CN108807930A - Ternary oxide/graphene-based combination electrode material preparation method and application - Google Patents
Ternary oxide/graphene-based combination electrode material preparation method and application Download PDFInfo
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- H—ELECTRICITY
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The present invention discloses a kind of ternary oxide/graphene-based combination electrode material preparation method and application, combination electrode material includes graphene, and further include ternary oxide particle, the surface of ternary oxide particle is coated completely by graphene, and composite material granular is assembled by graphene link between multiple ternary oxide particles.A kind of anode, including the composite material.The combination electrode material is applied in sodium-ion battery.Preparation method：By MnO2、NaF、Fe2O3, NiO and Na2CO3Ball milling is shaken by dry method, then the ternary material of fluorine doped is obtained by the reaction under high temperature air atmosphere, ternary material/graphene composite material of micro-nano structure is then obtained by surface graphene coated, assembling.Preparation method is simply controllable, and low energy consumption, at low cost, is suitable for large-scale industrial production.The result shows that the composite material material for the micro-nano structure being prepared has high capacity, sodium-ion battery field can be applied to.
Description
Technical field
The present invention relates to the technical fields of sodium-ion battery electrode material, and in particular to a kind of ternary oxide/graphite
Alkenyl combination electrode material preparation method and application.
Background technology
With society, expanding economy, energy consumption increasingly aggravates, and traditional fossil energy is constantly reduced, and the mankind are to tradition
While the consumption of fossil energy, cause environmental pollution serious, it is cleaning, renewable, cheap novel under this overall situation
The energy become national governments' exploitation to picture, the proportion of wind energy, solar energy and ocean energy in energy consumption is constantly increasing at present
Add, but these regenerative resources are affected by weather and period, there is apparent unstable, discontinuous and uncontrollable spy
Property, it needs to develop and build mating electric energy storage (energy storage) device i.e. battery to ensure the continuity and stabilization of power generation, power supply
Property, and large-scale battery energy storage is used for " peak load shifting " of electric power in power industry, it will significantly improve the confession of electric power
Contradiction is needed, the utilization rate of generating equipment is improved.Requirement of the large-scale energy-storage battery to electrode material has certain energy density, longevity
Outside life, safety have higher requirements, to cost, higher requirements are also raised.Lead-acid battery is although at low cost, but its raw material master
To be lead and sulfuric acid, there are environment easy to pollute, service life enable it is short, there are memory effect, battery weight greatly there is also transport at
This high problem；Although lithium ion battery has many advantages, such as that energy density is big, service life is long and memory-less effect,
Lithium raw material reserves are limited, and lithium ion battery is of high cost, and security performance is bad, in the long run, cannot meet extensive energy storage
It is required that.Compared with lithium ion battery, sodium-ion battery is resourceful, has a safety feature, and at low cost, environmentally friendly etc.
Advantage is very suitable for extensive stored energy application.Due to cheap, synthesis is easy the ternary oxide of stratiform, has high reason
By capacity, receive extensively note that but such oxide active it is relatively low, cycle performance is undesirable.
Invention content
Based on the above shortcoming, the present invention provides a kind of its preparation of ternary oxide/graphene-based combination electrode material
Methods and applications, the combination electrode material have high power capacity and excellent cyclical stability, can be used as the anode of sodium-ion battery
Materials'use.
The technology used in the present invention is as follows：A kind of ternary oxide/graphene-based combination electrode material, including graphite
Alkene, and further include ternary oxide particle, the surface of ternary oxide particle is coated completely by graphene, multiple ternary oxidations
It is linked by graphene between composition granule, to be assembled into composite material granular.
The present invention also has following technical characteristic：
1, the grain diameter of composite material as described above is 1~5 μm, is conducive to the stabilization of product structure, and reduce
By the corrosion of electrolyte, to improve cycle performance, the ternary oxide grain diameter that surface is coated with graphene is 200~
300nm；Be conducive to the raising of product electro-chemical activity.
