CN113113675B - Quasi-solid state flexible Zn-MnO2Battery and preparation method - Google Patents

Quasi-solid state flexible Zn-MnO2Battery and preparation method Download PDF

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CN113113675B
CN113113675B CN202110410201.9A CN202110410201A CN113113675B CN 113113675 B CN113113675 B CN 113113675B CN 202110410201 A CN202110410201 A CN 202110410201A CN 113113675 B CN113113675 B CN 113113675B
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battery
cts
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CN113113675A (en
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孔德志
屈迎奥
牛娇龙
张伟
吕思进
王烨
李新建
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Zhengzhou University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/38—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
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    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

The invention provides a quasi-solid flexible Zn-MnO2Battery and method of making, with Zn2+The PVA hydrogel is a matrix material of a battery diaphragm and an electrolyte, flexible carbon fiber Cloth (CTs) is used as a self-supporting current collector and a load of an electrode, and a hydrothermal and electrodeposition combined method is adopted to prepare alpha-MnO2@δ‑MnO2a/CTs nano composite array material anode, a Zn nanosheet material cathode is obtained by a one-step electrodeposition method, and then two self-supporting flexible electrodes are assembled into quasi-solid Zn-MnO2A battery. The invention provides Zn-MnO2The battery has the advantages of high energy density, excellent flexibility, high safety, quick charging, long cycle life and the like, and meanwhile, the battery has the characteristics of simple preparation process, low cost, environmental friendliness and the like, can well meet the requirements of various wearable devices on the battery, and has wide application prospects.

Description

Quasi-solid state flexible Zn-MnO2Battery and preparation method
Technical Field
The invention relates to the field of energy storage, in particular to quasi-solid flexible Zn-MnO2A battery and a preparation method thereof.
Background
With the rapid development of various portable and wearable electronic devices, the development of novel flexible energy storage devices also becomes a hot spot of scientific research, so that the research on batteries with high performance and bending resistance is the key for the development of wearable electronic products. In recent years, lithium ion batteries are the predominant energy storage devices in the market, but the lithium ion batteries have the defects of harsh assembly conditions, toxic organic electrolyte, insufficient safety coefficient, performance reduction or limited functions under extreme conditions and the like, and the application of the lithium ion batteries in wearable electronic products is seriously hindered. Therefore, in consideration of the problems and challenges in economic benefit, ecological environment, safety application and the like, researchers are devoted to vigorously develop and explore novel energy storage systems, and it is desirable to develop a green battery with high quality, low price and high cost performance. In contrast, the research and development of high-performance rechargeable aqueous batteries has led to another new stage of secondary battery research, and due to the characteristics of low cost, cleanness, environmental protection, high safety and the like, the secondary battery can meet the requirements of large-scale energy storage systems, and is gradually a hot spot in the research of electrochemical energy storage field in recent years.
In various water system energy storage devices, zinc resources are rich and low in price, meanwhile, the novel rechargeable zinc ion battery utilizes a neutral zinc salt as electrolyte, the manufacturing is simple, the cost is lower, the safety, the non-toxic and high specific capacity are realized, the flammable and explosive risks of the traditional lithium-based battery are avoided, the flexible zinc ion battery is a better choice for flexible electronic equipment, and people favor the zinc ion battery. In particular Zn-MnO2Batteries, because of their low cost, safety, non-toxicity, environmental friendliness, high voltage, and high energy density, may be of great interest as an ideal choice for flexible energy storage devices. However, most of the Zn-MnO reported in the current research2The battery uses blocky zinc and a binder, so that the specific capacity of the battery is still low, the capacity attenuation is serious, the rate capability is poor, and Zn-MnO is severely restricted2Commercial application of the battery. Therefore, a flexible Zn-MnO with high energy density, high rate and high stability is designed and developed2Batteries are of great significance.
