CN116014063B - Electrode of water-based zinc ion battery, preparation method and application thereof - Google Patents
Electrode of water-based zinc ion battery, preparation method and application thereof Download PDFInfo
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- CN116014063B CN116014063B CN202310306206.6A CN202310306206A CN116014063B CN 116014063 B CN116014063 B CN 116014063B CN 202310306206 A CN202310306206 A CN 202310306206A CN 116014063 B CN116014063 B CN 116014063B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 49
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229920002749 Bacterial cellulose Polymers 0.000 claims abstract description 69
- 239000005016 bacterial cellulose Substances 0.000 claims abstract description 69
- 239000004964 aerogel Substances 0.000 claims abstract description 37
- 238000010438 heat treatment Methods 0.000 claims abstract description 32
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 29
- -1 vanadate ions Chemical class 0.000 claims abstract description 24
- 238000004108 freeze drying Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000012528 membrane Substances 0.000 claims description 51
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 239000008367 deionised water Substances 0.000 claims description 28
- 229910021641 deionized water Inorganic materials 0.000 claims description 28
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 239000003792 electrolyte Substances 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 239000003365 glass fiber Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 claims description 8
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Substances [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
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- 230000007935 neutral effect Effects 0.000 claims description 5
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- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 abstract description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 10
- 229920000049 Carbon (fiber) Polymers 0.000 abstract description 7
- 239000004917 carbon fiber Substances 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 6
- 239000011159 matrix material Substances 0.000 abstract description 5
- 239000000835 fiber Substances 0.000 abstract description 3
- 238000005470 impregnation Methods 0.000 abstract description 3
- 238000007598 dipping method Methods 0.000 abstract 1
- 238000004080 punching Methods 0.000 description 9
- 230000008901 benefit Effects 0.000 description 7
- 239000011701 zinc Substances 0.000 description 6
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 5
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- 238000004146 energy storage Methods 0.000 description 5
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- 229910001935 vanadium oxide Inorganic materials 0.000 description 5
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- 238000006243 chemical reaction Methods 0.000 description 4
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- 230000003287 optical effect Effects 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
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- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 102000020897 Formins Human genes 0.000 description 1
- 108091022623 Formins Proteins 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
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- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The application discloses an electrode of a water-based zinc ion battery, a preparation method and application thereof. The preparation method mainly comprises the steps of preparation dipping, freeze drying and heat treatment. The vanadate ions are fully impregnated into the three-dimensional fiber network of the bacterial cellulose in the impregnation process. Through freeze drying, the bacterial cellulose is changed into ammonium metavanadate/bacterial cellulose aerogel, bacterial cellulose matrix is carbonized at high temperature, and the ammonium metavanadate is pyrolyzed to generate V 2 O 3 Obtaining the superfine V uniformly distributed on the three-dimensional carbon fiber network 2 O 3 Aerogel electrodes of nanoparticles.
Description
Technical Field
The application belongs to the technical field of water-based zinc ion batteries, and particularly relates to an electrode of a water-based zinc ion battery, a preparation method and application thereof.
Background
With the rapid development of flexible electronics and wearable energy storage devices, the need for lightweight, flexible energy storage power supplies is becoming more stringent. The lithium ion battery has the advantages of high energy density, high power density, long service life, excellent cycle stability and the like, and becomes one of the hot energy storage power supplies in the current new energy field. However, the used organic electrolyte has the potential safety hazard of inflammability and explosiveness, and has high production cost and poor environmental friendliness. Therefore, development of a novel energy storage power supply with green, safety, high performance and low cost is particularly important to development of wearable energy storage equipment.
In recent years, rechargeable aqueous zinc ion batteries based on aqueous electrolytes have shown great application prospects as alternative battery technologies due to their environmental and cost effectiveness. The water-based zinc ion battery not only has the advantages of safety, abundant zinc reserves, high theoretical capacity and the like, but also has the ion conductivity far higher than that of the nonaqueous electrolyte, thereby endowing the battery with excellent multiplying power performance. However, conventional battery manufacturing processes typically mix-coat active materials, binders, and conductive agents onto a metal current collector, and the addition of large proportions of inactive materials reduces the overall energy and power density of the battery. After long-time use, the contact density of the electrode material and the metal current collector interface becomes small, so that the electrode material is separated, and the service life is influenced. In addition, the preparation steps of stirring, coating, drying and the like are relatively complicated, and the time cost is high, so that the aqueous zinc ion battery based on the current collector-free electrode is one of the current research subjects.
