CN106745068A - A kind of preparation method and applications of the nanometer Prussian Blue of low defect - Google Patents
A kind of preparation method and applications of the nanometer Prussian Blue of low defect Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of the nanometer Prussian Blue of low defect, it is characterised in that comprise the following steps：Solution A is prepared using ferrous oxalate, sodium oxalate, B solution is prepared using sodium ferrocyanide；To surfactant, and ultrasonic agitation is added in B solution, C solution is designated as；By solution A ultrasonic agitation；C solution is added in the solution A after ultrasonic agitation, constant temperature stirring obtains blue precipitate；Blue precipitate is washed, after having washed, in 1 DEG C to 130 DEG C dried in vacuum overnight, is finally given Prussian blue.A kind of Prussian blue application as sodium-ion battery positive electrode material.The beneficial effects of the invention are as follows：Effectively reduce it is Prussian blue in the prior art in defect, and good cycling stability, after the current densities of 300mAhg 1 circulate 500 times, capacity is respectively 106mAhg 1 and 98mAhg 1, and capacity sustainment rate is high.
Description
Technical field
It is low the present invention relates to Coordinative Chemistry and sodium ion battery electrode material manufacturing technology crossing domain, more particularly to one kind
The preparation method and applications of the nanometer Prussian Blue of defect.
Background technology
21st century is the new energy epoch, and old fossil energy includes the increasingly depleted of oil, colliery and natural gas,
Problem of environmental pollution increasingly sharpens, and social concern is on the rise caused by lack of energy and environmental pollution, in current global range
Regional conflict and war major part all have the relation of countless ties with the energy.How energy crisis is solved, be human society
The important problem being faced with.The large-scale use of clean reproducible energy (water energy, wind energy, solar energy and tide energy) is to solve
The key point of energy crisis, wind energy and solar energy are with low cost, widely distributed, can be promoted in the whole world.But due to
Wind energy and solar energy have intermittent and periodic feature, and the electric energy that they are converted is connected to the grid, and power network can be caused very
Big load.Therefore, it is situated between in wind-powered electricity generation power plant, the energy storage that addition one is used for buffering between solar power plant and intelligent grid
Matter, is a very crucial problem, and this energy-accumulating medium will play a part of peak load shifting, and wind energy and solar energy are converted
A large amount of electrical power storages are got up, and are then sustained in intelligent grid when electric power is not enough, and this energy-accumulating medium is exactly green two
Primary cell.And future ideality energy storage pattern be use fusion of hydrogen nuclear energy, solar energy, wind energy, water-energy generating electricity, then by intelligence
Power network is by electrical power storage and be transported to life, production energy demand are supplied in city；Meanwhile, novel electric vehicle progressively takes
For orthodox car, electric automobile be also required to higher energy density, more power density novel energy-storing medium it is farther to realize
Distance travelled and by performance.These all explore new green secondary cell in the families that constantly advance science.
Now, green secondary cell of greatest concern is lithium ion battery, sodium-ion battery.The electronic vapour of lithium ion battery
The aspects such as car, portable power source and electronic product have obtained application widely, however in global range lithium resource reserves
It is limited, according to statistics, the reserves of global lithium are about 58M tons (with lithium carbonate as calculating basis), at present annual consumption carbonic acid
Ten thousand tons of lithium 7-8 so that the price of lithium carbonate rises year by year, this seriously constrains lithium ion battery answering in terms of extensive energy storage
With.In China, the skewness of lithium resource is mainly distributed on the high altitude localities such as Qinghai Lake and Lop Nur or western part remotely
Area, and where the lithium battery manufacturer of the country such as Xin Wangda, Ningde new energy (ATL), Hefei state pavilion and BYD etc.
Place is very remote apart from lithium resource original producton location distance, and go at present without suitable lithium resource reclaim mechanism, therefore, soon
In the future, lithium resource can face and petroleum gas identical shortage scene.Therefore, a kind of element that can replace lithium is found, is compeled
In the eyebrows and eyelashes.Sodium element has the physicochemical property similar to lithium, meanwhile, sodium element reserves enrich very much, and the quality in the earth's crust is rich
Spend is 2.64% so that the cost of sodium carbonate only less than 1/10th of lithium carbonate cost, therefore, sodium-ion battery is more applicable
In extensive energy storage and the energy demand in future.
