CN113690433B - High-entropy prussian blue material and preparation method thereof - Google Patents
High-entropy prussian blue material and preparation method thereof Download PDFInfo
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention discloses a high-entropy Prussian blue material, the molecular formula of which is NaxMyn [ Fe (CN) 6 ]z•wH 2 O, wherein M is n different transition metal elements, n is more than or equal to 5, yn is more than or equal to 0.01 and less than or equal to 0.90, y1+ y2+ y3+ y4+ y5 … + yn =1,w and 4.0,1.40 and x is more than or equal to 1.95,0.90 and z is more than or equal to 0.98. The high-entropy Prussian blue material is of a monoclinic phase structure, the micro morphology of the high-entropy Prussian blue material is large-size crystal particles, and crystal grains are uniform in size and are in a regular polyhedral morphology with a single shape. The invention also provides application of the high-entropy prussian blue material as a positive electrode material in a sodium ion battery and a preparation method thereof, and the high-entropy prussian blue material with high specific capacity, good rate capability and excellent cycle performance is obtained by adopting a coprecipitation method and through selection of source materials, design of a process and selection and control of process parameters in preparation.
Description
Technical Field
The invention relates to the technical field of energy materials, in particular to a Prussian blue type sodium ion battery positive electrode material and a preparation method thereof.
Background
Environmental and energy problems are becoming more severe due to the excessive use of fossil energy, such as greenhouse effect, atmospheric pollution and energy exhaustion, which are gradually affecting the production and life of human beings. The emergence of new clean energy can mitigate the above-mentioned crisis to a great extent, and therefore has received attention from global researchers. However, the new clean energy, represented by solar energy, tidal energy, wind energy and heat energy, is severely limited by the time and space conditions, and is difficult to directly generate high-quality energy supply, so that energy storage equipment is required to solve the energy throughput problem. Among them, the development of large-scale and low-cost energy storage power stations has become the focus of the contemporary scientific and engineering communities, and electrochemical energy storage devices represented by lithium ion and sodium ion batteries are excellent and relatively cheap energy carriers. The development of lithium ion batteries in the last two decades has proved their success in portable electronic and electric vehicles, however, the limited lithium resource has seriously hindered the sustainable development and large-scale application of lithium ion batteries. Sodium and lithium which are also the first main group have similar physicochemical properties, the working principle of corresponding electrode materials in the ion battery is very similar, and sodium is used as a crustal high-abundance element, so that the sodium ion battery has great potential and advantages particularly in the large-scale energy storage direction, and is low in cost and easy to obtain.
The core component of the sodium ion battery generally consists of four parts, namely a positive electrode, an electrolyte, a diaphragm and a negative electrode. In the charging process, na + is separated from the positive electrode in a sodium-rich state, and the electrolyte passes through the diaphragm and then enters the negative electrode; and the electrons move to the negative electrode along the external circuit for charge compensation. The discharging process is opposite to the former, and the two are highly reversible, so that the sodium ion battery has the charging and discharging functions.
The mainstream cathode materials of the sodium ion battery are hard carbon and NaTi2 (PO 4) 3, the hard carbon and the NaTi2 (PO 4) 3 are sufficiently researched, and the sodium ion battery has the characteristics of long circulation, high capacity and the like. The electrolyte of the sodium ion battery is also well solved, mainly comprises sodium salts such as NaPF6 and NaClO4 and ester solvents, and has the property similar to that of the electrolyte of the lithium ion battery.
Unlike the negative electrode and electrolyte, the positive electrode material remains the bottleneck of the sodium ion battery. Among them, sodium-electric anodes widely studied can be classified into three types: transition metal oxides, polyanionic compounds, and prussian blue analogs. The transition metal oxide and polyanion compound contain fluorine and oxygen bonds in the crystal structure, so that the Na + is subjected to larger chemical constraint energy in the transmission process in the crystal lattice, thereby influencing the deintercalation on the anode and causing the low rate performance of the material. Moreover, the transition metal oxide is accompanied with uncontrollable phase change in the charging and discharging processes, thereby causing serious reduction of the cycle life of the material; polyanionic compounds generally have a low specific capacity due to the large molecular weight of the anion. The synthesis methods of both generally involve high temperature solid phase methods, which require enormous energy consumption.
The chemical formula of the Prussian blue material is AxMa [ Mb (CN) 6]1-y, each transition metal atom is connected through cyanide to form a rigid and open cubic frame, and the Prussian blue material has a large pore channel structure, so that alkali metal ions can be freely transmitted and stored in the cubic frame. Because no oxygen and fluorine elements are contained, the Na + is less in chemical constraint energy in the transmission process in the crystal lattice, and the rate capability is outstanding. The average sodium storage potential of the Prussian blue material is generally higher than 3V, and when the transition metals in the structure have electrochemical activity, the Prussian blue material has a theoretical capacity of 170 mAh/g. Meanwhile, the preparation of the prussian blue material is generally a coprecipitation method, a hydrothermal method and a ball milling method, and the method has low energy consumption and mild conditions, so the method has a good commercial application prospect.
However, to be truly commercially viable, prussian blue-based materials still need to overcome the following obstacles: 1. due to the existence of factors such as water and the like, the prussian blue material is easy to generate side reaction with electrolyte in the circulating process so as to damage the structure, and meanwhile, the circulating life of the material is also seriously reduced due to the dissolution of transition metal (particularly Mn); 2. the Prussian blue material has poor electronic conductivity, and has the characteristics of high impedance, low rate performance and the like.
