CN104701531A - In-situ carbon-coating hexagon K0.7[Fe0.5Mn0.5]O2 nano material as well as preparation method and application thereof - Google Patents
In-situ carbon-coating hexagon K0.7[Fe0.5Mn0.5]O2 nano material as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to an in-situ carbon-coating hexagon K0.7[Fe0.5Mn0.5]O2 nano material as well as a preparation method and an application thereof. The material can serve as a sodium-ion battery positive active material which is formed by coating K0.7[Fe0.5Mn0.5]O2 hexagonal nano crystals with graphitized carbon layers; the diameter of the hexagonal nano crystals is 100-350nm; the thickness of the graphitized carbon layers is 6-10nm. The in-situ carbon-coating hexagon K0.7[Fe0.5Mn0.5]O2 nano material has the beneficial effects that the nano material with relatively uniform shape is finally prepared by combining methods of drying solutions and calcinating atmosphere; the material serves as a sodium-ion battery positive material active substance and shows relatively high specific discharge capacity and excellent cycling stability; on the other hand, the process is simple; the in-situ carbon-coating hexagon K0.7[Fe0.5Mn0.5]O2 nano material is prepared by simply drying and calcinating the solution; the energy consumption is relatively low.
Description
Technical field
The invention belongs to nano material and technical field of electrochemistry, be specifically related to the coated hexagon K of in-situ carbon
0.7[Fe
0.5mn
0.5] O
2nano material and preparation method thereof, this material can be used as sodium-ion battery positive electrode active materials.
Background technology
Along with the development of science and technology and the sharp increase of population, new century is also increasing to the consumption of the energy, the exhaustion of the non-renewable resources such as oil, coal and natural gas, the breach that clean energy resource makes up energy demand is found in an urgent demand, require the continuity sustainability of clean energy resource, so that meet instructions for use simultaneously.In existing main stream system, oil and coal are non-renewable energy resources, and it also can produce a large amount of CO in use consumption process
2, SO
2etc. harmful substance, the environment of depending on for existence to the mankind brings serious destruction.This just impels people more to pay attention to setting up novel, effective energy supply system, and while ensureing economic sustainable growth, it also should meet the requirement of environmental beneficial.Wherein, to tap a new source of energy and renewable and clean energy resource currently addresses these problems one of most effective method, new energy materials is then the development and utilization realizing new forms of energy, and supports basis and the core of its development.In numerous new energy systems, as wind energy, solar energy, biomass energy etc., it all possesses discontinuous characteristic, and to the system that it is effectively connected to the grid, so the conversion of the energy and storage device are indispensable.
Sodium-ion battery is the device that a kind of novel energy developed nearly ten years stores, and it has the features such as earth resource storage is abundant, cost is low compared with lithium ion battery, is considered to the main force of large-scale energy storage device of future generation.At present, mainly contain stratiform transition metal oxide, layer structure simple substance, phosphate system etc. and be used as its electrode material.Along with going deep into of research, not only cost is low to find stratiform transition metal oxide electrode material gradually, and its specific capacity is higher, is the good sodium-ion battery positive electrode material of a class.But stratiform transition metal oxide is difficult to obtain due to pure phase, and its pattern is difficult to nano flower and conductivity is poor, it is made to have high power capacity to be but difficult to bring into play completely on foot, just need us by the in-stiu coating of conductive materials, while improving its electronic conductivity, suppress the secondary agglomeration of its crystal grain, improve its chemical property.At present, the coated hexagon K of in-situ carbon
0.7[Fe
0.5mn
0.5] O
2nano material have not been reported.
Summary of the invention
The object of the present invention is to provide the coated hexagon K of a kind of in-situ carbon
0.7[Fe
0.5mn
0.5] O
2nano material and preparation method thereof, its preparation process is simple, and energy consumption is lower, and productive rate is higher, the coated hexagon K of in-situ carbon of gained
0.7[Fe
0.5mn
0.5] O
2nano material has good chemical property as sodium-ion battery positive material.
