CN111732112B - Manganese-doped modified zinc ion battery positive electrode active material and preparation method and application thereof - Google Patents
Manganese-doped modified zinc ion battery positive electrode active material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a manganese-doped modified zinc ion battery positive electrode active material and a preparation method and application thereof, wherein the positive electrode active material contains manganese zinc hexacyanoferrate, and the X-ray diffraction pattern of the manganese zinc hexacyanoferrate has absorption peaks at diffraction angles of 2 theta 9.68 degrees, 13.42 degrees, 14.00 degrees, 14.78 degrees, 16.16 degrees, 17.08 degrees, 19.46 degrees, 21.42 degrees, 21.64 degrees, 24.26 degrees, 34.60 degrees and 38.82 degrees, and the error of 2 theta is +/-0.2; preferably, the manganese zinc ferricyanide is prepared by a process comprising the steps of: the zinc salt aqueous solution, the manganese salt aqueous solution and the ferricyanate ion solution are mixed and then react to obtain the product. The positive active material can improve the performance of the zinc ferricyanide positive active material and obviously improve the cycle stability of the positive material.
Description
Technical Field
The invention belongs to the field of zinc ion batteries, and particularly relates to a manganese-doped modified zinc ion battery positive electrode active material, and a preparation method and application thereof.
Background
The zinc has rich resources, low cost, high capacity and environmental protection, and is considered to be one of the most promising cathode materials of a novel energy device. Therefore, aqueous zinc ion batteries (ZIB, zinc being the negative electrode) have been considered as a very promising alternative to the next generation of energy storage technologies. The development of high-performance cathode materials becomes the key of the development of zinc ion batteries. Prussian Blue Analogues (PBA) with an open framework structure allowing inclusion of Zn2+The rapid and reversible insertion/extraction of various cations in the PBA, and the simple manufacture process of the PBA, all of which make the PBA a positive electrode material of a zinc ion battery.
The invention discloses an electrolyte for a water-system zinc ion secondary battery and a preparation method and application thereof, wherein the invention has the application number of 201810208545.X, and the invention uses a Prussian blue analogue as a positive electrode active material, uses a metal zinc or zinc-carbon composite material as a negative electrode material, and uses soluble zinc salt, nickel salt, a pH buffering agent and deionized water to form the electrolyte, so that the coulombic efficiency and the cycle stability of the Prussian blue zinc ion battery are improved.
The invention discloses a preparation method of a zinc ion battery anode, which comprises the steps of mixing a divalent manganese salt solution and a potassium ferricyanide solution to prepare manganese ferricyanide, coating the manganese ferricyanide, a binder and a conductive agent on a current collector to prepare an electrode slice, and carrying out electrolytic activation by using the electrode slice as a cathode, a zinc electrode as an anode and zinc sulfate and manganese sulfate solutions as electrolytes to obtain the battery anode with the manganese ferricyanide embedded with zinc ions as an active substance. The positive electrode of the zinc ion battery obtained by the invention has high specific capacity and good cycle performance. However, the preparation process is complex, the cost is high, the regulation and control of the zinc-manganese ratio are difficult, and the stability of the product needs to be improved.
Disclosure of Invention
The technical problem solved by the invention is as follows: the inventor finds that zinc hexacyanoferrate (ZnHCF) is used as a battery active substance, the problem that zinc ions in the existing Aqueous Rechargeable Zinc Ion Batteries (ARZIBs) are difficult to rapidly migrate is solved, however, the severe phase change and electrochemical dissolution in the constant current circulation process cause that the ZnHCF has seriously reduced capacity and short circulation life in the circulation discharge process, the requirement of the high-energy density zinc ion battery cannot be met, and the further development of the high-energy density zinc ion battery is hindered.
The purpose of the invention is: aiming at the defects and shortcomings of the prior art, the Mn-doped modified ZnHCF positive active material and the preparation method and application thereof are provided.
In order to solve the problems, the invention adopts the technical means of doping Mn ions to prepare MnxZn3-x[Fe(CN)6]2·yH2The O anode active material improves the cycle performance of the anode material so as to meet the requirement of the high-energy density zinc ion battery.
Specifically, aiming at the defects of the prior art, the invention provides the following technical scheme:
a manganese-doped modified zinc-ion battery positive electrode active material comprising manganese zinc ferricyanide having an X-ray diffraction pattern with absorption peaks at diffraction angles 2 θ of 9.68 °, 13.42 °, 14.00 °, 14.78 °, 16.16 °, 17.08 °, 19.46 °, 21.42 °, 21.64 °, 24.26 °, 34.60 ° and 38.82 °, with a 2 θ error of ± 0.2.
Preferably, in the above cathode active material, the molecular formula of the zinc manganese hexacyanoferrate is MnxZn3-x[Fe(CN)6]2·yH2O, where 0 < x < 3 and y is 0 to 10, preferably 0 to 1.
Preferably, in the positive electrode active material, x is 0.03 to 0.50, preferably 0.05 to 0.30, more preferably 0.20 to 0.25, and still more preferably 0.20 to 0.22.