Disclosure of Invention
The object of the invention is therefore: the technical problems of short cycle life and poor rate capability when the existing Prussian blue materials are used as the positive electrode materials of the sodium ion battery are solved, and the high-entropy Prussian blue positive electrode materials of the sodium ion battery and the preparation method thereof are provided.
In order to achieve the above object, the present invention has the following technical solutions.
A high-entropy Prussian blue material with molecular formula of Na x M yn [Fe(CN) 6 ] z •wH 2 O, wherein M is n different transition metal elements; n is more than or equal to 5, yn is more than or equal to 0.01 and less than or equal to 0.90, y1+ y2+ y3+ y4+ y5 … + yn =1,0.90 and z is more than or equal to 0.98, and w is more than or equal to 4.0.
The value of x in the formula for characterizing the sodium content is as follows: x is more than or equal to 1.40 and less than or equal to 1.95, the content of sodium in the structure of the high-entropy Prussian blue material can be increased, on one hand, the charge-discharge specific capacity of the material can be increased, the structural stability and the cycle performance are improved through the high entropy on the premise that the initial charge-discharge specific capacity of the obtained high-entropy material is improved, and the rate capability is increased; in addition, the increase of the sodium content also ensures that the high-entropy Prussian blue material can obtain a monoclinic-phase single-phase structure, the increase of the sodium content in the material structure causes lattice distortion, so that relative peaks are split, the monoclinic-phase single-phase structure is formed, and the initial charge-discharge specific capacity of the material is increased.
Wherein the transition metal elements are at least five of iron, manganese, cobalt, nickel, copper, titanium and vanadium; wherein, the transition metal is selected to provide necessary guarantee for realizing the following purposes: firstly, the uniform mixed arrangement of different metal elements of each metal in a crystal structure can be realized when 5 or more transition metals (5 is less than or equal to n) are selected in the preparation process of the high-entropy prussian blue material, especially in a low-temperature preparation method, the dissolution of the metal elements is reduced, a stable integral structural framework of the high-entropy prussian blue is obtained, and the high cycle stability of the material in charge-discharge cycles is ensured; and reasonable collocation between the transition metal element providing the redox site and the transition metal of the stable structure is ensured, and the charging and discharging specific capacity can be improved while the stability of the structural framework is ensured by obtaining high composition entropy.
Further, the high-entropy prussian blue material is of a single-phase structure and is in a monoclinic phase, and compared with a normal cubic phase single-phase structure, the single-phase structure with the monoclinic phase can obviously improve the charge-discharge specific capacity of the material, which is one reason for the invention to obtain the high-entropy prussian blue material with the monoclinic phase structure.
Furthermore, the microscopic morphology of the high-entropy prussian blue material is large-size crystal particles, crystal grains are uniform in size, single and regular in shape, the length size of the particles averagely reaches 4-8 mu m, and the large-size crystal grains meet the requirement of industrial production coating when being applied to the positive electrode material of the sodium-ion battery. However, when the high-entropy prussian blue material is prepared, it is not easy to obtain large-size crystal particles, and the growth process and the overall morphology of the crystal particles need to be regulated and controlled in the preparation process so as to improve the particle size. The invention controls the preparation process and obtains good effect. For example, na obtained in example 1 1.9 Mn 0.2 Fe 0.2 Co 0.2 Ni 0.2 Cu 0.2 [Fe(CN) 6 ] 0.96 •1.2H 2 O is a single-phase structure of monoclinic phase, and the particles are in a standard shapeThe average length of single crystals is 6 mu m; na obtained in example 2 1.6 Ti 0.16 Mn 0.16 Fe 0.16 Co 0.2 Ni 0.16 Cu 0.16 [Fe(CN) 6 ] 0.93 ·2.1H 2 O is a monoclinic phase single-phase structure, crystal particles are in a regular spheroidal shape, and the average length of single crystals is 8 mu m; na as obtained in example 3 1.4 Mn 0.20 V 0.20 Ti 0.20 Ni 0.1 Cu 0.1 Cr 0.20 [Fe(CN) 6 ] 0.90 ·4H 2 And O is a single-phase structure with a high-crystallinity monoclinic phase, the single crystal presents a regular spherical polyhedron shape, and the average length of the single crystal is 4 mu m. The high-entropy prussian blue material can be determined from the single-phase structure and the regular large-size crystal particle morphology, and has high crystallinity; in addition, each characteristic peak in XRD test results of the high-entropy Prussian blue materials prepared from the examples shows a sharp characteristic, and the fact that the materials have high crystallinity can be directly verified. Therefore, the high-entropy prussian blue material can be directly judged, and even if the mixed-arrangement metal is more than 5 (5 is less than or equal to n), the invention realizes the uniform mixed arrangement of different elements of each metal in the crystal structure.
Also, since the high-entropy prussian blue material of the present invention realizes uniform mixing of various metal elements in the crystal structure to achieve high crystallinity, thereby effectively reducing introduction of vacancies and water, the high-entropy prussian blue material of the present invention has a water content of 4.0 or less (w.ltoreq.4.0), vacancies of less than 0.1 (vacancy content 1-Z, Z is 0.90. Ltoreq. Z.ltoreq.0.98 in the molecular formula), such as Na prepared in example 1 1.9 Mn 0.2 Fe 0.2 Co 0.2 Ni 0.2 Cu 0.2 [Fe(CN) 6 ] 0.96 ·1.2H 2 O, with a water content as low as 1.2, with a vacancy of 0.04. The introduction of vacancies and water in the crystal structure of the high-entropy Prussian blue material is reduced, the integral structure frame of the high-entropy Prussian blue is further stabilized, and the high-entropy Prussian blue material has higher cycle stability in charge-discharge cycles; on the other hand, the reduction of vacancies, tooThe charging and discharging specific capacity is also improved.