2, ternary oxide particle as described above is the O3 type layer structures of fluorine doped, and chemical general formula is
NaNixFeyMn1-x-yO2-zFz, wherein 0.2≤x≤0.4,0.3≤y≤0.6,0 z≤0.2 <.
3, graphene as described above is single-layer graphene.
4, a kind of anode, including a kind of ternary oxide/graphene-based combination electrode material as described above.
5, a kind of ternary oxide/graphene-based combination electrode material is applied in sodium-ion battery.
6, a kind of preparation method of grapheme composite positive electrode material, includes the following steps：
1) according to target product NaNixFeyMn1-x-yO2-zFz, wherein 0.2≤x≤0.4,0.3≤y≤0.6,0 z≤0.2 <,
By the MnO of stoichiometric ratio2、Fe2O3, NiO, NaF and Na2CO3It is uniform by dry method concussion ball milling mixing, then in 2MPa pressure
It is lower that powder is pressed into block；
2) by obtained block mixture pre-burning under air atmosphere, room temperature is then cooled to the furnace；
3) by after gained pre-burning object tentatively grinding, second of concussion ball milling is carried out, then by powder pressure under 2MPa pressure
At block；
4) what gained block pre-burning object was carried out to calcination under air atmosphere obtains the ternary oxide particle of Fluorin doped；
5) it is 1 by weight by the ternary oxide particle of graphene and the Fluorin doped of gained:5~1:15, through carrying out the
Ball milling is shaken three times, obtains ternary oxide/graphene-based composite positive pole.
Preferably, in step 1), the frequency for shaking ball milling is 15~25Hz, and the time is 1~5 hour, rational ball milling
Frequency and time are conducive to being uniformly mixed for raw material, are conducive to subsequently obtain uniform product, pressed powder can promote solid phase anti-
The uniformity of the progress and product answered.
Preferably, in step 2), heating rate is 2~10 DEG C/min, and calcined temperature is 300~500 DEG C, when pre-burning
Between be 2~10 hours；Rational heating rate, calcined temperature and time are conducive to obtain uniform pre-burning product, to obtain
Uniform final product, and these calcination parameters are to be mutually related.
Preferably, in step 3), second of concussion ball milling is carried out to pre-burning product, ball milling frequency is 15~25Hz, when
Between be 1~5 hour, and to ball milling product carry out compressing tablet process can promote the progress of solid phase reaction, favorably by handling above
In obtaining uniform product.
Preferably, in step 4), heating rate is 2~10 DEG C/min, and calcination temperature is 850~950 DEG C, when calcination
Between be 10~15 hours, too low temperature and too short disadvantage in time are in the formation of product, excessively high temperature and long time
Product grain will be caused excessive and the burning of sodium is lost, and these calcination parameters are to be mutually related, any deviation above-mentioned parameter is incited somebody to action
Less than the stratiform ternary oxide haveing excellent performance.
Preferably, in step 5), the frequency for shaking ball milling is 15~25Hz, and the time is 1~5 hour, control ball milling frequency
Rate and time are conducive to ternary oxide surface completely, uniformly coat.
Preferably, in the combination electrode material, the weight ratio of the ternary oxide particle of graphene and Fluorin doped is
1:8~1:12, excessively high graphene content will reduce the density and energy density per unit volume metric density of composite material, and to product electric conductivity
Influence little, too low graphene content will be unfavorable for improving the electric conductivity of product and ternary oxide cannot be carried out completely,
Uniformly cladding.
In the present invention, the graphene is commercialized graphene, is prepared using oxidation-reduction method, graphene surface contains
Oxygen-containing functional group, such as hydroxyl, carboxyl, epoxy group, graphene can be single layer, bilayer or few layer graphene.Preferably, described
Graphene is selected from single-layer graphene, and compared to double-deck or few layer graphene, single-layer graphene has better mechanical strength, can be with
Equably, fully to ternary oxide carry out surface cladding without rupture, can effectively inhibit particle directly with electrolysis
The contact of liquid, to inhibit the dissolving of manganese, iron, nickel to improve cycle life；Relative to double-deck or few layer graphene, sodium ion is more
It is easy to pass through from the fault location of single-layer graphene, into electrolyte, to be more advantageous to the activity for improving composite material.In addition,
The conductivity of single-layer graphene is higher, can improve the electro-chemical activity of composite material.Preferably, ternary oxide surface quilt
Graphene completely, uniformly coats.
