CN114620758A - Preparation method of copper oxide modified iron-based Prussian blue positive electrode material - Google Patents

Preparation method of copper oxide modified iron-based Prussian blue positive electrode material Download PDF

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CN114620758A
CN114620758A CN202210289939.9A CN202210289939A CN114620758A CN 114620758 A CN114620758 A CN 114620758A CN 202210289939 A CN202210289939 A CN 202210289939A CN 114620758 A CN114620758 A CN 114620758A
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sodium
solution
prussian blue
copper oxide
iron
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CN114620758B (en
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张露露
陈朝尧
傅心远
杨学林
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China Three Gorges University CTGU
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Abstract

The invention provides a copper oxide modified iron-based Prussian blue analogue cathode material and a preparation method thereof, and the specific process comprises the following steps: ferrous sulfate heptahydrate and sodium citrate are prepared into a uniform solution A according to a certain proportion, sodium ferrocyanide decahydrate and ascorbic acid are prepared into a uniform solution B according to a certain proportion, and polyvinylpyrrolidone and sodium chloride are dissolved in deionized water to form a solution C. And simultaneously adding the solution A and the solution B into the solution C through a peristaltic pump according to the same dropping speed, carrying out coprecipitation to form an iron-based Prussian blue material, and carrying out centrifugal washing and drying. Taking out a certain amount of precursor, dispersing in deionized water, performing ultrasonic treatment for half an hour, adding copper chloride, sodium bicarbonate and sodium dodecyl benzene sulfonate, stirring and heating to obtain a mixture, performing suction filtration and washing, drying in an oven overnight, and finally placing the mixture in a tubular furnace for low-temperature annealing to obtain the copper oxide modified composite material.

Description

Preparation method of copper oxide modified iron-based Prussian blue positive electrode material
Technical Field
The invention relates to a copper oxide modified iron-based Prussian blue positive electrode material and a preparation method thereof, belonging to the field of electrochemical power sources.
Background
The rapid development of large-scale smart grids and the energy demand for global sustainable development have driven the progress of battery energy storage devices. Energy storage efficiency, cost, service life and the like are the biggest problems faced by large-scale energy storage devices at present. Especially extending the life of energy storage devices is an important means to significantly reduce costs. Sodium resources have advantages in terms of reserves and costs, and also have considerable energy density, so that sodium-ion batteries are considered as the best choice for realizing large-scale energy storage, and positive electrode materials are the key for limiting the performance of the batteries.
Iron-based prussian blue sodium salt material (Na) x FeFe(CN)6Abbreviated as Fe-PB) has a three-dimensional open framework structure and a larger ion tunnel structure, and is beneficial to the transmission and storage of alkali metal ions. In addition, Fe-PB has two redox active sites and has a higher theoretical capacity (170 mAh g)-1). Therefore, the Prussian blue material has great advantages as a positive electrode material of the sodium-ion battery. However, during the synthesis process, the coordinated water can easily enter into the framework of Prussian blue and occupy certain sodium storage sites, and simultaneously, a large amount of Fe (CN) is generated6Defects, which can lead to a structure that is easily damaged during cycling. Thus, the cyclic properties and lower capacity of prussian blue-based materials limit their practical applications. Therefore, the modified iron-based Prussian blue anode material is modified by introducing copper oxide, the contact between Fe-PB and electrolyte can be reduced by the copper oxide coating, the occurrence of side reaction between active substances and the electrolyte is inhibited, the material structure is stabilized, the migration rate of sodium ions is improved, and the electrochemical performance of Fe-PB is effectively improved.
