CN100492726C - Manganese dioxide nanotube and nanowire electrode material, and preparation method and application thereof - Google Patents
Manganese dioxide nanotube and nanowire electrode material, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to gamma-MnO 2 Nanotube/nanowire electrode materials, methods of making and uses thereof. The manganese dioxide nano-tube/nano-wire composite material comprises a manganese dioxide nano-tube and a manganese dioxide nano-wire, wherein the content of the nano-tube is 40-50%, the length of a single nano-tube/nano-wire is 2-4 mu m, and the diameter is 75-85nm. The electrode material has larger specific surface area, can increase the contact between an active substance and electrodes, reduce the internal resistance of the battery, and improve the diffusion performance of protons, and has higher electrochemical capacity and good high-power and high-rate discharge performance when being used as an anode active substance of the battery and an alkaline zinc-manganese battery formed by taking electrolytic zinc particles as a cathode active substance.
Description
Technical Field
The invention relates to preparation of a nano material, in particular to a manganese dioxide nanotube and nanowire electrode material, a preparation method and application thereof. In particular, it is gamma-MnO 2 The nanotube and nanowire electrode material have larger specific surface area, can increase the contact between an active substance and the electrode, reduce the internal resistance of the battery, and improve the diffusion performance of protons, thereby improving the utilization rate of the active substance. gamma-MnO of 2-4 μm length and 75-85nm diameter 2 The alkaline zinc-manganese dioxide battery which is formed by the nanotube and the nanowire as the anode active material of the zinc-manganese dioxide battery and the cathode active material of 300-500nm electrolytic zinc particles has higher electrochemical capacity and good high-power and high-rate discharge performance.
Background
With the rapid development and the increasing popularization of small portable electronic products, the demand of the society for battery products is rapidly increased, wherein the alkaline zinc-manganese battery is popular with consumers due to higher cost performance and good electrochemical performance, gradually dominates the civil battery, is widely used on radios, recorders, full-automatic cameras, electronic instruments and electric toys, and becomes a battery which is most widely applied in primary batteries at present and has the largest output and output value.
How to improve the discharge performance of the battery and meet the market requirements is in front of a plurality of battery workers. Therefore, the production process, the battery structure, the positive and negative electrode compositions and other aspects of the battery are continuously explored at home and abroad. Among them, the utilization rate and electrochemical performance of the electrode material in the battery significantly affect the overall performance of the battery, and therefore, research and development on the performance of the manganese dioxide electrode material have become the focus of attention in recent years. For example, chinese patent CN1123584A, published 5/29/1996, discloses that adding 0.1-5wt% of anatase titanium dioxide to a conventional manganese dioxide positive electrode results in about 5% improvement in the useful life in an LR6 alkaline zinc-manganese battery test. Chinese patent CN1357934A, published in 2002, 7, 10, discloses a method of adding 0.1-5wt% of at least one of oxides of vanadium, niobium, tantalum, and titanium to a conventional manganese dioxide positive electrode, wherein the high-rate discharge time is prolonged by 5-10% compared with that of a common alkaline zinc-manganese battery.
In recent years, with the continuous development of nanotechnology, nano manganese dioxide has attracted attention of many researchers as a novel and efficient battery material. Chinese patent CN1513767A discloses a method for preparing ultrafine manganese dioxide, which comprises adding surfactant (ethanol or ethylene glycol) into soluble manganese salt to form micro-emulsion droplets, adding alkali to generate manganese hydroxide, oxidizing, dehydrating, and calcining to obtain ultrafine manganese dioxide powder. The particle diameter of manganese dioxide particles is about 50 nanometers, and the specific surface area is 100m 2 More than g, the hydrogen absorption effect of manganese dioxide in the zinc-manganese battery can be improved, thereby improving the capacity and the service life of the battery.
