CN115036502B - Based on ZnCo2O4Method for preparing negative electrode material of sodium ion battery by hollow carbon nano ring and application thereof - Google Patents
Based on ZnCo2O4Method for preparing negative electrode material of sodium ion battery by hollow carbon nano ring and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 84
- 239000002063 nanoring Substances 0.000 title claims abstract description 79
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 45
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 25
- 239000002131 composite material Substances 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000003792 electrolyte Substances 0.000 claims abstract description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002086 nanomaterial Substances 0.000 claims abstract description 9
- 239000002105 nanoparticle Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000011889 copper foil Substances 0.000 claims abstract description 8
- 239000011230 binding agent Substances 0.000 claims abstract description 6
- 239000006258 conductive agent Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 9
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 9
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 5
- 239000006230 acetylene black Substances 0.000 claims description 5
- 239000010405 anode material Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 5
- 238000005054 agglomeration Methods 0.000 abstract description 5
- 230000002776 aggregation Effects 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 229910052708 sodium Inorganic materials 0.000 abstract description 5
- 239000011734 sodium Substances 0.000 abstract description 5
- 239000010406 cathode material Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 4
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 3
- 150000004706 metal oxides Chemical class 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 230000005012 migration Effects 0.000 abstract 1
- 238000013508 migration Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 8
- 238000004146 energy storage Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- B82—NANOTECHNOLOGY
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- H01M4/139—Processes of manufacture
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Abstract
A method for preparing a negative electrode material of a sodium ion battery based on ZnCo 2O4/hollow carbon nanorings and application thereof. Firstly, preparing a ZnCo 2O4/hollow carbon nano ring composite material which takes a hollow carbon nano ring as a carrier and uniformly loads ZnCo 2O4 nano particles on the surface of the hollow carbon nano ring; secondly, znCo 2O4/hollow carbon nanomaterial, a conductive agent and a binder are mixed and water is used as a solvent to prepare the sodium ion battery cathode material. Finally, the negative electrode material is loaded on the copper foil to assemble the sodium ion battery. The negative electrode material can overcome the problems of larger volume expansion and poorer 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 the improvement of 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 the agglomeration of ZnCo 2O4 nano-particles, so that the ZnCo 2O4/hollow carbon nano-ring composite material shows excellent sodium storage performance.
Description
Technical Field
The invention belongs to the field of nano material preparation and novel battery energy storage, and relates to a method for preparing a sodium ion battery anode material based on ZnCo 2O4/hollow carbon nanorings 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 have been widely used because of their excellent performance, and play an important role. However, lithium resources are very limited and cannot meet the expanding energy storage field requirements. Meanwhile, the sodium ion battery is considered to be expected to replace a lithium ion battery in the future due to abundant sodium resources and low cost, and becomes a novel energy storage device capable of being utilized on a large scale. However, the current electrochemical performance of sodium ion batteries is significantly different from that of lithium ion batteries. 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, high specific capacity, high potential positive electrode materials have been greatly developed, and development of high specific capacity composite negative electrode materials faces a great challenge.
The transition metal oxide has the characteristics of low cost, environmental protection, large theoretical specific capacity and the like, and is a promising sodium ion battery anode material. Among them, co 3O4 is a classical electrode material because of its higher theoretical specific capacity. However, the application of Co 3O4 in sodium ion batteries is severely hampered by large volume changes during charge and discharge, low sodium ion diffusion kinetics, high toxicity, and high cost. Partial substitution of elemental Co in Co 3O4 with lower cost and environmentally friendly alternative elements (e.g., zinc, copper, nickel, magnesium, etc.), coupling of the two metal species not only improves conductivity, but also provides a rich redox reaction for the binary transition metal oxide. The introduction of zinc ions enables controlled variation of Co 3O4 due to its unchanged divalent state. Meanwhile, znCo 2O4 has complex chemical components, and a synergistic effect exists between two different metal ions, so that good conductivity and electrochemical activity are shown.
Various ZnCo 2O4 materials with different nanostructures, including nanoparticles, nanowires, nanofibers, porous core-shell structures and porous hollow spheres, have been widely studied as electrode materials for energy storage to date. Despite the great progress made, the problems of large volume changes and particle agglomeration in these conventional ZnCo 2O4 materials have not been effectively overcome. To solve these problems, an effective strategy is to anchor nano-scale ZnCo 2O4 on a conductive carbon substrate to build up a nanocomposite, which will have a better synergistic effect.
