CN114506860A - Iron-manganese-based Prussian blue solid solution and preparation method thereof - Google Patents
Iron-manganese-based Prussian blue solid solution and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of material synthesis, and relates to a ferro-manganese based Prussian blue solid solution and a preparation method thereof. The chemical formula of the iron-manganese-based Prussian blue solid solution is Nax1(MnxFey)[Fe(CN)6]x2·zH2And O, wherein manganese and iron elements are uniformly distributed from the edge to the center of the particle, the element molar ratio of Mn/Fe is 0.35-0.75, the Mn/Fe-based positive electrode material is used as a sodium ion positive electrode material, an inclined platform is shown between 3.45V and 3.8V in a first circle voltage-capacity curve, and an inclined platform is shown between 3.4V and 3.6V after multiple circles of circulation and stabilization. The method takes the water-alcohol solution composed of prussian white particles or prussian blue particles, sodium salt containing complexing agent and other sodium salts as slurry, takes the water-alcohol solution of divalent manganese salt or divalent iron salt and sodium salt containing complexing agent as solution, and adds the solution into the slurry at a certain temperatureCuring the slurry at 100-180 ℃ to obtain the iron-manganese based Prussian blue solid solution. The material has the charge-discharge characteristics of a single horizontal platform different from manganese-based Prussian white, and can greatly enhance the cycle stability of the sodium-ion battery.
Description
Technical Field
The invention belongs to the technical field of material synthesis, and particularly relates to a ferro-manganese based Prussian blue solid solution and a preparation method thereof.
Background
With the continuous development of global lithium resources, the cost of the lithium resources is always high, and the lithium ion battery gradually loses competitiveness in the field of large-scale energy storage. And compared with a lithium ion battery, the sodium ion battery has more advantages in cost and is always seen in the fields of large-scale energy storage and low-speed electric vehicles.
Among the numerous sodium ion positive electrode materials, manganese-based/iron-based prussian blue analog (Na)xM[Fe(CN)6]y·zH2O, M ═ Mn, Fe) has low raw material cost and simple synthesis method due to its high voltage platform and high specific capacity, and is very attractive in development and application prospects. Defect-free manganese-based prussian blue analog (Na)2Mn[Fe(CN)6]) The theoretical specific capacity is 170mAh/g, the charge-discharge platform is 3.56V/3.44V, and the charge-discharge platform is equivalent to a lithium iron phosphate anode material in a lithium battery, but the cycle stability of the charge-discharge platform is far from satisfactory. The reason for poor cycle stability is mainly Mn3+The material has Jahn-Teller effect, the structure is easy to distort in the charging and discharging process, and the dissolution of transition metal can also occur, so that the collapse of the crystal structure is caused in the long circulation process.
For this reason, surface modification based on manganese-based prussian white has made a lot of work to inhibit the dissolution of manganese ions. For example, in working of Chemical Engineering Journal 411(2021)128518, Ni was added dropwise to a Prussian white slurry2+In manganese-based Prussian white (Na)xMn[Fe(CN)6]y) Nickel-based Prussian blue (Na) is formed on the surfacexNi[Fe(CN)6]y) And a certain stabilizing effect can be achieved. However, the methods only carry out certain modification on the Prussian white on the surface, and the Prussian white in the bulk phase is not obviously improved, so that attenuation still occurs in the later period of circulation. In the Chinese patent application with publication number CN 106920964B, a stepwise precipitation method was used, first FeCl2With Na4Fe(CN)6The iron-based Prussian blue structure is generated through reaction, and then other substituted transition metal salts are added at a certain moment to finally generate the Prussian blue analogue with the gradient structure. However, the method often causes specific capacity loss due to the substitution mode of inactive elements, and meanwhile, the improvement measures do not essentially improve the charge-discharge mechanism of the iron-manganese-based Prussian blue solid solution as the anode material, so that the capacity attenuation is still relatively fast in charge-discharge cycles.
