CN106784780A - A kind of nickel-based oxide presoma and its preparation method and application - Google Patents
A kind of nickel-based oxide presoma and its preparation method and application Download PDFInfo
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- 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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- H—ELECTRICITY
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- 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 invention discloses a kind of nickel-based oxide presoma and its preparation method and application, including the according to target stoichiometric proportion configuration metal chloride solution of nickelic layered cathode material product, the metal chloride solution is NiaCobMcCl2, wherein x >=0.8, M is Mn or Al, wherein, a >=0.8,0.2 >=b > 0,0.2 >=c >=0 and a+b+c=1;After by the metal chloride solution ultrasonic atomizatio, under the conditions of 650 DEG C~950 DEG C, with O2It is carrier gas, flow rate of carrier gas carries out spray pyrolysis for 0.5L/min~20L/min, and the reaction time of spray pyrolysis is 5 seconds~30 seconds, obtains the nickel-based oxide presoma.Method of the present invention process is simple, can be used for the nickel-base anode material of composite structure and electrochemical performance using nickel-based oxide presoma of the invention, there is great application value in the high energy battery positive electrode field of electric motor car (EV) or hybrid electric vehicle (HEV).
Description
Technical field
The invention belongs to powder body material field, more particularly to a kind of nickel-based oxide presoma and preparation method thereof.
Background technology
Nickel-base anode material LiNixM1-xO2(x >=0.8, M is Co, one or more in Mn, Al etc.) actual reversible capacity
Up to 200mAhg-1Or it is higher, it is particularly suitable as the high energy battery positive pole material of electric motor car (EV) or hybrid electric vehicle (HEV)
Material.Spray pyrolysis have many advantages, such as flow is short, strong to adaptability to raw material, operation is simple, production capacity is big, production efficiency is high,
Be conducive to industrialized production;Product has spherical morphology, particle size controllable and is evenly distributed, specific surface area big, product component
Uniform the advantages of.Spray pyrolysis have been widely used for preparing the anode material for lithium-ion batteries of different crystal forms.
At present, it is raw material that relevant spray pyrolysis prepare the overwhelming majority in the document of positive electrode and use nitrate solution, and
And generally need to add in the solution additive (such as PVP, citric acid, urea) and can just obtain that there is more regular spherical morphology
Material;On the other hand, although in document with nitrate solution as raw material prepared by spinel structure positive electrode (such as
LiMn2O4), polyanionic positive electrode (for example:Li2MSiO4(M=Mn, Fe), LiCo1/3Mn1/3Fe1/3PO4) and stratiform it is low
Nickel positive electrode (such as LiNi1/3Co1/3Mn1/3O2) there is preferable chemical property, but prepared nickelic positive electrode is (such as
LiNi0.8Co0.2O2, LiNi0.8Co0.15Al0.05O2) chemical property it is all poor.Solubility, satiety due to variety classes salt
Had differences with the physicochemical properties such as degree, fusing point, pyrolysis temperature, atomized drop will be caused to form the machine of solid oxide composition granule
System is different, the final pattern for influenceing powder product, granularity and surface texture.Difference of the powder product at aspects such as pattern, structures
Property will produce significant impact to the chemical property of follow-up prepared positive electrode.At present, to using metal chloride to be sprayed for raw material
Mist pyrolysis prepares the research of lithium ion anode material seldom, is especially a lack of preparing nickel-base anode to many metal chloride spray pyrolysis
The research of material.Think that villaumite decomposition temperature is high compared with nitrate in document, the hydrogen chloride gas in tail gas know from experience etching apparatus, thus
Without the potential advantages that further oxide precursor prepared by research villaumite has on high-performance positive electrode is prepared.Cause
This, research metal chloride spray pyrolysis prepare the potential advantages of nickel-based oxide presoma, to preparing high-performance nickel-base anode material
Material important in inhibiting.
The content of the invention
The technical problems to be solved by the invention are to overcome the shortcomings of to be mentioned and defect in background above technology, there is provided a kind of
With the nickel-based oxide presoma that metal chloride is prepared as raw material spray pyrolysis.Without addition in the metal chloride solution for being used
Any additive, can be directly used for synthesizing nickel-base anode material by the nickel-based oxide presoma prepared by spray pyrolysis, adopt
Have good layer structure, height ratio capacity and excellent circulation steady with the nickel-base anode material synthesized by the oxide precursor
It is qualitative.
