CN110323427B - Hollow spherical composite material and preparation method and application thereof - Google Patents
Hollow spherical composite material and preparation method and application thereof Download PDFInfo
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/24—Alkaline accumulators
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- H01M4/00—Electrodes
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a hollow spherical composite material and a preparation method and application thereof, belongs to the technical field of secondary batteries, and particularly relates to the technical field of design and preparation of an alkaline zinc secondary battery cathode material. The composite material contains hollow spherical particles with the diameter of 1-5 mu m. Particularly, the hollow spherical particles with the diameter of 1-5 mu m are composed of short rod-shaped nanoparticles with the diameter of 20-50 nm. The preparation method comprises the steps of preparing a precursor by using at least one of benzenetricarboxylic acid and 2, 5-dihydroxy terephthalic acid as a reagent B through a solvothermal method, and then oxidizing and thermally treating the precursor to finally obtain the target material. The material has uniform granularity and no agglomeration phenomenon, and shows excellent cycle efficiency and cycle stability when being used as the cathode material of the alkaline zinc secondary battery. The invention has simple process, and the obtained product has excellent performance and is convenient for marketization of the zinc secondary battery.
Description
Technical Field
The invention discloses a hollow spherical composite material and a preparation method and application thereof, belongs to the technical field of secondary batteries, and particularly relates to the technical field of design and preparation of an alkaline zinc secondary battery cathode material.
Background
The alkaline zinc secondary battery is considered as one of the competitive energy storage tools due to its characteristics of high specific energy, stable working voltage, safety, environmental protection, etc. However, the zinc cathode is prone to deformation and dendrite growth during charge and discharge cycles, the deformation causes a series of problems (such as uneven current distribution, active material transfer and even falling off), the active material is lost due to the falling of dendrite, and in severe cases, the zinc cathode is pierced through the separator, which causes short circuit between the anode and the cathode and damages the battery.
Research has shown that the volume expansion of the active material caused by the interconversion of ZnO and Zn is one of the important causes of deformation. For this reason, the properties of the material are modified by the characteristics of the active material itself or by the addition of certain additives in order to alleviate the deformation and dendrite growth phenomena of the battery. Such as zinc oxide materials designed for 3D structures, metal oxide additives are introduced into the active material. However, the existing 3D structure material is complex in preparation process, and metal oxide additives are mostly introduced in a physical mixing and hydrolysis precipitation mode, so that the additives are not uniformly distributed and the effect is not obvious. Therefore, a new material preparation method is urgently needed to solve the above problems.
Disclosure of Invention
In the process of preparing the hollow spherical zinc oxide, metal oxide modification is carried out simultaneously, and the obtained hollow spherical zinc oxide material is uniformly modified and has no agglomeration phenomenon. The material shows good cycling stability when used as the cathode material of the alkaline zinc secondary battery, and effectively relieves the problems of deformation and zinc dendrite growth of the zinc cathode in the cycling process.
The invention relates to a hollow spherical composite material, which contains hollow spherical particles with the diameter of 1-5 mu m. Particularly, the hollow spherical particles with the diameter of 1-5 mu m are formed by short rod-shaped nano particles with the diameter of 20-50 nm; in the composite material, the mass percent of zinc oxide is 85-94%, the mass percent of the oxide of metal M1 is 5-10%, and the mass percent of the oxide of metal M2 is 1-5%.
The invention relates to a hollow spherical composite material, wherein metal M1 is at least one of Sn, Bi, In and Ag, and metal M2 is at least one of Sb, Al, Ca, Ni and Ti.
The invention relates to a preparation method of a hollow spherical composite material, which comprises the following steps:
step one
Dissolving a soluble compound of zinc and soluble compounds of metals M1 and M2 in a solvent according to a set ratio to obtain a solution A, and simultaneously dissolving a certain amount of reagent B, polyvinylpyrrolidone (PVP) and Triethylamine (TEA) in the same solvent in the same amount.