Disclosure of Invention
The invention provides quasi-solid state flexible Zn-MnO2The battery and the preparation method have the characteristics of high energy density, bending resistance, rechargeability, simple preparation process, low cost, environmental friendliness and the like, can well overcome the defects of strict environmental requirements, high process cost, complex procedures and the like in the traditional battery assembly process, and have wide application prospects.
The technical scheme for realizing the invention is as follows:
rechargeable high-performance quasi-solid Zn-MnO with high energy density and bending resistance2Battery, the quasi-solid Zn-MnO2The battery can contain Zn2+PVA of (2)The hydrogel is a matrix material of a battery diaphragm and an electrolyte, the flexible carbon fiber cloth is used as a self-supporting current collector and a load of an electrode, and a method combining hydrothermal treatment and electrodeposition is adopted to successfully realize alpha-MnO with high specific surface area and high capacity2/δ-MnO2The preparation method comprises the steps of preparing a nano composite array material anode, directly growing a Zn nanosheet material with controllable load capacity along with time on CTs through a one-step electrodeposition method to serve as a cathode, and assembling two self-supporting flexible electrodes into quasi-solid Zn-MnO2The battery still has good flexibility and can keep the stability of electrochemical performance under different stress states.
The specific preparation steps of the anode are as follows:
(1) Hydrothermal method: the pretreated carbon fiber cloth was immersed in 40 mL of potassium permanganate (KMnO)40.02-0.04M) aqueous solution, then sealing the reaction kettle and placing the reaction kettle into a drying oven to keep the temperature of 150-170 ℃ for 3-5 h, taking out a sample, washing the sample with deionized water, and drying the sample at 70 ℃ for 6h to obtain alpha-MnO2Nanowire arrays grown on CTs surfaces (alpha-MnO)2/CTs）；
(2) The electrodeposition method comprises the following steps: alpha-MnO obtained in the step (1)2the/CTs are used as working electrodes, graphite rods and Saturated Calomel Electrodes (SCE) are respectively used as counter electrodes and reference electrodes, and the three electrodes are immersed in MnSO4And CH3COONa in a mixed aqueous solution (each 45-55 mM) at a current density of 4.5-5.5 mA cm-2Electrodepositing for various times (30-120 s), and drying the sample obtained by electrodeposition at 70 ℃ for 12h;
(3) Annealing treatment in a CVD furnace: putting the sample obtained in the step (2) into an annealing furnace to anneal for 2-3 h at 425-475 ℃ in argon gas to obtain alpha-MnO2/δ-MnO2The nano composite array material is loaded on a carbon fiber cloth substrate (alpha-MnO)2@δ-MnO2/CTs) can be used directly as Zn-MnO2The positive electrode of the battery.
Said Zn-MnO2The positive electrode of the battery is formed by directly growing alpha-MnO on CTs by a method combining a hydrothermal method and electrodeposition2@δ-MnO2A nanocomposite array material; active materials in the positive electrode are taken to be, but not limited to, alpha-MnO2@δ-MnO2The nano composite array material can also be MnO2Base compounds (e.g. MnO)2@C，MnO2@ PPy, etc.).
The negative electrode is a 2D Zn nanosheet array with controllable loading capacity directly grown on the processed CTs by adopting a simple electrodeposition method. The active material in the negative electrode adopts but is not limited to a Zn nanosheet array, and can also be a Zn-based compound (such as Zn nanoparticles, zn @ C composite material and the like).
The preparation steps of the negative electrode are as follows: the pretreated carbon fiber cloth and the foil are respectively used as a working electrode and a reference electrode, and the electrolyte solution is ZnSO4·7H2O、Na2SO4And H3BO3The mixed solution of (4) (40 mL, concentrations of 0.52,1.06 and 0.40M, respectively), then at 10 mA cm-2The current density is kept for 30min, finally the sample is taken out and washed by deionized water and dried for 12h at 70 ℃, and the Zn nano-sheet with controllable load along with time can be obtained to directly grow on the carbon fiber cloth substrate (Zn/CTs) and can be directly used as Zn-MnO2The negative electrode of the cell.