Of the four crystal forms alpha-, beta-, gamma-and delta-in the presence of manganese dioxide, gamma-MnO 2 Due to the special double-chain structure, the zinc-manganese dioxide battery has high reaction activity and slow voltage attenuation in the discharging process, and is widely used as a positive electrode material of the zinc-manganese dioxide battery. Recently, gamma-MnO 2 The nano-rod and the nano-wire of (1) have been successfully synthesized [ Xunwang, yadongLi, synthesisFormation Mechanism of Manganese Dioxide Nanowires/Nanorods，Chem.Eur.J.2003，9， 300-306.；Yujie Xiong，Yi Xie，et al.，Growth of Well-Aligned γ-MnO 2 Monocrystalline Nanowires through a Coordination-Polymer-Precursor Route，Chem.Eur.J.2003，9， 1645-1651.]But with respect to gamma-MnO 2 The preparation of the nanotube and the research on the electrochemical performance are not reported at home and abroad. Compared with Electrolytic Manganese Dioxide (EMD), the nano manganese dioxide has small particle size and large specific surface area, can increase the contact between active substances and electrodes, reduce the internal resistance of the battery and improve the diffusion performance of protons, thereby effectively improving the utilization rate and the electrochemical activity of the battery. In particular, the unique microstructure of nanotubes, and the unusual characteristics resulting therefrom, would show potential applications in electrochemical performance. Thus: exploration of gamma-MnO 2 Preparation method of nanotube and for one-dimensional gamma-MnO 2 The research on the electrochemical properties of the nano material has very important significance for improving the comprehensive performance of the alkaline zinc-manganese dioxide battery. In addition, in order to further improve the discharge performance of the battery, it is also important that the cathode of the battery adopts high-specific surface area and high-purity electrolytic nano zinc particles.
Disclosure of Invention
The invention aims to provide a manganese dioxide nanotube and nanowire electrode material and a preparation method thereof. In particular, the gamma-MnO 2 The nanotube and the nano wire electrode material have larger specific surface area, can increase the contact between the active substance and the electrode, reduce the internal resistance of the battery, and improve the diffusion performance of protons, thereby improving the utilization rate of the active substance.
Another purpose of the invention is to provide gamma-MnO adopting manganese dioxide nanotubes and nanowire electrode material 2 The alkaline zinc-manganese dioxide battery which is composed of the nanotube and the nanowire as the anode active material of the battery and the electrolytic zinc particles as the cathode active material has higher electrochemical capacity and good high-power and high-rate discharge performance.
The manganese dioxide nanotube and nano wire electrode material consists of gamma-MnO 2 Nanotubes and nanotubesThe nano-wire consists of 40-50% of nano-tubes, the length of each single nano-tube and each nano-wire is 2-4 μm, and the diameter of each single nano-tube and each nano-wire is 75-85nm.
The gamma-MnO 2 The preparation method of the nanotube and the nanowire comprises the steps of reacting soluble manganese salt with alkali in a methanol solution of a surfactant, oxidizing and dehydrating the reaction product, and performing the following steps of:
1) Soluble manganese salt (MnSO) is added at room temperature 4 ，MnCl 2 ，MnAc 2 Etc.) the solution is added into the methanol solution of the surfactant, stirred for 2 hours at the rotating speed of 100r/min to form micro-emulsion droplets, and then added with alkali (KOH) solution to be mixed evenly;
2) Reacting in a high-pressure reaction kettle at 100-140 deg.C (preferably 120 deg.C), crystallizing for 10-20 hr;
3) After the reaction is finished, cooling to room temperature, washing for 3-5 times by using water and absolute ethyl alcohol respectively, and drying for 2-4 hours in vacuum at the temperature of 60-80 ℃ to obtain gamma-MnO 2 Nanotubes and nanowires.
The molar ratio of the reaction is soluble manganese salt: surfactant (b): base =1:1:1.
the invention provides an alkaline zinc-manganese dioxide battery, comprising: manganese dioxide positive pole, diaphragm, alkaline electrolyte and battery container, characterized by: the manganese dioxide positive electrode comprises an electrode material, and the electrode material comprises gamma-MnO 2 The nano-tube, the nano-wire and the activated carbon, wherein the zinc cathode comprises an electrode material, and the electrode material comprises nano-zinc particles, znO and PTFE. The gamma-MnO 2 Nanotube and nanowire, wherein the content of the nanotube is 40-50%, and single nanotubeThe length of the nano wire is 2-4 mu m, and the diameter is 75-85nm.
The invention provides an alkaline zinc-manganese dioxide battery which is a cylindrical AA (LR 6) battery, and the anode material of the battery comprises: 85% (all by mass) of gamma-MnO 2 Nanotube/nanowire, 8% activated carbon and 7% electrolyte (containing 40% KOH); the anode material includes: 65% of electrolytic nano zinc particles and 31% of electricityThe electrolyte solution (containing 40% of KOH), 3% of ZnO and 1% of PTFE.