Preferably, ternary oxide is the O3 type stratiform ternary oxides of fluorine doped, chemical general formula is that chemical general formula is
NaNixFeyMn1-x-yO2-zFz, wherein 0.2≤x≤0.4,0.3≤y≤0.6,0 z≤0.2 <；Further preferably 0.05 < z≤
0.15, rational Fluorin doped amount is conducive to improve the electro-chemical activity and structural stability of ternary oxide, is also beneficial to pass through
The interaction of oxygen-containing functional group, preferably compound with graphene in fluorine and graphene.
The invention has the advantages that and advantageous effect：
1, the present invention prepares graphene-based combination electrode material using concussion ball milling combination solid phase reaction, has simple for process
Controllably, at low cost, the advantages that period is short, low energy consumption and suitable industrialized production.
2, combination electrode material prepared by the present invention, nano grain surface of ternary oxide are complete by graphene, equal
On the one hand even cladding is conducive to improve the conductivity of composite material, and can prevent the dissolving of Mn, Fe, Ni in the electrolytic solution.Fluorin doped
Be conducive to the raising of product electro-chemical activity and the stability of structure, to improve the capacity and cycle life of product.
3, graphene-based combination electrode material prepared by the present invention, graphene can be assembled into micron order by one of sodium rice grade
Second particle, contact of the active material with electrolyte can be further decreased, reduce the generation of side reaction, be conducive to improve follow
The ring service life, and be conducive to the raising of energy density per unit volume metric density.
Description of the drawings
Fig. 1 is the X ray diffracting spectrum (XRD) of graphene-based composite positive pole prepared by embodiment 1；
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM) of graphene-based composite positive pole prepared by embodiment 1；
Fig. 3 is the transmission electron microscope picture (TEM) of graphene-based composite positive pole prepared by embodiment 1；
Fig. 4 is the charge and discharge electrograph of graphene-based composite positive pole prepared by embodiment 1.
Specific implementation mode
Below according to Figure of description citing, the present invention will be further described：
Embodiment 1
By NaNi1/3Fe1/3Mn1/3O1.95F0.05Target product, by the MnO of stoichiometric ratio2、NaF、Fe2O3, NiO and
Na2CO3(Na2CO3It is excessive that ball milling 2.5%) is shaken 3 hours by dry method, frequency 20Hz is shaken, then by powder under 2MPa pressure
End is pressed into block；Above-mentioned block mixture is placed in tube furnace, is warming up to 5 DEG C/min of heating rate under air atmosphere
400 DEG C, and pre-burning 4 hours at 400 DEG C, then cool to room temperature with the furnace；After above-mentioned gained pre-burning object tentatively grinding, carry out
Concussion ball milling 3 hours for the second time, shakes frequency 20Hz, powder is then pressed into block under 2MPa pressure；Above-mentioned block is pre-
It burns object to be placed in tube furnace, 900 DEG C, and the calcination 12 at 900 DEG C is warming up to 5 DEG C/min of heating rate under air atmosphere
Hour, then cool to room temperature with the furnace；By the ternary oxide of above-mentioned Fluorin doped and graphene by weight 10:1 mixing, through into
Row third time concussion ball milling 3 hours, shakes frequency 20Hz, obtains graphene-based composite positive pole.