Development of a suitable cathode material is also one of the problems to be solved in the field of aqueous zinc ion batteries.
The above information disclosed in this background section is only for enhancement of understanding of the background section of the application and therefore it may not form the prior art that is already known to those of ordinary skill in the art.
Disclosure of Invention
Based on the technical problem existing in the background art, the purpose of the application is as follows: the electrode of the water-based zinc ion battery, the preparation method and the application thereof are provided, the preparation process is simple, the process is pollution-free, the prepared aerogel electrode has the advantages of good flexibility, uniform distribution of vanadium oxide nano particles, good electrochemical performance at high surface loading and the like, the electrode does not need a current collector, and the electrode can avoid using an adhesive with poor conductivity, so that the integrity of the electrode is ensured, and the energy density of the battery is improved.
The application is realized by the following technical scheme:
the preparation method of the electrode of the water-based zinc ion battery comprises the following steps:
s1: cutting bacterial cellulose membrane into slices, soaking in deionized water, and regulating pH
To neutrality;
s2: mixing ammonium metavanadate powder with deionized water, heating and stirring uniformly to obtain ammonium metavanadate solution;
s3: taking out the bacterial cellulose membrane soaked in the step S1, washing the bacterial cellulose membrane for a plurality of times by deionized water, and soaking the bacterial cellulose membrane into the ammonium metavanadate solution prepared in the step S2 to obtain the bacterial cellulose membrane growing vanadate ions;
s4: placing the bacterial cellulose film growing vanadate ions obtained in the step S3 into liquid nitrogen for soaking for a preset time, and transferring to a freeze dryer for freeze drying treatment to remove solvent water;
s5: transferring the bacterial cellulose membrane growing vanadate ions after freeze-drying in the step S4 to a tube furnace, and performing heat treatment in nitrogen to obtain V 2 O 3 @ CNF aerogel electrode.
In some embodiments of the present application, in step S1, the bacterial cellulose film has a thickness of 3 to 10 mm.
In some embodiments of the present application, in step S1, the bacterial cellulose film has a thickness of 3 mm.
In some embodiments of the present application, in step S1, the bacterial cellulose film is cut into square patterns having an area of 3 to 5cm ×3 to 5 cm.
In some embodiments of the present application, in step S1, the bacterial cellulose film is cut into square patterns of area 5cm ×5 cm.
In some embodiments of the present application, in step S1, the bacterial cellulose membrane is immersed in deionized water for a period of time ranging from 24 to 48 h.
In some embodiments of the present application, in step S1, the bacterial cellulose membrane is immersed in deionized water for 24 hours.
In some embodiments of the present application, in step S2, the mass ratio of the ammonium metavanadate to deionized water is 0.5-2.5: 1000.
in some embodiments of the present application, in step S2, the mass ratio of ammonium metavanadate to deionized water is 0.585:1000.
in some embodiments of the present application, in step S3, the bacterial cellulose membrane is immersed in an ammonium metavanadate solution for a period of time ranging from 48 to 72 h, preferably 48 h.
In some embodiments of the present application, in step S4, the bacterial cellulose membrane grown with vanadate ions is immersed in liquid nitrogen for 1 to 5 min, preferably 2 min.
In some embodiments of the present application, in step S4, the bacterial cellulose membrane grown with vanadate ions is freeze dried in a freeze dryer for a period of 24-72 h, preferably 48 h.
In some embodiments of the present application, in step S5, the heat treatment temperature is 180-700 ℃, the heat preservation time is 0-2 h, the heating rate is 0-5 ℃/min, preferably the heat treatment temperature is 700 ℃, the heat preservation time is 2h, and the heating rate is 2 ℃/min.
On the other hand, the application also provides an electrode of the water-based zinc ion battery, which is prepared by the method.
In yet another aspect, the application further provides an application of the electrode in an aqueous zinc ion battery, wherein the V 2 O 3 The @ CNF aerogel is used as a battery anode, a pure zinc foil is used as a cathode, a glass fiber membrane is used as a diaphragm, and a zinc trifluoromethane sulfonate solution is used as an electrolyte.
