CN109786712B - Nickel and bismuth modified manganese dioxide cathode material and preparation method and application thereof - Google Patents
Nickel and bismuth modified manganese dioxide cathode material and preparation method and application thereof Download PDFInfo
- Publication number
- CN109786712B CN109786712B CN201910074935.7A CN201910074935A CN109786712B CN 109786712 B CN109786712 B CN 109786712B CN 201910074935 A CN201910074935 A CN 201910074935A CN 109786712 B CN109786712 B CN 109786712B
- Authority
- CN
- China
- Prior art keywords
- nickel
- bismuth
- manganese dioxide
- cathode material
- modified manganese
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a nickel and bismuth modified manganese dioxide cathode material and a preparation method and application thereof. The material is prepared by the following method: uniformly stirring potassium permanganate and hydrochloric acid in deionized water, then adding a certain amount of nickel nitrate and bismuth nitrate, and carrying out hydrothermal reaction to obtain a nickel and bismuth modified manganese dioxide powder cathode material; the nickel and bismuth modified manganese dioxide cathode material is suitable for zinc ion batteries. The nickel and bismuth modified manganese dioxide cathode material and the zinc ion battery with the cathode have good rate performance, cycle performance and long cycle life.
Description
Technical Field
The invention belongs to the field of zinc ion battery materials, and particularly relates to a nickel and bismuth modified manganese dioxide positive electrode material, and a preparation method and application thereof.
Background
The zinc ion battery is a safe and pollution-free secondary battery taking zinc powder or zinc sheets as a negative electrode material and manganese as a positive electrode material. Manganese dioxide has the advantages of low price and environmental friendliness, has outstanding ion storage performance due to the variable valence state of manganese, and has outstanding performance as an electrode material on chemical batteries such as novel zinc ion batteries and the like recently.
At present, research on manganese-based electrode materials mainly focuses on tetravalent manganese-based materials, but poor conductivity of the manganese-based electrode materials and increased volume change in the charging and discharging process cause poor rate performance and short cycle life, and further development of the manganese-based electrode materials is hindered.
Disclosure of Invention
In view of this, the present invention provides a nickel and bismuth modified manganese dioxide positive electrode material and a zinc ion battery, so as to improve the rate capability and cycle performance of the manganese dioxide positive electrode material and prolong the electrode life.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a nickel and bismuth modified manganese dioxide cathode material is characterized in that: the nickel and bismuth modified manganese dioxide cathode material is alpha-phase MnO added with nickel element and bismuth element 2 。
Furthermore, the atomic ratio of the nickel element, the bismuth element and the manganese element is 0.005-0.5: 1.
Furthermore, the nickel and bismuth modified manganese dioxide cathode material is in the shape of a nanorod, a nanowire or a nanobelt.
Furthermore, the length-diameter ratio of the nano rod, the nano wire or the nano belt is 30-100: 1, and the diameter is 30-110 nm.
The preparation method of the nickel and bismuth modified manganese dioxide cathode material is characterized by comprising the following steps of: the potassium permanganate and the hydrochloric acid are evenly stirred in the deionized water, and then the nickel nitrate and the bismuth nitrate are added to prepare the catalyst by hydrothermal reaction.
Furthermore, the atomic ratio of nickel element in the nickel nitrate and the bismuth nitrate to manganese element in the potassium permanganate is 0.005-0.5: 1.
Furthermore, the atomic ratio of the nickel element, the bismuth element and the manganese element in the potassium permanganate is 0.1:0.1: 1.
Further, the using amount of the potassium permanganate is 7 mmol; the concentration of the hydrochloric acid is 36 percent, and the dosage is 2.5 ml; the dosage of the nickel nitrate is 0.7 mmol; the amount of deionized water was 70 ml.
Further, the reaction temperature of the hydrothermal reaction is 160 ℃, and the reaction time is 10 hours.
The nickel and bismuth modified manganese dioxide cathode material is used for a zinc ion battery.
