CN109524649A - A kind of sodium-ion battery positive material of clad structure and its preparation method and application - Google Patents
A kind of sodium-ion battery positive material of clad structure and its preparation method and application Download PDFInfo
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- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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Abstract
The invention discloses sodium-ion battery positive materials of a kind of clad structure and its preparation method and application, which comprises choose/prepare covering liquid；It include the cladding presoma being made of metal salt and/or its hydrate in the covering liquid；The positive electrode of required cladding is put into cladding furnace, it is warming up to 200-1000 degree, it carries the covering liquid using compressed air or nitrogen or argon gas to enter in the cladding furnace, the cladding presoma is decomposed thermally to form oxide, is evenly coated at the surface of the positive electrode；Positive electrode obtained with oxide cladding layers is taken out to get the sodium-ion battery positive material of the clad structure is arrived.
Description
Technical field
The present invention relates to lithium battery material technical field more particularly to a kind of sodium-ion battery positive materials of clad structure
And its preparation method and application.
Background technique
The energy is the basis of social development, and secondary cell has played important function, lithium ion in the development of human society
Battery is widely applied because of its high-energy density, high power density.It today of lithium ion battery large-scale application, exposes
The problem of lithium resource and its common transition metal resource shortage.Lithium resource belongs to scarce resource, and distribution on global is extremely uneven
Weighing apparatus is the similar the same strategic resource of petroleum., working principle resourceful based on sodium and processing technology are consistent with lithium ion battery
Etc. characteristics, sodium-ion battery be considered as the useful supplement of the following lithium ion battery.
In recent years, increasingly abundant to the research of sodium-ion battery, and it has also come into industrialization initial stage.Most ground
The positive electrode system for studying carefully personnel's approval is layer structure material, because its gram volume is high, energy density is high, processing technology letter
It is single.But layer structure material is faced with and recycles unstable disadvantage, therefore method of the researcher by being coated to it
Improve its cycle performance, achieves certain achievement.
The interface of positive electrode and electrolyte after cladding is improved, and stabilizes structure, so being able to ascend
Cycle performance.Existing material coating method has two kinds of solid phase method, liquid phase method substantially.Solid phase method, which is faced with, coats non-uniform ask
Topic, also difficulty accomplishes to coat comprehensively；And liquid phase rule brings waste water, and the technology difficulty dried improves material cost,
Therefore method for coating needs to be improved.
Summary of the invention
The present invention provides sodium-ion battery positive materials of a kind of clad structure and its preparation method and application, by making
With vapour deposition process come clad anode material, so that cladding process is simpler, covered effect more preferably more evenly, more meets industrialization
Production.The interface that positive electrode is optimized after cladding promotes the cyclical stability of sodium-ion battery.
In a first aspect, the embodiment of the invention provides a kind of preparation sides of the sodium-ion battery positive material of clad structure
Method, comprising:
Choose/prepare covering liquid；It include the cladding forerunner being made of metal salt and/or its hydrate in the covering liquid
Body；
The positive electrode of required cladding is put into cladding furnace, is warming up to 200-1000 degree, using compressed air or nitrogen or
Argon gas carries the covering liquid and enters in the cladding furnace, and the cladding presoma is decomposed thermally to form oxide, uniformly coats
On the surface of the positive electrode；
Positive electrode obtained with oxide cladding layers is taken out to get the sodium-ion battery of the clad structure is arrived
Positive electrode.
Preferably, the cladding furnace is rotation atmosphere furnace.
Preferably, the required positive electrode coated is NaxM1aM2bO2；
Wherein, 0.6<x≤1, a>0, b>=0, a+b=1, and keep material electroneutral；M1 is metallic element, including Li,
One or more of Mg, Al, Ti, Mn, Fe, Co, Ni, Cu, Zn, Sn；M2 is one of nonmetalloid, including B, F, Si
Or it is several.
Preferably, the covering liquid for preparing specifically includes: presoma solid material being dissolved in corresponding solvent, described in formation
Covering liquid；
Wherein, the solvent includes: one or more of water, ethyl alcohol, N-Methyl pyrrolidone, acetone.
Preferably, the selection covering liquid specifically includes: using liquid cladding presoma as the covering liquid.