The present invention solves the problems of the technologies described above adopted technical scheme: the coated hexagon K of in-situ carbon
0.7[Fe
0.5mn
0.5] O
2the preparation method of nano material, comprises the steps:
1) potassium source, source of iron, manganese source and carbon source are joined in deionized water in the lump, be stirred to solution at a certain temperature and present light yellow clear shape;
2) by step 1) gained solution moves on to stirred in water bath again, obtains brownish red clear solution;
3) by step 2) gained solution is transferred in culture dish, evaporate to dryness at a constant temperature;
4) by step 3) solid of gained toasts under then transferring to rapidly high temperature, obtains porous solid structure;
5) by step 4) products therefrom grinding, then calcine under air conditions;
6) by step 5) products therefrom calcines under moving on to argon gas condition again, obtains the coated hexagon K of in-situ carbon
0.7[Fe
0.5mn
0.5] O
2nano material.
By such scheme, step 1) described in potassium source be KNO
3, K
2cO
3, K
2sO
4with the mixing of any one or they in KCl; Described source of iron is Fe (NO
3)
3.9H
2o and Fe
2(SO
4)
3.7H
2the mixing of any one or they in O; Described manganese source is Mn (CH
3cOO)
2and MnCO
3in the mixing of any one or they; Described carbon source is the mixing of any one or they in oxalic acid and citric acid.
By such scheme, described potassium source, source of iron, manganese source are that 7:5:5 joins and gets according to K:Fe:Mn elemental mole ratios; Step 1) K in described solution
+ion concentration range is 7/20-7/10mol/L.
By such scheme, step 2) described in bath temperature be 50-80 DEG C; Step 3) described in constant temperature under temperature be 60-90 DEG C; Step 4) described in baking temperature be 120-200 DEG C.
By such scheme, step 1) described in mixing time be 2-6 hour; Step 2) described in mixing time 6-12 hour; Step 3) described in drying time be 8-12 hour; Step 4) described in baking time be 8-12h; ; .
By such scheme, step 5) described in calcining heat be 200-500 DEG C, the time is 2-4 hour; Step 6) described in calcining heat be 600-1000 DEG C, the time is 8-12 hour.
The coated hexagon K of above-mentioned any preparation method's gained in-situ carbon
0.7[Fe
0.5mn
0.5] O
2nano material, by the coated K of graphitization carbon-coating
0.7[Fe
0.5mn
0.5] O
2the nanocrystalline formation of hexagon, the nanocrystalline diameter of described hexagon is 100-350nm, and wherein the thickness of graphitization carbon-coating is 6-10nm.
The coated hexagon K of described in-situ carbon
0.7[Fe
0.5mn
0.5] O
2nano material is as the application of sodium-ion battery positive electrode active materials.
The method that binding soln of the present invention is dried and atmosphere is calcined, using organic acid as carbon source, then by sintering carbonization in-stiu coating, finally obtains the coated hexagon K of in-situ carbon
0.7[Fe
0.5mn
0.5] O
2nano material.Result shows, and hexagon material morphology prepared by the method is homogeneous, and appearance graphitization carbon-coating is evenly coated.Hexagonal structure effectively can shorten the diffusion length of sodium ion in electrolyte, provides continuous print ion-transfer passage.And graphitization carbon-coating significantly can improve the conductivity of material, and can cushioning effect be played, active material can be provided to embed at sodium ion and deviate from volumetric expansion and the space needed for contraction in process, prevent from occurring from reuniting between each hexagon crystal grain, electrolyte penetrates into hexagon nanocrystal surface by carbon-coating, can also reduce the dissolving of active material.Therefore, the coated hexagon K of in-situ carbon provided by the invention
0.7[Fe
0.5mn
0.5] O
2nano material preparation technology is simply efficient, avoid the experiment condition using hydro-thermal etc. comparatively harsh, while its synthesis cost of reduction, significantly improve the chemical property of sodium-ion battery, improve its cyclical stability and high rate performance simultaneously, solve the shortcomings such as stratiform transition metal oxide system positive electrode conductivity is too poor, easy reunion, its chemical property is well brought into play, has huge development potentiality in sodium-ion battery application.