Disclosure of Invention
The invention aims to provide an iron-manganese-based Prussian blue solid solution and a preparation method thereof, and a charge-discharge mechanism of phase transition of manganese-based Prussian blue, which is characterized by having a single horizontal platform of 3.56V/3.44V, is changed, so that the cycle stability is improved.
The chemical formula of the iron-manganese-based Prussian blue solid solution provided by the embodiment of the invention can be expressed as Nax1(MnxFey)[Fe(CN)6]x2·zH2O, wherein 1.5<x1<2,0<x<1,0<y<1,0.5<x2<1, the element molar ratio of Mn/Fe is 0.35-0.75, and manganese or iron elements are uniformly distributed in the iron-manganese-based Prussian blue solid solution.
Correspondingly, the embodiment of the invention also provides a preparation method of the iron-manganese-based Prussian blue solid solution, which comprises the following steps:
(1) dispersing high-sodium Prussian blue particles or high-sodium Prussian white particles in a solvent to obtain slurry, adding a complexing agent or common sodium salt into the slurry, and dissolving to obtain high-sodium Prussian blue slurry or high-sodium Prussian white slurry;
(2) dissolving a divalent manganese salt or a divalent ferric salt in a solvent, and adding a complexing agent to obtain a divalent manganese salt solution or a divalent ferric salt solution;
(3) heating the high-sodium Prussian blue slurry or the high-sodium Prussian white slurry prepared in the step (1) to 120-180 ℃;
(4) adding the divalent manganese salt solution prepared in the step (2) into the high-sodium Prussian blue slurry prepared in the step (3) to obtain a mixed solution; or adding the ferrous salt solution prepared in the step (2) into the high-sodium Prussian white slurry prepared in the step (3) to obtain a mixed solution;
(5) curing the mixed solution obtained in the step (4) in an inert atmosphere to obtain slurry;
(6) and (5) filtering the slurry obtained in the step (5) to obtain a precipitate, washing and drying the precipitate to obtain the iron-manganese-based Prussian blue solid solution.
Alternatively, the high sodium Prussian blue particles have the formula NaxFe[Fe(CN)6]yThe molecular formula of the high-sodium Prussian white particles is NaxMn[Fe(CN)6]yTherein 1.5<x<2,0.5<y<1。
Optionally, in steps (1) and (2), the solvent is water or a mixture of water and ethanol, and the volume of the ethanol is 0% to 40%.
Optionally, in the step (1) and the step (2), the complexing agent is a mixture of one or more of disodium ethylenediamine tetraacetic acid, sodium citrate and sodium gluconate, and the molar concentration of the complexing agent in the high-sodium prussian blue slurry or the high-sodium prussian white slurry is 0.1mol/L to 1 mol/L.
Optionally, in the slurry of step (1), the mass ratio of the solution part to the solid part is: (5-40): 1.
Optionally, in the step (2), the divalent manganese salt or divalent iron salt is a mixture of one or more of chloride, sulfate or nitrate, and the molar concentration of the divalent manganese salt or divalent iron salt is 0.1mol/L to 1 mol/L.
Optionally, in the step (4), in the mixed solution, the volume ratio of the divalent manganese salt solution to the high-sodium prussian blue slurry is (0.5-2): 1, and the volume ratio of the divalent manganese salt solution or the divalent iron salt solution to the high-sodium prussian white slurry is (0.5-2): 1.
Optionally, the curing temperature is 100-180 ℃, and the curing time is 30-180 min; the inert atmosphere is nitrogen or argon.
Optionally, in the step (6), the drying temperature is 100 ℃ to 200 ℃, and the drying time is 1h to 12 h.
