CN114284496A - Preparation method of three-dimensional large-framework multi-level structure electrode material - Google Patents
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Abstract
The invention discloses a preparation method of a three-dimensional large-framework multi-level structure electrode material, and relates to the technical field of lithium ion battery cathode materials. The method comprises the following implementation steps: step 1, uniformly mixing PVP, cobalt salt and a medium solution, and dispersing to obtain a clear solution; step 2, drying to obtain a non-flowable colloid; step 3, sintering to obtain a Co/C framework; step 4, stirring the Co/C skeleton, cobalt salt, fluorine salt, urea and a medium solution to a premixed solution; step 5, carrying out hydrothermal reaction in a high-pressure reaction kettle to obtain a Co (OH) F/C precursor; and 6, heating the Co (OH) F/C precursor in the air or inert gas atmosphere for phosphorization, and naturally cooling to room temperature to obtain the three-dimensional large-framework multi-level structure electrode material. The problems of poor conductivity and large volume change of cobalt phosphide can be effectively solved, and the lithium ion battery cathode material with high specific capacity, high rate characteristic and long cycle life can be obtained.
Description
Technical Field
The invention relates to a lithium ion storage capacitor, in particular to the technical field of lithium ion battery cathode materials.
Background
As a novel environment-friendly and energy-saving green battery, the lithium ion battery attracts much attention in the field of new energy due to the characteristics of environmental protection, high specific capacity, long service life, high safety and the like, and has great application potential on large-scale power equipment such as electric automobiles and the like. The negative electrode material is one of the key factors influencing the performance of the lithium ion battery, however, the theoretical capacity of the graphite negative electrode material which is commercialized at present is relatively low, so the application of the graphite negative electrode material in the field of energy storage is limited. Therefore, the development of a novel high-performance anode material capable of replacing a graphite anode material is an urgent problem and also becomes a precondition for realizing leap of lithium ion batteries. In order to meet the demand, researchers in various countries are working on seeking new high-performance anode materials. In recent years, a transition metal Co (cobalt) simple substance has the advantages of rich source, low cost, environmental protection, higher theoretical specific capacity and the like, and is gradually a popular choice for the research of lithium ion battery cathode materials. However, when the simple substance Co is used as the lithium ion battery cathode material, large volume expansion is easy to occur in the charging and discharging processes, so that the phenomena of incineration, inactivation and the like of the material occur, and the lithium storage performance is greatly reduced.
Disclosure of Invention
The invention designs a cobalt phosphide/carbon multilevel structure electrode material with a three-dimensional large framework, and aims to solve the problems of poor rate characteristics and serious capacity attenuation caused by poor intrinsic conductivity and large volume change of cobalt phosphide during lithium storage.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a preparation method of a three-dimensional large-framework multi-level structure electrode material comprises the following steps:
step 1, uniformly mixing PVP, cobalt salt and a medium solution, and dispersing to obtain a clear solution;
step 2, transferring the clear solution to a corundum boat, putting the corundum boat into an oven and drying the corundum boat into a non-flowable colloid;
step 3, placing the colloid in air or inert gas atmosphere for sintering, wherein the sintering temperature is 700-900 ℃, and the sintering time is 2-5 hours, so as to obtain a Co/C framework;
step 4, uniformly stirring the Co/C framework, cobalt salt, fluorine salt, urea and a medium solution for 20-50 minutes to obtain a premixed solution;
step 5, placing the premixed solution into a high-pressure reaction kettle for hydrothermal reaction, wherein the reaction temperature is 110-130 ℃, and the reaction time is 8-12 hours, so as to obtain a Co (OH) F/C precursor;
and 6, respectively placing the Co (OH) F/C precursor and the sodium salt at the central position and upstream of the tubular furnace, heating in the air or inert gas atmosphere for phosphorization, wherein the heating rate is 2-8 ℃/min, the phosphorization temperature is 300-400 ℃, the phosphorization time is 2-4 hours, and naturally cooling to room temperature to obtain the three-dimensional large-framework multi-stage structure electrode material.
Furthermore, the mass ratio of the PVP, the Co salt and the medium solution substance in the step 1 is 1 (0.5-2): 30.
Preferably, the PVP of step 1 has a relative molecular weight of 24000 or 58000 or 1300000.
Preferably, the cobalt salt in step 1 is Co (NO)3)2∙6H2O、(CH2COO)2Co、CoCl2∙6H2O or any combination of more than one of the O.
Further, the medium solution in step 1 and step 4 is one or more of deionized water, ethanol and ethylene glycol in any mass combination.
Further, the mass ratio of the cobalt salt, the fluorine salt, the urea, the Co/C and the medium solution in the step 4 is 20: 2: 10: (1-10): (100-200).