The processing steps of the flexible carbon fiber Cloth (CTs) are as follows: carbon fiber Cloth (CTs) substrates were soaked in concentrated nitric acid (70%) for 24h at room temperature to increase their hydrophilicity, the resulting CTs were rinsed with distilled water until pH ≈ 7.0, and finally air-dried in an oven at 70 ℃ for 5 h.
The Zn-MnO2The battery shell is made of, but not limited to, PVC plastic film, and may be made of other flexible or malleable insulating film materials, such as PE packaging film, parafilm sealing film, etc.
The Zn-MnO2The battery is mainly used for testing specific capacity, electrochemical stability, rate capability, energy density, flexible application display and the like.
Said Zn-MnO2The cell may have a sheet-like or ribbon-like structure, and includes, in an outer package, an electrolyte layer and positive and negative electrode layers disposed above and below the electrolyte, respectively, the cell having a length of 5.0 cm,the width is 2.0 cm, and the thickness is 0.30 cm.
The spacing layers of the positive electrode and the negative electrode are PVA/ZnSO4+MnSO4A hydrogel polymer electrolyte.
Said Zn being contained2+The PVA hydrogel is polyvinyl alcohol/zinc sulfate + manganese sulfate (PVA/ZnSO)4+MnSO4) The gel electrolyte is prepared by the following steps: dispersing 6 g of PVA powder in 30 ml of deionized water, and stirring for 2 hours at 85-95 ℃ to dissolve the PVA powder into transparent gel; meanwhile, 9.66 g of ZnSO4And 0.453 g MnSO4Dissolving in 30 ml deionized water; subsequently adding ZnSO4And MnSO4The uniformly mixed solution was added to the PVA hydrogel and stirred for 30min.
The quasi-solid Zn-MnO2The battery is of a sheet-shaped or strip-shaped structure, and the shell comprises an electrolyte layer, and a positive electrode layer and a negative electrode layer which are respectively arranged above and below the electrolyte.
Quasi-solid state flexible Zn-MnO2The specific manufacturing steps of the battery are as follows:
(1) Quasi-solid state flexible Zn-MnO2The preparation process of the positive electrode and the negative electrode of the battery comprises the following steps: direct growth of electrochemically active nanostructure array materials, e.g. alpha-MnO, on treated carbon fiber Sheets (CTs) by hydrothermal or electrodeposition methods2/δ-MnO2The nano composite array and the Zn nanosheet array materials are respectively used as Zn-MnO2Positive and negative electrodes of the battery;
(2) Quasi-solid state flexible Zn-MnO2The blending process of the battery electrolyte comprises the following steps: znSO is added4And MnSO4Adding the uniformly mixed solution into the dissolved PVA hydrogel liquid, and continuously stirring for 30min to obtain uniform hydrogel-like slurry;
(3) Formation of quasi-solid state flexible Zn-MnO2The self-supporting positive and negative electrode active materials in the above process are partially immersed in Zn-containing solution2+Taking out the PVA hydrogel solution, standing the PVA hydrogel solution at room temperature for one night, attaching and assembling the positive electrode and the negative electrode after partial electrolyte is solidified, and standing the PVA hydrogel solution for a period of time to obtain the bendable quasi-solid flexible Zn-MnO2A battery.
The electrochemical reaction mechanism of the invention is shown as the following formula:
negative electrode:
xZn ↔ xZn2+ + 2xe-
and (3) positive electrode:
MnO2 + xZn2+ + 2xe- ↔ MnOOZnx(surface)
MnO2 + xZn2+ + 2xe- ↔ ZnxMnO2(inner layer)
The general reaction formula is as follows:
xZn + MnO2 ↔ MnOOZnx(surface)
xZn + MnO2 ↔ ZnxMnO2(inner layer)
The invention has the beneficial effects that: the rechargeable battery of the present invention utilizes zinc ion (Zn)2+) Reversible insertion or extraction in the crystal lattice of the anode material, and oxidation or zinc ion (Zn) of the cathode material mainly containing zinc element2+) The energy storage mechanism of reduction on the surface of the negative electrode and the special electrolyte are adopted, and the battery has the characteristics of high capacity and quick charging.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 shows the procedure of example 1, wherein (a-c) alpha-MnO growth on a carbon fiber cloth substrate by hydrothermal method2Microscopic scanning electron microscope images of the nanowire arrays; (d-f) in alpha-MnO by electrodeposition2Growth of delta-MnO on CTs2Nanosheets (i.e., zn-MnO)2Battery cathode material).