Preferably, the positive electrode by obtained with oxide cladding layers takes out to get the clad structure is arrived
Sodium-ion battery positive material specifically:
The positive electrode by obtained with oxide cladding layers takes out, and arrives the packet except iron by screening
Cover the sodium-ion battery positive material of structure.
Preferably, the metal salt and/or its hydrate specifically include:
The nitrate and its hydrate of Al, Mg, Ti, Zn, Zr, Nb or La, sulfate and its hydrate, one in organic salt
Kind is several.
Second aspect, the embodiment of the invention provides the sodium that preparation method described in a kind of above-mentioned first aspect is prepared
Ion battery positive electrode, sodium-ion battery positive material include: Layered Structural Positive Electrode Materials kernel and clad；
Layered structure positive electrode kernel is NaxM1aM2bO2, 0.6<x≤1, a>0, b>=0, a+b=1, and keep
Material electroneutral；M1 is one or more of metallic element, including Li, Mg, Al, Ti, Mn, Fe, Co, Ni, Cu, Zn, Sn；M2
For one or more of nonmetalloid, including B, F, Si；
The clad is the oxygen of Al, Mg, Ti, Zn, Zr, Nb or La for being coated on except Layered Structural Positive Electrode Materials kernel
Compound shell；
Wherein, in the sodium-ion battery positive material, the mass percent of the clad is 0.05%-20%.
The third aspect, the embodiment of the invention provides a kind of sodium ion secondary batteries, including described in above-mentioned second aspect
Sodium-ion battery positive material.
Fourth aspect, the embodiment of the invention provides a kind of purposes of sodium ion secondary battery described in above-mentioned third aspect,
The secondary cell is for electric tool, electric vehicle and solar power generation, wind-power electricity generation, smart grid peak regulation, distribution electricity
It stands, the energy storage device of backup power supply or communication base station.
The preparation method of the sodium-ion battery positive material of clad structure of the present invention is coated by using vapour deposition process
Positive electrode, so that cladding process is simpler, covered effect more preferably more evenly, more meets industrialized production.It is optimized after cladding
The interface of positive electrode promotes the cyclical stability of sodium-ion battery.Using the sodium ion electricity of positive electrode made from this method
Chi Zhong can be not only used for the power supply of electric tool and electric car, can be also used for solar power generation, wind-power electricity generation, intelligence
Peak load regulation network, the extensive energy storage device for being distributed power station, backup power supply or communication base station.
Detailed description of the invention
Below by drawings and examples, the technical solution of the embodiment of the present invention is described in further detail.
Fig. 1 is the preparation method schematic diagram of clad structure positive electrode described in embodiment 1；
Fig. 2 is the preparation method flow chart of clad structure positive electrode described in embodiment 1；
Fig. 3 is the SEM shape appearance figure of 2 chinese raw materials 1 of embodiment；
Fig. 4 is the SEM shape appearance figure of covering material 1 in embodiment 2；
Fig. 5 is the charge and discharge cycles figure of 2 chinese raw materials 1 of embodiment；
Fig. 6 is the charge and discharge cycles figure of covering material 1 in embodiment 2；
Fig. 7 is the SEM shape appearance figure of 3 chinese raw materials 2 of embodiment；
Fig. 8 is the SEM shape appearance figure of covering material 2 in embodiment 3；
Fig. 9 is the charge and discharge cycles figure of 3 chinese raw materials 2 of embodiment；
Figure 10 is the charge and discharge cycles figure of covering material 2 in embodiment 3；
Figure 11 is the SEM shape appearance figure of 4 chinese raw materials 3 of embodiment；
Figure 12 is the SEM shape appearance figure of covering material 3 in embodiment 4；
Figure 13 is the charge and discharge cycles figure of 4 chinese raw materials 3 of embodiment；
Figure 14 is the charge and discharge cycles figure of covering material 3 in embodiment 4.
Specific embodiment
Below with reference to embodiment, the present invention is further described in detail, but is not intended to limit guarantor of the invention
Protect range.
