CN109928409A - Prussian blue similar object and preparation method thereof, cathode material and application - Google Patents
Prussian blue similar object and preparation method thereof, cathode material and application Download PDFInfo
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Abstract
The present invention relates to a kind of Prussian blue similar object and preparation method thereof, cathode material and applications.The preparation method of Prussian blue similar object, comprising the following steps: take water as a solvent, the potassium ferricyanide and zinc nitrate are subjected to coprecipitation reaction, obtain reaction solution；Reaction solution is stood, sediment is obtained；And by drying precipitate, obtaining chemical formula is K2Zn3[Fe(CN)6]2Prussian blue similar object.The preparation method of above-mentioned Prussian blue similar object is easy to operate, and can obtain grain size in 300nm or so, the preferable Prussian blue similar object of cyclical stability.
Description
Technical field
The present invention relates to water system sodium-ion battery technical fields, more particularly to Prussian blue similar object and its preparation side
Method, cathode material and application.
Background technique
The environmental pollution as brought by the use of fossil fuel, renewable energy are a kind of effective solution measures.Greatly
Scale energy storage is the key that effective use intermittent renewable energy strategy.In nearest decades, researcher is had studied perhaps
A variety of rechargeable batteries, each has its strengths and weaknesses；But a kind of few batteries can meet stability height, cost simultaneously
Low and highly-safe feature.The energy density of metal hydride is low, and lithium ion battery raw material are expensive, and poor safety performance.
Due to the feature of intrinsic safety and low cost, the water system electrolyte rechargeable battery based on sodium ion insertion is considered as most
One of next-generation energy storage system with development prospect.The natural abundance and low cost of sodium further provide for this technology
Economic advantages, and it is suitable for the extensive energy stores of renewable energy.Most of tradition water system sodium-ion batteries all meet
The requirement of low cost, but the preparation method of traditional water system sodium-ion battery cathode material is relative complex, the crystalline substance of material obtained
Grain is not of uniform size, is not suitable for large-scale production and application.And the cyclical stability of traditional water system sodium-ion battery is poor.
Summary of the invention
Based on this, it is necessary to it is simple and can make that the grain size of Prussian blue similar object is uniform, follows to provide a kind of method
The preparation method of the preferable Prussian blue similar object of ring stability.
In addition, also providing a kind of Prussian blue similar object, cathode material and application.
A kind of preparation method of Prussian blue similar object, comprising the following steps:
It takes water as a solvent, the potassium ferricyanide and zinc nitrate is subjected to coprecipitation reaction, obtain reaction solution；
The reaction solution is stood, sediment is obtained；And
By the drying precipitate, obtaining chemical formula is K2Zn3[Fe(CN)6]2Prussian blue similar object.
The molar ratio of the potassium ferricyanide and the zinc nitrate is 1: 1~1: 2 in one of the embodiments,.
It is described in one of the embodiments, to take water as a solvent, the potassium ferricyanide and zinc nitrate are subjected to coprecipitation reaction, obtained
Include: to the step of reaction solution
The potassium ferricyanide and zinc nitrate difference is soluble in water, obtain potassium ferricyanide solution and zinc nitrate solution；
Under continuous agitation, the potassium ferricyanide solution is added in the zinc nitrate solution；And
Continue to stir 15min~20min, obtains the reaction solution.
The concentration of the potassium ferricyanide solution is 4mmol/L~8mmol/L, the nitric acid in one of the embodiments,
The concentration of zinc solution is 6mmol/L~12mmol/L.
In one of the embodiments, in described the step of standing the reaction solution, time of repose is 20h~for 24 hours.
It is described in one of the embodiments, that by the step of the drying precipitate, drying temperature is 60 DEG C~80 DEG C,
Drying time is 20h~for 24 hours.
In one of the embodiments, after described the step of obtaining sediment, the step by the drying precipitate
Before rapid, further include the steps that washing the sediment.
The Prussian blue similar object being prepared by the preparation method of above-mentioned Prussian blue similar object.
A kind of cathode material, the cathode material include active material, and the active material includes above-mentioned prussian blue
Like object.
Application of the above-mentioned cathode material in preparation water system sodium-ion battery.