The solvent is selected from at least one of N, N-Dimethylformamide (DMF), N-Diethylformamide (DEF) and ethanol, and the reagent B is at least one of benzenetricarboxylic acid and 2, 5-dihydroxyterephthalic acid. The benzene tricarboxylic acid is preferably 1,3, 5-benzene tricarboxylic acid. Preferably, B is 1,3, 5-benzenetricarboxylic acid.
Step two
Pouring the solution B1 obtained in the step one into the solution A, and performing ultrasonic treatment on the obtained mixed solution at the temperature of 20-50 ℃ for 5-30 min; then placing the mixed solution in a closed container, and reacting for 5-12 h at 80-180 ℃; cooling to room temperature, and centrifuging the reaction solution to obtain a solid product; washing the solid with absolute ethyl alcohol for 2-3 times, drying to obtain a precursor material, and calcining the precursor in a muffle furnace at 500-800 ℃ for 2-8 h to obtain the hollow spherical composite material.
The ultrasonic frequency is 25-40 kHz, and the calcining atmosphere is oxygen-containing atmosphere. Preferably, the reaction temperature is 100-130 ℃, and the reaction time is 6-10 h. The calcination temperature is 600-700 ℃, and the calcination time is 4-6 h. The oxygen-containing atmosphere comprises air.
In the process of the invention, reagent B is replaced by benzoic acid and phthalic acid, but the morphology and the structure of the obtained product are changed remarkably (cubic stacked compact structure).
As a preferable scheme, in the preparation method of the hollow spherical composite material, in the first step, the soluble compound of zinc is at least one of zinc acetate, zinc chloride, zinc oxalate, zinc sulfate and zinc nitrate; the soluble compound of the metals M1 and M2 is at least one of nitrate, oxalate, acetate, chloride and sulfate of the metals M1 and M2.
Preferably, in the first step, the soluble compound of zinc, the compounds of metals M1 and M2 and the reagent B are added in a ratio of 1-5: 1, preferably 2-5: 1, of the total mole number of the metal ions to the mole number of the reagent B. The total metal ion concentration is 10-50 mmol/L, preferably 20-30 mmol/L.
According to the preparation method of the hollow spherical composite material, the mass ratio of PVP to the reagent B in the first step is 1-5: 1, preferably 2-4: 1; TEA is added according to the proportion of 0.01-0.05 percent of the total volume of the solution, and preferably 0.02-0.035 percent.
The application of the hollow spherical composite material designed and prepared by the invention comprises the step of using the hollow spherical composite material as a negative electrode material of an alkaline zinc secondary battery.
According to the invention, the reagent B is combined with a special component, micron-scale three-dimensional hollow spherical particles formed by nano-scale particles are prepared by a solvothermal method, and the material combines hollow spherical zinc oxide and metal oxide modification, so that the problems of dendritic crystals and deformation of a zinc cathode in a circulation process are effectively relieved, and the circulation efficiency and the circulation life of a battery are improved.
When the hollow spherical composite material is used as the negative electrode material of the alkaline zinc secondary battery, the specific capacity of 180 cycles of circulation is kept above 600mAh g < -1 > and the average coulombic efficiency is kept above 91 percent in the 1C state.
After optimization, when the hollow spherical composite material is used as a negative electrode material of an alkaline zinc secondary battery, the specific capacity of 180 cycles of circulation is kept above 620mAh g-1 under the state of 1C, and the average coulombic efficiency is kept above 94%.
Compared with the prior art, the invention has the following technical advantages:
1) the metal oxide composite material has a specific three-dimensional space structure (hollow sphere), so that the metal oxide composite material has a buffering effect on growth of dendritic crystals, is favorable for full contact of electrolyte and active substances, and comprehensively improves the electrochemical performance of a negative electrode.
2) The invention adopts a solvent method, and metal oxide modification is carried out while zinc oxide is prepared, so that the uniformity of metal oxide modification is ensured. Meanwhile, the special reagent B is selected, so that the structure of the obtained product is ensured to be a hollow spherical structure.
3) The invention has simple process and convenient operation, and is beneficial to industrial production.