Carbon nanomaterial (graphene, carbon nanotube) has been widely used as battery energy storage material, but the layer-by-layer stacking of graphene and the mutual entanglement between carbon nanotubes caused by pi-pi effect seriously affect the full play of electrochemical properties of the carbon nanomaterial. The hollow carbon nano ring is used as a unique carbon nano material, can adapt to serious volume expansion due to the excellent mechanical strength, can inhibit the agglomeration of ZnCo 2O4 loaded on the surface of the hollow carbon nano ring in the continuous charge-discharge cycle process, and simultaneously improves the conductivity of the material. In addition, the hollow carbon nano ring is favorable for forming a continuous channel due to the porous and hollow structure of the annular wall, so that the transmission rate of electrolyte ions is greatly improved.
The preparation of ZnCo 2O4 composite materials generally involves multiple steps of reactions, and thus the procedures are generally complex, time-consuming and labor-consuming. From the practical applicability point of view, developing a more efficient and environment-friendly preparation method, synthesizing a ZnCo 2O4 composite electrode material with a specific structure and excellent electrochemical performance still faces a great challenge.
Disclosure of Invention
Aiming at the problems, the invention synthesizes the ZnCo 2O4/hollow carbon nano ring composite material by a simple hydrothermal mode. The ZnCo 2O4/hollow carbon nano ring composite material is prepared by uniformly loading ZnCo 2O4 nano particles on the surface of a hollow carbon nano ring. The ZnCo 2O4/hollow carbon nanoring composite material is used as a negative electrode of a sodium ion battery, and the composite material has high specific capacity and rate capability due to good electrochemical activity of ZnCo 2O4 and good conductivity of the hollow carbon nanoring. Meanwhile, as the hollow carbon nano ring has excellent mechanical strength, the agglomeration problem of ZnCo 2O4 in continuous charge and discharge cycles is effectively alleviated, so that the hollow carbon nano ring has excellent cycle stability.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method for preparing a negative electrode material of a sodium ion battery based on ZnCo 2O4/hollow carbon nanorings comprises the following steps:
First, preparing ZnCo 2O4/hollow carbon nano ring composite material
(1) Dissolving hollow carbon nano-rings and Co (Ac) 2·4H2O、Zn(Ac)2·2H2 O in a mixed solution of ethanol and deionized water, wherein the molar ratio of Co (Ac) 2·4H2 O to Zn (Ac) 2·2H2 O is 2:1, the concentration of Co (Ac) 2·4H2 O is 3.2-9.6g/L, and the concentration of Zn (Ac) 2·2H2 O is 1.4-4.2g/L. And adding ammonia water, wherein the volume ratio of the ammonia water to the ethanol water mixed solution is 1:100. Oil bath reaction is carried out for 16-24h at 70-90 ℃ to obtain reaction liquid.
(2) Transferring the reaction solution prepared in the step (1) into a high-pressure hydrothermal reaction kettle for hydrothermal reaction, wherein the hydrothermal reaction temperature is 120-180 ℃, the reaction time is 1-5h, and 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 the ZnCo 2O4/hollow carbon nano ring composite material.
Second, preparing the negative electrode material of the sodium ion battery
And mixing the ZnCo 2O4/hollow carbon nanomaterial, the conductive agent and the binder prepared in the first step according to the mass ratio of 8:1:1, and preparing the sodium ion battery anode material by using water as a solvent. The ZnCo 2O4/hollow carbon nano ring composite material takes a hollow carbon nano ring as a carrier, uniformly loads ZnCo 2O4 nano particles on the surface of the hollow carbon nano ring composite material, and can overcome the problems of larger volume expansion and poorer intrinsic conductivity of metal oxide in the sodium storage process.
The negative electrode material was supported on a copper foil at a loading of 1mg/cm 2. Sodium ion battery is assembled in a glove box by taking 1.0M sodium perchlorate solution (solvent ethylene carbonate/diethyl carbonate, volume ratio 1:1) as electrolyte
Further, in the first step (1), the volume ratio of the ethanol to deionized water in the mixed solution of the ethanol and the deionized water is 24:1.
Further, the outer diameter of the hollow carbon nano ring in the first step (1) is 100-300nm, the inner diameter is 50-250nm, and the concentration is 1g/L.
Further, in the first step (2), the vacuum drying temperature is 60-100 ℃ and the drying time is 10-24 hours.
Further, in the first step (3), the inert atmosphere includes nitrogen and argon.
Further, in the second step, the conductive agent is acetylene black, and the binder is carboxymethyl cellulose.
The application of preparing the negative electrode material of the sodium ion battery based on ZnCo 2O4/hollow carbon nanoring is that the negative electrode material is loaded on a copper foil when the sodium ion battery is loaded, and the loading capacity is 1mg/cm 2. The sodium ion battery was assembled in a glove box using 1.0M sodium perchlorate solution as the 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.