The iron-manganese based Prussian blue solid solution and the preparation method thereof have the advantages that:
according to the embodiment of the invention, the exchange rate and degree of Fe/Mn ions are effectively controlled by controlling the solvent environment and the type and content of the complexing agent, so that the solid solution with a specific structure is formed. The iron-manganese-based Prussian blue solid solution prepared by the method provided by the embodiment of the invention has the advantage that iron and manganese elements are uniformly distributed from the edge to the center of the particles. The solid solution has a charge-discharge mechanism different from that of manganese-based Prussian white, and is represented by a change from a single horizontal platform of 3.56V/3.44V corresponding to a phase change mechanism to an inclined platform on a charge-discharge curve, so that the cycling stability of the anode material of the sodium-ion battery is greatly enhanced.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It is obvious that the drawings in the following description are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
Fig. 1(a) is a first-turn charge-discharge curve diagram of the ferromanganese-based prussian blue solid solution of example 1 of the present invention, and (b) is a charge-discharge curve diagram of a typical high-sodium prussian white.
Fig. 2 is a charge-discharge curve diagram of the iron-manganese-based prussian blue solid solution of example 1 of the present invention after 30 cycles of 1C cycles.
FIG. 3 is a TEM electron micrograph and an EDS line scan of a solid solution of FeMnbPrussian blue according to example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The embodiment of the invention provides an iron-manganese-based Prussian blue solid solution, and the chemical formula of the iron-manganese-based Prussian blue solid solution can be expressed as Nax1(MnxFey)[Fe(CN)6]x2·zH2O, wherein 1.5<x1<2,0<x<1,0<y<1,0.5<x2<1, the element molar ratio of Mn or Fe is 0.35-0.75, and the manganese or iron elements are uniformly distributed in the iron-manganese-based Prussian blue solid solution.
Correspondingly, the embodiment of the invention also provides a preparation method of the iron-manganese-based Prussian blue solid solution, which comprises the following steps:
in the step 1, high-sodium prussian blue particles or high-sodium prussian white particles are dispersed in a solvent to obtain slurry, a complexing agent or common sodium salt is added into the slurry, and the high-sodium prussian blue slurry or the high-sodium prussian white slurry is obtained after dissolution.
In some embodiments, the high-sodium prussian blue particles have the formula NaxFe[Fe(CN)6]yThe molecular formula of the high-sodium Prussian white particles is NaxMn[Fe(CN)6]yTherein 1.5<x<2,0.5<y<1。
In some embodiments, the slurry has a mass ratio of solution fraction to solid fraction of: (5 to 40):1
In the step 2, a divalent manganese salt or a divalent iron salt is dissolved in a solvent, and a complexing agent is added to obtain a divalent manganese salt solution or a divalent iron salt solution.
In some embodiments, the solvent is water or a mixture of water and ethanol, and the volume of ethanol is 0% to 40%.
In some embodiments, the complexing agent is a mixture of one or more of disodium ethylenediamine tetraacetic acid, sodium citrate and sodium gluconate, and the molar concentration of the complexing agent in the high-sodium prussian blue slurry or the high-sodium prussian white slurry is 0.1mol/L to 1 mol/L.
In some embodiments, the divalent manganese salt or divalent iron salt is a mixture of one or more of chloride, sulfate or nitrate, and the molar concentration of the divalent manganese salt or divalent iron salt is 0.1mol/L to 1 mol/L.
In step 3, the high-sodium prussian blue slurry or the high-sodium prussian white slurry prepared in the step 1 is heated to 120-180 ℃.
In the step 4, adding the divalent manganese salt solution prepared in the step 2 into the high-sodium Prussian blue slurry prepared in the step 3 to obtain a mixed solution; or adding the ferrous salt solution prepared in the step 2 into the high-sodium Prussian white slurry prepared in the step 3 to obtain a mixed solution.
In some embodiments, the volume ratio of the divalent manganese salt solution to the high-sodium prussian blue slurry in the mixed solution is (0.5-2): 1, and the volume ratio of the divalent manganese salt solution or the divalent iron salt solution to the high-sodium prussian white slurry is (0.5-2): 1.
In step 5, the mixed solution of step 4 is aged in an inert atmosphere to obtain a slurry.
In some embodiments, the curing temperature is 100-180 ℃, and the curing time is 30-180 min; the inert atmosphere is nitrogen or argon.
And 6, filtering the slurry obtained in the step 5 to obtain a precipitate, washing and drying the precipitate to obtain the iron-manganese-based Prussian blue solid solution.
