CN115036502A - Based on ZnCo 2 O 4 Method for preparing sodium ion battery cathode material by hollow carbon nanorings and application - Google Patents

Based on ZnCo 2 O 4 Method for preparing sodium ion battery cathode material by hollow carbon nanorings and application Download PDF

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CN115036502A
CN115036502A CN202210773724.4A CN202210773724A CN115036502A CN 115036502 A CN115036502 A CN 115036502A CN 202210773724 A CN202210773724 A CN 202210773724A CN 115036502 A CN115036502 A CN 115036502A
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艾李申
赵宗彬
刘枳彤
王旭珍
邱介山
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Dalian University of Technology
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Abstract

Based on ZnCo 2 O 4 A method for preparing a sodium ion battery cathode material by using hollow carbon nano rings and application thereof. Firstly, preparing a hollow carbon nano-ring as a carrier and uniformly coating the surface of the hollow carbon nano-ringLoaded ZnCo 2 O 4 ZnCo nanoparticles 2 O 4 Hollow carbon nanoring composite material; secondly, ZnCo is mixed 2 O 4 The hollow carbon nano material, the conductive agent and the binder are mixed and then water is used as a solvent to prepare the negative electrode material of the sodium-ion battery. And finally, loading the negative electrode material on the copper foil to assemble the sodium-ion battery. The cathode material can overcome the problems of large volume expansion and poor intrinsic conductivity of metal oxide in the sodium storage process; the excellent mechanical strength, conductivity and chemical stability of the hollow carbon nano-ring are beneficial to improving the electrochemical cycle stability of the composite material, and in addition, the large specific surface area and the hollow structure are beneficial to the permeation and migration of electrolyte. The unique hollow nano-ring structure can promote the diffusion of sodium ions and prevent ZnCo 2 O 4 Agglomeration of nanoparticles to ZnCo 2 O 4 The hollow carbon nanoring composite material exhibits excellent sodium storage performance.

Description

Based on ZnCo 2 O 4 Method for preparing sodium ion battery cathode material by hollow carbon nanorings and application
Technical Field
The invention belongs to the field of nano material preparation and novel battery energy storage, and relates to a ZnCo-based battery 2 O 4 A method for preparing a sodium ion battery cathode material by using hollow carbon nano rings and application thereof.
Background
With the rapid development of portable electronic devices and electric vehicles, various energy storage devices have been developed. Among them, lithium ion batteries are widely used due to their excellent performance, and play an important role. However, lithium resources are very limited and cannot meet the expanding demand of energy storage field. Meanwhile, the sodium ion battery is expected to replace a lithium ion battery in the future due to rich sodium resources and low cost, and becomes a novel energy storage device capable of being utilized on a large scale. However, the electrochemical performance of the sodium ion battery is obviously different from that of the lithium ion battery. In order to obtain a sodium ion battery with higher energy density and longer cycle life, the key problem to be solved is material innovation; for example, a high-specific-capacity and high-potential cathode material is greatly developed, and development of a high-specific-capacity composite cathode material faces a great challenge.
The transition metal oxide has the characteristics of low cost, environmental friendliness, large theoretical specific capacity and the like, and is a promising sodium ionA battery negative electrode material. Wherein, Co 3 O 4 The electrode material is a classical electrode material due to higher theoretical specific capacity. However, due to large volume change, low sodium ion diffusion kinetics, large toxicity, high cost during charging and discharging, Co has a large specific surface area 3 O 4 The use in sodium ion batteries is severely hampered. Partial substitution of Co with less costly and environmentally friendly substitute elements (e.g., zinc, copper, nickel, magnesium, etc.) 3 O 4 The element Co in the composite material is coupled with two metal species, so that the conductivity is improved, and rich oxidation-reduction reaction is provided for binary transition metal oxide. Introduction of zinc ions enables Co to be incorporated due to its unchanged divalent state 3 O 4 A controllable change takes place. At the same time, ZnCo 2 O 4 The conductive metal ion has complex chemical components, and has a synergistic effect between two different metal ions, thereby showing good conductivity and electrochemical activity.