In order to solve the above technical problems, technical scheme proposed by the present invention is:
A kind of preparation method of nickel-based oxide presoma, comprises the following steps:
(1) according to target the stoichiometric proportion of nickelic layered cathode material product configures metal chloride solution, the metal chlorine
Salting liquid is NiaCobMcCl2, wherein x >=0.8, M is Mn or Al, wherein, a >=0.8,0.2 >=b > 0,0.2 >=c >=0 and a+b+
C=1;
(2) after by the metal chloride solution ultrasonic atomizatio, under the conditions of 650 DEG C~950 DEG C, with O2It is carrier gas, carrier gas
Flow velocity carries out spray pyrolysis for 0.5L/min~20L/min, and the reaction time of spray pyrolysis is 5 seconds~30 seconds, obtains the nickel
Base oxide presoma;
The nickel-based oxide presoma for using this method to prepare is the presoma of the spherical pattern of porous nano, Ci Zhongqian
The reactivity for driving body is high, and the positive electrode of excellent performance can be obtained with lithium carbonate reaction, and common precursor reaction is lived
Property it is low, the reaction of lithium hydroxide that need to be higher with reactivity could obtain the good positive electrode of performance.
In order to ensure that it is complete that villaumite is decomposed, obtain nickel-based oxide presoma of the present invention, it is necessary to 650 DEG C~
Spray pyrolysis are carried out under the conditions of 950 DEG C;Using oxygen or air as carrier gas, preferably oxygen, because the heat under oxygen atmosphere
Solution is more thorough;Also, it is pyrolyzed under oxygen or air atmosphere, due to foring the spherical pattern of porous nano so that material has
Big specific surface area, the area contacted with oxygen is big, so that preparing the metallic nickel on the surface of nickel-based oxide presoma
It is oxidized to+trivalent.The Ni that can be reduced in the positive electrode for preparing is prepared using the nickel-based oxide presoma2+, so that
Lithium nickel mixing is reduced, the purpose for improving properties of product is reached.
Preferably, in the step (1), total concentration of metal ions is 0.25mol/L~1.5mol/ in metal chloride solution
L.The too low then powder yield of concentration is too low, too high, and solution may be caused to be atomized.
In the step (2), the supersonic frequency of ultrasonic atomizatio is 1.7MHz, and condensation rate is 0.5mL/min~2mL/min.
To realize the purpose of the present invention, the present invention also provides a kind of preparation method system by the nickel-based oxide presoma
The standby nickel-based oxide presoma for obtaining, the nickel-based oxide presoma is by NiaCobMcOyRepresent, wherein, a >=0.6,0.4
>=b > 0,0.4 >=c >=0, and a+b+c=1,1.2 > y >=1, M is Mn or Al.The nickel-based oxide presoma once
Grain particle diameter is 10nm~200nm, and second particle particle diameter is 0.5 μm~8 μm, and its main body thing is mutually NiO, and primary particle includes center
Spheroid and the top layer for being coated on center spheroid, the nickel on the primary particle top layer is with Ni3+Based on, Ni in the nickel element of top layer3+Rub
Your percentage is 50%~80%.
The nickel-based oxide presoma is mixed with lithium salts, it is sintered can prepare with low lithium nickel mixing and
The nickel-base anode material of good cycling stability.
Compared with prior art, the advantage of the invention is that:
Metal chloride solution in the present invention need not add any additive can be directly used for spray pyrolysis prepare it is Ni-based
Oxide precursor;Prepared nickel-based oxide has greater activity, and the nickel on top layer is with Ni3+Based on;Using the nickel-based oxide
Nickel-base anode material prepared by presoma has low lithium nickel mixing degree, specific capacity high and excellent cyclical stability.
