CN115448326A - Ferromanganese iron binary-based Prussian blue analogue with less crystal water and preparation method thereof - Google Patents
Ferromanganese iron binary-based Prussian blue analogue with less crystal water and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of production of positive electrode materials of sodium-ion batteries, and relates to a ferromanganese iron binary-based Prussian blue analogue with less crystal water and a preparation method thereof; the specific molecular formula is Na x Mn a Fe 1‑a [Fe(CN) 6 ] y ·nH 2 X is more than or equal to 0,1.8 and less than or equal to 2, a is more than or equal to 0.05 and less than or equal to 0.5, y is more than or equal to 0.95 and less than or equal to 1, and n is less than or equal to 2; adding mother liquor, a sodium source and an auxiliary reagent into a complex reactor, and adding a sodium ferrocyanide solution, a manganous salt and a ferrous salt aqueous solution into the complex reactor to perform coprecipitation complexing and ageing reaction to form reaction slurry; sanding and solid-liquid separation; the mother liquor can be recycled; the yield of the ferromanganese iron binary Prussian blue analogue prepared by the invention is high and can reach more than 98 percent; the product has good cycle performance and high specific capacity.
Description
Technical Field
The invention belongs to the technical field of production of positive electrode materials of sodium-ion batteries, and particularly relates to a ferromanganese iron binary-based Prussian blue analogue with less crystal water and a preparation method thereof, which are applied to industrial green production of the positive electrode materials of the sodium-ion batteries.
Background
With the rapid development of electric vehicles and smart grid energy storage systems, secondary batteries have been increasingly used in the energy storage field as an energy storage technology with the highest energy efficiency. The lithium ion battery occupying the main market severely restricts the sustainable development of the lithium ion battery due to the shortage of lithium resources. And the sodium element of the same main group with lithium has similar physical and chemical properties and electrochemical characteristics with lithium, abundant reserves and low price, so that the sodium-ion battery becomes a lithium-ion battery substitute with great prospect.
The positive electrode material with high capacity and stability is a key factor for restricting the development of the sodium-ion battery. At present, polyanionic compounds, transition metal oxides, prussian blue analogs and the like are mainly used as sodium ion positive electrode materials, wherein the Prussian blue analogs are suitable for rapid migration of sodium ions with larger radius due to unique open frames and three-dimensional macroporous structures, have the advantages of no toxicity, low price, excellent electrochemical performance and the like, and are concerned by sodium storage materials with great potential.
Common preparation methods of the Prussian blue analogue serving as the sodium ion battery anode material include a coprecipitation method, a hydrothermal method and a ball milling method, wherein the coprecipitation method is safe and environment-friendly and is suitable for large-scale production, so that the Prussian blue analogue becomes a synthesis method commonly adopted in the existing research. Generally, the structural general formula of the synthesized Prussian blue type sodium ion battery positive electrode material can be expressed as
Wherein M represents transition metal ions such as Fe, mn, co, ni, cu, zn, etc.,
represents Fe (CN) 6 4- Structural defects and occupation by coordinated water moleculesAccordingly. Considering factors such as electrochemical performance, price and the like comprehensively, the M is considered to be the most suitable anode material for the sodium-ion battery at present when the M is Fe and Mn. The Mn-based Prussian white sodium ion cathode material Na containing small-size irregular particles and large-size cuboid particles simultaneously is prepared in patent CN108821310B 1.8 Mn[Fe(CN) 6 ] y ·nH 2 The discharge specific capacity of O,0.1C can reach 140mAh/g, after 300 times of circulation at 0.5C, the capacity can be kept at 104mAh/g, the capacity retention rate is 88%, and the charge-discharge platform is more than 3.6V. Although the existence of the cuboid particles with large sizes is favorable for slowing down the corrosion speed of the material by the electrolyte, the cycle life of the material is prolonged to a certain extent, but the material still cannot meet the requirements of practical batteries. Iron-based Prussian blue analogue Na X Fe[Fe(CN) 6 ] Y ·nH 2 O, although improved in cycle stability over manganese based prussian white, is still less desirable. And the energy density is lower due to the lower voltage platform and specific capacity of about 3.0V.