The preparation method of above-mentioned Prussian blue similar object is easy to operate, using the coprecipitation method in aqueous solution, can obtain
To Prussian blue similar object, without complicated preparation process.By coprecipitation reaction, and by reaction solution stand and to sediment into
The step of row is dried can make the grain size stability contorting for the Prussian blue similar object being prepared in 300nm or so,
Size is uniform, and it is demonstrated experimentally that the cyclical stability of Prussian blue similar object is preferable, can be used as water system sodium-ion battery cathode
The active material of material.
Detailed description of the invention
Fig. 1 is the flow chart of the preparation method of the Prussian blue similar object of an embodiment；
Fig. 2 is the energy spectrum analysis figure for the Prussian blue similar object that embodiment 1 is prepared；
Fig. 3 is the XRD spectra for the Prussian blue similar object that embodiment 1 is prepared；
Fig. 4 is the infrared spectrum for the Prussian blue similar object that embodiment 1 is prepared；
Fig. 5 is the SEM figure for the Prussian blue similar object that embodiment 1 is prepared；
Fig. 6 is the SEM figure for the Prussian blue similar object that comparative example 1 is prepared；
Fig. 7 is the Prussian blue similar object that is prepared of embodiment 1 in 5mVs-1Cyclic voltammetry curve under sweep speed；
Fig. 8 is the Prussian blue similar object that is prepared of comparative example 1 in 5mVs-1Cyclic voltammetry curve under sweep speed；
Fig. 9 is the SEM figure for the Prussian blue similar object that embodiment 2 is prepared；
Figure 10 is the SEM figure for the Prussian blue similar object that embodiment 3 is prepared；
Figure 11 is the SEM figure for the Prussian blue similar object that comparative example 2 is prepared；
Figure 12 is the SEM figure for the Prussian blue similar object that comparative example 3 is prepared；
Figure 13 is the SEM figure for the Prussian blue similar object that comparative example 4 is prepared；
Figure 14 is the SEM figure for the Prussian blue similar object that comparative example 5 is prepared；
Figure 15 is the Prussian blue similar object that is prepared of embodiment 2 in 5mVs-1Cyclic voltammetry curve under sweep speed；
Figure 16 is the Prussian blue similar object that is prepared of embodiment 3 in 5mVs-1Cyclic voltammetry curve under sweep speed；
Figure 17 is the Prussian blue similar object that is prepared of comparative example 2 in 5mVs-1Cyclic voltammetry curve under sweep speed；
Figure 18 is the Prussian blue similar object that is prepared of comparative example 3 in 5mVs-1Cyclic voltammetry curve under sweep speed；
Figure 19 is the Prussian blue similar object that is prepared of comparative example 4 in 5mVs-1Cyclic voltammetry curve under sweep speed；
Figure 20 is the Prussian blue similar object that is prepared of comparative example 5 in 5mVs-1Cyclic voltammetry curve under sweep speed.
Specific embodiment
To facilitate the understanding of the present invention, below in conjunction with specific embodiment to invention is more fully described.Tool
Preferred embodiment of the invention is given in body embodiment.But the invention can be realized in many different forms,
It is not limited to the examples described herein.On the contrary, purpose of providing these embodiments is makes to the disclosure
Understanding it is more thorough and comprehensive.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
Body embodiment purpose, it is not intended that in limitation the present invention.
Referring to Fig. 1, the preparation method of the Prussian blue similar object of an embodiment, comprising the following steps:
Step S110: taking water as a solvent, and the potassium ferricyanide and zinc nitrate are carried out coprecipitation reaction, obtain reaction solution.
Wherein, the molar ratio of the potassium ferricyanide and zinc nitrate is 1: 1~1: 2.Specifically, zinc nitrate is six water with the crystallization water
Close zinc nitrate.
Specifically, the step of taking water as a solvent, the potassium ferricyanide and zinc nitrate are carried out coprecipitation reaction, obtain reaction solution packet
It includes:
The potassium ferricyanide and zinc nitrate difference is soluble in water, obtain potassium ferricyanide solution and zinc nitrate solution；
Under continuous agitation, potassium ferricyanide solution is added in zinc nitrate solution and is mixed；And
Continue to stir 15min~20min, obtains reaction solution.
Wherein, the concentration of potassium ferricyanide solution is 4mmol/L~8mmol/L, the concentration of zinc nitrate solution be 6mmol/L~
12mmol/L.The pH of above-mentioned reaction solution is 4~5.
It in the step of above-mentioned potassium ferricyanide and zinc nitrate carry out coprecipitation reaction, carries out in aqueous solution, without adding acid
Property buffer solution, react it is safer.