In yet another aspect, an aqueous zinc ion battery, the V 2 O 3 The @ CNF aerogel is used as a battery anode, a pure zinc foil is used as a cathode, a glass fiber membrane is used as a diaphragm, and a zinc trifluoromethane sulfonate solution is used as an electrolyte.
In some embodiments of the present application, the aqueous zinc-ion battery is described in 1A g -1 After 200 cycles of current density, the battery still has 286.1mAh g -1 Is a function of the capacity of the battery.
The application has the advantages and beneficial effects as follows:
1. superfine V proposed in the present application 2 O 3 The aerogel electrode embedded by the nano particles is an integrated electrode, a current collector is not needed, relatively complicated preparation steps such as stirring, coating, drying and the like are avoided, meanwhile, adhesive doping with poor conductivity is avoided, the integrity of the electrode is ensured, and therefore the energy density of the battery is improved. The proportion of inactive substances is reduced, the electrode is light and thin, high-load battery assembly can be realized, and the electrochemical performance is good.
2. Superfine V proposed in the present application 2 O 3 The aerogel electrode embedded with the nano particles adopts a bacterial cellulose film with low cost as a carbon precursor material, and the carbonized carbon nanofiber network can reduce the transmission distance of zinc ions, promote electron transmission and increase the contact area of vanadium oxide and electrolyte.
3. Superfine V proposed in the present application 2 O 3 The aerogel electrode embedded by the nano particles has the characteristics of torsion, bending and the like, and can be conveniently integrated into a flexible battery device.
4. Superfine V proposed in the present application 2 O 3 The nano-particle embedded aerogel electrode is characterized in that the prepared superfine vanadium oxide is uniformly distributed on a carbon fiber network, larger specific surface area and more bare active sites are provided, the reaction process is quickened, and the water-based zinc ion battery assembled by the electrode preparation process shows excellent electrochemical performance.
5. Superfine V proposed in the present application 2 O 3 The aerogel electrode embedded with the nano particles has the advantages of simple production process, environment-friendly and safe electrode materials, realization of secondary recycling, realization of the hundred percent utilization of slurry in the preparation process, and reduction of resource waste.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the description of the embodiments will be briefly introduced below, it being obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic illustration of an electrode preparation process described herein;
FIG. 2 is a TGA graph of electrodes prepared in example 1 of the present application;
FIG. 3 is an SEM image of an electrode prepared in example 1 of the present application;
FIG. 4 is a schematic illustration of an electrode cut electrode sheet made in accordance with the present application;
FIG. 5 is a graph of electrochemical performance of a zinc-ion cell prepared in example 1 of the present application;
FIG. 6 is a graph of electrochemical performance of a high load zinc ion cell prepared in example 3 of the present application;
Detailed Description
The technical solutions of the present application will be clearly and completely described below with reference to the accompanying drawings and detailed description, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present application, and are only for illustrating the present application and should not be construed as limiting the scope of the present application.
All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present disclosure. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The applicant finds that the manganese-based material electrode is low in cost, green and safe, but is easily dissolved in the reaction process; cloth Lu Shilan analogue and organic compound electrode have excellent rate performance but still have a problem of low capacity. The vanadium-based compound has large physical theory capacity and various crystal structures, wherein V of hexagonal close-packed crystal structure 2 O 3 The ion implantation device has a tunnel-shaped 3D structure, and can realize rapid ion implantation and extraction. However, V 2 O 3 The intrinsic conductivity is poor, and the problem that the structure is easy to collapse in the charge and discharge process to cause the electrochemical performance to be reduced still needs to be solved, so as to solve the problems:
the electrode prepared by the application is superfine V 2 O 3 A nanoparticle-embedded aerogel electrode comprising a carbon fiber matrix having a three-dimensional network structure and a metal oxide distributed on the carbon fiber matrix; the carbon fiber matrix is obtained by heat treatment of bacterial cellulose; the metal oxide is superfine vanadium oxide; the aerogel electrode prepared by the application has the advantages of good flexibility, uniform distribution of vanadium oxide nano particles, good electrochemical performance at high surface loading and the like, and is free ofThe current collector is needed, relatively complicated preparation steps such as stirring, coating, drying and the like are avoided, meanwhile, adhesive doping with poor conductivity is avoided, the proportion of inactive substances is reduced, the electrode is light and thin, high-load battery assembly can be realized, and good electrochemical performance is achieved. The V is 2 O 3 The @ CNF aerogel is directly used as a battery anode, a pure zinc foil is used as a cathode, a glass fiber membrane is used as a diaphragm, and a zinc trifluoromethane sulfonate solution is used as an electrolyte, so that the obtained zinc ion battery shows excellent electrochemical performance.