Method of the present invention process is simple, can be used for composite structure using nickel-based oxide presoma of the invention and chemical property is excellent
Different nickel-base anode material, has pole in the high energy battery positive electrode field of electric motor car (EV) or hybrid electric vehicle (HEV)
Big application value.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
The accompanying drawing to be used needed for having technology description is briefly described, it should be apparent that, drawings in the following description are the present invention
Some embodiments, for those of ordinary skill in the art, on the premise of not paying creative work, can also basis
These accompanying drawings obtain other accompanying drawings.
Fig. 1 is the Ni-based oxidic precursor Ni of gained in the embodiment of the present invention 10.8Co0.1Mn0.1O1.1XRD spectrum.
Fig. 2 is the Ni-based oxidic precursor Ni of gained in the embodiment of the present invention 10.8Co0.1Mn0.1O1.1SEM spectrum.
Fig. 3 is the Ni-based oxidic precursor Ni of gained in the embodiment of the present invention 10.8Co0.1Mn0.1O1.1And nickel-base anode material
LiNi0.8Co0.1Mn0.1O2The XPS collection of illustrative plates of Ni in (b).
Fig. 4 is gained nickel-base anode material LiNi in the embodiment of the present invention 10.8Co0.1Mn0.1O2XRD spectrum.
Fig. 5 is gained nickel-base anode material LiNi in the embodiment of the present invention 10.8Co0.1Mn0.1O2SEM spectrum.
Fig. 6 is using gained LiNi in the embodiment of the present invention 10.8Co0.1Mn0.1O2During as positive electrode, battery is first
Charging and discharging curve figure.
Fig. 7 is using gained LiNi in the embodiment of the present invention 10.8Co0.1Mn0.1O2During as positive electrode, the circulation of battery
Performance map (2.8~4.3V, under the conditions of 25 DEG C).
Fig. 8 is the Ni-based oxidic precursor Ni of gained in the embodiment of the present invention 20.85Co0.075Mn0.075O1.08XRD spectrum.
Fig. 9 is the Ni-based oxidic precursor Ni of gained in the embodiment of the present invention 20.85Co0.075Mn0.075O1.08SEM spectrum.
Figure 10 is gained nickel-base anode material LiNi in the embodiment of the present invention 20.85Co0.075Mn0.075O2XRD spectrum.
Figure 11 is gained nickel-base anode material LiNi in the embodiment of the present invention 20.85Co0.075Mn0.075O2SEM spectrum.
Figure 12 is using gained LiNi in the embodiment of the present invention 20.85Co0.075Mn0.075O2During as positive electrode, battery
First charge-discharge curve map.
Figure 13 is using gained LiNi in the embodiment of the present invention 20.85Co0.075Mn0.075O2During as positive electrode, battery
Cycle performance figure (2.8~4.3V, under the conditions of 25 DEG C).
Figure 14 is the Ni-based oxidic precursor Ni of gained in the embodiment of the present invention 30.8Co0.15Al0.05O1.12XRD spectrum.
Figure 15 is the Ni-based oxidic precursor Ni of gained in the embodiment of the present invention 30.8Co0.15Al0.05O1.12SEM spectrum.
Figure 16 is gained nickel-base anode material Li Ni in the embodiment of the present invention 30.8Co0.15Al0.05O2XRD spectrum.
Figure 17 is gained nickel-base anode material Li Ni in the embodiment of the present invention 30.8Co0.15Al0.05O2SEM spectrum.
Figure 18 is using gained LiNi in the embodiment of the present invention 30.8Co0.15Al0.05O2During as positive electrode, the head of battery
Secondary charging and discharging curve.
Figure 19 is using gained LiNi in the embodiment of the present invention 30.8Co0.15Al0.05O2During as positive electrode, battery is followed
Ring performance map (2.8~4.3V, under the conditions of 25 DEG C).
Specific embodiment
For the ease of understanding the present invention, do more complete to inventing herein below in conjunction with Figure of description and preferred embodiment
Face, meticulously describe, but protection scope of the present invention is not limited to specific examples below.
Unless otherwise defined, all technical terms used hereinafter are generally understood that implication phase with those skilled in the art
Together.Technical term used herein is intended merely to describe the purpose of specific embodiment, is not intended to limitation of the invention
Protection domain.
Unless otherwise specified, various raw material, reagent, instrument and equipment used in the present invention etc. can be by city
Field is commercially available or can be prepared by existing method.
