CN104701531B - 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 are and in particular to original position carbon coating hexagon k0.7
[fe0.5mn0.5]o2Nano material and preparation method thereof, this material can be used as sodium-ion battery positive electrode active materials.
Background technology
With the sharp increase of scientific and technological development and population, new century is also increasing to the consumption of the energy, oil, coal
With the exhaustion of the non-renewable resources such as natural gas, an urgent demand is found clean energy resource to make up the breach of energy demand, will simultaneously
Seek the seriality sustainability of clean energy resource, in order to meet use requirement.In existing main stream system, oil and coal
Carbon is non-renewable energy resources, and it also can produce substantial amounts of co in using consumption process2、so2Deng harmful substance, give people class and rely
Serious destruction is brought with the environment of existence.This just promotes people more to pay attention to setting up new, effective energy supply system,
While ensureing economic sustainable growth, it also should meet the requirement of environmental beneficial.Wherein, tap a new source of energy and renewable
Clean energy resource is currently to solve one of these problem most efficient methods, and new energy materialses are then exploitation and the profits realizing new forms of energy
With, and support basis and the core of its development.In numerous new energy systems, such as wind energy, solar energy, biomass energy etc.,
It all possesses discontinuous characteristic, to system that it is effectively connected to the grid, then the conversion of the energy and storage device are not
Can or lack.
Sodium-ion battery, is a kind of device of the novel energy storage developed nearly ten years, compared with lithium ion battery its
Have that earth resource storage is abundant, low cost the features such as it is considered to be the main force of large-scale energy storage device of future generation.At present, main
Stratiform transition metal oxide, layer structure simple substance, phosphate system etc. is had to be used as its electrode material.Depth with research
Enter, gradually find stratiform transition metal oxide electrode material not only low cost, and its specific capacity is higher, is that a class is preferable
Sodium-ion battery positive electrode material.But stratiform transition metal oxide is difficult to obtain due to pure phase, and its pattern is difficult to nanometer
Flower is poor with electric conductivity so as to apprentice has high power capacity to be but difficult to bring into play completely it is necessary to we are by the original position of conductive materials
Cladding, suppresses the secondary agglomeration of its crystal grain while improving its electronic conductivity, improves its chemical property.At present, in situ
Carbon coating hexagon k0.7[fe0.5mn0.5]o2Nano material have not been reported.
Content of the invention
It is an object of the invention to provide a kind of original position carbon coating hexagon k0.7[fe0.5mn0.5]o2Nano material and its system
Preparation Method, its preparation process is simple, and energy consumption is relatively low, and yield is higher, the original position carbon coating hexagon k of gained0.7[fe0.5mn0.5]o2
Nano material has good chemical property as sodium-ion battery positive material.
The present invention solves above-mentioned technical problem the technical scheme is that original position carbon coating hexagon k0.7
[fe0.5mn0.5]o2The preparation method of nano material, comprises the steps:
1) potassium resource, source of iron, manganese source and carbon source are added in deionized water in the lump, stir at a certain temperature and to solution be in
Existing light yellow clear shape；
2) by step 1) resulting solution moves on to stirred in water bath again, obtains brownish red clear solution；
3) by step 2) resulting solution is transferred in culture dish, is evaporated at a constant temperature；
4) by step 3) solid of gained and then be quickly transferred to baking under high temperature, obtain porous solid structure；
5) by step 4) products therefrom grinding, then calcine under air conditionses；
6) by step 5) products therefrom moves on to and calcines under the conditions of argon, obtains original position carbon coating hexagon k0.7
[fe0.5mn0.5]o2Nano material.
By such scheme, step 1) described in potassium resource be kno3、k2co3、k2so4With any one in kcl or they
Mixing；Described source of iron is fe (no3)3.9h2O and fe2(so4)3.7h2Any one in o or their mixing；Described manganese
Source is mn (ch3coo)2And mnco3In any one or their mixing；Described carbon source is appointing in oxalic acid and citric acid
A kind of or their mixing of meaning.