FIG. 2 shows the current density at 5.0 mA cm during the procedure of example 1-2Electrodepositing alpha-MnO obtained from (a) 30 s, (b) 60 s, (c) 90 s, and (d) 120 s2/δ-MnO2Microscopic scanning electron microscope image of the nanocomposite array material.
FIG. 3 shows the results obtained during the steps carried out in example 1, (a-c) growth of an array of Zn nanoplates (i.e., zn-MnO) on a carbon fiber cloth substrate by an electrodeposition method2Battery negative electrode material) under a microscope; (d) Zn-MnO2An X-ray diffraction pattern of a battery negative electrode material.
FIG. 4 shows the quasi-solid state flexible Zn-MnO finally obtained in example 12The battery comprises (a) a device schematic diagram and (b-d) an electrochemical performance test.
FIG. 5 shows quasi-solid state flexible Zn-MnO finally obtained in example 12The battery, (a) tests the electrochemical performance under different bending states and displays the physical diagram; (b, c) flexible application display.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below with reference to embodiments of the present invention, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art based on the embodiments of the present invention without inventive step, are within the scope of the present invention.
Example 1
Rechargeable high-performance quasi-solid flexible Zn-MnO2The preparation method of the battery comprises the following steps:
(1) Pretreatment of flexible carbon fiber fabrics (CTs)
Soaking a carbon fiber Cloth (CTs) substrate in concentrated nitric acid (70%) at room temperature for 24 hours to improve the hydrophilicity, then washing the obtained CTs with distilled water until the pH value is approximately equal to 7.0, and finally drying the CTs in an oven at 70 ℃ for 5 hours in an air way;
(2) Self-supporting alpha-MnO2@δ-MnO2Preparation of/CTs Positive electrodes
First, alpha-MnO is introduced by a hydrothermal method2The nanowire array is directly grown on the processed CTs, and the specific steps are as follows: will be pre-treatedThe carbon fiber cloth was immersed in 40 mL of 0.03M potassium permanganate (KMnO)4) In the water solution, sealing the reaction kettle, putting the reaction kettle into a drying oven for keeping the temperature of 160 ℃ for 4h, taking out a sample, washing the sample with deionized water, and drying the sample at 70 ℃ for 6h to obtain alpha-MnO2Nanowire arrays grown on CTs surfaces (alpha-MnO)2/CTs) as shown in FIGS. 1 a-c;
then, electrodeposition is carried out on the alpha-MnO2Nanowire array surface coating interconnected delta-MnO2The nano-sheet comprises the following specific steps: alpha-MnO obtained in the step (1)2the/CTs are used as working electrodes, graphite rods and Saturated Calomel Electrodes (SCE) are respectively used as counter electrodes and reference electrodes, and the three electrodes are immersed in MnSO4And CH3COONa in a mixed aqueous solution (concentration: 50 mM) at a current density of 5.0 mA cm-2The electrodeposition time was 30 s, 60 s, 90 s and 120 s, and then the samples obtained by electrodeposition were dried at 70 ℃ for 12 hours;
finally, annealing treatment is carried out by a CVD furnace, thus obtaining the alpha-MnO2@δ-MnO2The CTs nano composite array material comprises the following specific steps: putting the sample obtained in the step (2) into an annealing furnace to anneal for 2h at 450 ℃ in argon gas to obtain alpha-MnO2/δ-MnO2The nano composite array material is loaded on a carbon fiber cloth substrate (alpha-MnO)2@δ-MnO2/CTs), electrodepositing 90 s to obtain alpha-MnO2/δ-MnO2The morphology characterization graphs of the nanocomposite array material samples are shown in figures 1d-f and 2c, and can be directly used as Zn-MnO2The positive electrode of the battery. It is noted that FIGS. 2a-d show α -MnO obtained at electrodeposition times of 30 s, 60 s, 90 s and 120 s, respectively2/δ-MnO2The appearance of the nano composite array material sample is characterized, and alpha-MnO can be observed from the graph along with the increase of the time of electrodeposition2Surface coating delta-MnO of nanowire array2The thicker the thickness of the nanosheet.