The X ray diffracting spectrum and scanning electron microscope (SEM) photograph of gained composite material are respectively such as Fig. 1-2, the wherein diffraction maximum of X-ray
Ternary oxide material can be attributed to, graphene is due to the uniform cladding and content is relatively low on ternary material, not in XRD
Display.Composite material second particle size is 1~5 μm.As shown in figure 3, from transmission electron microscope it is found that ternary material primary particle ruler
Very little is 200~300nm, and graphene completely, is uniformly coated in ternary material particle surface.
Electrochemical property test is carried out using gained composite material as sodium-ion battery positive material, current density is
10mA/g, voltage range are 2~4 volts, the use of electrolyte are 1mol/L NaPF6EC/DMC solution, diaphragm is glass fibre.
The cycle performance figure of resulting materials is as shown in figure 4, test shows that the capacity of the material for 118mAh/g or more, is shown higher
Capacity.
Comparative example 1
The preparation of material such as embodiment 1 is a difference in that in preparation process without introducing graphene.Studies have shown that at this time
The primary particle size of ternary material is micron order, through electro-chemical test, when not having to introduce graphene, identical test condition
Under, capacity is less than 100mAh/g.
Comparative example 2
The preparation of material such as embodiment 1 is a difference in that in preparation process without carrying out Fluorin doped.Studies have shown that at this time
The binding force of graphene and ternary material is weaker, and electro-chemical test shows the sample relatively adulterated, and the capacity undoped with sample is less than
110mAh/g or more.
Comparative example 3
The preparation of material such as embodiment 1 is a difference in that calcination temperature is 1000 DEG C, under higher calcination temperature, stone
Black alkene surface oxygen-containing functional group removal ratio more thoroughly, it is weaker with the binding force of ternary material, in addition, under high temperature sodium burning mistake compared with
More, the capacity of gained sample is less than 100mAh/g.
Comparative example 4
The preparation of material such as embodiment 1, not by concussion ball milling when difference raw material mixes, also without carrying out tabletting
And preheating, products therefrom contain dephasign, capacity is less than 100mAh/g.
Embodiment 2
By NaNi0.25Fe0.50Mn0.25O1.90F0.10Target product, by the MnO of stoichiometric ratio2、NaF、Fe2O3, NiO and
Na2CO3(Na2CO3It is excessive that ball milling 2.5%) is shaken 3 hours by dry method, frequency 20Hz is shaken, then by powder under 2MPa pressure
End is pressed into block；Above-mentioned block mixture is placed in tube furnace, is warming up to 5 DEG C/min of heating rate under air atmosphere
400 DEG C, and pre-burning 4 hours at 400 DEG C, then cool to room temperature with the furnace；After above-mentioned gained pre-burning object tentatively grinding, carry out
Concussion ball milling 3 hours for the second time, shakes frequency 20Hz, powder is then pressed into block under 2MPa pressure；Above-mentioned block is pre-
It burns object to be placed in tube furnace, 850 DEG C, and the calcination 15 at 850 DEG C is warming up to 5 DEG C/min of heating rate under air atmosphere
Hour, then cool to room temperature with the furnace；By the ternary oxide of above-mentioned Fluorin doped and graphene by weight 12:1 mixing, through into
Row third time concussion ball milling 3 hours, shakes frequency 20Hz, obtains graphene-based composite positive pole.Secondary of composite material
Particle size is 1~5 μm, and the second particle size of ternary material is 200~300nm, and graphene is complete in ternary material particle surface
Entirely, it uniformly coats.Test shows that the capacity of the material is 140mAh/g, shows higher capacity.