At present, the positive electrode of sodium-ion battery is generally stratified material, has (XO4) n- of three-dimensional framework how cloudy containing sodium
Ionic material, and negative pole uses hard carbon material.Hard carbon material at present can be with commercially available, and stable performance, therefore,
Determine that the capacity of sodium-ion battery, voltage it is critical only that positive electrode.Synthesis performance stabilization, electric industry platform positive electrode high
It is currently the study hotspot of scientific circles.Prussian blue and the like the class hot research material for being, its molecular formula is Na2-
XM ' [M " (CN) 6] 1-y yzH2O, for Prussian blue, two M atoms in molecular formula are all Fe, wherein, 0<x<2,
0<y<Fe (CN) 6 in 1, representative structure is vacant, and is occupied by water of coordination molecule..Match somebody with somebody caused by these omissions of Fe (CN) 6
Position hydrone can have a strong impact on Prussian blue electrochemistry storage sodium behavior, 4 points below of specific manifestation：1st, the omissions of Fe (CN) 6 subtract
Lack redox active centre, while reducing the Na contents in lattice, cause theoretical storage sodium capacity to diminish；2nd, Fe (CN) 6 lacks
Position can cause the water content in lattice to raise, and water of coordination molecule is difficult away, be oxidized under high potential and decomposed, and cause battery
The reduction of first week efficiency and cycle efficieny；3rd, lattice hydrone occupies the embedded site of part Na+, blocks Na+ insertion abjections
Path, so that available capacity is reduced；4th, the omissions of Fe (CN) 6 destroy the integrity degree of lattice, and Na+ easily makes in embedded abjection
Into chemical bond rupture, lattice distortion even structure collapses, so as to the capacity deep fades during long circulating can be caused, make Pu Lu
Scholar's blue material is unfavorable for large-scale application.Therefore, the Prussian blue of low defect is prepared to have great importance.
The content of the invention
The technical problems to be solved by the invention be to provide a kind of nanometer Prussian Blue of low defect preparation method and its
Using to overcome above-mentioned deficiency of the prior art.
The technical scheme that the present invention solves above-mentioned technical problem is as follows：A kind of preparation side of the nanometer Prussian Blue of low defect
Method, comprises the following steps：
Step one, according to ferrous oxalate：Sodium oxalate：The mol ratio of sodium ferrocyanide is (0.5-1)：(0-1)：(1-2's)
Amount, ferrous oxalate and sodium oxalate are added in the A beakers of 0.1ml to 100ml deionized waters to being loaded with, and to being loaded with
Sodium ferrocyanide is added in the B beakers of 0.1ml to 100ml deionized waters, resulting solution correspondence is designated as solution A and B is molten
Liquid；
Step 2, to surfactant, and ultrasonic agitation is added in B solution, be designated as C solution, it is standby；
Step 3, by solution A ultrasonic agitation, it is standby；
In step 4, the solution A being added to C solution after ultrasonic agitation, 24h to 96h is stirred in 20 DEG C to 30 DEG C, obtained
Blue precipitate；
Step 5, the blue precipitate that will be obtained in step 4 are washed with deionized at least three times, washed with methyl alcohol to
Less once, after having washed, in 1 DEG C to 130 DEG C dried in vacuum overnight, finally give Prussian blue.
The beneficial effects of the invention are as follows：By using oxalate and ferrous ion ferrous cyanogen root and Asia are less than with bit constant
Iron ion, is reacted using ferrous oxalate as source of iron and sodium ferrocyanide, the iron atom allowed in ferrous oxalate slowly release and and
Ferrous cyanogen root coordination, while the speed of growth by controlling Prussian blue monocrystalline, the mesh of Prussian blue middle defect is reduced to reach
, and good cycling stability, additionally, the Prussian blue chi for finally giving can be adjusted by regulating and controlling the addition of sodium oxalate
Very little, easy to operate, the present invention is also equipped with that raw material is cheap and easy to get, and synthesis technique is simple and convenient, tests favorable reproducibility.
On the basis of above-mentioned technical proposal, the present invention can also do following improvement.
Further, in the step one, ferrous oxalate：Sodium oxalate：The mol ratio of sodium ferrocyanide is 1：0：2.
Further, in the step one, ferrous oxalate：Sodium oxalate：The mol ratio of sodium ferrocyanide is 1：1：2.
Further, in the step 2, surfactant is F127.
Further, in the step 2, when ultrasonic agitation is carried out, it is necessary to the C solution that will be obtained is stirred to clear liquid.
Further, in the step 3, when ultrasonic agitation is carried out, it is necessary to solution A is stirred to clear liquid.
Further, in the step 4, whipping temp is 22 DEG C to 28 DEG C, and mixing time is 48h to 80h.