(3) Preparation of self-supporting Zn/CTs negative electrode
The pretreated carbon fiber cloth and the foil are respectively used as a working electrode and a reference electrode, and the electrolyte solution is ZnSO4·7H2O, Na2SO4And H3BO3The mixed solution of (4) (40 mL, concentrations of 0.52,1.06 and 0.40M, respectively), then at 10 mA cm-2The current density is kept for 30min, finally the sample is taken out and washed by deionized water and dried for 12h at 70 ℃, and the Zn nano-sheet with controllable load along with time can be obtained to directly grow on the carbon fiber cloth substrate (Zn/CTs) and can be directly used as Zn-MnO2The negative electrode of the cell, the topography of which is shown in FIGS. 3 a-c; in addition, fig. 3d shows XRD patterns of Zn/CTs, from which the peak positions corresponding to Zn can indicate that Zn nanoplatelets are deposited on the carbon fiber cloth substrate.
(4) PVA/ZnSO4+MnSO4Preparation of hydrogel electrolyte
ZnSO is added4、MnSO4Mixing with PVA in a certain proportion, dissolving in deionized water, heating and stirring to obtain the product, which comprises the following steps: dispersing 6 g of PVA powder in 30 ml of deionized water, and stirring for 2 hours at 85-95 ℃ to dissolve the PVA powder into transparent gel; meanwhile, 9.66 g of ZnSO4And 0.453 g MnSO4Dissolving in 30 ml deionized water; subsequently, znSO is added4And MnSO4The uniformly mixed solution was added to the PVA hydrogel and stirred for 30min.
(5) Quasi-solid state flexible Zn-MnO2Battery assembly technique
Adding Zn-MnO2Placing the positive and negative electrodes (containing active material) into the grooves, and dripping appropriate amount of PVA/ZnSO onto the electrodes4+MnSO4Hydrogel electrolyte, then standing overnight at room temperature to partially solidify it, and assembling the partial electrodes containing active material into complete Zn-MnO2A battery.
The schematic diagram of the cell structure is shown in FIG. 3 (a), in which PVA/ZnSO4+MnSO4The hydrogel electrolyte functions as both an electrolyte and an electrode separator. Finally, PVC plastic is used to form quasi-solid Zn-MnO with high flexibility and mechanical firmness2The cells were packaged and further tested for electrochemical performance and flexible application display. Wherein FIGS. 3b, 3c and 3d show respectivelyIs quasi-solid Zn-MnO2CV curve, charge-discharge curve and long cycle performance of the battery; FIG. 4a shows a quasi-solid Zn-MnO2CV curve performance test of the battery under different bending states and corresponding practical graphs under the corresponding bending states, and FIGS. 4b and 4c are quasi-solid Zn-MnO2Energy storage applications (lighting LED lights and driving electric motors, etc.) of the batteries are demonstrated.
Example 2
Rechargeable high-performance quasi-solid flexible Zn-MnO2Battery and preparation method
(1) Pretreatment of flexible carbon fiber fabrics (CTs)
Carbon fiber Cloth (CTs) substrates were soaked in concentrated nitric acid (70%) at room temperature for 24h to increase their hydrophilicity, the resulting CTs were rinsed with distilled water to pH 7.0, and finally air dried in an oven at 70 ℃ for 5 h.