The Prussian blue anode material with high sodium content is synthesized by adopting a coprecipitation method in CN110199420A and CN110235292A patents, and the molecular formula is Na x M a N b Fe(CN) 6 Wherein M and N are the same or different transition metals, each independently selected from Fe, co, mn, ni, cu, zn, cr, V, zr or Ti,1.8<x<2,0<a<1,0<b<1, a + b =1. The molecular formula of the Prussian blue analogue sodium-ion battery anode material synthesized by the coprecipitation method in the CN106920964A patent is Na x M y Fe 1-y [Fe(CN) 6 ]a·nH 2 0, wherein M is the transition metal element, x is more than or equal to 0.3 and less than or equal to 1.5, y is more than or equal to 0.05 and less than or equal to 0.5, Z is more than or equal to 0.7 and less than or equal to 0.9, and n is more than or equal to 1 and less than or equal to 3.75. Compared with single manganese-based and iron-based cathode materials, the synthesized Prussian blue-doped cathode material has excellent electrochemical performance and cycle stability, and the invention methods proposed in patents CN110199420A and CN110235292A are suitable for industrial amplification. However, sustainable production of closed cycle of the process is not considered in any of the three patents, and the process does not include: recycling mother liquor; the separation and recovery of the by-product sodium salt and the balance of water do not have industrial production value and are lack of large scaleA feasible industrial method for industrially producing the cathode material. Meanwhile, auxiliary reagents such as complexing agent, surfactant and the like are not added, so that the particle size of the synthesized product is still required to be further improved.
Disclosure of Invention
The invention overcomes the defects of the prior art and provides a ferromanganese iron binary-based Prussian blue analogue with less crystal water and a preparation method thereof.
In order to achieve the above object, the present invention is achieved by the following technical solutions.
A manganese iron binary group Prussian blue analogue with less crystal water has a molecular formula of Na x Mn a Fe 1-a [Fe(CN) 6 ] y ·nH 2 0，1.8≤x≤2，0.05≤a≤0.5，0.95≤y≤1，n≤2。
A preparation method of a ferromanganese iron binary-based Prussian blue analogue with less crystal water comprises the following steps:
1) Adding the mother solution, a sodium source and an auxiliary reagent which are used mechanically into a complex reactor, and under the protection of nitrogen and under the condition of high-speed stirring, feeding a sodium ferrocyanide solution, a manganous salt aqueous solution and a ferrite aqueous solution into the complex reactor for coprecipitation complex reaction and aging reaction to form reaction slurry; mn in aqueous solution 2+ With Fe 2+ In a molar ratio of 1.
2) And (3) performing sand grinding treatment on the ferromanganese dibasic Prussian blue analogue precipitate in the reaction slurry to form fine particles.
3) Carrying out solid-liquid separation on the reaction slurry after sanding to obtain a solid phase and a mother solution; part of the mother liquor is used as a raw material for the precipitation and complexation reaction in the step 1), and the other part of the mother liquor is fully settled.
4) Washing water and a wet product of the ferromanganese dibasic Prussian blue analogue are obtained by multiple steps of beating washing and high-efficiency separation of the fully-settled solid phase, and the wet product is subjected to vacuum drying and packaging to obtain a ferromanganese dibasic Prussian blue analogue product with the crystal water n =1.0-1.5, wherein the vacuum pressure of the vacuum drying is 2-5KPa, the drying temperature is 150-200 ℃, and the drying time is 10-20h;
5) And (3) evaporating, concentrating and centrifugally separating the mother liquor after full sedimentation to obtain a sodium salt wet product, drying to obtain a sodium salt byproduct, and circularly sleeving the centrifugal mother liquor for preparing the raw materials.