The electrolytic nano zinc particles used as the negative active material adopt a constant current method (the current density is 100 mA/cm) at 50 DEG C 2 ) Electrodepositing in alkali liquor to obtain (C.C.Yang, S.J.Lin, J.PowerSources2002, 112, 174-183.), wherein the nano zinc is a spindle-shaped structure consisting of 300-500nm particles and is accompanied with a small amount of dendritic structures.
The alkaline zinc-manganese battery of the present invention is a cylindrical AA-type battery (i.e., LR 6-type) having a diameter and a height of 14mm and 50mm, respectively, and a weight and a volume of 24g and 7.5cm, respectively -3 。
The battery is manufactured by the conventional method: to convert gamma-MnO 2 Mixing the anode materials such as the nano tube/the nano wire and the like, granulating, pressing a ring, loading into a steel shell, coating a sealant, then inserting a diaphragm, adding an electrolyte and a cathode zinc paste, then inserting a cathode current collector assembly, welding a cathode terminal, rolling the wire, curling the edge, and welding the anode terminal to obtain the finished product of the alkaline zinc-manganese dioxide battery. The anode material comprises 85% (by mass) of gamma-MnO 2 Nanotube/nanowire, 8% activated carbon and 7% electrolyte (40% KOH); the negative electrode material comprises a mixture of 65% of electrolytic nano zinc particles, 31% of electrolyte (40% of KOH), 3% of ZnO and 1% of PTFE. Electrochemical testing was performed on a potentiometric instrument model SI1260 from Solartron corporation, UK, a 1287 electrochemical interface Meter, and an Arbin (2001-T) charging and discharging system in the United states.
The invention provides high-performance gamma-MnO 2 Nanotube/nanowire positive electrode materials. Due to gamma-MnO 2 The nano tube/nano wire has larger specific surface area, can effectively increase the contact between the active substance and the electrode, reduce the internal resistance of the battery, improve the diffusion performance of protons and the exchange of water in the reaction process, thereby obviously improving the utilization rate of the active substance; particularly, the open and hollow structure of the nanotube enables the proton diffusion process in the electrode reaction to be easier to carry out and faster, thereby improving the high-power and high-rate discharge performance of the manganese dioxide electrode; electrolytic nano zincThe particles have the characteristics of high purity and large surface area, can ensure that solid and liquid phases are distributed more uniformly, effectively reduces the passivation and corrosion of zinc, and greatly improves the utilization rate of the zinc.
The invention has the advantages of adopting gamma-MnO 2 The nano tube/nano wire and electrolytic zinc are used as the anode and the cathode of the battery, so that the energy density, the electrochemical capacity, the high-power and high-rate discharge performance of the alkaline zinc-manganese battery can be effectively improved, and the method has important theoretical and practical significance for improving the performance of the alkaline zinc-manganese battery. The battery has wide application prospect as an alkaline zinc-manganese battery with high capacity, high power and excellent high-rate discharge performance.
Drawings
FIG. 1 Gamma-MnO obtained in example 1 of the present invention 2 Nanotube/nanowire (a) X-ray powder diffraction Pattern (b) [ MnO w ]Octahedron (c) [ 1X 1 ]]And [ 1X 2 ]]And (5) tunnel structure schematic.
FIG. 2 is a gamma-MnO prepared according to example 1 2 Electron microscopy images of nanotubes/nanowires; (a) Low-magnification scanning electron microscopy analysis (b) high-magnification scanning electron microscopy analysis (c) transmission electron microscopy analysis (d) high-resolution transmission electron microscopy analysis.
Fig. 3 is a schematic of (a) X-ray powder diffraction pattern of the electrolytic nano zinc particles and (b) spatial structure.
Fig. 4 is a scanning electron microscope analysis of the electrolytic nano zinc particles.
Fig. 5 shows a process for manufacturing an LR6 type alkaline zinc-manganese dioxide cell.
Fig. 6 is a cross-sectional view of an LR6 high power alkaline zinc-manganese dioxide cell made in accordance with example 5.