So far, various ZnCo with different nanostructures 2 O 4 Materials, including nanoparticles, nanowires, nanofibers, porous core-shell structures, and porous hollow spheres, have been widely studied as electrode materials for energy storage. Despite the great advances made, there are conventional ZnCo systems 2 O 4 The problems of large volume changes and particle agglomeration in the material have not yet been effectively overcome. To solve these problems, one effective strategy is to incorporate nano-sized ZnCo 2 O 4 Anchored on a conductive carbon substrate to build a nanocomposite, which will have a good synergistic effect.
Nanocarbon materials (graphene and carbon nanotubes) have been widely used as battery energy storage materials, but the graphene layer stacking and the mutual winding between the carbon nanotubes caused by pi-pi action seriously affect the full play of the electrochemical performance of the nanocarbon materials. The hollow carbon nanoring is used as a unique carbon nanomaterial, can adapt to severe volume expansion due to excellent mechanical strength, and can inhibit ZnCo loaded on the surface of the carbon nanoring 2 O 4 Agglomeration is carried out in the continuous charge-discharge cycle process, and the conductivity of the material is improved. In addition, the hollow carbon nanorings are porous due to the annular wall andthe cavity structure is beneficial to forming a continuous channel and greatly improves the transmission rate of electrolyte ions.
Preparation of ZnCo in general 2 O 4 Composites involve multiple reactions and are therefore often complex and time consuming and laborious to perform. From the practical applicability point of view, a more efficient and environment-friendly preparation method is developed to synthesize ZnCo with a specific structure and excellent electrochemical performance 2 O 4 Composite electrode materials still face significant challenges.
Disclosure of Invention
Aiming at the problems, the invention synthesizes ZnCo in a simple hydrothermal mode 2 O 4 Hollow carbon nanoring composite material. ZnCo 2 O 4 The hollow carbon nano-ring composite material is prepared by mixing ZnCo 2 O 4 The nano particles are uniformly loaded on the surface of the hollow carbon nano ring. ZnCo 2 O 4 The hollow carbon nano-ring composite material is used as the cathode of the sodium ion battery, because ZnCo 2 O 4 Good electrochemical activity and good conductivity of the hollow carbon nanoring, and the composite material has high specific capacity and rate capability. Meanwhile, the hollow carbon nanoring has excellent mechanical strength, so that ZnCo is effectively slowed down 2 O 4 Agglomeration problem during continuous charge and discharge cycles, making it excellent in cycle stability.
In order to achieve the purpose, the invention adopts the technical scheme that:
based on ZnCo 2 O 4 The method for preparing the negative electrode material of the sodium ion battery by the hollow carbon nanorings comprises the following steps:
first, preparation of ZnCo 2 O 4 Hollow carbon nano-ring composite material
(1) Hollow carbon nanorings, Co (Ac) 2 ·4H 2 O、Zn(Ac) 2 ·2H 2 O is dissolved in the mixed solution of ethanol and deionized water, wherein, Co (Ac) 2 ·4H 2 O and Zn (Ac) 2 ·2H 2 Molar ratio of O2: 1, Co (Ac) 2 ·4H 2 The concentration of O is 3.2-9.6g/L, Zn (Ac) 2 ·2H 2 The concentration of O is 1.4-4.2 g/L. Then is addedAdding ammonia water, wherein the volume ratio of the ammonia water to the ethanol water mixed solution is 1: 100. Carrying out oil bath reaction at 70-90 ℃ for 16-24h to obtain reaction liquid.
(2) And (2) transferring the reaction solution prepared in the step (1) into a high-pressure hydrothermal reaction kettle for hydrothermal reaction at the temperature of 120 ℃ and 180 ℃ for 1-5h, washing the solid product obtained by the hydrothermal reaction with ethanol and water respectively, and drying in vacuum.
(3) Calcining the dried product in the step (2) in protective inert atmosphere at the temperature of 250-450 ℃ for 3-10h to obtain ZnCo 2 O 4 Hollow carbon nanoring composite material.