The inventor applies the high-entropy Prussian blue material of the invention to a sodium-ion battery as a positive electrode material, and the cycle performance of the high-entropy Prussian blue material is as follows: 500 The maximum discharge capacity of the material under the mA/g current density is more than 103mAh/g, the specific capacity retention rate of the battery after 1000 cycles reaches 78.8%, and excellent cycle performance is shown; the rate capability of the high-entropy Prussian blue material is that the discharge specific capacity is more than 96.5mAh/g under the current density of 1000 mA/g, which shows that the high-entropy Prussian blue material has good rate capability and the specific capacity attenuation is reduced along with the increase of the current density. For example, na obtained in example 2 of the present invention 1.6 Ti 0.16 Mn 0.16 Fe 0.16 Co 0.2 Ni 0.16 Cu 0.16 [Fe(CN) 6 ] 0.93 ·2.1H 2 O:500 The maximum discharge capacity of the material under the mA/g current density is 103mAh/g, and the specific capacity retention rate of the battery after 1000 cycles is 78.8%; the multiplying power performance is shown in 1000 mA/g current density, and the specific discharge capacity is 96.5mAh/g. Na obtained in example 4 1.95 Mn 0.11 Fe 0.11 Co 0.11 Ni 0.12 Cu 0.11 Ti 0.11 V 0.11 Cr 0.11 Zn 0.11 [Fe(CN) 6 ] 0.98 ·0.5H 2 O:500 The maximum discharge capacity of the material under the mA/g current density is 120.2mAh/g, and the specific capacity retention rate of the battery after 1000 cycles is 82.5%; the multiplying power performance is shown in 1000 mA/g current density, and the specific discharge capacity is 116mAh/g.
The high-entropy Prussian blue material obtained by the invention solves the technical problems of short cycle life and poor rate capability when the conventional Prussian blue material is used as a positive electrode material of a sodium ion battery, and further improves the cycle life and the rate capability on the premise of improving the initial charge-discharge specific capacity. Naturally, obtaining a high entropy prussian blue type material as described above is determined by the selection of source materials, the process design of the preparation process, the selection and control of process parameters when the inventors prepare the material.
Therefore, the invention also provides a preparation method of the high-entropy prussian blue material, which comprises the following steps:
(1) Dissolving sodium ferrocyanide decahydrate, a complexing agent and a surface dispersing agent in a mixed solvent consisting of deionized water and an auxiliary solvent to obtain a precursor solution A for later use;
(2) Dissolving 5 or more transition metal salts and complexing agents in a mixed solvent consisting of deionized water and an auxiliary solvent to obtain a precursor liquid B for later use;
(3) Slowly dripping the precursor liquid B into the precursor liquid A for reaction, and then carrying out heat preservation stirring and aging treatment to obtain a suspension;
the precursor liquid B is added into the precursor liquid A in a slow dropwise adding mode, the reaction process is ensured to be that a small amount of the precursor liquid B is in the environment of a large amount of the precursor liquid A, so that various metal ions can be simultaneously and orderly released even under the condition that the precursor liquid B contains more than 5 metal ions, the metal ions can be orderly and uniformly mixed and arranged in a lattice structure, and uniform single-phase structure with high crystallinity and regular large-size crystals are obtained.
(4) And separating, washing and drying the suspension to obtain the high-entropy prussian blue material.
Further, the complexing agent is at least one of sodium citrate, 2,2' -bipyridine, 1-10-phenanthroline, ethylenediamine, disodium ethylene diamine tetraacetate and trisodium nitrilotriacetate; the use of the complexing agent also promotes the slow and synergistic rate release of transition metal ions of various metal ions, so that a more uniformly dispersed and equal-ratio reaction environment can be formed when the precursor is added dropwise, and the coprecipitation reaction is carried out with ferrocyanide, so that the slow growth of crystals is realized, the metal ions can be orderly and uniformly mixed and arranged in a lattice structure, and uniform single-phase structures with high crystallinity and regular large-size crystals are obtained. Further, the crystallinity of the material is improved, and sodium storage sites are increased, so that more sodium in the finally formed high-entropy prussian blue material structure is reserved, and the sodium content in the material structure is improved. More preferably, when the complexing agent itself is a sodium salt, such as sodium citrate, the reaction environment provides a sodium-rich reaction environment, thereby increasing the sodium content of the reaction product.
The surface dispersant is at least one of polyvinylpyrrolidone, hexadecyl trimethyl ammonium bromide, polycyclic aromatic hydrocarbon and sodium dodecyl benzene sulfonate. The use of the surface dispersing agent further promotes the ordered growth of crystal grains and promotes the ordered and uniform mixed arrangement of metal ions in a lattice structure; on the other hand, the addition of the surface dispersing agent has the effects of improving distribution, regulating and controlling the integral microscopic morphology of the material, enabling the material to reach a large size and increasing the particle size; thereby obtaining a uniform single-phase structure with high crystallinity and regular large-sized crystals.