Fig. 7 is a discharge curve of LR6 high power alkaline zinc manganese dioxide battery made in example 5 at different currents.
Fig. 8 is a discharge curve of LR6 high power alkaline zinc manganese dioxide battery made in example 5 at different resistances.
Fig. 9 shows the discharge curves of LR6 high power alkaline zn-mn batteries fabricated according to example 5 at different powers.
Fig. 10 is a resistance analysis during discharge of LR6 high power alkaline zinc-manganese dioxide cell made according to example 5.
Fig. 11 is a discharge curve at 20 ℃ for three AA-type batteries: (a) an LR6 high power alkaline zinc-manganese battery of the invention; (b) Gamma-MnO of the present invention 2 Alkaline zinc-manganese dioxide cell assembled by nano tube/nano wire and molten zinc; (c) A commercially available alkaline zinc-manganese cell of the LR6 type (DuracellMN 1600, 2005).
Fig. 12 is an SEM image of molten zinc.
Detailed Description
Example 1: gamma-MnO 2 Preparation of nanotubes/nanowires
At room temperature, adding MnSO 4 Dropwise adding the solution (100mL, 1M) into the methanol solution (100mL, 1M), then adding the NaOH solution (100mL, 1M), uniformly mixing, transferring into a 1L stainless steel high-pressure reaction kettle, reacting at 120 ℃ for 20 hours, cooling to room temperature after the reaction is finished, washing with distilled water and absolute ethyl alcohol for multiple times, and vacuum drying at 60 ℃ for 4 hours to obtain gamma-MnO 2 Nanotube/nanowire. Formation of gamma-MnO 2 The chemical reaction involved in the nanotube/nanowire is as follows:
[(MnSO 4 )(H 2 O)]+O 2 +OH - →γ-MnO 2
example 2:
Gamma-MnO prepared as described in example 1 2 The XRD spectrum of the nanotube/nanowire is shown in fig. 1 a. Calculating the unit cell parameter of a =6.366 according to the position and the intensity of the characteristic peak in the spectrogram
，b＝10.15，c＝4.089Belonging to orthorhombic system, the intensity and position of diffraction peak thereof and JCPDS standard card (No. 14-0644, a = 6.36)，b＝10.15，c＝4.09 ) Are matched and have no hetero-phase diffraction peak, which indicates that the gamma-MnO with higher purity is obtained 2 . The broadening of the diffraction peak is caused by the fact that the product is in the nanometer level and the crystal grains are extremely fine.
MnO 2 The basic structural unit of is [ MnO ] 6 ]Octahedron (FIG. 1 b), in gamma-MnO 2 Middle [ MnO ] 6 ]The octahedron is connected with adjacent octahedron by edge or vertex angle to form unique double-chain and single-chain intergrowth structure, i.e., [ 1X 1 ]]And [ 1X 2 ]]Tunnel structure (fig. 1 c). Gamma-MnO 2 Because of containing double chain structure, the cross section area is large, ion diffusion is easy, so the overpotential is small, the reaction activity is high, and the electrode material is widely used.
Example 3:
Gamma-MnO prepared as described in example 1 2 Scanning electron microscopy analysis of nanotubes/nanowires (fig. 2 a) shows: the product is the aggregate of nanotube and nanowire, the ratio of nanotube to nanowire is about 40% and 60%, the length of single nanotube or nanowire is 2-4 μm, the diameter is 75-85nm, and further magnified SEM analysis can observe the nanotubeOpen tubular structure, tube wall thickness about 20nm (fig. 2 b). TEM analysis (fig. 2 c) further confirmed that the product was an aggregate of nanowires and nanotubes. Single gamma-MnO 2 HRTEM analysis of nanowires (fig. 2 d) showed: the product has good degree of crystallization and uniform stripe width, and the interlayer spacing is about 0.213nm, which is consistent with gamma-MnO 2 The (002) surface spacing is consistent.