The embodiment of the present invention 1 provide a kind of sodium-ion battery positive material include: Layered Structural Positive Electrode Materials kernel and
Clad；
Layered Structural Positive Electrode Materials kernel is NaxM1aM2bO2, 0.6<x≤1, a>0, b>=0, a+b=1, and keep material
Electroneutral；M1 is one or more of metallic element, including Li, Mg, Al, Ti, Mn, Fe, Co, Ni, Cu, Zn, Sn；M2 is non-
One or more of metallic element, including B, F, Si；
Clad is the oxide of Al, Mg, Ti, Zn, Zr, Nb or La for being coated on except Layered Structural Positive Electrode Materials kernel
Shell；
Wherein, in sodium-ion battery positive material, the mass percent of clad is 0.05%-20%.
Above-mentioned material can be made by being illustrated in fig. 1 shown below method, be passed through in covering liquid by gas, carry covering liquid to gas
In atmosphere furnace, so that cladding presoma is thermally decomposed, positive electrode is coated.Its specific preparation method can be such as Fig. 2 institute
Shown in the flow chart shown, specifically comprise the following steps:
Step 110, choose/prepare covering liquid；
Specifically, include the cladding presoma being made of metal salt and/or its hydrate in covering liquid, wherein metal salt
And/or its hydrate be preferably the nitrate and its hydrate of Al, Mg, Ti, Zn, Zr, Nb or La, sulfate and its hydrate,
One or more of organic salt；
In this step, it can be directly using liquid cladding presoma as covering liquid, or with presoma solid material
It is dissolved in corresponding solvent and forms covering liquid.Solvent may include: one of water, ethyl alcohol, N-Methyl pyrrolidone, acetone or several
Kind, preferably water.
Step 120, the positive electrode of required cladding is put into cladding furnace, is warming up to 200-1000 degree, utilizes compressed air
Or nitrogen or argon gas carry covering liquid and enter in cladding furnace, cladding presoma is decomposed thermally to form oxide, is evenly coated at just
The surface of pole material；
Specifically, the positive electrode of required cladding is NaxM1aM2bO2；Wherein, 0.6<x≤1, a>0, b>=0, a+b=1,
And keep material electroneutral；M1 be one of metallic element, including Li, Mg, Al, Ti, Mn, Fe, Co, Ni, Cu, Zn, Sn or
It is several；M2 is one or more of nonmetalloid, including B, F, Si.
Furnace is coated preferably using the atmosphere furnace for having rotation function, as rotation atmosphere furnace.
Step 130, the positive electrode by obtained with oxide cladding layers takes out to get the sodium ion of clad structure is arrived
Cell positive material.
Preferably, after the positive electrode coated with oxide layer takes out, also iron is removed by screening, to further increase
Product quality.
The preparation method of the sodium-ion battery positive material of clad structure of the present invention is coated by using vapour deposition process
Positive electrode.The method for coating combines conventional vapor deposition method, has achieved the effect that material surface uniformly coats.By simple
Thermal decomposition, form oxide cladding layers on the surface of the material, covering amount is simply controllable, and clad is uniform, is very suitable to industrialize
It produces and uses.
The interface that positive electrode is optimized after cladding promotes the cyclical stability of sodium-ion battery.It is made using this method
Positive electrode sodium-ion battery in, can be not only used for the power supply of electric tool and electric car, can be also used for the sun
It can power generation, wind-power electricity generation, smart grid peak regulation, the extensive energy storage device for being distributed power station, backup power supply or communication base station.
Preparation below with some specific embodiments, to doping type cladding sodium-ion battery positive material of the invention
Journey, material characteristics, performance etc. are described in detail.
Embodiment 2
Firstly, choose positive electrode be Na0.9Cu0.22Fe0.30Mn0.48O2, raw material 1 are denoted as, particle scale D50 is
10μm.Covering liquid is made of aluminum nitrate and water, and concentration is 50g aluminum nitrate/100g water, and gas is selected as compressed air, stove choosing
It is selected as revolving burner.
Then, it weighs 100kg positive electrode to be placed in revolving burner, opens rotation and increase its contact area.Heating is opened,
In-furnace temperature is set to reach 700 degrees Celsius.Compressed air is opened, covering liquid is carried and enters furnace body, covering liquid and material are simultaneously
It is decomposed into Al at high temperature2O3, it is uniformly wrapped on material surface.700 degree of soaking times are set as 8 hours, and the time stops after
Ventilation.Cooling system is opened, furnace body cools down rapidly, and Al can be obtained after taking-up2O3The Na of cladding0.9Cu0.22Fe0.30Mn0.48O2,
It is denoted as covering material 1.