Drawings
FIG. 1 is a scanning electron micrograph of the material prepared in example 1;
FIG. 2 is a high-power scanning electron micrograph of the material prepared in example 1.
As can be seen from figure 1, the prepared material is spherical particles, the interior of the prepared material is hollow, and the particles and the particle size are uniform; FIG. 2 is an enlarged view of FIG. 1, and it can be seen from FIG. 2 that the spherical particles have a particle size of 1 μm, and further, the hollow structure is composed of rod-shaped nanoparticles.
Detailed Description
The following examples are carried out under the conditions described in the present invention and are intended to further illustrate the present invention without limiting the scope of the invention.
Example 1:
1) 0.75g of zinc nitrate hexahydrate, 0.05g of bismuth nitrate pentahydrate and 0.015g of aluminum chloride were weighed out and dissolved in 50ml of DMF, and 0.24g of 1,3, 5-trimesic acid, 1g of PVP and 40. mu.l of TEA were dissolved in another 50ml of DMF.
2) Slowly pouring the latter solution in the step one into the former solution, and performing ultrasonic treatment at 30 ℃ for 15 min; the ultrasonic frequency is 30kHz, the obtained mixed solution is transferred into a polytetrafluoroethylene inner container provided with a steel shell, and the reaction is carried out for 8 hours at 120 ℃; cooling to room temperature, centrifuging to separate out product, washing the product with anhydrous ethanol for 3 times, and vacuum drying at 100 deg.C for 12h to obtain yellow powdery precursor material;
3) and heating the obtained precursor to 650 ℃ at a speed of 4 ℃/min in an air atmosphere, and preserving the temperature for 5 hours to obtain a hollow spherical metal oxide composite material with the particle size of 1-5 mu m, wherein the primary particle size of the composite material is 20-50 nm.
4) The composite material and electrode additives (conductive carbon, sodium carboxymethylcellulose and polytetrafluoroethylene) are uniformly mixed to prepare a rubber-like mixture, the rubber-like mixture is coated on a copper mesh current collector according to the area of 1cm multiplied by 1cm, and is finally pressed into a pole piece of 0.3mm by a tablet press, a sintered nickel piece is used as a counter electrode, a 6mol/LKOH saturated zinc oxide solution is used as an electrolyte for cycle test, the specific capacity is 621.7mAh g < -1 > after 180 cycles of charge and discharge, and the average coulombic efficiency is kept at 94.3%.
Example 2:
1) 0.75g of zinc nitrate hexahydrate, 0.035g of stannous chloride dihydrate and 0.015g of aluminum chloride were weighed out and dissolved in 50ml of DMF, and 0.24g of trimesic acid, 1g of PVP and 40. mu.l of TEA were dissolved in another 50ml of DMF.
2) Slowly pouring the latter solution in the step one into the former solution, and carrying out ultrasonic treatment for 15 min; the ultrasonic frequency is 30KHz, the obtained mixed solution is transferred into a polytetrafluoroethylene inner container provided with a steel shell, and the reaction is carried out for 8 hours at 120 ℃; cooling to room temperature, centrifuging to separate product, washing with ethanol for 3 times, and vacuum drying at 100 deg.C for 12 hr;
3) and heating the obtained precursor to 650 ℃ at a speed of 4 ℃/min under an air atmosphere, and preserving the temperature for 5 hours to obtain the hollow spherical metal oxide nano composite material with the particle size of 1-5 mu m, wherein the primary particle size of the hollow spherical metal oxide nano composite material is 20-50 nm.
4) The nano composite material and electrode additives (conductive carbon, sodium carboxymethylcellulose and polytetrafluoroethylene) are uniformly mixed to prepare a rubber-like mixture, the rubber-like mixture is coated on a copper mesh current collector according to the area of 1cm multiplied by 1cm, finally, a tablet press is used for pressing a pole piece with the thickness of 0.3mm, a sintered nickel piece is used as a counter electrode, a 6mol/LKOH saturated zinc oxide solution is used as an electrolyte for cycle test, through 150 cycles of charge and discharge, the specific capacity is 604.2mAh g < -1 >, and the average coulombic efficiency is kept at 91.7%.