Disclosure of Invention
The invention aims to provide a copper oxide modified iron-based Prussian blue positive electrode material Na x FeFe(CN)6@ CuO (labeled Fe-PB @ CuO). The synthetic raw material of the Fe-PB @ CuO Prussian blue positive electrode material is ferrous sulfate heptahydrate FeSO4•7H2O, trisodium citrate dihydrate C6H5Na3O7•2H2O, sodium ferrocyanide decahydrate Na4Fe(CN)6•10H2O, ascorbic acid, sodium chloride NaCl, polyvinylpyrrolidone (K88-96) PVP, copper chloride CuCl2Sodium bicarbonate NaHCO3And sodium dodecylbenzenesulfonate SDBS. The preparation method comprises the following steps:
a modification method of an iron-based Prussian blue positive electrode material modified by copper oxide comprises the following steps:
(1) dissolving iron salt and a chelating agent in deionized water to form a mixed solution A; dissolving sodium ferrocyanide decahydrate and ascorbic acid in deionized water to form a solution B, and dissolving a dispersant polyvinylpyrrolidone and a sodium supplement agent in deionized water to form a solution C;
(2) adding solution A and solution B dropwise into solution C at the same time, adding2Heating and stirring in the atmosphere until the dropwise adding is finished, and then stirring, aging, centrifuging, washing and drying to obtain a precipitate D precursor;
(3) dispersing the precursor of the precipitate D obtained in the step (2) in deionized water, stirring, performing ultrasonic treatment, adding copper chloride, sodium bicarbonate and sodium dodecyl benzene sulfonate, performing water bath reaction under stirring, performing suction filtration, and drying to obtain a composite material;
(4) transferring the composite material obtained in the step (3) to a tubular furnace, and heating to 180 DEG under the protection of nitrogen gasoAnd C, preserving heat for 1-6 h, and cooling to room temperature to obtain the copper oxide modified iron-based Prussian blue cathode material, Fe-PB @ CuO for short.
Stirring Fe-PB @ CuO positive electrode material, acetylene black and polyvinylidene fluoride (PVDF) into slurry, coating the slurry on an aluminum foil, and drying, punching and pressing the film to prepare a pole piece.
In the step (1), the iron salt is at least one of ferrous sulfate heptahydrate, ferrous chloride or ferrous acetate; the molar ratio of the iron salt to the chelating agent is 1: 5-10.
The molar ratio of the sodium ferrocyanide decahydrate to the ferric salt in the step (1) is 1: 0.6-1.5.
The sodium supplement agent in the step (1) is sodium chloride NaCl and sodium carbonate Na2CO3Sodium acetate CH3COONa and sodium oxalate Na2C2O4Sodium nitrate NaNO3At least one of (1).
The mass ratio of the polyvinylpyrrolidone to the sodium supplement is 1-1.5: 2.5-3.
In the step (2), the solutionThe dropping speed of the solution A and the solution B is controlled to be 0.1-0.2 ml/min, and the solution A and the solution B are added in N2Under the atmosphere, the stirring speed is 450-500 rpm, and the reaction temperature is 40-60oC。
In the step (2), the molar ratio of the copper chloride to the sodium bicarbonate is 1:1-3, and the mass percent of the generated copper oxide is 2-10% of the precursor; the addition amount of the sodium dodecyl benzene sulfonate is 0.05-0.1% of the precursor.
In the process, sodium bicarbonate is firstly hydrolyzed to generate OH-Cu in copper chloride2+With OH-Reaction to form Cu (OH)2Finally at 200oSintering under C for 3h, Cu (OH)2Will decompose into CuO, and the sodium dodecylbenzenesulfonate acts as a dispersant to uniformly disperse the copper oxide on the surface of the prussian blue particles. If sodium bicarbonate and sodium dodecylbenzenesulfonate are added in advance in step one, they are washed away in the centrifugal washing step for forming iron-based prussian blue particles. Therefore, the iron-based Prussian blue cubic particles are synthesized in the steps (1) and (2), and then the copper chloride and the sodium bicarbonate are added, so that the copper oxide of the iron-based Prussian blue cubic particles slowly grows on the surfaces of the Prussian blue cubic particles to form the copper oxide coating. Copper chloride can only be added in step (3), if it is added in step (1) or (2), Cu will be formed on the one hand2+Doping, on the other hand, forming Prussian blue particles and Cu (OH)2The mixture of (2) can not meet the requirement of the scheme, so that CuO is uniformly coated on the surface of Prussian blue particles, and therefore, copper chloride can only be added in the step (3).
The temperature of the water bath in the step (3) is 50-80 DEGoC, the time is 1-12 h.