Testing electronic microscope is scanned to raw material 1 and covering material 1, result is as shown in Figure 3 and Figure 4.It can be with
Find out, the surface of raw material 1 is more smooth and uniform clad occurs in the surface of covering material 1, and clad carries out material
It is comprehensive to coat.
Using the above-mentioned raw material 1 being prepared and covering material 1 as the active matter of sodium-ion battery positive material
Matter, the preparation for sodium-ion battery.Specific steps are as follows: by the sodium-ion battery positive material active material prepared and conduction
Carbon black, binder Kynoar (PVDF) are mixed according to the mass ratio of 7:2:1, and suitable N-Methyl pyrrolidone is added
(NMP) solution, grinding forms slurry in the environment of air drying, and then slurry is evenly applied in current collector aluminum foil, dries
After dry, it is cut into the round pole piece that diameter is 12mm.Round pole piece under vacuum conditions, 120 DEG C drying 12 hours, be transferred to immediately
Glove box is spare.It is carried out in the glove box for being assemblied in Ar atmosphere of simulated battery, using metallic sodium as to electrode, with glass fibre
As diaphragm, with 1mol/L NaPF6Ethylene carbonate (EC)/dimethyl carbonate (DMC) (volume ratio be 1 ︰ 1) solution conduct
Electrolyte is assembled into CR2032 button cell.Using constant current charge-discharge mode, charge and discharge electrical measurement is carried out under 0.5C current density
Examination.Test condition are as follows: electric discharge is 2.5V by voltage, and charging is 4.05V by voltage.
Raw material 1 and the 0.5C of covering material 1 circulation figure as shown in Figure 5 and Figure 6, compare the cycle performance of two materials,
It can be seen that capacity retention ratio is 91.6% after 100 weeks circulations of raw material 1, and Al2O3Covering material 1 after cladding is 100
Capacity retention ratio is 97.2% after week, is had been significantly improved.The cladding of the present embodiment can be apparent from from circulation result
It works well.
Embodiment 3
Firstly, choose positive electrode be Na1.0Ni0.22Cu0.11Fe0.33Mn0.33O2, it is denoted as raw material 2, particle scale
D50 is 10 μm.Covering liquid is butyl titanate, and gas is selected as nitrogen, and stove is selected as revolving burner.
Then, it weighs 100kg positive electrode to be placed in revolving burner, opens rotation and increase its contact area.Heating is opened,
In-furnace temperature is set to reach 900 degrees Celsius.Compressed air is opened, covering liquid is carried and enters furnace body, covering liquid and material are simultaneously
It is decomposed into TiO at high temperature2, it is uniformly wrapped on material surface.900 degree of soaking times are set as 4 hours, and the time stops after
Ventilation.Cooling system is opened, furnace body cools down rapidly, and TiO can be obtained after taking-up2Cladding
Na1.0Ni0.22Cu0.11Fe0.33Mn0.33O2, it is denoted as covering material 2.
Testing electronic microscope is scanned to raw material 2 and covering material 2, result is as shown in Figure 7 and Figure 8.It can be with
Find out, equally, covering material 2 also there is one layer of uniform clad on surface.
Using the above-mentioned raw material 2 being prepared and covering material 2 as the active matter of sodium-ion battery positive material
Matter, the preparation for sodium-ion battery.It is assembled into CR2032 button cell, it is close in 0.5C electric current using constant current charge-discharge mode
Degree is lower to carry out charge-discharge test.Test condition are as follows: electric discharge is 2.0V by voltage, and charging is 4.0V by voltage.
Raw material 2 and the 0.5C of covering material 2 circulation figure as shown in Figure 9 and Figure 10, compare the cycle performance of two materials,
It can be seen that capacity retention ratio is 92.3% after 100 weeks circulations of raw material 2, and TiO2Covering material 2 after cladding is 100
Capacity retention ratio is 97.1% after week, and the cycle performance that can be seen that material after coating from circulation result is improved, and is shown
Cladding possesses better effect.