Example 4:
the negative active material is electrolytic zinc prepared by a constant current method, and XRD analysis (figure 3 a) shows that: the intensity and position of the characteristic peak of the product are consistent with the data of JCPDS standard card (No. 04-0831), and the product has a hexagonal close-packed structure (figure 3 b) and no hetero-phase diffraction peak, which indicates that the product is zinc with higher purity. Scanning electron microscopy analysis (fig. 4) showed: the product is mainly spindle-shaped (average length is about 2 μm, and is composed of 300-500nm particles), and small amount of dendritic zinc is also present, and the spindle-shaped and dendritic zinc has large specific surface area (up to 80 m) 2 /g。
Example 5:
manufacturing a battery: the LR6 (AA) type alkaline zinc-manganese dioxide battery is manufactured by the following conventional method: subjecting gamma-MnO to 2 Mixing the positive electrode materials such as the nanotube/nanowire and the like, granulating, pressing a ring, putting the ring into a steel shell, coating a sealant, then inserting a diaphragm, adding an electrolyte and a negative electrode zinc paste, then inserting a negative electrode current collector assembly, welding a negative electrode terminal, rolling the wire, curling the edge, and then welding the positive electrode terminal to obtain the finished product of the alkaline zinc-manganese dioxide battery (the flow chart is shown in figure 5). The anode comprises 85% (all by mass) of gamma-MnO 2 Nanotube/nanowire (gamma-MnO) 2 11g of nanotubes and nanowires), 8% of activated carbon and 7% of electrolyte (containing 40% of KOH); the negative electrode comprises 65% of electrolytic nano zinc particles, 31% of electrolyte (containing 40% of KOH) and 4% of a mixture of ZnO (nano ZnO particles is 0.3 g) and PTFE. The finished alkaline zinc-manganese dioxide battery is shown in figure 6, and the reference numbers in the figure have the meanings as follows: 1. steel shell 2, mnO 2 The device comprises a positive electrode 3, an exhaust valve 4, a positive electrode terminal 5, an isolation layer 6, negative electrode zinc paste 7, a negative electrode current collector 8, a sealing cap 9, a gasket 10 and a negative electrode terminal.
Example 6:
FIG. 7 shows the results obtained with gamma-MnO in example 5 2 The alkaline zinc-manganese dioxide battery assembled by the nano tube/nano wire and the electrolytic zinc continuously discharges to a constant current discharge curve of 0.8V under different currents (0.1, 0.2,0.5 and 1A) at 20 ℃. It can be seen from the figure that: the high-power alkaline zinc-manganese dioxide battery has stable discharge performance under different currents even if 1A of large current is usedDischarging by current for 2.9 hours, and discharging the commercial alkaline zinc-manganese dioxide battery for 1 hour under the same condition; as can be seen in conjunction with the data in table 1: the capacity and energy of the alkaline zinc-manganese battery are reduced slightly along with the increase of discharge current, which shows that the alkaline zinc-manganese battery has excellent high-rate discharge performance.
TABLE 1 discharge behavior at 20 ℃ of LR6 type high power alkaline zinc-manganese dioxide cell under different constant loads
Example 7:
FIG. 8 shows the measured values in gamma-MnO according to example 5 2 The alkaline zinc-manganese dioxide battery assembled by the nano tube/nano wire and the electrolytic zinc is continuously discharged to a constant resistance discharge curve of 0.8V under different resistances (1.5, 3,6 and 12 Ohms) at 20 ℃. As can be seen from the figure: when the alkaline zinc-manganese dioxide battery is discharged under 1.50hms and 30hms, the alkaline zinc-manganese dioxide battery can be respectively discharged for 3.7h and 7.5h continuously, and has higher capacity and energy, which shows that the alkaline zinc-manganese dioxide battery has good heavy-load discharge performance.
Example 8:
FIG. 9 shows the measured values for γ -MnO in example 5 2 The alkaline zinc-manganese dioxide battery assembled by the nano tube/nano wire and the electrolytic zinc is continuously discharged to a constant power discharge curve of 0.8V under different powers (0.25, 0.5,1, 2W) at 20 ℃. In combination with the data in table 1, it was found that: the alkaline zinc-manganese dioxide battery has good discharge performance under different powers, and particularly has basically the same capacity and energy under the high power conditions of 1W and 2W, which shows that the alkaline zinc-manganese dioxide battery has excellent high-power discharge performance.