Second, preparing the cathode material of the sodium-ion battery
ZnCo prepared in the first step 2 O 4 Mixing the hollow carbon nano material, the conductive agent and the binder according to the mass ratio of 8:1:1, and preparing the sodium-ion battery negative electrode material by using water as a solvent. Wherein, ZnCo 2 O 4 The hollow carbon nanoring composite material takes a hollow carbon nanoring as a carrier, and ZnCo is uniformly loaded on the surface of the hollow carbon nanoring 2 O 4 The nano-particles can overcome the problems of large volume expansion and poor intrinsic conductivity of metal oxides in the sodium storage process.
Loading the negative electrode material on a copper foil with the loading amount of 1mg/cm 2 . A sodium ion battery is assembled in a glove box by taking 1.0M sodium perchlorate solution (ethylene carbonate/diethyl carbonate as solvent in a volume ratio of 1:1) as electrolyte
Further, in the mixed solution of ethanol and deionized water in the first step (1), the volume ratio of ethanol to deionized water is 24: 1.
Further, the outer diameter of the hollow carbon nanoring in the first step (1) is 100-300nm, the inner diameter is 50-250nm, and the concentration is 1 g/L.
Further, in the first step (2), the vacuum drying temperature is 60-100 ℃, and the drying time is 10-24 h.
Further, in the first step (3), the inert atmosphere comprises nitrogen and argon.
Furthermore, in the second step, the conductive agent is acetylene black, and the binder is carboxymethyl cellulose.
Based on ZnCo 2 O 4 The application of the hollow carbon nanoring in preparing the negative electrode material of the sodium ion battery is characterized in that when the sodium ion battery is loaded, the negative electrode material is loaded on a copper foil, and the loading amount is 1mg/cm 2 . A sodium ion battery was assembled in a glove box using a 1.0M sodium perchlorate solution as an electrolyte.
Further, the solvent of the sodium perchlorate solution comprises ethylene carbonate and diethyl carbonate, and the volume ratio of the ethylene carbonate to the diethyl carbonate is 1: 1.
The experimental result shows that the invention is 1.0A g -1 Has 430mAh g at current density -1 The reversible specific capacity is maintained to be 340mAh g after 2000 cycles of circulation -1 And has excellent cycle stability. Meanwhile, the glass has excellent rate performance of 0.2, 0.5, 1, 2, 5A g -1 The specific discharge capacity of the alloy is 380 mAh g, 350 mAh g, 300 mAh g, 280 mAh g, 240mAh g -1
The invention has the beneficial effects that:
(1) ZnCo prepared by the invention 2 O 4 Hollow carbon nanoring composite material, due to sodium storage active substance ZnCo 2 O 4 The combination of the conductive matrix and the nano carbon material and the unique nano annular structure can provide higher specific capacity when used as a negative electrode material of a sodium ion battery, and show better cycle performance and rate capability in the charging and discharging process.
(2)ZnCo 2 O 4 The conductive metal has rich oxidation-reduction sites, and has a synergistic effect between two different metal ions, thereby showing good conductivity and electrochemical activity.
(3) The hollow carbon nano-ring has excellent mechanical strength, excellent conductivity and chemical stability, which are beneficial to electrochemical performance. Meanwhile, the electrolyte has a larger specific surface area and a hollow structure, so that the electrolyte is more favorable for permeation and transfer. The unique hollow nano-ring structure is beneficial to promoting sodium ion diffusion and preventing nano-particles from agglomerating, so that the charge and discharge performance of the composite material is superior to that of the traditional metal oxide nano-particles.
Drawings
FIG. 1 shows ZnCo obtained in example 1 of the present invention 2 O 4 Scanning electron microscope photos of the hollow carbon nano-ring composite material;
FIG. 2 shows ZnCo obtained in example 1 of the present invention 2 O 4 XRD pattern of the hollow carbon nano-ring composite material;
FIG. 3 shows ZnCo obtained in example 1 of the present invention 2 O 4 The CV curve of the test of the hollow carbon nano-ring composite material as the negative electrode of the sodium-ion battery at the sweep speed of 0.1 mV/s;
FIG. 4 shows ZnCo obtained in example 1 of the present invention 2 O 4 Hollow carbon nanoring composite material, ZnCo 2 O 4 And three materials of the hollow carbon nano ring are respectively used as the electrochemical properties of the cathode of the sodium ion battery: FIG. 4(a) shows a value of 1.0A g -1 Cycling performance at current density; fig. 4(b) is the rate capability at different current densities.
