CN109867308A - A kind of K2Fe3(SO4)3(OH)2Compound and its preparation and application - Google Patents
A kind of K2Fe3(SO4)3(OH)2Compound and its preparation and application Download PDFInfo
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Abstract
The present invention relates to K2Fe3(SO4)3(OH)2Compound and its preparation and application can prepare K using hydro-thermal method2Fe3(SO4)3(OH)2Compound and K2Fe3(SO4)3(OH)2/ C sodium-ion battery positive material；With preferable sodium-ion battery charge-discharge performance, cyclical stability is good, and operating voltage is suitable, can be used as sodium-ion battery positive material.
Description
Technical field
It is K the present invention relates to chemical formula2Fe3(SO4)3(OH)2Compound, sodium-ion battery positive material, this material
Preparation method and using the material make sodium-ion battery.
Background technique
It is increasingly serious with energy problem, non-renewable resources increasingly deficient and people recognize environmentally friendly importance
The continuous enhancing known, demand of the society to new energy is increasingly enhanced, and energy storage plays more and more important work in energy system
With.Before, the lithium ion battery as energy storage device important in new energy has attracted numerous resourcess for research, it is contemplated that lithium exists
Tellurian reserves are less and its higher price, recently the research weight of the K ion battery more abundant, more cheap to reserves
The attention of researcher is newly obtained.
Mainly there is K applied to the positive electrode of sodium-ion battery at present3Fe2(PO4)3、KFePO4F、K3Fe2(PO4)2F3With
KTiFeO3、KCoO3And KMnO3Deng.However, these materials still have many problems: specific capacity and operating voltage are lower, circulation
Stability difference and preparation difficulty etc., this severely limits the practical applications of these materials.Compared to phosphate, borate and silicic acid
Salt, sulfate have higher specific capacity and specific energy due to lower molal weight.Sulfate have narrower band gap and
Higher electronic conductivity.In addition, SO4Group also has inductive effect, and the operating voltage of positive electrode can be improved.And it is current
Research about sulfate sodium-ion battery positive material is also seldom, is worth further investigation.
Summary of the invention
It is an object of that present invention to provide a kind of K2Fe3(SO4)3(OH)2Compound and preparation method；
Another object of the present invention is to provide a kind of K2Fe3(SO4)3(OH)2/ C sodium-ion battery positive material
Still a further object of the present invention is to provide a kind of K2Fe3(SO4)3(OH)2The preparation side of/C sodium-ion battery positive material
Method；
Technical scheme is as follows:
K provided by the invention2Fe3(SO4)3(OH)2Compound.
K provided by the invention2Fe3(SO4)3(OH)2The preparation method of compound, preparation step are as follows: will contain K chemical combination
Object, compound containing Fe and compound containing S in molar ratio K:Fe:S=2:3:3 ratio after mixing, carry out chemical synthesis it is anti-
It answers, K is made2Fe3(SO4)3(OH)2Compound；
The compound containing K is the oxide of K, the carbonate of K, the nitrate of R or the oxalates of K；
The compound containing Fe is oxide, the sulfate of Fe and the oxalates of Fe of Fe；
The compound containing S is H2SO4、(NH4)2SO4Or FeSO4。
The K2Fe3(SO4)3(OH)2Compound is used as sodium-ion battery positive electrode active materials, sodium-ion battery anode
Material is K2Fe3(SO4)3(OH)2/ C-material, C mass content are 5-50%.
KFE provided by the invention2SO5The preparation method of/C sodium-ion battery positive material prepares K using hydro-thermal method2Fe3
(SO4)3(OH)2/ C sodium-ion battery positive material, its step are as follows:
1) ingredient: will contain K compound, compound containing Fe and compound containing S by K:Fe:S: oxalic acid is (1-3): 3:(1-3)
Molar ratio be added deionized water in stirring to formed solution, be added K2Fe3(SO4)3(OH)2The conductive carbon of quality 5%-50%
Super P, acetylene black, Kuraray, Ketjen black, carbon nanotube, graphene etc.) continue to be stirred until homogeneous suspension；
2) suspension is moved in the reaction kettle with polytetrafluoroethyllining lining of 100ml；
3) control parameters carry out materials synthesis: during the reaction kettle for filling above-mentioned ingredient is placed in convection oven；With
1-5 DEG C of rate rises to 150-250 DEG C；Heat preservation 10-40 hours；After reacting sufficiently, room temperature is down to the rate of 1-50 DEG C/h,
Obtain K2Fe3(SO4)3(OH)2/ C-material；
The compound containing K is in the oxide of K, the carbonate of K, the sulfate of K, the nitrate of K or the oxalates of K
It is one or two or more kinds of；
The compound containing Fe is one of oxalates of the oxide of Fe, the sulfate of Fe and Fe or two kinds or more；
The compound containing S is H3SO3、(NH4)2SO4And FeSO4One of or two kinds or more.