Preferably, the reaction temperature of the coprecipitation complexing reaction in the step 1) is 30-90 ℃; feeding for 1-5h; the aging reaction time is 1-10h.
Preferably, the fine particles of step 2) have a particle size of 300nm to 600nm.
Preferably, the washing water in the step 4) or the condensate generated by the evaporation and the concentration in the step 5) is used for preparing the sodium ferrocyanide solution and the manganous salt aqueous solution.
Preferably, the mother liquor separated by centrifugation in the step 5) enters a complexation reactor.
Preferably, the mass percentage of the manganous salt to the ferrous salt water solution is 3 percent of the lowest value, and the maximum value is close to a saturation state; the manganous salt is any one of manganous sulfate, manganous chloride, manganous nitrate, manganous acetate and manganous citrate, and the ferrous salt is any one of ferrous sulfate, ferrous chloride, ferrous nitrate, ferrous acetate and ferrous citrate.
Preferably, the sodium source is NaCl or Na 2 SO 4 The molar ratio of sodium ions to sodium ferrocyanide is 1-40.
Preferably, fe (CN) in sodium ferrocyanide solution 6 4- With Mn in aqueous solutions of manganous and ferrous salts 2+ +Fe 2+ In a molar ratio of 1.
Preferably, the auxiliary reagent is one or a mixture of more than two of EDTA sodium salt, sodium citrate, sodium gluconate, sodium benzoate, sodium dodecyl sulfate, polyvinylpyrrolidone PVP and the like; the molar ratio of the auxiliary reagent to the sodium ferrocyanide solution is 2-10.
The device for the production process of the superfine ferromanganese binary Prussian blue analogue comprises a raw material preparation tank and a complex reactor, wherein the raw material preparation tank is connected with the complex reactor; the complex reactor is connected with the circulating sanding device in and out; the discharge hole of the complex reactor is connected with a solid-liquid separator; the mother liquor outlet of the solid-liquid separator is respectively connected with the raw material preparation tank and the concentration evaporatorConnecting, wherein a solid phase outlet of the device is connected with a pulping and washing machine; the washing water outlet of the pulping and washing machine and sodium ferrocyanide/Mn 2+ 、Fe 2+ The salt preparation tank is connected, and the wet product outlet of the salt preparation tank is connected with a vacuum drier/packaging machine; the concentration evaporator is respectively connected with the centrifugal machine and the condenser; solid phase outlet of centrifuge and Na + The salt dryer is connected, and the mother liquor is connected with the raw material preparation tank; the condensed water outlet of the condenser is respectively connected with sodium ferrocyanide/Mn 2+ 、Fe 2+ The salt preparation tank is connected with the wastewater treatment system.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a production process of an ultrafine ferromanganese dibasic Prussian blue analogue which is suitable for industrial mass production application and is used as a positive electrode material of a nano-doped Prussian blue sodium-ion battery, the process method is simple, the mother solution, unreacted materials and auxiliary reagents can be fully recycled, evaporated condensed water can be recycled and reused to the maximum extent, sustainable green production is realized, the product yield is high and can reach more than 98 percent; the product has good cycle performance and high specific capacity.
The method adopts the sodium ferrocyanide solution, the manganous salt and ferrous salt solution to be dripped into the complexing reactor to carry out the coprecipitation complexing reaction and the aging reaction with the sodium source, HCN is not released in the reaction process, and the production process is safe and environment-friendly.
Drawings
FIG. 1 is a flow chart of the production process of the superfine ferromanganese binary Prussian blue analogue.
FIG. 2 is an SEM image of the product of example 1.
Figure 3 is a XRD comparison of the products of example 1 and comparative example 1.
FIG. 4 is a graph comparing constant current charging and discharging at 17 mA/g current density for the products of example 1 and comparative example 1.