FIG. 5 shows ZnCo obtained in example 1 of the present invention 2 O 4 The negative electrode of sodium ion battery made of hollow carbon nano-ring composite material is 1.0A g -1 Long cycle performance plot at current density.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the following examples.
Example 1:
negative electrode material ZnCo of sodium ion battery 2 O 4 A preparation method of the hollow carbon nanoring comprises the following steps:
(1) weighing 100mg hollow carbon nanoring, 320mgCo (Ac) 2 ·4H 2 O、140mgZn(Ac) 2 ·2H 2 Dissolving O in a mixed solution of 96mL of ethanol and 4mL of deionized water, adding 1mL of ammonia water, and carrying out oil bath at 70 ℃ for 24 h;
(2) transferring the reaction solution prepared in the step (1) into a high-pressure hydrothermal reaction kettle, carrying out hydrothermal reaction for 5 hours at 120 ℃, fully washing the product for 3 times by using ethanol and water respectively, and carrying out vacuum drying for 10 hours at 100 ℃.
(3) Calcining the dried product of the step (2) for 10 hours at 250 ℃ in a nitrogen atmosphere to obtain ZnCo 2 O 4 Hollow carbon nanoring composite material.
ZnCo prepared by the embodiment 2 O 4 The scanning electron microscope of the hollow carbon nano-ring composite material is shown in figure 1, and the scanning electron microscope shows that the prepared ZnCo is prepared 2 O 4 The hollow carbon nanoring composite material is ZnCo 2 O 4 The nano particles are uniformly distributed on the surface of the hollow carbon nano ring. To ZnCo 2 O 4 XRD analysis is carried out on the hollow carbon nano-ring composite material, as shown in figure 2, and the corresponding ZnCo is displayed at the same time 2 O 4 Standard characteristic diffraction peaks.
ZnCo prepared in this example 2 O 4 The negative electrode material is prepared from the hollow carbon nano-ring composite material, acetylene black and carboxymethyl cellulose according to the mass ratio of 8:1:1, a current collector is a copper foil, 1.0M sodium perchlorate solution (ethylene carbonate/diethyl carbonate as a solvent, the volume ratio is 1:1) is used as electrolyte, and a sodium ion half-cell is assembled in a glove box. The cyclic voltammetry test was performed on a Bio-Logic electrochemical workstation with a voltage window of 0.01-3.0V and a sweep rate of 0.1mV/s, with a distinct characteristic redox peak (see FIG. 3). The electrochemical performance of the battery is tested on a Land CT 2001A type battery test system to obtain ZnCo 2 O 4 The hollow carbon nano-ring composite material is 1.0A g -1 Has 430mAh g at current density -1 The reversible specific capacity of the composite material is obviously superior to that of a single-component hollow carbon nano ring and ZnCo 2 O 4 A material. Meanwhile, in the rate capability, ZnCo 2 O 4 The hollow carbon nano-ring composite material is 0.2, 0.5, 1, 2, 5A g -1 The specific discharge capacity of the lithium ion battery is 380 mAh g, 350 mAh g, 300 mAh g, 280 mAh g and 240mAh g respectively -1 Also obviously superior to single-component hollow carbon nanorings and ZnCo 2 O 4 Material (see fig. 4). Hollow carbon nanorings and ZnCo in terms of long cycle performance 2 O 4 After 2000 cycles, the specific capacity of the material is kept at 340mAh g -1 And has excellent cycle stability (as shown in figure 5).
