative electrode, and taking 1M LiTFSI/DOL (dimethyl Ether) (1:1) +2 percent LiNO as electrolyte3And assembled into a CR2025 button cell in a glove box filled with argon. And carrying out constant-current charge and discharge tests at room temperature (25 ℃) at a current density of 0.5C (837mAh/g), wherein the charge and discharge cut-off voltage is 1.7-2.8V. The first discharge specific capacity is 1298mAh/g, and the specific capacity is kept at 1023mAh/g after 100 times of circulation.
Example 4
Mixing 5 kg of starch and 5 kg of 150nm SiO2Adding the template dispersion liquid, 80 g of nickel acetate and 50 g of sodium dodecyl sulfate into 10L of deionized water, stirring for 5 hours at the temperature of 80 ℃ to prepare uniform spray slurry, adding the slurry into a spray pyrolysis system through a peristaltic pump, setting the spray amount passing through the spray system to be 20mL/min and the atomization pressure to be 20MPa in an ammonia atmosphere, carrying out spray pyrolysis on the spray solution in a high-temperature pyrolysis furnace chamber at the temperature of 800 ℃, and collecting spray pyrolysis products. And mixing the product with 5L of 5mol/L sodium hydroxide solution, and washing the silicon dioxide template in a reaction kettle at the temperature of 80 ℃. The material is uniform spherical particles with the particle size of about 10 microns, and the pore volume is 2.13cm3(iv) a specific surface area of 1759m2The inner part of the spherical particles is composed of hollow carbon with the diameter of about 150 nanometers, the thickness of the inner hole wall of the carbon ball is 3.28nm, the content of nickel element in the whole material is 1.5 wt.%, and the content of nitrogen element in the material is 4.8 wt.%. High-speed ball milling and mixing the nickel nitride and nitrogen-doped porous carbon ball material with sulfur powder for 2h according to the mass ratio of 2:8, heating to 155-190 ℃ under the protection of argon, preserving heat for 24h to obtain the nickel nitride and nitrogen-doped porous carbon ball/sulfur composite cathode material, and obtaining the actual sulfur content of 78.4 wt% through thermogravimetric test.
The composite positive electrode material obtained in example 4, conductive carbon black and polyvinylidene fluoride (PVDF) were uniformly mixed in a mass ratio of 8:1:1, and dispersed in NMP of a certain mass to prepare a slurry (solid content is 80 wt%), and then coated on an aluminum foil current collector, and vacuum-dried at 60 ℃ to obtain a lithium-sulfur battery positive electrode sheet. The battery assembly and testing was: punching the positive plate into an electrode plate with the diameter of 13mm, taking a metal lithium plate as a negative electrode, and taking 1M LiTFSI/DOL (dimethyl Ether) (1:1) +2 percent LiNO as electrolyte3And assembled into a CR2025 button cell in a glove box filled with argon. And carrying out constant-current charge and discharge tests at room temperature (25 ℃) at a current density of 0.5C (837mAh/g), wherein the charge and discharge cut-off voltage is 1.7-2.8V. The first discharge specific capacity is 1256mAh/g, and the specific capacity after 100 times of circulation is kept 1054 mAh/g.
Comparative example 1
Compared with the example 3, the difference is mainly that the in-situ dispersion active particle structure is not successfully constructed in one step, specifically:
5 kg of starch, 5 kg of 150nmSiO2Adding the template dispersion liquid and 50 g of sodium dodecyl sulfate into 10L of deionized water, stirring for 5 hours at the temperature of 80 ℃ to prepare uniform spray slurry, adding the slurry into a spray pyrolysis system through a peristaltic pump, setting the spray amount passing through the spray system to be 20mL/min and the atomization pressure to be 20MPa in an ammonia atmosphere, carrying out spray pyrolysis on the spray solution in a high-temperature pyrolysis furnace chamber at the temperature of 1000 ℃ in the ammonia atmosphere, and collecting spray pyrolysis products. Mixing the product with 5mol/L sodium hydroxide solution 5L, washing off the silicon dioxide template in a reaction kettle at 80 ℃, filtering and drying, wherein the material is uniform spherical particles with the particle size of about 5 microns, and the pore volume is 2.29cm3Per g, specific surface area 1783m2And/g, the inside of the spherical particles is composed of hollow carbon with the diameter of about 150 nanometers, and the thickness of the inner hole wall of the carbon sphere is 3.22 nm. The nitrogen-doped porous carbon ball material and sulfur powder are subjected to high-speed ball milling and mixing for 2h in a mass ratio of 2:8, then the temperature is raised to 155-190 ℃ under the protection of argon, the temperature is kept for 24h, the nitrogen-doped porous carbon ball/sulfur composite anode material is obtained, and the actual sulfur content is 79.8 wt% through thermogravimetric testing.