The temperature rising rate in the tubular furnace in the step (4) is 1 to 10oC/min, annealing temperature of 180-oAnd C, keeping the temperature for 1-6 h.
Compared with the prior art, the Fe-PB @ CuO composite material disclosed by the invention has the following remarkable characteristics:
(1) the invention has the advantages of low cost of raw materials, rich iron sources and copper sources, simple preparation process, no need of high-temperature treatment and suitability for large-scale industrial production;
（2）180-phase 250 of preparation processoC, the low-temperature heat treatment process obviously reduces the content of crystal water of the material, provides more space for the storage of sodium ions and improves the capacity of the material;
(3) the iron-based Prussian blue material is modified by the copper oxide, and the side reaction between the active material and the electrolyte plays a good shielding role.
Drawings
Figure 1 is a comparison of XRD of samples prepared in examples 1, 2, 3 with a standard card.
FIG. 2 is a graph comparing the cycle performance of samples prepared in examples 3, 4, and 5.
Fig. 3 is an SEM image of the sample prepared in example 1.
Fig. 4 is an SEM image of the sample prepared in example 3.
FIG. 5 shows the samples prepared in example 1 at 20 mA g-1The charge-discharge curves of circles 1, 2, 10 and 50 at the current density of (a).
FIG. 6 shows the samples prepared in example 2 at 20 mA g-1The charge-discharge curves of circles 1, 2, 10 and 50 at the current density of (a).
FIG. 7 shows the results of example 3 when the sample is prepared at 20 mA g-1The charge-discharge curves of circles 1, 2, 10 and 50 at the current density of (a).
FIG. 8 shows examples 1, 2 and 3 at 20 mA g-1Current density of (a).
FIG. 9 shows examples 1, 2 and 3 at 1A g-1Current density of (a).
FIG. 10 is a graph of the cycle performance of the composite material.
The specific implementation mode is as follows:
the following is a description of embodiments that further illustrate the essential features and advantages of the invention.
Example 1
Adding 5 mmol of FeSO4·7H2O and 25 mmol Na3C6H5O7·2H2O was dissolved in 50 ml of deionized water to form solution A, 5 mmol Na4Fe(CN)6·10H2O and 1 g C6H8O6Dissolving in 50 ml of deionized water to form a solution B; dissolving 1 g of polyvinylpyrrolidone PVP and 3 g of NaCl in deionized water to form solution C; solution A and solution B were added dropwise to solution C at a rate of 10 ml/h at 50oC, dripping while stirring in a water bath, heating for 12 h until the solution becomes white suspension after dripping is finished, continuing stirring for 12 h, and aging for 24 h; then, respectively centrifuging and washing the mixture for three times by using deionized water and absolute ethyl alcohol on a centrifuge with the rotating speed not less than 8000 rpm/min; finally, the dark blue solid is placed in a vacuum oven 120oAnd C, drying for 24 h to obtain the product iron-based Prussian blue cathode material which is marked as Fe-PB. Stirring the obtained Fe-PB positive electrode material with acetylene black and polyvinylidene fluoride (PVDF) to form slurry, coating the slurry on an aluminum foil, and drying, punching and pressing the film to obtain a positive electrode material pole piece. 1M NaClO containing 2 wt.% FEC and taking metallic sodium as a counter electrode and Grade GF/D as a diaphragm4and/(EC + DMC + EMC) (EC: DMC: EMC =1:1:1) is a battery assembled by the electrolyte to carry out constant-current charge and discharge tests, and the voltage range is 2.0-4.2V. FIG. 1 is a comparison of XRD of Fe-PB with that of standard card, which is consistent with that of standard card (JCPDS, number 52-1907), and has no obvious impurity peaks, but at 24.2, 38.6, 49.4oThe peak separation phenomenon appears at the equal parts and presents a typical monoclinic phase. FIG. 3 is an SEM image, and it can be seen that Fe-PB is a smooth-surfaced cubic morphology. FIG. 5 is a graph showing the difference between 20 mA g-1The first discharge capacity can reach 134.2 mAh g though the first discharge capacity can reach the charge-discharge curve chart of the circles 1, 2, 10 and 50 of the Fe-PB anode material under the current density of (1)-1But the capacity of the second turn is significantly reduced (118.3 mAh g)-1) The reason is that the irreversible side reaction is generated between the anode material of the first circle of charge-discharge curve and the electrolyte, so that an irreversible platform appears at about 4.0V. As can be seen from the comparison of the cycle performance in FIG. 8, Fe-PB is at 20 mA g-1After 50 cycles of charge and discharge under current density, the capacity is only kept at 89.3 mAh g-1Left and right, the cycling stability is poor. As can be seen from the comparison of the cycle performance in FIG. 9, Fe-PB is at 1A g-1The circulating 200 cycles under the current density is only 62.8 mAh g-1The specific capacity, the cycling stability is very poor and the capacity is very low.