Further, it is with 5000rp/min when being washed with deionized and being washed with methyl alcohol in the step 5
Speed carries out centrifuge washing.
Further, in the step 5, after having washed, in 100 DEG C to 125 DEG C dried in vacuum overnight.
A kind of Prussian blue application as sodium-ion battery positive electrode material.
The beneficial effects of the invention are as follows：After 300mAhg-1 current densities circulate 500 times, capacity is respectively 106mAhg-1
And 98mAhg-1, capacity sustainment rate is higher.
Brief description of the drawings
Fig. 1 is Fe-HCF-NC1Stereoscan photograph；
Fig. 2 is Fe-HCF-NC2Stereoscan photograph；
Fig. 3 is Fe-HCF-NC1Transmission electron microscope photo；
Fig. 4 is Fe-HCF-NC2Transmission electron microscope photo；
Fig. 5 is Prussian blue prepared by example to be fabricated to after button cell the long circulating performance under constant current 300mAhg-1
Figure.
Specific embodiment
Principle of the invention and feature are described below in conjunction with accompanying drawing, example is served only for explaining the present invention, and
It is non-for limiting the scope of the present invention.
Embodiment one：As shown in Figure 1, Figure 3, a kind of preparation method of the nanometer Prussian Blue of low defect, including following step
Suddenly：
S01,0.18g ferrous oxalates and 0.968g sodium ferrocyanides are weighed, be dissolved in be loaded with 100ml deionized waters respectively
A beakers, it is loaded with the B beakers of 100ml deionized waters, correspondence is designated as solution A and B solution；
S02, to adding 100mgF127 in B solution, and ultrasonic agitation to solution becomes clear liquid, is designated as C solution, standby；
S03, by solution A ultrasonic agitation to solution become clear liquid, it is standby；
In S04, the solution A being added to C solution after ultrasonic agitation, in stirring 24h under 20 DEG C to 30 DEG C of steady temperature
To 96h, wherein, concretely 20 DEG C of steady temperature, 22 DEG C, 22.4 DEG C, 24.8 DEG C, 25.7 DEG C, 27.2 DEG C, 28 DEG C, 30 DEG C is
Ensure iron atom in ferrous oxalate slowly release and and ferrous cyanogen root coordination and conveniently regulating and controlling, by testing repeatedly
Go out, steady temperature optimal value be 24.8 DEG C, mixing time can for 24h, 48h, 52.6h, 57.9h, 60.7h, 72.1h, 74.8h,
78.2h, 80h, 96h, but according to optimal steady temperature, drawn under this steady temperature by testing repeatedly, mixing time
Optimal is 72.1h, and now, the iron atom in ferrous oxalate with ferrous cyanogen root coordination most efficiently, obtains light blue sediment；
S05, the light blue sediment that will be obtained in S04 are washed with deionized three times, be washed once with methyl alcohol, have washed
Afterwards, in 1 DEG C to 130 DEG C dried in vacuum overnight, wherein, temperature under vacuum can for 1 DEG C, 100 DEG C, 107 DEG C, 114.1 DEG C,
117.6 DEG C, 120.4 DEG C, 123.7 DEG C, 125 DEG C, 130 DEG C, but during according to optimal steady temperature and optimal stirring
Between, Optimal Temperature corresponding under vacuo is drawn for 120.4 DEG C by testing repeatedly, additionally, the overnight institute in being dried overnight
The corresponding time be 5h to 12h, finally give it is Prussian blue, its chemical formula be Fe-HCF-NC1。
The chemical formula of ferrous oxalate is FeC2O4, sodium ferrocyanide chemical formula be Na4Fe(CN)6·10H2O, is scanned through
Electron microscope and transmitted electron observation find Fe-HCF-NC1Size in 200nm or so.