It is that K typically can be obtained below2Fe3(SO4)3(OH)2The chemical reaction of compound:
2KOH+3FeSO4=K2Fe3(SO4)3(OH)2
The present invention has the advantages that obtained positive electrode specific capacity with higher and operating voltage, preferable circulation is steady
It is qualitative.K2Fe3(SO4)3(OH)2/ C sodium-ion battery positive material specific capacity with higher reaches 125mAh/g；Its work electricity
It is pressed between 2-4.2V, specific capacity is still able to maintain 95% or more after 100 circulations.
Detailed description of the invention
Fig. 1 is K of the present invention2Fe3(SO4)3(OH)2The SEM picture of/C sodium-ion battery positive material.
Fig. 2 is K of the present invention2Fe3(SO4)3(OH)2The polycrystal powder X ray diffracting spectrum of/C.
Fig. 3 is K of the present invention2Fe3(SO4)3(OH)2Crystal structure figure.
Fig. 4 is K of the present invention2Fe3(SO4)3(OH)2/ C positive electrode material 0.2C multiplying power, 3-4.3V range charging and discharging curve.
Fig. 5 is K of the present invention2Fe3(SO4)3(OH)2The stable circulation linearity curve of/C positive electrode material in 0.2C.
Specific embodiment
Embodiment 1K2Fe3(SO4)3(OH)2It is prepared by the hydro-thermal of compound
The KOH of 0.02mol is dissolved in the beaker equipped with 50ml deionized water, the FeSO of 0.01mol is then added4,
In 70-80 DEG C of water bath with thermostatic control then the K of 0.02mol is added to being in green solution in stirring2SO4It is molten to continue stirring formation green
Liquid.The solution is placed in the reaction kettle with polytetrafluoroethyllining lining, reaction kettle is put into convection oven.With 1-10 DEG C/
Stove is risen to 200 DEG C by the heating rate of min, is kept the temperature 24 hours, is finally down to room temperature with the speed of 1-10 DEG C/min.It will reaction
Product filtering cleaning obtains K2Fe3(SO4)3(OH)2Compound.
By 1 gained composite material of embodiment, the mass ratio according to both active material, conductive black, binder is 8:1:1
It is dissolved in appropriate N-Methyl pyrrolidone and being uniformly mixed, be coated into the electrode film with a thickness of 0.15mm, vacuum with wet film maker
It is cut into the electrode slice that diameter is 12mm with slicer after drying, weighs and calculate the quality of active material.Simultaneously using Na piece as
Anode, using Celgard 2500 as diaphragm, the NaPF of 1mol/L6EC+DMC (volume ratio 1:1) solution be electrolyte,
Button cell is dressed up in the glove box full of argon gas.Then the battery of assembly is subjected to electro-chemical test, respectively in 2-4.3V
It is tested under constant current conditions.Test result is as shown in Figures 4 and 5, it can be seen that K2Fe3(SO4)3(OH)2Electric discharge specific volume with higher
Amount reaches 125mAh/g, and has good high rate performance and cycle performance, and 100 circulation volumes keep 80% or more.
Comparative example 1: Na is used0.4MnO2It is applied in sodium-ion battery as positive electrode active materials, battery other conditions are equal
Same Examples 1 and 2.Test result shows that its specific capacity only has 80mAhg-1, while its capacity just decays to after 50 circulations
50mAhg-1.In addition, its charge/discharge capacity under 5C multiplying power only remains 40mAhg-1.