Preferably, in the above positive electrode active material, the manganese zinc ferricyanide is prepared by a method comprising the steps of:
mixing a zinc salt aqueous solution, a manganese salt aqueous solution and an iron cyanate ion solution, and then reacting to obtain the iron manganese cyanide zinc;
wherein the molar ratio of the zinc element in the zinc salt to the manganese element in the manganese salt is (0.01-100): 1, preferably (90-99): (1-10), the molar ratio of the total amount of the zinc element and the manganese element to the iron element in the ferricyanate ion is (0.1-10): 1, preferably (0.5-2): 1.
the invention also provides a preparation method of the positive active material, which is characterized by comprising the following steps:
mixing a zinc salt aqueous solution, a manganese salt aqueous solution and a ferricyanide ion solution, and then reacting to obtain the positive active material;
wherein the molar ratio of the zinc element in the zinc salt to the manganese element in the manganese salt is (0.01-100): 1, the molar ratio of the total amount of the zinc element and the manganese element to the iron element in the ferricyanate ion is (0.1-10): 1.
preferably, in the above preparation method, the molar ratio of the zinc element in the zinc salt to the manganese element in the manganese salt is (90-99): (1-10).
Preferably, in the above preparation method, the molar ratio of the total amount of the zinc element and the manganese element to the iron element in the ferricyanate ion is (0.5-2): 1.
preferably, in the preparation method, the concentration of the zinc salt is 0.018-0.02mol/L, the concentration of the manganese salt is 0.001-0.10mol/L, and the concentration of the iron cyanate ion is 0.01-0.03 mol/L.
Preferably, in the above preparation method, the molar ratio of the manganese element in the manganese salt to the zinc element in the zinc salt is (3-10): (93-95), more preferably (6.5-7.5): (92.5-93.5), more preferably 7: 93.
preferably, in the above preparation method, the preparation method comprises the following steps:
(1) mixing a zinc salt aqueous solution and a manganese salt aqueous solution;
(2) adding the obtained mixed solution into a ferricyanate ion solution;
(3) and (3) stirring the mixture obtained in the step (2), and standing to obtain the manganese-doped modified zinc ion battery positive electrode active material.
Preferably, in the above preparation method, in the step (2), the mixed solution is added into the ferricyanate ion solution at a rate of 50-100 ml/h.
Preferably, in the preparation method, in the step (3), the stirring speed is 400-1200rpm, the stirring time is 30min-24h, and the standing time is 1h-12 h.
Preferably, the preparation method further comprises a drying process of the obtained positive electrode active material, wherein the drying process is carried out at the temperature of 40-70 ℃ and for the time of 6-12 h, preferably 50-70 ℃, and more preferably 60-70 ℃.
Preferably, in the above preparation method, the zinc salt is selected from zinc sulfate, zinc nitrate, zinc acetate, zinc perchlorate, zinc chloride, zinc bromide or zinc iodide; the manganese salt is selected from manganese sulfate, manganese nitrate, manganese acetate, manganese perchlorate, manganese chloride, manganese bromide or manganese iodide; the raw material of the ferricyanate ion is selected from potassium ferricyanate, sodium ferricyanide or ferricyanic acid.
The invention also provides a zinc ion battery positive electrode material which is characterized by comprising the positive electrode active material, a conductive agent and a binder, wherein the positive electrode active material accounts for 60-92% of the positive electrode material by mass.
Preferably, in the positive electrode material, the conductive agent accounts for 5-37% of the positive electrode material by mass, and the binder accounts for 2.5-30% of the positive electrode material by mass.
Preferably, in the above cathode material, the conductive agent is selected from an amorphous carbon material or a graphitized carbon material, preferably conductive carbon black, carbon nanotubes, graphene, acetylene black or activated carbon, and the binder is selected from polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl alcohol, sodium carboxymethylcellulose or styrene butadiene rubber.
The invention also provides a preparation method of the positive electrode material of the zinc ion battery, which is characterized by comprising the following steps:
the method comprises the steps of mixing raw materials including a positive electrode active material, a conductive agent and a binder, adding a dispersing agent, and mixing to form the positive electrode material.
Preferably, in the above method for preparing the positive electrode material for a zinc ion battery, the dispersant is selected from water, ethanol or N-methylpyrrolidone, isopropanol or methanol.
The invention also provides a zinc ion battery electrode, which is characterized by comprising the positive electrode active material or the positive electrode material.
The invention also provides a preparation method of the zinc ion battery electrode, which is characterized by comprising the following steps:
mixing raw materials containing a positive electrode active material, a conductive agent and a binder, adding a dispersing agent, coating the obtained product on a conductive current collector, and drying to obtain the zinc ion battery electrode.
Preferably, the conductive current collector is selected from carbon paper, carbon cloth, carbon felt, titanium foil, stainless steel foil, copper foil, aluminum foil, nickel foam or copper foam.
The present invention also provides a zinc ion battery comprising the positive electrode active material, the positive electrode material, or the zinc ion battery electrode.
The invention also provides the application of the positive active material, the positive material or the zinc ion battery electrode in the field of energy storage.
The term "zinc ion battery" as used herein refers to: in a battery that operates by virtue of zinc ions moving between positive and negative electrodes, the zinc ions may be present in the active material of the positive or negative electrode of the battery, or may be present in the electrolyte.
The term ZnHCF as used herein refers to a zinc ferricyanide positive active material.
