CN107863485B - Cathode material of water-based zinc ion battery - Google Patents
Cathode material of water-based zinc ion battery Download PDFInfo
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- CN107863485B CN107863485B CN201711080427.7A CN201711080427A CN107863485B CN 107863485 B CN107863485 B CN 107863485B CN 201711080427 A CN201711080427 A CN 201711080427A CN 107863485 B CN107863485 B CN 107863485B
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- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000010406 cathode material Substances 0.000 title description 2
- 239000000463 material Substances 0.000 claims abstract description 32
- 239000000758 substrate Substances 0.000 claims abstract description 18
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 239000010405 anode material Substances 0.000 claims abstract description 8
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 3
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 3
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 34
- 229910001220 stainless steel Inorganic materials 0.000 claims description 19
- 239000010935 stainless steel Substances 0.000 claims description 19
- 239000007774 positive electrode material Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000006260 foam Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 5
- 230000001351 cycling effect Effects 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000011572 manganese Substances 0.000 description 9
- 239000002057 nanoflower Substances 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000010335 hydrothermal treatment Methods 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- TYTHZVVGVFAQHF-UHFFFAOYSA-N manganese(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Mn+3].[Mn+3] TYTHZVVGVFAQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Abstract
The invention discloses a water system zinc ion battery anode material. The preparation method of the material is a one-step hydrothermal method, and comprises the steps of adding a certain amount of potassium permanganate into deionized water, stirring at room temperature to obtain a dark purple solution, transferring the obtained solution into a high-pressure kettle, adding a three-dimensional substrate material into the solution, and carrying out hydrothermal reaction; after the hydrothermal reaction is cooled, the three-dimensional substrate material is washed for a plurality of times and then dried in an oven, and the nano flower-shaped spherical manganous-manganic oxide material which grows on the three-dimensional substrate material uniformly is obtained. The prepared material is firstly applied to the preparation of the anode material of the water system zinc ion battery, has high specific capacity and good cycling stability, has mild reaction conditions and simple process, and is suitable for large-scale production.
Description
Technical Field
The invention belongs to the technical field of high-energy water system zinc ion battery materials, and particularly relates to a novel water system zinc ion battery positive electrode material.
Background
The water system zinc ion battery is a novel secondary battery which is popular in recent years, has high energy density and high power density, is nontoxic in battery material, low in price and simple in preparation process, and has high application value and development prospect in the field of large-scale energy storage. It is more attractive that zinc ions have a divalent charge so that the battery can provide a higher storage capacity, and that the battery has high ion conductivity using an environmentally friendly aqueous electrolyte.
Among the positive electrode materials of the aqueous zinc-ion batteries currently used for research, manganese oxide is considered to be the most potential positive electrode material because of its large storage capacity, low price, low toxicity and many manganese valence states. For example, various polymorphic MnO2Have different reaction mechanisms. Manganese sesquioxide also exhibits excellent zinc ion storage properties. However, it is not limited toThe ionic and electronic conductivities of these oxides of manganese are low, limiting their electrochemical performance. Therefore, there is a strong need to search for a new positive electrode material to promote the charge and discharge of divalent zinc ions. As an example, past research has focused on aqueous zinc-ion battery anodes where manganese is a single monovalent based manganese oxide. ZnMn with multi-valence Mn2O4Manganese vacancy in spinel is Zn2+The diffusion and migration of ions contribute to provide a viable search for mixed-valence manganese oxides as the positive electrode of zinc-ion batteries. Mangano manganic oxide (Mn)2+O·Mn3+ 2O3) In which there is naturally coexisting Mn2+And Mn3+It has been demonstrated to have the high activity of metal air cells (ORR) due to the tendency to form defects, and it may also have good application prospects in aqueous zinc ion batteries. However, Mn is not currently being considered3O4As a research on the anode of the water-based zinc ion battery, the method can not only construct the Mn without a binding agent which can greatly improve the electrochemical performance3O4And a cathode. The invention provides a simple method for synthesizing a positive electrode material of a three-dimensional substrate material loaded with nanometer flower-shaped spherical manganous-manganic oxide for a zinc ion battery, and has very important significance for promoting commercialization of the zinc ion battery.
Disclosure of Invention
The invention aims to provide a positive electrode material of an aqueous zinc ion battery. In particular to a positive material which is stable in structure, high in specific capacity, excellent in cycling stability and high in rate performance and grows on a three-dimensional substrate in a nano flower ball-shaped manganous-manganic oxide load mode. The synthesis method is simple, has low cost and can be used for large-scale industrial production.