Example 2
The preparation steps are the same as example 1, only 200 mg of dried blue powder obtained by taking out and drying is dispersed in 100 ml of deionized water, stirred for 10min, ultrasonically treated for 30 min, then 0.1 g of SDBS is added, and the mixture is stirred at 60 DEGoStirring in water bath for 6 hr, vacuum filtering, and filtering at 80 deg.CoDrying in an oven C overnight to obtain a composite material, transferring the dried material into a tube furnace, and performing drying in a nitrogen atmosphere at a temperature of 3 DEG CoThe temperature rise rate of C/min is increased to 200oAnd C, preserving the heat for 3h, cooling to room temperature to obtain a relatively dry iron-based Prussian blue positive electrode material, and marking as Fe-PB-T. Stirring the obtained Fe-PB-T positive electrode material with acetylene black and polyvinylidene fluoride (PVDF) to form slurry, coating the slurry on an aluminum foil, and drying, punching and pressing the film to obtain a positive electrode material pole piece. 1M NaClO containing 2 wt.% FEC and taking metallic sodium as a counter electrode and Grade GF/D as a diaphragm4And (EC + DMC + EMC) (EC: DMC: EMC =1:1:1) is a battery assembled by the electrolyte, and the voltage range is 2.0-4.2V. FIG. 1 is a comparison of XRD of Fe-PB-T with that of standard card, which is consistent with that of standard card (JCPDS, number 52-1907), has no obvious impurity peak, shows good crystallinity, and is in typical cubic phase. Description 200oThe low-temperature sintering of C can obviously reduce the crystal water in the material, so that the material is changed from a monoclinic phase to a cubic phase. FIG. 6 is a graph showing the difference between 20 mA g-1Under the current density of the Fe-PB-T anode material, the first discharge capacity can reach 135.6 mAh g through the charging and discharging curve charts of the 1 st circle, the 2 nd circle, the 10 th circle and the 50 th circle of the Fe-PB-T anode material-1. As can be seen from the comparison of the cycle performance in FIG. 8, Fe-PB-T is at 20 mA g-1After 50 cycles of charge-discharge under current density, the capacity is only kept at 107.1 mAh g-1Left and right, the circulation stability is better. As can be seen from the comparison of the cycle performance in FIG. 9, Fe-PB-T is at 1A g-173.4 mAh g is obtained when 200 cycles are circulated under the current density-1The specific capacity, the cycling stability is good and the capacity is high.