The invention has the beneficial effects as follows: the method that binding soln of the present invention is dried and atmosphere is calcined, using organic acid as carbon source, then by sintering carbonization in-stiu coating, suppress growth and the reunion of crystal grain, finally obtain the coated hexagon K of the comparatively homogeneous in-situ carbon of pattern
0.7[Fe
0.5mn
0.5] O
2nano material.It is as sodium-ion battery positive material active material, shows higher specific discharge capacity and good cyclical stability; Secondly, present invention process is simple, is dried and be the coated hexagon K of in-situ carbon after calcination processing by simple solution
0.7[Fe
0.5mn
0.5] O
2nano material, energy consumption is lower.The quality of the graphitized carbon in the coaxial configuration obtained accounts for the 5.0-9.0% of raw material gross mass, is conducive to the marketization and promotes.
As sodium-ion battery positive material, under the current density of 100mA/g, its specific discharge capacity is 169.4mAh/g, under the high current density of 1000mA/g, its circulation 800 times after, capability retention is respectively up to 78.2%.This result shows the coated hexagon K of in-situ carbon
0.7[Fe
0.5mn
0.5] O
2nano material has excellent storage sodium performance, is the potential application material of sodium-ion battery.
Accompanying drawing explanation
Fig. 1 is the coated hexagon K of in-situ carbon of the embodiment of the present invention 1
0.7[Fe
0.5mn
0.5] O
2the XRD figure of nano material;
Fig. 2 is the coated hexagon K of in-situ carbon of the embodiment of the present invention 1
0.7[Fe
0.5mn
0.5] O
2the Raman spectrogram of nano material;
Fig. 3 is the coated hexagon K of in-situ carbon of the embodiment of the present invention 1
0.7[Fe
0.5mn
0.5] O
2the TG figure of nano material;
Fig. 4 is the coated hexagon K of in-situ carbon of the embodiment of the present invention 1
0.7[Fe
0.5mn
0.5] O
2the FT-IR figure of nano material;
Fig. 5 is the coated hexagon K of in-situ carbon of the embodiment of the present invention 1
0.7[Fe
0.5mn
0.5] O
2nano material SEM schemes;
Fig. 6 is the coated hexagon K of in-situ carbon of the embodiment of the present invention 1
0.7[Fe
0.5mn
0.5] O
2the distribution diagram of element of nano material;
Fig. 7 is the coated hexagon K of in-situ carbon of the embodiment of the present invention 1
0.7[Fe
0.5mn
0.5] O
2the TEM figure of nano material;
Fig. 8 is the coated hexagon K of in-situ carbon of the embodiment of the present invention 1
0.7[Fe
0.5mn
0.5] O
2the HRTEM figure of nano material;
Fig. 9 is the coated hexagon K of in-situ carbon of the embodiment of the present invention 1
0.7[Fe
0.5mn
0.5] O
2the high rate performance figure of nano material;
Figure 10 is the coated hexagon K of in-situ carbon of the embodiment of the present invention 1
0.7[Fe
0.5mn
0.5] O
2the cyclic voltammetry curve figure of nano material;
Figure 11 is the coated hexagon K of in-situ carbon of the embodiment of the present invention 1
0.7[Fe
0.5mn
0.5] O
2the low range cycle performance figure of nano material;
Figure 12 is the coated hexagon K of in-situ carbon of the embodiment of the present invention 1
0.7[Fe
0.5mn
0.5] O
2the high rate cyclic performance map of nano material.