A positive electrode material of a water-based zinc ion battery is prepared by the following method: adding a certain amount of potassium permanganate into deionized water, stirring at room temperature to obtain a dark purple solution, transferring the obtained solution into a high-pressure reaction kettle, adding a three-dimensional substrate material into the solution, carrying out hydrothermal reaction, cooling the hydrothermal reaction, taking out the three-dimensional substrate material, washing, and drying to obtain the potassium permanganate solution.
The three-dimensional substrate comprises a stainless steel net, foamed nickel, carbon fiber cloth or a titanium metal net.
The concentration of the potassium permanganate solution is 0.01-0.1 mol/L.
The volume of the solution is 50-80% of the volume of the high-pressure reaction kettle.
After the reaction is finished, the load capacity of the trimanganese tetroxide on the three-dimensional substrate material is 0.3-0.4 mgcm-2. Too little load affects the performance of the anode material, too much load is wasted on one hand, and on the other hand, the performance of the anode material cannot be optimized.
The conditions of the hydrothermal reaction are as follows: reacting for 12-48 h at 160-200 ℃.
The three-dimensional substrate material is dried for 8-14 hours at 50-70 ℃ to obtain the anode material of the water-based zinc ion battery.
Compared with the prior art, the invention has the following advantages:
the invention synthesizes the nanometer flower-shaped spherical manganous-manganic oxide material with uniform appearance and the composite material thereof by a simple hydrothermal method. The composite material is characterized in that the structure of the nanometer flower ball is closely attached to the three-dimensional substrate, and the three-dimensional substrate has good conductivity, so that the conductivity of the material is greatly improved, and the electrochemical performance of the material is obviously improved. The invention firstly converts Mn3O4The method is applied to the anode of the water system zinc ion battery. The manganous-manganic oxide composite three-dimensional substrate material disclosed by the invention has very high actual specific capacity, such as 100mA g-1At a current density of 296mAhg-1Specific capacity, high cycling stability at 500mA g-1The capacity is not attenuated after the current density is cycled for 500 times, and the specific discharge capacity is far higher than that of other manganese oxide anode materials, such as MnO2[Electrochimica Acta 112(2013)138-143；Chemistry ofMaterials 2015 273609-3620]，Mn2O3[Electrochimica Acta 229(2017)422-428]。
Drawings
FIG. 1 is an XRD spectrum (a) and an XPS energy spectrum (b) of Mn2p orbitals of trimanganese tetroxide grown on a stainless steel mesh in example 1;
FIG. 2 is (a) SEM image and (b) TEM image of trimanganese tetroxide grown on stainless steel mesh in example 1;
FIG. 3 is (a) cyclic voltammogram of trimanganese tetroxide grown on a stainless steel mesh in example 1; (b)100mAg-1Charge-discharge cycle performance and charge-discharge curve of (1); (c)500mA g-1The charge-discharge cycle performance of (1);
FIG. 4 is an SEM image of trimanganese tetroxide grown on a stainless steel mesh in example 2;
fig. 5 is an SEM image of trimanganese tetroxide grown on a stainless steel mesh in example 3.
Fig. 6 is an XRD pattern of the manganomanganic oxide powder sample in example 4.
Detailed Description
The following examples are intended to further illustrate the invention without limiting it.
Example 1
Adding 1mmol KMnO4Adding into 40ml distilled water, stirring at room temperature to obtain dark purple solution, transferring the solution into autoclave, and adding a piece of stainless steel mesh (2X3 cm)2) After 24 hours hydrothermal treatment at 160 ℃ and cooling, the stainless steel mesh was washed several times and then dried in an oven at 60 ℃. Obtaining the mangano-manganic oxide material growing on the stainless steel net.
FIG. 1(a) is an XRD pattern of example 1 of the present invention. As can be seen, the peaks of 3 stainless steel nets are removed, which is good for Mn3O4And (7) corresponding. FIG. 1(b) is an analysis investigating the valence state of manganese, showing 2p of Mn3/2And 2p1/2The peak position of (c). Fig. 2(a) is a scanning electron microscope picture of the manganomanganic oxide material grown on the stainless steel mesh prepared in example 1, which shows that the manganomanganic oxide material has a uniform and closely-arranged nano flower ball structure, and each nano flower ball is formed by combining ultrathin nano sheets. Fig. 2(b) shows a transmission electron microscope picture of the sample prepared in example 1, further confirming that the synthesized spherical material is a nano flower.