FIG. 5 is a graph comparing the cycle performance at a current density of 170mA/g for the products of example 1 and comparative example 1.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail with reference to the embodiments and the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. The technical solution of the present invention is described in detail below with reference to the embodiments and the drawings, but the scope of protection is not limited thereto.
Example 1
A preparation method of ferromanganese iron binary Prussian blue analogue with less crystal water refers to fig. 1, and the specific steps are as follows:
(1) Mother liquor to be used for mechanical application is 4m 3 Adding NaCl and sodium citrate into a complex reactor, and stirring at high speed for 3m under the protection of nitrogen 3 Sodium ferrocyanide solution and 3m 3 Adding manganous chloride and ferrous chloride aqueous solution into a complex reactor in a flowing manner to perform coprecipitation complex reaction and aging reaction to form reaction slurry;
wherein the mass percentages of the manganous chloride and the ferrous chloride aqueous solution are respectively 8%; mn in aqueous solution 2+ With Fe 2+ 1; fe (CN) in sodium ferrocyanide solution 6 4- With Mn in aqueous solutions of manganous and ferrous salts 2+ +Fe 2+ 1.2 in a molar ratio of 1; the molar ratio of sodium ions to sodium ferrocyanide is 20. The molar ratio of sodium citrate to sodium ferrocyanide solution was 2.
The reaction temperature of the coprecipitation complexing reaction is 75 ℃; adding the mixture in a flowing way for 2h; the aging reaction time is 6h.
(2) Sanding the manganese iron binary group Prussian blue analogue precipitate in the reaction slurry to form fine particles; the fine particles have a particle size of 300nm to 600nm.
(3) Carrying out solid-liquid separation on the reaction slurry after sanding to obtain a solid phase and a mother solution; part of mother liquor is used as raw material for the precipitation complexing reaction in the step 1), and the other part of mother liquor is fully precipitated.
(4) Washing water and a wet product of the superfine ferromanganese dibasic Prussian blue analogue are obtained by carrying out 5-time step beating washing and high-efficiency separation on the solid phase after full sedimentation, vacuum drying and packaging are carried out on the wet product of the superfine ferromanganese dibasic Prussian blue analogue to obtain a ferromanganese dibasic Prussian blue analogue product with the crystal water n =1.1, and the yield is calculated to be about 98.5%. The washing water generated in the step can be used for preparing a sodium ferrocyanide solution and a manganous salt aqueous solution. The vacuum pressure is 5KPa, the drying temperature is 180 ℃, the drying time is 15h, and the crystal water n of the ferromanganese binary Prussian blue analogue is =1.0.
(5) And (3) evaporating, concentrating and centrifugally separating the mother liquor after full sedimentation to obtain a sodium salt wet product, drying to obtain a sodium salt byproduct, and circularly sleeving the centrifugal mother liquor for preparing the raw materials.
Comparative example 1
The preparation process of the iron prussian blue cathode material is similar to that of example 1, except that manganous chloride and Fe (CN) in sodium ferrocyanide solution are not added during synthesis 6 4- With Fe in aqueous ferrous salt solutions 2+ The molar ratio of (a) to (b) is 1.2, and the other reaction conditions are the same.
The experimental results refer to FIGS. 2-5.
Example 2
A preparation method of ferromanganese iron binary Prussian blue analogue with less crystal water refers to fig. 1, and the specific steps are as follows:
(1) Mother liquor to be used for mechanical application is 4m 3 、Na 2 SO 4 And adding sodium citrate into a complex reactor, and stirring at high speed for 3m under the protection of nitrogen 3 Sodium ferrocyanide solution and 3m 3 Adding manganous sulfate and ferrous sulfate aqueous solution into a complex reactor to perform coprecipitation complex reaction and aging reaction to form reaction slurry;
wherein the mass percentages of the manganous sulfate and the ferrous sulfate aqueous solution are respectively 8%; mn in aqueous solution 2+ With Fe 2+ 1; fe (CN) in sodium ferrocyanide solution 6 4- With Mn in aqueous solutions of manganous and ferrous salts 2+ +Fe 2+ 1.2, and the molar ratio of (A) to (B) is 1; the molar ratio of sodium ions to sodium ferrocyanide is 20. The molar ratio of sodium citrate to sodium ferrocyanide solution is 2.