Embodiment
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
Embodiment 1:
The coated hexagon K of in-situ carbon
0.7[Fe
0.5mn
0.5] O
2the preparation method of nano material, it comprises the steps:
1) by 7.0mmol KNO
3, 5.0mmol Fe (NO
3)
3.9H
2o, 5.0mmol Mn (CH
3cOO)
2join in 20mL deionized water in the lump with 6.0g oxalic acid, at 25 DEG C, be stirred to solution present light yellow clear shape;
2) by step 1) gained solution moves on to 80 DEG C of stirred in water bath 4 hours again, obtains brownish red clear solution;
3) by step 2) gained solution is transferred in culture dish, dry under 80 DEG C of constant temperature;
4) by step 3) then the solid of gained to transfer to rapidly under 180 DEG C of high temperature baking 12 hours, obtains porous solid structure;
5) by step 4) products therefrom grinding, then calcine 3 hours under 300 DEG C of air conditionses;
6) by step 5) to move on under 600,800 and 1000 DEG C of argon gas conditions calcining more respectively 8 hours, obtain the coated hexagon K of in-situ carbon
0.7[Fe
0.5mn
0.5] O
2nano material.
With the coated hexagon K of in-situ carbon of this experiment invention
0.7[Fe
0.5mn
0.5] O
2nano material is example, determines through x-ray diffractometer, and as shown in Figure 1, X-ray diffracting spectrum (XRD) shows, calcines the coated hexagon K of the in-situ carbon obtained at different temperatures
0.7[Fe
0.5mn
0.5] O
2the peak position of nano material is consistent, and product has higher crystallinity.As shown in Figure 2, Raman analysis calcines the coated hexagon K of the in-situ carbon obtained under demonstrating different temperatures
0.7[Fe
0.5mn
0.5] O
2carbon in nano material is graphited carbon.As shown in Figure 3, thermogravimetric analysis calcines the coated hexagon K of the in-situ carbon obtained under different temperatures is described
0.7[Fe
0.5mn
0.5] O
2the carbon content of nano material is respectively 5.0%, 7.0% and 9.0%.As shown in Figure 4, FT-IR test result shows the coated hexagon K of the in-situ carbon obtained at different temperatures
0.7[Fe
0.5mn
0.5] O
2nano material has identical valence bond structure.As shown in Figure 5, field emission scanning electron microscope (FESEM) test shows, the coated hexagon K of the in-situ carbon obtained under 800 DEG C of conditions
0.7[Fe
0.5mn
0.5] O
2the pattern of nano material is comparatively homogeneous, and better dispersed, hexagonal diameter is approximately 100-350nm.And the K obtained under 600 DEG C of conditions
0.7[Fe
0.5mn
0.5] O
2appearance of nano material is comparatively chaotic, and crystal grain does not also grow complete, the K obtained under 1000 DEG C of conditions
0.7[Fe
0.5mn
0.5] O
2comparatively serious reunion is there occurs between nano material hexagon particle.As shown in Figure 6, the K obtained under different temperatures
0.7[Fe
0.5mn
0.5] O
2nano material K, Fe and Mn tri-kinds of Elemental redistribution are all very even.As shown in Figure 7, transmission electron microscope (TEM) more clearly demonstrates the coated hexagon K of in-situ carbon
0.7[Fe
0.5mn
0.5] O
2the concrete structure of nano material, it is by the coated hexagon K of graphitization carbon-coating
0.7[Fe
0.5mn
0.5] O
2nanocrystal forms, and wherein the thickness of coated carbon-coating is about 5-8nm.As shown in Figure 8, can find obvious lattice fringe under high magnification transmission electron microscope (HRTEM), inner hexagon is nanocrystalline is monocrystalline.As shown in Table 1, inductively coupled plasma test result shows, the coated hexagon K of the in-situ carbon obtained under different calcining heat
0.7[Fe
0.5mn
0.5] O
2in nano material, the element ratio of K, Fe and Mn is very close to 7:5:5.