(2) Self-supporting alpha-MnO2@δ-MnO2Preparation of/CTs Positive electrodes
First, alpha-MnO is introduced by a hydrothermal method2The nanowire array is directly grown on the processed CTs, and the specific steps are as follows: the pretreated carbon fiber cloth was immersed in 40 mL of 0.04M potassium permanganate (KMnO)4) In the water solution, sealing the reaction kettle, putting the reaction kettle into a drying oven to keep the temperature at 170 ℃ for 3 hours, taking out a sample, washing the sample with deionized water, and drying the sample at 70 ℃ for 6 hours to obtain alpha-MnO2Nanowire arrays grown on CTs surfaces (alpha-MnO)2/CTs）；
Then, electrodeposition is carried out on the alpha-MnO2Nanowire array surface coating interconnected delta-MnO2The nano-sheet comprises the following specific steps: alpha-MnO obtained in the step (1)2the/CTs are used as working electrodes, graphite rods and Saturated Calomel Electrodes (SCE) are respectively used as counter electrodes and reference electrodes, and the three electrodes are immersed into MnSO4And CH3COONa in a mixed aqueous solution (concentration: 55 mM) at a current density of 5.5 mA cm-2Electrodepositing for 30 s, and drying the sample obtained by electrodeposition at 70 ℃ for 12h;
finally, annealing treatment is carried out by a CVD furnace, thus obtaining the alpha-MnO2@δ-MnO2The CTs nano composite array material comprises the following specific steps: putting the sample obtained in the step (2) into an annealing furnace to anneal for 2h at 475 ℃ in argon gas to obtain alpha-MnO2/δ-MnO2The nano composite array material is loaded on a carbon fiber cloth substrate (alpha-MnO)2@δ-MnO2/CTs), alpha-MnO from 30 s of electrodeposition2/δ-MnO2The morphology of the nanocomposite matrix material sample is characterized as shown in FIG. 2 a.
(3) Preparation of self-supporting Zn/CTs negative electrode
The pretreated carbon fiber cloth and the foil are respectively used as a working electrode and a reference electrode, and the electrolyte solution is ZnSO4·7H2O, Na2SO4And H3BO3The mixed solution of (4) (40 mL, concentrations of 0.55,1.10 and 0.45M, respectively), then at 10 mA cm-2The current density is kept for 30min, finally, the sample is taken out and washed by deionized water and dried for 12h at 70 ℃, so that the Zn nano-sheet with the controllable loading capacity along with time can be obtained and directly grows on the carbon fiber cloth substrate (Zn/CTs), and can be directly used as Zn-MnO2The negative electrode of the cell.
(4) PVA/ZnSO4+MnSO4Preparation of hydrogel electrolyte
ZnSO is added4、MnSO4Mixing with PVA in a certain proportion, dissolving in deionized water, heating and stirring to obtain the product, which comprises the following steps: 6.2 Dispersing PVA powder in 30 ml of deionized water, and stirring for 2 hours at 85-95 ℃ to dissolve the PVA powder into transparent gel; meanwhile, 9.8 g of ZnSO4And 0.46 g MnSO4Dissolving in 30 ml deionized water; subsequently, znSO is added4And MnSO4The uniformly mixed solution was added to the PVA hydrogel and stirred for 30min.
(5) Quasi-solid state flexible Zn-MnO2Battery assembly technique
Adding Zn-MnO2The positive and negative electrodes (containing active material) are put in the groove, and proper amount of PVA/ZnSO is dropped on the electrode4+MnSO4Hydrogel electrolyte, then standing overnight at room temperature to partially quasi-solidify it, and then adding active materialPartial electrodes are assembled face to form complete Zn-MnO2Cell, in which PVA/ZnSO4+MnSO4The hydrogel electrolyte functions as both an electrolyte and an electrode separator. Finally, PVC plastics are used to provide highly flexible, mechanically strong quasi-solid Zn-MnO2The battery is packaged, and further tested for electrochemical performance and flexible application display, electrochemical performance test and flexible application display.