The reaction temperature of the coprecipitation complexing reaction is 70 ℃; feeding for 3h; the aging reaction time is 6h.
(2) Carrying out sand grinding treatment on the ferromanganese dibasic Prussian blue analogue precipitate in the reaction slurry to form fine particles; the fine particles have a particle size of 500nm to 600nm.
(3) Carrying out solid-liquid separation on the reaction slurry after sanding to obtain a solid phase and a mother solution; part of the mother liquor is used as a raw material for the precipitation and complexation reaction in the step 1), and the other part of the mother liquor is fully settled.
(4) Washing water and a wet product of the superfine ferromanganese dibasic Prussian blue analogue are obtained by carrying out 5-time step beating washing and high-efficiency separation on the solid phase after full sedimentation, vacuum drying and packaging are carried out on the wet product of the superfine ferromanganese dibasic Prussian blue analogue to obtain a ferromanganese dibasic Prussian blue analogue product with the crystal water n =1.3, and the yield is calculated to be about 98.3%. The washing water generated in the step can be used for preparing a sodium ferrocyanide solution and a manganous salt aqueous solution. The vacuum pressure is 5KPa, the drying temperature is 170 ℃, the drying time is 10h, and the crystal water n of the manganese iron binary Prussian blue analogue is =1.3.
(5) And (3) evaporating, concentrating and centrifugally separating the mother liquor after full sedimentation to obtain a sodium salt wet product, drying to obtain a sodium salt byproduct, and circularly sleeving the centrifugal mother liquor for preparing the raw materials.
Example 3
A preparation method of ferromanganese iron binary-based Prussian blue analogue with less crystal water refers to fig. 1, and the specific steps are as follows:
(1) Mother liquor to be used for mechanical application is 4m 3 、Na 2 SO 4 And adding sodium citrate into a complex reactor, and stirring at high speed for 3m under the protection of nitrogen 3 Sodium ferrocyanide solution and 3m 3 Adding manganous sulfate and ferrous sulfate aqueous solution into a complex reactor to perform coprecipitation complex reaction and aging reaction to form reaction slurry;
wherein, the weight percentages of the manganous sulfate and the ferrous sulfate aqueous solution are respectively 10%; mn in aqueous solution 2+ With Fe 2+ In a molar ratio of 1; fe (CN) in sodium ferrocyanide solution 6 4- With Mn in aqueous solutions of manganous and ferrous salts 2+ +Fe 2+ 1.2 in a molar ratio of 1; the molar ratio of sodium ions to sodium ferrocyanide is 20. The molar ratio of the sodium citrate to the sodium ferrocyanide solution is 2:1。
The reaction temperature of the coprecipitation complex reaction is 75 ℃; feeding for 2h; the aging reaction time is 6h.
(2) Carrying out sand grinding treatment on the ferromanganese dibasic Prussian blue analogue precipitate in the reaction slurry to form fine particles; the fine particles have a particle size of 500nm to 600nm.
(3) Carrying out solid-liquid separation on the reaction slurry after sanding to obtain a solid phase and a mother solution; part of the mother liquor is used as a raw material for the precipitation and complexation reaction in the step 1), and the other part of the mother liquor is fully settled.