The coated hexagon K of in-situ carbon
0.7[Fe
0.5mn
0.5] O
2nano material is as sodium-ion battery positive electrode active materials, and all the other steps of the assemble method of sodium-ion battery are identical with common preparation method.The assemble method of sodium-ion battery is as follows, adopts the coated hexagon K of in-situ carbon
0.7[Fe
0.5mn
0.5] O
2nano material is as active material, and acetylene black is as conductive agent, and polytetrafluoroethylene is as binding agent, and the mass ratio of active material, acetylene black, Kynoar is 70:20:10; After they fully being mixed in proportion, add a small amount of isopropyl alcohol, grinding evenly, twin rollers is pressed the electrode slice that about 0.5mm is thick; It is for subsequent use after 24 hours that the positive plate pressed is placed in the oven drying of 80 DEG C.Take concentration as 1mol/cm
3naClO
4solution is as electrolyte, and the ethylene carbonate of its solvent to be mass ratio be 1:1 mixing and dimethyl carbonate, with sodium metal sheet for negative pole, carry out electrochemical property test between 1.5-4.0V.
As shown in Figure 9, the coated hexagon K of the in-situ carbon obtained under 800 DEG C of conditions
0.7[Fe
0.5mn
0.5] O
2nano material has excellent high rate performance, and it is under the current density of 100mA/g, and initial capacity is the product being higher than 600 DEG C and 1000 DEG C.After the test of continuous print multiplying power, its multiplying power response rate is also the highest.
As shown in Figure 10, the coated hexagon K of in-situ carbon
0.7[Fe
0.5mn
0.5] O
2the CV curve of nano material, does not have obvious redox peak in charge and discharge process.
As shown in figure 11, the coated hexagon K of in-situ carbon
0.7[Fe
0.5mn
0.5] O
2nano material when permanent direct current charge-discharge, with the coated hexagon K of the in-situ carbon obtained under 800 DEG C of conditions
0.7[Fe
0.5mn
0.5] O
2nano material is example, and the constant current charge-discharge test result of carrying out under 100mA/g shows, its first discharge specific capacity can reach 169.4mAh/g, and after 200 circulations, capability retention reaches 75.1%.With the coated hexagon K of the in-situ carbon obtained under 600 DEG C of conditions
0.7[Fe
0.5mn
0.5] O
2nano material is example, and the constant current charge-discharge test result of carrying out under 100mA/g shows, its first discharge specific capacity is 140.7mAh/g, for capability retention reaches 66.8% after 100 circulations.With the coated hexagon K of the in-situ carbon obtained under 1000 DEG C of conditions
0.7[Fe
0.5mn
0.5] O
2nano material is example, and the constant current charge-discharge test result of carrying out under 100mA/g shows, its first discharge specific capacity is 156.1mAh/g, for capability retention reaches 63.9% after 100 circulations.With the coated hexagon K of the in-situ carbon obtained under 800 DEG C of conditions
0.7[Fe
0.5mn
0.5] O
2nano material is example, and the constant current charge-discharge test result of carrying out under 200mA/g shows, be originally capacity is 137.8mAh/g, for capability retention reaches 86.1% after 300 circulations.With the coated hexagon K of the in-situ carbon obtained under 800 DEG C of conditions
0.7[Fe
0.5mn
0.5] O
2nano material is example, and the constant current charge-discharge test result of carrying out under 500mA/g shows, after 250 circulations, its capacity is almost undamped, and with the coated hexagon K of the in-situ carbon obtained under 600 DEG C of conditions
0.7[Fe
0.5mn
0.5] O
2nano material is example, and the constant current charge-discharge test result of carrying out under 500mA/g shows, for capability retention is only 14.9% after its 100 times circulations.
As shown in figure 12, the coated hexagon K of the in-situ carbon obtained under 800 DEG C of conditions
0.7[Fe
0.5mn
0.5] O
2nano material is under higher current density 1000mA/g, and after 800 circulations, its capability retention is respectively up to 78.2%.
