CN112951612B - Aqueous sodium-ion battery capacitor hybrid device with bismuth oxide cathode and preparation method thereof - Google Patents
Aqueous sodium-ion battery capacitor hybrid device with bismuth oxide cathode and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B82Y40/00—Manufacture or treatment of nanostructures
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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Abstract
The invention relates to a bismuth oxide cathode water system sodium ion battery capacitor hybrid device and a preparation method thereof, wherein the preparation method comprises the following steps: (1) soaking the glass fiber diaphragm in sodium sulfate solution, taking out the diaphragm and clamping the diaphragm in Bi 2 O 3 Battery type negative electrode and delta-MnO 2 A sandwich structure is formed between the capacitance type anodes; (2) and integrally packaging the sandwich structure in a plastic packaging film, filling sodium sulfate electrolyte, and completely packaging to obtain the target product. Compared with the prior art, the electrode provided by the invention has the advantages of easily obtained preparation raw materials, simple experimental conditions and operation steps, low cost and capability of batch production, and simultaneously, Bi 2 O 3 //MnO 2 The battery capacitor hybrid device has a 2.4V potential window, breaks through the limitation of the 2V potential window of the water system battery capacitor hybrid device, and has higher energy density and power density.
Description
Technical Field
The invention belongs to the technical field of battery capacitor materials, and relates to a bismuth oxide cathode water system sodium ion battery capacitor hybrid device and a preparation method thereof.
Background
In the society characterized by the continuous popularization and increasing frequency of vehicles, people pay increasing attention to solving the problem of energy consumption of motor vehicles. Vehicle-mounted braking energy recovery technology based on an energy storage system is an important way to effectively reduce energy cost. To be able to efficiently store and utilize this braking energy, it is desirable that the energy storage system possess both a high power density and a high energy density. Considering implementation cost and deployment volume, the secondary battery and the electrochemical capacitor cannot meet the requirements of the vehicle-mounted regenerative braking device. To compensate for the gap between the battery and the capacitor, a hybrid battery-capacitor device based on battery and capacitor electrodes is a newer energy storage device that can provide enhanced energy and power at the super-capacitor level.
The battery capacitor hybrid device is classified into an organic system and an aqueous system by the arrangement of the electrolyte. The battery capacitor hybrid device of the organic system has a wider potential window, but has the defects of high price, toxicity, environmental pollution and the like; in contrast, the aqueous battery capacitor hybrid device has a fast ion mobility and high environmental compatibility, and has a much higher tolerance to the outside than the organic system, so researchers have also been working on developing the battery capacitor hybrid device in the aqueous system. However, the water-based battery capacitor hybrid device also has the following two problems: the potential window is small and the energy density and the power density are low. Therefore, the selection of the anode and the cathode with higher specific capacity and larger potential window is an effective method for solving the defects of the capacitor hybrid device of the water-based battery.
Due to the progress of capacitor hybrid devices of aqueous lithium ion batteries, sodium ion batteries and aqueous lithium ion batteries in recent years, researchers have also continuously searched capacitor hybrid devices of aqueous sodium ion batteries. Nevertheless, due to the limitations of the reaction kinetics and stability of the electrode materialThus, only a few anode materials can be used in neutral sodium electrolyte solutions, such as the classic NASICON type NaTi 2 (PO 4 ) 3 Na of tunnel structure 0.44 [Mn 1-x Ti x ]O 2 And polyimide, and the like. For example, NaTi 2 (PO 4 ) 3 Has good electrochemical characteristics and stable cycle performance in sodium sulfate electrolyte, but has relatively low capacity (less than or equal to 150mA h g) due to the conventional interlayer type charge storage mechanism -1 ). The negative electrode material with multiple electron conversion reaction mechanisms can store more charges, so that the exploration of the electrode material of the kind can further improve the overall performance of the capacitor hybrid device of the future aqueous sodium-ion battery. The present invention has been made in view of the above problems.
Disclosure of Invention
The invention aims to provide a bismuth oxide cathode aqueous sodium ion battery capacitor hybrid device and a preparation method thereof, and aims to solve the problems of small potential window, low capacity and the like of the aqueous battery capacitor hybrid device.
The purpose of the invention can be realized by the following technical scheme:
one of the technical schemes of the invention provides a bismuth oxide cathode water system sodium ion battery capacitor hybrid device which is composed of Bi 2 O 3 Battery-type negative electrode, glass fiber separator and delta-MnO 2 And packaging the capacitor type anode after forming a sandwich structure.
The second technical scheme of the invention provides a preparation method of a bismuth oxide cathode water system sodium ion battery capacitor hybrid device, which comprises the following steps:
(1) soaking the glass fiber diaphragm in sodium sulfate solution, taking out the diaphragm and clamping the diaphragm in Bi 2 O 3 Battery type negative electrode and delta-MnO 2 A sandwich structure is formed between the capacitance type anodes;
(2) and integrally packaging the sandwich structure in a plastic packaging film, filling sodium sulfate electrolyte, and completely packaging to obtain the target product.
Further, in the step (1), theOf Bi 2 O 3 The preparation process of the battery type negative electrode comprises the following steps:
(A) dissolving bismuth nitrate pentahydrate in a mixed solvent of ethylene glycol and ethanol to obtain a mixed solution I;
(B) soaking the carbon cloth subjected to hydrophilic modification in the mixed solution I, performing ultrasonic treatment, transferring to a hydrothermal kettle for hydrothermal reaction, removing the carbon cloth subjected to the hydrothermal reaction, cleaning and drying to obtain Bi 2 O 3 a/CC electrode sheet;
(C) adding Bi 2 O 3 Annealing the/CC (carbon cloth) electrode slice to obtain Bi 2 O 3 A battery-type negative electrode.
Furthermore, in the step (A), the addition ratio of the bismuth nitrate pentahydrate, the ethylene glycol and the ethanol is (0.8-1.2) g: (15-20) mL: (32-36) mL. Preferably, the addition ratio of the bismuth nitrate pentahydrate, the ethylene glycol and the ethanol is 0.97 g: 17mL of: 34 mL. The mixed solvent of ethylene glycol and ethanol can ensure that bismuth nitrate can be completely dissolved.
Further, in the step (B), the hydrophilic modification process of the carbon cloth specifically comprises: and (3) sequentially placing the carbon cloth in ethanol, nitric acid and deionized water for ultrasonic treatment to complete hydrophilic modification. Specifically, the membrane may be first soaked in ethanol for 20min, then treated with 10% (mass fraction) nitric acid for 20min, and finally soaked in deionized water for 20 min.