By such scheme, described potassium resource, source of iron, manganese source are joined for 7:5:5 according to k:fe:mn elemental mole ratios and are taken；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℃；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 little
When；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 be 2-4 hour；Step 6) described in
Calcining heat is 600-1000 DEG C, and the time is 8-12 hour.
Above-mentioned any preparation method gained original position carbon coating hexagon k0.7[fe0.5mn0.5]o2Nano material, by graphitization
Carbon-coating coats k0.7[fe0.5mn0.5]o2The nanocrystalline formation of hexagon, the nanocrystalline a diameter of 100-350nm of described hexagon, its
The thickness of middle graphitization carbon-coating is 6-10nm.
Described original position carbon coating hexagon k0.7[fe0.5mn0.5]o2Nano material is as sodium-ion battery positive-active material
The application of material.
The method that binding soln of the present invention is dried and atmosphere is calcined, using organic acid as carbon source, then passes through to sinter carbonization
In-stiu coating, finally gives original position carbon coating hexagon k0.7[fe0.5mn0.5]o2Nano material.Result shows, prepared by the method
Hexagon material morphology homogeneous, appearance graphitization carbon-coating is evenly coated.Hexagonal structure can effectively shorten sodium in electrolyte
The diffusion length of ion, provides continuous ion-transfer passage.And graphitization carbon-coating can be greatly improved the electric conductivity of material, and
Cushioning effect can be played it is provided that active material sodium ion embed and abjection during volumetric expansion and shrink required
Space, prevents from occurring between each hexagon crystal grain from reuniting, electrolyte can penetrate into hexagon nanocrystal surface by carbon-coating,
The dissolving of active substance can also be reduced.Therefore, the original position carbon coating hexagon k that the present invention provides0.7[fe0.5mn0.5]o2Nanometer
Material preparation process is simply efficient, it is to avoid using the more harsh experiment condition such as hydro-thermal, reducing the same of its synthesis cost
When, the chemical property of sodium-ion battery is greatly improved, improves its cyclical stability and high rate performance simultaneously, solve stratiform
The shortcomings of transition metal oxide system positive electrode electric conductivity too poor, easy reunion, is so as to chemical property has been given play to well
Come, have 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 passes through to sinter carbonization in-stiu coating, the growth of suppression crystal grain and reunion, finally gives the more homogeneous in-situ carbon of pattern
Cladding hexagon k0.7[fe0.5mn0.5]o2Nano material.It shows higher as sodium-ion battery positive material active substance
Specific discharge capacity and good cyclical stability；Secondly, present invention process is simple, is dried by simple solution and calcination processing
It is original position carbon coating hexagon k afterwards0.7[fe0.5mn0.5]o2Nano material, energy consumption is relatively low.Graphite in obtained coaxial configuration
The quality changing carbon accounts for the 5.0-9.0% of raw material gross mass, is conducive to marketization popularization.
As sodium-ion battery positive material, under the electric current density of 100ma/g, its specific discharge capacity is 169.4mah/
G, under the high current density of 1000ma/g, after it circulates 800 times, capability retention is up to 78.2% respectively.This result shows
Original position carbon coating hexagon k0.7[fe0.5mn0.5]o2Nano material has excellent storage sodium performance, is the potential of sodium-ion battery
Application material.