Embodiment two：As shown in Figure 2, Figure 4 shows, a kind of preparation method of the nanometer Prussian Blue of low defect, including following step
Suddenly：
S01,0.18g ferrous oxalates and 0.13g sodium oxalates are weighed, be dissolved in the A beakers for being loaded with 100ml deionized waters, claimed
0.968g sodium ferrocyanides are taken, is dissolved in the B beakers for being loaded with 100ml deionized waters, resulting solution correspondence is designated as solution A
And B solution；
S02, to adding 100mgF127 in B solution, and ultrasonic agitation to solution becomes clear liquid, is designated as C solution, standby；
S03, by solution A ultrasonic agitation to solution become clear liquid, it is standby；
In S04, solution A C solution being added to after ultrasonic agitation, 72h is stirred in 25 DEG C, wherein, steady temperature is specific
It can be 20 DEG C, 22 DEG C, 22.4 DEG C, 24.8 DEG C, 25.7 DEG C, 27.2 DEG C, 28 DEG C, 30 DEG C, in order to ensure the iron in ferrous oxalate is former
Sub slowly release is simultaneously coordinated and conveniently regulating and controlling with ferrous cyanogen root, is drawn by testing repeatedly, and steady temperature optimal value is 24.8
DEG C, mixing time can be 24h, 48h, 52.6h, 57.9h, 70.7h, 72.1h, 74.8h, 78.2h, 80h, 96h, but according to most
Excellent steady temperature, and sodium oxalate addition, drawn under this steady temperature by testing repeatedly, mixing time is optimal to be
70.7h, now, the iron atom in ferrous oxalate with ferrous cyanogen root coordination most efficiently, obtains dark blue precipitate thing；
S05, the dark blue precipitate thing that will be obtained in S04 are washed with deionized three times, be washed once with methyl alcohol, have washed
Afterwards, in 120 DEG C of dried in vacuum overnight, wherein, temperature under vacuum can for 1 DEG C, 100 DEG C, 107 DEG C, 114.1 DEG C, 117.6 DEG C,
120.4 DEG C, 123.7 DEG C, 125 DEG C, 130 DEG C, but according to optimal steady temperature and optimal mixing time, by anti-
Multiple experiment draws Optimal Temperature corresponding under vacuo for 120.4 DEG C, additionally, the overnight corresponding time in being dried overnight
Be 5h to 12h, finally give it is Prussian blue, its chemical formula be Fe-HCF-NC2。
The chemical formula of sodium oxalate is Na2C2O4.It is scanned through electron microscope and transmitted electron observation finds Fe-HCF-NC2
Size in 500nm or so.
The temperature during stirring capacity after 300mAhg-1 current densities circulate 500 times Prussian blue to final gained
Influence, by testing repeatedly, draws following data, as shown in table 1：
Table 1
| Temperature/DEG C | 10 | 20 | 22 | 22.4 | 24.8 | 25.7 | 27.2 | 28 | 30 | 40 |
| Fe-HCF-NC1 | 78 | 86 | 94 | 99 | 106 | 104 | 98 | 92 | 83 | 60 |
| Fe-HCF-NC2 | 73 | 78 | 84 | 93 | 98 | 89 | 84 | 77 | 70 | 61 |
When the temperature in stirring is 24.8 DEG C as shown in Table 1, prepared is Prussian blue in 300mAhg-1 current densities
Circulate the capacity highest after 500 times.
Application examples：
The Prussian blue method for preparing electrode slice prepared using embodiment one or embodiment two：
S100, by prepare it is Prussian blue mix with conductive agent Super-P, according to quality 70mgVs20mg, use agate
Both materials are fully ground half an hour by mortar, and the powder that will be bonded on wall every 5 minutes is scraped off and re-grind；
S110, first in mortar add 1ml isopropanols, then again in mortar be added dropwise 10mgPTFE (inclined polytetrafluoroethyl-nes
Alkene), the mixture in mortar is fully ground to drying；
S120, resulting black solid is rolled into a ball into bead after, be ground into the thick films of about 0.03mm with roll squeezer；
S130, by resulting film in 120 DEG C of vacuum drying chambers dry 12 hours；
S140, square (electrode tablet quality about 1.5mg) that dried diaphragm is cut into about 0.8cm*0.8cm；
S150, the diaphragm that will be cut out are positioned over the aluminium net top of diameter 1.2cm, with two pieces of stainless steel moulds by diaphragm and aluminium
Network folder is placed in tablet press machine after living, and is suppressed 30 seconds under the conditions of 15Mp, that is, obtain Prussian blue material electrodes piece.
The assembling of sodium-ion battery is again that, to electrode, electrolyte is 1mol/LNaClO with metallic sodium piece4EC (ethyl carbon
Acid esters)+DEC (divinyl carbonate)+FEC (fluorinated ethylene carbonate) (volume ratio 1:1：0.05) solution, barrier film is glass fibers
Dimension film, is assembled into button cell (water oxygen content is below 1ppm) in the glove box full of argon gas atmosphere, and in constant current
Performance test is circulated under conditions of 150mAhg-1.