(4) Washing water and a wet product of the ferromanganese dibasic Prussian blue analogue are obtained by carrying out 5-time step beating washing and high-efficiency separation on the solid phase after full sedimentation, vacuum drying and packaging are carried out on the wet product of the ferromanganese dibasic Prussian blue analogue to obtain a ferromanganese dibasic Prussian blue analogue product with the crystal water n =1.3, and the yield is calculated to be about 98.2%. The washing water generated in the step can be used for preparing a sodium ferrocyanide solution and a manganous salt aqueous solution. The vacuum pressure is 5KPa, the drying temperature is 160 ℃, the drying time is 10h, and the crystal water n of the manganese iron binary Prussian blue analogue is =1.5.
(5) And (3) evaporating, concentrating and centrifugally separating the mother liquor after full sedimentation to obtain a sodium salt wet product, drying to obtain a sodium salt byproduct, and circularly sleeving the centrifugal mother liquor for preparing the raw materials.
The device adopted by the method comprises a raw material preparation tank and a complex reactor, wherein the raw material preparation tank is connected with the complex reactor; the complexing reactor is connected with a circulating frosting device; the discharge port of the complexing reactor is connected with a solid-liquid separator; the mother liquor outlet of the solid-liquid separator is respectively connected with the raw material preparation tank and the concentration evaporator, and the solid phase outlet of the solid-liquid separator is connected with the pulping washer; the washing water outlet of the pulping and washing machine and sodium ferrocyanide/Mn 2+ 、Fe 2+ The salt preparation tank is connected, and the wet product outlet of the salt preparation tank is connected with a vacuum drier/packaging machine; the concentration evaporator is respectively connected with the centrifugal machine and the condenser; solid phase outlet of the centrifuge and Na + The salt dryer is connected, and the mother liquor is connected with the raw material preparation tank; the condensed water outlet of the condenser is connected with sodium ferrocyanide/Mn respectively 2+ 、Fe 2+ The salt preparation tank is connected with the wastewater treatment system.
The solid-liquid separator of the reaction slurry includes: (1) a settler; (2) a filter/vessel with media; (3) The optimum choice of the butterfly centrifuge, the horizontal screw centrifuge and the jet centrifuge is the centrifugal butterfly centrifuge or the horizontal screw centrifuge.
The step beating washing is that the last washing water is used for the next time, the 1 st washing water is used for the last time, the washing water is sleeved into the mother liquor, and the last time is used for evaporating condensed water by deoxidation.
While the invention has been described in further detail with reference to specific preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A ferromanganese iron binary Prussian blue analogue with less crystal water is characterized in that the molecular formula is
Na x Mn a Fe 1-a [Fe(CN) 6 ] y ·nH 2 0，1.8≤x≤2，0.05≤a≤0.5，0.95≤y≤1，n≤2。
2. The preparation method of the ferromanganese iron binary Prussian blue analogue with less crystal water as claimed in claim 1, characterized by comprising the following steps:
1) Adding the mother solution, a sodium source and an auxiliary reagent which are used mechanically into a complex reactor, under the protection of nitrogen and under the condition of high-speed stirring, adding a sodium ferrocyanide solution, a manganous salt and a ferrous salt aqueous solution into the complex reactor in a flowing manner to carry out coprecipitation complex reaction and aging reaction to form reaction slurry; mn in aqueous solution 2+ With Fe 2+ 1 to 19 in a molar ratio of 1;
2) Carrying out sand grinding treatment on the ferromanganese dibasic Prussian blue analogue precipitate in the reaction slurry to form fine particles;
3) Carrying out solid-liquid separation on the reaction slurry after sanding to obtain a solid phase and a mother solution; taking part of mother liquor as a raw material for the precipitation and complexation reaction in the step 1), and fully settling the other part of mother liquor;
4) Washing water and a wet product of the ferromanganese dibasic Prussian blue analogue are obtained by multiple steps of beating washing and high-efficiency separation of the fully-settled solid phase, and the wet product is subjected to vacuum drying and packaging to obtain a ferromanganese dibasic Prussian blue analogue product with the crystal water n =1.0-1.5, wherein the vacuum pressure of the vacuum drying is 2-5KPa, the drying temperature is 150-200 ℃, and the drying time is 10-20h;
5) And (3) evaporating, concentrating and centrifugally separating the mother liquor after full sedimentation to obtain a sodium salt wet product, drying to obtain a sodium salt byproduct, and circularly sleeving the centrifugal mother liquor for preparing the raw materials.