Step S120: reaction solution is stood, and obtains sediment.
Specifically, time of repose is 20h~for 24 hours.After the step of reaction solution is stood, the step of obtaining sediment it
Before, further include the steps that reaction solution is centrifuged.
Step S130: by drying precipitate, obtaining chemical formula is K2Zn3[Fe(CN)6]2Prussian blue similar object.
It wherein, is 60 DEG C~80 DEG C by the temperature of drying precipitate.Drying time is 20h~for 24 hours.
Further include the steps that washing sediment between step S120 and step S130.Specifically, it is respectively adopted
Deionized water and ethyl alcohol wash sediment.Washing times are respectively three times.
After the step of drying precipitate, obtaining chemical formula is K2Zn3[Fe(CN)6]2Prussian blue similar object step
Before rapid, further includes: the step of being ground sediment.
Specifically, the color of Prussian blue similar object is light green color.
The preparation method of above-mentioned Prussian blue similar object has at least the following advantages:
(1) above-mentioned preparation method uses simple coprecipitation method, easy to operate without complicated preparation flow, is easy to
Actual production.
(2) the grain size stability contorting for the Prussian blue similar object that above-mentioned preparation method obtains is in 300nm or so.It compares
In the Prussian blue similar object that traditional preparation method is prepared, there is bigger specific surface area.And above-mentioned preparation method system
The cyclical stability of standby obtained Prussian blue similar object is preferable.
(3) above-mentioned preparation method can carry out in aqueous solution, compared to traditional preparation method in an acidic solution into
Row, it is safer, stable.
(4) for above-mentioned preparation method using the potassium ferricyanide and zinc nitrate as raw material, cost of material is low, is easy to get.
The Prussian blue similar object of one embodiment is prepared by the preparation method of above-mentioned Prussian blue similar object.It is above-mentioned
The grain size of Prussian blue similar object has biggish specific surface area, and good cycling stability in 300nm or so.
The cathode material of one embodiment, wherein cathode material includes active material, and active material includes prussian blue
Like object.The good cycling stability of above-mentioned Prussian blue similar object, can be as the active material of cathode material.
The preparation method of the cathode material of one embodiment, comprising the following steps:
Prussian blue similar object is mixed with carbon black, Kynoar, obtains mixture；And
Mixture is coated in foam nickel surface, obtains water system sodium-ion battery cathode material.
Specifically, by weight it is (7~8) by Prussian blue similar object and carbon black, Kynoar: (1~2): (1~
2) it is mixed.After the step of Prussian blue similar object is mixed with carbon black, Kynoar, the step of mixture is obtained
Before rapid, further include the steps that grinding.Wherein, the time of grinding is 20min~30min.
Specifically, mixture is coated in foam nickel surface, and is coated with the nickel foam of mixture at 60 DEG C~80 DEG C
Lower heat preservation 20h~for 24 hours, obtain water system sodium ion cathode material.
The preparation method of above-mentioned water system sodium-ion battery cathode material passes through Prussian blue similar object and carbon black and gathers inclined
Vinyl fluoride is mixed, and is coated in foam nickel surface, and method is simple, and water system sodium-ion battery cathode material obtained shows
Good chemical property out.Above-mentioned cathode material can be used in water system sodium-ion battery, and safety is higher.
Application of the water system sodium-ion battery cathode material of one embodiment in preparation water system sodium-ion battery.Wherein,
The charging/discharging voltage section of water system sodium-ion battery cathode material is in 0V~1.2V.The cathode material of above-mentioned water system sodium-ion battery
With good chemical property, can be used in water system sodium-ion battery.
The following are specific embodiment parts:
Embodiment 1
The preparation method of the water system sodium-ion battery cathode material of the present embodiment, includes the following steps:
(1) potassium ferricyanide solid and zinc nitrate solid are weighed respectively for 1: 1 in molar ratio, and be dissolved in water respectively, obtain dense
The zinc nitrate solution that the potassium ferricyanide solution and concentration that degree is 8mmol/L are 8mmol/L.Then potassium ferricyanide solution is being stirred
Under the conditions of, it is poured slowly into zinc nitrate solution, and continue stirring 15 minutes, obtains reaction solution.
(2) reaction solution is stood to 24 hours at room temperature, is then centrifuged, sediment is obtained.By sediment point
It is not washed respectively three times with deionized water and ethyl alcohol.