The invention has the advantages that: ZnHCF synthesized by the traditional coprecipitation method has poor cycle performance, and in order to improve the ZnHCF performance, the cycle performance of ZnHCF is well improved by doping Mn ions. The specific capacity retention rate of the product prepared by the invention can reach 98.7% at most after 200 cycles, and the cycling stability of the anode material is greatly improved.
Drawings
FIG. 1 is an X-ray diffraction pattern of comparative example 1, comparative example 2, example 1, example 2, example 3, example 4, and example 5.
FIG. 2 is an SEM photograph of the material obtained in comparative example 1, at a magnification of 50000.
FIG. 3 is an SEM photograph of the material obtained in example 2, at 50000 times magnification.
FIG. 4 is an SEM photograph of the material obtained in example 4, at 50000 times magnification.
FIG. 5 shows the results of comparative example 1, comparative example 2, example 1, example 2, example 3, example 4 and example 5 at 250mA · g-1The current multiplying power constant current charge-discharge cycle performance test chart.
Detailed Description
In view of the poor cycle performance of ZnHCF as the positive electrode material of the zinc ion battery, the invention provides a Mn doping technical means, a zinc ion battery positive electrode material taking ferrimanganic cyanide zinc as an active substance, a preparation method and application thereof.
In a preferred embodiment, the present invention provides the following technical solutions:
the molecular formula of the ferricyanide manganese zinc is MnxZn3-x[Fe(CN)6]2·yH2O, where 0 < x < 3 and y is 0 to 10, preferably 0 to 1.
Preferably, in the above cathode material, the manganese zinc ferricyanide is prepared by a method comprising the following steps:
and mixing the zinc salt aqueous solution, the manganese salt aqueous solution and the ferricyanide ion solution, reacting, standing, separating and drying to obtain the ferricyanide manganese zinc.
Preferably, in the above cathode material, the reaction process includes the following steps:
under the stirring state, adding zinc salt and manganese salt aqueous solution into ferricyanate ion solution at the speed of 50-100mL/h, and reacting under the stirring state after blending.
Preferably, in the positive electrode material, the stirring speed is 400-1200 rpm.
Preferably, in the positive electrode material, the reaction time is 30min-24h, and the standing time is 1h-12 h.
Preferably, in the above-mentioned cathode material, the zinc salt is selected from zinc sulfate, zinc nitrate, zinc acetate, zinc perchlorate, zinc chloride, zinc bromide or zinc iodide; the manganese salt is selected from manganese sulfate, manganese nitrate, manganese acetate, manganese perchlorate, manganese chloride, manganese bromide or manganese iodide; the raw material of the ferricyanate ion is selected from potassium ferricyanate, sodium ferricyanide or ferricyanic acid.
Preferably, in the cathode material, the temperature in the drying process is 40-70 ℃ and the time is 6-12 h.
The invention also provides a preparation method of the cathode material, which is characterized by comprising the following steps:
the raw materials containing the positive electrode active material, the conductive agent and the binder are mixed, then the dispersing agent is added, and the mixture is mixed to form the positive electrode material.
Preferably, in the above preparation method, the dispersant is selected from water, ethanol, N-methylpyrrolidone, isopropanol or methanol.
Mixing raw materials containing a positive electrode active material, a conductive agent and a binder, adding a dispersing agent, coating the obtained product on a conductive current collector, and drying to obtain the zinc ion battery electrode.
Preferably, the conductive current collector is selected from carbon paper, carbon cloth, carbon felt, titanium foil, stainless steel foil, copper foil, aluminum foil, nickel foam or copper foam.
In a preferred embodiment, the preparation process flow of the zinc ion positive electrode material and the zinc ion battery is as follows:
mixing and coprecipitating a zinc salt solution and a manganese salt solution + a ferricyanide ion solution, centrifugally collecting → mixing ferricyanide manganese zinc → an active material, a conductive agent and a binder → coating the mixture to prepare a positive electrode → the positive electrode is used for assembling the zinc ion battery.
In another preferred embodiment, the zinc ion positive electrode material and the zinc ion battery of the invention are prepared by the following steps:
(1) and (3) iron manganese cyanide zinc synthesis: mixing a zinc salt aqueous solution (soluble zinc salts such as zinc nitrate, zinc sulfate, zinc chloride and the like) and a manganese salt aqueous solution (soluble manganese salts such as manganese nitrate, manganese sulfate, manganese chloride and the like) according to a certain proportion (the molar ratio of zinc to manganese can be between 0.01 and 100), then blending with a ferricyanide aqueous solution (sodium ferricyanide and potassium ferricyanide) to obtain a mixture, standing, separating by centrifugation or filtration, and drying to obtain ferricyanide zinc manganese;
(2) mixing an active material (ferricyanide manganese zinc), a conductive agent (comprising an amorphous carbon material and/or a graphitized carbon material) and a binder (comprising high polymer materials such as polytetrafluoroethylene, polyvinylidene fluoride and polyvinyl alcohol) according to a certain proportion (the mass ratio of the active material to the binder can be 60-92%, the conductive agent to 5-37% and the binder to 2.5-30%) in the mixture, and adding a dispersing agent (water, ethanol or N-methyl pyrrolidone) to form paint-like slurry;
(3) the obtained slurry can be coated on a conductive current collector (including carbon paper, carbon cloth, carbon felt, titanium foil, stainless steel foil, copper foil, aluminum foil, foamed nickel and foamed copper) by spin coating, blade coating, spray coating and dip coating, and dried to obtain an electrode plate, wherein the electrode loading can be 0.1-30 mg/cm2；
(4) The obtained electrode plate can be used for assembling a zinc ion battery (comprising an aqueous solution system and an organic system) as a positive electrode of the zinc ion battery.