Brief description
Fig. 1 is the original position carbon coating hexagon k of the embodiment of the present invention 10.7[fe0.5mn0.5]o2The xrd figure of nano material；
Fig. 2 is the original position carbon coating hexagon k of the embodiment of the present invention 10.7[fe0.5mn0.5]o2The Raman spectrum of nano material
Figure；
Fig. 3 is the original position carbon coating hexagon k of the embodiment of the present invention 10.7[fe0.5mn0.5]o2The tg figure of nano material；
Fig. 4 is the original position carbon coating hexagon k of the embodiment of the present invention 10.7[fe0.5mn0.5]o2The ft-ir figure of nano material；
Fig. 5 is the original position carbon coating hexagon k of the embodiment of the present invention 10.7[fe0.5mn0.5]o2Nano material sem is schemed；
Fig. 6 is the original position carbon coating hexagon k of the embodiment of the present invention 10.7[fe0.5mn0.5]o2The Elemental redistribution of nano material
Figure；
Fig. 7 is the original position carbon coating hexagon k of the embodiment of the present invention 10.7[fe0.5mn0.5]o2The tem figure of nano material；
Fig. 8 is the original position carbon coating hexagon k of the embodiment of the present invention 10.7[fe0.5mn0.5]o2The hrtem figure of nano material；
Fig. 9 is the original position carbon coating hexagon k of the embodiment of the present invention 10.7[fe0.5mn0.5]o2The high rate performance of nano material
Figure；
Figure 10 is the original position carbon coating hexagon k of the embodiment of the present invention 10.7[fe0.5mn0.5]o2The circulation volt of nano material
Peace curve chart；
Figure 11 is the original position carbon coating hexagon k of the embodiment of the present invention 10.7[fe0.5mn0.5]o2The low range of nano material
Cycle performance figure；
Figure 12 is the original position carbon coating hexagon k of the embodiment of the present invention 10.7[fe0.5mn0.5]o2The high magnification of nano material
Cycle performance figure.
Specific embodiment
For a better understanding of the present invention, it is further elucidated with present disclosure with reference to embodiment, but the present invention
Content is not limited solely to the following examples.
Embodiment 1:
Original position carbon coating hexagon k0.7[fe0.5mn0.5]o2The preparation method of nano material, it comprises the steps:
1) by 7.0mmol kno3、5.0mmol fe(no3)3.9h2o、5.0mmol mn(ch3coo)2With 6.0g oxalic acid one
And be added in 20ml deionized water, stir at 25 DEG C and assume light yellow clear shape to solution；
2) by step 1) resulting solution moves on to 80 DEG C of stirred in water bath 4 hours again, obtains brownish red clear solution；
3) by step 2) resulting solution is transferred in culture dish, it is dried under 80 DEG C of constant temperature；
4) by step 3) solid of gained and then be quickly transferred to toast 12 hours under 180 DEG C of high temperature, obtain 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) move on to respectively again and calcine 8 hours under the conditions of 600,800 and 1000 DEG C of argon, obtain original position carbon coating
Hexagon k0.7[fe0.5mn0.5]o2Nano material.
Original position carbon coating hexagon k with this experiment invention0.7[fe0.5mn0.5]o2As a example nano material, through x- ray
Diffractometer determines, as shown in figure 1, X-ray diffraction collection of illustrative plates (xrd) shows, calcines the original position carbon coating obtaining at different temperatures
Hexagon k0.7[fe0.5mn0.5]o2The peak position of nano material is consistent, and product has higher crystallinity.As shown in Fig. 2 Raman divides
Analysis shows calcines the original position carbon coating hexagon k obtaining under different temperatures0.7[fe0.5mn0.5]o2Carbon in nano material is
Graphited carbon.As shown in figure 3, calcining, under thermogravimetric analysiss explanation different temperatures, the original position carbon coating hexagon k obtaining0.7
[fe0.5mn0.5]o2The carbon content of nano material is respectively 5.0%, 7.0% and 9.0%.As shown in figure 4, ft-ir test result
Show the original position carbon coating hexagon k obtaining at different temperatures0.7[fe0.5mn0.5]o2Nano material has identical valence link knot
Structure.As shown in figure 5, field emission scanning electron microscope (fesem) test shows, the original position carbon coating hexagon obtaining under the conditions of 800 DEG C
k0.7[fe0.5mn0.5]o2The pattern of nano material is more homogeneous, and preferably, hexagonal diameter is about 100-350nm to dispersibility.