(3) sediment after washing is put into drying box at a temperature of 60 DEG C and be dried within 24 hours.It collects shallow
Green sample, and be put in mortar, it is fully ground uniformly, it is K that Prussian blue similar object, which is made,2Zn3[Fe(CN)6]2。
(4) K is weighed respectively for 8: 1: 1 in mass ratio2Zn3[Fe(CN)6]2Material, carbon black and Kynoar, and carry out
Mixing, grinding 20min, obtain mixture.Mixture is coated in foam nickel surface, and nickel foam is put into drying box 60
24 hours are kept the temperature at a temperature of DEG C, water system sodium-ion battery cathode material is made.
Embodiment 2
The preparation method of the water system sodium-ion battery cathode material of the present embodiment, includes the following steps:
(1) potassium ferricyanide solid and zinc nitrate solid are weighed respectively for 1: 2 in molar ratio, and be dissolved in water respectively, obtain dense
The zinc nitrate solution that the potassium ferricyanide solution and concentration that degree is 6mmol/L are 12mmol/L.Then potassium ferricyanide solution is being stirred
It under the conditions of mixing, is poured slowly into zinc nitrate solution, and continues stirring 20 minutes, obtain reaction solution.
(2) reaction solution is stood to 20 hours at room temperature, is then centrifuged, sediment is obtained.By sediment point
It is not washed respectively three times with deionized water and ethyl alcohol.
(3) sediment after washing is put into drying box at a temperature of 80 DEG C and be dried within 20 hours.It collects shallow
Green sample, and be put in mortar, it is fully ground uniformly, it is K that Prussian blue similar object, which is made,2Zn3[Fe(CN)6]2。
(4) K is weighed respectively for 7: 2: 1 in mass ratio2Zn3[Fe(CN)6]2Material, carbon black and Kynoar, and carry out
Mixing, grinding 30min, obtain mixture.Mixture is coated in foam nickel surface, and nickel foam is put into drying box 80
20 hours are kept the temperature at a temperature of DEG C, water system sodium-ion battery cathode material is made.
Embodiment 3
The preparation method of the water system sodium-ion battery cathode material of the present embodiment, includes the following steps:
(1) potassium ferricyanide solid and zinc nitrate solid are weighed respectively for 1: 1.5 in molar ratio, and be dissolved in water respectively, obtain
The zinc nitrate solution that the potassium ferricyanide solution and concentration that concentration is 4mmol/L are 6mmol/L.Then potassium ferricyanide solution is being stirred
It under the conditions of mixing, is poured slowly into zinc nitrate solution, and continues stirring 18 minutes, obtain reaction solution.
(2) reaction solution is stood to 22 hours at room temperature, is then centrifuged, sediment is obtained.By sediment point
It is not washed respectively three times with deionized water and ethyl alcohol.
(3) sediment after washing is put into drying box at a temperature of 70 DEG C and be dried within 22 hours.It collects shallow
Green sample, and be put in mortar, it is fully ground uniformly, it is K that Prussian blue similar object, which is made,2Zn3[Fe(CN)6]2。
(4) K is weighed respectively for 7: 1: 2 in mass ratio2Zn3[Fe(CN)6]2Material, carbon black and Kynoar, and carry out
Mixing, grinding 25min, obtain mixture.Mixture is coated in foam nickel surface, and nickel foam is put into drying box 70
22 hours are kept the temperature at a temperature of DEG C, water system sodium-ion battery cathode material is made.
Comparative example 1
The Prussian blue similar object of this comparative example the preparation method is as follows:
(1) potassium ferricyanide solid and zinc nitrate solid are weighed respectively for 1: 1 in molar ratio, and be dissolved in water respectively, obtain dense
The zinc nitrate solution that the potassium ferricyanide solution and concentration that degree is 8mmol/L are 8mmol/L.Then potassium ferricyanide solution is being stirred
Under the conditions of, it is poured slowly into zinc nitrate solution, and continue stirring 15 minutes, obtains reaction solution.
(2) reaction solution is stood to 24 hours at room temperature, is then centrifuged, sediment is obtained.By sediment point
It is not washed respectively three times with deionized water and ethyl alcohol, obtains Prussian blue similar object.