Example 3
Rechargeable high-performance quasi-solid flexible Zn-MnO2Battery and preparation method
(1) Pretreatment of flexible carbon fiber fabrics (CTs)
Carbon fiber Cloth (CTs) substrates were soaked in concentrated nitric acid (70%) at room temperature for 24h to increase their hydrophilicity, the resulting CTs were rinsed with distilled water to pH 7.0, and finally air dried in an oven at 70 ℃ for 5 h.
(2) Self-supporting alpha-MnO2@δ-MnO2Preparation of/CTs Positive electrodes
First, alpha-MnO is introduced by a hydrothermal method2The nanowire array is directly grown on the processed CTs, and the specific steps are as follows: the pretreated carbon fiber cloth was immersed in 40 mL of 0.02M potassium permanganate (KMnO)4) In the water solution, sealing the reaction kettle, putting the reaction kettle into a drying oven to keep the temperature at 150 ℃ for 5 h, taking out a sample, washing the sample with deionized water, and drying the sample at 70 ℃ for 6h to obtain alpha-MnO2Nanowire arrays grown on CTs surfaces (alpha-MnO)2/CTs）；
Then, using electrodeposition method to deposit on alpha-MnO2Nanowire array surface coating interconnected delta-MnO2The nano-sheet comprises the following specific steps: the alpha-MnO obtained in the step (1)2the/CTs are used as working electrodes, graphite rods and Saturated Calomel Electrodes (SCE) are respectively used as counter electrodes and reference electrodes, and the three electrodes are immersed in MnSO4And CH3COONa in a mixed aqueous solution (concentration: 45 mM) at a current density of 4.5 mA cm-2Performing electrodeposition for 120 s, and drying the electrodeposited sample at 70 ℃ for 12h;
finally, annealing treatment is carried out by a CVD furnaceObtaining alpha-MnO2@δ-MnO2The CTs nano composite array material comprises the following specific steps: putting the sample obtained in the step (2) into an annealing furnace to anneal for 3 hours at 425 ℃ in argon to obtain alpha-MnO2/δ-MnO2The nano composite array material is loaded on a carbon fiber cloth substrate (alpha-MnO)2@δ-MnO2/CTs), electrodepositing 120 s to obtain alpha-MnO2/δ-MnO2The morphology of the nanocomposite matrix material sample is characterized as shown in figure 2 d.
(3) Preparation of self-supporting Zn/CTs negative electrode
The pretreated carbon fiber cloth and the foil are respectively used as a working electrode and a reference electrode, and the electrolyte solution is ZnSO4·7H2O, Na2SO4And H3BO3The mixed solution of (4) (40 mL, concentrations of 0.55,1.10 and 0.45M, respectively), then at 10 mA cm-2The current density is kept for 30min, finally the sample is taken out and washed by deionized water and dried for 12h at 70 ℃, and the Zn nano-sheet with controllable load along with time can be obtained to directly grow on the carbon fiber cloth substrate (Zn/CTs) and can be directly used as Zn-MnO2The negative electrode of the battery.
(4) PVA/ZnSO4+MnSO4Preparation of hydrogel electrolyte
ZnSO is added4、MnSO4Mixing with PVA in a certain proportion, dissolving in deionized water, heating and stirring to obtain the product, which comprises the following steps: 6.2 Dispersing PVA powder in 30 ml of deionized water, and stirring for 2 hours at 85-95 ℃ to dissolve the PVA powder into transparent gel; at the same time, 9.8 g of ZnSO4And 0.46 g MnSO4Dissolving in 30 ml deionized water; subsequently, znSO is added4And MnSO4The uniformly mixed solution was added to the PVA hydrogel and stirred for 30min.
(5) Quasi-solid state flexible Zn-MnO2Battery assembly technique
By reacting Zn with MnO2The positive and negative electrodes (containing active material) are put in the groove, and proper amount of PVA/ZnSO is dropped on the electrode4+MnSO4Hydrogel electrolyte, and then placing the electrolyte in a room temperature environmentPartially allowed to partially solidify and then partially electrode-face-to-face with active material to form a complete Zn-MnO2Cell of PVA/ZnSO4+MnSO4The hydrogel electrolyte functions as both an electrolyte and an electrode separator. Finally, PVC plastics are used to provide highly flexible, mechanically strong quasi-solid Zn-MnO2The cells were packaged and further tested for electrochemical performance and flexible application display, electrochemical performance testing and flexible application display.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the scope of the present invention, which is intended to cover any modifications, equivalents, improvements, etc. within the spirit and scope of the present invention.