Embodiment:
Embodiment 1
The preparation method of the nickel-based oxide presoma of the present embodiment, comprises the following steps:
(1) by NiCl2、CoCl2And MnCl2According to 8:1:1 ratio (mol ratio) is made into total concentration of metal ions and is
The solution of 0.5mol/L;
(2) solution that step (1) configuration is obtained is carried out into spray pyrolysis, the supersonic frequency of ultrasonic atomizatio after ultrasonic atomizatio
It is 1.7MHz, condensation rate is 0.8mL/min, and spray pyrolysis temperature is 850 DEG C, and carrier gas is O2, flow rate of carrier gas is 6L/min, is obtained
Ni0.8Co0.1Mn0.1O1.1Nickel-based oxide presoma.
To the nickel-based oxide presoma Ni of the present embodiment0.8Co0.1Mn0.1O1.1Thing phase and pattern detected.
Fig. 1 is Ni0.8Co0.1Mn0.1O1.1XRD spectrum, it is known that there is NiO, MnCo in nickel-based oxide presoma2O4And
Ni6MnO8Three thing phases.Fig. 2 is Ni0.8Co0.1Mn0.1O1.1SEM spectrum, it is known that nickel-based oxide presoma is by many particle diameters
It is the porous solid microsphere that the aggregate particle size that the primary particle of 50nm~80nm is constituted is 0.5 μm~8 μm.Fig. 3 (a) is
Ni0.8Co0.1Mn0.1OxThe XPS collection of illustrative plates of middle Ni, it is known that primary particle includes center spheroid and is coated on the top layer of center spheroid, table
Nickel element in layer is with Ni3+Based on, Ni in the nickel element of top layer3+Molar percentage is 51.27%.
By the nickel-based oxide presoma Ni of the present embodiment0.8Co0.1Mn0.1O1.1Mix with lithium carbonate, it is sintered to obtain
LiNi0.8Co0.1Mn0.1O2Nickel-base anode material.
To the nickel-base anode material LiNi of the present embodiment0.8Co0.1Mn0.1O2Thing phase, pattern and chemical property examined
Survey.
Fig. 4 is the nickelic layered cathode material LiNi of gained0.8Co0.1Mn0.1O2XRD spectrum, it is known that material has good
Layer structure and low lithium nickel mixing degree.Fig. 5 is the LiNi of the nickelic layered cathode material of gained0.8Co0.1Mn0.1O2SEM figure
Spectrum, it is known that resulting materials are the other amorphous pellets of submicron order.Fig. 3 (b) is the nickelic layered cathode material of gained
LiNi0.8Co0.1Mn0.1O2The XPS collection of illustrative plates of middle Ni elements, it is known that in the nickel element of positive electrode, Ni3+The molar percentage of ion
It is 92.98%.Fig. 6 is using the nickelic layered cathode material LiNi of the present embodiment gained0.8Co0.1Mn0.1O2As positive electrode
When, the first charge-discharge curve map of battery, first discharge specific capacity and first charge-discharge efficiency divide under 0.1C multiplying powers after measured
Wei not 205.1mAhg-1With 81.1%;Fig. 7 is using the nickelic layered cathode material LiNi of the present embodiment gained0.8Co0.1Mn0.1O2
During as positive electrode, the ring performance map (2.8~4.3V, under the conditions of 25 DEG C) of battery, as seen from the figure, and under 1C multiplying powers, circulation
Specific discharge capacity and capability retention after 100 times are respectively 173.0mAhg-1With 95.6%.
Embodiment 2:
The preparation method of the nickel-base anode material of the present embodiment, comprises the following steps:
(1) by NiCl2、CoCl2And MnCl2According to 34:3:3 ratio (mol ratio) is made into total concentration of metal ions and is
The solution of 0.5mol/L;
(2) solution that step (1) configuration is obtained is carried out into spray pyrolysis, the supersonic frequency of ultrasonic atomizatio after ultrasonic atomizatio
It is 1.7MHz, condensation rate is 1.5mL/min, and spray pyrolysis temperature is 750 DEG C, and carrier gas is O2, flow rate of carrier gas is 2L/min, is obtained
Nickel-based oxide presoma Ni0.85Co0.075Mn0.075Ox。
Thing phase and pattern to the nickel-based oxide presoma of the present embodiment are detected.