Example 3
The preparation steps are the same as example 1, only 200 mg of dried blue powder obtained by taking out and drying is dispersed in 100 ml of deionized water, stirred for 10min, subjected to ultrasonic treatment for 30 min, and then added with 20 mg of CuCl2、40 mg NaHCO3And 0.1 g of SDBS,at 60oStirring in water bath for 6 hr, vacuum filtering, and filtering at 80 deg.CoDrying in a drying oven for one night to obtain a composite material; the material obtained after drying was transferred to a tube furnace under nitrogen as protective gas with 3oThe temperature rise rate of C/min is increased to 200oAnd C, preserving the heat for 3h, and cooling to room temperature to obtain the CuO modified iron-based Prussian blue cathode material which is marked as Fe-PB @4% CuO. Stirring the obtained Fe-PB @4% CuO positive electrode material, acetylene black and polyvinylidene fluoride (PVDF) into slurry, coating the slurry on an aluminum foil, and drying, punching and pressing the film to obtain a positive electrode material pole piece. 1M NaClO containing 2 wt.% FEC and taking metallic sodium as a counter electrode and Grade GF/D as a diaphragm4And (EC + DMC + EMC) (EC: DMC: EMC =1:1:1) is a battery assembled by the electrolyte, and the voltage range is 2.0-4.2V. FIG. 1 is a comparison of the XRD of Fe-PB @4% CuO with standard card, consistent with standard card (JCPDS, number 52-1907), with no significant miscellaneous peaks, showing good crystallinity, in the typical cubic phase. FIG. 2 is a comparison graph of the cycle performance of composite materials with different CuO coating amounts, wherein the Fe-PB @4% CuO anode material is at 20 mA g-1The first discharge capacity of the lithium secondary battery is 143.9 mAh g-1After 50 times of circulation, the specific discharge capacity is 129.8 mAh g-1Capacity and cycle stability are the best of the three ratios. FIG. 4 is an SEM image showing that Fe-PB @4% CuO still maintains the cubic morphology but has a rough surface. FIG. 7 is a graph showing the difference between 20 mA g-1Under the current density of (1), a charge-discharge curve chart of rings 1, 2, 10 and 50 of the Fe-PB @4% CuO anode material shows that the first discharge capacity can reach 143.9 mAh g-1The capacity is very high. As can be seen from the comparison of the cycle performance in FIG. 8, Fe-PB @4% CuO was at 20 mA g-1After 50 cycles of charge-discharge circulation under current density, the capacity is still kept at 129.8 mAh g-1Left and right, the circulation stability is good. As can be seen from the comparison of the cycle performance in FIG. 9, Fe-PB @4% CuO is at 1A g-1The current density still has 93.9 mAh g when 200 cycles are circulated-1The specific capacity, the cycling stability and the capacity are high.
Example 4
The preparation procedure is as in example 1, except that 200 mg of dried blue powder, which is obtained by taking out and drying, is dispersed in 100 ml deionized water, stirring for 10min, ultrasonic treating for 30 min, and adding 10 mg CuCl2、20 mg NaHCO3And 0.1 g SDBS at 60oStirring in water bath for 6 hr, vacuum filtering, and filtering at 80 deg.CoDrying in a drying oven for one night to obtain a composite material; the material obtained after drying was transferred to a tube furnace under nitrogen as protective gas with 3oThe temperature rise rate of C/min is increased to 200oAnd C, preserving the heat for 3h, and cooling to room temperature to obtain the CuO modified iron-based Prussian blue cathode material which is marked as Fe-PB @2% CuO. Stirring the obtained Fe-PB @2% CuO positive electrode material, acetylene black and polyvinylidene fluoride (PVDF) into slurry, coating the slurry on an aluminum foil, and drying, punching and pressing the film to obtain a positive electrode material pole piece. 1M NaClO containing 2 wt.% FEC and taking metallic sodium as a counter electrode and Grade GF/D as a diaphragm4And (EC + DMC + EMC) (EC: DMC: EMC =1:1:1) is a battery assembled by the electrolyte, and the voltage range is 2.0-4.2V. FIG. 2 is a comparison graph of the cycle performance of composite materials with different CuO coating amounts, wherein the Fe-PB @2% CuO anode material is at 20 mA g-1The first discharge capacity at the current density of (2) was 143.4 mAh g-1After 50 times of circulation, the specific discharge capacity is 122.1 mAh g-1The coulomb efficiency can be basically maintained at 100%.