The manganese-doped zinc ion battery positive electrode active material, the preparation method and the application thereof are further described by specific examples.
In the following examples, the information on the instruments used is:
thermogravimetric analyzer: the manufacturer: netzsch, model: STA 449F 5 Jupiter.
Scanning electron microscope: the manufacturer: zeiss, model number: ultra 5.
An electrochemical workstation: the manufacturer: shanghai Chenghua, type: CHI 660E.
In the following examples, information on the reagents used is shown in the following table:
conductive carbon black: specification Super P, manufacturer Timcal.
Polyvinylidene fluoride: solef5130, manufacturer: suwei.
Other reagents are analytically pure, and the purchase manufacturers are Chinese medicine reagents.
Comparative example 1
Preparation of Zn3[Fe(CN)6]2(ZnHCF for short) and the steps are as follows:
(1) weighing 0.5751g of ZnSO4·7H2O, adding into 100mL deionized water to prepare 0.02mol/L ZnSO4An aqueous solution;
(2) weighing 0.6585g K3Fe(CN)6Adding into 100mL deionized water to prepare 0.02mol/L K3Fe(CN)6An aqueous solution;
(3) 100mL of ZnSO4The aqueous solution was added to 100mL K at a rate of 100mL/h3Fe(CN)6Stirring vigorously (stirring at 1000rpm) to form a mixture;
(4) keeping the mixture vigorously stirred (the stirring speed is 1000rpm) for 12 hours, and then standing for 6 hours to obtain a product;
(5) the product was centrifuged, washed several times with deionized water until all salts were removed, and dried at 70 ℃ for 12 hours to give zinc ferricyanide Zn3[Fe(CN)6]2And (3) a solid.
Analyzing the zinc ferricyanide solid by an X-ray diffractometer to obtain an XRD curve and Zn3[Fe(CN)6]2The rhombohedral phase standard maps (JCPDS card numbers 38-688) are consistent, which indicates that the product obtained in comparative example 1 is Zn with a rhombohedral structure3[Fe(CN)6]2A material.
The zinc hexacyanoferrate product obtained in comparative example 1 was prepared into an electrode sheet and subjected to electrochemical testing, the procedure was as follows:
0.28g of the above Zn was added to 0.8mL of NMP (N-methylpyrrolidone) as a dispersant3[Fe(CN)6]2Uniformly stirring the solid, 0.08g of conductive carbon black (Super P) and 0.04g of polyvinylidene fluoride, coating the mixture on a titanium foil material, and drying the titanium foil material at 70 ℃ to obtain a zinc hexacyanoferrate electrode slice;
the button cell is manufactured by taking the zinc hexacyanoferrate electrode slice as a positive electrode, taking a zinc slice as a negative electrode and taking 1mol/L zinc sulfate aqueous solution as electrolyte, and then electrochemical test is carried out.
Comparative example 2
Preparation of Mn3[Fe(CN)6]2(abbreviated as MnHCF) comprises the following steps:
(1) weighing 0.3579g Mn (NO)3)2Adding the mixture into 100mL of deionized water to prepare 0.02mol/L Mn (NO)3)2An aqueous solution;
(2) weighing 0.6585g K3Fe(CN)6Adding into 100mL deionized water to prepare 0.02mol/L K3Fe(CN)6An aqueous solution;
(3) 100mL of Mn (NO)3)2The aqueous solution was added to 100mL K at a rate of 100mL/h3Fe(CN)6Stirring vigorously (stirring at 1000rpm) to form a mixture;
(4) keeping the mixture vigorously stirred (the stirring speed is 1000rpm) for 12 hours, and then standing for 6 hours to obtain a product;
(5) centrifuging the product, washing with deionized water several times until all salts are removed, and drying at 70 deg.C for 12 hr to obtain manganese ferricyanide Mn3[Fe(CN)6]2And (3) a solid.
The manganese hexacyanoferrate solid is analyzed by an X-ray diffractometer, and the obtained XRD curve is consistent with a cubic phase standard spectrum (JCPDS No. 38-687), which indicates that the product obtained in the comparative example 2 is Mn with a cubic structure3[Fe(CN)6]2A material.
Referring to comparative example 1, the manganese hexacyanoferrate product obtained in comparative example 2 was prepared into an electrode sheet and subjected to electrochemical testing.