The nano flower ball-shaped trimanganese tetroxide material grown on the stainless steel mesh prepared in example 1 was used as the positive electrode, zinc metal was used as the negative electrode, and 2M ZnSO was used as the negative electrode4+0.1M MnSO4The constant current charge and discharge experiment of the battery is tested by adopting L and CT2001A equipment of Wuhan blue-electricity company under room temperature, the test voltage range is 1-1.8V, and the reference is Zn/Zn2+。
Fig. 3 shows electrochemical properties of the nano flower-shaped spherical trimanganese tetroxide material grown on the stainless steel mesh prepared in the example. Wherein, FIG. 3(a) is a cyclic voltammogram; (b)100mAg-1Charge-discharge cycle performance and charge-discharge curve of (1); (c)500mAg-1The charge-discharge cycle performance of (1). At 100mAg-1The maximum specific discharge capacity is 296mAh g-1And has high specific discharge capacity. Simultaneously has stable charge and discharge platform and excellent cycle stability (such as at 500 mAg)-1With little capacity loss, for 500 cycles). It can be seen that the nano flower-shaped spherical trimanganese tetroxide material grown on the stainless steel mesh has excellent electrochemical properties.
Example 2
Adding 1mmol KMnO4Adding into 40ml distilled water, stirring at room temperature to obtain dark purple solution, transferring the solution into autoclave, and adding a piece of stainless steel mesh (2X3 cm)2) The hydrothermal treatment was carried out at 160 ℃ for 6 hours, and after cooling, the stainless steel mesh was washed several times and then dried in an oven at 60 ℃. Obtaining the target product. FIG. 4 is an SEM photograph of the material obtained in example 2.
Example 3
Adding 1mmol KMnO4Adding into 40ml distilled water, stirring at room temperature to obtain dark purple solution, transferring the solution into autoclave, and adding a piece of stainless steel mesh (2X3 cm)2) The hydrothermal treatment was carried out at 160 ℃ for 12 hours, and after cooling, the stainless steel mesh was washed several times and then dried in an oven at 60 ℃. Obtaining the target product. FIG. 5 is an SEM photograph of the material obtained in example 3.
Example 4
Adding 1mmol KMnO4Adding into a mixture of 35ml of distilled water and 5ml of alcohol, stirring at room temperature to obtain a dark purple solution, transferring the obtained solution into an autoclave, performing hydrothermal treatment at 160 ℃ for 24 hours, cooling, washing the obtained product for multiple times, and drying in an oven at 60 ℃. Obtaining the target product. Figure 5 is an XRD pattern of the material obtained in example 4.
Claims (5)
1. A water-based zinc ion battery anode material is characterized by being prepared by the following steps of adding a certain amount of potassium permanganate into deionized water, stirring at room temperature to obtain a dark purple solution, transferring the obtained solution into a high-pressure reaction kettle, adding a three-dimensional substrate material into the solution, carrying out hydrothermal reaction at 160-200 ℃ for 12-48 hours, cooling the hydrothermal reaction, taking out the three-dimensional substrate material, washing, and drying to obtain the nano flower-shaped spherical manganous manganic oxide-loaded anode material of the three-dimensional substrate material, wherein the concentration of the potassium permanganate solution is 0.01-0.1 mol/L.
2. The water-based zinc-ion battery positive electrode material as claimed in claim 1, wherein the three-dimensional substrate comprises a stainless steel mesh, a nickel foam, a carbon fiber cloth or a titanium metal mesh.
3. The water-based zinc-ion battery positive electrode material according to claim 1, wherein the volume of the solution is 50% to 80% of the volume of the autoclave.
4. The aqueous zinc-ion battery positive electrode material according to claim 1, wherein the amount of the trimanganese tetroxide loaded on the three-dimensional substrate material after the reaction is completed is 0.3 to 0.4mg cm-2。
5. The aqueous zinc-ion battery positive electrode material according to claim 1, wherein the aqueous zinc-ion battery positive electrode material is obtained by drying at 50 to 70 ℃ for 8 to 14 hours.
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| JP3663071B2 (en) * | 1999-02-26 | 2005-06-22 | 三洋電機株式会社 | Sealed alkaline zinc storage battery |
| CN105977501B (en) * | 2016-05-19 | 2018-10-19 | 中南大学 | A kind of high-performance hydrogen reduction MnO2-Mn3O4/ carbon nano tube composite catalyst and its preparation method and application |
| CN107230784B (en) * | 2017-06-22 | 2020-05-22 | 山东大学 | Spherical graphene/manganous-manganic oxide composite material and preparation method and application thereof |
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