Experimental results show that the invention has reversible specific capacity of 430mAh g -1 under the current density of 1.0A g -1, the specific capacity is kept at 340mAh g -1 after 2000 circles of circulation, and the invention has excellent circulation stability. Meanwhile, the lithium ion battery has excellent rate capability, and the specific discharge capacities of the lithium ion battery are 380, 350, 300, 280 and 240mAh g -1 respectively under the current densities of 0.2, 0.5, 1,2 and 5A g -1.
The beneficial effects of the invention are as follows:
(1) The ZnCo 2O4/hollow carbon nano ring composite material prepared by the invention can provide higher specific capacity as a negative electrode material of a sodium ion battery due to the combination of the sodium storage active substance ZnCo 2O4 and the conductive matrix nano carbon material and the unique nano ring structure, and has better cycle performance and multiplying power performance in the charge and discharge process.
(2) ZnCo 2O4 has rich redox sites, and the synergistic effect exists between two different metal ions, so that good conductivity and electrochemical activity are shown.
(3) The hollow carbon nano ring has excellent mechanical strength, excellent conductivity and chemical stability, and is favorable for electrochemical performance. Meanwhile, the large specific surface area and the hollow structure are more beneficial to the permeation and transfer of electrolyte. The unique hollow nano-ring structure is beneficial to promoting the diffusion of sodium ions and preventing the agglomeration of nano-particles, so that the charge-discharge performance of the composite material is superior to that of the traditional metal oxide nano-particles.
Drawings
FIG. 1 is a scanning electron microscope photograph of ZnCo 2O4/hollow carbon nanoring composite material obtained in example 1 of the present invention;
FIG. 2 is an XRD pattern of ZnCo 2O4/hollow carbon nanoring composite material obtained in example 1 of the present invention;
FIG. 3 is a CV curve of the ZnCo 2O4/hollow carbon nanoring composite material obtained in example 1 of the present invention tested at a sweep rate of 0.1mV/s for a negative electrode of a sodium ion battery;
Fig. 4 shows electrochemical properties of ZnCo 2O4/hollow carbon nanoring composite material, znCo 2O4, and hollow carbon nanoring obtained in example 1 of the present invention as negative electrode of sodium ion battery, respectively: FIG. 4 (a) is a cycle performance at a current density of 1.0A g -1; fig. 4 (b) shows the rate performance at different current densities.
Fig. 5 is a long-cycle performance graph of ZnCo 2O4/hollow carbon nanoring composite obtained in example 1 of the present invention as a negative electrode of sodium ion battery at a current density of 1.0A g -1.
Detailed Description
The invention is further illustrated in the following in connection with the specific embodiments, but the invention is not limited to the following examples.
Example 1:
A preparation method of a sodium ion battery cathode material ZnCo 2O4/hollow carbon nano ring comprises the following steps:
(1) Weighing a mixed solution of 100mg of hollow carbon nano ring and 320mgCo (Ac) 2·4H2O、140mgZn(Ac)2·2H2 O dissolved in 96mL of ethanol and 4mL of deionized water, adding 1mL of ammonia water, and carrying out oil bath at 70 ℃ for 24 hours;
(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 ℃, washing the product with ethanol and water for 3 times, and carrying out vacuum drying for 10 hours at 100 ℃.
(3) And (3) calcining the dried product in the step (2) for 10 hours at the temperature of 250 ℃ in a nitrogen atmosphere to obtain the ZnCo 2O4/hollow carbon nano ring composite material.
The scanning electron microscope of the ZnCo 2O4/hollow carbon nanoring composite material prepared by the embodiment is shown in figure 1, and the scanning electron microscope shows that the prepared ZnCo 2O4/hollow carbon nanoring composite material is that ZnCo 2O4 nano particles are uniformly distributed on the surface of the hollow carbon nanoring. XRD analysis was performed on the ZnCo 2O4/hollow carbon nanoring composite, as shown in FIG. 2, while showing the corresponding standard characteristic diffraction peaks of ZnCo 2O4.