Example 1
Preparation of Mn0.03Zn2.97[Fe(CN)6]2·yH2O (MZHCF for short), the following steps:
(1) weighing 0.5693g of ZnSO4·7H2O and 0.0035g Mn (NO)3)2Adding into 100mL deionized water to prepare0.0198mol/L ZnSO4And 0.0002mol/L of Mn (NO)3)2Mixing the solution;
(2) weighing 0.6585g K3Fe(CN)6Adding into 100mL deionized water to prepare 0.02mol/L K3Fe(CN)6An aqueous solution;
(3) 100mL of ZnSO4With Mn (NO)3)2The mixed solution was added to 100mL K at a rate of 50mL/h3Fe(CN)6Stirring vigorously (at 500rpm) to form a mixture;
(4) keeping the mixture vigorously stirred (the stirring speed is 500rpm) for 12 hours, and then standing for 6 hours to obtain a product;
(5) washing the reaction product with deionized water and ethanol, and drying at 70 deg.C for 12 hr to obtain Mn0.03Zn2.97[Fe(CN)6]2·yH2And (4) O solid.
Example 2
Preparation of Mn0.09Zn2.91[Fe(CN)6]2·yH2O, the steps are as follows:
(1) weighing 0.5579g of ZnSO4·7H2O and 0.0107g Mn (NO)3)2Adding into 100mL deionized water to prepare 0.0194mol/L ZnSO4And 0.0006mol/L of Mn (NO)3)2Mixing the solution;
(2) weighing 0.6585g K3Fe(CN)6Adding into 100mL deionized water to prepare 0.02mol/L K3Fe(CN)6An aqueous solution;
(3) 100mL of ZnSO4With Mn (NO)3)2The mixed solution was added to 100mL K at a rate of 100mL/h3Fe(CN)6Stirring the aqueous solution vigorously (at 800rpm) to form a mixture;
(4) keeping the mixture vigorously stirred (the stirring speed is 800rpm) for 12 hours, and then standing for 6 hours to obtain a product;
(5) washing the reaction product with deionized water and ethanol, and drying at 70 deg.C for 12 hr to obtain Mn0.09Zn2.91[Fe(CN)6]2·yH2And (4) O solid.
Example 3
Preparation of Mn0.15Zn2.85[Fe(CN)6]2·yH2O, the steps are as follows:
(1) weighing 0.5463g of ZnSO4·7H2O and 0.0180g Mn (NO)3)2Adding into 100mL deionized water to prepare ZnSO with the concentration of 0.0190mol/L4And 0.0010mol/L of Mn (NO)3)2Mixing the solution;
(2) weighing 0.6585g K3Fe(CN)6Adding into 100mL deionized water to prepare 0.02mol/L K3Fe(CN)6An aqueous solution;
(3) 100mL of ZnSO4With Mn (NO)3)2The mixed solution was added to 100mL K at a rate of 100mL/h3Fe(CN)6Stirring vigorously (stirring at 1000rpm) to form a mixture;
(4) keeping the mixture vigorously stirred (the stirring speed is 1000rpm) for 12 hours, and then standing for 6 hours to obtain a product;
(5) washing the reaction product with deionized water and ethanol, and drying at 70 deg.C for 12 hr to obtain Mn0.15Zn2.85[Fe(CN)6]2·yH2And (4) O solid.
Example 4
Preparation of Mn0.21Zn2.79[Fe(CN)6]2·yH2O, the steps are as follows:
(1) weighing 0.5349g of ZnSO4·7H2O and 0.0251g Mn (NO)3)2Adding into 100mL deionized water to prepare 0.0186mol/L ZnSO4And 0.0014mol/L of Mn (NO)3)2Mixing the solution;
(2) weighing 0.6585g K3Fe(CN)6Adding into 100mL deionized water to prepare 0.02mol/L K3Fe(CN)6An aqueous solution;
(3) 100mL of ZnSO4With Mn (NO)3)2The mixed solution was added to 100mL K at a rate of 100mL/h3Fe(CN)6Stirring the aqueous solution vigorously (at 800rpm) to form a mixture;
(4) keeping the mixture vigorously stirred (the stirring speed is 800rpm) for 12 hours, and then standing for 6 hours to obtain a product;
(5) washing the reaction product with deionized water and ethanol, and drying at 70 deg.C for 12 hr to obtain Mn0.21Zn2.79[Fe(CN)6]2·yH2And (4) O solid.
Example 5
Preparation of Mn0.30Zn2.70[Fe(CN)6]2·yH2O, the steps are as follows:
(1) weighing 0.5176g of ZnSO4·7H2O and 0.0358g Mn (NO)3)2Adding into 100mL deionized water to prepare 0.0180mol/L ZnSO4And 0.0020mol/L of Mn (NO)3)2Mixing the solution;
(2) weighing 0.6585g K3Fe(CN)6Adding into 100mL deionized water to prepare 0.02mol/L K3Fe(CN)6An aqueous solution;
(3) 100mL of ZnSO4With Mn (NO)3)2The mixed solution was added to 100mL K at a rate of 100mL/h3Fe(CN)6Stirring vigorously (at 500rpm) to form a mixture;
(4) keeping the mixture vigorously stirred (the stirring speed is 500rpm) for 12 hours, and then standing for 6 hours to obtain a product;
(5) washing the reaction product with deionized water and ethanol, and drying at 70 deg.C for 12 hr to obtain Mn0.30Zn2.70[Fe(CN)6]2·yH2And (4) O solid.