And the k obtaining under the conditions of 600 DEG C0.7[fe0.5mn0.5]o2Appearance of nano material is more chaotic, and crystal grain does not also grow completely, and 1000
The k obtaining under the conditions of DEG C0.7[fe0.5mn0.5]o2More serious reunion is there occurs between nano material hexagon granule.As Fig. 6
K that is shown, obtaining under different temperatures0.7[fe0.5mn0.5]o2Nano material k, fe and tri- kinds of Elemental redistribution of mn are all very uniform.As figure
Shown in 7, transmission electron microscope (tem) more clearly from shows original position carbon coating hexagon k0.7[fe0.5mn0.5]o2Nano material
Concrete structure, it coats hexagon k by graphitization carbon-coating0.7[fe0.5mn0.5]o2Nanocrystal forms, and wherein coats the thickness of carbon-coating
Degree is about 5-8nm.As shown in figure 8, caning be found that obvious lattice fringe under high magnification transmission electron microscope (hrtem), the six of inside
Side shape is nanocrystalline to be monocrystalline.As shown in Table 1, inductively coupled plasma test result shows, obtains under different calcining heats
Original position carbon coating hexagon k0.7[fe0.5mn0.5]o2In nano material, the element ratio of k, fe and mn is sufficiently close to 7:5:5.
Original position carbon coating hexagon k0.7[fe0.5mn0.5]o2Nano material is as sodium-ion battery positive electrode active materials, sodium
Remaining step of the assemble method of ion battery is identical with common preparation method.The assemble method of sodium-ion battery is as follows, adopts
Original position carbon coating hexagon k0.7[fe0.5mn0.5]o2, as active material, acetylene black is as conductive agent, polytetrafluoroethyl-ne for nano material
As binding agent, active material, acetylene black, the mass ratio of Kynoar are 70:20:10 to alkene；They are fully mixed in proportion
After conjunction, add a small amount of isopropanol, grind uniformly, the thick electrode slice of about 0.5mm is pressed on twin rollers；The positive plate pressing is placed in 80
DEG C oven drying standby after 24 hours.With concentration as 1mol/cm3naclo4As electrolyte, its solvent for mass ratio is solution
The ethylene carbonate of 1:1 mixing and dimethyl carbonate, with metallic sodium piece as negative pole, carry out chemical property between 1.5-4.0v
Test.
As shown in figure 9, the original position carbon coating hexagon k obtaining under the conditions of 800 DEG C0.7[fe0.5mn0.5]o2Nano material
There is excellent high rate performance,, under the electric current density of 100ma/g, initial capacity is to be higher than 600 DEG C and 1000 DEG C of product for it
Thing.After the test of continuous multiplying power, its multiplying power response rate is also highest.
As shown in Figure 10, original position carbon coating hexagon k0.7[fe0.5mn0.5]o2The cv curve of nano material, in discharge and recharge
Obvious redox peaks are not had in journey.