And (2) uniformly mixing the composite positive electrode material obtained in the comparative example 1, conductive carbon black and polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, dispersing the mixture in NMP with a certain mass to prepare slurry (the solid content is 80 wt%), coating the slurry on an aluminum foil current collector, and drying the aluminum foil current collector in vacuum at the temperature of 60 ℃ to obtain the lithium-sulfur battery positive electrode plate. The battery assembly and testing was: punching the positive plate into an electrode plate with the diameter of 13mm, taking a metal lithium plate as a negative electrode, and taking 1M LiTFSI/DOL (dimethyl Ether) (1:1) +2 percent LiNO as electrolyte3And assembled into a CR2025 button cell in a glove box filled with argon. And carrying out constant-current charge and discharge tests at room temperature (25 ℃) at a current density of 0.5C (837mAh/g), wherein the charge and discharge cut-off voltage is 1.7-2.8V. The first discharge specific capacity is 1158mAh/g, and after 100 times of circulation, the specific capacity is kept at 869 mAh/g. Comparative example 3 shows that the specific capacity and the cycling performance of the active particles, which are dispersed and distributed, are significantly deteriorated without in-situ construction.
Comparative example 2
Compared with the example 3, the difference is mainly that the spraying process is not carried out with in-situ ammoniation, specifically:
5 kg of starch, 5 kg of 50nmSiO2Adding the template dispersion liquid, 80 g of nickel acetate and 50 g of sodium dodecyl sulfate into 10L of deionized water, stirring for 5 hours at the temperature of 80 ℃ to prepare uniform spray slurry, adding the slurry into a spray pyrolysis system through a peristaltic pump, setting the spray amount passing through the spray system to be 20mL/min and the atomization pressure to be 20MPa under the argon atmosphere, carrying out spray pyrolysis on the spray solution in a high-temperature pyrolysis furnace chamber under the argon atmosphere at the temperature of 1000 ℃, and collecting spray pyrolysis products. Mixing the product with 5mol/L sodium hydroxide solution 5L, washing off the silicon dioxide template in a reaction kettle at 80 ℃, filtering and drying, wherein the material is uniform spherical particles with the particle size of about 5 microns, and the pore volume is 2.31cm3Per g, specific surface area 1661m2(ii) in terms of/g. The inside of the spherical particles is composed of hollow carbon with the diameter of about 50 nanometers, and the thickness of the inner hole wall of the carbon sphere is 3.11 nm. The content of the material element nickel is 1.4%. The porous carbon ball material and sulfur powder are subjected to high-speed ball milling and mixing for 2h in a mass ratio of 2:8, then the temperature is raised to 155-190 ℃ under the protection of argon, the temperature is kept for 24h, the nickel-doped porous carbon ball/sulfur composite positive electrode material is obtained, and the actual sulfur content is 79.8 wt% through thermogravimetric testing.
And (3) uniformly mixing the composite positive electrode material obtained in the comparative example 2, conductive carbon black and polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, dispersing the mixture in NMP with a certain mass to prepare slurry (the solid content is 80 wt%), coating the slurry on an aluminum foil current collector, and drying the aluminum foil current collector in vacuum at the temperature of 60 ℃ to obtain the lithium-sulfur battery positive electrode plate. The battery assembly and testing was: punching the positive plate into an electrode plate with the diameter of 13mm, taking a metal lithium plate as a negative electrode, and taking 1M LiTFSI/DOL (dimethyl Ether) (1:1) +2 percent LiNO as electrolyte3And assembled into a CR2025 button cell in a glove box filled with argon. And carrying out constant-current charge and discharge tests at room temperature (25 ℃) at a current density of 0.5C (837mAh/g), wherein the charge and discharge cut-off voltage is 1.7-2.8V. The first discharge specific capacity was 1189mAh/g, the specific capacity remained 952mAh/g after 100 cycles as in comparative example 1, it can be seen that spray pyrolysis was not performed in an ammonia atmosphere, resulting in failure to convert elemental nickel into nickel nitride, andthe carbon-based material cannot be doped with elemental nitrogen, so that the overall catalytic activity of the material is not high, the adsorption capacity to polysulfide is not strong, and the rate performance of the cycle stability of the lithium-sulfur battery cannot be well exerted.