Example 2:
negative electrode material ZnCo of sodium ion battery 2 O 4 Hollow carbon nano-meterA ring preparation method comprising the steps of:
(1) 100mg of hollow carbon nanoring, 640mgCo (Ac) 2 ·4H 2 O、280mgZn(Ac) 2 ·2H 2 Dissolving O in a mixed solution of 96mL of ethanol and 4mL of deionized water, adding 1mL of ammonia water, and carrying out oil bath at 80 ℃ for 20 h;
(2) transferring the reaction solution prepared in the step (1) into a high-pressure hydrothermal reaction kettle, carrying out hydrothermal reaction for 3h at 150 ℃, fully washing the product for 3 times by using ethanol and water respectively, and carrying out vacuum drying for 12h at 80 ℃.
(3) Calcining the dried product of the step (2) for 6 hours at 350 ℃ in an argon atmosphere to obtain ZnCo 2 O 4 Hollow carbon nanoring composite material.
ZnCo prepared in this example 2 O 4 The negative electrode material is prepared from the hollow carbon nano-ring composite material, acetylene black and carboxymethyl cellulose according to the mass ratio of 8:1:1, a current collector is a copper foil, 1.0M sodium perchlorate solution (ethylene carbonate/diethyl carbonate as a solvent, the volume ratio is 1:1) is used as electrolyte, and a sodium ion half-cell is assembled in a glove box. The electrochemical performance of the battery is tested on a Land CT 2001A type battery test system to obtain ZnCo 2 O 4 The hollow carbon nano-ring composite material is 1.0A g -1 Has 400mAh g at current density -1 The reversible specific capacity of the resin is kept at 290mAh g after 1000 cycles -1
Example 3:
negative electrode material ZnCo of sodium ion battery 2 O 4 A preparation method of the hollow carbon nanoring comprises the following steps:
(1) 100mg of hollow carbon nanoring, 960mgCo (Ac) 2 ·4H 2 O、420mgZn(Ac) 2 ·2H 2 Dissolving O in a mixed solution of 96mL of ethanol and 4mL of deionized water, adding 1mL of ammonia water, and carrying out oil bath at 90 ℃ for 16 h;
(2) transferring the reaction solution prepared in the step (1) into a high-pressure hydrothermal reaction kettle, carrying out hydrothermal reaction for 1h at 180 ℃, fully washing the product for 3 times by using ethanol and water respectively, and carrying out vacuum drying for 24h at 60 ℃.
(3) Calcining the dried product of the step (2) for 3 hours at 450 ℃ in an argon atmosphere to obtain ZnCo 2 O 4 Hollow carbon nanoA rice-ring composite material.
ZnCo prepared in this example 2 O 4 The negative electrode material is prepared from the hollow carbon nano-ring composite material, acetylene black and carboxymethyl cellulose according to the mass ratio of 8:1:1, a current collector is a copper foil, 1.0M sodium perchlorate solution (ethylene carbonate/diethyl carbonate as a solvent in a volume ratio of 1:1) is used as electrolyte, and a sodium ion half-cell is assembled in a glove box. The electrochemical performance of the battery is tested on a Land CT 2001A type battery test system to obtain ZnCo 2 O 4 The hollow carbon nano-ring composite material is 1.0A g -1 Has 360mAh g under the current density -1 The reversible specific capacity is kept at 240mAh g after 1000 cycles -1
The above-mentioned embodiments only express the embodiments of the present invention, but not should be understood as the limitation of the scope of the invention patent, it should be noted that, for those skilled in the art, many variations and modifications can be made without departing from the concept of the present invention, and these all fall into the protection scope of the present invention.