The following tests were carried out on the above comparative examples and examples:
XRD detection
The crystal structure was analyzed by powder X-ray diffraction (XRD, Bruker D8Advance X) with a Cu target (K α ═ 1/1.54056), and the results are shown in fig. 1.
As can be seen from fig. 1, the X-ray diffraction patterns of the manganese zinc hexacyanoferrate described in examples 1 to 5 have absorption peaks at diffraction angles of 9.68 °, 13.42 °, 14.00 °, 14.78 °, 16.16 °, 17.08 °, 19.46 °, 21.42 °, 21.64 °, 24.26 °, 34.60 ° and 38.82 °, wherein a plurality of peaks shown at 9.68 °, 13.42 °, 14.00 °, 16.16 °, 19.46 °, 21.42 ° and 21.64 ° correspond to (012), (104), (110), (113), (024), (116) and (211), respectively, rhombohedral phase ZnHCF (JCPDS card number 38-688); meanwhile, several new peaks at 14.78 °, 17.08 °, 24.26 °, 34.60 ° and 38.82 ° correspond to (111), (200), (220), (400) and (420) of cubic MnHCF (JCPDS No. 38-687). As the Mn content increases, the (200) peak intensity of the cubic phase increases, while the (113) peak of the rhombohedral phase decreases. This result suggests that cubic manganese: the proportion of rhombohedrons increases with increasing Mn content. The cubic structure of ZnHCF strongly depends on the structure of the crystals in [ Fe (CN)6]Vacancy occupied Zeolite Water, Mn since all samples were subjected to the same drying procedure2+The partial substitution stabilizes the zeolite water molecules within the lattice. MnHCF has a lower peak position than cubic ZnHCF, indicating that the lattice expansion is due to
Ion radius ratio of
Is large. It can be seen that in examples 1 to 5, manganese was successfully doped into zinc hexacyanoferrate.
SEM-EDS analysis
Scanning electron microscopy (SEM-EDS, Zeiss Ultra 5) equipped with energy dispersive X-ray spectroscopy was used to investigate the morphology and composition of the samples.
SEM pictures of comparative example 1, example 2 and example 4 are shown in FIGS. 2, 3 and 4, respectively, and it can be seen that the sample obtained in comparative example 1 is a nano-cube with a particle size of 200nm to 500 nm. The MZHCF samples obtained in the examples are all cubic, smooth in surface and enlarged in diameter to 400-500 nm.
Sample composition was studied by EDS and results indicated: mn of example 1, example 2, example 3, example 4 and example 5: the ratios of (Mn + Zn) were 0.02, 0.03, 0.06, 0.07 and 0.12, respectively. These values are close to the reactant ratios used in the preparation process.
3. Thermogravimetric analysis
The weight loss ratio was observed by thermogravimetric analysis under nitrogen atmosphere heated to 150 degrees, and y was calculated to be 0 in the molecular formula of the products obtained in example 1, example 2, example 3, example 4 and example 5.
4. Electrochemical testing
The manganese zinc hexacyanoferrate products obtained in the examples 1 to 5 are prepared into electrode slices and subjected to electrochemical test, and the steps are as follows:
0.28g of manganese zinc hexacyanoferrate solid obtained in each example, 0.08g of conductive carbon black (Super P) and 0.04g of polyvinylidene fluoride are uniformly stirred by taking 0.8mL of NMP (N-methylpyrrolidone) as a dispersing agent, coated on a titanium foil material and dried at 70 ℃ to obtain the manganese zinc hexacyanoferrate electrode sheet.
The button cell is manufactured by taking the ferricyanide manganese zinc electrode slice as a positive electrode, taking a zinc slice as a negative electrode and taking 1mol/L zinc sulfate aqueous solution as electrolyte, and then electrochemical test is carried out.
The charge and discharge cycle performance curves of the electrode sheets obtained in the comparative example and the example under the condition of 250mA/g and 5C are detected by an electrochemical workstation, and the result is shown in FIG. 5.
The first-cycle discharge capacity of ZnHCF obtained in comparative example 1 was 51.8mA g-1. With successive cycles, the capacity slowly decreases over the first 150 cycles and then rapidly decreases over the next 50 cycles. The discharge capacity is 16.4 mA-g after 200 times of cycle test-1Only 31.7% of the initial capacity. The MnHCF obtained in comparative example 2 had a low initial discharge capacity of 43.2mA g-1. After 10 cycles of activation, the capacity increased to a maximum of 89.9mAh g-1But decreases rapidly in subsequent cycles. After 200 cycles, 21.1% of the initial capacity (only 10.1% of the maximum capacity) was retained. The resulting MZHCF samples of all examples show improved cycling performance. Example 1Initial discharge capacities of example 2, example 3, example 4 and example 5 were 47.3, 39.5, 46.8, 40.7 and 45.6mAh · g, respectively-1. The capacity increase in the first few cycles is due to electrode activation. The maximum discharge capacities of example 1, example 2, example 3, example 4 and example 5 were 52.6, 40.9, 46.9, 45.7 and 45.6mAh g, respectively-1. The capacity retention rates of the respective comparative examples and examples are shown in the table below, and it is understood from the table that the zinc manganese ferricyanide obtained in examples 1 to 5 greatly improves the cycle stability of the zinc ferricyanide positive electrode material.