Fig. 8 is Ni0.85Co0.075Mn0.075O1.08XRD spectrum, it is known that there is NiO and MnCo in product2O4Two thing phases.
Fig. 9 is Ni0.85Co0.075Mn0.075O1.08SEM spectrum, it is known that nickel-based oxide presoma be by many particle diameters be 40nm~
The aggregate particle size of the primary particle composition of 80nm is 0.5 μm~6 μm of porous solid microsphere.Primary particle include center spheroid and
The top layer of center spheroid is coated on, the nickel element in top layer is with Ni3+Based on, determined by XPS methods, Ni in the nickel element of top layer3+
Molar percentage is 67.3%.
By the Ni of the present embodiment0.85Co0.075Mn0.075O1.08Nickel-based oxide presoma mixes with lithium carbonate, sintered
To nickel-base anode material LiNi0.85Co0.075Mn0.075O2。
To the nickel-base anode material LiNi of the present embodiment0.85Co0.075Mn0.075O2Thing phase, pattern and chemical property enter
Row detection.
Figure 10 is the nickelic layered cathode material LiNi of gained0.85Co0.075Mn0.075O2XRD spectrum, it is known that material has good
Good layer structure and low lithium nickel mixing degree.Figure 11 is the nickelic layered cathode material LiNi of gained0.85Co0.075Mn0.075O2
SEM spectrum, it is known that resulting materials be the other amorphous pellets of submicron order.Determined by XPS, the nickelic stratiform of the present embodiment
In the nickel element of positive electrode, Ni3+Molar percentage be 91.7%.Figure 12 is using the present embodiment nickelic layered cathode of gained
Material LiNi0.85Co0.075Mn0.075O2During as positive electrode, the first charge-discharge curve map of battery, as seen from the figure, material exists
First discharge specific capacity and first charge-discharge efficiency are respectively 215.5mAhg under 0.1C multiplying powers-1With 82.3%;Figure 13 is using this
Embodiment gained LiNi0.85Co0.075Mn0.075O2During as positive electrode, ring performance map (2.8~4.3V, 25 DEG C of conditions of battery
Under), as seen from the figure, specific discharge capacity and capability retention after circulating 100 times under 1C multiplying powers are respectively 181.0mAhg-1With
96.3%.
Embodiment 3:
The preparation method of the nickel-base anode material of the present embodiment, comprises the following steps:
(1) by NiCl2, CoCl2And AlCl3According to 8:1.5:0.5 ratio (mol ratio) is made into total concentration of metal ions and is
The solution of 0.5mol/L;
(2) solution that step (1) configuration is obtained is carried out into spray pyrolysis, the supersonic frequency of ultrasonic atomizatio after ultrasonic atomizatio
It is 1.7MHz, condensation rate is 1.7mL/min, and spray pyrolysis temperature is 800 DEG C, and carrier gas is O2, flow rate of carrier gas is 6L/min, is obtained
Nickel-based oxide presoma Ni0.8Co0.15Al0.05O1.12。
To the nickel-based oxide presoma Ni of the present embodiment0.8Co0.15Al0.05O1.12Thing phase and pattern detected.
Figure 14 is Ni0.8Co0.15Al0.05O1.12XRD spectrum, NiO thing phases are only detected in product as seen from the figure, this be because
For the content of Al is little, the lattice of NiO is entered in the form of adulterating, so the diffraction maximum of the compound of Al will not be shown.Figure 15
It is Ni0.8Co0.15Al0.05O1.12SEM spectrum, it is known that nickel-based oxide presoma be by many particle diameters for 30nm~60nm one
The aggregate particle size of secondary particle composition is 0.5 μm~5 μm of porous solid microsphere.During primary particle includes center spheroid and is coated on
The top layer of bulbus cordis body, the nickel element in top layer is with Ni3+Based on, determined by XPS, Ni in the nickel element of top layer3+Molar percentage is
75.6%.