Example 5
The preparation steps are the same as example 1, only 200 mg of dried blue powder obtained by taking out and drying is dispersed in 100 ml of deionized water, stirred for 10min, subjected to ultrasonic treatment for 30 min, and then 30 mg of CuCl is added2、60 mg NaHCO3And 0.1 g SDBS at 60oStirring in water bath for 6 hr, vacuum filtering, and filtering at 80 deg.CoDrying in a drying oven overnight to obtain a composite material; the material obtained after drying was transferred to a tube furnace under nitrogen as protective gas with 3oThe temperature rise rate of C/min reaches 200oAnd C, preserving the heat for 3h, and cooling to room temperature to obtain the CuO modified iron-based Prussian blue anode material which is marked as Fe-PB @6% CuO. Stirring the obtained Fe-PB @6% CuO positive electrode material, acetylene black and polyvinylidene fluoride (PVDF) into slurry, coating the slurry on an aluminum foil, and drying, punching and pressing the film to obtain a positive electrode material pole piece. 1M NaClO containing 2 wt.% FEC and taking metallic sodium as a counter electrode and Grade GF/D as a diaphragm4/(EC+DMC+EMC) And (EC: DMC: EMC =1:1:1) is an electrolyte to assemble the battery for constant-current charge and discharge tests, and the voltage range is 2.0-4.2V. FIG. 2 is a comparison graph of cycle performance of composite materials with different CuO coating amounts, and the Fe-PB @6% CuO anode material is at 20 mA g-1The first discharge capacity of the lithium secondary battery is 127.9 mAh g under the current density-1After 50 times of circulation, the specific discharge capacity is only 104.2 mAh g-1The coulomb efficiency can be basically maintained at 100%.
Example 6
The preparation steps are the same as example 1, only 200 mg of dried blue powder obtained by taking out and drying is dispersed in 100 ml of deionized water, stirred for 10min, subjected to ultrasonic treatment for 30 min and then added with 20 mg of CuCl2And 0.1 g SDBS at 60oStirring in water bath for 6 hr, vacuum filtering, and filtering at 80 deg.CoDrying in a drying oven overnight to obtain a composite material; the material obtained after drying was transferred to a tube furnace under nitrogen as protective gas with 3oThe temperature rise rate of C/min reaches 200oAnd C, preserving the heat for 3h, and cooling to room temperature to obtain the iron-based Prussian blue anode material which is marked as Fe-PB-S. Stirring the obtained Fe-PB-S positive electrode material with acetylene black and polyvinylidene fluoride (PVDF) to form slurry, coating the slurry on an aluminum foil, and drying, punching and pressing the film to obtain a positive electrode material pole piece. 1M NaClO containing 2 wt.% FEC and taking metallic sodium as a counter electrode and Grade GF/D as a diaphragm4And (EC + DMC + EMC) (EC: DMC: EMC =1:1:1) is a battery assembled by the electrolyte, and the voltage range is 2.0-4.2V. FIG. 10 is a comparison graph of the cycle performance of the composite material, with Fe-PB-N positive electrode material at 100 mA g-1The first discharge capacity of the lithium secondary battery is 90.0 mAh g under the current density-1After 50 times of circulation, the specific discharge capacity is only 67.1 mAh g-1The capacity retention rate is very low, and the material cannot react with copper chloride because sodium bicarbonate is not added, so that the coating effect cannot be achieved, so that the material is very easy to generate side reaction with an electrolyte in the circulation process, and cannot be used as a buffer layer for sodium ion deintercalation, and the circulation performance of the material is very poor.
Example 7
The procedure is as in example 1 except that 200 mg of dried blue powder, taken out and dried, is dispersed in 100 ml of deionized waterStirring in water for 10min, ultrasonic treating for 30 min, and adding 20 mg CuCl2And 40 mg NaHCO3At 60, inoStirring in water bath for 6 hr, vacuum filtering, and filtering at 80 deg.CoDrying in a drying oven for one night to obtain a composite material; the material obtained after drying was transferred to a tube furnace under nitrogen as protective gas with 3oThe temperature rise rate of C/min reaches 200oAnd C, preserving the heat for 3h, cooling to room temperature to obtain the CuO modified iron-based Prussian blue cathode material, and marking as Fe-PB-N. Stirring the obtained Fe-PB-N positive electrode material with acetylene black and polyvinylidene fluoride (PVDF) to form slurry, coating the slurry on an aluminum foil, and drying, punching and pressing the film to obtain a positive electrode material pole piece. 1M NaClO containing 2 wt.% FEC and taking metallic sodium as a counter electrode and Grade GF/D as a diaphragm4And (EC + DMC + EMC) (EC: DMC: EMC =1:1:1) is a battery assembled by the electrolyte, and the voltage range is 2.0-4.2V. FIG. 10 is a comparison graph of the cycle performance of the composite material, with the Fe-PB-S positive electrode material at 100 mA g-1The first discharge capacity of the lithium secondary battery is 90.9 mAh g under the current density-1After 50 times of circulation, the specific discharge capacity is only 83.3 mAh g-1And sodium dodecyl benzene sulfonate is not added as a dispersing agent, so that the condition of uneven coating is easily formed in the coating process, and the performance is deteriorated.

Claims (9)

1. The method for modifying the iron-based Prussian blue cathode material modified by copper oxide is characterized by comprising the following steps of:
(1) dissolving iron salt and a chelating agent in deionized water to form a mixed solution A; dissolving sodium ferrocyanide decahydrate and ascorbic acid in deionized water to form a solution B, and dissolving a dispersing agent polyvinylpyrrolidone and a sodium supplement agent in the deionized water to form a solution C;
(2) dropping solution A and solution B into solution C at the same time, and adding solution C and solution B into solution C at the same time2Heating and stirring in the atmosphere until the dropwise adding is finished, and stirring, aging, centrifuging, washing and drying to obtain a precipitate D precursor;
(3) dispersing the precursor of the precipitate D obtained in the step (2) in deionized water, stirring, performing ultrasonic treatment, adding copper chloride, sodium bicarbonate and sodium dodecyl benzene sulfonate, performing water bath reaction under stirring, performing suction filtration, and drying to obtain a composite material;
(4) transferring the composite material obtained in the step (3) to a tubular furnace, and heating to 180 DEG under the protection of nitrogen gasoAnd C, preserving the heat for 1-6 h, and cooling to room temperature to obtain the copper oxide modified iron-based Prussian blue cathode material.
2. The method for preparing the copper oxide modified iron-based Prussian blue cathode material according to claim 1, wherein in the step (1), the iron salt is at least one of ferrous sulfate heptahydrate, ferrous chloride or ferrous acetate; the molar ratio of the iron salt to the chelating agent is 1: 5-10.
3. The method for preparing the copper oxide modified iron-based Prussian blue cathode material according to claim 1, wherein the molar ratio of the sodium ferrocyanide decahydrate to the iron salt in the step (1) is 1: 0.6-1.5.
4. The method for preparing the copper oxide modified iron-based Prussian blue cathode material according to claim 1, wherein the sodium supplement agent in the step (1) is sodium chloride (NaCl) or sodium carbonate (Na)2CO3Sodium acetate CH3COONa and sodium oxalate Na2C2O4Sodium nitrate NaNO3At least one of (1).
5. The preparation method of the copper oxide modified iron-based Prussian blue cathode material as claimed in claim 1, wherein the mass ratio of the polyvinylpyrrolidone to the sodium supplement agent is 1-1.5: 2.5-3.
6. The method for preparing the copper oxide modified iron-based Prussian blue cathode material as claimed in claim 1, wherein in the step (2), the dropping speed of the solution A and the solution B is controlled to be 0.1-0.2 ml/min, and the dropping speed is controlled to be N2Under the atmosphere, the stirring speed is 450-500 rpm, and the reaction temperature is 40-60 DEG CoC。
7. The preparation method of the copper oxide modified iron-based Prussian blue cathode material according to claim 1, wherein in the step (2), the molar ratio of copper chloride to sodium bicarbonate is 1:1-3, and the mass percent of the generated copper oxide is 2-10% of the mass percent of the precursor; the addition amount of the sodium dodecyl benzene sulfonate is 0.05-0.1% of the precursor.
8. The method for preparing the copper oxide modified iron-based Prussian blue cathode material as claimed in claim 1, wherein the temperature of the water bath in the step (3) is 50-80%oC, the time is 1-12 h.
9. The method for preparing the copper oxide modified iron-based Prussian blue cathode material according to claim 1, wherein the temperature rise rate in the tubular furnace in the step (4) is 1-10oC/min, annealing temperature of 180-oAnd C, keeping the temperature for 1-6 h.
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