Comparative example 2
Prussian blue similar object in this comparative example the preparation method is as follows:
(1) potassium ferricyanide solid and zinc nitrate solid are weighed respectively for 1: 3 in molar ratio, and be dissolved in water respectively, obtain dense
The zinc nitrate solution that the potassium ferricyanide solution and concentration that degree is 4mmol/L are 12mmol/L.Then potassium ferricyanide solution is being stirred
It under the conditions of mixing, is poured slowly into zinc nitrate solution, and continues stirring 15 minutes, obtain reaction solution.
(2) reaction solution is stood to 24 hours at room temperature, is then centrifuged, sediment is obtained.By sediment point
It is not washed respectively three times with deionized water and ethyl alcohol.
(3) sediment after washing is put into drying box at a temperature of 60 DEG C and be dried within 24 hours.It collects shallow
Green sample, and be put in mortar, it is fully ground uniformly, it is K that Prussian blue similar object, which is made,2Zn3[Fe(CN)6]2。
Comparative example 3
The Prussian blue similar object of this comparative example the preparation method is as follows:
(1) potassium ferricyanide solid and zinc nitrate solid are weighed respectively for 1: 1 in molar ratio, and be dissolved in water respectively, obtain dense
The zinc nitrate solution that the potassium ferricyanide solution and concentration that degree is 8mmol/L are 8mmol/L.Then potassium ferricyanide solution is being stirred
Under the conditions of, it is poured slowly into zinc nitrate solution, and continue stirring 15 minutes, obtains reaction solution.
(2) reaction solution is stood to 24 hours at room temperature, is then centrifuged, sediment is obtained.By sediment point
It is not washed respectively three times with deionized water and ethyl alcohol.
(3) sediment after washing is put into drying box at a temperature of 100 DEG C and be dried within 24 hours.It collects shallow
Green sample, and be put in mortar, it is fully ground uniformly, it is K that Prussian blue similar object, which is made,2Zn3[Fe(CN)6]2。
Comparative example 4
The Prussian blue similar object of this comparative example the preparation method is as follows:
(1) potassium ferricyanide solid and zinc nitrate solid are weighed respectively for 1: 1 in molar ratio, and be dissolved in water respectively, obtain dense
The zinc nitrate solution that the potassium ferricyanide solution and concentration that degree is 8mmol/L are 8mmol/L.Then potassium ferricyanide solution is being stirred
Under the conditions of, it is poured slowly into zinc nitrate solution, and continue stirring 15 minutes, obtains reaction solution.
(2) reaction solution is stood to 2 hours at room temperature, is then centrifuged, sediment is obtained.Sediment is distinguished
It is respectively washed three times with deionized water and ethyl alcohol.
(3) sediment after washing is put into drying box at a temperature of 60 DEG C and be dried within 24 hours.It collects shallow
Green sample, and be put in mortar, it is fully ground uniformly, it is K that Prussian blue similar object, which is made,2Zn3[Fe(CN)6]2。
Comparative example 5
The Prussian blue similar object of this comparative example the preparation method is as follows:
(1) potassium ferricyanide solid and zinc nitrate solid are weighed respectively for 1: 1 in molar ratio, and be dissolved in water respectively, obtain dense
The zinc nitrate solution that the potassium ferricyanide solution and concentration that degree is 8mmol/L are 8mmol/L.Then salt is added into zinc nitrate solution
Acid, adjusting pH is 3.0, under agitation by potassium ferricyanide solution, is poured slowly into acid zinc nitrate solution, and persistently stir
It mixes 15 minutes, obtains reaction solution.
(2) reaction solution is stood to 24 hours at room temperature, is then centrifuged, sediment is obtained.By sediment point
It is not washed respectively three times with deionized water and ethyl alcohol.
(3) sediment after washing is put into drying box at a temperature of 60 DEG C and be dried within 24 hours.It collects shallow
Green sample, and be put in mortar, it is fully ground uniformly, it is K that Prussian blue similar object, which is made,2Zn3[Fe(CN)6]2。
Prussian blue similar object obtained in embodiment 1 is subjected to following test:
(1) energy spectrum analysis is carried out to Prussian blue similar object using the EVO type scanning electron microscope of Zeiss company.Power spectrum
It is as shown in Figure 2 and Table 1 to analyze result.From Fig. 2 in table 1 as can be seen that Zn element in Prussian blue similar object shared by ratio
Example is 12%, and is uniformly distributed in the material.