Comparative example 3
The comparative example 3 corresponds to the example 4 except that the temperature of the spray pyrolysis was reduced to 700 c, and the discharge capacity was 1125mAh/g in the first cycle and 859mAh/g after 100 cycles.
Comparative example 4
The procedure of comparative example 4 followed the procedure of example 2, except that SiO was added2The particle size of the template increased from 500nm to 1 μm, and the other conditions remained unchanged. The test conditions of example 2 were used for the determination. The comparative experiment results show that the first circle of the battery using the material has discharge capacity of 1024mAh/g, and the discharge capacity after 100 circles is 793mAh/g
Comparative example 5
The procedure of comparative example 5 followed the procedure of example 1 except that SiO was added2The particle size of the template is reduced from 50nm to 10nm, and other conditions are kept unchanged. The test conditions of example 1 were used for the determination. The first-circle discharge capacity of the battery using the material is 957mAh/g, and the discharge capacity after 100 circles is 730 mAh/g.
Comparative example 6
The implementation route of comparative example 6 adopts the technical route of example 4, except that the surfactant Sodium Dodecyl Sulfate (SDS) is not added in the raw materials. An ideal structure of through holes uniformly distributed inside the carbon spheres is not prepared. The first-circle discharge capacity of the battery using the material is 844mAh/g, and the discharge capacity after 100 circles is 675 mAh/g.
Comparative example 7
The implementation route of comparative example 7 adopts the technical route of example 4, only hydrofluoric acid is used for replacing a hot alkali etching template in the template removing process, and the comparison experiment result shows that the hydrofluoric acid removes the template and simultaneously removes active catalytic components. The first circle of the battery using the material has discharge capacity of 988mAh/g, and the discharge capacity after 100 circles is 774 mAh/g.
Comparative example 8
Compared with the embodiment 4, the method mainly discusses the physical mixing effect of the carbon material and the nickel nitride, and specifically comprises the following steps:
the implementation route of the comparative example 8 adopts the technical route of the example 4, except that a nickel source is not added in the raw materials, other process parameters are kept unchanged, the porous carbon sphere material is prepared, a certain amount of commercial nickel nitride powder is mixed with the prepared porous carbon sphere material, the porous carbon sphere nickel nitride composite material is prepared by ball milling and mixing uniformly, and the technical route of the example 4 is adopted for subsequent sulfur carrying and electrochemical performance evaluation. The first-circle discharge capacity of the battery using the material is 894mAh/g, and the discharge capacity after 100 circles is 674 mAh/g.
Comparative example 9
Discussing the effect of non-one-step spray forming, specifically:
the implementation route of comparative example 9 adopts the technical route of comparative example 8, except that the prepared porous carbon sphere material is not ball-milled and mixed with a commercial nickel nitride material, but is subjected to an impregnation treatment with a nickel source (nickel acetate), and after drying, the impregnated porous carbon sphere material is fired at 800 ℃. The first-circle discharge capacity of the battery using the material is 969mAh/g, and the discharge capacity after 100 circles is 736 mAh/g.
Comparative example 10
Comparative example 10 was carried out by following the same procedure as in example 1 except that the spray pyrolysis was carried out at 1000 ℃ in an ammonia gas atmosphere, and the spray pyrolysis was carried out at 300 ℃ in an argon gas atmosphere, and the pyrolysis product was transferred to an atmosphere furnace and heat-treated at 800 ℃ in an ammonia gas atmosphere. The subsequent de-templating and sulfur loading and subsequent electrochemical performance characterization followed the technical route of example 4. The first circle of the battery using the material has a discharge capacity of 1047mAh/g, and the discharge capacity of 863mAh/g after 100 circles.