As shown in figure 11, original position carbon coating hexagon k0.7[fe0.5mn0.5]o2Nano material in permanent direct current charge-discharge, with
The original position carbon coating hexagon k obtaining under the conditions of 800 DEG C0.7[fe0.5mn0.5]o2As a example nano material, carry out under 100ma/g
Constant current charge-discharge test result show, its first discharge specific capacity up to 169.4mah/g, 200 times circulation after capability retention
Reach 75.1%.With the original position carbon coating hexagon k obtaining under the conditions of 600 DEG C0.7[fe0.5mn0.5]o2As a example nano material,
The constant current charge-discharge test result carrying out under 100ma/g shows, its first discharge specific capacity is 140.7mah/g, 100 circulations
Reach 66.8% for capability retention afterwards.With the original position carbon coating hexagon k obtaining under the conditions of 1000 DEG C0.7[fe0.5mn0.5]o2
As a example nano material, the constant current charge-discharge test result carrying out under 100ma/g shows, its first discharge specific capacity is
156.1mah/g, reaches 63.9% for capability retention after 100 circulations.With the original position carbon coating six obtaining under the conditions of 800 DEG C
Side shape k0.7[fe0.5mn0.5]o2As a example nano material, the constant current charge-discharge test result carrying out under 200ma/g shows, initially
Capacity is 137.8mah/g, reaches 86.1% for capability retention after 300 circulations.With the in-situ carbon obtaining under the conditions of 800 DEG C
Cladding hexagon k0.7[fe0.5mn0.5]o2As a example nano material, the constant current charge-discharge test result carrying out under 500ma/g shows,
After 250 circulations, its capacity is almost undamped, and the original position carbon coating hexagon k to obtain under the conditions of 600 DEG C0.7
[fe0.5mn0.5]o2As a example nano material, the constant current charge-discharge test result carrying out under 500ma/g shows, after its 100 times circulations
It is only 14.9% for capability retention.
As shown in figure 12, the original position carbon coating hexagon k obtaining under the conditions of 800 DEG C0.7[fe0.5mn0.5]o2Nano material
Under higher electric current density 1000ma/g, after 800 circulations, its capability retention is up to 78.2% respectively.
The original position carbon coating hexagon k of table 1 example 1 gained at different temperatures0.7[fe0.5mn0.5]o2Nano material
Icp test result
Embodiment 2:
1) by 3.5mmol k2co3、2.5mmol fe2(so4)3.9h2o、2.5mmol mn2co3With 2.0g citric acid in the lump
It is added in 20ml deionized water, stir at 25 DEG C and assume light yellow clear shape to solution；
2) by step 1) resulting solution moves on to 60 DEG C of stirred in water bath 6 hours again, obtains brownish red clear solution；
3) by step 2) resulting solution is transferred in culture dish, it is dried under 60 DEG C of constant temperature；
4) by step 3) solid of gained and then be quickly transferred to toast 10 hours under 120 DEG C of high temperature, obtain 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) move on to again and calcine 12 hours under the conditions of 600 DEG C of argon, obtain original position carbon coating hexagon k0.7
[fe0.5mn0.5]o2Nano material.
Original position carbon coating hexagon k with the present embodiment gained0.7[fe0.5mn0.5]o2As a example nano material, under 100ma/g
The constant current charge-discharge test result carrying out shows, its first discharge specific capacity up to 160.8ma/g, after 100 circulations, protect by capacity
Holdup reaches 88.2%.
Embodiment 3:
1) by 3.5mmol kno3、1.75mmol k2so4、2.5mmol fe(no3)3.9h2o、1.25mmolfe2(so4)3.7h2o、2.5mmol mn(ch3coo)2、1.25mmol mn2co3, 2.0g oxalic acid and 2.0g citric acid be added to 40ml in the lump and go
In ionized water, stir at 25 DEG C and assume light yellow clear shape to solution；
2) by step 1) resulting solution moves on to 50 DEG C of stirred in water bath 6 hours again, obtains brownish red clear solution；
3) by step 2) resulting solution is transferred in culture dish, it is dried under 90 DEG C of constant temperature；
4) by step 3) solid of gained and then be quickly transferred to toast 10 hours under 200 DEG C of high temperature, obtain 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) move on to again and calcine 10 hours under the conditions of 1000 DEG C of argon, obtain original position carbon coating hexagon k0.7
[fe0.5mn0.5]o2Nano material.
Original position carbon coating hexagon k with the present embodiment gained0.7[fe0.5mn0.5]o2As a example nano material, under 200ma/g
The constant current charge-discharge test result carrying out shows, its first discharge specific capacity, up to 137.8mah/g, is capacity after 300 circulations
Conservation rate reaches 86.1%.