The auxiliary solvent is at least one of ethanol, ethylene glycol, acetic acid, ethanolamine, n-butanol, methanol, formic acid and propanol.
Furthermore, the volume ratio of the deionized water to the auxiliary solvent in the precursor solutions a and B is any ratio, and the same auxiliary solvent and the same ratio are used in the precursor solutions a and B. Furthermore, the concentration of the complexing agent in the precursor liquid A and the precursor liquid B is 0.1 to 3mol/L, the concentration refers to the volume ratio of the molar quantity of the complexing agent to deionized water in a solvent of the precursor liquid, and the same concentration is adopted in the precursor liquid A and the precursor liquid B. When the precursor is dripped, the consistency and the uniformity of the reaction environment are ensured, the improvement of the distribution is promoted, the integral microscopic morphology of the material is regulated, and the effects of large size and particle size increase are achieved.
Furthermore, the concentration of the surface dispersing agent in the precursor liquid A is 10-300g/L, and the concentration refers to the volume ratio of the mass of the surface dispersing agent to the deionized water in the precursor liquid A.
Further, the transition metal salt is at least five of iron salt, manganese salt, cobalt salt, nickel salt, copper salt, titanium salt and vanadium salt;
the transition metal salt is at least one of fluoride salt, chloride salt, bromide salt, iodide salt, acetate, nitrate, sulfate, oxalate and ethylenediamine tetraacetate.
Further, the flow rate of the precursor liquid B dropwise added to the precursor liquid A in the step (3) is 1 mL/min-50 mL/min;
further, in the step (3), in the reaction process of dropwise adding the precursor liquid B into the precursor liquid A, heating the precursor liquid A to a target temperature and stirring simultaneously, introducing protective gas, keeping the temperature and stirring until the precursor liquid B is sufficiently and reversely added, and then carrying out aging treatment. Wherein the target temperature is 25-100 ℃; the protective gas is at least one of air, nitrogen and argon; the stirring speed is 200-1500 rpm, and the heat preservation stirring time is 1-48 h; the aging time is 1-48 h.
Further, the separation in the step (4) adopts a centrifugal method; the rotating speed of the centrifugation is 6000 to 10000rpm, and the time is 5 to 10 minutes;
the drying in the step (4) is vacuum drying, and the vacuum degree is 10 -6 -10 -2 pa, drying temperature is 100-160 ℃, and drying time is 6-24 hours.
The technical scheme of the invention has the following advantages:
1. the high-entropy prussian blue material provided by the invention is prepared by adopting a coprecipitation method, more than 5 metal ions are used in the material, and the coprecipitation rates of various metal ions are different, so that how to realize orderly and synchronous release of various metal ions in a reaction is the key to realize high crystallinity of the high-entropy prussian blue material, obtain a uniform large-size single-phase crystal structure and finally obtain the high-cycle stability and good rate performance. According to the invention, the precursor liquid B is slowly dripped into the precursor liquid A, and the complexing agent and the dispersing agent are used in the precursor liquid A, B, so that more than 5 transition metal salts release transition metal ions at a slow and synergistic rate, and the transition metal ions and ferrocyanide are subjected to coprecipitation reaction, thereby realizing the slow growth of crystals, and also realizing the uniform mixed arrangement of different elements in a crystal structure, and enabling the generated high-entropy Prussian blue sodium ion battery anode material to have high crystallinity, a single and consistent phase structure and a proper particle size. The high crystallinity reduces the introduction of vacancies and water, increases sodium storage sites, improves the specific capacity, stabilizes the integral structural framework of the high-entropy prussian blue and has higher cycle stability in charge-discharge cycles.
2. According to the preparation method of the high-entropy Prussian blue type sodium ion battery anode material, the selection and the usage amount of the complexing agent and the solvent in the precursor liquid A, B are consistent, the precursor liquid A, B is ensured to have the same liquid environment, and the precipitation of reaction substances caused by different liquid environments in the process of dripping the precursor liquid B to the precursor liquid is avoided; and the continuous and consistent reaction environment promotes the overall microcosmic appearance regulation of the material, so that the material achieves the effects of large size and particle size improvement. 3. The high-entropy Prussian blue type sodium ion battery positive electrode material provided by the invention has a single-phase structure of a monoclinic phase, has a structure mixed arrangement caused by high entropy, and greatly reduces the Zingiber Taylor effect of transition metal elements in the Prussian blue material on the premise of ensuring high specific capacity, so that the dissolution of the elements is reduced, and the long-term circulation stability of the corresponding sodium ion battery is greatly improved. And the cooperative work among various different transition metal elements can further ensure the specific capacity and simultaneously improve the multiplying power performance of the material structure.
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, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a schematic diagram of a reaction apparatus of a preparation method of a prussian blue sodium-ion battery positive electrode material in an embodiment of the invention.
Fig. 2 is an SEM electron micrograph of the prussian blue-based sodium ion battery positive electrode material prepared in examples 1 to 4 of the present invention.
Fig. 3 is an XRD pattern of the prussian blue-based sodium-ion battery cathode material prepared in examples 1-4 of the present invention.
FIG. 4 is a cycle performance diagram of the organic electrolyte system sodium-ion half-cell with a Prussian blue material as the positive electrode, prepared in examples 1-4 of the present invention, at a current density of 500 mA/g.
Fig. 5 is a rate performance graph of the organic electrolyte system sodium ion half-cell with the prussian blue material as the positive electrode prepared in the embodiments 1-4 of the invention under the current density of 10, 100, 200, 500, 1000, 1500 mA/g.