Embodiment 4
Firstly, choose positive electrode be Na1.0Ni0.33Fe0.33Mn0.33O2, raw material 3 are denoted as, particle scale D50 is
10μm.Covering liquid is made of magnesium acetate and water, and solubility is 40g magnesium acetate/100g water, and gas is selected as argon gas, stove selection
For revolving burner.
Then, it weighs 100kg positive electrode to be placed in revolving burner, opens rotation and increase its contact area.Heating is opened,
In-furnace temperature is set to reach 400 degrees Celsius.Argon gas is opened, covering liquid is carried and enters furnace body, covering liquid and material and in height
It is decomposed into MgO under temperature, is uniformly wrapped on material surface.400 degree of soaking times are set as 12 hours, and stopping is logical after the time arrives
Gas.Cooling system is opened, furnace body cools down rapidly, and the Na of MgO cladding can be obtained after taking-up1.0Ni0.33Fe0.33Mn0.33O2, it is denoted as
Covering material 3.
Testing electronic microscope is scanned to raw material 3 and covering material 3, result is as is illustrated by figs. 11 and 12.It can
To find out, the surface of raw material 3 is more smooth and uniform clad occurs in the surface of covering material 3.
Using the above-mentioned raw material 3 being prepared and covering material 3 as the active matter of sodium-ion battery positive material
Matter, the preparation for sodium-ion battery.It is assembled into CR2032 button cell, it is close in 0.5C electric current using constant current charge-discharge mode
Degree is lower to carry out charge-discharge test.Test condition are as follows: electric discharge is 2.0V by voltage, and charging is 4.0V by voltage.
Raw material 3 and the 0.5C of covering material 3 circulation figure as shown in Figure 13 and Figure 14, compare the cyclicity of two materials
It can, it will thus be seen that capacity retention ratio is 88.5% after 100 weeks circulations of raw material 3, and the covering material 3 after MgO cladding exists
Capacity retention ratio is 95.0% after 100 weeks, it was demonstrated that the validity of cladding also demonstrates the feasibility of method for coating.
Embodiment 5
Firstly, choose positive electrode be NaNi1/3Fe2/9B1/9Mn1/3O2, raw material 4 are denoted as, particle scale D50 is
10μm.Covering liquid is made of magnesium acetate and water, and solubility is 40g magnesium acetate/100g water, and gas is selected as argon gas, stove selection
For revolving burner.
Then, it weighs 100kg positive electrode to be placed in revolving burner, opens rotation and increase its contact area.Heating is opened,
In-furnace temperature is set to reach 400 degrees Celsius.Argon gas is opened, covering liquid is carried and enters furnace body, covering liquid and material and in height
It is decomposed into MgO under temperature, is uniformly wrapped on material surface.400 degree of soaking times are set as 12 hours, and stopping is logical after the time arrives
Gas.Cooling system is opened, furnace body cools down rapidly, and the NaNi of MgO cladding can be obtained after taking-up1/3Fe2/9B1/9Mn1/3O2, it is denoted as
Covering material 4.
Using the above-mentioned raw material 4 being prepared and covering material 4 as the active matter of sodium-ion battery positive material
Matter, the preparation for sodium-ion battery.It is assembled into CR2032 button cell, it is close in 0.5C electric current using constant current charge-discharge mode
Degree is lower to carry out charge-discharge test.Test condition are as follows: electric discharge is 2.0V by voltage, and charging is 4.0V by voltage.
Compare the cycle performance of two materials: capacity retention ratio is 90.7% after 100 weeks circulations of raw material 4, and MgO packet
Covering material 2 after the covering capacity retention ratio after 100 weeks is 95.9%, from circulation result can be seen that cladding after material follow
Ring performance is improved, and shows that cladding possesses better effect.
The preparation method of the clad structure sodium-ion battery positive material provided in the above embodiment of the present invention, by using
Vapour deposition process carrys out clad anode material, so that cladding process is simpler, covered effect more preferably more evenly, more meets industrial metaplasia
It produces.The interface that positive electrode is optimized after cladding promotes the cyclical stability of sodium-ion battery.The sodium-ion battery can be applied
In the power battery or solar power generation of low-speed electronic vehicle, wind-power electricity generation, smart grid peak regulation, distribution power station, backup power supply
Or the large-scale energy storage systems such as communication base station.