As shown in figure 5, by the Prussian blue electrode slice good cycle obtained by electro-chemical test, in 300mAhg-1
After current density circulates 500 times, capacity is respectively 106mAhg-1 and 98mAhg-1, and capacity sustainment rate is higher, in Fig. 5, is located at
The curve of top is Fe-HCF-NC1The long circulating performance curve under constant current 300mAhg-1 is fabricated to after button cell, is located at
The curve of lower section is Fe-HCF-NC2Long circulating performance curve under constant current 300mAhg-1 is fabricated to after button cell.
Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment is example
Property, it is impossible to limitation of the present invention is interpreted as, one of ordinary skill in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, changes, replacing and modification.
Claims (10)
1. a kind of preparation method of the nanometer Prussian Blue of low defect, it is characterised in that comprise the following steps：
Step one, according to ferrous oxalate：Sodium oxalate：The mol ratio of sodium ferrocyanide is (0.5-1)：(0-1)：The amount of (1-2), to
It is loaded with and ferrous oxalate and sodium oxalate is added in the A beakers of 0.1ml to 100ml deionized waters, and to being loaded with 0.1ml extremely
Sodium ferrocyanide is added in the B beakers of 100ml deionized waters, resulting solution correspondence is designated as solution A and B solution；
Step 2, to surfactant, and ultrasonic agitation is added in B solution, be designated as C solution, it is standby；
Step 3, by solution A ultrasonic agitation, it is standby；
In step 4, the solution A being added to C solution after ultrasonic agitation, 24h to 96h is stirred in 20 DEG C to 30 DEG C, obtain blueness
Sediment；
Step 5, the blue precipitate that will be obtained in step 4 are washed with deionized at least three times, and at least one is washed with methyl alcohol
It is secondary, after having washed, in 1 DEG C to 130 DEG C dried in vacuum overnight, finally give Prussian blue.
2. a kind of preparation method of the nanometer Prussian Blue of low defect according to claim 1, it is characterised in that the step
In rapid one, ferrous oxalate：Sodium oxalate：The mol ratio of sodium ferrocyanide is 1：0：2.
3. a kind of preparation method of the nanometer Prussian Blue of low defect according to claim 1, it is characterised in that the step
In rapid one, ferrous oxalate：Sodium oxalate：The mol ratio of sodium ferrocyanide is 1：1：2.
4. a kind of preparation method of the nanometer Prussian Blue of low defect according to claim 1, it is characterised in that the step
In rapid two, surfactant is F127.
5. a kind of preparation method of the nanometer Prussian Blue of low defect according to claim 1, it is characterised in that the step
In rapid two, when ultrasonic agitation is carried out, it is necessary to the C solution that will be obtained is stirred to clear liquid.
6. a kind of preparation method of the nanometer Prussian Blue of low defect according to claim 1, it is characterised in that the step
In rapid three, when ultrasonic agitation is carried out, it is necessary to solution A is stirred to clear liquid.
7. a kind of preparation method of the nanometer Prussian Blue of low defect according to claim 1, it is characterised in that the step
In rapid four, whipping temp is 22 DEG C to 28 DEG C, and mixing time is 48h to 80h.
8. a kind of preparation method of the nanometer Prussian Blue of low defect according to claim 1, it is characterised in that the step
It is that centrifuge washing is carried out with the speed of 5000rp/min when being washed with deionized and being washed with methyl alcohol in rapid five.
9. a kind of preparation method of the nanometer Prussian Blue of low defect according to claim 1, it is characterised in that the step
In rapid five, after having washed, in 100 DEG C to 125 DEG C dried in vacuum overnight.
10. a kind of according to any Prussian blue application as sodium-ion battery positive electrode material of claim 1 to 9.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107673371A (en) * | 2017-09-06 | 2018-02-09 | 华中科技大学 | Pyrophosphate aids in the preparation method of the Prussian blue similar thing of synthesized high-performance |
| CN108054443A (en) * | 2017-12-15 | 2018-05-18 | 南京理工大学 | Water system sodium ion secondary battery |
| CN109088068A (en) * | 2017-06-13 | 2018-12-25 | 宁德时代新能源科技股份有限公司 | sodium ion battery |
| CN110002466A (en) * | 2019-04-28 | 2019-07-12 | 电子科技大学 | Ferrous cyanogen manganese potassium prussian blue cubic crystal of low water low defect and preparation method thereof |
| CN114956121A (en) * | 2022-06-20 | 2022-08-30 | 郑州轻工业大学 | High-crystallization Prussian blue analogue material and preparation method and application thereof |
| WO2023071352A1 (en) * | 2021-10-26 | 2023-05-04 | 广东邦普循环科技有限公司 | Preparation method for prussian blue sodium-ion battery positive electrode material |
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