Fig. 6 is a charge-discharge curve diagram of the prussian blue sodium-ion battery cathode material prepared in example 1 of the present invention.
Detailed Description
The following examples are provided to better understand the present invention, not to limit the present invention to the best mode, and not to limit the content and protection scope of the present invention, and it is within the protection scope of the present invention that anyone can combine the features of the present invention with other prior art to obtain any product that is the same or similar to the present invention, and apply it to lithium ion battery, potassium ion battery, etc. similar to sodium ion battery.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
The embodiment provides a preparation method of a high-entropy Prussian blue type sodium ion battery positive electrode material, which comprises the following steps:
dissolving 3mol of sodium ferrocyanide decahydrate, 10g of polyvinylpyrrolidone and 2mol of sodium citrate in a mixed solvent consisting of 1L of deionized water and 100mL of absolute ethyl alcohol to obtain a precursor solution A;
dissolving 0.3mol of manganese sulfate, 0.3mol of copper sulfate, 0.3mol of nickel acetate, 0.3mol of cobalt chloride, 0.3mol of ferric nitrate and 2mol of sodium citrate in a mixed solvent consisting of 1L of deionized water and 100mL of absolute ethyl alcohol to obtain a precursor solution B;
the coprecipitation reaction is carried out by adopting the device shown in fig. 1, wherein a container A is filled with a precursor liquid A, a container B is filled with a precursor liquid B, the precursor liquid B is slowly dripped into the container A at the speed of 1mL/min by utilizing a peristaltic pump through a silica gel tube, the liquid is heated to 90 ℃ through a temperature-controlled stirring device, and the stirring speed is 400rpm. After the precursor B is dropwise added, keeping the temperature and stirring for 5 hours continuously, and then standing and aging for 40 hours to obtain a sample suspension;
and centrifuging the sample suspension at 6000rpm for 10min, washing the obtained sample precipitate for multiple times by using deionized water and ethanol, and drying the product in a vacuum oven with the temperature of 120 ℃ and the vacuum degree of 1pa for 10h to obtain the high-entropy Prussian blue type sodium-ion battery positive electrode material.
The molecular formula of the obtained material is Na through element analysis and ICP test 1.9 Mn 0.2 Fe 0.2 Co 0.2 Ni 0.2 Cu 0.2 [Fe(CN) 6 ] 0.96 ·1.2H 2 O。
According to SEM test analysis, the high-entropy Prussian blue sodium-ion battery cathode material prepared by the example is in a spheroidal polyhedron shape, and the average length of a single crystal is 6 micrometers. The SEM spectrum is shown in FIG. 2 (a).
According to XRD test analysis, the high-entropy Prussian blue type sodium ion battery cathode material prepared by the embodiment presents an obvious monoclinic phase Prussian blue characteristic peak, and the high-entropy Prussian blue type sodium ion battery cathode material is high in crystallinity and is of a single-phase structure. The X-ray diffraction pattern is shown in fig. 3.
The high-entropy Prussian blue type sodium ion battery positive electrode material prepared by the example is assembled into a sodium ion half battery, and the cycle performance of the sodium ion half battery is tested. As shown in FIG. 4, the maximum discharge capacity of the material under the current density of 500 mA/g is 109mAh/g, the specific capacity retention rate of the battery after 1000 cycles is 84.2%, and the battery shows excellent cycle performance.
The high-entropy Prussian blue type sodium ion battery positive electrode material prepared by the example is assembled into a sodium ion half battery, and the rate capability of the sodium ion half battery is tested. As shown in FIG. 5, the specific discharge capacity was 99.5mAh/g at a current density of 1000 mA/g. The high-entropy prussian blue material prepared by the invention has good rate capability and small specific capacity attenuation along with the increase of current density.
Fig. 6 is a charge-discharge curve diagram of the prussian blue type sodium-ion battery cathode material prepared in example 1 of the present invention. As can be seen, there are two voltage plateaus between about 3.3V and 2.7 to 2.8V in the initial charging and discharging curves. The voltage platform between 2.7 and 2.8V is derived from the contribution of high-spin Fe contrast capacity on one hand and the contribution of sodium content in the material structure on the other hand. This also confirms that the high-entropy prussian blue-like material obtained by the present invention has a high sodium content in the structure and a real content of high-spin Fe of the above formula. The guarantee of the sodium content also plays a key role in finally obtaining a monoclinic phase structure and further improving the specific capacity of the material.
Example 2
The embodiment provides a preparation method of a high-entropy prussian blue sodium-ion battery cathode material, which comprises the following steps of:
dissolving 4mol of sodium ferrocyanide decahydrate, 20g of hexadecyl trimethyl ammonium bromide and 1mol of 1-10-phenanthroline in a mixed solvent consisting of 1L of deionized water and 300mL of anhydrous n-butyl alcohol to obtain a precursor solution A;
dissolving 0.4mol of manganese chloride, 0.4mol of copper oxalate, 0.4mol of nickel acetate, 0.4mol of cobalt ethylenediamine tetraacetate, 0.4mol of ferric nitrate, 0.4mol of titanium chloride and 1mol of 1-10-phenanthroline in a mixed solvent consisting of 1L of deionized water to obtain a precursor solution B;
the coprecipitation reaction is carried out by adopting the device shown in fig. 1, wherein a container A is filled with the precursor liquid A, a container B is filled with the precursor liquid B, the precursor liquid B is slowly dripped into the container A at the speed of 5mL/min by a peristaltic pump through a silica gel tube, the temperature of the liquid is raised to 60 ℃ by a temperature-controlled stirring device, and the stirring speed is 200rpm. After the precursor B is dripped, keeping the temperature and stirring for 10 hours continuously, standing and aging for 20 hours to obtain a sample suspension;
and centrifuging the sample suspension at 9000rpm for 15min, washing the obtained sample precipitate for multiple times by using deionized water and ethanol, and drying the product in a vacuum oven with the temperature of 120 ℃ and the vacuum degree of 0.001pa for 12h to obtain the high-entropy Prussian blue type sodium-ion battery positive electrode material.