Above-described specific embodiment has carried out further the purpose of the present invention, technical scheme and beneficial effects
It is described in detail, it should be understood that being not intended to limit the present invention the foregoing is merely a specific embodiment of the invention
Protection scope, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of the sodium-ion battery positive material of clad structure, which is characterized in that the described method includes:
Choose/prepare covering liquid；It include the cladding presoma being made of metal salt and/or its hydrate in the covering liquid；
The positive electrode of required cladding is put into cladding furnace, is warming up to 200-1000 degree, utilizes compressed air or nitrogen or argon gas
It carries the covering liquid to enter in the cladding furnace, the cladding presoma is decomposed thermally to form oxide, is evenly coated at institute
State the surface of positive electrode；
Positive electrode obtained with oxide cladding layers is taken out to get positive to the sodium-ion battery of the clad structure
Material.
2. the preparation method of the sodium-ion battery positive material of clad structure according to claim 1, which is characterized in that institute
Cladding furnace is stated as rotation atmosphere furnace.
3. the preparation method of the sodium-ion battery positive material of clad structure according to claim 1, which is characterized in that institute
The positive electrode coated needed for stating is NaxM1aM2bO2；
Wherein, 0.6<x≤1, a>0, b>=0, a+b=1, and keep material electroneutral；M1 is metallic element, including Li, Mg, Al,
One or more of Ti, Mn, Fe, Co, Ni, Cu, Zn, Sn；M2 is one of nonmetalloid, including B, F, Si or several
Kind.
4. the preparation method of the sodium-ion battery positive material of clad structure according to claim 1, which is characterized in that institute
It states and prepares covering liquid and specifically include:
Presoma solid material is dissolved in corresponding solvent, the covering liquid is formed；
Wherein, the solvent includes: one or more of water, ethyl alcohol, N-Methyl pyrrolidone, acetone.
5. the preparation method of the sodium-ion battery positive material of clad structure according to claim 1, which is characterized in that institute
Selection covering liquid is stated to specifically include:
Using liquid cladding presoma as the covering liquid.
6. the preparation method of the sodium-ion battery positive material of clad structure according to claim 1, which is characterized in that institute
The positive electrode by obtained with oxide cladding layers is stated to take out to get the sodium-ion battery anode material of the clad structure is arrived
Material specifically:
The positive electrode by obtained with oxide cladding layers takes out, and cladding knot is arrived except iron by screening
The sodium-ion battery positive material of structure.
7. the preparation method of the sodium-ion battery positive material of clad structure according to claim 1, which is characterized in that institute
It states metal salt and/or its hydrate specifically includes:
One of the nitrate and its hydrate of Al, Mg, Ti, Zn, Zr, Nb or La, sulfate and its hydrate, organic salt or
It is several.
8. the sodium-ion battery positive material that -7 any preparation methods are prepared, feature exist according to claim 1
In the sodium-ion battery positive material includes: Layered Structural Positive Electrode Materials kernel and clad；
Layered structure positive electrode kernel is NaxM1aM2bO2, 0.6<x≤1, a>0, b>=0,
A+b=1, and keep material electroneutral；M1 is metallic element, including Li, Mg, Al, Ti, Mn, Fe, Co, Ni, Cu, Zn, Sn
One or more of；M2 is one or more of nonmetalloid, including B, F, Si；
The clad is the oxide of Al, Mg, Ti, Zn, Zr, Nb or La for being coated on except Layered Structural Positive Electrode Materials kernel
Shell；
Wherein, in the sodium-ion battery positive material, the mass percent of the clad is 0.05%-20%.
9. a kind of sodium ion secondary battery, which is characterized in that the sodium ion secondary battery includes described in the claims 8
Sodium-ion battery positive material.
10. a kind of purposes including sodium ion secondary battery described in the claims 9, which is characterized in that the secondary electricity
Pond is for electric tool, electric vehicle and solar power generation, wind-power electricity generation, smart grid peak regulation, distribution power station, backup power supply
Or the energy storage device of communication base station.
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