Compared with the prior art, the nickel and bismuth modified manganese dioxide cathode material and the zinc ion battery with the cathode have the following advantages:
the nickel and bismuth modified manganese dioxide cathode material and the zinc ion battery with the cathode have good rate performance, cycle performance and long cycle life.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of unmodified and nickel and bismuth modified manganese dioxide positive electrode materials prepared in examples 1-4 and comparative example 1;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the Ni-Bi modified manganese dioxide cathode material obtained in examples 1-4. Wherein (a) - (d) correspond to SEM images of the cathode materials described in examples 1-4, respectively;
FIG. 3 is a cycle life curve and a coulombic efficiency curve for a cell of example 2 at a current density of 500 mA/g;
FIG. 4 is a graph showing the cycle performance of the cells of examples 1 to 4 and the cell of comparative example 1 at a current density of 300 mA/g;
FIG. 5 is a plot of cyclic voltammograms for the cell of example 2 and the cell of comparative example 1 at a scan rate of 0.5 mV/s.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The invention is explained in detail below with reference to the embodiments and the drawings.
Example 1
A nickel and bismuth modified manganese dioxide cathode material is prepared by the following method: stirring 7mmol of potassium permanganate and 2.5ml of hydrochloric acid (the concentration is 36%) in 70ml of deionized water uniformly, then adding 0.035mmol of nickel nitrate and 0.035mmol of bismuth nitrate, stirring vigorously for 30 minutes under the condition of 1000 revolutions per minute, pouring the solution into a 100ml of polytetrafluoroethylene high-pressure reaction kettle, carrying out hydrothermal reaction for 10 hours under the condition of 160 ℃, cooling to room temperature, washing the reaction solution until the solution is neutral, carrying out suction filtration, drying for 12 hours at 80 ℃, and grinding for 45 minutes to obtain a nickel and bismuth modified manganese dioxide powder anode material, wherein the atomic ratio of manganese elements to nickel elements and bismuth elements of the anode material prepared in the embodiment is 1:0.005:0.005, and the anode material is marked as' MnO 2 :Ni,Bi＝1:0.005”。
Example 2
A nickel and bismuth modified manganese dioxide cathode material is prepared by the following method: stirring 7mmol of potassium permanganate and 2.5ml of hydrochloric acid (the concentration is 36%) in 70ml of deionized water uniformly, then adding 0.7mmol of nickel nitrate and 0.7mmol of bismuth nitrate, stirring vigorously for 30 minutes under the condition of the rotation speed of 1000 revolutions per minute, pouring the solution into a 100ml of polytetrafluoroethylene high-pressure reaction kettle,carrying out hydrothermal reaction for 10 hours at 160 ℃, cooling to room temperature, washing the reaction solution until the solution is neutral, carrying out suction filtration, drying for 12 hours at 80 ℃, and grinding for 45 minutes to obtain the nickel-bismuth modified manganese dioxide powder cathode material, wherein the atomic ratio of manganese element to nickel element and bismuth element of the cathode material prepared in the embodiment is 1:0.1:0.1, and the anode material is marked as' MnO 2 :Ni,Bi＝1:0.1”。
Example 3
A nickel and bismuth modified manganese dioxide cathode material is prepared by the following method: stirring 7mmol of potassium permanganate and 2.5ml of hydrochloric acid (the concentration is 36%) uniformly in 70ml of deionized water, then adding 2.45mmol of nickel nitrate and 2.45mmol of bismuth nitrate, stirring vigorously for 30 minutes at the rotation speed of 1000 r/min, pouring the solution into a 100ml of polytetrafluoroethylene high-pressure reaction kettle, carrying out hydrothermal reaction for 10 hours at 160 ℃, cooling to room temperature, washing the reaction solution until the solution is neutral, carrying out suction filtration, drying for 12 hours at 80 ℃, and grinding for 45 minutes to obtain a nickel and bismuth modified manganese dioxide powder anode material, wherein the atomic ratio of manganese elements to nickel elements and bismuth elements in the anode material prepared in the embodiment is 1:0.35:0.35, and the anode material is marked as MnO 2 :Ni,Bi＝1:0.35”。
Example 4
A nickel and bismuth modified manganese dioxide cathode material is prepared by the following method: stirring 7mmol of potassium permanganate and 2.5ml of hydrochloric acid (the concentration is 36%) uniformly in 70ml of deionized water, then adding 3.5mmol of nickel nitrate and 3.5mmol of bismuth nitrate, stirring vigorously for 30 minutes at the rotation speed of 1000 r/min, pouring the solution into a 100ml of polytetrafluoroethylene high-pressure reaction kettle, carrying out hydrothermal reaction for 10 hours at 160 ℃, cooling to room temperature, washing the reaction solution until the solution is neutral, carrying out suction filtration, drying for 12 hours at 80 ℃, and grinding for 45 minutes to obtain a nickel and bismuth modified manganese dioxide powder anode material, wherein the atomic ratio of manganese elements to nickel elements and bismuth elements in the anode material prepared in the embodiment is 1:0.5:0.5, and the anode material is marked as' MnO 2 :Ni,Bi＝1:0.5”。
Example 5
A zinc ion battery comprises a manganese dioxide positive electrode, a zinc negative electrode, a diaphragm, electrolyte and a battery shell; the specification of the battery case is 2032; the manganese dioxide positive electrode is one of the nickel and bismuth modified manganese dioxide positive electrode materials described in examples 1-4.