Example 1:
superfine V of this example 2 O 3 The preparation method of the aerogel electrode embedded by the nano particles comprises the following steps:
step 1: bacterial cellulose films of thickness 3 mm were cut into square patterns of 5cm by 5cm, transferred to deionized water, immersed in 24h, and adjusted to neutral PH.
Step 2: mixing ammonium metavanadate powder with deionized water, heating and stirring to a uniform state, wherein the mass ratio of ammonium metavanadate to deionized water is 0.585:1000.
step 3: and (3) taking out the bacterial cellulose membrane soaked in the step (1), washing the bacterial cellulose membrane for a plurality of times by deionized water, and soaking the bacterial cellulose membrane into the ammonium metavanadate solution prepared in the step (2) for 48h to obtain the bacterial cellulose membrane growing vanadate ions.
Step 4: and (3) immersing the bacterial cellulose membrane growing vanadate ions obtained in the step (3) in liquid nitrogen for 1min, and after the sample structure is frozen and fixed, transferring to a freeze dryer for freeze drying 24 and h, and removing solvent water.
Step 5: transferring the bacterial cellulose membrane growing vanadate ions after freeze-drying in the step 4 to a tube furnace, and performing heat treatment in nitrogen to obtain V 2 O 3 @ CNF aerogel. The heat treatment temperature is 700 ℃, the heat preservation time is 2h, and the heating rate is 2 ℃/min.
The method for assembling the aqueous zinc ion button cell described in this example 1 is as follows:
step 6: the obtained electrode is cut into pieces by a sheet punching machine, and square electrodes of 0.8cm multiplied by 0.8cm can be selected.
Step 7: the zinc foil negative electrode of 0.8cm ×0.8cm was obtained by punching in the same manner and dimensions as in the above step 6, and the zinc foil thickness was 0.02 mm.
Step 8: and (3) sequentially placing a positive electrode, a glass fiber diaphragm and a negative electrode in a lamination mode, and dropwise adding zinc trifluoromethane sulfonate electrolyte with the concentration of 3mol/L between the positive electrode and the negative electrode.
Example 2:
superfine V of this example 2 O 3 The preparation method of the aerogel electrode embedded by the nano particles comprises the following steps:
step 1: bacterial cellulose films of thickness 3 mm were cut into square patterns of 5cm x 5cm, transferred to deionized water, soaked 48h, and adjusted to neutral PH.
Step 2: mixing ammonium metavanadate powder with deionized water, heating and stirring to a uniform state, wherein the mass ratio of ammonium metavanadate to deionized water is 2.34:1000.
step 3: and (3) taking out the bacterial cellulose membrane soaked in the step (1), washing the bacterial cellulose membrane for a plurality of times by deionized water, and soaking the bacterial cellulose membrane into the ammonium metavanadate solution prepared in the step (2) for 60 h to obtain the bacterial cellulose membrane growing vanadate ions.
Step 4: and (3) immersing the bacterial cellulose membrane growing vanadate ions obtained in the step (3) in liquid nitrogen for 2 min, and after the sample structure is frozen and fixed, transferring to a freeze dryer for freeze drying 48 and h, and removing solvent water.
Step 5: transferring the bacterial cellulose membrane growing vanadate ions after freeze-drying in the step 4 to a tube furnace, and performing heat treatment in nitrogen to obtain V 2 O 3 @ CNF aerogel. The heat treatment temperature is 700 ℃, the heat preservation time is 2h, and the heating rate is 2 ℃/min.
The method for assembling the aqueous zinc ion button cell described in this example 2 is as follows:
step 6: the obtained electrode is cut into pieces by a sheet punching machine, and a round electrode with the diameter of 1.2 cm multiplied by 1.2 cm can be selected.
Step 7: the zinc foil cathode of 1.2 cm ×1.2 cm was obtained by punching in the same manner and size as in step 6, and the zinc foil thickness was 0.02 mm.
Step 8: and (3) sequentially placing a positive electrode, a glass fiber diaphragm and a negative electrode in a lamination mode, and dropwise adding zinc trifluoromethane sulfonate electrolyte with the concentration of 3mol/L between the positive electrode and the negative electrode.