Comparative example 2: Na is used3V2(PO4)3It is applied in sodium-ion battery as positive electrode active materials, battery other conditions
Same Examples 1 and 2.Test result shows, capacity 105mAhg-1, but 100 circulation volumes only remain 70mAhg-1.?
Capacity is maintained at 60mAhg under 10C multiplying power-1。
By comparison as it can be seen that the present invention has preferable sodium-ion battery charge-discharge performance, cyclical stability and forthright again
It can be good.
Claims (6)
1. a kind of K2Fe3(SO4)3(OH)2Compound.
2. K described in a kind of claim 12Fe3(SO4)3(OH)2The preparation method of compound, it is characterised in that: preparation step is such as
Under, K compound, the compound of Fe containing divalent, compound containing S will be contained after mixing, K:Fe:S molar ratio=(1- in mixture
3): 3:(1-3), by hydro-thermal method synthetic reaction, K is made2Fe3(SO4)3(OH)2Compound.
3. preparation method described in accordance with the claim 1, it is characterised in that:
The compound containing K is one of the oxide of K, the carbonate of K, the sulfate of K, the nitrate of K or oxalates of K
Or two kinds or more；
The compound of Fe containing divalent is one of the oxide of divalent Fe or the sulfate of Fe or two kinds；
The compound containing S is H2SO4、(NH4)2SO4Or FeSO4One of or two kinds or more.
4. according to preparation method described in claim 2 or 3, which is characterized in that prepare K using hydro-thermal method2Fe3(SO4)3(OH)2
Compound, its step are as follows:
1) ingredient: it will contain and be stirred to formation uniformly in K compound, the compound of Fe containing divalent and the addition deionized water of compound containing S
Solution, wherein K:Fe:S molar ratio be (1-3): 3:(1-3) molar ratio；
2) solution is transferred in reaction kettle and is sealed；
3) reaction kettle is placed in convection oven；150-250 DEG C is risen to from room temperature with 1-5 DEG C of rate；Heat preservation 10-40 hours；
After reacting sufficiently, room temperature is down to the rate of 1-50 DEG C/h, obtains K2Fe3(SO4)3(OH)2Compound.
5. K described in a kind of claim 12Fe3(SO4)3(OH)2Application of the compound in sodium-ion battery, it is characterised in that: institute
State K2Fe3(SO4)3(OH)2Compound is used as sodium-ion battery positive electrode active materials, and sodium-ion battery positive material is
K2Fe3(SO4)3(OH)2/ C-material, C mass content are 5-50%.
6. applying according to claim 5, which is characterized in that prepare K using hydro-thermal method2Fe3(SO4)3(OH)2/ C sodium ion
Cell positive material, its step are as follows:
1) ingredient: K compound, compound containing Fe and compound containing S will be contained and added by K:Fe:S for the molar ratio of (1-3): 3:(1-3)
Enter stirring in deionized water and K is added to solution is formed2Fe3(SO4)3(OH)2The conductive carbon of quality 5%-50% continues stirring extremely
Uniform suspension；
2) suspension is moved in reaction kettle；
3) control parameters carry out materials synthesis: the reaction kettle for filling above-mentioned ingredient is placed in convection oven；With 1-5 DEG C
Rate rises to 150-250 DEG C from room temperature；Heat preservation 10-40 hours；After reacting sufficiently, room temperature is down to the rate of 1-50 DEG C/h,
Obtain K2Fe3(SO4)3(OH)2/ C-material；
The compound containing K is one of the oxide of K, the carbonate of K, the sulfate of K, the nitrate of K or oxalates of K
Or two kinds or more；
The compound containing Fe is one of oxalates of the oxide of Fe, the sulfate of Fe and Fe or two kinds or more；
The compound containing S is H2SO4、(NH4)2SO4And FeSO4One of or two kinds or more；
Conductive carbon is one or more of Super P, acetylene black, Kuraray, Ketjen black, carbon nanotube, graphene.
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| CN105271158A (en) * | 2015-09-16 | 2016-01-27 | 湘潭大学 | Method for preparing shuttle-shaped single-layer sheet-like NaTi2 (PO4) 3 electrode material |
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Application publication date: 20190611 |