The manganese dioxide positive electrode is prepared by adopting the following method: weighing 0.3g of manganese dioxide powder, weighing the manganese dioxide powder, polyvinylidene fluoride and acetylene black according to the mass ratio of 7:2:1, then putting the manganese dioxide powder, the polyvinylidene fluoride and the acetylene black together with 3ml of N-methyl pyrrolidone into a mortar, grinding the mixture until glue liquid is in a honey state, coating the glue liquid on a stainless steel thin substrate, putting the stainless steel thin substrate into a vacuum drying oven for drying, and finally cutting the glue liquid into small positive wafers with the diameter of 10mm by using a slicing machine to obtain the lithium ion battery; the manganese dioxide powder is one of the nickel and bismuth modified manganese dioxide cathode materials in examples 1-4;
the zinc cathode is prepared in the following way: weighing 0.5g of zinc powder, weighing the zinc powder, polyvinylidene fluoride and acetylene black according to the mass ratio of 8:1:1, then putting the zinc powder, the polyvinylidene fluoride and the acetylene black together with 3ml of N-methylpyrrolidone into a mortar, grinding the mixture until a glue solution is in a honey state, coating the glue solution on a stainless steel thin substrate, putting the stainless steel thin substrate into a vacuum drying oven for drying, and finally cutting the stainless steel thin substrate into a negative tiny wafer with the diameter of 14mm by using a slicer to obtain the zinc powder;
the zinc ion battery is manufactured in the following way: at room temperature, assembling the battery according to the stacking sequence from bottom to top and injecting electrolyte, wherein the negative electrode shell is larger than the gasket and 0.2ml electrolyte, the negative electrode wafer is larger than the gasket and 0.2ml electrolyte, the diaphragm and 0.2ml electrolyte are larger than the positive electrode wafer and 0.2ml electrolyte, the gasket and 0.2ml electrolyte are larger than the elastic sheet, and the positive electrode shell is larger than the negative electrode shell; the cells are then packaged on a packaging machine. The zinc ion batteries were numbered as "example 1 battery", "example 2 battery", "example 3 battery", and "example 4 battery", and respectively corresponded to the zinc ion batteries manufactured from the positive electrode materials described in examples 1 to 4.
Comparative example 1
A zinc ion battery using an unmodified manganese dioxide material and a positive electrode of the material was used as a comparative example. The unmodified manganese dioxide material is prepared by adopting the following method: 7mmol of potassium permanganate and 2.5ml of hydrochloric acid (concentration)36%) in 70ml deionized water, stirring uniformly, pouring the solution into a 100ml polytetrafluoroethylene high-pressure reaction kettle, carrying out hydrothermal reaction for 10 hours at 160 ℃, cooling to room temperature, washing the reaction solution until the solution is neutral, carrying out suction filtration, drying for 12 hours at 80 ℃, and grinding for 45 minutes to obtain an unmodified manganese dioxide powder anode material marked as' pure MnO 2 ”。
The zinc ion battery having an unmodified manganese dioxide positive electrode has the same structure as in example 5, except that the positive electrode is the unmodified manganese dioxide positive electrode material prepared in this example. The zinc ion cell was numbered as "comparative example 1 cell".
FIG. 1 is a result of characterization using an X-ray diffraction (XRD) instrument of unmodified and nickel and bismuth modified manganese dioxide positive electrode materials prepared in examples 1 to 4 and comparative example 1. By analyzing the spectrogram, XRD characteristic peaks and alpha-phase MnO of the unmodified nickel and bismuth modified manganese dioxide anode material obtained by the experiment can be known 2 The characteristic peaks (PDF #44-0141) are identical, which shows that the object-like structures of the unmodified nickel and bismuth modified manganese dioxide positive electrode material are alpha-phase MnO 2 。
Fig. 2 is a result of characterization of the nickel and bismuth modified manganese dioxide cathode materials prepared in examples 1 to 4 using a Scanning Electron Microscope (SEM). Wherein (a) - (d) correspond to SEM images of the cathode materials described in examples 1-4, respectively; from SEM images (a-d), the product prepared in examples 1-4 is in the shape of a nanorod, nanobelt or nanowire structure, the length-diameter ratio of the nanorod, nanobelt or nanowire is 30-100: 1, and the diameter of the nanorod, nanobelt or nanowire is 30-110 nm.