Example 3:
superfine V of this example 2 O 3 The preparation method of the aerogel electrode embedded by the nano particles comprises the following steps:
step 1: bacterial cellulose films 10mm thick were cut into square patterns 5cm x 5cm, transferred to deionized water, soaked 48h, and adjusted to neutral PH.
Step 2: mixing ammonium metavanadate powder with deionized water, heating and stirring to a uniform state, wherein the mass ratio of ammonium metavanadate to deionized water is 0.585:1000.
step 3: and (3) taking out the bacterial cellulose membrane soaked in the step (1), washing the bacterial cellulose membrane for a plurality of times by deionized water, and soaking the bacterial cellulose membrane into the ammonium metavanadate solution prepared in the step (2) for 72 h to obtain the bacterial cellulose membrane growing vanadate ions.
Step 4: and (3) immersing the bacterial cellulose membrane growing vanadate ions obtained in the step (3) in liquid nitrogen for 2 min, and after the sample structure is frozen and fixed, transferring to a freeze dryer for freeze drying 72 and h, and removing solvent water.
Step 5: transferring the bacterial cellulose membrane growing vanadate ions after freeze-drying in the step 4 to a tube furnace, and performing heat treatment in nitrogen to obtain V 2 O 3 @ CNF aerogel. The heat treatment temperature is 700 ℃, the heat preservation time is 2h, and the heating rate is 2 ℃/min.
The method for assembling the aqueous zinc ion button cell described in this example 3 is as follows:
step 6: the obtained electrode is cut into pieces by a sheet punching machine, and square electrodes with the length of 0.8cm multiplied by 0.8cm can be selected.
Step 7: the zinc foil negative electrode of 0.8cm ×0.8cm was obtained by punching in the same manner and dimensions as in the above step 6, and the zinc foil thickness was 0.02 mm.
Step 8: and (3) sequentially placing a positive electrode, a glass fiber diaphragm and a negative electrode in a lamination mode, and dropwise adding zinc trifluoromethane sulfonate electrolyte with the concentration of 3mol/L between the positive electrode and the negative electrode.
Example 4:
this embodiment is superiorThin V 2 O 3 The preparation method of the aerogel electrode embedded by the nano particles comprises the following steps:
step 1: bacterial cellulose films 10mm thick were cut into square patterns 5cm by 5cm, transferred to deionized water, immersed for 48h, and adjusted to neutral pH.
Step 2: mixing ammonium metavanadate powder with deionized water, heating and stirring to a uniform state, wherein the mass ratio of ammonium metavanadate to deionized water is 0.585:1000.
step 3: and (3) taking out the bacterial cellulose membrane soaked in the step (1), washing the bacterial cellulose membrane for a plurality of times by deionized water, and soaking the bacterial cellulose membrane into the ammonium metavanadate solution prepared in the step (2) for 72 h to obtain the bacterial cellulose membrane growing vanadate ions.
Step 4: and (3) immersing the bacterial cellulose membrane growing vanadate ions obtained in the step (3) in liquid nitrogen for 2 min, and after the sample structure is frozen and fixed, transferring to a freeze dryer for freeze drying 72 and h, and removing solvent water.
Step 5: transferring the bacterial cellulose membrane growing vanadate ions after freeze-drying in the step 4 to a tube furnace, and performing heat treatment in nitrogen to obtain V 2 O 3 @ CNF aerogel. The heat treatment temperature is 700 ℃, the heat preservation time is 2h, and the heating rate is 2 ℃/min.
The method for assembling the aqueous zinc ion button cell described in this example 4 is as follows:
step 6: the obtained electrode is cut into pieces by a sheet punching machine, and square electrodes of 0.8cm multiplied by 0.8cm can be selected.
Step 7: the zinc foil negative electrode of 0.8cm ×0.8cm was obtained by punching in the same manner and dimensions as in the above step 6, and the zinc foil thickness was 0.02 mm.
Step 8: the square positive pole piece after cutting is longitudinally stacked on a battery positive pole shell in a lamination mode, and the load capacity is 10 mg/cm 2 And sequentially placing a glass fiber diaphragm and a negative electrode, and dropwise adding zinc trifluoromethane sulfonate electrolyte with the concentration of 3mol/L between the positive electrode and the negative electrode.