The ZnCo 2O4/hollow carbon nano ring composite material prepared in the embodiment, acetylene black and carboxymethyl cellulose are prepared into a negative electrode material according to the mass ratio of 8:1:1, a current collector is copper foil, 1.0M sodium perchlorate solution (solvent ethylene carbonate/diethyl carbonate, volume ratio is 1:1) is taken as electrolyte, and a sodium ion half cell is assembled in a glove box. Cyclic voltammogram tests were 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 distinct redox characteristic peaks (see FIG. 3). The electrochemical performance of the ZnCo 2O4/hollow carbon nanoring composite material is tested on a Land CT 2001A battery test system, and the reversible specific capacity of 430mAh g -1 is measured under the current density of 1.0A g -1, which is obviously superior to that of single-component hollow carbon nanoring and ZnCo 2O4 materials. Meanwhile, in the aspect of rate capability, the discharge specific capacities of the ZnCo 2O4/hollow carbon nano ring composite material are 380, 350, 300, 280 and 240mAh g -1 respectively under the current densities of 0.2, 0.5, 1, 2 and 5A g -1, and the discharge specific capacities are also obviously superior to those of single-component hollow carbon nano rings and ZnCo 2O4 materials (as shown in figure 4). In terms of long cycle performance, the specific capacity of the hollow carbon nano-ring and ZnCo 2O4 material after 2000 cycles is kept at 340mAh g -1, and the hollow carbon nano-ring and ZnCo 2O4 material has excellent cycle stability (as shown in figure 5).
Example 2:
A preparation method of a sodium ion battery cathode material ZnCo 2O4/hollow carbon nano ring comprises the following steps:
(1) Weighing a mixed solution of 100mg of hollow carbon nano ring and 640mgCo (Ac) 2·4H2O、280mgZn(Ac)2·2H2 O dissolved in 96mL of ethanol and 4mL of deionized water, adding 1mL of ammonia water, and carrying out oil bath at 80 ℃ for 20h;
(2) Transferring the reaction solution prepared in the step (1) into a high-pressure hydrothermal reaction kettle, carrying out hydrothermal reaction for 3 hours at 150 ℃, washing the product with ethanol and water for 3 times, and carrying out vacuum drying at 80 ℃ for 12 hours.
(3) Calcining the dried product of the step (2) for 6 hours at 350 ℃ in an argon atmosphere to obtain the ZnCo 2O4/hollow carbon nano ring composite material.
The ZnCo 2O4/hollow carbon nano ring composite material prepared in the embodiment, acetylene black and carboxymethyl cellulose are prepared into a negative electrode material according to the mass ratio of 8:1:1, a current collector is copper foil, 1.0M sodium perchlorate solution (solvent ethylene carbonate/diethyl carbonate, volume ratio is 1:1) is taken as electrolyte, and a sodium ion half cell is assembled in a glove box. Electrochemical performance of the ZnCo 2O4/hollow carbon nanoring composite material was tested on a Land CT 2001A battery test system, and the reversible specific capacity of 400mAh g -1 was measured at a current density of 1.0A g -1, and the specific capacity was maintained at 290mAh g -1 after 1000 cycles.
Example 3:
A preparation method of a sodium ion battery cathode material ZnCo 2O4/hollow carbon nano ring comprises the following steps:
(1) Weighing a mixed solution of 100mg of hollow carbon nano ring and 960mgCo (Ac) 2·4H2O、420mgZn(Ac)2·2H2 O dissolved in 96mL of ethanol and 4mL of deionized water, adding 1mL of ammonia water, and carrying out oil bath at 90 ℃ for 16h;
(2) Transferring the reaction solution prepared in the step (1) into a high-pressure hydrothermal reaction kettle, performing hydrothermal reaction at 180 ℃ for 1h, washing the product with ethanol and water for 3 times, and performing vacuum drying at 60 ℃ for 24h.
(3) Calcining the dried product of the step (2) for 3 hours at 450 ℃ in an argon atmosphere to obtain the ZnCo 2O4/hollow carbon nano ring composite material.
The ZnCo 2O4/hollow carbon nano ring composite material prepared in the embodiment, acetylene black and carboxymethyl cellulose are prepared into a negative electrode material according to the mass ratio of 8:1:1, a current collector is copper foil, 1.0M sodium perchlorate solution (solvent ethylene carbonate/diethyl carbonate, volume ratio is 1:1) is taken as electrolyte, and a sodium ion half cell is assembled in a glove box. Electrochemical performance of the ZnCo 2O4/hollow carbon nanoring composite material was tested on a Land CT 2001A battery test system, and the reversible specific capacity of 360mAh g -1 was measured at a current density of 1.0A g -1, and the specific capacity was maintained at 240mAh g -1 after 1000 cycles.
The examples described above represent only embodiments of the invention and are not to be understood as limiting the scope of the patent of the invention, it being pointed out that several variants and modifications may be made by those skilled in the art without departing from the concept of the invention, which fall within the scope of protection of the invention.