Furthermore, in the step (B), the temperature of the hydrothermal reaction is 140-. Preferably, the temperature of the hydrothermal reaction is 160 ℃ and the reaction time is 5 h.
Further, in the step (C), the annealing process specifically includes: at Ar/H 2 Keeping the temperature for 0.5-1.5h at the temperature of 120-180 ℃ under the condition of mixed gas. Preferably, the annealing temperature is 150 ℃ and the holding time is 1 h. Meanwhile, the temperature rise rate is preferably 5 ℃/min during the annealing process. And Ar/H 2 The volume fraction of hydrogen in the mixed gas was 5%. Bi 2 O 3 the/CC electrode is annealed in an inert gas containing a small amount of hydrogen to improve crystallinity and interfacial adhesion.
Further, in the step (1), the delta-MnO 2 The preparation process of the capacitive anode comprises the following specific steps:
(a) dissolving manganese acetate and ammonium acetate in water to obtain a mixed solution II;
(b) soaking the carbon cloth subjected to hydrophilic modification in the second mixed solution for ultrasonic treatment, taking out the carbon cloth as a working electrode, taking a Pt sheet as a counter electrode, taking a saturated calomel electrode as a reference electrode and taking the second mixed solution as an electrolyte, and performing electrochemical deposition to obtain MnO 2 a/CC electrode sheet;
(c) MnO of 2 Annealing the/CC electrode slice to obtain delta-MnO 2 A capacitive anode.
Furthermore, in the step (a), the ratio of the addition amount of the manganese acetate, the ammonium acetate and the water is (0.2-0.3) g: (0.12-0.18) g: 100 mL. Preferably, the addition ratio of the manganese acetate, the ammonium acetate and the water is 0.24 g: 0.15 g: 100 mL.
Further, in the step (b), the current for electrochemical deposition is 1.2-2.0mA, and the deposition time is 5000-10000 s. Preferably, the current for electrochemical deposition is 1.6mA, and the deposition time is 8000 s.
Further, in the step (c), the annealing process specifically comprises: keeping the temperature at 500 ℃ for 20-40min under the air condition at 300-. Preferably, the annealing temperature is 400 ℃, and the holding time is 30 min. Meanwhile, the temperature rise rate is preferably 10 ℃/min during the annealing process.
Further, the hydrophilic modification process of the carbon cloth can be referred to the above Bi 2 O 3 And a carbon cloth modification process in the battery type negative electrode preparation process.
Further, in the step (1), the concentration of the sodium sulfate solution is 0.8-1.2mol L -1 Preferably 1mol/L, and the soaking time is 0.5-1.5h, preferably 1 h. Here the separator is soaked in electrolyte beforehand to ensure the device conductivity.
Further, in the process of integrally packaging the sandwich structure in the transparent plastic packaging film, the positions of the Ti sheet tabs are reserved on the two sides of the positive electrode and the negative electrode before complete plastic packaging.
Further, in the step (2), sodium sulfate is filledThe concentration of the hydrolysate is also 0.8-1.2mol L -1 Preferably 1 mol/L.
Compared with the prior art, the invention has the following advantages:
(1) the invention adopts simple hydrothermal method and electrochemical deposition method to grow Bi on the carbon cloth in situ 2 O 3 Nanosheet array and MnO 2 The nanosheet array avoids the use of a binder, can fully utilize active substances of the electrode plate, eliminates the influence of other substances, and provides convenience for accurately researching the electrochemical behavior of the active substances;
(2) prepared Bi 2 O 3 And MnO with MnO 2 The carbon fibers are wrapped by the nanosheet array structure which is uniformly distributed, and the three-dimensional array structure which is relatively ordered and has a certain gap can provide a faster electron and ion transmission path, so that the electrochemical reaction kinetics of the electrode plate is improved. In addition, sufficient space is reserved among the three-dimensional nanosheet structures to relieve the volume expansion of the active substance in the electrochemical cycle test process, so that the cycle life of the battery capacitor hybrid device can be further prolonged;
(3) first use of Bi 2 O 3 /CC electrode sheet and MnO 2 Novel water system Bi assembled by CC electrode slices 2 O 3 //MnO 2 The sodium ion battery capacitor hybrid device has a high potential window of 2.4V, successfully breaks through the limitation of a 2V potential window of a water system device, and can provide larger energy density and power density at the same time. It is worth noting that the assembled device can still supply power to the digital timer under the condition of folding by 180 degrees, which shows that the assembled device has certain flexible function at the same time.
Drawings
FIG. 1a shows Bi 2 O 3 SEM image of/CC electrode obtained at 2 μm;
FIG. 1b shows Bi 2 O 3 SEM image of/CC electrode obtained at 200 nm;
FIG. 1c shows Bi 2 O 3 TEM images of the nanoplatelets obtained at 100 nm;
FIG. 1d is Bi 2 O 3 HRTEM image of nanosheets obtained at 4nmAn image;
FIG. 1e is Bi 2 O 3 XPS full spectrum of/CC electrode;
FIG. 1f shows Bi 2 O 3 Raman spectra of the/CC electrode and the carbon cloth;
FIG. 1g is an XPS spectrum of Bi 4f orbits;
FIG. 1h shows Bi 2 O 3 XRD pattern of/CC electrode;
FIG. 2a shows Bi 2 O 3 The electrode concentration of the/CC is 1mol L -1 From 10mV s under sodium sulfate electrolyte -1 To 60mV s -1 Cyclic voltammograms of sweep rate;
FIG. 2b shows Bi 2 O 3 The electrode concentration of the/CC is 1mol L -1 Constant current charge/discharge curves at different current densities in the presence of sodium sulfate electrolyte;
FIG. 2c shows Bi 2 O 3 The specific capacity graph of the/CC electrode is calculated based on the discharge time in the constant current charge-discharge test under different current densities;
FIG. 2d is Bi 2 O 3 the/CC electrode is at 12mA cm -2 Long cycle stability plot at current density;
FIG. 3a is MnO 2 SEM image of/CC electrode obtained at 20 μm;
FIG. 3b is MnO 2 SEM image of/CC electrode obtained at 5 μm;
FIG. 3c is MnO 2 TEM images of the nanoplatelets obtained at 75 nm;
FIG. 3d is MnO 2 HRTEM image of the nanosheet obtained at 5 nm;
FIG. 3e is MnO 2 XRD pattern of/CC electrode;
FIG. 3f is MnO 2 Raman spectra of the/CC electrode and the carbon cloth;
FIG. 3g is MnO 2 XPS full spectrum of/CC electrode;
FIG. 3h is an XPS spectrum of Mn2p orbitals;
FIG. 3i is an XPS spectrum of the O1s orbit;
FIG. 4a is MnO 2 The electrode concentration of the/CC is 1mol L -1 From 5mV s under sodium sulfate electrolyte -1 To 50mV s -1 Sweep rate cyclic voltammogram；