The iron-manganese-based Prussian blue solid solution prepared by the embodiment of the invention is used as a sodium ion anode material, the voltage-capacity curve of the first circle shown by the iron-manganese-based Prussian blue solid solution is an inclined platform between 3.45V and 3.8V, the voltage-capacity curve shown by the iron-manganese-based Prussian blue solid solution is an inclined platform between 3.42V and 3.55V after the iron-manganese-based Prussian blue solid solution is subjected to cyclic multi-circle stabilization, the charge and discharge mechanism of the anode material is changed into a solid solution de-intercalation mechanism, the charge and discharge characteristics of the anode material are different from those of manganese-based Prussian white single horizontal platform, and the cyclic stability of a sodium ion battery can be greatly enhanced. So that the cycle stability is greatly enhanced.
An embodiment of the method of the invention is described below:
example 1
(1) Dispersing 2g of high-sodium Prussian white particles with the molecular formula of Na1.88Mn [ Fe (CN)6] 0.973.2.18H 2O in 40ml of water to obtain slurry, adding 2g of complexing agent sodium citrate and 1g of sodium chloride into the slurry, and dissolving to obtain high-sodium Prussian white slurry, wherein the solid content in the slurry is 4.65%;
(2) the molecular formula is FeCl2·4H2Dissolving 0.5g ferric chloride of O in 30ml water, adding 1g complexing agent sodium citrate to obtain a ferrous salt solution;
(3) heating the high-sodium Prussian white slurry prepared in the step (1) to 150 ℃;
(4) adding the ferrous salt solution prepared in the step (2) into the high-sodium Prussian white slurry prepared in the step (3) at the speed of 1ml/min to obtain a mixed solution;
(5) curing the mixed solution obtained in the step (4) at 150 ℃ for 70min in an argon atmosphere to obtain slurry;
(6) and (3) filtering the slurry obtained in the step (5) to obtain a precipitate, washing the precipitate, and drying at 150 ℃ for 6 hours to obtain the iron-manganese-based Prussian blue solid solution.
In the iron-manganese-based Prussian blue solid solution prepared in the embodiment 1, the Mn/Fe ratio of the crystal structure is 0.39 through ICP-OES test, the crystal structure is used as a positive electrode material of a sodium ion battery, a sodium sheet is used as a negative electrode, and 0.5M NaPF is used6And (2) assembling a button half cell by taking EC, PC and 5% wt FEC as electrolyte, circulating at 1C between 2V and 4.2V, and keeping the capacity retention rate at 96% after circulating for 150 circles. Fig. 1(a) is a first-turn charge-discharge curve graph of the iron-manganese-based prussian blue solid solution prepared in example 1, fig. 1(b) is a typical charge-discharge curve graph of high-sodium prussian white, and it can be seen by comparing fig. 1(a) with fig. 1(b) that the charge-discharge curve of the typical high-sodium prussian white is a single horizontal platform of 3.56V/3.44V, and after the iron-manganese-based prussian blue solid solution is formed, the first-turn charge-discharge curve thereof is an oblique platform between 3.45V and 3.8V. Fig. 2 is a charge-discharge curve diagram of the iron-manganese-based prussian blue solid solution of example 1 of the present invention after 30 cycles of 1C cycles. As can be seen from fig. 2, the stable charge-discharge curve after 30 cycles is a sloping plateau between 3.42V and 3.55V. The tilted plateau charge-discharge mechanism represented in fig. 1(a) and fig. 2 is a solid solution deintercalation mechanism of sodium ions in crystal lattice. FIG. 3(a) is a TEM electron micrograph of the FeMndPrussian blue solid solution of example 1, FIG. 3(b) is an EDS line scan of the FeMndPrussian blue solid solution of example 1, and the ordinate of the EDS is the relative strength (M) of the transition metali-Mmin)/(Mmax-Mmin). Unlike the element described in publication No. CN 106920964B, CN 112645354 a, which has a gradient structure, it can be seen from fig. 3(a) that the distribution of fe and mn elements from the edge of the particle to the center of the particle is substantially uniform, and in combination with the charge and discharge curves of fig. 1(a) and fig. 2, it can be concluded that the structure of the fe-mn-based prussian blue solid solution prepared in this example is a solid solution structure, which makes the stability thereof significantly enhanced without losing capacity.