Embodiment 3
By NaNi0.40Fe0.30Mn0.30O1.85F0.15Target product, by the MnO of stoichiometric ratio2、NaF、Fe2O3, NiO and
Na2CO3(Na2CO3It is excessive that ball milling 2.5%) is shaken 3 hours by dry method, frequency 20Hz is shaken, then by powder under 2MPa pressure
End is pressed into block；Above-mentioned block mixture is placed in tube furnace, is warming up to 5 DEG C/min of heating rate under air atmosphere
400 DEG C, and pre-burning 4 hours at 400 DEG C, then cool to room temperature with the furnace；After above-mentioned gained pre-burning object tentatively grinding, carry out
Concussion ball milling 3 hours for the second time, shakes frequency 20Hz, powder is then pressed into block under 2MPa pressure；Above-mentioned block is pre-
It burns object to be placed in tube furnace, 950 DEG C, and the calcination 10 at 950 DEG C is warming up to 5 DEG C/min of heating rate under air atmosphere
Hour, then cool to room temperature with the furnace；By the ternary oxide of above-mentioned Fluorin doped and graphene by weight 8:1 mixing, through into
Row third time concussion ball milling 3 hours, shakes frequency 20Hz, obtains graphene-based composite positive pole.Secondary of composite material
Particle size is 1~5 μm, and the second particle size of ternary material is 200~300nm, and graphene is complete in ternary material particle surface
Entirely, it uniformly coats.Test shows that the capacity of the material is 130mAh/g, shows higher capacity.
Embodiment 4
A kind of preparation method of ternary oxide/graphene-based combination electrode material, steps are as follows：
1) according to target product NaNixFeyMn1-x-yO2-zFz, wherein 0.2≤x≤0.4,0.3≤y≤0.6,0 z≤0.2 <,
By the MnO of stoichiometric ratio2、Fe2O3, NiO, NaF and Na2CO3It is uniform by dry method concussion ball milling mixing, shake the frequency of ball milling
For 25Hz, the time is 1 hour, and powder is then pressed into block under 2MPa pressure；
2) by obtained block mixture pre-burning under air atmosphere, heating rate is 10 DEG C/min, and calcined temperature is
500 DEG C, burn-in time is 2 hours, then cools to room temperature with the furnace；
3) by after gained pre-burning object tentatively grinding, second of concussion ball milling is carried out, the frequency for shaking ball milling is 25Hz, time
It is 1 hour, powder is then pressed into block under 2MPa pressure；
4) what gained block pre-burning object was carried out to calcination under air atmosphere obtains the ternary oxide particle of Fluorin doped, calcination
Temperature is 850 DEG C, and calcination time is 15 hours, and heating rate is 10 DEG C/min；
5) it is 1 by weight by the O3 type layer structure ternary oxides particle of graphene and the Fluorin doped of gained:5, warp
Third time concussion ball milling is carried out, the frequency for shaking ball milling is 25Hz, and the time is 1 hour, obtains ternary oxide/graphene-based multiple
Close positive electrode.
Embodiment 5
A kind of preparation method of ternary oxide/graphene-based combination electrode material, steps are as follows：
1) according to target product NaNixFeyMn1-x-yO2-zFz, wherein 0.2≤x≤0.4,0.3≤y≤0.6,0 z≤0.2 <,
By the MnO of stoichiometric ratio2、Fe2O3, NiO, NaF and Na2CO3It is uniform by dry method concussion ball milling mixing, shake the frequency of ball milling
For 15Hz, the time is 5 hours, and powder is then pressed into block under 2MPa pressure；
2) by obtained block mixture pre-burning under air atmosphere, heating rate is 2 DEG C/min, calcined temperature 300
DEG C, burn-in time is 10 hours, then cools to room temperature with the furnace；
3) by after gained pre-burning object tentatively grinding, second of concussion ball milling is carried out, the frequency for shaking ball milling is 15Hz, time
It is 5 hours, powder is then pressed into block under 2MPa pressure；
4) what gained block pre-burning object was carried out to calcination under air atmosphere obtains the ternary oxide particle of Fluorin doped, calcination
Temperature is 950 DEG C, and calcination time is 10 hours, and heating rate is 2 DEG C/min；
5) it is 1 by weight by the ternary oxide particle of graphene and the Fluorin doped of gained:15, through carrying out third time shake
Ball milling is swung, the frequency for shaking ball milling is 15Hz, and the time is 5 hours, obtains ternary oxide/graphene-based composite positive pole.