FIG. 4b is MnO 2 The electrode concentration of the/CC is 1mol L -1 Constant current charge/discharge curves at different current densities in the presence of sodium sulfate electrolyte;
FIG. 4c is MnO 2 The specific capacity graph of the/CC electrode is calculated based on the discharge time in the constant current charge-discharge test under different current densities;
FIG. 4d is MnO 2 the/CC electrode is at 16mA cm -2 Long cycle stability plot at current density;
FIG. 5a shows Bi 2 O 3 /CC electrode and MnO 2 A capacitive matching map of the/CC electrode;
FIG. 5b shows Bi 2 O 3 //MnO 2 1mol L of battery capacitor hybrid device -1 From 10mV s under sodium sulfate electrolyte -1 To 60mV s -1 Cyclic voltammograms of sweep rate;
FIG. 5c shows Bi 2 O 3 //MnO 2 1mol L of battery capacitor hybrid device -1 Constant current charge/discharge curves at different current densities in the presence of sodium sulfate electrolyte;
FIG. 5d is Bi 2 O 3 //MnO 2 The battery capacitor hybrid device is based on a specific capacity graph calculated by discharging time in constant current charging and discharging tests under different current densities;
FIG. 5e is Bi 2 O 3 //MnO 2 Ragone plots of battery-capacitor hybrid devices with other commercial electrochemical energy storage devices;
FIG. 5f is Bi 2 O 3 //MnO 2 A power supply diagram of the digital timer is provided under the flat state of the battery capacitor hybrid device;
FIG. 5g is Bi 2 O 3 //MnO 2 A power supply diagram of the digital timer is provided when the battery capacitor hybrid device is folded by 180 degrees;
FIG. 5h is Bi 2 O 3 //MnO 2 The battery capacitor hybrid device is 8mA cm -2 Long cycling stability plot at current density.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed embodiment and a specific operation process are given, but the scope of the present invention is not limited to the following embodiment.
The aqueous sodium ion battery capacity hybrid device of the bismuth oxide negative electrode of the present invention will be explained.
The invention provides a bismuth oxide cathode water system sodium ion battery capacitor hybrid device, which is composed of Bi 2 O 3 Battery-type negative electrode, glass fiber separator and delta-MnO 2 And packaging the capacitor type anode after forming a sandwich structure.
The invention aims to solve the problems of small potential window and low capacity of a capacitor hybrid device of a water-based battery, thereby providing a solution for widening the potential window and improving the capacity, and designing a Bi-based capacitor hybrid device 2 O 3 Novel neutral sodium ion battery capacitor hybrid device-Bi of negative electrode 2 O 3 //MnO 2 。Bi 2 O 3 As a material which has been extensively studied in the fields of industrial production and photocatalysis, it is often used as an additive for suppressing hydrogen evolution, and therefore it also has a large potential window in an aqueous electrolyte as a negative electrode. In addition, Bi 2 O 3 Conversion reaction in neutral sodium sulfate solution to
The process involves multiple electron transfer, and theoretically, a large amount of charge accumulation and release can be brought to the electrode. In order to maximize the energy density and power density of the battery capacitor hybrid device, it is also important to balance the charge, weight and volume with the battery type electrode using the capacitor type electrode having a higher specific capacity. MnO 2 As a common capacitance type positive electrode material, the material has excellent pseudo-capacitance performance, higher specific capacity and stable cycle life, and also has a potential window of more than 1V in a neutral water system electrolyte. Interestingly, MnO 2 Has a plurality of crystal forms due to rich valence, and the structure of the crystal form comprises alpha, beta, gamma, delta, lambda and R types, and MnO with a tunnel structure 2 Has been widely used in the research of the capacitor hybrid device of the neutral sodium ion battery. Delta-MnO in contrast to alpha-, beta-, gamma-and lambda-MnO 2 2 Having a typical layered structure with an interlayer spacing of
These structural features have been demonstrated to have high electrochemical kinetics and good cycling stability. Theoretically, delta-MnO is used 2 Designed Bi 2 O 3 The base aqueous battery capacitor hybrid device can simultaneously realize high energy and power density, and ensure that the device has certain cycle stability.
Next, a method for producing an aqueous sodium ion battery capacity hybrid device having a bismuth oxide negative electrode will be described in detail.
The invention respectively adopts a simple hydrothermal method and an electrodeposition method to prepare Bi 2 O 3 Negative electrode and delta-MnO 2 And the anode takes sodium sulfate as electrolyte, and a two-electrode system is adopted to verify the electrochemical performance of the anode. The electrode provided by the invention has the advantages of easily obtained preparation raw materials, simple experimental conditions and operation steps, low cost and capability of batch production. It is noted that Bi designed by the present invention 2 O 3 //MnO 2 The battery capacitor hybrid device has a 2.4V potential window, breaks through the limitation of the 2V potential window of the water system battery capacitor hybrid device, and has higher energy density and power density.
Specifically, the preparation method of the aqueous sodium-ion battery capacitor hybrid device with the bismuth oxide cathode provided by the invention comprises the following steps:
(1) soaking the glass fiber diaphragm in sodium sulfate solution, taking out the diaphragm and clamping the diaphragm in Bi 2 O 3 Battery type negative electrode and delta-MnO 2 A sandwich structure is formed between the capacitance type anodes;
(2) and (3) integrally packaging the sandwich structure in a plastic packaging film, filling sodium sulfate electrolyte, and completely packaging to obtain the target product.
In some embodiments, in step (1), said Bi 2 O 3 The preparation process of the battery type negative electrode comprises the following steps:
(A) dissolving bismuth nitrate pentahydrate in a mixed solvent of ethylene glycol and ethanol to obtain a mixed solution I;
(B) soaking the carbon cloth subjected to hydrophilic modification in the mixed solution I, performing ultrasonic treatment, transferring to a hydrothermal kettle for hydrothermal reaction, removing the carbon cloth subjected to the hydrothermal reaction, cleaning and drying to obtain Bi 2 O 3 a/CC electrode sheet;
(C) adding Bi 2 O 3 Annealing the/CC (carbon cloth) electrode slice to obtain Bi 2 O 3 A battery-type negative electrode.