TABLE 1 Charge-discharge cycling performance of comparative examples and examples
Example 6
Preparation of Mn1.0Zn2.0[Fe(CN)6]2·yH2O, the steps are as follows:
(1) weighing 0.3853g of ZnSO4·7H2O and 0.1199g Mn (NO)3)2Adding into 100mL deionized water to prepare 0.0134mol/L ZnSO4And 0.0067mol/L of Mn (NO)3)2Mixing the solution;
(2) weighing 0.6585g K3Fe(CN)6Adding into 100mL deionized water to prepare 0.02mol/L K3Fe(CN)6An aqueous solution;
(3) 100mL of ZnSO4With Mn (NO)3)2The mixed solution was added to 100mL K at a rate of 100mL/h3Fe(CN)6Stirring vigorously (stirring at 1000rpm) to form a mixture;
(4) keeping the mixture vigorously stirred (the stirring speed is 1000rpm) for 12 hours, and then standing for 6 hours to obtain a product;
(5) washing the reaction product with deionized water and ethanol, and drying at 70 deg.C for 12 hr to obtain Mn1.0Zn2.0[Fe(CN)6]2·yH2And (4) O solid.
After detection by an X-ray diffractometer, the XRD pattern of the manganese zinc ferricyanide obtained in the embodiment is similar to that of embodiment 1, and the positions of characteristic peaks are the same as those of embodiment 1.
As can be seen from thermogravimetric analysis, in the molecular formula of the manganese zinc ferricyanide obtained in this example, y is 0.
The zinc hexacyanoferrate product obtained in example 6 was prepared into an electrode sheet and subjected to electrochemical testing, the procedure was as follows:
0.60g of the above Zn was added to 0.8mL of NMP (N-methylpyrrolidone) as a dispersant3[Fe(CN)6]2Uniformly stirring the solid, 0.12g of conductive carbon black (Super P) and 0.04g of polyvinylidene fluoride, coating the mixture on a titanium foil material, and drying the titanium foil material at 70 ℃ to obtain a zinc hexacyanoferrate electrode slice; the button cell is manufactured by taking the zinc hexacyanoferrate electrode slice as a positive electrode, taking a zinc slice as a negative electrode and taking 1mol/L zinc sulfate aqueous solution as electrolyte, and then electrochemical test is carried out.
The charge-discharge cycle performance curve of the electrode plate obtained in the embodiment is detected by the same method as that of the embodiment 1, the initial capacity is 43.5mAh/g, the capacities after 50, 100 and 200 cycles are 40.6mAh/g, 36.3mAh/g and 15.1mAh/g respectively, and the capacity retention rate of 200 cycles is 34.7%.
Example 7
Preparation of Mn2.0Zn1.0[Fe(CN)6]2·yH2O, the steps are as follows:
(1) weighing 0.1926g of ZnSO4·7H2O and 0.2398g Mn (NO)3)2Adding into 100mL deionized water to prepare 0.0067mol/L ZnSO4And Mn (NO) of 0.0134mol/L3)2Mixing the solution;
(2) weighing 0.6585g K3Fe(CN)6Adding into 100mL deionized water to prepare 0.02mol/L K3Fe(CN)6An aqueous solution;
(3) 100mL of ZnSO4With Mn (NO)3)2The mixed solution was added to 100mL K at a rate of 100mL/h3Fe(CN)6Stirring vigorously (stirring at 1000rpm) to form a mixture;
(4) keeping the mixture vigorously stirred (the stirring speed is 1000rpm) for 12 hours, and then standing for 6 hours to obtain a product;
(5) washing the reaction product with deionized water and ethanol, and drying at 70 deg.C for 12 hr to obtain Mn2.0Zn1.0[Fe(CN)6]2·yH2And (4) O solid.
After detection by an X-ray diffractometer, the XRD pattern of the manganese zinc ferricyanide obtained in the embodiment is similar to that of embodiment 1, and the positions of characteristic peaks are the same as those of embodiment 1.
As can be seen from thermogravimetric analysis, in the molecular formula of the manganese zinc ferricyanide obtained in this example, y is 0.
The zinc hexacyanoferrate product obtained in example 6 was prepared into an electrode sheet and subjected to electrochemical testing, the procedure was as follows:
0.60g of the above Zn was added to 0.8mL of NMP (N-methylpyrrolidone) as a dispersant3[Fe(CN)6]2Uniformly stirring the solid, 0.10g of conductive carbon black (Super P) and 0.30g of polyvinylidene fluoride, coating the mixture on a titanium foil material, and drying at 70 ℃ to obtain a zinc hexacyanoferrate electrode slice; the button cell is manufactured by taking the zinc hexacyanoferrate electrode slice as a positive electrode, taking a zinc slice as a negative electrode and taking 1mol/L zinc sulfate aqueous solution as electrolyte, and then electrochemical test is carried out.
The charge-discharge cycle performance curve of the electrode plate obtained in the embodiment is detected by the same method as that of the embodiment 1, the initial capacity is 46.1mAh/g, the capacities after 50, 100 and 200 cycles are 42.3mAh/g, 30.2mAh/g and 12.6mAh/g respectively, and the capacity retention rate of 200 cycles is 27.3%.