Claims (10)
1. a kind of ternary oxide/graphene-based combination electrode material, including graphene, which is characterized in that further include ternary oxygen
The surface of compound particle, ternary oxide particle is coated completely by graphene, by graphene between multiple ternary oxide particles
Link, to be assembled into composite material granular.
2. a kind of ternary oxide according to claim 1/graphene-based combination electrode material, which is characterized in that described
Composite material grain diameter be 1~5 μm, surface be coated with graphene ternary oxide grain diameter be 200~
300nm。
3. a kind of ternary oxide according to claim 1/graphene-based combination electrode material, which is characterized in that described
Ternary oxide be fluorine doped O3 type layer structures, chemical general formula NaNixFeyMn1-x-yO2-zFz, wherein 0.2≤x≤0.4,
0.3≤y≤0.6,0 z≤0.2 <.
4. a kind of ternary oxide according to claim 1/graphene-based composite positive pole, which is characterized in that described
Graphene be single-layer graphene.
5. a kind of anode, it is characterised in that：The anode includes one kind three according to any one of claim 1~2
First oxide/graphene-based combination electrode material.
6. according to a kind of ternary oxide of claim 1~2 any one of them/graphene-based combination electrode material in sodium ion
It is applied in battery.
7. a kind of system according to a kind of ternary oxide of claim 1~2 any one of them/graphene-based combination electrode material
Preparation Method, which is characterized in that steps are as follows：
1) according to target product NaNixFeyMn1-x-yO2-zFz, wherein 0.2≤x≤0.4,0.3≤y≤0.6,0 z≤0.2 <, will change
Learn the MnO of metering ratio2、Fe2O3, NiO, NaF and Na2CO3It is uniform by dry method concussion ball milling mixing, it then will under 2MPa pressure
Powder is pressed into block；
2) by obtained block mixture pre-burning under air atmosphere, room temperature is then cooled to the furnace；
3) by after gained pre-burning object tentatively grinding, second of concussion ball milling is carried out, powder is then pressed into block under 2MPa pressure
Body；
4) what gained block pre-burning object was carried out to calcination under air atmosphere obtains the ternary oxide particle of Fluorin doped；
5) it is 1 by weight by the ternary oxide particle of graphene and the Fluorin doped of gained:5~1:15, through carrying out third time
Ball milling is shaken, ternary oxide/graphene-based composite positive pole is obtained.
8. a kind of preparation method of ternary oxide according to claim 7/graphene-based combination electrode material, feature
It is, in step 1) and step 3), the frequency for shaking ball milling is 15~25Hz, and the time is 1~5 hour；In step 5), ball is shaken
The frequency of mill is 15~25Hz, and the time is 1~5 hour.
9. a kind of preparation method of ternary oxide according to claim 7/graphene-based combination electrode material, feature
It is, in step 2), heating rate is 2~10 DEG C/min, and calcined temperature is 300~500 DEG C, and burn-in time is 2~10 small
When.
10. a kind of preparation method of ternary oxide according to claim 7/graphene-based combination electrode material, special
Sign is, in step 4), heating rate is 2~10 DEG C/min, and calcination temperature is 850~950 DEG C, and calcination time is 10~15
Hour.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110838581A (en) * | 2019-11-22 | 2020-02-25 | 中山大学 | Nickel oxide/fourth-period transition metal oxide/graphene ternary composite electrode material and preparation method thereof |
| CN111924898A (en) * | 2020-08-10 | 2020-11-13 | 苏州科技大学 | Sodium ion battery NaFe with good circulation stability1/3Ni1/3Ti1/3O2Rapid homogeneous phase synthesis method of anode material |
| CN112968165A (en) * | 2020-12-31 | 2021-06-15 | 天津中电新能源研究院有限公司 | Modified sodium ion positive electrode material, modified sodium ion electrode and preparation method |
| CN115448321A (en) * | 2022-09-29 | 2022-12-09 | 惠州亿纬锂能股份有限公司 | Layered oxide material and preparation method and application thereof |
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