Example 9:
the increase of internal resistance of the common commercial alkaline zinc-manganese dioxide battery under high-rate discharge condition is larger, which is a main reason for faster reduction of capacity and energy in the discharge process. And adopting nano material as electricityThe electrode material can greatly reduce internal resistance and effectively improve the high-current discharge performance. Resistance analysis (fig. 10) showed that: as in example 5 with gamma-MnO 2 When the alkaline zinc-manganese dioxide battery assembled by the nano tube/nano wire and the electrolytic zinc is continuously discharged under different load conditions, the internal resistance increases slightly. For example, at the beginning of discharge, its internal resistance is lower than 0.10hms, and at the end of continuous discharge under a load of 2.4Ohms, its internal resistance is lower than 0.450hms, which is a small increase compared to the ordinary commercial alkaline zinc-manganese battery. Illustrating the use of gamma-MnO 2 The nanotube/nanowire and electrolytic zinc as electrode materials can obviously reduce the increase of internal resistance in the discharge process, which plays an important role in improving the discharge performance of the battery.
Example 10:
to compare and illustrate the effect of different electrode materials on cell performance, gamma-MnO was used 2 An LR6 type alkaline zinc-manganese battery was fabricated in the same manner as in example 5, using nanotubes/nanowires and commercially available molten zinc. Meanwhile, the electrochemical performance of a commercially available AA battery (domestic DuracellMN1600, 2005) was tested and compared.
Fig. 11 is a discharge curve of three AA-type batteries (two assembled batteries and a commercially available battery) discharged continuously at a current of 100mA to 0.8V at 20 ℃. As seen from the figure: the discharge curve shapes of the three batteries are similar; both assembled cells had longer discharge times, higher discharge plateaus, and higher discharge capacities than the commercial cells. Of the two assembled cells, the high power alkaline zinc-manganese battery of the invention has a specific gamma-MnO 2 The better discharge performance of the nanotube/nanowire and molten zinc assembled cell is mainly due to the fact that the anode active material electrolytic zinc of the high-power alkaline zinc-manganese dioxide cell of the invention has a larger specific surface area than the commercially available molten zinc (fig. 12 is an SEM image of the molten zinc).
By comparing electrochemical performance tests of three alkaline zinc-manganese batteries, it can be seen that: the alkaline zinc-manganese dioxide battery has higher electrochemical capacity, high power and high rate discharge performance. This results from nanoscale electrodesThe material has the characteristics of structure: gamma-MnO as positive electrode active material 2 The nanotube/nanowire has larger specific surface area, so that the contact between an active substance and electrodes can be effectively increased, the internal resistance of a battery is reduced, the diffusion performance of protons is improved, and the exchange of water in the reaction process is improved, so that the utilization rate of the nanotube/nanowire is remarkably improved, and experiments show that when the nanotube/nanowire is discharged at 0.1A, gamma-MnO is generated 2 The utilization rate of the nano tube/nano wire can reach 91 percent; particularly, the opening and hollow structure of the nanotube enables the proton diffusion process in the electrode reaction to be easier to carry out, the speed is higher, and the high-power and high-rate discharge performance of the manganese dioxide electrode is improved; the cathode is composed of electrolytic zinc with large surface area and high purity, so that solid and liquid phases can be distributed more uniformly, the passivation and corrosion of zinc are effectively reduced, and the utilization rate of zinc is greatly improved. Therefore, the battery has higher electrochemical capacity and good high-power and high-rate discharge performance, can meet different working conditions, is a high-power alkaline zinc-manganese battery with excellent performance, and has wide application prospect.
Claims (10)
1. The manganese dioxide nanotube and nano wire electrode material is characterized by that it is made up by using gamma-MnO 2 The nano-tube and the nano-wire are composed, wherein the content of the nano-tube is 40-50%, the length of the single nano-tube and the nano-wire is 2-4 μm, and the diameter is 75-85nm.
2. The method for preparing manganese dioxide nanotube and nanowire electrode material as claimed in claim 1, which comprises reacting soluble manganese salt in methanol solution of surfactant with alkali, oxidizing, and dehydrating, and is characterized by comprising the following steps:
1) Adding soluble manganese salt solution into methanol solution of surfactant at room temperature, stirring at 100r/min for 2 hr to form micro-emulsified liquid drop, adding alkali, and mixing;
2) Reacting in a high-pressure reaction kettle at 100-140 ℃, and crystallizing for 10-20 hours;
3) After the reaction is finished, cooling to room temperature, washing for 3-5 times by using water and absolute ethyl alcohol respectively, and drying for 2-4 hours in vacuum at the temperature of 60-80 ℃.