Furthermore, in the step (A), the addition ratio of the bismuth nitrate pentahydrate, the ethylene glycol and the ethanol is (0.8-1.2) g: (15-20) mL: (32-36) mL. Preferably, the addition ratio of the bismuth nitrate pentahydrate, the ethylene glycol and the ethanol is 0.97 g: 17mL of: 34 mL.
Further, in the step (B), the hydrophilic modification process of the carbon cloth specifically comprises: and (3) sequentially placing the carbon cloth in ethanol, nitric acid and deionized water for ultrasonic treatment to complete hydrophilic modification. Specifically, the membrane may be first soaked in ethanol for 20min, then treated with 10% (mass fraction) nitric acid for 20min, and finally soaked in deionized water for 20 min.
Furthermore, in the step (B), the temperature of the hydrothermal reaction is 140-. Preferably, the temperature of the hydrothermal reaction is 160 ℃ and the reaction time is 5 h.
Further, in the step (C), the annealing process specifically includes: at Ar/H 2 Keeping the temperature for 0.5-1.5h at the temperature of 120-180 ℃ under the condition of mixed gas. Preferably, the annealing temperature is 150 ℃, and the holding time is 1 h. Meanwhile, the temperature rise rate is preferably 5 ℃/min during the annealing process. And Ar/H 2 The volume fraction of hydrogen in the mixed gas is preferably 5%.
In some embodiments, in step (1), the delta-MnO 2 Capacitance type anodeThe preparation process specifically comprises the following steps:
(a) dissolving manganese acetate and ammonium acetate in water to obtain a mixed solution II;
(b) soaking the carbon cloth subjected to hydrophilic modification in the second mixed solution for ultrasonic treatment, taking out the carbon cloth as a working electrode, taking a Pt sheet as a counter electrode, taking a saturated calomel electrode as a reference electrode and taking the second mixed solution as an electrolyte, and performing electrochemical deposition to obtain MnO 2 a/CC electrode sheet;
(c) MnO of 2 Annealing the/CC electrode slice to obtain delta-MnO 2 A capacitive anode.
Furthermore, in the step (a), the ratio of the addition amount of the manganese acetate, the ammonium acetate and the water is (0.2-0.3) g: (0.12-0.18) g: 100 mL. Preferably, the addition ratio of the manganese acetate, the ammonium acetate and the water is 0.24 g: 0.15 g: 100 mL.
Further, in the step (b), the current for electrochemical deposition is 1.2-2.0mA, and the deposition time is 5000-10000 s. Preferably, the current for electrochemical deposition is 1.6mA, and the deposition time is 8000 s.
Further, in the step (c), the annealing process specifically comprises: keeping the temperature at 500 ℃ for 20-40min under the air condition at 300-. Preferably, the annealing temperature is 400 ℃, and the holding time is 30 min. Meanwhile, the temperature rise rate is preferably 10 ℃/min during the annealing process.
Further, the hydrophilic modification process of the carbon cloth can be referred to the above Bi 2 O 3 And (3) a carbon cloth modification process in the battery type negative electrode preparation process.
In some embodiments, in step (1), the sodium sulfate solution has a concentration of 0.8 to 1.2mol L -1 Preferably 1mol/L, and the time of soaking treatment is 0.5-1.5h, preferably 1 h.
In some embodiments, in the process of integrally packaging the sandwich structure in the transparent plastic packaging film, before complete plastic packaging, positions of Ti sheet tabs are reserved on both sides of the positive and negative electrodes.
In some embodiments, in step (2), the concentration of the sodium sulfate electrolyte is also 0.8 to 1.2mol L -1 Preferably 1 mol/L.
The design principle of the invention is as follows:
1、Bi 2 O 3 the reaction equation in neutral sodium sulfate is:
compared with the traditional battery type electrode which stores charge by utilizing an intercalation reaction mechanism, the electrode has the advantages that Bi is added 2 O 3 The conversion reaction mechanism of (2) can provide up to 6 electrons, and theoretically can provide higher capacity. In addition, the invention discovers Bi through electrochemical characterization 2 O 3 In 1mol L of -1 The negative potential window in the sodium sulfate solution can reach-1.2V, and the precipitation of hydrogen in a water system can be greatly inhibited.
2、MnO 2 Having a plurality of crystal forms, wherein delta-MnO 2 Has a stable layered structure, not only provides guarantee for the circulation stability of the electrolyte, but also ensures the rapid embedding and removing of ions in the electrolyte. Meanwhile, the invention verifies delta-MnO through experiments 2 At 1mol L -1 The positive potential window in the sodium sulfate solution can reach 1V, and the precipitation of oxygen in a water system can be greatly inhibited.
3. In view of the above considerations, the present invention utilizes Bi 2 O 3 Negative electrode and delta-MnO 2 The novel aqueous sodium-ion battery capacitor hybrid device prepared by the anode can theoretically reach a potential window of 2.4V, and the 2V potential window limit of the traditional aqueous battery capacitor hybrid device is broken through. Notably, thanks to Bi 2 O 3 Cell type negative electrode with high capacity and delta-MnO 2 The capacitive type anode has the characteristics of high electrochemical reaction speed and high cycling stability, and the novel water system Bi of the invention 2 O 3 //MnO 2 The sodium ion battery capacitor hybrid device can have high energy density and power density at the same time, and has a certain cycle life.
The above embodiments will be described in more detail with reference to specific examples.
In the following examples, unless otherwise specified, the starting materials or the treatment techniques are all conventional and commercially available materials or conventional treatment techniques in the art.
Example 1:
Bi 2 O 3 preparation of Battery-type negative electrode
(1) Cutting a carbon cloth with the size of 4cm multiplied by 4cm, carrying out hydrophilic treatment on the carbon cloth, firstly soaking the carbon cloth in ethanol for 20min by ultrasonic treatment, then carrying out ultrasonic treatment on the carbon cloth by using 10% nitric acid for 20min, and finally soaking the carbon cloth in deionized water for 20min by ultrasonic treatment;
(2) dissolving 0.97g of bismuth nitrate pentahydrate in 17ml of ethylene glycol and 34ml of ethanol to obtain a mixed solution;
(3) soaking the carbon cloth subjected to hydrophilic treatment in the mixed solution for ultrasonic treatment for 30min, and then completely transferring the carbon cloth into a 90ml stainless steel hot kettle;
(4) the hydrothermal kettle is placed in an air-blowing drying box, the temperature is set to be 160 ℃, and the reaction time is 5 hours;
(5) after the hydrothermal reaction is finished, taking out the carbon cloth, washing the carbon cloth with water and ethanol for multiple times, and then placing the carbon cloth in a forced air drying oven to dry the carbon cloth at the temperature of 60 ℃;
(6) finally, the obtained Bi 2 O 3 (hydrogen volume fraction 5%) on Ar/H with/CC electrode sheet 2 Annealing in a tube furnace under the condition of mixed gas, wherein the annealing temperature is 150 ℃, and the heating rate is 5 ℃ for min -1 Keeping the temperature for 1h to obtain Bi 2 O 3 A battery-type negative electrode.