Example 2
(1) The molecular formula is Na1.88Mn[Fe(CN)6]0.973·2.18H2Dispersing 5g of high-sodium Prussian white particles of O in 40ml of water-alcohol solution, wherein the volume ratio of water to alcohol in the water-alcohol solution is as follows: adding 1g of sodium chloride into the slurry, and dissolving to obtain high-sodium Prussian white slurry with the solid content of 11.9%;
(2) the molecular formula is FeCl2·4H2Dissolving 1.0g of ferric chloride of O in 30ml of water, and adding 1g of complexing agent sodium citrate to obtain a ferrous salt solution;
(3) heating the high-sodium Prussian white slurry prepared in the step (1) to 120 ℃;
(4) adding the ferrous salt solution prepared in the step (2) into the high-sodium Prussian white slurry prepared in the step (3) at the speed of 0.5ml/min to obtain a mixed solution;
(5) curing the mixed solution obtained in the step (4) at 120 ℃ for 180min in a nitrogen atmosphere to obtain slurry;
(6) and (3) filtering the slurry obtained in the step (5) to obtain a precipitate, washing the precipitate, and drying at 120 ℃ for 4 hours to obtain the iron-manganese-based Prussian blue solid solution.
The Mn/Fe ratio of the crystal structure is 0.52 through ICP-OES test, the crystal structure is used as a positive electrode material of a sodium ion battery, a sodium sheet is used as a negative electrode, and 0.5M NaPF6And (2) assembling a button half cell by taking EC, PC and 5% wt FEC as electrolyte, and circulating the cell at 1C between 2V and 4.2V, wherein the capacity retention rate is 92% after 150 circles of circulation.
Example 3
(1) The molecular formula is Na1.74Fe[Fe(CN)6]0.90·2.07H2Dispersing 2g of high-sodium Prussian blue particles of O in 40ml of water to obtain slurry, adding 2g of sodium chloride into the slurry, and dissolving to obtain high-sodium Prussian blue slurry with the solid content of 4.8%;
(2) the molecular formula is MnCl2·4H2Dissolving 1g of manganese chloride of O in 30ml of water, and adding 1g of complexing agent sodium citrate to obtain a manganous salt solution;
(3) heating the high-sodium Prussian blue slurry prepared in the step (1) to 180 ℃;
(4) adding the ferrous salt solution prepared in the step (2) into the high-sodium Prussian blue slurry prepared in the step (3) at the speed of 1ml/min to obtain a mixed solution;
(5) curing the mixed solution obtained in the step (4) at 180 ℃ for 60min in an inert atmosphere to obtain slurry;
(6) and (3) filtering the slurry obtained in the step (5) to obtain a precipitate, washing the precipitate, and drying at 200 ℃ for 60min to obtain the iron-manganese-based Prussian blue solid solution.
The Mn/Fe ratio of the crystal structure is 0.60 through ICP-OES test, the crystal structure is used as a positive electrode material of a sodium ion battery, a sodium sheet is used as a negative electrode, and 0.5M NaPF6And C, PC (1: 1 (vol)) 5% wt FEC (FEC) is used as an electrolyte, the electrolyte is assembled into a button half cell, the button half cell is cycled at 1C between 2V and 4.2V, and the capacity retention rate is 93% after 150 cycles of cycling.