3. The method of claim 2, wherein the reaction is carried out at a temperature of 120 ℃ for crystallization.
4. The method for preparing manganese dioxide nanotubes and nanowire electrode materials according to claim 2, characterized in that the molar ratio of the reactants is soluble manganese salt: surfactant (b): base =1:1:1.
5. a method for preparing manganese dioxide nanotubes and a nanowire electrode material according to claim 1, which comprises the steps of reacting a soluble manganese salt solution in a methanol solution of a surfactant with alkali, oxidizing and dehydrating, and is characterized by comprising the following steps:
1) MnSO soluble manganese salt is added at room temperature 4 Adding into methanol solution of surfactant, stirring at 100r/min for 2 hr to form micro-emulsified liquid drop, adding alkali, and mixing;
2) Reacting in a high-pressure reaction kettle at 120 ℃, and crystallizing for 20 hours;
3) After the reaction is finished, cooling to room temperature, washing for 3-5 times by using water and absolute ethyl alcohol respectively, and drying for 4 hours in vacuum at the temperature of 60 ℃.
6. The method according to claim 5, wherein the molar ratio of the reactants is soluble manganese salt: surfactant (b): base =1:1:1.
7. an alkaline zinc-manganese battery comprising: manganese dioxide positive pole, zinc negative pole, diaphragm, alkaline electrolyte and battery container, its characterized in that: the manganese dioxide positive electrode comprisesAn electrode material comprising gamma-MnO 2 The cathode comprises a nanotube, a nanowire and activated carbon, wherein the zinc cathode comprises an electrode material, and the electrode material comprises nano zinc particles, znO and PTFE;
the gamma-MnO 2 The nano-tubes and the nano-wires, wherein the content of the nano-tubes is 40-50%, the length of each single nano-tube and each single nano-wire is 2-4 mu m, and the diameter of each single nano-tube and each single nano-wire is 75-85nm;
the nano zinc particles are spindle-shaped electrolytic zinc consisting of particles of 300-500 nm.
8. The alkaline zinc-manganese dioxide cell of claim 7, wherein said γ -MnO is 2 Nanotube and nanowire: activated carbon mass ratio =85:8; the nano zinc particle ZnO: PTFE mass ratio =3:1.
9. the alkaline zinc-manganese dioxide cell as claimed in claim 7, which is a cylindrical AA cell, and the positive electrode material of the cell comprises, in mass percent:
γ-MnO 2 85% of nano tube and nano wire
8 percent of active carbon
40% of KOH electrolyte 7%
The anode material comprises the following components in percentage by mass:
65 percent of electrolytic nano zinc particles
40% of KOH electrolyte 31%
ZnO 3％
PTFE 1％。
10. The alkaline zinc-manganese dioxide cell of claim 9, whereinThe diameter and height of the cylindrical AA-type battery are 14mm and 50mm respectively, and the weight and volume are 24g and 7.5cm respectively -3 。
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| JP5313543B2 (en) * | 2008-04-28 | 2013-10-09 | パナソニック株式会社 | Lithium battery |
| CN103682303B (en) * | 2013-11-11 | 2016-03-02 | 江苏华东锂电技术研究院有限公司 | Lithium ion battery anode active material and preparation method thereof and lithium ion battery |
| CN104701205B (en) * | 2015-02-13 | 2017-11-17 | 武汉理工大学 | In-situ characterization performance test methods based on single nano-wire electrode material |
| CN109148877A (en) * | 2018-07-30 | 2019-01-04 | 桑顿新能源科技有限公司 | Rechargeable zinc-manganese battery and preparation method thereof |
| CN109687040A (en) * | 2018-12-21 | 2019-04-26 | 香港城市大学成都研究院 | Compressible rechargeable zinc-manganese battery and battery-sensor integrated device based on same |
| CN111554515B (en) * | 2020-05-11 | 2021-12-21 | 深圳美诺克科技有限公司 | MnO (MnO)2Supercapacitor electrode material for modifying biomass porous carbon and preparation method thereof |
| CN113061910B (en) * | 2021-03-22 | 2021-11-12 | 长沙学院 | Electrolytic manganese dioxide and preparation method and application thereof |
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