3. The method for preparing the ferromanganese iron binary-based Prussian blue analogue with less crystal water as claimed in claim 2, wherein the reaction temperature of the coprecipitation complexation reaction in the step 1) is 30-90 ℃; feeding for 1-5h; the aging reaction time is 1-10h.
4. The method for preparing ferromanganese iron binary Prussian blue analogue with less crystal water as claimed in claim 2, wherein the particle size of the fine particles in step 2) is 300nm-600nm.
5. The method for preparing ferromanganese iron binary based Prussian blue analogue with less crystal water as claimed in claim 2, wherein the washing water in step 4) or the condensate generated by the evaporation and concentration in step 5) is used for preparing sodium ferrocyanide solution and manganous salt aqueous solution.
6. The method for preparing low-crystal-water ferromanganese iron binary Prussian blue analogue as claimed in claim 2, wherein the mother liquor obtained by centrifugal separation in step 5) enters a complex reactor.
7. The method for preparing manganese iron binary Prussian blue analogue with less crystal water as claimed in claim 2, wherein the minimum value of the mass percentage of manganous salt to ferrous salt water solution is 3%, and the maximum value is near saturation state; the manganous salt is any one of manganous sulfate, manganous chloride, manganous nitrate, manganous acetate and manganous citrate, and the ferrous salt is any one of ferrous sulfate, ferrous chloride, ferrous nitrate, ferrous acetate and ferrous citrate.
8. The method for preparing the ferromanganese iron binary Prussian blue analogue with less crystal water as claimed in claim 2, wherein the sodium source is NaCl or Na 2 SO 4 The molar ratio of sodium ions to sodium ferrocyanide is 1-40.
9. The method for preparing mangenese iron diyl prussian blue analogue with less crystal water according to claim 2, wherein Fe (CN) in sodium ferrocyanide solution 6 4- With Mn in aqueous solutions of manganous and ferrous salts 2+ +Fe 2+ In a molar ratio of 1.
10. The method for preparing the ferromanganese iron binary Prussian blue analogue with less crystal water as claimed in claim 2, wherein the auxiliary reagent is one or a mixture of more than two of EDTA sodium salt, sodium citrate, sodium gluconate, sodium benzoate, sodium dodecyl sulfate and polyvinylpyrrolidone PVP; the molar ratio of the auxiliary reagent to the sodium ferrocyanide solution is 2-10.
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| CN117430134A (en) * | 2023-12-21 | 2024-01-23 | 山东海化集团有限公司 | Preparation method of ferromanganese-based Prussian blue sodium electric positive electrode material and positive electrode material prepared by method |
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| CN106920964A (en) * | 2017-04-05 | 2017-07-04 | 浙江大学 | A kind of prussian blue sodium-ion battery positive material and preparation method thereof |
| CN114940502A (en) * | 2022-07-26 | 2022-08-26 | 鸿兴(山西)新能源材料有限公司 | Production method and device of manganese-based prussian white |
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| CN106920964A (en) * | 2017-04-05 | 2017-07-04 | 浙江大学 | A kind of prussian blue sodium-ion battery positive material and preparation method thereof |
| CN114940502A (en) * | 2022-07-26 | 2022-08-26 | 鸿兴(山西)新能源材料有限公司 | Production method and device of manganese-based prussian white |
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| CN117430134A (en) * | 2023-12-21 | 2024-01-23 | 山东海化集团有限公司 | Preparation method of ferromanganese-based Prussian blue sodium electric positive electrode material and positive electrode material prepared by method |
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