The coated hexagon K of in-situ carbon of table 1 example 1 gained at different temperatures
0.7[Fe
0.5mn
0.5] O
2the ICP test result of nano material
Embodiment 2:
1) by 3.5mmol K
2cO
3, 2.5mmol Fe
2(SO
4)
3.9H
2o, 2.5mmol Mn
2cO
3join in 20mL deionized water in the lump with 2.0g citric acid, at 25 DEG C, be stirred to solution present light yellow clear shape;
2) by step 1) gained solution moves on to 60 DEG C of stirred in water bath 6 hours again, obtains brownish red clear solution;
3) by step 2) gained solution is transferred in culture dish, dry under 60 DEG C of constant temperature;
4) by step 3) then the solid of gained to transfer to rapidly under 120 DEG C of high temperature baking 10 hours, obtains porous solid structure;
5) by step 4) products therefrom grinding, then calcine 3 hours under 400 DEG C of air conditionses;
6) by step 5) to move on under 600 DEG C of argon gas conditions calcining again 12 hours, obtain the coated hexagon K of in-situ carbon
0.7[Fe
0.5mn
0.5] O
2nano material.
With the coated hexagon K of the in-situ carbon of the present embodiment gained
0.7[Fe
0.5mn
0.5] O
2nano material is example, and the constant current charge-discharge test result of carrying out under 100mA/g shows, its first discharge specific capacity can reach 160.8mA/g, and after 100 circulations, capability retention reaches 88.2%.
Embodiment 3:
1) by 3.5mmol KNO
3, 1.75mmol K
2sO
4, 2.5mmol Fe (NO
3)
3.9H
2o, 1.25mmolFe
2(SO
4)
3.7H
2o, 2.5mmol Mn (CH
3cOO)
2, 1.25mmol Mn
2cO
3, 2.0g oxalic acid and 2.0g citric acid join in 40mL deionized water in the lump, at 25 DEG C, be stirred to solution present light yellow clear shape;
2) by step 1) gained solution moves on to 50 DEG C of stirred in water bath 6 hours again, obtains brownish red clear solution;
3) by step 2) gained solution is transferred in culture dish, dry under 90 DEG C of constant temperature;
4) by step 3) then the solid of gained to transfer to rapidly under 200 DEG C of high temperature baking 10 hours, obtains porous solid structure;
5) by step 4) products therefrom grinding.Then calcine 2 hours under 500 DEG C of air conditionses;
6) by step 5) to move on under 1000 DEG C of argon gas conditions calcining again 10 hours, obtain the coated hexagon K of in-situ carbon
0.7[Fe
0.5mn
0.5] O
2nano material.
With the coated hexagon K of the in-situ carbon of the present embodiment gained
0.7[Fe
0.5mn
0.5] O
2nano material is example, and the constant current charge-discharge test result of carrying out under 200mA/g shows, its first discharge specific capacity can reach 137.8mAh/g, for capability retention reaches 86.1% after 300 circulations.
Embodiment 4:
1) by 3.5mmol K
2sO
4, 2.5mmol Fe
2(SO
4)
3.7H
2o, 2.5mmol Mn
2cO
3join in 30mL deionized water in the lump with 4.0g citric acid, at 25 DEG C, be stirred to solution present light yellow clear shape;
2) by step 1) gained solution moves on to 80 DEG C of stirred in water bath 6 hours again, obtains brownish red clear solution;
3) by step 2) gained solution is transferred in culture dish, dry under 75 DEG C of constant temperature;
4) by step 3) then the solid of gained to transfer to rapidly under 150 DEG C of high temperature baking 9 hours, obtains porous solid structure;
5) by step 4) products therefrom grinding, then calcine 2.5 hours under 400 DEG C of air conditionses;
6) by step 5) to move on under 800 DEG C of argon gas conditions calcining again 9 hours, obtain the coated hexagon K of in-situ carbon
0.7[Fe
0.5mn
0.5] O
2nano material.
With the coated hexagon K of the in-situ carbon of the present embodiment gained
0.7[Fe
0.5mn
0.5] O
2nano material is example, and the constant current charge-discharge test result of carrying out under 500mA/g shows, its first discharge specific capacity can reach 114.9mAh/g, and after 200 circulations, capability retention reaches 92.3%.