Comparative example
The traditional laminated electrode structure is adopted, an anode is obtained on a stainless steel foil by directly coating active substances, a cathode is made of zinc foil, and the water-based zinc ion battery is assembled after cutting.
Preparation of battery pole piece
Step 1: chinese medicine V 2 O 3 Mixing with conductive carbon black and polyvinylidene fluoride (PVDF) binder in N-methyl pyrrolidone (NMP) to form uniform slurry, and coating the slurry on stainless steel foil with an applicator having an opening size of 100 μm, a stainless steel thickness of 0.02 mm and an active material surface load of 1.5 mg cm -2 。
Step 2: the coated electrode was placed in a forced air heated oven and dried at 80℃for 12h to remove NMP.
Step 3: the obtained electrode is cut into pieces by a sheet punching machine, and square electrodes with the length of 0.8cm multiplied by 0.8cm can be selected.
Step 4: and (3) blanking to obtain a zinc foil cathode with the thickness of 0.02 cm multiplied by 0.8cm by adopting the same method and size as in the step 3, wherein the thickness of the zinc foil is 0.02 mm.
FIG. 1 is a superfine V described in the present application 2 O 3 Schematic of the process for preparing nanoparticle embedded aerogel electrodes. V making 2 O 3 The process of @ CNF aerogel mainly comprises several steps of impregnation, freeze-drying and heat treatment. The precursor is selected to be bacterial cellulose having an extremely high water content, for example, 99% water. The vanadate ions are fully impregnated into the three-dimensional fiber network of the bacterial cellulose in the impregnation process. By freeze-drying, it is converted into ammonium metavanadate/bacterial cellulose aerogel. Further, bacterial cellulose matrix is carbonized at high temperature, and ammonium metavanadate is pyrolyzed to generate V 2 O 3 Obtaining the superfine V uniformly distributed on the three-dimensional carbon fiber network 2 O 3 Aerogel electrodes of nanoparticles.
FIG. 2 is a superfine V powder prepared in example 1 of the present application 2 O 3 Nanoparticle embedded aerogel electrode TGA profile. In air at 5 deg.C for min -1 Is measured by thermogravimetric analysis 2 O 3 Carbon content of @ CNF aerogel. As shown, the weight loss below 212 ℃ can be attributed to the reduction in free water; the weight change between 247℃and 600℃is due to V 2 O 3 Is of (2) and carbonAnd (3) burning.
FIG. 3 is a superfine V powder prepared in example 1 of the present application 2 O 3 SEM image of nanoparticle embedded aerogel electrode. The carbonized fiber is crosslinked to form a three-dimensional conductive network (shown as (a) in figure 3 and (b) in figure 3) which is conducive to rapid ion transfer, and the superfine V formed by pyrolysis is shown as (c) in figure 3 2 O 3 The nano particles are uniformly distributed on the whole carbon fiber network, so that larger specific surface area and more bare active sites are provided, and the reaction process is quickened; from (d) in FIG. 3, clear lattice fringes at pitches of 0.205, 0.218 and 0.248 nm can be observed, corresponding to hexagonal phase V, respectively 2 O 3 (202), (113) and (110).
FIG. 4 is a superfine V described in the present application 2 O 3 Schematic illustration of cut pole piece of aerogel electrode embedded with nano particles. Fig. 4 (a) and fig. 4 (b) are optical images of the bacterial cellulose membrane after lyophilization and heat treatment, respectively; fig. 4 (c) is an optical image of a bacterial cellulose membrane that is ammonium metavanadate after lyophilization; FIG. 4 (d) shows the V formed after the heat treatment 2 O 3 An optical image of @ CNF aerogel electrode; as shown in fig. 4 (e), V 2 O 3 The @ CNF aerogel has the advantage of being lightweight and thin, which will facilitate the assembly of high surface area cells; FIG. 4 (f) is the ultrafine V in example 3 2 O 3 An optical image of the nanoparticle embedded aerogel electrode after heat treatment.
Fig. 5 is a graph of electrochemical performance of a zinc ion cell prepared in example 1 of the present application. By V pair 2 O 3 At 1mV s, the zinc ion battery assembled by the @ CNF aerogel electrode -1 The Cyclic Voltammetry (CV) test (fig. 5 (a)), the voltage range during charge and discharge was determined to be 0.2-1.6V; as shown in (b) of fig. 5, when the current density is 0.1. 0.1A g -1 When the assembled battery is subjected to charge and discharge test, the change of the charge and discharge curve shows that the material is undergoing stable reversible reaction and high-efficiency Zn 2+ Storing a process; it can be observed from (c) in figure 5 that the carbon nanofiber network of high specific surface area and high conductivity facilitates zinc storage,thereby being capable of endowing the material with excellent multiplying power performance; as shown in (d) of FIG. 5, at 1A g -1 After 200 cycles of current density, the battery still has 286.1mAh g -1 Indicating that the battery has excellent cycle performance.