Example 3
The other conditions were the same as in example 1 except that: the stannous chloride dihydrate added in the step 1 is changed into 0.02g of indium chloride.
The obtained product is subjected to cycle test, and after 180 cycles of charge and discharge, the specific capacity is 614.2mAh g-1, and the average coulombic efficiency is 93.2%.
Comparative example 1:
unlike example 1, comparative example 1 did not add bismuth nitrate pentahydrate in step 1, the other steps were identical. Obtaining the hollow spherical metal oxide nano composite material with the particle size of 1-5 mu m, wherein the primary particle size of the hollow spherical metal oxide nano composite material is 20-50 nm.
The obtained material and electrode additives (conductive carbon, sodium carboxymethylcellulose and polytetrafluoroethylene) are uniformly mixed to prepare a rubber-like mixture, the rubber-like mixture is coated on a copper mesh current collector according to the area of 1cm multiplied by 1cm, and is finally pressed into a pole piece of 0.3mm by a tablet press, a sintered nickel piece is used as a counter electrode, a 6mol/LKOH saturated zinc oxide solution is used as an electrolyte for cycle test, the specific capacity is attenuated to 467.2mAh g < -1 > through 112 cycles of charge and discharge, and the average coulombic efficiency is 70.9%.
Comparative example 2:
unlike example 1, comparative example 2 did not add aluminum chloride in step 1, and the other steps were identical. Obtaining the hollow spherical metal oxide nano composite material with the diameter of 1-5 mu m. The primary particle size is 20-50 nm.
The obtained material and electrode additives (conductive carbon, sodium carboxymethylcellulose and polytetrafluoroethylene) are uniformly mixed to prepare a rubber-like mixture, the rubber-like mixture is coated on a copper mesh current collector according to the area of 1cm multiplied by 1cm, and is finally pressed into a pole piece of 0.3mm by a tablet press, a sintered nickel piece is used as a counter electrode, a 6mol/LKOH saturated zinc oxide solution is used as an electrolyte for cycle test, and after 125 cycles of charge and discharge, the specific capacity is 486.3mAh g < -1 >, and the average coulombic efficiency is 73.8%.
Comparative example 3:
unlike example 2, comparative example 2 reduced the amount of stannous chloride dihydrate added to 0.015g in step 1, consistent with the other steps. Obtaining the hollow spherical metal oxide nano composite material with the particle size of 1-5 mu m, wherein the primary particle size of the hollow spherical metal oxide nano composite material is 20-50 nm.
The obtained material and electrode additives (conductive carbon, sodium carboxymethylcellulose and polytetrafluoroethylene) are uniformly mixed to prepare a rubber-like mixture, the rubber-like mixture is coated on a copper mesh current collector according to the area of 1cm multiplied by 1cm, and is finally pressed into a pole piece of 0.3mm by a tablet press, a sintered nickel piece is used as a counter electrode, a 6mol/LKOH saturated zinc oxide solution is used as an electrolyte for cycle test, and after 95 cycles of charge and discharge, the specific capacity is 407.8mAh g < -1 >, and the average coulombic efficiency is 61.9%.
Comparative example 4(PVP amount)
The other conditions were the same as in example 1, except that: the amount of PVP added in step 1 was 0.2 g.
The obtained product is subjected to cycle test, and after 130 cycles of charge and discharge, the specific capacity is 574.2mAh g < -1 >, and the average coulombic efficiency is 87.2%.
COMPARATIVE EXAMPLE 5(TEA amount)
The other conditions were the same as in example 1 except that: no TEA was added in step 1.
The obtained product is subjected to cycle test, and after 120 cycles of charge and discharge, the specific capacity is 487.5mAh g < -1 >, and the average coulombic efficiency is 74.0%.
Comparative example 6
The other conditions were the same as in example 1 except that: the amount of TEA added in step 1 was 60. mu.l.