Embodiment 4:
1) by 3.5mmol k2so4、2.5mmol fe2(so4)3.7h2o、2.5mmol mn2co3With 4.0g citric acid in the lump
It is added in 30ml deionized water, stir at 25 DEG C and assume light yellow clear shape to solution；
2) by step 1) resulting solution moves on to 80 DEG C of stirred in water bath 6 hours again, obtains brownish red clear solution；
3) by step 2) resulting solution is transferred in culture dish, it is dried under 75 DEG C of constant temperature；
4) by step 3) solid of gained and then be quickly transferred to toast 9 hours under 150 DEG C of high temperature, obtain porous solid knot
Structure；
5) by step 4) products therefrom grinding, then calcine 2.5 hours under 400 DEG C of air conditionses；
6) by step 5) move on to again and calcine 9 hours under the conditions of 800 DEG C of argon, obtain original position carbon coating hexagon k0.7
[fe0.5mn0.5]o2Nano material.
Original position carbon coating hexagon k with the present embodiment gained0.7[fe0.5mn0.5]o2As a example nano material, under 500ma/g
The constant current charge-discharge test result carrying out shows, its first discharge specific capacity up to 114.9mah/g, after 200 circulations, protect by capacity
Holdup reaches 92.3%.
Embodiment 5:
1) by 14.0mmol kno3、10.0mmol fe(no3)3.9h2o、10.0mmol mn(ch3coo)2With 5.0g Fructus Citri Limoniae
Acid is added in 40ml deionized water in the lump, stirs and assume light yellow clear shape to solution at 25 DEG C；
2) by step 1) resulting solution moves on to 50 DEG C of stirred in water bath 6 hours again, obtains brownish red clear solution；
3) by step 2) resulting solution is transferred in culture dish, it is dried under 80 DEG C of constant temperature；
4) by step 3) solid of gained and then be quickly transferred to toast 12 hours under 160 DEG C of high temperature, obtain 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) move on to again and calcine 12 hours under the conditions of 700 DEG C of argon, obtain original position carbon coating hexagon k0.7
[fe0.5mn0.5]o2Nano material.
Original position carbon coating hexagon k with the present embodiment gained0.7[fe0.5mn0.5]o2As a example nano material, under 100ma/g
The constant current charge-discharge test result carrying out shows, its first discharge specific capacity, up to 170.5mah/g, is capacity after 100 circulations
Conservation rate reaches 81.2%.
Embodiment 6:
1) by 7.0mmol kno3、2.5mmol fe2(so4)3.7h2o、2.5mmol mn2co3, 2.0g oxalic acid and 2.0g lemon
Lemon acid is added in 20ml deionized water in the lump, stirs and assume light yellow clear shape to solution at 25 DEG C；
2) by step 1) resulting solution moves on to 65 DEG C of stirred in water bath 6 hours again, obtains brownish red clear solution；
3) by step 2) resulting solution is transferred in culture dish, it is dried under 75 DEG C of constant temperature；
4) by step 3) solid of gained and then be quickly transferred to toast 12 hours under 170 DEG C of high temperature, obtain 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) move on to again and calcine 10.5 hours under the conditions of 900 DEG C of argon, obtain original position carbon coating hexagon k0.7
[fe0.5mn0.5]o2Nano material.
Original position carbon coating hexagon k with the present embodiment gained0.7[fe0.5mn0.5]o2As a example nano material, under 100ma/g
The constant current charge-discharge test result carrying out shows, its first discharge specific capacity up to 159.8mah/g, after 100 circulations, protect by capacity
Holdup reaches 80.9%.