Embodiment 5:
1) by 14.0mmol KNO
3, 10.0mmol Fe (NO
3)
3.9H
2o, 10.0mmol Mn (CH
3cOO)
2join in 40mL deionized water in the lump with 5.0g citric acid, at 25 DEG C, be stirred to solution present light yellow clear shape;
2) by step 1) gained solution moves on to 50 DEG C of stirred in water bath 6 hours again, obtains brownish red clear solution;
3) by step 2) gained solution is transferred in culture dish, dry under 80 DEG C of constant temperature;
4) by step 3) then the solid of gained to transfer to rapidly under 160 DEG C of high temperature baking 12 hours, obtains porous solid structure;
5) by step 4) products therefrom grinding, then calcine 3.5 hours under 350 DEG C of air conditionses.
6) by step 5) to move on under 700 DEG C of argon gas conditions calcining again 12 hours, obtain the coated hexagon K of in-situ carbon
0.7[Fe
0.5mn
0.5] O
2nano material.
With the coated hexagon K of the in-situ carbon of the present embodiment gained
0.7[Fe
0.5mn
0.5] O
2nano material is example, and the constant current charge-discharge test result of carrying out under 100mA/g shows, its first discharge specific capacity can reach 170.5mAh/g, for capability retention reaches 81.2% after 100 circulations.
Embodiment 6:
1) by 7.0mmol KNO
3, 2.5mmol Fe
2(SO
4)
3.7H
2o, 2.5mmol Mn
2cO
3, 2.0g oxalic acid and 2.0g citric acid join in 20mL deionized water in the lump, at 25 DEG C, be stirred to solution present light yellow clear shape;
2) by step 1) gained solution moves on to 65 DEG C of stirred in water bath 6 hours again, obtains brownish red clear solution;
3) by step 2) gained solution is transferred in culture dish, dry under 75 DEG C of constant temperature;
4) by step 3) then the solid of gained to transfer to rapidly under 170 DEG C of high temperature baking 12 hours, obtains porous solid structure;
5) by step 4) products therefrom grinding, then calcine 3.5 hours under 450 DEG C of air conditionses;
6) by step 5) to move on under 900 DEG C of argon gas conditions calcining again 10.5 hours, obtain the coated hexagon K of in-situ carbon
0.7[Fe
0.5mn
0.5] O
2nano material.
With the coated hexagon K of the in-situ carbon of the present embodiment gained
0.7[Fe
0.5mn
0.5] O
2nano material is example, and the constant current charge-discharge test result of carrying out under 100mA/g shows, its first discharge specific capacity can reach 159.8mAh/g, and after 100 circulations, capability retention reaches 80.9%.
Embodiment 7:
1) by 7.0mmol KNO
3, 5.0mmol Fe (NO
3)
3.9H
2o, 5.0mmol Mn (CH
3cOO)
2join in 40mL deionized water in the lump with 8.0g oxalic acid, at 25 DEG C, be stirred to solution present light yellow clear shape;
2) by step 1) gained solution moves on to 80 DEG C of stirred in water bath 3 hours again, obtains brownish red clear solution;
3) by step 2) gained solution is transferred in culture dish, dry under 70 DEG C of constant temperature;
4) by step 3) then the solid of gained to transfer to rapidly under 200 DEG C of high temperature baking 8 hours, obtains porous solid structure;
5) by step 4) products therefrom grinding, then calcine 3 hours under 300 DEG C of air conditionses;
6) by step 5) to move on under 800 DEG C of argon gas conditions calcining again 10 hours, obtain the coated hexagon K of in-situ carbon
0.7[Fe
0.5mn
0.5] O
2nano material.
With the coated hexagon K of the in-situ carbon of the present embodiment gained
0.7[Fe
0.5mn
0.5] O
2nano material is example, and the constant current charge-discharge test result of carrying out under 100mA/g shows, its first discharge specific capacity can reach 167.2mAh/g, and after 100 circulations, capability retention reaches 82.7%.