Table 1
(2) XRD analysis, Cu are carried out to Prussian blue similar object using the D5000 type X-ray diffractometer of Siemens Company
Target, K α radiation source.Obtained X ray diffracting spectrum is as shown in Figure 3.From figure 3, it can be seen that K2Zn3[Fe(CN)6]2With just
Hand over symmetry.And spectrogram is compared with PDF card base, determine that Prussian blue similar object is K2Zn3[Fe(CN)6]2。
(3) using 6700 type spectrometer of Nicolet Magna to Prussian blue similar object progress infrared analysis, obtain as
Infrared spectrum shown in Fig. 4.Figure 4, it is seen that in 2100cm-1And 2186cm-1Infrared peak, correspond to sample products
The stretching vibration of middle C ≡ N.In 549cm-1And 443cm-1Neighbouring infrared peak corresponds to Fe-C ≡ N-Fe stretching vibration.?
1612cm-1And 3600cm-1Infrared peak correspond to H2O-H stretch mode and H-O-H beam mode in O.
The above test shows that the Prussian blue similar object being prepared in embodiment 1 is K2Zn3[Fe(CN)6]2。
By the Prussian blue similar object being prepared in 1~embodiment of embodiment 3 and 1~comparative example of comparative example 5 respectively into
Row scanning electron microscope test, cyclic voltammetry and specific surface area test.Wherein, using the supra 55VP of Zeiss company
Type scanning electron microscope observes the microscopic appearance of Prussian blue similar object.Electrochemical Characterization is carried out using three-electrode system,
The sodium perchlorate for being 1 mole using stoichiometry is electrolyte, and carbon black is to electrode, and Ag/AgCl is reference electrode, to Prussian blue
Analog carries out cyclic voltammetry.Cyclic voltammetry curve obtains on the 20 type electrochemical workstation of WAVEDRIVE of PINE company
?.Using Brunauer-Emmett-Teller assay specific surface area.Shown in test result is as follows:
Embodiment 1 is with the scanning electron microscope image of the Prussian blue similar object in comparative example 1 respectively such as Fig. 5 and Fig. 6
It is shown.From figure 5 it can be seen that the Prussian blue similar object K in embodiment 12Zn3[Fe(CN)6]2Show cube of rule
Body structure, grain size are about 300nm.Prussian blue similar object it can be seen from Fig. 6 in comparative example 1 due to not into
Row heat treatment, the difference in size of Prussian blue similar object is larger, and uneven.
Embodiment 1 and the cyclic voltammetry curve of the Prussian blue similar object in comparative example 1 difference are as shown in Figure 7 and Figure 8.From
As can be seen that including a pair of good redox in the cyclic voltammetry curve of the Prussian blue similar object in embodiment 1 in Fig. 7
Process, in+1.05/+0.69V.And the Prussian blue similar object in embodiment 1 can be stable circulation several times.And from Fig. 8
It can be seen that not including apparent oxidation-reduction process in the cyclic voltammetry curve of the Prussian blue similar object of comparative example 1.
The specific surface area data of the Prussian blue similar object of each embodiment and comparative example of table 2
From Table 2, it can be seen that the Prussian blue similar object material as made from embodiment is than being made Prussia in comparative example
Blue analog material has bigger specific surface area.
The SEM for the Prussian blue similar object that 2~embodiment of embodiment 3,2~comparative example of comparative example 5 are prepared schemes difference
As shown in Fig. 9~Figure 10, Figure 11~Figure 14.From Fig. 9 and Figure 10 as can be seen that embodiment 2 and embodiment 3 be prepared it is general
Shandong scholar's indigo plant analog shows the cube structure of rule under a scanning electron microscope, and size is uniform, and grain size exists respectively
400nm and 200nm.And from Figure 11~Figure 14 as can be seen that 2~comparative example of comparative example 5 be prepared it is Prussian blue similar
Object is also easy to produce reunion, in irregular shape, and grain size is inhomogenous.
The cyclic voltammetric for the Prussian blue similar object that 2~embodiment of embodiment 3,2~comparative example of comparative example 5 are prepared is bent
Line is respectively as shown in Figure 15~Figure 16, Figure 17~Figure 20.As can be seen that prepared by embodiment 2 and embodiment 3 from Figure 15~Figure 16
Comprising a pair of good oxidation-reduction process in the cyclic voltammetry curve of obtained Prussian blue similar object, and can be stable follow
Ring is several times.And it can be seen that the Prussian blue similar object that 2~comparative example of comparative example 5 is prepared from Figure 17~Figure 20
It does not include apparent oxidation-reduction process in cyclic voltammetry curve.