Embodiment 7:
1) by 7.0mmol kno3、5.0mmol fe(no3)3.9h2o、5.0mmol mn(ch3coo)2With 8.0g oxalic acid one
And be added in 40ml deionized water, stir at 25 DEG C and assume light yellow clear shape to solution；
2) by step 1) resulting solution moves on to 80 DEG C of stirred in water bath 3 hours again, obtains brownish red clear solution；
3) by step 2) resulting solution is transferred in culture dish, it is dried under 70 DEG C of constant temperature；
4) by step 3) solid of gained and then be quickly transferred to toast 8 hours under 200 DEG C of high temperature, obtain porous solid knot
Structure；
5) by step 4) products therefrom grinding, then calcine 3 hours under 300 DEG C of air conditionses；
6) by step 5) move on to again and calcine 10 hours under the conditions of 800 DEG C of argon, obtain original position carbon coating hexagon k0.7
[fe0.5mn0.5]o2Nano material.
Original position carbon coating hexagon k with the present embodiment gained0.7[fe0.5mn0.5]o2As a example nano material, under 100ma/g
The constant current charge-discharge test result carrying out shows, its first discharge specific capacity up to 167.2mah/g, after 100 circulations, protect by capacity
Holdup reaches 82.7%.
Claims (7)
1. original position carbon coating hexagon k0.7[fe0.5mn0.5]o2The preparation method of nano material, comprises the steps:
1) potassium resource, source of iron, manganese source and carbon source are added in deionized water in the lump, stir at a certain temperature present to solution shallow
Yellow transparent shape；Described carbon source is any one or their mixing in oxalic acid and citric acid；
2) by step 1) resulting solution moves on to stirred in water bath again, obtains brownish red clear solution；
3) by step 2) resulting solution is transferred in culture dish, is evaporated at a constant temperature；
4) by step 3) solid of gained and then be quickly transferred to baking under high temperature, baking temperature is 120-200 DEG C, obtains loose
Solid structure；
5) by step 4) products therefrom grinding, then calcine under air conditionses；Described calcining heat is 200-500 DEG C, when
Between be 2-4 hour；
6) by step 5) products therefrom moves on to and calcines under the conditions of argon, and described calcining heat is 600-1000 DEG C, and the time is
8-12 hour, obtains original position carbon coating hexagon k0.7[fe0.5mn0.5]o2Nano material.
2. original position carbon coating hexagon k according to claim 10.7[fe0.5mn0.5]o2The preparation method of nano material, its
Be characterised by: step 1) described in potassium resource be kno3、k2co3、k2so4With any one in kcl or their mixing；Described
Source of iron is fe (no3)3·9h2O and fe2(so4)3·7h2Any one in o or their mixing；Described manganese source is mn
(ch3coo)2And mnco3In any one or their mixing.
3. original position carbon coating hexagon k according to claim 20.7[fe0.5mn0.5]o2The preparation method of nano material, its
It is characterised by: described potassium resource, source of iron, manganese source are joined for 7:5:5 according to k:fe:mn elemental mole ratios and taken；Step 1) described solution
Middle k+Ion concentration range is 7/20-7/10mol/l.
4. original position carbon coating hexagon k according to claim 10.7[fe0.5mn0.5]o2The preparation method of nano material, its
Be characterised by: step 2) described in bath temperature be 50-80 DEG C；Step 3) described in constant temperature under temperature be 60-90 DEG C.
5. original position carbon coating hexagon k according to claim 40.7[fe0.5mn0.5]o2The preparation method of nano material, its
Be characterised by: step 1) described in mixing time be 2-6 hour；Step 2) described in mixing time 6-12 hour；Step 3) institute
The time that is evaporated stated is 8-12 hour；Step 4) described in baking time be 8-12h.
6. the original position carbon coating hexagon k of the preparation method gained described in a kind of any one by claim 1-50.7
[fe0.5mn0.5]o2Nano material, coats k by graphitization carbon-coating0.7[fe0.5mn0.5]o2The nanocrystalline formation of hexagon, described six
The nanocrystalline a diameter of 100-350nm of side shape, the wherein thickness of graphitization carbon-coating are 6-10nm.
7. the original position carbon coating hexagon k described in claim 60.7[fe0.5mn0.5]o2Nano material is as sodium-ion battery positive pole
The application of active material.
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