Claims (8)
1. the coated hexagon K of in-situ carbon
0.7[Fe
0.5mn
0.5] O
2the preparation method of nano material, comprises the steps:
1) potassium source, source of iron, manganese source and carbon source are joined in deionized water in the lump, be stirred to solution at a certain temperature and present light yellow clear shape;
2) by step 1) gained solution moves on to stirred in water bath again, obtains brownish red clear solution;
3) by step 2) gained solution is transferred in culture dish, evaporate to dryness at a constant temperature;
4) by step 3) solid of gained toasts under then transferring to rapidly high temperature, obtains porous solid structure;
5) by step 4) products therefrom grinding, then calcine under air conditions;
6) by step 5) products therefrom calcines under moving on to argon gas condition again, obtains the coated hexagon K of in-situ carbon
0.7[Fe
0.5mn
0.5] O
2nano material.
2. the coated hexagon K of in-situ carbon according to claim 1
0.7[Fe
0.5mn
0.5] O
2the preparation method of nano material, is characterized in that: step 1) described in potassium source be KNO
3, K
2cO
3, K
2sO
4with the mixing of any one or they in KCl; Described source of iron is Fe (NO
3)
3.9H
2o and Fe
2(SO
4)
3.7H
2the mixing of any one or they in O; Described manganese source is Mn (CH
3cOO)
2and MnCO
3in the mixing of any one or they; Described carbon source is the mixing of any one or they in oxalic acid and citric acid.
3. the coated hexagon K of in-situ carbon according to claim 2
0.7[Fe
0.5mn
0.5] O
2the preparation method of nano material, is characterized in that: described potassium source, source of iron, manganese source are that 7:5:5 joins and gets according to K:Fe:Mn elemental mole ratios; Step 1) K in described solution
+ion concentration range is 7/20-7/10mol/L.
4. the coated hexagon K of in-situ carbon according to claim 1
0.7[Fe
0.5mn
0.5] O
2the preparation method of nano material, is characterized in that: step 2) described in bath temperature be 50-80 DEG C; Step 3) described in constant temperature under temperature be 60-90 DEG C; Step 4) described in baking temperature be 120-200 DEG C.
5. the coated hexagon K of in-situ carbon according to claim 4
0.7[Fe
0.5mn
0.5] O
2the preparation method of nano material, is characterized in that: step 1) described in mixing time be 2-6 hour; Step 2) described in mixing time 6-12 hour; Step 3) described in drying time be 8-12 hour; Step 4) described in baking time be 8-12h.
6. the coated hexagon K of in-situ carbon according to claim 1
0.7[Fe
0.5mn
0.5] O
2the preparation method of nano material, is characterized in that: step 5) described in calcining heat be 200-500 DEG C, the time is 2-4 hour; Step 6) described in calcining heat be 600-1000 DEG C, the time is 8-12 hour.
7. the coated hexagon K of any preparation method of claim 1-6 gained in-situ carbon
0.7[Fe
0.5mn
0.5] O
2nano material, by the coated K of graphitization carbon-coating
0.7[Fe
0.5mn
0.5] O
2the nanocrystalline formation of hexagon, the nanocrystalline diameter of described hexagon is 100-350nm, and wherein the thickness of graphitization carbon-coating is 6-10nm.
8. the coated hexagon K of in-situ carbon according to claim 7
0.7[Fe
0.5mn
0.5] O
2nano material is as the application of sodium-ion battery positive electrode active materials.
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| CN106784651A (en) * | 2016-11-22 | 2017-05-31 | 武汉理工大学 | Connection nano-material and its preparation method and application in carbon-encapsulated iron potassium manganate |
| CN109155395A (en) * | 2016-05-12 | 2019-01-04 | 艾利电力能源有限公司 | Positive electrode for nonaqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery |
| US20190067696A1 (en) * | 2015-12-07 | 2019-02-28 | National Institute Of Advanced Industrial Science And Technology | Potassium compound and positive electrode active material for potassium ion secondary batteries containing same |
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| CN104701531B (en) | 2017-01-18 |
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