Example 4
(1) 5g of molecular formula Na1.74Fe[Fe(CN)6]0.90·2.07H2Dispersing the high-sodium Prussian blue particles of O in 40ml of water-alcohol solution (the volume ratio of water to ethanol is 9:1) to obtain slurry, adding 1g of sodium citrate into the slurry, and dissolving to obtain high-sodium Prussian blue slurry with the solid content of 12.3%;
(2) 2g of MnCl2·4H2Dissolving O in 30ml of water, and adding 1g of complexing agent sodium gluconate to obtain a divalent manganese salt solution;
(3) heating the high-sodium Prussian blue slurry prepared in the step (1) to 120 ℃;
(4) adding the ferrous salt solution prepared in the step (2) into the high-sodium Prussian blue slurry prepared in the step (3) at the speed of 2ml/min to obtain a mixed solution;
(5) curing the mixed solution obtained in the step (4) at 120 ℃ for 180min in an argon atmosphere to obtain slurry;
(6) and (3) filtering the slurry obtained in the step (5) to obtain a precipitate, washing the precipitate, and drying at 100 ℃ for 12 hours to obtain the iron-manganese-based Prussian blue solid solution.
The Mn/Fe ratio of the crystal structure is 0.45 through ICP-OES test, the crystal structure is used as a positive electrode material of a sodium ion battery, and a sodium sheet is usedAs a negative electrode, 0.5M NaPF6And (2) assembling a button half cell by taking EC, PC and 5% wt FEC as electrolyte, and circulating the cell at 1C between 2V and 4.2V, wherein the capacity retention rate is 92% after 150 circles of circulation.
Example 5
(1) The molecular formula is Na1.88Mn[Fe(CN)6]0.973·2.18H2Dispersing 8g of high-sodium Prussian white particles of O in 40ml of water to obtain slurry, adding 1.5g of ethylene diamine tetraacetic acid and 1g of sodium chloride into the slurry, and dissolving to obtain high-sodium Prussian white slurry with the solid content of 19%;
(2) the molecular formula is FeCl2·4H2Dissolving 1.5g of ferric chloride of O in 30ml of water, and adding 2g of complexing agent sodium gluconate to obtain a ferrous salt solution;
(3) heating the high-sodium Prussian white slurry prepared in the step (1) to 180 ℃;
(4) adding the ferrous salt solution prepared in the step (2) into the high-sodium Prussian white slurry prepared in the step (3) at the speed of 1ml/min to obtain a mixed solution;
(5) curing the mixed solution obtained in the step (4) at 180 ℃ for 120min in an argon atmosphere to obtain slurry;
(6) and (3) filtering the slurry obtained in the step (5) to obtain a precipitate, washing the precipitate, and drying at 180 ℃ for 6 hours to obtain the iron-manganese-based Prussian blue solid solution.
The Mn/Fe ratio of the crystal structure is 0.42 through ICP-OES test, the crystal structure is used as a positive electrode material of a sodium ion battery, a sodium sheet is used as a negative electrode, and 0.5M NaPF6And C, PC (1: 1 (vol)) 5% wt FEC (FEC) is used as an electrolyte, the electrolyte is assembled into a button half cell, the button half cell is cycled at 1C between 2V and 4.2V, and the capacity retention rate is 93% after 150 cycles of cycling.
Example 6
(1) 2g of molecular formula Na1.74Fe[Fe(CN)6]0.90·2.07H2Dispersing the high-sodium Prussian blue particles of O in 40ml of water-alcohol solution (the volume ratio of water to ethanol is 9:1) to obtain slurry, adding 2g of common sodium salt sodium chloride into the slurry, and dissolving to obtain high-sodium Prussian blue slurry with the solid content of 4.5%;
(2) 2g of MnCl2·4H2Dissolving O in 30ml of water, and adding 1g of complexing agent disodium ethylene diamine tetraacetate to obtain a divalent manganese salt solution;
(3) heating the high-sodium Prussian blue slurry prepared in the step (1) to 120 ℃;
(4) adding the ferrous salt solution prepared in the step (2) into the high-sodium Prussian blue slurry prepared in the step (3) at the speed of 1.5ml/min to obtain a mixed solution;
(5) curing the mixed solution obtained in the step (4) at 120 ℃ for 180min in an argon atmosphere to obtain slurry;
(6) and (3) filtering the slurry obtained in the step (5) to obtain a precipitate, washing the precipitate, and drying at 140 ℃ for 12 hours to obtain the iron-manganese-based Prussian blue solid solution.