Comparative example 11
The technical route of comparative example 11 followed the technical route of example 4, except that the precursor slurry was not spray pyrolyzed, but dried, followed by heat treatment at 800 degrees celsius in an ammonia atmosphere for 3 hours, followed by fragmentation of the pyrolysis product, followed by template removal, sulfur loading, and electrochemical evaluation followed the technical route of example 4. The first-turn discharge capacity of the battery using the material is 1126mAh/g, and the discharge capacity after 100 turns is 895 mAh/g.
Claims (10)
1. A nickel nitride @ nitrogen-doped porous carbon sphere material is characterized by comprising a plurality of template etching holes and porous carbon spheres with through hole structures;
the carbon skeleton of the porous carbon sphere is nitrogen-doped disordered carbon; active particles are dispersed and distributed in the framework in situ; the active particles are nickel nitride particles coated with surface in-situ graphitized carbon.
2. The nickel nitride @ nitrogen-doped porous carbon sphere material of claim 1, wherein the particle size of the porous carbon spheres is 1-50 microns;
the porous carbon spheres are internally formed by etching hole structures by high-conductivity templates with thin-wall large pore volumes and communicated mutually, and the etching holes of the templates have the pore diameters of 50-500 nm; preferably uniform pores; further preferably, the deviation of the particle size of the template for forming the etching hole of the template is less than or equal to 3 percent;
the specific surface area of the porous carbon material is 1000-2500 m2/g；
The total pore volume is 1-5 cm3(ii)/g; the pore volume is 1.5-2.5 cm3/g；
The ratio Id/Ig is 0.2-2.
3. The nickel nitride @ nitrogen-doped porous carbon sphere material of claim 1, wherein, in the nickel nitride @ nitrogen-doped porous carbon sphere material,
the content of N element is 1-10 wt.%; the content of nickel element is 1-10 wt%.
4. A spray pyrolysis preparation method of the nickel nitride @ nitrogen-doped porous carbon sphere material as claimed in any one of claims 1 to 3 is characterized by comprising the following steps:
step (1): nickel source, carbon source and SiO2Dispersing a template and a surfactant in a solvent to obtain precursor slurry; the SiO2The particle size of the template is 50-500 nm;
step (2): and (2) carrying out spray pyrolysis on the precursor slurry obtained in the step (1) in an ammonia atmosphere at 800-1200 ℃, and then etching to remove the silicon dioxide template to obtain the silicon dioxide template.
5. The preparation method according to claim 4, wherein in the step (1), the nickel source is one or more of nickel nitrate, nickel acetate, nickel sulfate and nickel chloride;
preferably, the surfactant in the step (1) is one or more of PVP, CTAB and SDS;
preferably, the carbon source is at least one of tapioca starch, sucrose, tapioca flour, pitch and phenolic resin;
preferably, in the step (1), the weight ratio of the nickel source, the surfactant, the carbon source and the silica template is 0.1-5: 0.1-1: 45-50: 45-50 parts of;
the solvent is at least one of water, alcohol, isopropanol and glycol;
in the spray pyrolysis precursor slurry, the content of the solvent is 10-90%.
6. The process according to claim 4 or 5, wherein the spray pyrolysis is carried out under the following conditions: the spraying amount is 5-50 mL/min, and the atomizing pressure is 5-35 MPa.
7. The production method according to claim 4 or 5, wherein the etching is alkali etching;
the alkali liquor adopted by the alkali etching is solution of alkali metal hydroxide;
the concentration of the alkali liquor is 5-10M, the temperature in the etching process is 80-120 ℃, and the time is 5-10 hours.
8. The composite cathode active material for the lithium-sulfur battery is characterized by comprising the nickel nitride @ nitrogen-doped porous carbon sphere material in any one of claims 1 to 3 or the nickel nitride @ nitrogen-doped porous carbon sphere material prepared by the preparation method in any one of claims 4 to 7, and further comprising a simple substance sulfur source filled in the porous carbon sphere;
preferably, the sulfur carrying amount of the composite positive electrode active material is 60-80 wt%.
9. A positive electrode material for a lithium-sulfur battery, comprising the composite positive electrode active material according to claim 8, further comprising a conductive agent and a binder;
preferably, the content of the conductive agent is 5-10 wt%; the content of the binder is 5-10 wt%.
10. A lithium sulfur battery, wherein a positive electrode of the lithium sulfur battery comprises the composite positive electrode active material according to claim 8;
preferably, the positive electrode material according to claim 9.
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