Fig. 3 is a cycle life curve and coulombic efficiency curve for the battery of example 2 at a current density of 500 mA/g. It can be seen from the figure that the specific capacity of the battery of example 2 is not reduced and is still kept at a high level after 1000 times of cyclic charge and discharge processes under the current density of 500mA/g, and the coulombic efficiency of the battery of example 2 is also kept at a level above 90%, and the results show that the battery of example 2 has good cyclic performance and long cycle life.
FIG. 4 is a graph showing the cycle performance of the cells of examples 1 to 4 and the cell of comparative example 1 at a current density of 300 mA/g. It can be seen from the graph that the specific capacity of the batteries of examples 2 and 4 is maintained at a higher level (more than 75%) than that of the battery of comparative example 1 after 100 times of cyclic charge and discharge processes at a current density of 300mA/g, while the specific capacity of the battery of comparative example 1 is reduced to 22.7% of that of the battery of comparative example 1, which indicates that the battery of example 2 has better cycle performance than the battery of comparative example 1.
FIG. 5 is a plot of cyclic voltammograms for the cell of example 2 and the cell of comparative example 1 at a scan rate of 0.5 mV/s. The larger current of the peak means better electrode reaction kinetics and better rate performance, and the smaller potential difference of the peak means the polarization of the electrode prepared by the material is smaller. It can be seen from fig. 5 that the cell of example 2 has a higher peak current and a reduced potential difference from the cell of comparative example 1, indicating that the cell of example 2 has better electrode reaction kinetics, better rate capability and less polarization.
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 invention, so that any modifications, equivalents, improvements and the like, which are within the spirit and principle of the present invention, should be included in the scope of the present invention.
Claims (2)
1. A preparation method of a nickel and bismuth modified manganese dioxide cathode material is characterized by comprising the following steps: the nickel and bismuth modified manganese dioxide cathode material is alpha-phase MnO added with nickel element and bismuth element 2 (ii) a The nickel and bismuth modified manganese dioxide cathode material is in the shape of a nanorod, a nanowire or a nanobelt;
the atomic ratio of the nickel element, the bismuth element and the manganese element is 0.1:0.1: 1;
the preparation method comprises the steps of uniformly stirring potassium permanganate and hydrochloric acid in deionized water, then adding nickel nitrate and bismuth nitrate, and carrying out hydrothermal reaction to prepare the potassium permanganate-bismuth nitrate nano-particles;
the using amount of the potassium permanganate is 7 mmol; the concentration of the hydrochloric acid is 36 percent, and the dosage is 2.5 ml; the dosage of the nickel nitrate is 0.7 mmol; the dosage of bismuth nitrate is 0.7 mmol; the dosage of the deionized water is 70 ml;
the reaction temperature of the hydrothermal reaction is 160 ℃, and the reaction time is 10 hours;
the nickel and bismuth modified manganese dioxide cathode material is used for a zinc ion battery.