By the nickel-based oxide presoma Ni of the present embodiment0.8Co0.15Al0.05O1.12Mix with lithium carbonate, it is sintered to obtain
Nickel-base anode material LiNi0.8Co0.15Al0.05O2。
To the nickel-base anode material LiNi of the present embodiment0.8Co0.15Al0.05O2Thing phase, pattern and chemical property carry out
Detection.
Figure 16 is the nickelic layered cathode material LiNi of gained0.8Co0.15Al0.05O2XRD spectrum, as seen from the figure material have
Good layer structure and low lithium nickel mixing degree.Figure 17 is the nickelic layered cathode material LiNi of gained0.8Co0.15Al0.05O2
SEM spectrum, as seen from the figure resulting materials be the other amorphous pellets of submicron order.By XPS determine, the present embodiment it is nickelic
In the nickel element of layered cathode material, Ni3+Molar percentage be 92.9%.Figure 18 is using the nickelic layered cathode material of gained
LiNi0.8Co0.15Al0.05O2During as positive electrode, the first charge-discharge curve map of battery, as seen from the figure, under 0.1C multiplying powers
First discharge specific capacity and first charge-discharge efficiency are respectively 194.6mAhg-1With 85.1%.Figure 19 is using the nickelic stratiform of gained
Positive electrode LiNi0.8Co0.15Al0.05O2During as positive electrode, the cycle performance figure of battery, as seen from the figure, under 1C multiplying powers
Circulate specific discharge capacity and capability retention after 100 times and be respectively 167.2mAhg-1With 93.4%.
Claims (7)
1. a kind of preparation method of nickel-based oxide presoma, it is characterised in that comprise the following steps:
(1) according to target the stoichiometric proportion of nickelic layered cathode material product configures metal chloride solution, and the metal chloride is molten
Liquid is NiaCobMcCl2, wherein x >=0.8, M is Mn or Al, wherein, a >=0.8,0.2 >=b > 0,0.2 >=c >=0 and a+b+c=
1;
(2) after by the metal chloride solution ultrasonic atomizatio, under the conditions of 650 DEG C~950 DEG C, with O2It is carrier gas, flow rate of carrier gas is
0.5L/min~20L/min carries out spray pyrolysis, and the reaction time of spray pyrolysis is 5 seconds~30 seconds, obtains the Ni-based oxidation
Thing presoma.
2. the preparation method of nickel-based oxide presoma according to claim 1, it is characterised in that in the step (1), gold
Total concentration of metal ions is 0.25mol/L~1.5mol/L in category chloride solution.
3. the preparation method of nickel-based oxide presoma according to claim 1, it is characterised in that the supersonic frequency of ultrasonic atomizatio
Rate is 1.7MHz, and condensation rate is 0.5mL/min~2mL/min.
4. a kind of nickel-based oxide presoma, it is characterised in that before the nickel-based oxide as described in claims 1 to 3 any one
The preparation method for driving body is prepared.
5. nickel-based oxide presoma according to claim 4, it is characterised in that the nickel-based oxide presoma by
NiaCobMcOyRepresent, wherein, a >=0.8,0.2 >=b > 0,0.2 >=c >=0, and a+b+c=1,1.2 > y >=1, M is Mn or Al.
6. nickel-based oxide presoma according to claim 4, it is characterised in that characterized in that, the nickel-based oxide
The primary particle particle diameter of presoma is 10nm~200nm, and second particle particle diameter is 0.5~8 μm, and main body thing is mutually NiO, described one
Secondary particle includes center spheroid and is coated on the top layer of center spheroid, Ni in the nickel element on top layer3+The molar percentage of ion is
50%~80%.
7. the application of nickel-based oxide presoma described in a kind of claim 4 to 6 any one, it is characterised in that by the nickel
Base oxide presoma is used to prepare nickel-base anode material.
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CN108878875A (en) * | 2018-06-19 | 2018-11-23 | 中南大学 | The preparation method of fluorophosphoric acid vanadium sodium |
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CN110085845A (en) * | 2019-05-13 | 2019-08-02 | 中南大学 | A kind of nickel-base anode material and preparation method thereof with core-shell structure |
CN110085848A (en) * | 2019-05-17 | 2019-08-02 | 中南大学 | A kind of lithium-rich manganese-based anode material and preparation method thereof |
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