Example 2:
δ-MnO 2 preparation of capacitive anode
(1) Cutting a carbon cloth with the size of 2cm multiplied by 2cm, carrying out hydrophilic treatment on the carbon cloth, firstly soaking the carbon cloth in ethanol for 20min by ultrasonic treatment, then carrying out ultrasonic treatment on the carbon cloth by using 10% nitric acid for 20min, and finally soaking the carbon cloth in deionized water for 20min by ultrasonic treatment;
(2) dissolving 0.24g of manganese acetate and 0.15g of ammonium acetate in 100ml of deionized water to obtain a mixed solution;
(3) soaking the carbon cloth subjected to hydrophilic treatment in the mixed solution for 30min by ultrasonic treatment;
(4) clamping the carbon cloth treated in the step (3) by using a polytetrafluoroethylene clamp as a working electrode, taking a Pt sheet as a counter electrode, taking a saturated calomel electrode as a reference electrode, taking the mixed solution prepared in the step (2) as electrolyte, and assembling a standard three-electrode system;
(5) carrying out constant current deposition on the assembled standard three-electrode system by using a Shanghai Chenghua electrochemical workstation CHI 760E, wherein the current is 1.6mA, and the deposition time is 8000 s;
(6) finally, MnO obtained in step (5) 2 Annealing the/CC electrode plate in a muffle furnace under the air condition, wherein the annealing temperature is 400 ℃, and the heating speed is 10 ℃ for min -1 The heat preservation time is 30min, and delta-MnO is obtained 2 A capacitive anode.
Example 3:
Bi 2 O 3 //MnO 2 preparation of battery capacitor hybrid device
(1) Adding Bi 2 O 3 Electrode sheet for/CC (i.e., Bi obtained in example 1) 2 O 3 Battery type negative electrode) and MnO 2 [ delta ] -MnO of example 2 2 Capacitive anode) is cut into the size of 1cm multiplied by 2cm, and the glass fiber diaphragm is cut into the size of 1.2cm multiplied by 2.2cm, so that the area of the diaphragm is slightly larger than that of the positive and negative electrode plates;
(2) fully soaking the glass fiber diaphragm in 1mol L -1 Soaking in sodium sulfate solution for 1 h;
(3) clamping the soaked glass fiber diaphragm in Bi 2 O 3 /CC electrode sheet and MnO 2 A sandwich structure is formed in the middle of the/CC electrode slice;
(4) integrally packaging the sandwich structure formed in the step (3) in a transparent plastic packaging film, and reserving positions for placing Ti sheet tabs on the two sides of the positive electrode and the negative electrode before complete plastic packaging;
(5) filling with 1mol L Using a Syringe -1 After the sodium sulfate electrolyte is prepared, the whole device is completely encapsulated by a heat sealing machine to obtain Bi 2 O 3 //MnO 2 A battery-capacitor hybrid device.
Material phase characterization
The morphology and structure of the material are characterized by a Hitachi S-4800 Scanning Electron Microscope (SEM) with an energy dispersive X-ray spectrometer and a JEOL TEM-2100 high resolution projection electron microscope (HRTEM). The X-ray diffraction pattern (XRD) was tested using Cu ka radiation in a Bruker D8 Advance diffractometer. The raman spectrum was obtained using a confocal microscope laser raman spectrometer (Rainshaw invia). X-ray photoelectron spectroscopy (XPS, Kratos Axis Ultra DLD X-ray photoelectron spectrometer) is used for valence state analysis of materials.
Characterization of electrochemical Properties of materials
The mass of the active material on all the electrode pads was measured using an electronic balance with a measurement accuracy of 0.01 mg. Both Cyclic Voltammetry (CV) and constant current charge-discharge testing (GCD) were performed at room temperature on CHI 760E (shanghai chenhua). For the test of the electrochemical performance of a single electrode, the test is carried out under a standard three-electrode system, wherein a Pt sheet and a saturated calomel electrode are respectively used as a counter electrode and a reference electrode, and the electrolyte is always 1mol L -1 Sodium sulfate solution. In a two-electrode configuration, Bi 2 O 3 a/CC electrode as negative electrode, delta-MnO 2 the/CC electrode is used as a positive electrode. In addition, the two electrodes and the glass fiber diaphragm are combined into a sandwich structure, and then are packaged by using a flexible plastic film to form a device capable of being practically applied.
Specific capacity of a single electrode sheet (C g) -1 ) The discharge time is calculated based on a constant current charge-discharge curve and combined with the following formula to obtain (formula 1):
C＝I×t/m (1)
wherein I is the discharge current density (mA cm) -2 ) T is a discharge time(s), and m is an active material amount per unit area of the electrode sheet (mg cm) -2 ). It is noted that the capacity calculation of the battery capacity hybrid device is the same as (1), but m is the sum of the two electrode sheet active material masses. The conversion of the capacity unit is as follows:
1C g -1 ＝1/V F g -1 (2)
1mAh g -1 ＝1×10 -3 A g -1 ×3600s＝3.6C g -1 (3)
wherein V is the working voltage of the electrode plate potential window or the battery capacitor hybrid device.
And finally, calculating the energy density and the power density (E and P) of the battery-capacitor hybrid device by using the formulas (4) and (5) respectively.
E＝0.5C V 2 /3.6 (4)
P＝3600E/Δt (5)
Where C is the specific capacity of the hybrid device (F g) -1 ) V is the operating voltage of the battery-capacitor hybrid device, and Δ t is the discharge time of the battery-capacitor hybrid device.