Preferably, the fluorine salt in step 4 is NH4F. One or more of LiF and tetrabutylammonium fluoride in any mass combination.
Further, the mass ratio of the Co (OH) F/C precursor to the sodium salt in the step 6 is 1: (5-10).
Preferably, the sodium salt in step 6 is Na3PO2、Na2HPO2、NaH2PO2、Na3PO4、Na2HPO4、NaH2PO4One or more than one arbitrary mass combination.
In the scheme, the polyvinylpyrrolidone (PVP) is formed by homopolymerization of monomer N-vinyl pyrrolidone (NVP), and is a water-soluble linear high molecular compound. Has the functions of colloid-like protection, film-forming property, cohesiveness, hygroscopicity, solubilization or aggregation, complexing ability with certain compounds and the like. The polyvinylpyrrolidone has both hydrophilic group and lipophilic group in its molecule, so that it can be dissolved in water and most of organic solvent (such as alcohol, carboxylic acid, amine and halohydrocarbon), and its toxicity is low, physiological compatibility is good, and its solubility in water is limited by its viscosity.
In the scheme, in the steps 4 and 5, the Co/C framework, the cobalt salt, the villaumite and the urea which are generated in the previous step are uniformly stirred with a medium solution, and are placed in a high-pressure reaction kettle for hydrothermal reaction, the surface of the material surface of the Co/C framework is modified by fluorination, and a carbon fluoride material with fluorine element gradient is formed under the hydrolysis action of the urea, so that the carbon surface is in a porous graphene shape, more cobalt phosphide particles loaded on active sites are ensured, the conductivity can be increased, the transmission capability of lithium ions is accelerated, and a good continuous conductive network is formed. And the addition of the fluorinion increases the nucleophilicity of the reactant, is beneficial to the generation of subsequent CoP in the phosphating process, and avoids Co2P, etc. are produced.
Step 6, respectively placing Co (OH) F/C precursor and sodium salt in the central position and upstream phosphorization process of the tubular furnace, placing the sodium salt and the Co (OH) F/C precursor in the center of the tubular sintering furnace side by side, ensuring uniform heating in the sintering process, and simultaneously placing sodium hypophosphite in the upstream position for heating and decomposing to generate PH3The gases flow downstream of the sintering furnace with inert gas introduction, and the co (oh) F/C precursor is phosphated by vapor deposition.
In step 6, fluorine is replaced by sodium salt, because the carbon fluoride battery has voltage hysteresis in the discharging process and the performance of the battery is influenced along with a large amount of heat consumption. By controlling the fluorine-carbon ratio, fluorinated and non-fluorinated parts coexist on the nano scale, and the part of the central unfluorinated graphite-like structure is used as an electron rapid transport part, so that the generation of intrinsic electron conduction defects caused by C-F bonds formed by fluorination can be remarkably reduced, and the ohm drop is further caused.
According to the method, partial fluorination is carried out by controlling the fluorination temperature and the fluorination time of a high-temperature fluorination method, carbon fibers are used as precursors, the surfaces of the carbon fibers are fluorinated by controlling the reaction temperature, and nanoscale unfluorinated carbon atoms in carbon fiber tubes are reserved as products, so that the conductivity of the carbon fluoride material is increased, and the power density of the lithium/carbon fluoride battery is greatly improved.
According to the technical scheme, the three-dimensional framework carbon material prepared by a chemical blow molding method is used as a primary structure to form a three-dimensional and continuous conductive network, the metal cobalt source in the primary structure is used for carrying out in-situ loading of cobalt phosphide with a secondary structure to enhance the stability of the multi-level structure, the hydrothermal method is adopted to regulate and control the cobalt phosphide with an ex-situ loading tertiary structure into a micro-morphology structure of the multi-level structure on the primary structure, so that a three-dimensional large framework cobalt phosphide/carbon multi-level structure is obtained, fine holes exist in a lamellar structure of the formed three-dimensional conductive network, lithium storage at active sites is facilitated, a high-speed channel for lithium ion insertion/extraction and electronic conduction and a buffer space for volume expansion of the cobalt phosphide are constructed. The successful construction of the three-dimensional large-framework cobalt phosphide/carbon multi-stage structure can fully exert the intrinsic characteristics and the synergistic mechanism of each stage of structure, construct a high-speed channel for lithium ion insertion/removal and electron conduction and a buffer space for cobalt phosphide volume expansion, solve the problems of poor conductivity and large volume change of cobalt phosphide, and obtain the lithium ion battery cathode material with high specific capacity, high rate characteristics and long cycle life.
Drawings
FIG. 1, example one resulting crystalline form of a composite CoP of cobalt phosphide and carbon;
FIG. 2, SEM (scanning electron) image of the resulting CoP/C electrode material;
FIG. 3, example one resulting CoP/C charge and discharge capacity;
FIG. 4, example one resulting graph of the cycling performance of CoP/C at 1C;
FIG. 5, charge and discharge capacity of CoP/C obtained in example two;
FIG. 6, graph of the cycle performance at 1C for the resulting CoP/C of example two;
FIG. 7, charge and discharge capacities of CoP/C obtained in example III;
FIG. 8, graph of cycle performance at 1C for CoP/C obtained in example three.
Detailed Description
The first embodiment is as follows:
(1) 1g PVP (molecular weight 58000) was dissolved in deionized water (30 mL) and dissolved thoroughly to a clear solution, and then 1g Co (NO) was added to the solution3)2∙6H2And O, stirring for 30mins to obtain a clear pink solution, directly transferring the solution into a corundum boat, drying in an oven at 70 ℃ for 36h to obtain a non-flowable pink colloid, and sintering at 750 ℃ for 3h in an argon environment.
(2) 4.365g of Co (NO)3)2∙6H2O、0.437g NH4F. 2.180g of urea was dissolved in 40 mL of deionized water and stirred for 30min, then Co/C (0.28g) was added to the solution and stirred until thoroughly mixed. The reaction was carried out in a 100 mL stainless steel autoclave lined with Teflon at 120 ℃ for 10 h.
(3) 0.1g of Co (OH) F/C sample and 0.5g of NaH2PO2The powder is respectively placed at the upstream and the central position of a tube furnace, the temperature is raised under the argon condition, the heating rate is 5 ℃/min, the temperature is kept for 3 hours at 300 ℃, Co (OH) F/C is converted into CoP/C, and then the temperature is naturally cooled to the room temperature.
As shown in FIG. 1, the composite of cobalt phosphide and carbon obtained in example one well maintained the crystalline form of CoP.
As shown in FIG. 2, SEM (scanning electron) image of the CoP/C electrode material obtained in example one, rod-shaped nanoparticles were prepared.
As shown in FIG. 3, the charge and discharge capacities of CoP/C obtained in example one at different magnifications of 0.5C, 1C, 3C, 5C, 10C and 0.5C are 537/539, 425/427, 360/361, 298/295, 224/240 and 487/475 mAh/g respectively.
As shown in FIG. 4, the cycle performance at 1C for the resulting CoP/C of example one can see that the cycle efficiency is close to 100% over the cycle period.
Example two:
(1) 1g of PVP (molecular weight 1300000)Dissolved in deionized water (30 mL) to dissolve it sufficiently to a clear solution, and then 1.5g Co (NO) was added to the above solution3)2∙6H2And O, stirring for 30mins to obtain a clear pink solution, directly transferring the solution into a corundum boat, drying in an oven at 70 ℃ for 36h to obtain a non-flowable pink colloid, and sintering at 750 ℃ for 3h in an argon environment.
(2) 4.365g of Co (NO)3)2∙6H2O、0.437g NH4F. 2.180g of urea was dissolved in 40 mL of deionized water and stirred for 30min, then Co/C (0.36g) was added to the solution and stirred until thoroughly mixed. The reaction was carried out in a 100 mL stainless steel autoclave lined with Teflon at 110 ℃ for 12 h.
(3) 0.1g of Co (OH) F/C sample and 1g NaH2PO2The powder is respectively placed at the upstream and the central position of a tube furnace, the temperature is preserved for 3 hours at 350 ℃ under the argon condition, the heating rate is 8 ℃/min, Co (OH) F/C is converted into CoP/C, and then the mixture is naturally cooled to the room temperature.
As shown in FIG. 5, the charge and discharge capacities of CoP/C obtained in example two at different magnifications of 0.5C, 1C, 3C, 5C, 10C and 0.5C are 507/511, 446/455, 406/410, 358/361, 281/283 and 505/507 mAh/g respectively.
As shown in FIG. 6, the cycle performance of CoP/C at 1C obtained in example two shows that the cycle efficiency approaches 100% throughout the cycle.
Example three:
(1) 1g PVP (molecular weight 1300000) was dissolved in deionized water (30 mL) and dissolved thoroughly to a clear solution, then 1.5g CoCl was added to the above solution2∙6H2And O, stirring for 30mins to obtain a clear pink solution, directly transferring the solution into a corundum boat, drying in an oven at 70 ℃ for 36h to obtain a non-flowable pink colloid, and sintering at 750 ℃ for 5h in an argon environment.
(2) 4.365g of CoCl2∙6H2O、0.437g NH4F. 2.180g of urea was dissolved in 40 mL of deionized water, stirred for 30min, and then Co/C (0.218g) was added to the solutionIn the solution, stirring was carried out until complete mixing. The reaction was carried out in a 100 mL stainless steel autoclave lined with Teflon at 120 ℃ for 8 h.
(3) 0.1g of Co (OH) F/C sample and 1g NaH2PO2And NaH2PO4The mixed powder (ratio 1: 1) is respectively placed at the upstream and the central position of a tube furnace, the temperature is kept for 5 hours at 350 ℃ under the condition of argon, the heating rate is 2 ℃/min, Co (OH) F/C is converted into CoP/C, and then the mixture is naturally cooled to the room temperature.
As shown in FIG. 7, the charge and discharge capacities of CoP/C obtained in example three at different magnifications of 0.5C, 1C, 3C, 5C, 10C and 0.5C are 444/446, 398/400, 345/350, 280/281, 211/213 and 455/457 mAh/g respectively.
As shown in FIG. 8, the cycle performance of CoP/C at 1C obtained in example three is close to 100% in the cycle efficiency.
Claims (9)
1. A preparation method of a three-dimensional large-framework multi-level structure electrode material comprises the technological processes of obtaining a Co/C framework, manufacturing a Co (OH) F/C precursor and phosphorizing, and is characterized in that: the preparation method comprises the following specific preparation steps:
step 1, uniformly mixing PVP, cobalt salt and a medium solution, and dispersing to obtain a clear solution;
step 2, transferring the clear solution to a corundum boat, putting the corundum boat into an oven and drying the corundum boat into a non-flowable colloid;
step 3, placing the colloid in air or inert gas atmosphere for sintering, wherein the sintering temperature is 700-900 ℃, and the sintering time is 2-5 hours, so as to obtain a Co/C framework;
step 4, uniformly stirring the Co/C framework, cobalt salt, fluorine salt, urea and a medium solution for 20-50 minutes to obtain a premixed solution;
step 5, placing the premixed solution into a high-pressure reaction kettle for hydrothermal reaction, wherein the reaction temperature is 110-130 ℃, and the reaction time is 8-12 hours, so as to obtain a Co (OH) F/C precursor;
and 6, respectively placing the Co (OH) F/C precursor and the sodium salt at the central position and upstream of the tubular furnace, heating in the air or inert gas atmosphere for phosphorization, wherein the heating rate is 2-8 ℃/min, the phosphorization temperature is 300-400 ℃, the phosphorization time is 2-4 hours, and naturally cooling to room temperature to obtain the three-dimensional large-framework multi-stage structure electrode material.
2. The preparation method of the three-dimensional large-framework multi-level structure electrode material according to claim 1, characterized in that: the mass ratio of PVP, cobalt salt and medium solution substances in the step 1 is 1: (0.5-2): 30.
3. the preparation method of the three-dimensional large-framework multi-level structure electrode material according to claim 2, characterized in that: the relative molecular weight of PVP in the step 1 is 24000 or 58000 or 1300000.
4. The preparation method of the three-dimensional large-framework multi-level structure electrode material according to claim 2, characterized in that: the cobalt salt in step 1 is Co (NO)3)2∙6H2O、(CH2COO)2Co、CoCl2∙6H2O or any combination of more than one of the O.
5. The preparation method of the three-dimensional large-framework multi-level structure electrode material according to claim 1, characterized in that: the medium solution in the steps 1 and 4 is one or more of deionized water, ethanol and ethylene glycol in any mass combination.
6. The preparation method of the three-dimensional large-framework multi-level structure electrode material according to claim 1, characterized in that: the mass ratio of the cobalt salt, the villiaumite, the urea, the Co/C and the medium solution in the step 4 is 20: 2: 10: (1-10): (100-200).
7. The method for preparing the three-dimensional large-framework multi-level structure electrode material according to claim 6, wherein the method comprises the following steps: the villiaumite in the step 4 is NH4F. Of LiF, tetrabutylammonium fluorideOne or more than one of any mass combination.
8. The preparation method of the three-dimensional large-framework multi-level structure electrode material according to claim 1, characterized in that: the mass ratio of the Co (OH) F/C precursor to the sodium salt in the step 6 is 1: (5-10).
9. The method for preparing the three-dimensional large-framework multi-level structure electrode material according to claim 8, wherein the method comprises the following steps: the sodium salt in the step 6 is Na3PO2、Na2HPO2、NaH2PO2、Na3PO4、Na2HPO4、NaH2PO4One or more than one arbitrary mass combination.
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