The obtained product is subjected to cycle test, and after 134 cycles of charge and discharge, the specific capacity is 589.5mAh g-1, and the average coulombic efficiency is 89.5%.
Claims (10)
1. A hollow spherical composite material is characterized in that: the composite material contains hollow spherical particles with the diameter of 1-5 mu m; the hollow spherical particles with the diameter of 1-5 mu m are composed of short rod-shaped nano particles with the diameter of 20-50 nm; in the composite material, the mass percentage of zinc oxide is 85-94%, the mass percentage of metal M1 oxide is 5-10%, and the mass percentage of metal M2 oxide is 1-5%;
the metal M1 is at least one selected from Sn, Bi and In, and the metal M2 is Al.
2. A method of making the hollow sphere composite of claim 1, wherein; the method comprises the following steps:
step one
Dissolving a soluble compound of zinc and soluble compounds of metals M1 and M2 in a solvent according to a set proportion to obtain a solution A, and simultaneously dissolving a certain amount of a reagent B, polyvinylpyrrolidone PVP and triethylamine TEA in the same solvent with the same amount to obtain a solution B1;
the solvent is selected from at least one of N, N-dimethylformamide DMF, N-diethylformamide DEF and ethanol, and the reagent B is at least one of benzenetricarboxylic acid and 2, 5-dihydroxyterephthalic acid;
step two
Pouring the solution B1 obtained in the step one into the solution A, and performing ultrasonic treatment on the obtained mixed solution at the temperature of 20-50 ℃ for 5-30 min; then placing the mixed solution in a closed container, and reacting for 5-12 h at 80-180 ℃; cooling to room temperature, and centrifuging the reaction solution to obtain a solid product; washing the solid with absolute ethyl alcohol for 2-3 times, drying to obtain a precursor material, and calcining the precursor in a muffle furnace at 500-800 ℃ for 2-8 h to obtain the hollow spherical composite material.
3. The method of claim 2, wherein: the ultrasonic frequency is 25-40 kHz, and the calcining atmosphere is oxygen-containing atmosphere.
4. The method of claim 2, wherein: the reaction temperature is 100-130 ℃, and the reaction time is 6-10 h; the calcining temperature is 600-700 ℃, and the time is 4-6 h.
5. The method of claim 2, wherein: in the first step, the soluble compound of zinc is at least one of zinc acetate, zinc chloride, zinc oxalate, zinc sulfate and zinc nitrate; the soluble compound of the metal M1 and M2 is at least one of nitrate, oxalate, acetate, chloride and sulfate of the metal M1 and M2.
6. The method of claim 2, wherein: in the first step, a soluble compound of zinc, a compound of metals M1 and M2 and a reagent B are added according to the proportion that the ratio of the total mole number of metal ions to the mole number of the reagent B is 1-5: 1, and the total concentration of the metal ions is 10-50 mmol/L.
7. The method of claim 2, wherein: the mass ratio of the PVP to the reagent B in the first step is 1-5: 1; and adding TEA according to the proportion of 0.01-0.05 percent of the total volume of the solution.
8. Use of a hollow sphere composite material according to claim 1, wherein: the application comprises the step of using the hollow spherical composite material as a negative electrode material of an alkaline zinc secondary battery.
9. Use of a hollow sphere composite material according to claim 8, wherein: when the hollow spherical composite material is used as the cathode material of the alkaline zinc secondary battery, the specific capacity of 100-180 circles of circulating zinc is kept at 600mAh g under the 1C state-1Above, the average coulombic efficiency remained above 91%.
10. Use of a hollow sphere composite material according to claim 8, wherein: when the hollow spherical composite material is used as a negative electrode material of an alkaline zinc secondary battery, the specific capacity of 180 circles of circulation is kept at 620mAh g under the state of 1C-1Above, the average coulombic efficiency remained above 94%.
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| KR102601605B1 (en) * | 2017-12-27 | 2023-11-14 | 삼성전자주식회사 | Anode, Lithium battery comprising anode, and Preparation method of anode |
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