The molecular formula of the obtained material is Na through element analysis and ICP test 1.6 Ti 0.16 Mn 0.16 Fe 0.16 Co 0.2 Ni 0.16 Cu 0.16 [Fe(CN) 6 ] 0.93 ·2.1H 2 O。
According to SEM test analysis, the high-entropy Prussian blue type sodium ion battery cathode material prepared by the example shows a spheroidal morphology, and the average length of a single crystal is 8 μm. The SEM spectrum is shown in FIG. 2 (b).
According to XRD test analysis, the high-entropy Prussian blue type sodium ion battery cathode material prepared by the example shows an obvious monoclinic phase Prussian blue characteristic peak, and the high-entropy Prussian blue type sodium ion battery cathode material is high in crystallinity and is of a single-phase structure. The X-ray diffraction pattern is shown in fig. 3.
The high-entropy Prussian blue type sodium ion battery positive electrode material prepared by the example is assembled into a sodium ion half battery, and the cycle performance of the sodium ion half battery is tested. As shown in FIG. 4, the maximum discharge capacity of the material under the current density of 500 mA/g is 103mAh/g, the specific capacity retention rate of the battery after 1000 cycles is 78.8%, and the battery shows excellent cycle performance.
The high-entropy Prussian blue type sodium ion battery positive electrode material prepared by the example is assembled into a sodium ion half battery, and the rate capability of the sodium ion half battery is tested. As shown in FIG. 5, the specific discharge capacity was 96.5mAh/g at a current density of 1000 mA/g. The high-entropy prussian blue material prepared by the invention has good rate capability and small specific capacity attenuation along with the increase of current density.
Example 3
The embodiment provides a preparation method of a high-entropy Prussian blue type sodium ion battery positive electrode material, which comprises the following steps:
dissolving 1mol of sodium ferrocyanide decahydrate, 300g of sodium dodecyl benzene sulfonate and 0.1mol of disodium ethylene diamine tetraacetate in a mixed solvent consisting of 1L of deionized water and 100mL of anhydrous methanol to obtain a precursor solution A;
dissolving 0.2mol of manganese sulfate, 0.1mol of copper sulfate, 0.1mol of nickel acetate, 0.2mol of titanium chloride, 0.2mol of vanadium chloride, 0.2mol of chromium chloride and 0.001mol of disodium ethylene diamine tetraacetate in a mixed solvent consisting of 1L of deionized water and 500mL of absolute ethyl alcohol to obtain a precursor solution B;
the coprecipitation reaction is carried out by adopting the device shown in fig. 1, wherein a container A is filled with the precursor liquid A, a container B is filled with the precursor liquid B, the precursor liquid B is slowly dripped into the container A at the speed of 50mL/min by a peristaltic pump through a silica gel tube, the temperature of the liquid is raised to 30 ℃ by a temperature-controlled stirring device, and the stirring speed is 1000rpm. After the precursor B is dropwise added, keeping the temperature and stirring for 1h continuously, and then standing and aging for 48h to obtain a sample suspension;
and centrifuging the sample suspension at 6000rpm for 10min, washing the obtained sample precipitate for multiple times by using deionized water and ethanol, and drying the product in a vacuum oven with the temperature of 120 ℃ and the vacuum degree of 10^ (-6) pa for 12h to obtain the high-entropy Prussian blue type sodium-ion battery anode material.
The molecular formula of the obtained material is Na through element analysis and ICP test 1.4 Mn 0.20 V 0.20 Ti 0.20 Ni 0.1 Cu 0.1 Cr 0.20 [Fe(CN) 6 ] 0.90 ·4H 2 O。
According to SEM test analysis, the high-entropy Prussian blue sodium-ion battery cathode material prepared by the embodiment presents a spheroidal polyhedron shape, and the average length of a single crystal is 4 microns. The SEM spectrum is shown in FIG. 2 (c).
According to XRD test analysis, the high-entropy Prussian blue type sodium ion battery cathode material prepared by the embodiment presents an obvious monoclinic phase Prussian blue characteristic peak, and the high-entropy Prussian blue type sodium ion battery cathode material is high in crystallinity and is of a single-phase structure. The X-ray diffraction pattern is shown in fig. 3.
The high-entropy prussian blue sodium-ion battery cathode material prepared by the example is assembled into a sodium-ion half battery, and the cycle performance of the sodium-ion half battery is tested. As shown in FIG. 4, the maximum discharge capacity of the material under the current density of 500 mA/g is 116.4mAh/g, the specific capacity retention rate of the battery after 1000 cycles is 79.2%, and the excellent cycle performance is shown.