2. The method for preparing the nickel and bismuth modified manganese dioxide cathode material according to claim 1, wherein the method comprises the following steps: the length-diameter ratio of the nano rods, the nano wires or the nano belts is 30-100: 1, and the diameter of the nano rods, the nano wires or the nano belts is 30-110 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910074935.7A CN109786712B (en) | 2019-01-25 | 2019-01-25 | Nickel and bismuth modified manganese dioxide cathode material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910074935.7A CN109786712B (en) | 2019-01-25 | 2019-01-25 | Nickel and bismuth modified manganese dioxide cathode material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109786712A CN109786712A (en) | 2019-05-21 |
| CN109786712B true CN109786712B (en) | 2022-09-13 |
Family
ID=66502670
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910074935.7A Active CN109786712B (en) | 2019-01-25 | 2019-01-25 | Nickel and bismuth modified manganese dioxide cathode material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109786712B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112886004B (en) * | 2021-01-11 | 2022-05-03 | 北京科技大学 | Cathode material of water-based zinc ion battery and matched electrolyte |
| CN115566150A (en) * | 2021-07-01 | 2023-01-03 | 陈璞 | Neutral or weakly acidic system water system zinc ion battery positive electrode material and preparation method and application thereof |
| CN114029067B (en) * | 2021-11-16 | 2022-05-20 | 西安炳鑫环保科技有限公司 | Material for efficiently degrading organic wastewater |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4451543A (en) * | 1983-09-29 | 1984-05-29 | Ford Motor Company | Rechargeable zinc/manganese dioxide cell |
| CN102013527B (en) * | 2009-09-08 | 2012-08-29 | 清华大学深圳研究生院 | Rechargeable zinc ion battery |
| CN102683757B (en) * | 2011-03-15 | 2014-10-22 | 清华大学深圳研究生院 | High-capacity rechargeable zinc ion battery |
| CN102299389A (en) * | 2011-07-19 | 2011-12-28 | 浙江理工大学 | High-performance rechargeable battery |
| EP2917956A4 (en) * | 2012-11-09 | 2016-06-22 | Univ City New York Res Found | Secondary zinc-manganese dioxide batteries for high power applications |
| CN104261479B (en) * | 2014-09-28 | 2017-03-08 | 上海第二工业大学 | A kind of metal doping nano manganese bioxide electrode material and preparation method thereof |
| CN107004860B (en) * | 2014-10-13 | 2020-11-06 | 纽约城市大学研究基金会 | Mixed material cathode for secondary alkaline batteries |
| 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 |
-
2019
- 2019-01-25 CN CN201910074935.7A patent/CN109786712B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN109786712A (en) | 2019-05-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109786712B (en) | Nickel and bismuth modified manganese dioxide cathode material and preparation method and application thereof | |
| Wang et al. | α-Fe 2 O 3-mediated growth and carbon nanocoating of ultrafine SnO 2 nanorods as anode materials for Li-ion batteries | |
| CN105977460B (en) | A kind of graphene composite material, preparation method and application | |
| CN108767216A (en) | Anode material for lithium-ion batteries and its synthetic method with the full concentration gradient of variable slope | |
| JP2016103477A (en) | Positive electrode material for sodium secondary battery | |
| WO2005096415A1 (en) | Positive electrode active material for non-aqueous electrolyte secondary cell | |
| CN107732234B (en) | Er and Zr metal ion mixed doped ternary cathode material and preparation method thereof | |
| CN113889603A (en) | Sodium ion battery positive electrode material and preparation method thereof | |
| Gao et al. | Methanothermal reduction of mixtures of PbSO4 and PbO2 to synthesize ultrafine α-PbO powders for lead acid batteries | |
| CN108428878A (en) | A kind of preparation method of ZnO/NiO/C composite negative pole materials for lithium ion battery | |
| JP7121219B1 (en) | Method for producing lithium metal composite oxide | |
| Mohamed et al. | Heterostructure necklace-like NiO-NiCo2O4 hybrid with superior catalytic capability as electrocatalyst for Li-O2 batteries | |
| CN109768262B (en) | Cadmium modified manganese dioxide positive electrode material and preparation method and application thereof | |
| CN107949939A (en) | Lithium metal oxide material, its purposes in the cathode of secondary cell and the method for being used to prepare such lithium metal oxide material | |
| Chao et al. | La-doped SnO2 synthesis and its electrochemical property | |
| JP4674347B2 (en) | Layered manganese dioxide nanobelt and method for producing the same | |
| CN107215902A (en) | A kind of preparation method of lithium ion battery negative material niobic acid iron | |
| JPH10172564A (en) | Active material, its manufacture, and lithium ion secondary battery using active material | |
| CN108832111B (en) | LiNi0.8Co0.15Al0.05O2Positive electrode material and preparation method thereof | |
| CN110729481A (en) | Lithium ion battery negative active material MnxFe1-xC2O4Synthetic method and application | |
| CN113871582B (en) | Nickel-based positive electrode material for sodium ion battery capable of being used for filling conductive material | |
| CN104300136A (en) | One-dimensional manganese oxide/carbon coaxial hollow nanorod as well as preparation method and application of nanorod | |
| US20170062802A1 (en) | Polynary composite oxide, preparation method and use thereof | |
| CN1765732A (en) | Method for preparing Li, Ni, Mn oxide material by adopting low-heat solid phase reaction | |
| Ding et al. | Employing a 100° C-dried mixture that contained KMnO4 and SnCl4 as an anode material for lithium ion batteries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |