CN105990567B - A kind of preparation method of Prussian blue analogue nano material and its application in sodium-ion battery - Google Patents
A kind of preparation method of Prussian blue analogue nano material and its application in sodium-ion battery Download PDFInfo
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- CN105990567B CN105990567B CN201510067537.4A CN201510067537A CN105990567B CN 105990567 B CN105990567 B CN 105990567B CN 201510067537 A CN201510067537 A CN 201510067537A CN 105990567 B CN105990567 B CN 105990567B
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- prussian blue
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- potassium ferrocyanide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
This application discloses a kind of preparation method of Prussian blue analogue nano material and its applications in sodium-ion battery.The preparation method of such prussian blue nano material prepares Prussian blue analogue nano material using coprecipitation at least using the salt containing metallic element M and potassium ferrocyanide as raw material；The chemical composition of the Prussian blue analogue nano material is MHCNFe, and wherein metallic element M is selected from least one of Ni, Cu, Fe, Co.This method is simple, low in raw material price, is suitble to large-scale industrial production.Prepared Prussian blue analogue nano material, has nano-scale and partial size is relatively uniform, is used as sodium-ion battery negative electrode active material, has very high cyclical stability.
Description
Technical field
This application involves a kind of preparation methods of Prussian blue analogue nano material, Prussian blue analogue nanometer material prepared therefrom
Material and the application as negative electrode active material in sodium-ion battery, belong to sodium-ion battery field.
Background technique
With the aggravation of globalization process, fossil resources imbalance between supply and demand becomes increasingly conspicuous, and problem of environmental pollution is on the rise, and seeks
Looking for and develop alternative green energy resource becomes current scientific and technological circle and the problem of industrial circle is paid close attention to jointly.In recent years, lithium-ion electric
Chi Yiqi unique advantage is used widely in the fields such as electric vehicle and hand portable equipment, and is constantly explored and be applied to electricity
The research in the fields such as power driven tools, new energy motor, but due to the finiteness of lithium resource is fundamentally unable to satisfy and uses
Chronicity and cheapness, therefore the exploration and exploitation of the new sustainable chemical energy source used are extremely urgent, sodium source is as lithium source
Congeners, performance is close with lithium, and source is very rich, is one of the selection of most attraction.
Sodium-ion battery key problem in technology is material, and exploitation has the electrode material of de-/embedding ability of high stable, including anode
Material and negative electrode material become the Main way of sodium-ion battery research.At present for Na/S, Na/NiCl2Battery has had
More research simultaneously achieves part commercialization achievement.But due to β-Al2O3Electrolyte could be only presented under the high temperature conditions
Higher ionic conductivity out causes sodium-ion battery to be can be only achieved in higher temperature range (523k~573k) using mark
Standard can not be applied to daily production and living.In recent years, sodium-ion battery under room temperature was widely studied, still
It since sodium ion size is much larger than lithium ion, is not easy to form the embedding sodium compound of reversible high proportion, at present major part carbon material, gold
Belonging to oxide cathode material, there is poorly reversible notable defects.And some alloys be used as sode cell negative electrode material when, sodium from
Volume change caused by son insertion and abjection is more significant, and cyclical stability is poor.
Summary of the invention
According to the one aspect of the application, a kind of preparation method of Prussian blue analogue nano material is provided, this method is simple,
Low in raw material price is suitble to large-scale industrial production.Prepared Prussian blue analogue nano material has nano-scale and grain
Diameter is uniform, is used as sodium-ion battery negative electrode active material, has very high cyclical stability.
The preparation method of the Prussian blue analogue nano material, which is characterized in that in acid condition, at least to contain gold
The salt and potassium ferrocyanide for belonging to element M are raw material, prepare Prussian blue analogue nano material using coprecipitation；
The chemical composition of the Prussian blue analogue nano material is MHCNFe, and wherein metallic element M is selected from Ni, Cu, Fe, Co
At least one of.
Preferably, the acid condition is no more than 3.0 condition for pH value.
Preferably, the metallic element M is selected from Ni and/or Cu.
Preferably, the preparation method of the Prussian blue analogue nano material, which is characterized in that potassium ferrocyanide will be contained
Aqueous solution is added in the solution containing metallic element M, after mixing, stirs 2~10h, gained precipitating is the general Shandong of class
Scholar's indigo plant nano material；The solution containing metallic element M is buffer solution of the pH value 1.0~3.0 containing metallic element M.
Preferably, in the buffer solution containing metallic element M, buffer system is potassium chloride-hydrochloric acid.
Preferably, the concentration of metallic element M is 0.02~10mol/L in the aqueous solution containing metallic element M；It is described
The concentration of potassium ferrocyanide is 0.015~10mol/L in aqueous solution containing potassium ferrocyanide.It is further preferred that described contain
The concentration for having metallic element M in the aqueous solution of metallic element M is 0.2~10mol/L；The aqueous solution containing potassium ferrocyanide
The concentration of middle potassium ferrocyanide is 0.15~10mol/L.
Preferably, the molal quantity Yu the water containing potassium ferrocyanide of the GOLD FROM PLATING SOLUTION category element M containing metallic element M
The mole ratio of potassium ferrocyanide is M: potassium ferrocyanide=1: 0.5~2 in solution.It is further preferred that described contain metal
The molal quantity of the molal quantity of metallic element M and potassium ferrocyanide in the aqueous solution containing potassium ferrocyanide in the aqueous solution of element M
Than for M: potassium ferrocyanide=1: 1~2.It is further preferred that metallic element M in the aqueous solution containing metallic element M
The mole ratio of potassium ferrocyanide is M: potassium ferrocyanide=1: 1 in molal quantity and the aqueous solution containing potassium ferrocyanide.
Preferably, the upper limit of the mixing time range is selected from 10 hours, 8 hours, 6 hours, lower limit be selected from 5 hours, it is 4 small
When, 2 hours.It is further preferred that the mixing time is 5~10 hours.
Preferably, the partial size of the Prussian blue analogue nano material is in 30nm~50nm.
According to the another aspect of the application, a kind of negative electrode active material is provided, which is characterized in that contain any of the above-described method
The Prussian blue analogue nano material being prepared.
According to the another aspect of the application, a kind of sodium-ion battery, including positive plate, negative electrode tab, diaphragm and electrolysis are provided
Liquid, which is characterized in that the negative electrode tab includes above-mentioned negative electrode active material.
Preferably, the electrolyte includes organic solvent and sodium salt；The sodium salt is NaPF6；The organic solvent includes
Ethylene carbonate (being abbreviated as EC) and dimethyl carbonate (being abbreviated as DMC).
Those skilled in the art can select suitable isolation film according to actual needs.Preferably, the isolation film is glass
Tunica fibrosa.
The beneficial effect that the present invention can generate includes at least:
(1) preparation method of Prussian blue analogue nano material provided by the present application, this method is easy to operate, and raw material sources are rich
Richness, it is low in cost, it is suitble to large-scale industrial production.
(2) the Prussian blue analogue nano material obtained according to the application preparation method is used as anode material of lithium-ion battery,
With very high cyclical stability.
Detailed description of the invention
Fig. 1 is sample 6#~9#X-ray diffraction spectrogram.
Fig. 2 is sample 6#Stereoscan photograph.
Fig. 3 is battery C6#Volumetric properties curve.
Specific embodiment
The application is described in detail below by embodiment, but the application is not limited to these embodiments.
D8Advance type X-ray diffractometer of the X-ray powder diffraction material phase analysis (XRD) of sample in Brooker company
Upper progress, Cu target, K α radiation source.
The stereoscan photograph of sample is shot using the S-4800 type scanning electron microscope of Hitachi, Ltd.
The electric property of battery measures on the LAND battery test system of Lan Bo test equipment Co., Ltd, Wuhan City.
1 sample 1 of embodiment#~sample 5#Preparation
Aqueous solution containing potassium ferrocyanide is added in the buffer solution containing metallic element M, after mixing, stirring
For a period of time, it reacts it sufficiently, obtains the flocculent deposit of different colours.After gained precipitation and centrifugal separation, deionized water is used
It washs at least more than three times, to get the Prussian blue analogue nano material after 80 DEG C of vacuum drying.
See Table 1 for details for sample number into spectrum, raw material, preparation condition.
Table 1
2 sample 6 of embodiment#~sample 9#Preparation
Aqueous solution containing potassium ferrocyanide is added in the buffer solution containing metallic element M, after mixing, stirring
For a period of time, it reacts it sufficiently, obtains flocculent deposit.After gained precipitation and centrifugal separation, be washed with deionized three times, in
To get the Prussian blue analogue nano material after 80 DEG C of vacuum drying.
See Table 2 for details for sample number into spectrum, raw material, preparation condition.
Table 2
3 sample 1 of embodiment#~sample 9#XRD characterization
Respectively to sample 1#~sample 9#XRD characterization is carried out, the results show that sample 1#~sample 9#It is that high-purity has
The sample of Prussian blue crystal structure.With sample 6#~9#For Typical Representative, XRD spectra is as shown in Figure 1.Sample 1#~sample
5#XRD spectra and sample 6#Close, i.e., peak position is identical with shape, and according to the variation of synthesis condition, relative peak intensities are ± 10%
Fluctuation in range shows that synthetic product has the feature of Prussian blue crystal structure.
4 sample 1 of embodiment#~sample 9#Scanning electron microscope characterization
Using scanning electron microscope to sample 1#~sample 9#It carries out pattern to be analyzed, as a result consistent with testing graininess result, sample
Product 1#~sample 9#For the nano particle of 30~50nm of partial size, and particle diameter distribution is relatively uniform, and Typical Representative is sample 6#, electricity
Mirror photo is as shown in Figure 1.
5 battery C1 of embodiment#~battery C9#Preparation
Negative electrode tab N1#~N9#Preparation
Respectively with sample 1#~sample 9#As negative electrode active material, negative electrode tab is prepared, the specific steps are as follows:
Negative electrode active material, conductive agent conductive black, bonding agent polyvinylidene fluoride are mixed in N-Methyl pyrrolidone
It closes uniformly, negative electrode slurry is made.In its slurry solids ingredient comprising 70% negative electrode active material, 20% conductive black,
10% polyvinylidene fluoride.Negative electrode slurry is uniformly coated on the negative current collector copper foil with a thickness of 20 μm, is then existed
It is sliced after being dried at 85 DEG C, tabletting, weighing is to get negative electrode tab.Respectively with sample 1#~sample 9#As negative electrode active material
Material, the negative electrode tab being prepared are denoted as N1 respectively#~N9#。
The preparation of electrolyte
By the ratio of ethylene carbonate (being abbreviated as EC), dimethyl carbonate (being abbreviated as DMC) in mass ratio EC: DMC=1: 1
It is uniformly mixed, obtains non-aqueous organic solvent.NaPF is added into non-aqueous organic solvent6, obtain NaPF6Concentration is the molten of 1mol/L
Liquid, as electrolyte.
Sodium ion secondary battery C1#~C9#Preparation
Using glass fibre membrane as diaphragm.
Using metallic sodium as positive plate, half-cell is assembled.
Respectively with N1#~N9#As the sodium-ion battery that negative electrode tab is prepared, it is denoted as battery C1 respectively#~battery C9#。
6 battery C1 of embodiment#~battery C9#Specific capacity test
Respectively to the battery C1 prepared in embodiment 5#~battery C9#Specific capacity tested, method particularly includes:
At 25 DEG C, 0.01V is discharged to according to certain discharge current；After electric discharge, battery standing 5 minutes；Then
With certain current density constant-current charge to 3V, after charging, battery standing is put after five minutes with identical current density constant current
Electricity is to 0.01V；Battery stands 5 minutes after completely filling, then with the charging of identical condition.
Battery C1#~battery C5#In 50mA/g charging and discharging currents density, the specific capacity of the voltage range of 0.01-3V such as table 3
It is shown.Battery C6#~battery C9#Test result and battery C1#~battery C5#It is similar, wherein battery C6#Specific capacity with following
The variation of ring number is as shown in Figure 3.The Prussian blue structure nano material is as sodium-ion battery it can be seen from table 3 and Fig. 3
Cycle charge-discharge specific capacity is kept preferably when negative electrode material, stable cycle performance.
Table 3
The announcement of book according to the above description, the application those skilled in the art can also carry out above embodiment
Change and modification appropriate.Therefore, the application is not limited to specific embodiment disclosed and described above, to the application's
Some modifications and changes should also be as falling into the protection scope of claims hereof.
Claims (7)
1. a kind of preparation method of Prussian blue analogue nano material, which is characterized in that in acid condition, at least to contain metal
The salt and potassium ferrocyanide of element M are raw material, prepare Prussian blue analogue nano material using coprecipitation；
The chemical composition of the Prussian blue analogue nano material is MHCNFe, and wherein metallic element M is Ni；
Aqueous solution containing potassium ferrocyanide is added in the solution containing metallic element M, after mixing, stirring 2~10 is small
When, gained precipitating is the Prussian blue analogue nano material；
The solution containing metallic element M is the buffer solution containing metallic element M of pH value 1.0~3.0；
The partial size of the Prussian blue analogue nano material is 30~50nm；
In the buffer solution containing metallic element M, buffer system is potassium chloride-hydrochloric acid.
2. preparation method according to claim 1, which is characterized in that the GOLD FROM PLATING SOLUTION containing metallic element M belongs to member
The concentration of plain M is 0.02~10mol/L；The concentration of potassium ferrocyanide is 0.015 in the aqueous solution containing potassium ferrocyanide
~10mol/L.
3. preparation method according to claim 1, which is characterized in that the GOLD FROM PLATING SOLUTION containing metallic element M belongs to member
The concentration of plain M is 0.2~10mol/L；In the aqueous solution containing potassium ferrocyanide the concentration of potassium ferrocyanide be 0.15~
10mol/L。
4. preparation method according to claim 1, which is characterized in that the GOLD FROM PLATING SOLUTION containing metallic element M belongs to member
The mole ratio of potassium ferrocyanide is M: potassium ferrocyanide=1 in the molal quantity and the aqueous solution containing potassium ferrocyanide of plain M:
0.5~2.
5. a kind of negative electrode active material, which is characterized in that the class being prepared containing any one of Claims 1-4 the method
Prussian blue nano material.
6. a kind of sodium-ion battery, including positive plate, negative electrode tab, isolation film and electrolyte, which is characterized in that in the negative electrode tab
Include the negative electrode active material described in claim 5.
7. sodium-ion battery according to claim 6, which is characterized in that the electrolyte includes organic solvent and sodium salt；
The sodium salt is NaPF6；The organic solvent includes ethylene carbonate and dimethyl carbonate.
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| CN106898744A (en) * | 2017-03-10 | 2017-06-27 | 华南师范大学 | The preparation method and application of prussian blue nanoporous frame material |
| CN106920922A (en) * | 2017-04-11 | 2017-07-04 | 西南大学 | The preparation method of the positive electrodes of KTiFe (CN) 6 |
| CN109088068B (en) * | 2017-06-13 | 2020-05-19 | 宁德时代新能源科技股份有限公司 | Sodium ion battery |
| CN107364875A (en) * | 2017-06-22 | 2017-11-21 | 全球能源互联网研究院 | A kind of method and sodium-ion battery for preparing Prussian blue positive electrode |
| CN107364874A (en) * | 2017-06-22 | 2017-11-21 | 全球能源互联网研究院 | A kind of Prussian blue method for preparing anode material and sodium-ion battery |
| CN109728292B (en) * | 2017-10-30 | 2021-02-23 | 宁德时代新能源科技股份有限公司 | Prussian blue type positive electrode material for sodium ion battery, preparation method of Prussian blue type positive electrode material and sodium ion battery |
| CN109728296B (en) * | 2017-10-30 | 2020-09-11 | 宁德时代新能源科技股份有限公司 | Prussian blue positive electrode material, preparation method thereof and electrochemical energy storage device |
| CN109841832B (en) * | 2017-11-29 | 2021-05-04 | 宁德时代新能源科技股份有限公司 | Positive plate and electrochemical cell |
| CN108091875B (en) * | 2017-12-29 | 2020-05-08 | 暨南大学 | Prussian blue derived iron-cobalt-nickel sulfide and preparation method and application thereof |
| CN109279626B (en) * | 2018-09-20 | 2022-01-28 | 合肥师范学院 | Nano-sheet potassium ion battery positive electrode material, preparation method thereof and potassium ion battery |
| CN109437338B (en) * | 2018-11-30 | 2021-03-02 | 福州大学 | Preparation method of sawtooth-like nickel-cobalt-iron Prussian blue sintered oxide nano material |
| CN111600011A (en) * | 2020-04-24 | 2020-08-28 | 国网浙江省电力有限公司电力科学研究院 | Doped prussian blue material and preparation method and application thereof |
| CN112194178B (en) * | 2020-10-20 | 2021-06-01 | 福州大学 | Titanium dioxide and Prussian blue ordered assembly state mesomorphic nano material and preparation method thereof |
| CN114414514B (en) * | 2022-01-20 | 2023-12-22 | 中山大学 | Preparation method of manganese Prussian blue nano enzyme and application of manganese Prussian blue nano enzyme in alcohol concentration detection |
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