The high-entropy Prussian blue type sodium ion battery positive electrode material prepared by the example is assembled into a sodium ion half battery, and the rate capability of the sodium ion half battery is tested. As shown in FIG. 5, the specific discharge capacity was 108mAh/g at a current density of 1000 mA/g. The high-entropy prussian blue material prepared by the invention has good rate capability and small specific capacity attenuation along with the increase of current density.
Example 4
The embodiment provides a preparation method of a high-entropy Prussian blue type sodium ion battery positive electrode material, which comprises the following steps:
dissolving 6mol of sodium ferrocyanide decahydrate, 10g of polycyclic aromatic hydrocarbon, 3mol2,2' -bipyridine in a mixed solvent composed of 1L of deionized water and 100mL of anhydrous ethylene glycol to obtain a precursor solution A;
dissolving 0.3mol of manganese ethylene diamine tetracetate, 0.3mol of copper sulfate, 0.3mol of nickel acetate, 0.3mol of cobalt fluoride, 0.3mol of ferric nitrate, 0.3mol of titanium chloride, 0.3mol of vanadium chloride, 0.3mol of zinc acetate, 0.3mol of chromium chloride and 3mol of 2,2' -bipyridyl in a mixed solvent consisting of 1L of deionized water and 100mL of absolute ethyl alcohol to obtain a precursor B;
the device shown in fig. 1 is adopted to carry out coprecipitation reaction, wherein a container A is filled with a precursor liquid A, a container B is filled with a precursor liquid B, the precursor liquid B is slowly dripped into the container A at the speed of 2mL/min by a peristaltic pump through a silica gel tube, the liquid is heated to 25 ℃ by a temperature-controlled stirring device, and the stirring speed is 1500rpm. After the precursor B is dropwise added, keeping the temperature and stirring for 20h, standing and aging for 1h to obtain a sample suspension;
and centrifuging the sample suspension at 6000rpm for 10min, washing the obtained sample precipitate for multiple times by using deionized water and ethanol, and drying the product in a vacuum oven with the temperature of 120 ℃ and the vacuum degree of 1pa for 24h to obtain the high-entropy Prussian blue type sodium-ion battery positive electrode material.
The molecular formula of the obtained material is Na through elemental analysis and ICP test 1.95 Mn 0.11 Fe 0.11 Co 0.11 Ni 0.12 Cu 0.11 Ti 0.11 V 0.11 Cr 0.11 Zn 0.11 [Fe(CN) 6 ] 0.98 ·0.5H 2 O。
According to SEM test analysis, the high-entropy Prussian blue sodium-ion battery cathode material prepared by the embodiment presents a spheroidal polyhedron crystal shape, and the average length of a single crystal is 4 μm. The SEM spectrum is shown in FIG. 2 (d).
According to XRD test analysis, the high-entropy Prussian blue type sodium ion battery cathode material prepared by the embodiment shows an obvious monoclinic phase Prussian blue characteristic peak, which indicates that the high-entropy Prussian blue type sodium ion battery cathode material has high crystallinity and is of a single-phase structure, and an X-ray diffraction pattern is shown in figure 3.
The high-entropy Prussian blue type sodium ion battery positive electrode material prepared by the example is assembled into a sodium ion half battery, and the cycle performance of the sodium ion half battery is tested. As shown in FIG. 4, the maximum discharge capacity of the material under the current density of 500 mA/g is 120.2mAh/g, the specific capacity retention rate of the battery after 1000 cycles is 82.5%, and excellent cycle performance is shown.
The high-entropy prussian blue sodium-ion battery positive electrode material prepared by the example is assembled into a sodium-ion half battery, and the rate capability of the sodium-ion half battery is tested. As shown in FIG. 5, the specific discharge capacity was 116mAh/g at a current density of 1000 mA/g. The high-entropy prussian blue material prepared by the invention has good rate capability and small specific capacity attenuation along with the increase of current density.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. This need not be, nor should it be exhaustive of all embodiments. And obvious variations or modifications derived therefrom are intended to be within the scope of the invention. Naturally, although the invention exemplifies the application of the high-entropy prussian blue material prepared by the examples to the assembly of a sodium-ion battery cathode material into a sodium-ion half battery, the application cannot limit the possibility of applying the high-entropy prussian blue material to a lithium ion battery, a potassium ion battery and the like similar to the sodium-ion battery, and cannot limit the lithium ion battery and the potassium ion battery cathode material similar to the high-entropy prussian blue material of the invention, which is led out by the skilled person according to the preparation method of the examples of the invention, and the obvious changes are all within the scope of the invention.
Claims (8)
1. The high-entropy Prussian blue type sodium ion battery positive electrode material is characterized in that: the molecular formula of the high-entropy Prussian blue type sodium ion battery positive electrode material is NaxMyn [ Fe (CN) 6 ]z·wH 2 O, wherein M is n different transition metal elements, n is more than or equal to 5, yn is more than or equal to 0.01 and less than or equal to 0.90, y1+ y2+ y3+ y4+ y5 … + yn =1,w and 4.0,1.40 and x is more than or equal to 1.95,0.90 and z is more than or equal to 0.98, and the high-entropy Prussian blue sodium-ion battery positive electrode material is in a monoclinic phase structure; the high-entropy Prussian blue sodium-ion battery cathode material has the microscopic morphology of large-size crystal particles, the crystal grains are uniform in size, uniform and regular spheroidal polyhedrons in shape, and the length size of the particles is 4-8 mu m on average.