Claims (9)

1. Based on ZnCo 2 O 4 The method for preparing the negative electrode material of the sodium ion battery by using the hollow carbon nanorings is characterized by comprising the following steps of:
first, preparation of ZnCo 2 O 4 Hollow carbon nano-ring composite material
(1) Hollow carbon nanorings, Co (Ac) 2 ·4H 2 O、Zn(Ac) 2 ·2H 2 Dissolving O in mixed solution of ethanol and deionized water, wherein, Co (Ac) 2 ·4H 2 O and Zn (Ac) 2 ·2H 2 Molar ratio of O2: 1, Co (Ac) 2 ·4H 2 The concentration of O is 3.2-9.6g/L, Zn (Ac) 2 ·2H 2 The concentration of O is 1.4-4.2 g/L; adding ammonia water, wherein the volume ratio of the ammonia water to the ethanol water mixed solution is 1: 100; carrying out oil bath reaction at 70-90 ℃ for 16-24h to obtain reaction liquid;
(2) transferring the reaction solution prepared in the step (1) into a high-pressure hydrothermal reaction kettle for hydrothermal reaction at the temperature of 120 ℃ and 180 ℃ for 1-5h, washing the solid product obtained by the hydrothermal reaction with ethanol and water respectively, and drying in vacuum;
(3) calcining the dried product in the step (2) in protective inert atmosphere at the temperature of 250-450 ℃ for 3-10h to obtain ZnCo 2 O 4 Hollow carbon nanoring composite material;
second, preparing the cathode material of the sodium-ion battery
ZnCo prepared in the first step 2 O 4 Mixing hollow carbon nano material, conductive agent and binder, and preparing the negative electrode material of the sodium ion battery by using water as a solvent, wherein ZnCo 2 O 4 The hollow carbon nano-ring composite material takes hollow carbon nano-rings as carriers, and ZnCo is uniformly loaded on the surfaces of the hollow carbon nano-rings 2 O 4 A nanoparticle; loading the negative electrode material on a copper foil with the loading amount of 1mg/cm 2 A sodium ion battery was assembled in a glove box using a 1.0M sodium perchlorate solution as an electrolyte.
2. ZnCo-based composition according to claim 1 2 O 4 The method for preparing the sodium ion battery cathode material from the hollow carbon nanorings is characterized in that in the first step (1), the volume ratio of ethanol to deionized water is 24:1 in a mixed solution of ethanol and deionized water.
3. ZnCo-based composition according to claim 1 2 O 4 The method for preparing the sodium ion battery cathode material by the hollow carbon nanoring is characterized in that in the first step (1), the outer diameter of the hollow carbon nanoring is 100-300nm, the inner diameter is 50-250nm, and the concentration is 1 g/L.
4. ZnCo-based composition according to claim 1 2 O 4 The method for preparing the sodium ion battery cathode material by the hollow carbon nanorings is characterized in that in the first step (2), the vacuum drying temperature is 60-100 ℃, and the drying time is 10-24 hours.
5. A method according to claim 1ZnCo 2 O 4 The method for preparing the sodium ion battery cathode material by using the hollow carbon nanorings is characterized in that in the first step (3), inert atmosphere comprises nitrogen and argon.
6. ZnCo-based composition according to claim 1 2 O 4 The method for preparing the sodium ion battery cathode material by the hollow carbon nanorings is characterized in that in the second step, the conductive agent is acetylene black, and the binder is carboxymethyl cellulose.
7. ZnCo-based composition according to claim 1 2 O 4 The method for preparing the negative electrode material of the sodium ion battery by the hollow carbon nanorings is characterized in that in the second step, ZnCo 2 O 4 The mass ratio of the hollow carbon nano material to the conductive agent to the binder is 8:1: 1.
8. ZnCo-based catalyst according to any one of claims 1 to 7 2 O 4 The application of the hollow carbon nanoring in preparing the negative electrode material of the sodium ion battery is characterized in that when the sodium ion battery is loaded, the negative electrode material is loaded on a copper foil, and the loading amount is 1mg/cm 2 (ii) a A sodium ion battery was assembled in a glove box using a 1.0M sodium perchlorate solution as an electrolyte.
9. ZnCo-based composition according to claim 8 2 O 4 The application of the hollow carbon nanoring in preparing the sodium ion battery negative electrode material is characterized in that a solvent of a sodium perchlorate solution comprises ethylene carbonate and diethyl carbonate, and the volume ratio of the ethylene carbonate to the diethyl carbonate is 1: 1.
CN202210773724.4A 2022-07-01 2022-07-01 Based on ZnCo2O4Method for preparing negative electrode material of sodium ion battery by hollow carbon nano ring and application thereof Active CN115036502B (en)

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