The Mn/Fe ratio of the crystal structure is 0.65 through ICP-OES test, the crystal structure is used as a positive electrode material of a sodium ion battery, a sodium sheet is used as a negative electrode, and 0.5M NaPF6And C, PC (EC), 1:1(vol) and 5% wt FEC (FEC) are used as electrolyte, the button half cell is assembled and circulated under 1C between 2V and 4.2V, and the capacity retention rate is 90% after 150 cycles of circulation.
While the foregoing is directed to the preferred embodiment of the present disclosure, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (10)
1. The iron-manganese based Prussian blue solid solution is characterized in that the chemical formula is Nax1(MnxFey)[Fe(CN)6]x2·zH2O, wherein 1.5<x1<2,0<x<1,0<y<1,0.5<x2<1, the element molar ratio of Mn/Fe is 0.35-0.75, and manganese or iron elements are uniformly distributed in the iron-manganese-based Prussian blue solid solution.
2. The preparation method of the iron-manganese-based Prussian blue solid solution is characterized by comprising the following steps of:
(1) dispersing high-sodium Prussian blue particles or high-sodium Prussian white particles in a solvent to obtain slurry, adding a complexing agent or common sodium salt into the slurry, and dissolving to obtain high-sodium Prussian blue slurry or high-sodium Prussian white slurry;
(2) dissolving a divalent manganese salt or a divalent ferric salt in a solvent, and adding a complexing agent to obtain a divalent manganese salt solution or a divalent ferric salt solution;
(3) heating the high-sodium Prussian blue slurry or the high-sodium Prussian white slurry prepared in the step (1) to 120-180 ℃;
(4) adding the divalent manganese salt solution prepared in the step (2) into the high-sodium Prussian blue slurry prepared in the step (3) to obtain a mixed solution; or adding the ferrous salt solution prepared in the step (2) into the high-sodium Prussian white slurry prepared in the step (3) to obtain a mixed solution;
(5) curing the mixed solution obtained in the step (4) in an inert atmosphere to obtain slurry;
(6) and (5) filtering the slurry obtained in the step (5) to obtain a precipitate, washing and drying the precipitate to obtain the iron-manganese-based Prussian blue solid solution.
3. The method of claim 2, wherein the high-sodium Prussian blue particles have the formula NaxFe[Fe(CN)6]yThe molecular formula of the high-sodium Prussian white particles is NaxMn[Fe(CN)6]yIn which 1.5<x<2,0.5<y<1。
4. The method according to claim 2, wherein the solvent in steps (1) and (2) is water or a mixture of water and ethanol, and the volume of ethanol is 0-40%.
5. The preparation method according to claim 2, wherein in the step (1) and the step (2), the complexing agent is a mixture of one or more of disodium ethylenediamine tetraacetic acid, sodium citrate and sodium gluconate, and the molar concentration of the complexing agent in the high-sodium prussian blue slurry or the high-sodium prussian white slurry is 0.1mol/L to 1 mol/L.
6. The method according to claim 2, wherein in the step (1), the mass ratio of the solution portion to the solid portion in the slurry is: (5-40): 1.
7. The preparation method according to claim 2, wherein in the step (2), the divalent manganese salt or the divalent iron salt is one or a mixture of more of chloride, sulfate or nitrate, and the molar concentration of the divalent manganese salt or the divalent iron salt is 0.1mol/L to 1 mol/L.
8. The method according to claim 2, wherein in the step (4), the volume ratio of the divalent manganese salt solution to the high-sodium prussian blue slurry in the mixed solution is (0.5 to 2):1, and the volume ratio of the divalent manganese salt solution or the divalent iron salt solution to the high-sodium prussian white slurry is (0.5 to 2): 1.
9. The method according to claim 2, wherein in the step (5), the curing temperature is 100 to 180 ℃, and the curing time is 30 to 180 min; the inert atmosphere is nitrogen or argon.
10. The method according to claim 2, wherein in the step (6), the drying temperature is 100 ℃ to 200 ℃ and the drying time is 1h to 12 h.
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