Claims (8)

1. Quasi-solid flexible Zn-MnO2The preparation method of the battery is characterized in that: the quasi-solid Zn-MnO2The battery is prepared into alpha-MnO by adopting a method combining hydrothermal and electrodeposition2/δ-MnO2A Zn nanosheet material is directly grown on the flexible carbon fiber cloth by a one-step electrodeposition method to serve as a negative electrode;
the specific preparation steps of the positive electrode are as follows:
(1) Hydrothermal method: immersing the pretreated carbon fiber cloth into a potassium permanganate aqueous solution, then carrying out sealing reaction, taking out a sample, washing and drying to obtain alpha-MnO2/CTs；
(2) The electrodeposition method comprises the following steps: the alpha-MnO obtained in the step (1)2the/CTs are used as working electrodes, graphite rods and saturated calomel electrodes are used as counter electrodes and reference electrodes respectively, and the three electrodes are immersed in MnSO4And CH3In the mixed aqueous solution of COONa, electrodepositing to obtain a sample, and drying;
(3) Annealing treatment in a CVD furnace: annealing the sample obtained in the step (2) in an annealing furnace to obtain alpha-MnO2@δ-MnO2/CTs；
The concentration of the potassium permanganate aqueous solution in the step (1) is 0.02-0.04M;
m in the step (2)nSO4And CH3The concentration of COONa is 45-55 mM;
the quasi-solid Zn-MnO2The battery can contain Zn2+The PVA hydrogel is a matrix material of a battery diaphragm and an electrolyte, and the two self-supporting flexible electrodes are assembled into quasi-solid Zn-MnO by using flexible carbon fiber cloth as a self-supporting current collector and a load of the electrodes2A battery.
2. The method of claim 1, wherein: in the step (1), the sealing reaction temperature is 150-170 ℃, and the time is 3-5 h.
3. The production method according to claim 1, characterized in that: the electro-deposition current density in the step (2) is 4.5-5.5 mA cm-2The electrodeposition time is 30-120 s.
4. The production method according to claim 1, characterized in that: the annealing temperature in the step (3) is 425-475 ℃, and the time is 2-3 h.
5. The method according to claim 1, wherein the negative electrode is prepared by the steps of: the pretreated carbon fiber cloth and the foil are respectively used as a working electrode and a reference electrode, and the electrolyte solution is ZnSO4·7H2O、Na2SO4And H3BO3Then at 10 mA cm-2The current density is kept for 30min, and finally the sample is taken out and washed by deionized water and dried for 12h at the temperature of 70 ℃, so that the cathode material Zn/CTs can be obtained.
6. The production method according to claim 1 or 5, wherein the pre-treated carbon fiber cloth is treated by the following steps: and (2) soaking the carbon fiber cloth substrate in concentrated nitric acid at room temperature for 24h, washing the obtained CTs with distilled water until the pH value is approximately equal to 7.0, and finally drying in an oven at 70 ℃ for 5 h.
7. Root of herbaceous plantsThe method according to claim 1, wherein the Zn is contained2+The preparation steps of the PVA hydrogel are as follows: dispersing PVA powder in deionized water and stirring to obtain transparent gel; znSO is added4And MnSO4Adding the uniform mixed solution into PVA transparent gel, stirring to obtain the Zn-containing solution2+The PVA hydrogel of (1).
8. Quasi-solid Zn-MnO prepared by the method of any one of claims 1 to 52A battery, characterized in that: the quasi-solid Zn-MnO2The battery is in a sheet-shaped or strip-shaped structure and is applied to wearable equipment.
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