Bi in example 1 2 O 3 Characterization of the phase
FIG. 1a shows Bi 2 O 3 In the case of uniform growth on carbon fibers, FIG. 1b is an SEM image thereof at 200 nm. Bi grown on carbon cloth fiber as shown in the figure 2 O 3 The film is composed of nanosheets which are highly connected with one another to form a more ordered three-dimensional nanosheet array structure. FIG. 1c is a TEM image at 100nm obtained by transmission electron microscopy for further study of Bi 2 O 3 The structural information of (1). Bi 2 O 3 A High Resolution Transmission Electron Microscope (HRTEM) photograph of the nanosheets at 4nm is shown in FIG. 1d, Bi 2 O 3 Exhibit clear lattice fringes with interplanar spacing of about 0.28nm, corresponding to Bi 2 O 3 (200) crystal plane of (1). In addition, the invention also carries out X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy tests, and the XPS full spectrum in figure 1e and the Raman spectrum in figure 1f accurately show the existence of Bi and O elements. 115, 138 and 304cm in Raman spectrum (FIG. 1f) -1 The peak appearing at corresponds to Bi 2 O 3 Wherein the D peak and the G peak correspond to the characteristic peaks of the carbon cloth substrate. The XPS spectrum of the Bi 4f orbital of FIG. 1g was then analyzed to have two peaks at binding energies of 164.4eV and 159.1eV, with a spin spacing of 5.3eV corresponding to Bi 2 O 3 Bi 4f in (1) 5/2 And Bi 4f 7/2 A track. Finally, the composition of the array film on the carbon cloth was further confirmed using X-ray diffraction (XRD). As shown in fig. 1h, except for the sourceAll other diffraction peaks except the diffraction peak of the carbon cloth substrate (JCPDS card number 75-444) are well matched with delta-Bi with face-centered cubic configuration 2 O 3 (JCPDS card numbers 27-052). Notably, the intensities of the (111) and (200) peaks are relatively high, indicating that Bi 2 O 3 The preferred orientation of the nano-sheet film growing on the carbon cloth.
Bi in example 1 2 O 3 Characterization of the electrochemical Properties of
FIG. 2a shows Bi 2 O 3 The electrode concentration of the/CC is 1mol L -1 In the sodium sulfate electrolyte, the concentration of the electrolyte is 10mV s obtained by utilizing a three-electrode system test -1 To 60mV s -1 Although the sweep rate increases, two pairs of distinct redox peaks are always present in the cyclic voltammograms at different sweep rates. At 10mV s -1 The cyclic voltammograms at sweep rate were analyzed and the reduction peaks at-0.3V and-0.8V corresponded well to Bi 3+ →Bi 2+ To Bi 2+ →Bi 0 The reaction process of (1). As the sweep rate increases, the reduction peak of the cyclic voltammogram gradually shifts to a lower voltage and the oxidation peak gradually shifts to a higher voltage, and the polarization is caused by Bi 2 O 3 Inherent electrochemical kinetics factors. In FIG. 2b, Bi 2 O 3 The constant current charge-discharge (GCD) curve of the/CC electrode is between 4 and 16mA cm -2 Shows a significant charge-discharge plateau at each current density, consistent with the redox peak phenomenon appearing in the cyclic voltammogram of fig. 2 a. Meanwhile, the corresponding specific capacity is calculated according to the discharge time of the electrode sheet at each current density in fig. 2b, and is plotted as a function image related to the current density, as shown in fig. 2 c. At 4mA cm -2 Below, Bi 2 O 3 The maximum specific capacity of the/CC electrode is about 955.3C g -1 (265.4mAh g -1 ). When the current density increased to 16mA cm -2 When is Bi 2 O 3 the/CC electrode can still provide 272.9C g -1 (75.8mAh g -1 ) The high capacity is far superior to battery-type cathode materials that utilize intercalation mechanisms to store charge. Furthermore, at 12mA cm -2 At current density of Bi 2 O 3 The cycle stability of the/CC electrode sheet was tested and the results are shown in FIG. 2 d. Since Bi 2 O 3 The charge storage is carried out through a phase change mechanism, and a small part of Bi simple substance generated by the transition delay of the crystal structure is remained in the electrode slice to cause the gradual reduction of the capacity of the electrode slice. However, Bi prepared in example 2 2 O 3 The electrode with the/CC nanosheet array structure is 1mol L -1 The capacity of the sodium sulfate electrolyte is still kept at the original 66 percent after 1000 times of circulation, and the acceptable circulation stability is shown. In conclusion, Bi 2 O 3/ Due to the excellent performance of the CC electrode and the uniform three-dimensional nanosheet array structure, the gaps among the nanosheets can effectively relieve the volume expansion of the active material in the reaction process, and the improvement of the cycling stability is facilitated.
MnO in example 2 2 Characterization of the phase
To be based on Bi 2 O 3 The energy density and the power density of the water system sodium ion battery capacitor hybrid device are maximized, and the invention selects delta-MnO with large capacity and stable layered structure 2 To match Bi 2 O 3 A battery-type negative electrode. In the present invention, delta-MnO 2 the/CC electrode was prepared using a simple electrochemical deposition method. As shown in fig. 3a, b, the carbon fibers have been uniformly deposited with interconnected nano-sheets and formed into an ordered three-dimensional array structure. FIG. 3c is a TEM image at 75nm obtained using transmission electron microscopy for further study of MnO 2 The structural information of (1). FIG. 3d is MnO at 5nm 2 HRTEM image of the nanosheet shows lattice fringes with good resolution, the lattice spacing is approximately equal to 0.67nm, and delta-MnO is formed 2 Corresponds to (001) plane of (a). To further demonstrate the phase of the product, all bragg diffraction peaks can be well indexed to δ -MnO as shown in XRD figure 3e 2 (JCPDS card numbers 18-802) and carbon cloth-based JCPDS card numbers 75-444). The above results are consistent with the Raman spectrum shown in FIG. 3f, where 640cm is -1 The peak at (A) is layered delta-MnO 2 The characteristic Mn-O peaks, D peak (1360cm-1) and G peak (1600cm-1) of (B) are derived from the carbon cloth substrate. Further, the present inventionThe valence and bonding structure of Mn and O were also analyzed by XPS, the XPS survey is shown in FIG. 3g, and the XPS spectra of the Mn2p and O1s orbitals are shown in FIG. 3h, i. From FIG. 3h, it can be observed that the binding energies of the two peaks of Mn2p are located at 654.1 and 642.4eV, respectively, which is attributed to Mn 4+ Mn2p in (1) 1/2 And Mn2p 3/2 . Meanwhile, the orbital peak of O1s (FIG. 3i) can be divided into three peaks at 532.3, 531.4 and 529.9eV, which correspond to water of crystallization (OH-H), hydroxyl group (Mn-OH) and delta-MnO, respectively 2 (Mn-O-Mn).