The above experiment shows the Prussian blue similar object material grains size being prepared in embodiment on the left side 300nm
The right side, size is uniform, and specific surface area is larger and cyclical stability is preferable.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of preparation method of Prussian blue similar object, which comprises the following steps:
It takes water as a solvent, the potassium ferricyanide and zinc nitrate is subjected to coprecipitation reaction, obtain reaction solution；
The reaction solution is stood, sediment is obtained；And
By the drying precipitate, obtaining chemical formula is K2Zn3[Fe(CN)6]2Prussian blue similar object.
2. the preparation method of Prussian blue similar object according to claim 1, which is characterized in that the potassium ferricyanide and institute
The molar ratio for stating zinc nitrate is 1: 1~1: 2.
3. the preparation method of Prussian blue similar object according to claim 1, which is characterized in that it is described to take water as a solvent,
The step of carrying out coprecipitation reaction, obtain reaction solution the potassium ferricyanide and zinc nitrate include:
The potassium ferricyanide and zinc nitrate difference is soluble in water, obtain potassium ferricyanide solution and zinc nitrate solution；
Under continuous agitation, the potassium ferricyanide solution is added in the zinc nitrate solution；And
Continue to stir 15min~20min, obtains the reaction solution.
4. the preparation method of Prussian blue similar object according to claim 3, which is characterized in that the potassium ferricyanide solution
Concentration be 4mmol/L~8mmol/L, the concentration of the zinc nitrate solution is 6mmol/L~12mmol/L.
5. the preparation method of Prussian blue similar object according to claim 1, which is characterized in that described by the reaction solution
In the step of standing, time of repose is 20h~for 24 hours.
6. the preparation method of Prussian blue similar object according to claim 1, which is characterized in that described by the sediment
In dry step, drying temperature is 60 DEG C~80 DEG C, and drying time is 20h~for 24 hours.
7. the preparation method of Prussian blue similar object according to claim 1, which is characterized in that the sediment that obtains
It is described by before the step of the drying precipitate after step, further include the steps that washing the sediment.
8. the prussian blue being prepared by the preparation method of the described in any item Prussian blue similar objects of claim 1~7
Like object.
9. a kind of cathode material, which is characterized in that the cathode material includes active material, and the active material includes that right is wanted
Prussian blue similar object described in asking 8.
10. application of the cathode material as claimed in claim 9 in preparation water system sodium-ion battery.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113772644A (en) * | 2020-06-09 | 2021-12-10 | 东莞理工学院 | Bimetallic phosphide and preparation method and application thereof |
| CN114203982A (en) * | 2021-11-01 | 2022-03-18 | 江苏大学 | Preparation method of vanadium-based Prussian blue analogue/carbon nanotube composite material and application of vanadium-based Prussian blue analogue/carbon nanotube composite material to water-based zinc ion battery anode |
| CN114477232A (en) * | 2022-01-24 | 2022-05-13 | 郑州大学 | High-quality K2Zn3[Fe(CN)6]2Preparation of crystals and use thereof |
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2019
- 2019-02-25 CN CN201910137100.1A patent/CN109928409A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113772644A (en) * | 2020-06-09 | 2021-12-10 | 东莞理工学院 | Bimetallic phosphide and preparation method and application thereof |
| CN114203982A (en) * | 2021-11-01 | 2022-03-18 | 江苏大学 | Preparation method of vanadium-based Prussian blue analogue/carbon nanotube composite material and application of vanadium-based Prussian blue analogue/carbon nanotube composite material to water-based zinc ion battery anode |
| CN114477232A (en) * | 2022-01-24 | 2022-05-13 | 郑州大学 | High-quality K2Zn3[Fe(CN)6]2Preparation of crystals and use thereof |
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Inventor after: Li Tiexin Inventor after: Fan Hongbo Inventor after: Qiu Yongfu Inventor after: Jin Jutao Inventor after: Su Dawei Inventor before: Li Tiexin Inventor before: Wu Wenjian Inventor before: Fan Hongbo Inventor before: Qiu Yongfu Inventor before: Jin Jutao Inventor before: Su Dawei Inventor before: Wang Guoxiu |
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Application publication date: 20190625 |