2. The method for preparing the high-entropy Prussian blue type sodium-ion battery positive electrode material as claimed in claim 1, is characterized by comprising the following steps of:
(1) Dissolving sodium ferrocyanide decahydrate, a complexing agent and a surface dispersing agent in a mixed solvent consisting of deionized water and an auxiliary solvent to obtain a precursor solution A;
(2) Dissolving 5 or more transition metal salts and complexing agents in a mixed solvent consisting of deionized water and an auxiliary solvent to obtain a precursor liquid B;
(3) Dropwise adding the precursor liquid B into the precursor liquid A for reaction, and then carrying out heat preservation stirring and aging treatment to obtain a suspension;
(4) And separating, washing and drying the suspension to obtain the high-entropy Prussian blue type sodium ion battery positive electrode material.
3. The preparation method of the high-entropy prussian blue sodium-ion battery positive electrode material according to claim 2, which is characterized in that: the complexing agent is at least one of sodium citrate, 2,2' -bipyridine, 1-10-phenanthroline, ethylenediamine tetraacetic acid and trisodium nitrilotriacetate; the concentration of the complexing agent in the precursor liquid A and the precursor liquid B, namely the volume ratio of the molar quantity of the complexing agent to the deionized water in the solvent of the precursor liquid is 0.001-3 mol/L, and the same concentration is adopted in the precursor liquid A and the precursor liquid B.
4. The preparation method of the high-entropy prussian blue sodium-ion battery positive electrode material according to claim 2, which is characterized in that: the surface dispersant is at least one of polyvinylpyrrolidone, cetyl trimethyl ammonium bromide, polycyclic aromatic hydrocarbon and sodium dodecyl benzene sulfonate; the concentration of the surface dispersing agent in the precursor liquid A, namely the volume ratio of the mass of the surface dispersing agent to the deionized water in the solvent in the precursor liquid A is 10-300 g/L.
5. The preparation method of the high-entropy prussian blue sodium-ion battery positive electrode material according to claim 2, which is characterized in that: and (3) dropwise adding the precursor liquid B to the precursor liquid A at a flow rate of 1-50 mL/min.
6. The preparation method of the high-entropy prussian blue sodium-ion battery cathode material according to claim 2, characterized in that: the auxiliary solvent is one of ethanol, ethylene glycol, acetic acid, ethanolamine, n-butanol, methanol, formic acid and propanol; the volume ratio of the deionized water to the auxiliary solvent in the precursor liquid A and the precursor liquid B is any ratio, and the same auxiliary solvent and the same ratio are adopted in the precursor liquid A and the precursor liquid B.
7. The preparation method of the high-entropy prussian blue sodium-ion battery cathode material according to claim 2, characterized in that: the transition metal salt is at least five of iron salt, manganese salt, cobalt salt, nickel salt, copper salt, titanium salt, vanadium salt, zinc salt and chromium salt; the transition metal salt is at least one of fluoride salt, chloride salt, bromide salt, iodide salt, acetate, nitrate, sulfate, oxalate and ethylenediamine tetraacetate.
8. The application of the high-entropy Prussian blue type sodium-ion battery positive electrode material according to claim 1 is characterized in that: the high-entropy Prussian blue sodium-ion battery cathode material is applied to a sodium-ion battery and used as a cathode material.
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| CN114212804B (en) * | 2021-12-15 | 2022-12-09 | 武汉理工大学 | Prussian white positive electrode material and preparation method and application thereof |
| CN114388796B (en) * | 2021-12-17 | 2023-07-07 | 合肥国轩高科动力能源有限公司 | Doped positive electrode material, preparation method and sodium ion battery |
| WO2023123414A1 (en) * | 2021-12-31 | 2023-07-06 | 宁德时代新能源科技股份有限公司 | Positive electrode active material, sodium ion secondary battery comprising same, and electric apparatus |
| CN114538520B (en) * | 2022-01-12 | 2023-07-25 | 华南师范大学 | Preparation method and application of hollow metal oxide |
| CN114477233A (en) * | 2022-02-16 | 2022-05-13 | 温州大学碳中和技术创新研究院 | Preparation method of high-entropy polymetallic Prussian blue and analogues thereof and sodium-ion battery |
| CN114618503B (en) * | 2022-03-23 | 2023-07-07 | 中国科学院赣江创新研究院 | High-entropy oxide oxygen storage material and preparation method and application thereof |
| CN115124050A (en) * | 2022-06-01 | 2022-09-30 | 湖州超钠新能源科技有限公司 | Alkali metal doped Prussian blue material and preparation method and application thereof |
| CN114805450A (en) * | 2022-06-15 | 2022-07-29 | 国网智能电网研究院有限公司 | Preparation method and application of high-entropy Prussian blue sodium ion battery cathode material |
| CN115057456A (en) * | 2022-06-15 | 2022-09-16 | 国网智能电网研究院有限公司 | Method for preparing Prussian blue on large scale |
| CN115367771A (en) * | 2022-07-07 | 2022-11-22 | 华南理工大学 | High-stability micron-sized cubic Prussian blue and analogue thereof, and preparation method and application thereof |
| CN115571896B (en) * | 2022-10-10 | 2023-07-14 | 湖北宇浩高科新材料有限公司 | Modification method and application of iron-based Prussian blue |
| CN116443894A (en) * | 2023-04-12 | 2023-07-18 | 上海汉行科技有限公司 | Sodium ion battery positive electrode material and preparation method and application thereof |
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