MnO in example 2 2 Characterization of the electrochemical Properties of
FIG. 4a shows MnO 2 The electrode concentration of the/CC is 1mol L -1 In the sodium sulfate electrolyte, the concentration of the electrolyte is 5mV s obtained by utilizing a three-electrode system test -1 To 50mV s -1 Cyclic voltammograms at different scan rates, MnO as the scan rate increases 2 The cyclic voltammetry curve of the/CC electrode still keeps the shape of an approximate rectangle, and the MnO is verified 2 Based on
The pseudocapacitive behavior of (a). Furthermore, in cyclic voltammograms at low scan rates, the two broad redox peaks at 0.83V and 1.06V may correspond to Na + The insertion and extraction process. Also, fig. 4b shows delta-MnO at each current density 2 The constant current charge-discharge curve of the/CC always presents linear potential-time response, and the results further prove that delta-MnO 2 With acceptable capacitance performance, consistent with the results of the previous cyclic voltammograms. Delta-MnO 2 The specific capacity of the/CC electrode sheet under each current density is shown in figure 4c, and is 4mA cm -2 At current density of delta-MnO 2 The specific capacity of the/CC is about 439.3C g -1 (366.1F g -1 ) (ii) a When the current density increased to 16mA cm -2 In the case of delta-MnO 2 the/CC can still provide 302.7C g -1 (252.2F g -1 ) The capacity retention rate of the electrode is as high as 68.9 percent, which proves that the electrode has excellent rate capability. At the same time, delta-MnO 2 the/CC electrode is at highStability test for up to 15000 cycles (Current Density: 16mA cm) -2 ) Also shows excellent performance, as shown in fig. 4d, the capacity retention rate is as high as 98.7%. Notably, in the first 6000 cycles, delta-MnO 2 The specific capacity of the/CC electrode is improved (up to 378.7C g-1), which is mainly composed of Na + Is caused by the embedding mechanism of (1). Delta-MnO 2 The ultrahigh specific capacity and excellent cycle stability of the/CC electrode are attributed to a relatively ordered three-dimensional nanosheet array structure and delta-MnO 2 They provide a faster path for electron transport and can sufficiently realize Na + Diffusion of (2).
Bi in example 3 2 O 3 //MnO 2 Battery capacitance hybrid device performance characterization
To further verify Bi 2 O 3 Feasibility of electrodes to build large potential window cell-capacitor hybrid devices in neutral sodium-ion electrolyte, example 3 with Bi 2 O 3 the/CC nanosheet array electrode is a battery type cathode, delta-MnO 2 the/CC nanosheet array electrode is an insertion layer type pseudocapacitance anode and 1mol L -1 Sodium sulfate solution as neutral aqueous electrolyte with complete Bi 2 O 3 //MnO 2 A battery-capacitor hybrid device. In delta-MnO 2 In the performance test of (2), delta-MnO 2 the/CC electrode showed a continuous capacity increase in the first 6000 cycles, probably due to Na + Gradual activation of the intercalation. Based on the above conditions, before capacity matching of the positive and negative poles, the delta-MnO is firstly matched 2 the/CC electrode was activated. FIG. 5a shows Bi 2 O 3 [ delta ] -MnO after/CC cathode and activation 2 the/CC positive pole is at 10mV s -1 The cyclic voltammetry curves prove that the stored charge capacities of the two electrodes are matched on the basis of integral calculation. By using Bi 2 O 3 Wide voltage window (-1.2-1V) and MnO of CC cathode 2 Voltage range of CC anode from 0 to 1.2V, Bi designed by the invention 2 O 3 //MnO 2 The cell capacitor hybrid device can operate in the ultra high voltage window of 0-2.4V, the result of which is shown by the cyclic voltammogram of FIG. 5bAnd (6) line verification. According to the search of the present invention, based on Bi 2 O 3 In the aqueous mixing apparatus of the electrode, 2.4V is the highest voltage window currently achieved.
FIG. 5c shows Bi 2 O 3 //MnO 2 The battery capacitor hybrid device is 1-8mA cm -2 Constant current charge-discharge curves at different current densities exhibiting non-linear voltage-time response with Bi alone 2 O 3 Charging and discharging platform of negative electrode and MnO 2 The linear voltage-time responses of the two electrodes are different. The non-linear relationship of the galvanostatic charge-discharge curve indicated that the kinetic behavior of the hybrid system is related to diffusion limitation, which is in contrast to the cyclic voltammogram behavior in fig. 5b and Bi 2 O 3 The charge storage mechanism of the electrodes based on phase change is consistent. In addition, FIG. 5d shows the specific mass capacity versus area capacity of the total device at different current densities, at 1, 2, 4, 6 and 8mA cm -2 At current density of (3), the neutral sodium ion Bi designed by us 2 O 3 The specific capacity of the battery capacitor hybrid device// MnO2 is up to about 215C g -1 (268.4C cm -2 )，106.7C g -1 (133.3C cm -2 )，70.6C g -1 (88.2C cm -2 )，62.7C g -1 (78.3C cm -2 ) And 56.3C g -1 (70.3C cm -2 )。
Bi 2 O 3 //MnO 2 The Ragone plot of the hybrid device of battery capacitance is shown in fig. 5e, and the energy density and power density are calculated using the formula shown in the electrochemical characterization of the material in combination with the specific capacity of the device and compared with the electrochemical energy storage devices that have been commercialized at present. Neutral sodium ion Bi designed in example 3 2 O 3 //MnO 2 The hybrid battery-capacitor device can provide energy density (71.7Wh kg) superior to nickel-metal hydride (Ni-MH), nickel-cadmium (Ni-Cd) and Lead-acid (Lead-acid) batteries simultaneously -1 ；400.5W kg -1 ) Power density (3204.3W kg) -1 ；18.8Wh kg -1 ) And makes up for the short plate of performance between the lithium ion battery (Li-ion battery) and the commercial Electric Double Layer Capacitor (EDLC). To further prove that the present invention can be applied to practice, the present invention utilizes Bi 2 O 3 [ negative ] CC electrode and MnO 2 CC cathode and immersion 1mol L -1 The glass fiber filter paper of the sodium sulfate solution is used as a diaphragm, and finally a flexible plastic package film is used for wrapping to prepare a complete device. After full charging, the device is able to effectively power the digital timer (as shown in fig. 5 f) and also to keep the digital timer on in a 180 ° bent state (as shown in fig. 5 g). In addition, under the potential window of 2.4V, the invention is at 8mA cm -2 The neutral sodium ion Bi is studied under the constant current charging and discharging mode 2 O 3 //MnO 2 Cycling stability performance of the cell capacitor hybrid (prepared in example 3) (fig. 5 h). The device can be cycled up to 1500 cycles and still maintain an initial capacity value of about 77.2%. Neutral sodium ion Bi designed by the invention 2 O 3 //MnO 2 The improvement of the overall performance of the battery capacitor hybrid device is attributed to the high capacity Bi for storing charge by the phase change mechanism 2 O 3 Delta-MnO having excellent negative electrode and cycle stability 2 And (4) a positive electrode.