Fig. 6 is a graph of electrochemical performance of a high load zinc ion cell prepared in example 3 of the present application. At a loading of 5mg cm -2 At this time, the battery was subjected to a rate test showing V 2 O 3 The @ CNF aerogel electrode can still obtain better multiplying power performance under the condition of improving load, and the multiplying power performance is 0.1A g -1 At a current density of 307mAh g -1 (fig. 6 (a) and fig. 6 (b)).
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and are not limiting thereof; although the present application has been described in detail with reference to the foregoing embodiments, one of ordinary skill in the art will appreciate that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not drive the essence of the corresponding technical solutions to depart from the spirit and scope of the technical solutions of the embodiments of the present application.
Claims (10)
1. The preparation method of the electrode of the water-based zinc ion battery is characterized by comprising the following steps of:
s1: cutting and slicing the bacterial cellulose membrane, soaking in deionized water, and regulating the PH value to be neutral;
s2: mixing ammonium metavanadate powder with deionized water, heating and stirring uniformly to obtain ammonium metavanadate solution; s3: taking out the bacterial cellulose membrane soaked in the step S1, washing the bacterial cellulose membrane for a plurality of times by deionized water, and soaking the bacterial cellulose membrane into the ammonium metavanadate solution prepared in the step S2 to obtain the bacterial cellulose membrane growing vanadate ions;
s4: placing the bacterial cellulose membrane growing vanadate ions obtained in the step S3 into liquid nitrogen for soaking for a preset time, and then transferring the bacterial cellulose membrane to a freeze dryer for freeze drying treatment, and removing solvent water;
s5: lyophilizing step S4The bacterial cellulose film growing vanadate ions is moved to a tube furnace and is subjected to heat treatment in nitrogen to obtain V 2 O 3 A @ CNF aerogel electrode;
in the step S2, the mass ratio of the ammonium metavanadate to the deionized water is 0.5-2.5: 1000.
2. the method for producing an electrode of an aqueous zinc ion battery according to claim 1, wherein in step S1, the bacterial cellulose film thickness is 3 to 10 mm.
3. The method for producing an electrode of an aqueous zinc ion battery according to claim 1, wherein in step S1, the bacterial cellulose film is cut into a square pattern having an area of 3 to 5cm ×3 to 5 cm.
4. The method for preparing an electrode of an aqueous zinc-ion battery according to claim 1, wherein in step S2, the mass ratio of ammonium metavanadate to deionized water is 2.5:1000.
5. the method for preparing an electrode of an aqueous zinc ion battery according to claim 1, wherein in step S3, the bacterial cellulose membrane is immersed in an ammonium metavanadate solution for a period of time of 48 to 72 h.
6. The method for preparing an electrode of an aqueous zinc ion battery according to claim 1, wherein in the step S4, the bacterial cellulose membrane growing vanadate ions is immersed in liquid nitrogen for 1-5 min.
7. The method for preparing an electrode of an aqueous zinc ion battery according to claim 1, wherein in step S4, the bacterial cellulose membrane growing vanadate ions has a freeze drying time of 24 to 72 h in a freeze dryer.
8. The method for preparing an electrode of an aqueous zinc-ion battery according to claim 1, wherein in the step S5, the heat treatment temperature is 180-700 ℃, the heat preservation time is 0-2 h, and the heating rate is 0-5 ℃/min.
9. An electrode of an aqueous zinc ion battery, characterized in that the electrode is prepared by the preparation method of any one of claims 1-8.
10. The use of an electrode of an aqueous zinc-ion battery according to claim 9, wherein the electrode of an aqueous zinc-ion battery is used in an aqueous zinc-ion battery, and the V 2 O 3 The @ CNF aerogel is used as a battery anode, a pure zinc foil is used as a cathode, a glass fiber membrane is used as a diaphragm, and a zinc trifluoromethane sulfonate solution is used as an electrolyte.
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