Claims (8)
1. The method for preparing the negative electrode material of the sodium ion battery based on the ZnCo 2O4/hollow carbon nano ring is characterized by comprising the following steps of:
First, preparing ZnCo 2O4/hollow carbon nano ring composite material
(1) Dissolving hollow carbon nano-rings and Co (Ac) 2·4H2O、Zn(Ac)2·2H2 O in a mixed solution of ethanol and deionized water, wherein the molar ratio of Co (Ac) 2·4H2 O to Zn (Ac) 2·2H2 O is 2:1, the concentration of Co (Ac) 2·4H2 O is 3.2-9.6g/L, and the concentration of Zn (Ac) 2·2H2 O is 1.4-4.2g/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 for 16-24h at 70-90 ℃ to obtain a reaction liquid; in the mixed solution of the ethanol and the deionized water, the volume ratio of the ethanol to the deionized water is 24:1; the outer diameter of the hollow carbon nano ring is 100-300nm, and the inner diameter is 50-250nm;
(2) Transferring the reaction solution prepared in the step (1) into a high-pressure hydrothermal reaction kettle for hydrothermal reaction, wherein the hydrothermal reaction temperature is 120-180 ℃, the reaction time is 1-5h, and washing and vacuum drying solid products obtained by the hydrothermal reaction with ethanol and water respectively;
(3) Calcining the dried product in the step (2) in a protective inert atmosphere at the temperature of 250-450 ℃ for 3-10 hours to obtain a ZnCo 2O4/hollow carbon nano ring composite material;
Second, preparing the negative electrode material of the sodium ion battery
Mixing the ZnCo 2O4/hollow carbon nano material, a conductive agent and a binder which are prepared in the first step, and adopting water as a solvent to prepare a negative electrode material of the sodium ion battery, wherein the ZnCo 2O4/hollow carbon nano ring composite material takes a hollow carbon nano ring as a carrier, and uniformly loads ZnCo 2O4 nano particles on the surface of the hollow carbon nano ring composite material; the negative electrode material is loaded on a copper foil with the loading capacity of 1mg/cm 2, a 1.0M sodium perchlorate solution is taken as an electrolyte, and the sodium ion battery is assembled in a glove box.
2. The method for preparing the negative electrode material of the sodium ion battery based on the ZnCo 2O4/hollow carbon nanoring, which is disclosed in claim 1, is characterized in that the concentration of the hollow carbon nanoring in the mixed solution of ethanol and deionized water in the first step (1) is 1g/L.
3. The method for preparing the negative electrode material of the sodium ion battery based on the ZnCo 2O4/hollow carbon nanoring according to claim 1, wherein in the first step (2), the vacuum drying temperature is 60-100 ℃ and the drying time is 10-24h.
4. The method for preparing the negative electrode material of the sodium ion battery based on the ZnCo 2O4/hollow carbon nanoring according to claim 1, wherein in the first step (3), the inert atmosphere comprises nitrogen and argon.
5. The method for preparing the negative electrode material of the sodium ion battery based on the ZnCo 2O4/hollow carbon nanoring according to claim 1, wherein in the second step, the conductive agent is acetylene black, and the binder is carboxymethyl cellulose.
6. The method for preparing the negative electrode material of the sodium ion battery based on the ZnCo 2O4/hollow carbon nanoring according to claim 1, wherein in the second step, the mass ratio of the ZnCo 2O4/hollow carbon nanomaterial, the conductive agent and the binder is 8:1:1.
7. The use of ZnCo 2O4/hollow carbon nanoring-based anode material for sodium ion battery according to any one of claims 1-6, wherein when loading sodium ion battery, the anode material is loaded on copper foil with a loading amount of 1mg/cm 2; the sodium ion battery was assembled in a glove box using 1.0M sodium perchlorate solution as the electrolyte.
8. The application of preparing a negative electrode material of a sodium ion battery based on ZnCo 2O4/hollow carbon nano rings according to claim 7, wherein 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.
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| KR20160124964A (en) * | 2015-04-20 | 2016-10-31 | 인하대학교 산학협력단 | Ultra-thin hollow carbon nanospheres for sodium ion storing and manufacturing method thereof |
| CN106887575A (en) * | 2017-03-14 | 2017-06-23 | 深圳先进技术研究院 | A kind of cobalt acid zinc/graphene composite negative pole and preparation method thereof and lithium ion battery |
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| KR20160124964A (en) * | 2015-04-20 | 2016-10-31 | 인하대학교 산학협력단 | Ultra-thin hollow carbon nanospheres for sodium ion storing and manufacturing method thereof |
| CN106887575A (en) * | 2017-03-14 | 2017-06-23 | 深圳先进技术研究院 | A kind of cobalt acid zinc/graphene composite negative pole and preparation method thereof and lithium ion battery |
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