As described above, Bi prepared in the above examples 1 to 3 2 O 3 The electrode has certain electrochemical reversibility under neutral condition, and complete phase transition reaction
Occurs in a wide voltage range of-1.2 to 1V, and effectively suppresses the generation of hydrogen gas. Based on the advantages, the designed Bi 2 O 3 the/CC cathode may also provide a relatively appreciable capacity in neutral solution. At 4mA cm -2 At a current density of Bi 2 O 3 the/CC electrode has a thickness of up to-955.3C g -1 (265.4mAh g -1 ) The maximum specific capacity of (a). Most importantly, we have for the first time developed a neutral sodium ion Bi of 2.4V 2 O 3 //MnO 2 A battery-capacitor hybrid device. Bi benefiting from high capacity 2 O 3 Negative electrode and delta-MnO with stable layered structure 2 Positive electrode, designed neutral sodium ion Bi 2 O 3 //MnO 2 The hybrid device of battery and capacitor can provide high simultaneouslyEnergy density and power density. The invention creates possibility for solving the problem of low capacity of the sodium ion water-based battery capacitor hybrid device, and provides a design scheme for promoting the practical application of the water-based battery capacitor hybrid device.
In the above embodiments, the experimental raw materials or process parameters may be arbitrarily adjusted (i.e., adjusted to the end values or any intermediate values) within the following ranges according to actual conditions:
for example, the addition ratio of the bismuth nitrate pentahydrate, the glycol and the ethanol is (0.8-1.2) g: (15-20) mL: (32-36) mL; the temperature of the hydrothermal reaction is 140 ℃ and 180 ℃, and the reaction time is 3-7 h; bi 2 O 3 The process of the/CC annealing treatment specifically comprises the following steps: at Ar/H 2 Keeping the temperature for 0.5-1.5h at the temperature of 120-180 ℃ under the condition of mixed gas. Preferably, the annealing temperature is 150 ℃, and the heat preservation time is 1 h;
the addition ratio of the manganese acetate, the ammonium acetate and the water is (0.2-0.3) g: (0.12-0.18) g: 100 mL; the current of the electrochemical deposition is 1.2-2.0mA, and the deposition time is 5000-; MnO (MnO) 2 The annealing process of the/CC electrode slice is as follows: under the air condition, the temperature is kept for 20-40min at the temperature of 300-;
the concentration of the sodium sulfate solution used for soaking and filling is 0.8-1.2mol L -1 。
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (4)
1. The preparation method of the aqueous sodium-ion battery capacitor hybrid device with the bismuth oxide cathode is characterized in that the hybrid device is prepared from Bi 2 O 3 Battery-type negative electrode, glass fiber separator, and delta-MnO 2 Packaging the capacitor type positive electrode after forming a sandwich structure;
the preparation method comprises the following steps:
(1) soaking the glass fiber diaphragm in sodium sulfate solution, taking out the diaphragm and clamping the diaphragm in Bi 2 O 3 Battery type negative electrode and delta-MnO 2 A sandwich structure is formed between the capacitance type anodes;
(2) integrally packaging the sandwich structure in a plastic packaging film, filling sodium sulfate electrolyte, and completely packaging to obtain a target product;
in the step (1), the Bi 2 O 3 The preparation process of the battery type negative electrode comprises the following steps:
(A) dissolving bismuth nitrate pentahydrate in a mixed solvent of ethylene glycol and ethanol to obtain a mixed solution I;
(B) soaking the carbon cloth subjected to hydrophilic modification in the mixed solution I, performing ultrasonic treatment, transferring to a hydrothermal kettle for hydrothermal reaction, taking out the carbon cloth subjected to the hydrothermal reaction, cleaning and drying to obtain Bi 2 O 3 a/CC electrode sheet;
(C) adding Bi 2 O 3 Annealing the/CC electrode slice to obtain Bi 2 O 3 A battery-type negative electrode;
in the step (C), the annealing process specifically comprises: at Ar/H 2 Under the condition of mixed gas, preserving the heat for 0.5 to 1.5 hours at the temperature of 120-;
in the step (1), the delta-MnO 2 The preparation process of the capacitive anode comprises the following specific steps:
(a) dissolving manganese acetate and ammonium acetate in water to obtain a mixed solution II;
(b) soaking the carbon cloth subjected to hydrophilic modification in the second mixed solution for ultrasonic treatment, taking out the carbon cloth as a working electrode, taking a Pt sheet as a counter electrode, taking a saturated calomel electrode as a reference electrode and taking the second mixed solution as an electrolyte, and performing electrochemical deposition to obtain MnO 2 a/CC electrode sheet;
(c) MnO of 2 Annealing the/CC electrode slice to obtain delta-MnO 2 A capacitive positive electrode;
in the step (1), the concentration of the sodium sulfate solution is 0.8-1.2mol L -1 The soaking time is 0.5-1.5 h;
in the step (b), the current of the electrochemical deposition is 1.2-2.0mA, and the deposition time is 5000-;
in the step (c), the annealing process specifically comprises: keeping the temperature at 500 ℃ for 20-40min under the air condition at 300-.
2. The method for preparing an aqueous sodium ion battery capacitance hybrid device with a bismuth oxide cathode according to claim 1, wherein in the step (A), the addition amount ratio of bismuth nitrate pentahydrate, ethylene glycol and ethanol is (0.8-1.2) g: (15-20) mL: (32-36) mL.
3. The method for preparing the aqueous sodium-ion battery capacitor hybrid device with the bismuth oxide cathode according to claim 1, wherein in the step (B), the hydrophilic modification process of the carbon cloth specifically comprises the following steps: sequentially placing the carbon cloth in ethanol, nitric acid and deionized water for ultrasonic treatment to complete hydrophilic modification;
in the step (B), the temperature of the hydrothermal reaction is 140 ℃ and 180 ℃, and the reaction time is 3-7 h.
4. The method for preparing the aqueous sodium-ion battery capacitor hybrid device with the bismuth oxide cathode according to claim 1, wherein in the step (a), the addition amount ratio of the manganese acetate to the ammonium acetate to the water is (0.2-0.3) g: (0.12-0.18) g: 100 mL.
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