Example 8
Manganese-doped zinc hexacyanoferrate was prepared by analogy with the procedure of example 2, with the following differences:
(5) washing the reaction product with deionized water and ethanol, and drying at 50 deg.C for 8 hr to obtain Mn0.09Zn2.91[Fe(CN)6]2·yH2And (4) O solid.
After detection by an X-ray diffractometer, the XRD pattern of the manganese zinc ferricyanide obtained in the embodiment is similar to that of embodiment 1, and the positions of characteristic peaks are the same as those of embodiment 1.
As can be seen from thermogravimetric analysis, in the molecular formula of the manganese zinc ferricyanide obtained in this example, y is 1.
The charge-discharge cycle performance curve of the electrode plate obtained in the embodiment is detected by the same method as that of the embodiment 1, the initial capacity is 45.3mAh/g, the capacities after 50, 100 and 200 cycles are 39.2mAh/g, 30.6mAh/g and 16.1mAh/g respectively, and the capacity retention rate of 200 cycles is 35.5%.
Example 9
Prepared by the similar procedure of example 2
Manganese-doped zinc hexacyanoferrate, with the following differences:
(5) washing the reaction product with deionized water and ethanol, and drying at 40 deg.C for 10 hr to obtain Mn0.09Zn2.91[Fe(CN)6]2·yH2And (4) O solid.
After detection by an X-ray diffractometer, the XRD pattern of the manganese zinc ferricyanide obtained in the embodiment is similar to that of embodiment 1, and the positions of characteristic peaks are the same as those of embodiment 1.
As can be seen from thermogravimetric analysis, in the molecular formula of the manganese zinc ferricyanide obtained in this example, y is 10.
The charge-discharge cycle performance curve of the electrode plate obtained in the embodiment is detected by the same method as that of the embodiment 1, the initial capacity is 39.2mAh/g, the capacities after 50, 100 and 200 cycles are 34.3mAh/g, 27.5mAh/g and 10.1mAh/g respectively, and the capacity retention rate of 200 cycles is 25.8%.
In conclusion, the Mn-doped modified positive electrode active material for the zinc ion battery can well improve the cycle performance of ZnHCF, greatly improve the specific capacity retention rate after 200 cycles and greatly improve the cycle stability of the positive electrode material.
Claims (9)
1. A manganese-doped and modified positive electrode active material for an aqueous solution system zinc ion battery, characterized by comprising zinc manganese ferricyanide, wherein the X-ray diffraction pattern of the zinc manganese ferricyanide has absorption peaks at diffraction angles 2 θ of 9.68 °, 13.42 °, 14.00 °, 14.78 °, 16.16 °, 17.08 °, 19.46 °, 21.42 °, 21.64 °, 24.26 °, 34.60 ° and 38.82 °, and the error of 2 θ is ± 0.2;
wherein the molecular formula of the ferricyanide manganese zinc is MnxZn3-x[Fe(CN)6]2·yH2O, wherein x is 0.21 and y is 0.
2. A method for producing the positive electrode active material according to claim 1, comprising the steps of:
mixing a zinc salt aqueous solution, a manganese salt aqueous solution and a ferricyanide ion solution, and then reacting to obtain the positive active material;
wherein the molar ratio of the zinc element in the zinc salt to the manganese element in the manganese salt is (90-99): (1-10), the molar ratio of the total amount of the zinc element and the manganese element to the iron element in the ferricyanate ion is (0.5-2): 1.
3. the production method according to claim 2, wherein the production method comprises the steps of:
(1) mixing a zinc salt aqueous solution and a manganese salt aqueous solution;
(2) adding the obtained mixed solution into a ferricyanate ion solution;
(3) and (3) stirring the mixture obtained in the step (2), and standing to obtain the manganese-doped modified zinc ion battery positive electrode active material.
4. The production method according to claim 2 or 3, wherein the zinc salt is selected from zinc sulfate, zinc nitrate, zinc acetate, zinc perchlorate, zinc chloride, zinc bromide, or zinc iodide; the manganese salt is selected from manganese sulfate, manganese nitrate, manganese acetate, manganese perchlorate, manganese chloride, manganese bromide or manganese iodide; the raw material of the ferricyanate ion is selected from potassium ferricyanate, sodium ferricyanide or ferricyanic acid.
5. A positive electrode material for an aqueous solution system zinc-ion battery, comprising the positive electrode active material according to claim 1, a conductive agent, and a binder, wherein the positive electrode active material accounts for 60% to 92% of the mass of the positive electrode material.
6. The positive electrode material according to claim 5, wherein the conductive agent accounts for 5-37% of the positive electrode material by mass, and the binder accounts for 2.5-30% of the positive electrode material by mass.
7. An electrode for zinc ion battery in aqueous solution system, comprising the positive electrode active material according to claim 1 or the positive electrode material according to claim 5 or 6.
8. An aqueous solution system zinc ion battery comprising the positive electrode active material according to claim 1, or the positive electrode material according to claim 5 or 6, or the zinc ion battery electrode according to claim 7.
9. Use of the positive electrode active material of claim 1, or the positive electrode material of claim 5 or 6, or the zinc ion battery electrode of claim 7 in the field of energy storage.
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